BAK SEONGMU (JP)
HITOMI SEIICHI (JP)
| WO1999026951A1 | 1999-06-03 | |||
| WO1999026952A1 | 1999-06-03 | |||
| WO2011071052A1 | 2011-06-16 |
| JP2008268267A | 2008-11-06 | |||
| EP1826200A2 | 2007-08-29 |
| CLAIMS 1. A near infrared absorptive liquid composition comprising a copper compound, a compound having a polymerizable group, and 50 to 80% by mass of a solvent. 2. The near infrared absorptive liquid composition of Claim 1, wherein the copper compound is a phosphorus-containing copper compound or copper sulfonate compound. 3. The near infrared absorptive liquid composition of Claim 1, wherein the copper compound is a copper phosphate compound . 4. The near infrared absorptive liquid composition of any one of Claims 1 to 3, wherein the compound having a polymerizable group is a multifunctional monomer. 5. The near infrared absorptive liquid composition of any one of Claims 1 to 4, wherein the compound having a polymerizable group is a polymerizable monomer represented by any of the formulae (MO-1) to (MO-5) below: [Chemical Formula 1] R T: *- CH2j * -OCH2- ^ -OCH2CH2- -OCH2CH2CH2 — OCH2CH2CH CH2- Z: 0-C-N-(CH2— N-C-O— 6 H m H ό (in the formulae, n respectively represents 0 to 14, and m respectively represents 1 to 8. Each of a plurality of (R) s, (T) s and (Z)s in a single molecule may respectively be same or different. When T represents an oxyalkylene group, the carbon terminal thereof is bound to R. At least one of (R) s is a polymerizable group.) 6. The near infrared absorptive liquid composition of any one of Claims 1 to 4, wherein the compound having a polymerizable group is has the polymerizable group at the side chain thereof. 7. The near infrared absorptive liquid composition of any one of Claims 1 to 6, further comprising a polymerization initiator . 8. The near infrared absorptive liquid composition of any one of Claims 3 to 7, wherein the copper phosphate compound is formed using the compound represented by the formula (1) below : Formula (1) (HO)n-P(=0)-(OR2)3-n (in the formula, R2 represents a Ci_i8 alkyl group, C6-i8 aryl group, Ci-18 aralkyl group, or Ci_i8 alkenyl group, or -OR2 represents a C4-i0o polyoxyalkyl group, C4-100 (meth) acryloyloxyalkyl group, or C4-100 (meth) acryloylpolyoxyalkyl group, and n represents 1 or 2.) 9. The near infrared absorptive liquid composition of Claim 8, wherein, in the formula (1), -OR2 represents a C4-100 (meth) acryloyloxyalkyl group, or C4-100 (meth) acryloylpolyoxyalkyl group. 10. The near infrared absorptive liquid composition of any one of Claims 1 to 9, wherein the compound having a polymerizable group contains a (meth ) acryloyloxy group. 11. The near infrared absorptive liquid composition of any one of Claims 1 to 10, used in the form of film coated on an image sensor for solid state image sensing device. 12. A near infrared cut filter manufactured using the near infrared absorptive liquid composition described in any one of Claims 1 to 11. 13. A camera module comprising a substrate of solid state image sensing device, and the near infrared cut filter described in Claim 12, disposed on the light receiving side of the substrate of solid state image sensing device. 14. A method of manufacturing a camera module which comprises a substrate of solid state image sensing device, and a near infrared cut filter disposed on the light receiving side of the substrate of solid state image sensing device, the method comprising : forming a film by coating the near infrared absorptive liquid composition described in any one of Claims 1 to 11, on the light receiving side of the substrate of solid state image sensing device. 15. The method of manufacturing a camera module of Claim 14, wherein the film is formed on microlenses on the light receiving side of the substrate of solid state image sensing device . 16. The method of manufacturing a camera module of Claim 14 or 15, comprising curing, by irradiation of light, the film formed by coating the infrared absorptive liquid composition. |
NEAR INFRARED ABSORPTIVE LIQUID COMPOSITION, NEAR INFRARED CUT FILTER USING THE SAME, METHOD OF MANUFACTURING THE SAME, AND CAMERA MODULE AND METHOD OF MANUFACTURING THE SAME
TECHNICAL FIELD
[0001]
The present invention relates to a near infrared absorptive liquid composition, a near infrared cut filter using the same and a method of manufacturing the same, and, a camera module and a method of manufacturing the same.
BACKGROUND ART
[0002]
In recent years, CCD and CMOS image sensors have been used as a solid state image sensing device for color imaging, while being incorporated into video camera, digital still camera, and mobile phone with camera function and so forth. These solid state image sensing devices use, in the light receiving sections thereof, a silicon photodiode which is sensitive in the near infrared region, and therefore need luminosity correction. Near infrared cut filter has often been used for this purpose.
[0003]
Near infrared absorptive composition has been known as a material for composing such near infrared cut filter (Patent Literature 1) . According to Patent Literature 1, the near infrared absorptive composition is formed into a layer typically by vacuum evaporation, to thereby form a near infrared shielding layer. There is, however, a demand for a near infrared absorptive liquid composition which may be formed into a film by coating. CITATION LIST
[Patent Literature]
[0004]
[Patent Literature 1] International Patent W099/26952, Pamphlet SUMMARY OF THE INVENTION
TECHNICAL PROBLEM
[0005]
The present invention was conceived to address the problems described above, and an object thereof is to provide a near infrared absorptive liquid composition which may be formed into a layer by coating, and is excellent in near infrared shielding performance.
SOLUTION TO PROBLEM
[0006]
In these circumstances, the present inventors found out from our extensive investigations that the problems may be solved by using a copper phosphate compound as a near infrared absorber. More specifically, the problems were solved by the configuration <1>, preferably by configurations <2> to <16> below .
[0007]
<1> A near infrared absorptive liquid composition comprising a copper compound, a compound having a polymerizable group, and 50 to 80% by mass of a solvent.
<2> The near infrared absorptive liquid composition of <1>, wherein the copper compound is a phosphorus-containing copper compound or copper sulfonate compound.
<3> The near infrared absorptive liquid composition of <1>, wherein the copper compound is a copper phosphate compound. <4> The near infrared absorptive liquid composition of any one of <1> to <3>, wherein the compound having a polymerizable group is a multifunctional monomer.
<5> The near infrared absorptive liquid composition of any one of <1> to <4>, wherein the compound having a polymerizable group is a polymerizable monomer represented by any of the formulae (MO-1) to (MO-5) below:
[Chemical Formula 1] OH
T: *-{CH 2 5 * -OCH 2 - — OCH 2 CH 2 - — OCH 2 CH 2 CH 2 - — OCH 2 CH 2 CH 2 CH 2 -
7 . — 0-C-N-{CH 2 -N-C-0—
O H M H O
(in the formulae, n respectively represents 0 to 14, and m respectively represents 1 to 8. Each of a plurality of (R)s, (T)s and (Z)s in a single molecule may respectively be same or different. When T represents an oxyalkylene group, the carbon terminal thereof is bound to R. At least one of (R) s is a polymerizable group.)
<6> The near infrared absorptive liquid composition of any one of <1> to <4>, wherein the compound having a polymerizable group is has the polymerizable group at the side chain thereof. <7> The near infrared absorptive liquid composition of any one of <1> to <6>, further comprising a polymerization initiator.
<8> The near infrared absorptive liquid composition of any one of <3> to <7>, wherein the copper phosphate compound is formed using the compound represented by the formula (1) below: Formula (1)
(HO) n -P(=0)-(OR 2 )3 -n
(in the formula, R 2 represents a Ci_ 18 alkyl group, C 6 -i8 aryl group, Ci-18 aralkyl group, or Ci_i 8 alkenyl group, or -OR 2 represents a C4-100 polyoxyalkyl group, C4-100
(meth) acryloyloxyalkyl group, or C4-100
(meth) acryloylpolyoxyalkyl group, and n represents 1 or 2.) <9> The near infrared absorptive liquid composition of <8>, wherein, in the formula (1), -OR 2 represents a C4-100
(meth) acryloyloxyalkyl group, or C4-100
(meth) acryloylpolyoxyalkyl group.
<10> The near infrared absorptive liquid composition of any one of <1> to <9>, wherein the compound having a polymerizable group contains a (meth) acryloyloxy group.
<11> The near infrared absorptive liquid composition of any one of <1> to <10>, used in the form of film coated on an image sensor for solid state image sensing device.
<12> A near infrared cut filter manufactured using the near infrared absorptive liquid composition described in any one of <1> to <11>.
<13> A camera module comprising a substrate of solid state image sensing device, and the near infrared cut filter described in <12>, disposed on the light receiving side of the substrate of solid state image sensing device.
<14> A method of manufacturing a camera module which comprises a substrate of solid state image sensing device, and a near infrared cut filter disposed on the light receiving side of the substrate of solid state image sensing device, the method comprising:
forming a film by coating the near infrared absorptive liquid composition described in any one of <1> to <11>, on the light receiving side of the substrate of solid state image sensing device.
<15> The method of manufacturing a camera module of <14>, wherein the film is formed on microlenses on the light receiving side of the substrate of solid state image sensing device. <16> The method of manufacturing a camera module of <14> or <15>, comprising curing, by irradiation of light, the film formed by coating the infrared absorptive liquid composition.
ADVANTAGEOUS EFFECTS OF INVENTION
[0008]
By the present invention, a near infrared absorbing layer is now formable by coating.
BRIEF DESCRIPTION OF DRAWINGS
[0009]
[FIG. 1] A schematic cross sectional view illustrating a configuration of a camera module provided with a solid state image sensing device according to an embodiment of the present invention .
[FIG. 2] A schematic cross sectional view illustrating a substrate of solid state image sensing device according to the embodiment of the present invention.
DESCRIPTION OF EMBODIMENTS
[0010]
The present invention will now be detailed below. While the description on the constituents may be made based on representative embodiments of the present invention, the present invention is not limited thereto. Note that any numerical range expressed by wording "to" means a numerical range which includes the numerals placed before and after "to" as a lower limit value and an upper limit value.
In this specification, " (meth ) acrylate" means acrylate and methacrylate , " (meth) acryl" means acryl and methacryl , and " (meth) acryloyl" means acryloyl and methacryloyl . The monomer in the context of the present invention is
discriminated from oligomer or from polymer, and means compounds having a weight average molecular weight of 2,000 or smaller. In this specification, polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. Polymerizable functional group means a group which takes part in polymerization reaction. Note, in this specification, that the term of "group (group of atoms)" preceded by neither "substituted" nor
"unsubstituted" include both of groups having substituent and groups having no substituent. For example, "alkyl group" not only includes alkyl group having no substituent ( unsubstituted alkyl group) , but also alkyl group having substituent
(substituted alkyl group) .
Near infrared radiation in the context of the present invention means light in the wavelength range from 700 to 2500 nm.
[0011]
The near infrared absorptive liquid composition of the present invention, the near infrared cut filter, the camera module having such near infrared cut filter and such substrate of solid state image sensing device, and the method of manufacturing such camera module will be detailed below. The description below on the constituents may otherwise be made on representative embodiments of the present invention, but not intended to limit the present invention to these
embodiments .
[0012]
The near infrared absorptive liquid composition of the present invention (occasionally referred to as "composition of the present invention", hereinafter) characteristically contains a copper compound, a compound having a polymerizable group (occasionally referred to as "polymerizable compound") , and 50 to 80% by mass of a solvent. These components will be detailed below.
[0013]
<Copper Compound>
The copper compound used in the present invention is not specifically limited, so long as it shows a maximum absorption wavelength in the range from 700 nm to 1000 nm (near-infrared region) .
The copper compound used in the present invention may be a copper complex or not be a copper complex, wherein the copper complex is preferable.
When the copper compound used in the present invention is a copper complex, ligand L is not specifically limited so long as it can coordinate on a copper ion. Examples of the ligand include compounds having sulfonic acid, phosphoric acid, phosphate ester, phosphonic acid, phosphonate ester,
phosphinic acid, phosphinate ester, carboxylic acid, carbonyl (ester, ketone), amine, amide, sulfonamide, urethane, urea, alcohol, thiol and so forth. Among them, sulfonic acid, phosphoric acid, phosphate ester, phosphonic acid, phosphonate ester, phosphinic acid and phosphinate ester are preferable, and sulfonic acid, phosphate ester, phosphonate ester, and phosphinate ester are more preferable.
Specific examples of the copper compound used in the present invention are preferably phosphorus-containing copper compound, copper sulfonate compound, copper carboxylate compound, or copper compound represented by the formula (A) below. The phosphorus-containing compound may be referred to the compounds described in O2005/030898 , from line 27 on page 5 to line 20 on page 7, the contents of which are incorporated herein by reference.
The copper phosphate compound used in the present invention will be detailed below.
[0014]
<<Copper Phosphate Compound>>
The composition of the present invention preferably contains a copper phosphate compound, a polymerizable compound, and 50 to 80% by mass of a solvent.
The composition of the present invention contains a copper phosphate compound, the content of which relative to the solid content of the composition is preferably 20 to 95% by mass, and more preferably 30 to 80% by mass. The copper phosphate compound may be composed of a single species or two or more species. When the copper phosphate is composed of two or more species, the total content falls within the
above-described ranges.
[0015]
The copper phosphate compound used in the present invention is preferably formed by using a phosphate ester compound, and more preferably by using a compound represented by the formula (1) below:
Formula (1)
(HO) n -P(=0)-(OR 2 ) 3 -n
(in the formula, each R 2 represents a Ci-is alkyl group, C 6 _i 8 aryl group, Ci_i 8 aralkyl group, or Ci-ie alkenyl group, or each -OR 2 represents a C4-100 polyoxyalkyl group, C -100
(meth) acryloyloxyalkyl group, or C4-100
(meth) acryloylpolyoxyalkyl group, and n represents 1 or 2.)
When n is 1, (R 2 )s may be same with, or different from each other. [0016]
In the formula, at least one -OR 2 preferably represents a C4-100 (meth) acryloyloxyalkyl group, or C 4 - 10 o
(meth) acryloylpolyoxyalkyl group, and more preferably represents a C4-100 (meth) acryloyloxyalkyl group.
The 0 4 -!οο polyoxyalkyl group, C4-100
(meth) acryloyloxyalkyl group, or C4-100
(meth) acryloylpolyoxyalkyl group preferably has 4 to 20 carbon atoms, and more preferably has 4 to 10 carbon atoms.
In the formula (1), R 2 is preferably a Ci_i 8 alkyl group or C 6 -i8 aryl group, more preferably a Ci-10 alkyl group or C 6 -i 0 aryl group, furthermore preferably a C io aryl group, and particularly a phenyl group.
In the present invention, when n is 1, one of R 2 exists preferably in the form of -OR 2 which preferably represents a C4-100 (meth) acryloyloxyalkyl group, or C4-100
(meth) acryloylpolyoxyalkyl group, and the other of R 2 preferably exists in the form of -OR 2 or represents alkyl group.
[0017]
The phosphate ester compound in the present invention is exemplified by phosphate monoester (n=2 in the formula (1)), and phosphate diester (n=l in the formula (1)), wherein phosphate diester is preferable from the viewpoints of near infrared shielding performance and solubility.
[0018]
The copper phosphate complex exists in the form of a copper complex (copper compound) in which phosphate esters coordinate on copper as the center metal. Copper in the copper phosphate complex is a divalent copper, and may typically be produced by a reaction between a copper salt and a phosphate ester. It is therefore predicted that any near infrared absorptive compound, containing copper and the phosphate ester compound, has a copper phosphate complex formed therein.
The copper phosphate compound used in the present invention preferably has a molecular weight of 300 to 1,500, and more preferably 320 to 900.
[0019]
Examples of the phosphate ester compound as sources for the copper phosphate compound preferably used in the present invention will be listed below. The present invention is, of course, not limited thereto.
In Tables below, R 1 and R 2 represent those in the formula below. In Tables below, indicates a bonding site for an oxygen atom in the formula below.
[0020]
[Table 1]
A-18 H -CH 2 (CH 2 ) 8 CH 3
A-19 -CH 2 (CH 2 ) 8 CH 3 -CH 2 (CH 2 ) 8 CH 3
A-20 H -CH 2 (CH 2 ) 6 CH(CH 3 ) 2
[0021]
[Table 2]
R 1 o._o
R 2 0' "OH
R 1 R 2
A-21 -CH 2 (CH 2 ) 6 CH(CH 3 ) 2 -CH 2 (CH 2 ) 6 CH(CH 3 ) 2
A-22 H
A-23
A-24 H -CH 2 (CH 2 ) 14 CH(CH 3 ) 2
A-25 -CH 2 (CH 2 ) 14 CH(CH 3 ) 2 -CH 2 (CH 2 )i 4 CH(CH 3 ) 2
A-26 H ""C 6 H 5
A-27 -C 6 H 5
A-28 H -CH 2 CH 2 OCH 3
A-29 -CH 2 CH 2 CH 3 -CH 2 CH 2 OCH 3
A-30 H -CH 2 CH 2 OCH 2 CH 3
A-31 -CH 2 CH 2 OCH 2 CH 3 -CH 2 CH 2 OCH 2 CH 3
A-32 H - (C 2 H 4 0) 2 C 2 H 5
A-33 - (C 2 H 4 0) 2 C 2 H 5 - (C 2 H 4 0) 2 C 2 H 5
A-34 H - (C 2 H 4 0) 2 C 4 H 9
A-35 - (C 2 H 4 0) 2 C 4 H 9 - ( C 2 H 4 0) 2 C 4 H9
A-36 H -C 2 H 4 OCH 2 CH(CH 3 ) 2
A-37 -C 2 H 4 OCH 2 CHCH 3 ) 2 -C 2 H 4 OCH 2 CH (CH 3 ) 2
A-38 H -(C 2 H 4 0)2CH2CH(CH 3 )2
A-39 - (C 2 H 4 0) 2 CH 2 CHCH 3 ) 2 -(C 2 H 4 0) 2 CH 2 CH(CH 3 ) 2
A-40 H -CH (CH 3 ) CH 2 OCH 3 [0022] [Table 3] A-69 -CH (CH 2 CH 3 ) CH 2 OC (=0) CH2CH3 -CH (CH2CH3) CH 2 OC (=0) CH2CH3
A-70 H -CH 2 CH (CH2CH3) OC (=0) CH2CH3
A-71 -CH 2 CH (CH2CH3) OC (=0) CH2CH3 -CH 2 CH (CH2CH3) OC (=0) CH2CH3
A-72 -CH (CH2CH3) CH 2 OC (=0) CH2CH3 -CH 2 CH (CH2CH3) OC (=0) CH2CH3
A-73 H -CH (CH 3 ) CH 2 OC (=0) CH (CH 3 ) 2
A-74 -CH (CH 3 ) CH 2 OC (=0) CH (CH 3 ) 2 -CH (CH 3 ) CH 2 OC (=0) CH (CH 3 ) 2
A-75 H -CH 2 CH (CH 3 ) OC (=0) CH (CH 3 ) 2
A-76 -CH 2 CH (CH 3 ) OC (=0) CH (CH 3 ) 2 -CH 2 CH (CH 3 ) OC (=0) CH (CH 3 ) 2
A-77 -CH 2 CH (CH 3 ) OC (=0) CH (CH 3 ) 2 -CH (CH 3 ) CH 2 OC (=0) CH (CH 3 ) 2
A-78 H -CH (CH2CH3) CH 2 0C (=0) CH (CH 3 ) 2
A-79 -CH (CH2CH3) CH2OC (=0) CH (CH 3 ) 2 -CH (CH2CH3) CH 2 0C (=0) CH (CH 3 ) 2
A-80 H -CH 2 CH (CH2CH3) OC (=0) CH (CH 3 ) 2
[0024]
[Table 5]
[0025] [Table 6]
[0026]
Specific examples of the phosphate ester compound preferably used in the present invention may be referred to the description in paragraphs [0041] to [0045] of
JP-A-2001-354945 (paragraph [0059] of correspondent U.S. Patent No. 2003/0160217 Al ) , the contents of which are incorporated herein by reference.
[0027]
Method of synthesizing and preferable examples of the copper phosphate compound used in the present invention may be referred to the description in International Patent Publication W099/26952, pamphlet, the contents of which are incorporated herein by reference.
In the synthesis of the copper phosphate compound, commercially-available phosphonic acid products such as Phosmer M, Phosmer PE, Phosmer PP (from Unichemical Co. Ltd.) may be used.
[0028]
<<Other Copper Compounds>>
Besides the phosphorus-containing copper compounds described above, also the copper compounds having carboxylic ester ligands listed below may be used as the copper compound usable in the present invention. The present invention is, of course, not limited thereto. In Tables below, R 1 represents R 1 in the formula below. In Tables, indicates a bonding site for the COOH group in the formula below.
[0029]
[Table 7]
[0030]
The copper compound used in the present invention may al be a compound represented by the formula (A) below: Cu(L) ni - (X) n2 Formula (A)
In the formula (A) , L represents a ligand which can coordinate on copper, and X is absent, or represents a halogen atom, H 2 0, N0 3 , C10 4 , S0 4 , CN, SCN, BF 4 , PF 6 , BPh 4 (Ph represents a phenyl group) or alcohol. Each of nl and n2 independently represents an integer of 1 to 4.
The ligand L has a substituent which contains C, N, 0 or S as an atom capable of coordinating on copper, and more preferably has a group containing N, 0 or S having thereon lone pair(s) . Preferable ligands L are synonymous to the ligands L described above. The coordinatable group contained in the molecule is not only limited to a single species, but also two or more species, and may be either in a dissociated form or a non-dissociated form. If the group has a non-dissociated form, X is absent.
[0031]
<Compound Having a Polymeri zable Group>
The composition of the present invention contains a polymerizable compound. Family of this sort of compound is widely known in this industrial field, and they may be used in the present invention without special limitation. They may have any chemical form of, for example, monomer, oligomer, prepolymer and polymer.
The polymerizable compound may be either monofunctional or polyfunctional , where it is preferably polyfunctional . By containing the polyfunctional compound, the composition may further be improved in the near infrared shielding performance and heat resistance. The number of functional groups is preferably 2 to 8, although not specifically limited.
[0032]
<<Polymeri zable Monomer and Polymerizable Oligomer>>
A first preferable embodiment of the composition of the present invention contains a monomer having a polymerizable group (polymerizable monomer) or an oligomer having a polymerizable group (polymerizable oligomer) (the
polymerizable monomer and the polymerizable oligomer may collectively be referred to as "polymerizable monomer, etc.", hereinafter) , as the polymerizable compound.
[0033] Examples of the polymeri zable monomer, etc. include unsaturated carboxylic acid (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, and preferably include ester formed between unsaturated carboxylic acid and aliphatic polyhydric alcohol compound, and amide formed between unsaturated carboxylic acid and aliphatic multi-valent amine compound. Also preferably used are adducts of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxy group, amino group, or mercapto group, with monofunctional or polyfunctional isocyanates or epoxy compounds; and dehydration condensation products with monofunctional or polyfunctional carboxylic acid. Also preferably used are adducts of unsaturated carboxylic acid esters or amides having an electronphilic substituent such as isocyanate group or epoxy group, with monofunctional or polyfunctional alcohols, amines, or thiols; and substitution products formed between unsaturated carboxylic acid esters or amides having an eliminatable substituent such as halogen group or tosyloxy group, with monofunctional or polyfunctional alcohols, amines, or thiols. Other examples usable herein include compounds obtained by replacing the above-described unsaturated carboxylic acid with unsaturated phosphonic acid, vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
Specific example of these compounds are described in paragraphs [0095] to [0108] of JP-A-2009-288705, all of which are also preferably used in the present invention.
[0034]
The polymerizable monomer, etc. is also preferably a compound having at least one addition-polymerizable ethylene group, and having an ethylenic unsaturated group and showing a boiling point under normal pressure of 100°C or above. The examples of which include polyfunctional acrylate and methacrylate, and mixture of them, exemplified by
monofunctional acrylate and methacrylate such as polyethylene glycol mono (meth) acrylate , polypropylene glycol
mono (meth) acrylate, and phenoxyethyl (meth) acrylate;
compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohol, followed by conversion into (meth) acrylate, such as polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentylglycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth ) acrylate , hexanediol (meth) acrylate, trimethylolpropane
tri ( acryloyloxypropyl ) ether,
tri (acryloyloxyethyl ) isocyanurate , glycerin and
trimethylolethane; urethane (meth ) acrylates such as those described in JP-B-S 8-41708, JP-B-S50-6034 and
JP-A-S51-37193 ; polyester acrylates such as those described in JP-A-S48-64183, JP-B-S49-43191 and JP-B-S52-30 90 ; and epoxy acrylates obtained by reacting epoxy polymer with (meth) acrylic acid.
Other examples include polyfunctional (meth) acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenic unsaturated group, such as glycidyl (meth ) acrylate .
Other examples of preferable polymerizable monomer usable herein include compounds having a fluorene ring and two or more ethylenic polymerizable groups , and cardo polymer, such as those described in JP-A-2010-160418, JP-A-2010-129825, Japanese Patent No. 4364216 and so forth.
[0035]
As the compound having an ethylenic unsaturated group and showing a boiling point under normal pressure of 100°C or above, also the compounds described in paragraphs [0254] to [0257] of JP-A-2008-292970 are preferable.
[0036]
Also usable herein as the polymerizable monomer are the compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohol, followed by conversion into (meth) acrylate, such as those represented by the formulae (1) and (2) and specifically enumerated in JP-A-H10- 62986.
[0037]
The polymerizable monomer used in the present invention is more preferably polymerizable monomers represented by the formulae (MO-1) to (MO-5) below: [Chemical Formula 2]
CH 3
R: H 2 C=C-C-0— H 2 C=C-C-0— — 0-C-(CH 2 }-C-OH — 0-C-N-fCH 2 )-C-OH
'm π u ^ 'mn
H 0 , O . o m o . o H m o
T: *-/CH 2 -* — OCH 2 - — OCH 2 CH 2 - — OCH 2 CH 2 CH 2 - — OCH 2 CH 2 CH 2 CH 2 -
∑ ■ — O— — 0-C-N-fCH 2 V- N-C-O—
O H m H o
(In the formula , eachn represents 0 to 14, and each m represents 1 to 8. A plurality of each of (R) s, (T) s and ( Z ) s in a single molecule may be same with, or different from each other. When T represents an oxyalkylene group, the carbon terminal thereof is bound to R. At least one of (R)s represents a polymerizable group . )
[0038]
n is preferably 0 to 5, and more preferably 1 to 3. m is preferably 1 to 5, and more preferably 1 to 3. R preferably represents below:
[Chemical Formula 3]
H 2 C=C-C-0- H 2 C=C-C-0- — 0-C-^CH 2 — C-OH C -OH
H o # 6 m o 6 H m o
, , or
and preferably represents below: [Chemical Formula 4]
CH 3
H 2 C=C-C-0— H 2 C=C-C-0—
M o o
or
The radical polymerizable monomers represented by the formulae (MO-1) to (MO-5) are specifically exemplified by those described in paragraphs [0248] to [0251] of JP-A-2007-269779, which are also preferably used in the present invention.
[0039]
In particular, the polymerizable monomer, etc. is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; from Nippon Kayaku Co. Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; from Nippon Kayaku Co. Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; from Nippon Kayaku Co. Ltd.), dipentaerythritol
hexa (meth) acrylate (commercially available as KAYARAD DPHA; from Nippon Kayaku Co. Ltd.), or structures having these (meth ) acryloyl groups bound via a ethylene glycol or propylene glycol residue. Also oligomer type compounds of them are usable .
RP-1040 (from Nippon Kayaku Co. Ltd.) is exemplified.
[0040]
The polymerizable monomer, etc. may also be a
multif nctional monomer, and may have an acid group such as carboxyl group, sulfonic acid group, phosphoric acid group or the like. Accordingly, any polymerizable monomer having an unreacted carboxyl group, such as for the case where the ethylenic compound is a mixture as described above, may be used in its intact form, or if necessary, the ethylenic compound may be introduced with an acid group by allowing a hydroxyl group thereof to react with a non-aromatic carboxylic anhydride Specific examples of the non-aromatic carboxylic anhydride usable herein include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.
[0041]
In the present invention, the monomer having an acid group is an ester formed between an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is preferably a multifunctional monomer introduced with an acid group by allowing an unreacted hydroxyl group of an aliphatic polyhydroxy compound to react with a non-aromatic carboxylic anhydride, and is particularly such ester obtained by using pentaerythritol and/or dipentaerythritol as the aliphatic polyhydroxy compound. Examples of commercially available polybasic acid-modified acrylic oligomer include Aronix Series M-305, M-510 and M-520 from Toagosei Co. Ltd.
The multifunctional monomer having an acid group preferably has an acid value of 0.1 to 40 mg KOH/g, and particularly 5 to 30 mg KOH/g. If the acid value of the multifunctional monomer is too small, the solubility in the process of development may degrade, whereas if it is too large, manufacturing and handling become difficult,
photopolymerization performance may degrade, and curing performance characterized by surface smoothness of pixels may degrade. Accordingly, when two or more species of
multifunctional monomer having different acid groups, or when a multifunctional monomer having no acid group is used in combination, it is necessary to adjust the acid value of the multifunctional monomer as a whole so as to fall within the ranges described above.
[0042]
The composition also preferably contains, as the polymerizable monomer, etc., a polyfunctional monomer having a caprolactone structure.
The polyfunctional monomer having a caprolactone structure is not specifically limited so long as it has in the molecule thereof a caprolactone structure. The examples of which include ε-caprolactone-modified polyfunctional
(meth) acrylate which is obtainable by esterifying a polyhydric alcohol such as trimethylolethane , di-trimethylolethane , trimethylolpropane , di-trimethylolpropane , pentaerythritol, di-pentaerythritol , tri-pentaerythritol , glycerin,
diglycerol or trimethylolmelamine, using (meth) acrylic acid and ε-caprolactone . Among them, the polyfunctional monomer having a caprolactone structure represented by the formula (1) below is preferable
[0043]
[Chemical Formula
CH 2 0— R CH 2 0—
R OCH 2 C I CH 2 — O CH 2 — CI CH 2 0 R ( 1 )
CH 2 0— R CH 2 0— R
(In the formula, all of, or one to five of six (R) s represent a group represented by the formula (2) below, and the residual represents a group represented by the formula (3) below.)
[0044]
[Chemical Formula 6]
O O R 1
* 4— C— CH 2 CH 2 CH 2 CH 2 CH 2 o— C C=CH 2 ( 2 )
(In the formula, R 1 represents a hydrogen atom or methyl group, m represents an integer of 1 or 2, and indicates an atomic bonding . )
[0045]
[Chemical Formula 7]
(In the formula, R 1 represents a hydrogen atom or methyl group, and Nx *" indicates an atomic bonding.)
[0046]
Such polyfunctional monomer having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co. Ltd. under the trade name of KAYARAD DPCA Series, which includes DPCA-20 (a compound represented by the formulae (1) to (3), where m=l, the number of groups represented by the formula (2) is 2, all (R 1 ) s represent a hydrogen atom) , DPCA-30 (in the same formulae, m=l, the number of groups represented by the formula (2) is 3, all (R 1 ) s represent a hydrogen atom), DPCA-60 (in the same formulae, m=l, the number of groups represented by the formula (2) is 6, all (R 1 ) s represent a hydrogen atom), and DPCA-120 (in the same formulae, m=2, the number of groups represented by the formula (2) is 6, all (R 1 ) s represent a hydrogen atom) .
In the present invention, a single species of the polyfunctional monomer having a caprolactone structure may be used alone, or two or more species may be used in a mixed manner.
[0047]
The polymerizable monomer, etc. in the present invention is also preferably at least one species selected from the group consisting of compounds represented by the formula (i) or (ii) below .
[0048]
[Chemical Formula 8]
CH 2 - HE) -X CH 2 -CHE) -X
XHE) n ^CH 2 --G-CH 2 -0-CH 2 — G-CH 2 -0-(E) n — X (Ml
0H 2 -0-(E) n -X AlHr-CMEJr f -X
[0049]
In the formulae (i) and (ii), each E independently represents - ( (CH 2 ) y CH 2 0 ) - , or - ( (CH 2 ) y CH (CH 3 ) 0) -, each y independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, methacryloyl group, hydrogen atom, or carboxyl group.
In the formula (i), the total number of acryloyl group and methacryloyl group is 3 or 4, each m independently represents an integer of 0 to 10, and the individual (m) s add up to an integer of 0 to 40. When the individual (m) s add up to 0, any one of (X) s represents a carboxyl group.
In the formula (ii), the total number of acryloyl group and methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the individual (n) s add up to an integer of 0 to 60. When the individual (n) s add up to 0, any one of (X) s represents a carboxyl group.
[0050]
In the formula (i), m preferably represents an integer of 0 to 6, and more preferably of 0 to 4. The individual (m) s preferably add up to an integer of 2 to 40, more preferably to an integer of 2 to 16, and particularly to an integer of 4 to 8.
In the formula (ii), n preferably represents an integer of 0 to 6, and more preferably 0 to 4. The individual (n) s preferably add up to an integer of 3 to 60, more preferably to an integer of 3 to 24, and particularly to an integer of 6 to 12.
In the formula (i) or formula (ii), - ( (CH 2 ) y CH 2 0) - or - ( (CH 2 ) y CH (CH 3 ) 0) - is preferably bound to X, at the terminal thereof on the oxygen atom side.
[0051]
A single species of the compound represented by the formula (i) or (ii) may be used alone, or two or more species thereof may be used in combination. In particular, a compound having acryloyl groups for all of six (X) s in the formula (ii) is preferable.
[0052]
The compound represented by the formula (i) or (ii) may be synthesized by publicly known processes, such as a process of proceeding a ring-opening addition polymerization of pentaerytyritol or dipentaerytyritol with ethylene oxide or propylene oxide to thereby combine the ring-opened skeleton, and a process of allowing, for example, (meth) acryloyl chloride to react with the terminal hydroxyl group of the ring-opened skeleton, to thereby introduce a (meth) acryloyl group. The individual processes have been well-known, so that those skilled in the art will readily synthesize the compound represented by the formula (i) or (ii).
[0053]
Among the compounds represented by the formula (i) or (ii), pentaerythritol derivative and/or dipentaerythritol
derivative are more preferable.
More specifically, compounds represented by the formulae (a) to (f ) below (also referred to as "Exemplary Compounds (a) to (f)", hereinafter) are exemplified, and among them, Exemplary Compounds (a), (b) , (e) and (f) are preferable
[0054]
[Chemical Formula 9]
(all (n)s add up to 6)
(all (n)s add up to 12)
(all (n)s add up to 12)
[0055]
[Chemical Formula 10]
(all (n)s add up to 6)
5 \ 'm (all (m)s add up to 4)
[0056]
Examples of the polymerizable monomer, etc. represented by the formulae (i), (ii) which are commercially available include SR-494 from Sartomer, which is a tetrafunctional acrylate having four ethyleneoxy chains, DPCA-60 which is a hexafunctional acrylate having six pentylenoxy chains, and TPA-330 which is a trifunctional acrylate having three isobutylenoxy chains, the both from Nippon Kayaku Co. Ltd.
[0057]
Other preferable examples of the polymerizable monomer, etc. include urethane acrylates described in JP-B-S48-41708 , JP-A-S51-37193, JP-B-H2-32293 and JP-B-H2-16765, and urethane compounds having an ethylene oxide-based skeleton described in JP-B-S58-49860, JP-B-S56-1765 , JP-B-S62-39417 and JP-B-S62-39418. Moreover, by using, as the polymeri zable monomer, etc. , an addition polymerizable monomer having in the molecule thereof an amino structure or sulfide structure, described in JP-A-S63-277653, JP-A-S 63-260909 and
JP-A-H01-105238 , it is now possible to obtain a curable composition with a very high speed.
Examples of the polymerizable monomer, etc. which are commercially available include urethane oligomer UAS-10, UAB-140 (from Sanyo-Kokusaku Pulp Co. Ltd.), UA-7200 (from Shin-Nakamura Chemical Co . Ltd.), DPHA-4 OH ( from Nippon Kayaku Co. Ltd.), and UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (from Kyoeisha Chemical Co. Ltd.) .
[0058]
Also polyfunctional thiol compound having in the molecule thereof two or more mercapto (SH) groups is preferable as the polymerizable monomer, etc. In particular, a compound represented by the formula (I) below is preferable.
[0059]
[Chemical Formula 11]
(In the formula, R 1 represents an alkyl group, R 2 represents an aliphatic group with a valency of n, which may contain atom ( s ) other than carbon atom, R° represents an alkyl group but not H, and n represents 2 to 4.)
[0060]
The polyfunctional thiol compound represented by the formula (I) is exemplified, together with structural formula, by 1 , 4-bis ( 3-mercaptobutyryloxy) butane [formula (II)], 1, 3, 5-tris ( 3-mercaptobutyloxyethyl ) -1, 3, 5-triazine—2 , 4, 6 ( 1H, 3H, 5H) -trione [formula (III)], and pentaerythritol tetrakis ( 3-mercaptobutyrate ) [formula (IV)]. Only a single species of these polyfunctional thiols may be used alone, or two or more species thereof may be used in combination. [0061]
[Chemical Formula
(Π)
For the composition of the present invention, it is also preferable to use, as the polymeri zable monomer, etc., a polymeri zable monomer or oligomer having in the molecule thereof two or more epoxy groups or oxetanyl groups. Specific examples of these compounds will be described in the section of "Polymer Having Polymerizable Group in Side Chain" in the next .
[0063]
<<Polymer Having Polymerizable Group in Side Chain>>
A second preferable embodiment of the composition of the present invention relates to a composition which contains, as the polymerizable compound, a polymer having a polymerizable group in the side chain thereof.
Examples of the polymerizable group include ethylenic unsaturated double bond group, epoxy group, and oxetanyl group .
[0064]
<<<Polymer Having Ethylenic Unsaturated Bond in Side Chain>>> The polymer having an ethylenic unsaturated bond in the side chain thereof is preferably a polymer having, as the unsaturated double bond moiety thereof, at least one functional group selected from those represented by the formulae (1) to (3) below.
[0065]
[Chemical Formula 13]
Formula (1)
[0066]
In the formula (1), each of R 1 to R 3 independently represents a hydrogen atom or monovalent organic group. R 1 is preferably exemplified by hydrogen atom or alkyl group which may have a substituent, and in particular, hydrogen atom and methyl group are preferable by virtue of their high radical reactivity. Each of R 2 and R 3 is independently exemplified by hydrogen atom, halogen atom, amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, alkylsulfonyl group which may have a substituent, and arylsulfonyl group which may have a substituent. Among them, hydrogen atom, carboxyl group, alkoxycarbonyl group, alkyl group which may have a substituent, and aryl group which may have a substituent are preferable by virtue of their high radical reactivity.
[0067]
X represents an oxygen atom, sulfur atom, or -N(R 12 )-, and R 12 represents a hydrogen atom or monovalent organic group. R 12 is exemplified by an alkyl group which may have a substituent, among which a hydrogen atom, methyl group, ethyl group, and isopropyl group are preferable by virtue of their high radical reactivity .
[0068] Examples of the substituent which may be introduced herein include alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, halogen atom, amino group, alkylamino group, arylamino group, carboxyl group,
alkoxycarbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, and arylsulfonyl group.
[0069]
[Chemical Formula 14]
FORMULA (2) [0070]
In the formula (2), each of R 4 to R 8 independently represents a hydrogen atom or monovalent organic group. Each of R 4 to R 8 is preferably a hydrogen atom, halogen atom, amino group, dialkylamino group, carboxy group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, alkylsulfonyl group which may have a substituent, and arylsulfonyl group which may have a substituent. Among them, hydrogen atom, carboxy group, alkoxycarbonyl group, alkyl group which may have a substituent, and aryl group which may have a substituent are preferable.
[0071]
Examples of the substituent which may be introduced herein are similar to those represented by the formula (1) . Y represents an oxygen atom, sulfur atom, or -N(R 12 )-. R 12 is synonymous to R 12 in the formula (1), the same will also apply to the preferable examples thereof.
[0072]
[Chemical Formula 15] Formula (3)
[0073]
In the formula (3), R 9 is preferably exemplified by hydrogen atom or alkyl group which may have a substituent. Among them, hydrogen atom and methyl group are preferable by virtue of their high radical reactivity. Each of R 10 and R 11 independently represents a hydrogen atom, halogen atom, amino group, dialkylamino group, carboxy group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, alkylsulfonyl group which may have a substituent, and arylsulfonyl group which may have a substituent. Among them, hydrogen atom, carboxy group, alkoxycarbonyl group, alkyl group which may have a substituent, and aryl group which may have a substituent are preferable by virtue of their high radical reactivity.
[0074]
Examples of the substituent which may be introduced herein are similar to those represented by the formula (1) . Z represents an oxygen atom, sulfur atom, -N(R 13 )-, or phenylene group which may have a substituent. R 13 is exemplified by an alkyl group which may have a substituent. Among them, methyl group, ethyl group and isopropyl group are preferable by virtue of their high radical reactivity.
[0075]
The polymer having an ethylenic unsaturated bond in the side chain thereof, in the present invention, is preferably a compound which contains, in one molecule thereof, 20 moll or more and less than 95 mol% of a structural unit having the functional group represented by the formulae (1) to (3) . The range is more preferably 25 to 90 mol%, and furthermore preferably 30 mol% or more and less than 85 moll.
[0076]
The polymer compound which contains the structural unit having the group represented by the formulae (1) to (3) may be synthesized based on the methods described in paragraphs [0027] to [0057] of JP-A-2003-262958. Among the methods, Method of Synthesis 1) described in the patent literature is preferably used, which will be described in below.
[0077]
(Polymer Having Ethylenic Unsaturated Bond and Acid Group in Side Chain )
The polymer having an ethylenic unsaturated bond is preferably a polymer additionally having an acid group.
The acid group in the context of the present invention is a dissociative group with a pKa of 14 or smaller, wherein preferable examples include -COOH, -S0 3 H, -P0 3 H 2 , -OS0 3 H, -OP0 2 H 2 , -PhOH, -S0 2 H, -S0 2 NH 2 , -S0 2 NHCO-, and -S0 2 NHS0 2 - . Among them, -COOH, -S0 3 H and -P0 3 H 2 are preferable, and -COOH is more preferable .
[0078]
The polymer containing in the side chain thereof an acid group and an ethylenic unsaturated bond may be obtained, for example, by adding an ethylenic unsaturated group-containing epoxy compound to a carboxy group of a carboxyl
group-containing, alkali-soluble polymer.
[0079]
The carboxyl group-containing polymer includes 1) polymer obtained by radical polymerization or ion
polymerization of a carboxyl group-containing monomer, 2) polymer obtained by radical or ion polymerization of an acid anhydride-containing monomer, and succeeding hydrolysis or half-esterification of the acid anhydride unit, and 3) epoxy acrylate obtained by modifying an epoxy polymer with a unsaturated monocarboxylic acid and an acid anhydride.
[0080]
Specific examples of the carboxy group-containing, vinyl-based polymer include homopolymer obtained by
polymerization of unsaturated carboxylic acid, used as the carboxyl group-containing monomer, such as (meth ) acrylic acid, 2-succinoloyloxyethyl methacrylate, 2-malenoloyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate,
2-hexahydrophthaloyloxyethyl methacrylate, maleic acid, fumaric acid, itaconic acid, and crotonic acid; and copolymer obtained by polymerization of these unsaturated carboxylic acids with a vinyl monomer having no carboxyl group, such as styrene, -methyl styrene, methyl (meth ) acrylate , ethyl (meth) acrylate , propyl (meth) acrylate, isopropyl
(meth) acrylate , butyl (meth ) acrylate , vinyl acetate, acrylonitrile , (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethylacrylate , crotonic acid glycidyl ether, (meth) acrylic acid chloride, benzyl
(meth) acrylate, hydroxyethyl (meth ) acrylate ,
N-methylolacrylamide , Ν,Ν-dimethyl acrylamide,
N-methacryloyl morpholine, , -dimethylaminoethyl
(meth ) acrylate , and , N-dimethylaminoethyl acrylamide.
[0081]
Other examples include polymer obtained by
co-polymerizing maleic anhydride with styrene, a-methyl styrene or the like, and then half-esterifying or hydrolysing the maleic anhydride unit moiety with a monohydric alcohol such as methanol, ethanol, propanol, butanol, or hydroxyethyl (meth) acrylate .
[0082]
Among them, the carboxyl group-containing polymer, and in particular, (meth) acrylic acid-containing (meth) acrylic acid (co)polymer is preferable. Specific examples of these copolymers include methyl methacrylate/methacrylic acid copolymer described in JP-A-S60-208748 , methyl
methacrylate/methyl acrylate/methacrylic acid copolymer described in JP-A-S60-214354 , benzyl methacrylate/methyl methacrylate/methacrylic acid/2-ethylhexyl acrylate
copolymer described in JP-A-H5-36581 , methyl
methacrylate/n-butyl methacrylate/2-ethylhexyl
acrylate/methacrylic acid copolymer described in
JP-A-H5-333542 , styrene/methyl methacrylate/methyl
acrylate/methacrylic acid copolymer described in
JP-A-H7-261407, methyl methacrylate/n-butyl
acrylate/2-ethylhexyl acrylate/methacrylic acid copolymer described in JP-A-H10-110008 , and methyl methacrylate/n-butyl acrylate/2-ethylhexyl acrylate/styrene/methacrylic acid copolymer described in JP-A-H10-198031.
[0083]
The polymer having in the side chain thereof an acid group and a polymerizable group, in the present invention, is preferably a polymer having, as the unsaturated double bond moiety thereof, at least one structural unit represented by the formulae (1-1) to (3-1) below.
[0084]
[Chemical Formula 16]
Formula (1 - 1 )
Formula (2- 1 )
Formula (3- 1 )
[0085]
In the formulae (1-1) to (3-1), each of A 1 , A 2 and A 3 independently represents an oxygen atom, sulfur atom, or -N(R 21 )-, where R 21 represents an alkyl group which may have substituent. Each of G 1 , G 2 and G 3 independently represents divalent organic group. Each of X and Z independently represents an oxygen atom, sulfur atom, or -N(R )-, where R represents an alkyl group which may have a substituent. Y represents an oxygen atom, sulfur atom, phenylene group which may have a substituent, or -N(R 23 )-, where R 23 represents an alkyl group which may have a substituent. Each of R to R independently represents a monovalent substituent.
[0086]
In the formula (1-1), each of R 1 to R 3 independently represents a monovalent substituent, which is exemplified by hydrogen atom, and alkyl group additionally having a substituent. Among them, each of R 1 and R 2 preferably represents a hydrogen atom, and R 3 is preferably represents a hydrogen atom or methyl group.
Each of R 4 to R 6 independently represents a monovalent substituent. R 4 is exemplified by hydrogen atom or alkyl group which may additionally have a substituent. Among them, hydrogen atom, methyl group, and ethyl group are preferable. Each of R 5 and R 6 independently represents a hydrogen atom, halogen atom, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may additionally have a substituent, aryl group which may additionally have a substituent, alkoxy group which may additionally have a substituent, aryloxy group which may additionally have a substituent, alkylsulfonyl group which may additionally have a substituent, and arylsulfonyl group which may additionally have a substituent . Among them, hydrogen atom, alkoxycarbonyl group, alkyl group which may additionally have a substituent, and aryl group which may additionally have a substituent are preferable .
Examples of the substituent which may be introduced herein include methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group, methyl group, ethyl group, and phenyl group.
[0087]
A 1 represents an oxygen atom, sulfur atom, or -N(R 21 )-, and X represents an oxygen atom, sulfur atom or -N (R 22 ) - . Each of R 21 and R 22 is exemplified by alkyl group which may have a substituent .
G 1 represents a divalent organic group, wherein an alkylene group which may have a substituent is preferable. More preferably, G 1 is exemplified by Ci-20 alkylene group which may have a substituent, C3-20 cycloalkylene group which may have a substituent, and C6-20 aromatic group which may have a substituent. Among them, Ci-10 straight-chain or branched alkylene group which may have a substituent, C 3 _i 0 cycloalkylene group which may have a substituent, and C6-12 aromatic group which may have a substituent are preferable by virtue of their performances related to strength, developability and so forth.
The substituent on G 1 is preferably a hydroxyl group.
[0088]
In the formula (2-1) , each of R 7 to R 9 independently represents a monovalent substituent, preferably exemplified by hydrogen atom, and alkyl group which may additionally have a substituent, wherein each of R 7 and R 8 preferably represents a hydrogen atom, and R 9 preferably represents a hydrogen atom or methyl group.
Each of R 10 to R 12 independently represents a monovalent substituent. Specific examples of the substituent include hydrogen atom, halogen atom, dialkylamino group,
alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may additionally have a substituent, aryl group which may additionally have a substituent, alkoxy group which may additionally have a substituent, aryloxy group which may additionally have a substituent, alkylsulfonyl group which may additionally have a substituent, and arylsulfonyl group which may additionally have a substituent. Among them, hydrogen atom, alkoxycarbonyl group, alkyl group which may additionally have a substituent, and aryl group which may additionally have a substituent are preferable.
Examples of the substituent which may be introduced herein are similar to those represented by the formula (1-1) .
[0089]
A 2 represents an oxygen atom, sulfur atom, or -N(R 21 )-, where R 21 is exemplified by hydrogen atom and alkyl group which may have a substituent.
G 2 represents a divalent organic group, which is preferably an alkylene group which may have a substituent. More preferably, G 2 is exemplified by Ci-20 alkylene group which may have a substituent, C3-20 cycloalkylene group which may have a substituent, and C6-20 aromatic group which may have a substituent. Among them, Ci-10 straight-chain or branched alkylene group which may have a substituent, C3-10 cycloalkylene group which may have a substituent, and C 6 _i 2 aromatic group which may have a substituent are preferable by virtue of their performances related to strength, developability and so forth.
The substituent on G 2 is preferably a hydroxyl group.
[0090]
Y represents an oxygen atom, sulfur atom, -N(R 23 )-, or phenylene group which may have a substituent. R 23 is exemplified by hydrogen atom, and alkyl group which may have a substituent.
[0091]
In the formula (3-1), each of R 13 to R 15 independently represents a monovalent substituent, which is exemplified by hydrogen atom, and alkyl group which may have a substituent. Among them, each of R 13 and R 14 preferably represents a hydrogen atom, and R 15 preferably represents a hydrogen atom or methyl group.
Each of R to R independently represents a monovalent substituent, wherein each of R 16 to R 20 is exemplified by hydrogen atom, halogen atom, dialkylamino group,
alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may additionally have a substituent, aryl group which may additionally have a substituent, alkoxy group which may additionally have a substituent, aryloxy group which may additionally have a substituent, alkylsulfonyl group which may additionally have a substituent, and arylsulfonyl group which may additionally have a substituent. Among them, hydrogen atom, alkoxycarbonyl group, alkyl group which may additionally have a substituent, and aryl group which may additionally have a substituent are preferable. Examples of the substituent which may be introduced herein are similar to those represented by the formula (1) .
A 3 represents an oxygen atom, sulfur atom, or -N(R 21 )-, and Z represents an oxygen atom, sulfur atom, or -N(R 22 )-. Examples of R 21 and R 22 are similar to those represented by the formula ( 1 ) . [0092]
G 3 represents a divalent organic group, which is preferably an alkylene group which may have a substituent. G 3 is preferably exemplified by Ci_ 2 o alkylene group which may have a substituent, C3-20 cycloalkylene group which may have a substituent, and C6-20 aromatic group which may have a substituent. Among them, Ci-10 straight-chain or branched alkylene group which may have a substituent, C3-10 cycloalkylene group which may have a substituent, C6-12 aromatic group which may have a substituent are preferable by virtue of their performances related to strength, developability and so forth.
The substituent on G 3 is preferably a hydroxyl group.
[0093]
The polymer having in the side chain thereof an acid group and a polymerizable group in the present invention is preferably a compound which contains in the molecule thereof 20 mol% or more and less than 95 mol% of the structural units represented by the formulae (1-1) to (3-1) , from the viewpoint of improving the curability and of reducing residue in development. The content is more preferably 25 to 90 mol%, and furthermore preferably 30 mol% or more and less than 85 mol%.
[0094]
Preferable examples of the structural unit having an ethylenic unsaturated bond and an acid group include polymer compounds 1 to 17 listed below.
[0095]
[Chemical Formula 17]
[0096]
[Chemical Formula [0097]
[Chemical Formula 19] [0098]
[Chemical Formula 20]
[0099]
The polymer having in the side chain thereof an acid group and an ethylenic unsaturated bond in the present invention necessarily has a photopolymeri zable unsaturated bond, from the viewpoint of improving photo-sensitivity, and necessarily has an acid group such as COOH, S0 3 H, P0 3 H 2 , OS0 3 H, OP0 2 H 2 , from the viewpoint of making it alkali-developable. The polymer containing in the side chain thereof an acid group and an ethylenic unsaturated bond in the present invention preferably has an acid value of 20 to 300, preferably 40 to 200, and more preferably 60 to 150, from the viewpoint of harmonizing dispersion stability, developability and sensitivity.
[0100]
(Polymer Having Ethylenic Unsaturated Bond and Urethane Group in Side Chain)
The polymer having in the side chain thereof a
polymerizable group is also preferably a polymer having, in the side chain thereof, an ethylenic unsaturated bond and an urethane group (occasionally referred to as "urethane polymer", hereinafter) .
The urethane polymer is a polyurethane polymer having, as the basic skeleton thereof, a structural unit represented by a reaction product formed between at least one species of diisocyanate compound represented by the formula (4) below, and at least one species of diol compound represented by the formula (5) below (properly referred to as "specific polyurethane polymer", hereinafter) .
[0101]
OCN-X°-NCO Formula (4)
HO-Y°-OH Formula (5)
[0102]
In the formulae (4) and (5), each of X° and Y° independently represents a divalent organic residue.
[0103]
If at least either one of the diisocyanate compound represented by the formula (4) and the diol compound represented by the formula (5) has at least one of the group represented by the formulae (1) to (3) corresponded to the unsaturated double bond moieties, then the specific
polyurethane polymer, having the group (s) represented by the formulae (1) to (3) introduced into the side chain thereof, is produced as a reaction product of the diisocyanate compound and the diol compound. According to this method, the specific polyurethane polymer in the present invention may readily be manufactured, more easily than by a method of replacing or introducing a desired side chain after reaction and production of the polyurethane polymer.
[0104]
1) Diisocyanate Compound
The diisocyanate compound represented by the formula (4) is exemplified by compound obtained by addition reaction of a triisocyanate compound, and one equivalent of a
monofunctional alcohol or a monofunctional amine having an unsaturated group.
The triisocyanate compound is exemplified by those listed below, but not -limited thereto.
[0105]
[Chemical Formula 21]
OCN-(CH 2 ) 4 -CH-NCO OC -iCH^s-CH-CCH^-NCO
C0 2 C 2 H 4 -NCO NCO
OCN— (CH 2 ) 3 - 3— NCO
OCN— (CH 2 ) 4 -CH-NCO
C0 2 C 2 H 4 -NCO
[0106]
[Chemical Formula
[0107]
The monofunctional alcohol or monofunctional amine compound having an unsaturated group are exemplified by those listed below, but not limited thereto.
[0108]
[Chemical Formula 23]
[0109]
[Chemical Formula
[0110]
[Chemical Formula
[0112]
A method of introducing an unsaturated group into the side chain of the polyurethane polymer is preferably such as using, as a source material for manufacturing the polyurethane polymer, a diisocyanate compound having an unsaturated group in the side chain thereof. The diisocyanate compound obtained by addition reaction of a triisocyanate compound and one equivalent of a monofunctional alcohol or monofunctional amine compound having an unsaturated group, and having an unsaturated group in the side chain thereof, is exemplified by those listed below, but not limited thereto.
[0113]
[Chemical Formula 27]
[0114]
[Chemical Formula
;oii5]
[Chemical Formula 29]
OCN— (CH 2 ) 3 -<pH— (CHg);
CH 2 -NCO
[0116]
[Chemical Formula 30]
[0117]
[Chemical Formula 31]
[0118]
[Chemical Formula 32]
[0119]
[Chemical Formula 33]
OCN-{CH 2 ) 6 -NHCQ, H
N-(CH2) 6 -N-C-f†N. OCN-(CH 2 ) 6 -NHCO O
[0120]
[Chemical Formula
[0121]
The specific polyurethane polymer used in the present invention may, for example, be co-polymerized with a diisocyanate compound other than the above-described diisocyanate compound having an unsaturated group, from the viewpoint of improving the compatibility with the other components in the polymerizable composition, and of improving the shelf stability.
[0122]
The diisocyanate compound to be co-polymerized is exemplified by those listed below. A diisocyanate compound represented by the formula (6) below is preferable.
[0123]
OCN-L x -NCO Formula (6)
[0124]
In formula (6), L 1 represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. As necessary, L 1 may have other functional group non-reactive with an isocyanate group, such as ester, urethane, amide and ureido group .
[0125]
The diisocyanate compound represented by the formula (6) specifically includes those listed below.
The examples include aromatic diisocyanate compound such as 2,4-tolylene diisocyanate, dimer of 2,4-tolylene
diisocyanate, 2 , 6-tolylenedilene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4 , ' -diphenylmetane diisocyanate, 1 , 5-naphthylene diisocyanate, and
3, 3' -dimethylbiphenyl-4 , 4' -diisocyanate; aliphatic
diisocyanate compound such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine diisocyanate, and dimer acid diisocyanate; alicyclic diisocyanate compound such as isophorone diisocyanate,
4,4' -methylenebis ( cyclohexylisocyanate ) , methyl
cyclohexane-2 , 4 - ( or -2 , 6- ) diisocyanate, and
1, 3- (isocyanatemethyl) cyclohexane; and diisocyanate compound obtained as a reaction product of a diol and a diisocyante, such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate.
[0126]
2) Diol Compound
The diol compound represented by the formula (5) is broadly exemplified by polyether diol compound, polyester diol compound, and polycarbonate diol compound.
[0127]
A preferable method of introducing an unsaturated group into the side chain of the polyurethane polymer, other than the above-described method, is such as using, as a source material for manufacturing the polyurethane polymer, a diol compound having in the side chain thereof an unsaturated group. The diol compound may be a commercially available product such as trimethylolpropane monoallyl ether, or may be a compound readily manufactured by a reaction of a halogenated diol compound, triol compound, or aminodiol compound, with a carboxylic acid having an unsaturated group, acid chloride, isocyanate, alcohol, amine, thiol, or halogenated alkyl compound. The compound is specifically exemplified by tho listed below, but not limited thereto.
[0128]
[Chemical Formula 35]
[0129]
[Chemical Formula
[0130]
[Chemical Formula
[0131]
[Chemical Formula
[0132]
More preferable polymer in the present invention is exemplified by polyurethane resin obtained by using, in the process of synthesizing polyurethane, a diol compound represented by the formula (G) below, as at least one of diol compounds having an ethylenic unsaturated linking group.
[0133]
[Chemical Formula 39]
F orm ula (G)
[0134]
In the formula (G) , each of R 1 to R 3 independently represents a hydrogen atom or monovalent organic group, A represents a divalent organic residue, X represents an oxygen atom, sulfur atom, or -N(R 12 )-, where R 12 represents a hydrogen atom or monovalent organic group.
Note that R 1 to R 3 and X in the formula (G) are synonymous to R 1 to R 3 and X in the formula (1), the same will also apply to the preferable examples thereof.
By using the polyurethane polymer derived from such diol compound, it is supposed that an excessive molecular motion of the polymer principal chain is suppressed by the
contribution of a secondary alcohol with a large steric hindrance, and thereby the film strength is improved.
Specific examples of the diol compound represented by the formula (G) , which may preferably be used for the synthesis of the specific polyurethane polymer, will be listed below.
[0135]
[Chemical Formula 40]
[0136]
[Chemical Formula
[0137]
[Chemical Formula
[0138]
The specific polyurethane polymer used in the present invention may, for example, be co-polymerized with a diol compound other than the above-described diol compound having an unsaturated group, from the viewpoint of improving the compatibility with the other components in the polymerizable composition, and of improving the shelf stability.
Such diol compound is exemplified by the above-described polyether diol compound, polyester diol compound, and polycarbonate diol compound.
[0139]
The polyether diol compound is exemplified by compounds represented by the formulae (7), (8), (9), (10) and (11) below, and, a random copolymer composed of ethylene oxide having a terminal hydroxy group and propylene oxide. [0140]
[Chemical Formula
HO— (CH 2 CHO) a — H ( 7 )
14
R
HO— (CH 2 CH 2 CHO) b — H ( 8 )
14
R
HO-(CH 2 CH 2 CH 2 CH 2 O) c — H ( 9 )
HO-(CH 2 CH 2 O) d — (CH 2 CHO) e — (CH 2 CH 2 O) d
CH 3
[0141]
In the formulae (7) to (11), R "1"1* represents a hydrogen atom or methyl group, and X 1 represents the groups below. Each of a, b, c, d, e, f and g represents an integer of 2 or larger, and preferably an integer of 2 to 100.
[0142]
[Chemical Formula 44]
" CHoCH -CH 2 CH—
CH 3
[0143]
The polyether diol compounds represented by the formulae (7) and (8) are specifically exemplified by those listed below .
The examples include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol,
hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1 , 2-propylene glycol, tri-1 , 2-propylene glycol, tetra-1 , 2-propylene glycol, hexa-1 , 2-propylene glycol-, di-1 , 3-propylene glycol, tri-1 , 3-propylene glycol,
tetra-1 , 3-propylene glycol, di-1 , 3-butylene glycol,
tri-1, 3-butylene glycol, hexa-1 , 3-butylene glycol,
polyethylene glycol with a weight average molecular weight of 1,000, polyethylene glycol with a weight average molecular weight of 1,500, polyethylene glycol with a weight average molecular weight of 2,000, polyethylene glycol with a weight average molecular weight of 3,000, polyethylene glycol with a weight average molecular weight of 7,500, polypropylene glycol with a weight average molecular weight of 400, polypropylene glycol with a weight average molecular weight of 700, polypropylene glycol with a weight average molecular weight of 1,000, polypropylene glycol with a weight average molecular weight of 2,000, polypropylene glycol with a weight average molecular weight of 3,000, and polypropylene glycol with a weight average molecular weight of 4,000.
[0144]
The polyether diol compound represented by the formula (9) is exemplified by those listed below.
The examples include PTMG650, PTMG1000, PTMG2000 and PTMG3000 (trade names) from Sanyo Chemical Industries, Ltd.
[0145]
The polyether diol compound represented by the formula (10) is specifically exemplified by those listed below.
The examples include Newpole PE-61, Newpole PE-62, Newpole PE-64, Newpole PE-68, Newpole PE-71, Newpole PE-74, Newpole PE-75, Newpole PE-78, Newpole PE-108, Newpole PE-128 and Newpole PE-61 (tradenames) from Sanyo Chemical Industries , Ltd.
[0146]
The polyether diol compound represented by the formula (11) is specifically exemplified by those listed below.
The examples include Newpole BPE-20, Newpole BPE-20F, Newpole BPE-20NK, Newpole BPE-20T, Newpole BPE-20G, Newpole BPE-40, Newpole BPE-60, Newpole BPE-100, Newpole BPE-180, Newpole BPE-2P, Newpole BPE-23P, Newpole BPE-3P and Newpole BPE-5P (trade names) from Sanyo Chemical Industries, Ltd.
[0147] The random copolymer composed of ethylene oxide having a terminal hydroxyl group and propylene oxide is exemplified by those listed below.
The examples include Newpole 50HB-100, Newpole 50HB-260, Newpole 50HB-400, Newpole 50HB-660, Newpole 50HB-2000 and Newpole 50HB-5100 (trade names) from Sanyo Chemical Industries, Ltd.
[0148]
The polyester diol compound is exemplified by compounds represented by the formulae (12) and (13) below.
[0149]
[Chemical Formula 45]
o o
HO-L 2 — (0-C-L 3 -C-0— L 2 ) n1 -OH ( 1 2 ) O
HO-L 4 — (0-C-L 5 ) n2 -OH ( 1 3 )
[0150]
In the formulae (12) and (13), L 2 , L 3 and L 4 may be same with, or different from each other, each of which represents a divalent aliphatic or aromatic hydrocarbon group, and L 5 represents a divalent aliphatic hydrocarbon group. It is preferable that each of L 2 to L 4 independently represents an alkylene group, alkenylene group, alkynylene group, or arylene group, and L 5 represents an alkylene group. Each of L 2 to L 5 may contain other functional group non-reactive with
isocyanate group, such as ether, carbonyl, ester, cyano, olefin, urethane, amide, ureido group or halogen atom. Each of nl and n2 independently represents an integer of 2 or larger, and preferably an integer of 2 to 100.
The polycarbonate diol compound is exemplified by compound represented by the formula (14) .
[0151]
[Chemical Formula 46] HO-L 6 —(0-C-L 6 ) n3 -OH (1 )
[0152]
In the formula (14), (L 6 ) s are same with, or different from each other, and each of which represents a divalent aliphatic or aromatic hydrocarbon group. L 6 preferably represents an alkylene group, alkenylene group, alkynylene group, and arylene group . L 6 may contain other functional group non-reactive with isocyanate group, such as ether, carbonyl, ester, cyano, olefin, urethane, amide, ureido group or halogen atom. n3 represents an integer of 2 or larger, and preferably an integer of 2 to 100.
[0153]
The diol compound represented by the formula (12), (13) or (14) specifically include (Exemplary Compound No.l) to (Exemplary Compound No.18) listed below. In the specific examples, n represents an integer of 2 or larger.
[0154]
[Chemical Formula 47]
( No.6)
( No.8)
HO-CH 2 CH 2 — (OC 9(CH 2 ) 5 )
( No.
( No. 1 0)
HO-(CH 2 ) 5 — (OCO(CH 2 ) 5 ) OH
( No. 1 1 )
9
HO-(CH 2 ) 4 — (OCO(CH 2 ) 4 ) ir OH
[0156]
[Chemical Formula ( No.
( No.
( No.
( No. 1 6 )
( No.
( No. 1 8 )
HO-(CH 2 ) m -†OC(CH 2 ) 4 CO-(CH 2 ) m O†H
O o n
m= 2 , 4
[0157]
In synthesis of the specific polyurethane polymer, a diol compound having a substituent non-reactive with isocyanate group may be used in addition to the above-described diol compound. Examples of such diol compound include those listed below .
[0158] HO-L 7 -0-CO-L 8 -CO-0-L 7 -OH (15)
HO-L 8 -CO-0-L 7 -OH (16)
[0159]
In the formulae (15) and (16) , L 7 and L 8 may be same with, or different from each other, and each of which represents a divalent aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group, which may have a substituent (for example, alkyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, and halogen atom such as -F, -CI, -Br, -I) . As necessary, each of L 7 and L 8 may have therein other functional group non-reactive with isocyanate group, such as carbonyl group, ester group, urethane group, amide group, or ureido group. L 7 and L 8 may form a ring.
[0160]
In synthesis of the specific polyurethane polymer, a diol compound having a carboxyl group may be used in addition to the above-described diol compound.
Examples of such diol compound include those represented by the formulae (17) to (19) .
[0161]
[Chemical Formula 50]
[0162]
In the formulae (17) to (19), R 15 represents a hydrogen atom, alkyl group, aralkyl group, aryl group, alkoxy group, or aryloxy group, which may have a substituent (exemplified by the individual groups of cyano, nitro, halogen atom such as -F, -CI, -Br, -I, -C0NH 2 , -COOR 16 , -OR 16 , -NHCONHR 16 , -NHCOOR 16 , -NHCOR 16 , and -OCONHR 16 (R 16 represents a Ci_i 0 alkyl group, or C7-15 aralkyl group.)), and preferably represents a hydrogen atom, Ci-8 alkyl group, or C 6 _i 5 aryl group. L 9 , L 10 and L 11 may be same with, or different from each other, and each of which represents a single bond, or a divalent aliphatic or aromatic hydrocarbon group which may have a substituent (for example, alkyl, aralkyl, aryl, alkoxy and halogeno groups are preferable) , preferably represents a C1-.20 alkylene group, or Ce-15 arylene group, and furthermore preferably a Ci-8 alkylene group. As necessary, L 9 to L 11 may have therein other functional group non-reactive with isocyanate group, such as carbonyl, ester, urethane, amide, ureido, or ether group. Any two or three of R 15 , L 7 , L 8 and L 9 may form a ring.
Ar represents a trivalent aromatic hydrocarbon group, and preferably a C is aromatic group.
[0163]
The diol compound having a carboxyl group represented by the formulae (17) to (19) is exemplified by those listed below.
The examples include 3 , 5-dihydroxy benzoic acid, 2 , 2-bis (hydroxymethyl ) propionic acid,
2 , 2-bis (2-hydroxyethyl ) propioic acid,
2 , 2-bis ( 3-hydroxypropyl ) propionic acid, bis (hydroxymethyl ) acetic acid, bis ( 4 -hydroxyphenyl ) acetic acid,
2 , 2-bis (hydroxymethyl ) butyric acid,
, 4 -bis ( 4 -hydroxyphenyl ) pentanoic acid, tartaric acid, N, -dihydroxyethylglycine, and
N, —bis (2-hydroxyethyl ) -3-carboxy-propionamide .
[0164]
By the presence of a carboxyl group, the polyurethane polymer is preferably given a capability of forming hydrogen bond and alkali-solubility. More specifically, the
polyurethane polymer having in the side chain thereof an ethylenic unsaturated binding group is a polymer further having a carboxyl group in the side chain thereof. More specifically, a polyurethane polymer having 0.3 meq/g or more of ethylenic unsaturated binding group in the side chain thereof, and 0.4 meq/g or more of carboxyl group in the side chain thereof, is particularly preferable for use as the binder polymer in the present invention.
[0165]
For synthesis of the specific polyurethane polymer, compounds derived from tetracarboxylic dianhydride
ring-opened by a diol compound, represented by the formulae (20) to (22) below, may be used in addition to the
above-described diol. Examples of such diol compound include those listed below.
[0166]
[Chemical Formula 51]
[0167]
In the formulae (20) to (22) , L 12 represents a single bond, divalent aliphatic or aromatic hydrocarbon group which may have a substituent (for example, alkyl, aralkyl, aryl, alkoxy, halogeno, ester and amide groups are preferable), -CO-, -SO-, -S0 2 -, -0- or -S-, and preferably represents a single bond, Ci_i 5 divalent aliphatic hydrocarbon group, -CO-, -S0 2 -, -0- or -S-. R 17 and R 18 may be same or different, each of which represents a hydrogen atom, alkyl group, aralkyl group, aryl group, alkoxy group, or halogeno group, and preferably represents a hydrogen atom, Ci-8 alkyl group, C6-15 aryl group, Ci-e alkoxy group or halogeno group. Any two of L 12 , R 17 and R 18 may combine to form a ring.
[0168]
R 19 and R 20 may be same or different, each of which represents a hydrogen atom, alkyl group, aralkyl group, aryl group or halogeno group, and preferably represents a hydrogen atom, Ci-e alkyl, or C 6 -i5 aryl group. Any of two L 12 , R 19 and R 20 may combine to form a ring. L 13 and L 14 may be same or different, each of which represents a single bond, double bond, or divalent aliphatic hydrocarbon group, and preferably represents a single bond, double bond, or methylene group. A represents a mononuclear or polynuclear aromatic ring, and preferably represents a Ce-18 aromatic ring.
[0169]
The compounds represented by the formula (20), (21) or (22) include those listed below.
The examples include aromatic tetracarboxylic
dianhydride such as pyromellitic dianhydride,
3,3' ,4,4' -benzophenonetetracarboxylic dianhydride,
3, 3' , 4, 4' -diphenyltetracarboxylic dianhydride,
2, 3, 6, 7-naphthalene tetracarboxylic dianhydride,
1 , 4 , 5 , 8 -naphthalene tetracarboxylic dianhydride,
4, 4' -sulfonyldiphthalic dianhydride,
2, 2-bis (3, 4-dicarboxyphenyl ) propane dianhydride,
bis (3, 4-dicarboxyphenyl) ether dianhydride,
4, 4'- [3, 3' - ( al kylphosphoryldiphenylene ) -bis ( iminocarbonyl ) ] diphthalic dianhydride,
[0170]
adduct of hydroquinone diacetate and trimellitic anhydride, and adduct of diacetyl diamine and trimellitic anhydride; alicyclic tetracarboxylic dianhydride such as
5- (2, 5-dioxotetrahydrofuryl ) -3-methyl-3-cyclohexene-l, 2-di carboxylic anhydride (Epiclon B-4400, from DIC Corporation),
1.2.3.4 -cyclopentanetetracarboxylic dianhydride,
1.2. .5-cyclohexanetetracarboxylic dianhydride, and tetrahydrofurantetracarboxylic dianhydride; and aliphatic tetracarboxylic dianhydride such as
1.2.3. -butanetetracarboxylic dianhydride, and
1.2.4.5-pentanetetracarboxylic dianhydride .
[0171]
Methods of introducing such compound, derived from the tetracarboxylic dianhydride ring-opened by the diol compound, into the polyurethane polymer are exemplified by those exemplified below:.
a) a method of allowing an alcohol-terminated compound, which is obtained by ring-opening of the tetracarboxylic dianhydride by the diol compound, to react with a diisocyanate compound; and
b) a method of allowing an alcohol-terminated urethane compound, which is obtained by a reaction between a
diisocyanate compound and an excessive amount of diol compound, to react with the tetracarboxylic dianhydride.
[0172]
The diol compound used for the ring-opening reaction is specifically exemplified by those listed below.
The examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1 , 6-hexanediol ,
2-butene-l , 4-diol , 2 , 2 , -trimethyl-l , 3-pentanediol,
1 , 4-bis- -hydroxyethoxycyclohexane, cyclohexane dimethanol, tricyclodecane dimethanol, hydrogenated bisphenol-A,
hydrogenated bisphenol-F, ethylene oxide adduct of bisphenol-A, propylene oxide adduct of bisphenol-A, ethylene oxide adduct of bisphenol-F, propylene oxide adduct of bisphenol-F, ethylene oxide adduct of hydrogenated bisphenol-A, propylene oxide adduct of hydrogenated bisphenol-A, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis (2-hydroxyethyl ) -2 , 4-tolylene dicarbamate,
2 , -tolylene-bis (2-hydroxyethyl carbamide),
bis ( 2-hydroxyethyl ) -.m-xylylene dicarbamate, and
bis (2-hydroxyethyl) isophthalate .
[0173]
The specific polyurethane polymer usable in the present invention may be synthesized by dissolving the diisocyanate compound and the diol compound into an aprotic solvent, by adding a publicly known catalyst with an activity suited to reactivity of the both, and by heating the mixture . Molar ratio (M a :M b ) of the diisocyanate and the diol compound used for the synthesis is preferably 1:1 to 1.2:1. As a result of treatment with alcohols or amines, a product with desired characteristics regarding molecular weight or viscosity may be obtained in a final form having no residual isocyanate group remained therein.
[0174]
Amount of introduction of the ethylenic unsaturated bond into the specific polyurethane polymer in the present invention is, on the basis of equivalent, preferably 0.3 meq/g or more, and more preferably 0.35 to 1.50 meq/g of ethylenic unsaturated binding group in the side chain. The polyurethane polymer is particularly preferable as the binder polymer in the present invention, when it contains, together with the ethylenic unsaturated binding group, 0.4 meq/g or more, and more preferably 0.45 to 1.00 meq/g of carboxy group in the side chain.
[0175]
Molecular weight of the specific polyurethane polymer in the present invention is preferably 10,000 or larger on the basis of weight average molecular weight, and more preferably in the range from 40,000 to 200,000. In particular, the polyurethane polymer exerts excellent in strength of the image-forming region and will be excellent in developability of non-image-forming region with an aqueous alikali developing solution, by adjusting the weight average molecular weight in the above-described ranges.
[0176]
The specific polyurethane polymer in the present invention is also preferably used when it has a unsaturated group at the polymer terminal or in the principal chain thereof. By virtue of the presence of the unsaturated group at the polymer terminal or in the principal chain, crosslinking reaction may be enhanced between the polymerizable compound and the specific polyurethane polymer, or among the specific polyurethane polymers, and thereby strength of the photo-cured product may increase. It is particularly preferable for the unsaturated group herein to contain a carbon-carbon double bond, in view of readiness in the crosslinking reaction.
[0177]
Methods of introducing the unsaturated group into the polymer terminal include those described in the next. That is, in the process of treating the residual isocyanate group at the polymer terminal with alcohols or amines, in the synthesis of the polyurethane polymer described above, it suffices to use alcohols or amines having an unsaturated group. This sort of compound is specifically exemplified by those similar to Exemplary Compounds listed above as the monofunctional alcohol or monofunctional amine compound having an unsaturated group.
The unsaturated group is more preferably introduced into the side chain of the polymer, rather than at the polymer terminal, in view of readiness of control in the amount of introduction, increased amount of introduction, and improved efficiency of the crosslinking reaction.
The ethylenic unsaturated binding group to be introduced is preferably a methacryloyl group, acryloyl group or styryl group from the viewpoint of formability of film hardened by crosslinking, and is more preferably a methacryloyl group or acryloyl group. Methacryloyl group is more preferable, from the viewpoint of achieving both of formability of film hardened by crosslinking and storability.
The amount of introduction of methacryloyl group is preferably 0.30 meq/g or more as described previously, and is more preferable in the range from 0.35 to 1.50 meq/g . In short , the polyurethane polymer having 0.35 to 1.50 meq/g of methacryloyl group introduced into the side chain thereof is a most preferable embodiment of the binder polymer in the present invention.
[0178]
Methods of introducing the unsaturated group into the principal chain is exemplified by method of using a diol compound, having an unsaturated group in the principal chain thereof, for synthesis of the polyurethane polymer. The diol compound having, in the principal chain thereof, an unsaturated group is exemplified by those described below. The examples include cis-2-butene-l , 4-diol , trans-2-butene-l , 4-diol , and polybutadienediol .
[0179]
The specific polyurethane polymer in the present invention may be used together with an alkali-soluble polymer which contains a polyurethane polymer having a structure different from that of the specific polyurethane polymer. For example, the specific polyurethane polymer may be used together with a polyurethane polymer having an aromatic group in the principal chain and/or side chain thereof.
[0180]
( Styrene-Based Polymer Having Ethylenic Unsaturated Bond in Side Chain)
In the present invention, also a styrene-based polymer having in the side chain thereof an ethylenic unsaturated bond (occasionally referred to as "styrene-based polymer", hereinafter) may preferably be used. The styrene-based polymer more preferably has at least either one of a styrenic double bond represented by the formula (23) below (styrene and oi-methyl styrenic double bond) , and, a vinylpyridinium group represented by the formula (24) below.
[0181]
[Chemical Formula 52]
Formula (23)
[0182]
In the formula (23), R 21 represents a hydrogen atom or methyl group. R 22 represents a substitutable arbitrary atom or group of atoms. k represents an integer of 0 to .
The styrenic double bond represented by the formula (23) is bound to the polymer principal chain, via a linking group composed of a single bond, or, arbitrary atom or group of atoms, wherein mode of bonding is not specifically limited.
Preferable examples of the repeating unit of the polymer compound having the functional group represented by the formula (23) are listed below, but not intended to limit the present invention to these examples.
[0183]
[Chemical Formula 53]
[0184] [Chemical Formula 54]
methyl group. R represents a substitutable arbitrary atom or group of atoms . m represents an integer of 0 to 4. A ~ represents an anion. The pyridinium ring may have a form of benzopyridinium condensed with a benzene ring as a substituent, examples of which include quinolium group and isoquinolium group .
The vinylpyridinium group represented by the formula (24 ) is bound to the polymer principal chain via a linking group composed of a single bond, or, a linking group composed of arbitrary atom or group of atoms, wherein mode of bonding is not specifically limited.
Preferable examples of the repeating unit of the polymer compound having the functional group represented by the formula (24) are listed below, but not intended to limit the present invention to these examples.
[0188]
[Chemical Formula 57]
[0189] One possible method of synthesizing the styrene-based polymer is such as allowing monomers, having a functional group represented by the formula (23) or (24), and having a functional group co-polymerizable with other copolymeri zable component, to react thereamong, according to any of publicly known co-polymerization processes. The styrene-based polymer herein may be a homopolymer composed of only one species of the functional group represented by either one of the formulae (23) and (24), or may be a copolymer composed of two or more species of the functional group represented by either one of, or both of the formulae (23) and (24).
[0190]
The styrene-based polymer may also be a copolymer containing other co-polymerizable monomer having none of these functional groups. The co-polymerizable monomer in this case is preferably a carboxyl group-containing monomer for the purpose of imparting the polymer with solubility into an aqueous alkali solution, and is exemplified by acrylic acid, methacrylic acid, acrylic acid 2-carboxyethyl ester, methacrylic acid 2-carboxyethyl ester, crotonic acid, maleic acid, fumaric acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, and 4 -carboxystyrene .
[0191]
It is also preferable to synthesize, and then use, a (multi ) polymer by introducing other monomer component, other than the monomer having the carboxyl group, into the copolymer. The monomer possibly introduced into the copolymer in this case is properly selectable from styrene derivative such as styrene, 4-methylstyrene , 4-hydroxystyrene , 4 -acetoxystyrene ,
4-carboxystyrene, 4-aminostyrene, chloromethyl styrene, and 4 -methoxystyrene ; vinylphosphonic acid, vinylsulfonic acid and salt thereof, styrenesulfonic acid and salt thereof, 4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole ,
N-vinylcarbazole , 4-vinylbenzyltrimethyl ammonium chloride, N-vinylimidazole quaternari zed with methyl chloride,
4-vinylbenzylpyridinium chloride, acrylonitrile,
methacrylonitrile , phenyl maleimide , hydroxyphenyl maleimide , vinyl esters such as vinyl acetate, vinyl chloroacetate , vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate; vinyl ethers such as methyl vinyl ether and butylvinyl ether; N-vinylpyrrolidone , acryloyl morpholine, vinyl chloride, vinylidene chloride, allyl alcohol, and
vinyltrimethoxysilane .
[0192]
When such copolymer described above is used as the styrene-based polymer, ratio of repeating unit having the functional group (s) represented by the formula (23) and/or formula (24), relative to the total copolymer composition, is preferably 20% by mass or more, and more preferably 40% by mass or more. In this range, a crosslinked system excellent in expressing the effect of the present invention and highly sensitive may be provided.
[0193]
The styrene-based polymer may become water soluble by having a quaternary salt structure in the repeating unit thereof. When the polymeri zable composition of the present invention containing such polymer is used for a recording layer of a lithgraphic printing plate precursor, the recording layer is now developable with water after the exposure.
In particular, for the case where the styrene-based polymer has the functional group represented by the formula (23) in the repeating unit thereof, and has a quaternary salt structure in the linking group which links the principal chain and the functional group represented by the formula (23) (for example, specific examples P-6, P-23 and P-24), the
styrene-based polymer may be a homopolymer having such structure, whereas in other cases, it is preferably a copolymer with other co-polymerizable monomer listed below. The examples include -vinylbenzyl trimethyl ammonium chloride,
acryloyloxyethyl trimethyl ammonium chloride,
methacryloyloxyethyl trimethyl ammonium chloride,
dimethylaminopropyl acrylamide quaternarized with methyl chloride, N-vinylimidazole quaternarized with methyl chloride, and 4-vinylbenzylpyridinium chloride.
When the styrene-based polymer has the functional group represented by the formula (24) in the repeating unit thereof, the styrene-based polymer may be a homopolymer, or may be a copolymer with other co-polymerizable monomer. [0194]
For the case where the styrene-based polymer is configured as a copolymer introduced with carboxyl group, the polymer is now also developable with an aqueous alkali solution. In any of these cases, the ratio of the repeating unit having the functional group (s) represented by the formula (23) and/or formula (24) is preferably 20% by mass or more. Introduction of any other repeating unit is arbitrarily selectable, depending on purposes.
[0195]
Molecular weight of the styrene-based polymer is preferably in the range from 10,000 to 300,000 on the basis of weight average molecular weight, and more preferably in the range from 15, 000 to 200, 000, and most preferably in the range from 20,000 to 150,000.
[0196]
(Other Polymer Having Ethylenic Unsaturated Bond in Side Chain) The other polymer having an ethylenic unsaturated bond in the side chain thereof is exemplified by novolac polymer having an ethylenic unsaturated group in the side chain thereof, and specifically exemplified by polymer obtained by
introducing an ethylenic unsaturated bond, into the side chain of a polymer described in JP-A-H9-269596, by a method described in JP-A-2002-62648.
Examples include acetal polymer having an ethylenic unsaturated bond in the side chain thereof, described in
JP-A-2002-162741.
Examples also include polyamide-based polymer having an ethylenic unsaturated bond in the side chain thereof described in Japanese Patent Application No. 2003-321022, and a polymer obtained by introducing an ethylenic unsaturated bond, into the side chain of the polyamide polymer cited therein, by a method described in JP-A-2002-62648.
Examples also include polyimide polymer having an ethylenic unsaturated bond in the side chain thereof described in Japanese Patent Application No. 2003-339785, and a polymer obtained by introducing an ethylenic unsaturated bond, into the side chain of the polyimide polymer cited therein, by a method described in JP-A-2002-62648. [0197]
(Polymer Having Epoxy Group or Oxetanyl Group in Side Chain)
In the present invention, also preferably contains a polymer having an epoxy group or oxetanyl group in the side chain thereof. The polymer having an epoxy group in the side chain thereof, and polymerizable monomer or oligomer having in the molecule thereof two or more epoxy groups are
specifically exemplified by bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and aliphatic epoxy resin.
These compounds may be commercially available, or may be obtained by introducing an epoxy group into the side chain of the polymer.
[0198]
For example, the bisphenol-7A type epoxy resin is commercially available as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (all from Japan Epoxy Resin Co. Ltd.), EPICLON860, EPICLON1050,
EPICLON1051, EPICLON1055 (all from DIC Corporation) and so forth, bisphenol-F type epoxy resin is commercially available as JER806, JER807, JER4004, JER4005, JER4007, JER4010 (all from Japan Epoxy Resin Co. Ltd.), EPICLON830, EPICLON835 (all from DIC Corporation), LCE-21, RE-602S (all from Nippon Kayaku Co. Ltd.) and so forth, the phenol novolac-type epoxy resin is commercially available as JER152, JER154, JER157S70, JER157S65, (all from Japan Epoxy Resin Co. Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (all from DIC Corporation) and so forth, the cresol novolac-type epoxy resin is
commercially available as EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (all from Japan Epoxy Resin Co. Ltd. ) , EOCN-1020 (from Nippon Kayaku Co. Ltd.) and so forth, and the aliphatic epoxy resin is commercially available as ADEKA RESIN EP-4080S, ditto EP-4085S, ditto EP-4088S (all from Adeka Corporation) , Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB 3600, ditto PB 4700 (all from Daicel Chemical Industries, Ltd.), Denacol EX-212L, EX-214L,
EX-216L, EX-321L, EX-850L (all from Nagase ChemteX
Corporation) and so forth. Other examples include ADEKA RESIN EP-4000S, ditto EP-4003S, ditto EP-4010S, ditto EP-4011S (all from Adeka Corporation) , NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all from Adeka Corporation), and JER1031S (from Japan Epoxy Resin Co. Ltd.) .
[0199]
The polymer having in the side chain thereof an oxetanyl group, and the polymeri zable monomer or oligomer having in the molecule thereof two or more oxetanyl groups, are specifically exemplified by Aron Oxethane OXT-121, OXT-221, OX-SQ, PNOX (all from Toagosei Co. Ltd.).
[0200]
For the synthesis based on introduction into the side chain of the polymer, the introduction reaction may be allowed to proceed by using, as a catalyst, a tertiary amine such as triethylamine and benzylmethylamine ; quaternary ammonium salt such as dodecyltrimethylammonium chloride,
tetramethylammonium chloride and tetraethylammonium chloride; pyridine, triphenyl or the like, in an organic solvent, at a reaction temperature of 50 to 150°C, for several to several tens of hours. Amount of introduction of the alicyclic epoxy unsaturated compound is preferably controlled so as to adjust the acid value of the obtainable polymer to 5 to 200 KOH-mg/g. The molecular weight on the weight average basis is preferably 500 to 5,000,000, and more preferably 1,000 to 500,000.
While compounds having a glycidyl group as the epoxy group, such as glycidyl (meth ) acrylate and allyl glycidyl ether may be used as the epoxy unsaturated compound, preferable is an unsaturated compound having an alicyclic epoxy group, examples of which are listed below.
[0201]
[Chemical Formula 58]
[0202]
Details regarding these polymerizable compounds, including the structures thereof, independent use or combined use, and amount of addition, are arbitrarily selectable depending on the final performance design of the near infrared absorptive liquid composition. For example, from the viewpoint of sensitivity, the larger the content of the unsaturated group per one molecule, the better, wherein two or larger functionality is preferable. From the viewpoint of enhancing the strength of the near infrared cut filter, 3 or larger functionality is preferable. Also a method of controlling both of sensitivity and strength, by using polymerizable compounds with different numbers of
functionality and different polymerizable groups (acrylic acid ester, methacrylic acid ester, styrene-based compound, vinyl ether-based compound, etc.), is effective. Selection and method of use of the polymerizable compound are important factors, also in consideration of compatibility and dispersibility with other components (metal oxide, dye, polymerization initiator, etc. ) contained in the near infrared absorptive liquid composition. For example, the
compatibility may be improved by using a low purity compound, or by using two or more compound in combination. It is also possible to select a specific structure from the viewpoint of improving adhesiveness with a hard surface such as a support.
[0203]
Amount of addition of the polymerizable compound to the composition of the present invention is 1 to 80% by weight of the total solid content excluding the solvent, more preferably 15 to 70% by weight, and particularly 20 to 60% by weight.
The polymerizable compound may be of a single species, or of two or more species. When two or more species are used, the total content is adjusted to the ranges described above.
[0204]
<Binder Polymer>
The near infrared absorptive liquid composition of the present invention may further contain a binder polymer, in addition to the polymerizable compound, as necessary, for example for the purpose of improving film characteristics. An alkali-soluble resin is preferably used as the binder polymer. Use of the alkali-soluble resin is effective in improving the heat resistance, and in finely controlling the coatability.
[0205]
The alkali-soluble resin is properly selectable from linear organic high polymers, having in the molecule thereof (preferably, in the molecule having an acrylic copolymer or styrene-based copolymer in the principal chain) at least one group capable of enhancing alkali solubility. Polyhydroxy styrene-based resin, polysiloxane-based resin, acrylic resin, acrylamide-based resin, and acryl /acrylamide copolymer resin are preferable from the viewpoint of heat resistance, whereas, acrylic resin, acrylamide-based resin, and acryl /acrylamide copolymer resin are preferable from the viewpoint of controlling the developability .
The group capable of enhancing alkali solubility (also referred to as "acid group", hereinafter) is exemplified by carboxyl group, phosphoric acid group, sulfonic acid group, and phenolic hydroxyl group. Those making the resin soluble into organic solvent and developable with a weak-alkaline aqueous solution are preferable. (Meth ) acrylic acid is particularly preferable. The acid group may be of a single species, or of two or more species.
Examples of monomer capable of adding an acid group after polymerization include a monomer having a hydroxy group such as 2-hydroxyethyl (meth ) acrylate , a monomer having an epoxy group such as glycidyl (meth ) acrylate , and a monomer having an isocyanate group such as 2-isocyanate ethyl (meth) acrylate . The group for introducing an acid group may be of a single species or of two or more species. The acid group may be introduced into the alkali-soluble binder, for example, by polymerizing the monomer having the acid group and/or the monomer capable of adding an acid group after polymerization (occasionally referred to as "acid group introducing monomer", hereinafter) as a monomer component. For the case where the acid group is introduced by using, as the monomer component, the monomer capable of introducing an acid group after polymerization, a treatment for adding the acid group described later will be necessary after the polymerization.
[0206]
The alkali-soluble resin may be manufactured, for example, by a publicly known radical polymerization process.
Conditions for polymerization regarding temperature, pressure, species and amount of radical initiator, and species of solvent are readily adjustable by those skilled in the art, and may also be determined by experiments.
[0207]
The linear organic high polymer used as the
alkali-soluble resin is preferably a polymer having a carboxylic acid in the side chain thereof, examples of which include methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially-esterified maleic acid copolymer, alkali-soluble phenol resin such as novolac-type resin, and, acidic cellulose derivative having a carboxylic acid in the side chain thereof, and adduct of hydroxy group-containing polymer with acid anhydride. Copolymer composed of (meth) acrylic acid and other monomer co-polymerizable therewith is particularly preferable as the alkali-soluble resin. The other monomer co-polymerizable with (meth) acrylic acid is exemplified by alkyl (meth) acrylate, aryl
(meth) acrylate and vinyl compound. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth ) acrylate , ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth ) acrylate , isobutyl (meth ) acrylate , pentyl
(meth ) acrylate , hexyl (meth ) acrylate , octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl
(meth ) acrylate , naphthyl (meth ) acrylate and cyclohexyl
(meth) acrylate ; and examples of the vinyl compound include styrene, -methyl styrene, vinyltoluene , glycidyl
methacrylate , acrylonitrile , vinyl acetate,
N-vinylpyrrolidone , tetrahydrofuryl methacrylate,
polystyrene macromonomer, and polymethyl methacrylate macromonomer . As N-substituted maleimide monomers described in JP-A-H10-300922, N-phenylmaleimide and
N-cyclohexylmaleimide are exemplified. The other monomer co-polymerizable with (meth ) acrylic acid may be of a single species, or of two or more species.
[0208]
The alkali-soluble resin also preferably contains, as essential polymer component (A) , polymer (a) which essentially contains a compound (referred to as "ether dimer", hereinafter) , represented by the formula (ED) below:
[Chemical Formula 59]
Formula (ED)
(in the formula (ED) , each of R 1 and R 2 independently represents a hydrogen atom or a Ci-25 hydrocarbon group which may have a substituent ) . In this way, the composition of the present invention may form a cured coated film especially excellent in the heat resistance and translucency. In the formula (1) representing the ether dimer, the C 1 -25 hydrocarbon group which may have a substituent represented by R 1 and R 2 is exemplified by, but not specially limited to, straight-chain or branched alkyl group such as methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, and 2-ethylhexyl groups; aryl group such as phenyl group; alicyclic group such as cyclohexyl, t-butylcyclohexyl , dicyclopentadienyl , tricyclodecanyl , isobornyl, adamantyl, and
2-methyl-2-adamantyl groups; alkoxy-substituted alkyl group such as 1-methoxyethyl , and 1-ethoxyethyl groups; and aryl group-substituted alkyl group such as benzyl group. Among them, substituents having a primary or secondary carbon less eliminatable by acid or heat , such as methyl , ethyl, cyclohexyl and benzyl, are preferable from the viewpoint of heat resistance .
[0209]
Specific examples of the ether dimer include
dimethyl-2, 2' - [oxybis (methylene) ] bis-2-propenoate,
diethyl-2,2'-[ oxybis (methylene ) ]bis-2-propenoate,
di (n-propyl ) -2 , 2 ' - [ oxybis (methylene ) ] bis-2-propenoat e , di (isopropyl) -2,2'- [oxybis (methylene) ] bis-2-propenoate, di(n-butyl)-2,2'-[oxybis (methylene ) ]bis-2-propenoate, di (isobutyl )-2, 2' -[oxybis (methylene ) ]bis-2-propenoate, di ( t-butyl ) -2, 2' - [oxybis (methylene ) ]bis-2-propenoate, di ( t-amyl ) -2 , 2 ' - [oxybis (methylene ) ]bis-2-propenoate,
di (stearyl ) -2, 2' - [oxybis (methylene ) ]bis-2-propenoate, di(lauryl)-2,2'- [oxybis (methylene ) ]bis-2-propenoate,
di (2-ethylhexyl) -2, 2' - [oxybis (methylene) ] bis-2-propenoate, di ( 1-methoxyethyl )-2,2'-[oxybis (methylene ) ]bis-2-propenoat e,
di (1-ethoxyethyl) -2, 2' - [oxybis (methylene ) ]bis-2-propenoate, dibenzyl-2, 2' -[oxybis (methylene ) ]bis-2-propenoate,
diphenyl-2 , 2 ' - [oxybis (methylene ) ] bis-2-propenoat e ,
dicyclohexyl-2, 2' - [oxybis (methylene ) ] bis-2-propenoate , di (t-butylcyclohexyl) -2, 2' - [oxybis (methylene ) ]bis-2-propen oate ,
di (dicyclopentadienyl ) -2 , 2 '-[ oxybis (methylene ) ] bis-2-prope . noate ,
di (tricyclodecanyl) -2, 2' - [oxybis (methylene ) ] bis-2-propenoa te ,
di (isobornyl ) -2 , 2 ' - [oxybis (methylene) ] bis-2-propenoate , diadamantyl-2 , 2 ' - [oxybis (methylene ) ]bis-2-propenoate, and di (2 -methyl-2-adamantyl) -2,2'- [oxybis (methylene) ] bis-2-pro penoate. Among them, particularly preferable are
dimethy1-2 , 2' - [oxybis (methylene) ] bis-2-propenoate,
diethyl-2, 2' - [oxybis (methylene) ] bis-2-propenoate,
dicyclohexyl-2, 2' - [oxybis (methylene ) ]bis-2-propenoate, and dibenzyl-2, 2' - [oxybis (methylene ) ] bis-2-propenoate. The ether dimer may be of a single species, or may be two or more species. The structure derived from the compound represented by the formula (ED) may be co-polymerized with other monomer ( s ) .
[0210]
The novolac resin is exemplified by condensates obtained by condensing phenols and aldehydes under the presence of an acid catalyst. The phenols are exemplified by phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol , cathecol, resorcinol, pyrogallol, naphthol, and bisphenol-A.
The aldehydes are exemplified by formaldehyde, paraformaldehyde, acetaldehyde , propionaldehyde , and benzaldehyde .
The phenols and aldehydes may be used independently, or in combination of two or more species.
Specific examples of the novolac resin include condensate of metacresol, paracresol or mixture them, with formalin.
The novolac resin may be controlled in the molecular weight distribution thereof, typically by fractionation. The novolac resin may also be mixed with a low molecular weight component having a phenolic hydroxy group such as bisphenol-C and bisphenol-A.
[0211]
As the alkali-soluble resin, particularly preferable are multi-component copolymer such as composed of benzyl
(meth) acrylate/ (meth) acrylic acid copolymer, and benzyl (meth) acrylate/ (meth) acrylic acid/other monomer. Other examples include copolymer having 2-hydroxyethyl methacrylate co-polymerized therein, and those described in JP-A-H7-140654 including 2 -hydroxypropyl (meth) acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, and 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl
methacrylate/methacrylic acid copolymer.
[0212]
Acid value of the alkali-soluble resin is preferably 30 mg KOH/g to 200 mg KOH/g, more preferably 50 mg KOH/g to 150 mg KOH/g, and most preferably 70 to 120 mg KOH/g.
Weight average molecular weight (Mw) of the
alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20, 000.
[0213]
Content of the binder polymer contained in the composition of the present invention is 1% by mass to 80% by mass of the total solid content of the composition, more preferably 10% by mass to 70% by mass, and furthermore preferably 20 to 60% by mass.
[0214]
<Solvent>
The composition of the present invention contains 50 to 80% by mass, relative to the whole composition, of a solvent. The solvent may be of a single species, or of two or more species . When two or more species are used, the total content is adjusted to the range described above. The content of the solvent in the composition is preferably 50 to 75% by mass, and more preferably 51 to 70% by mass.
The solvent used in the present invention is properly selectable depending on purposes, without special limitation so long as it may uniformly dissolve or disperse therein the individual components of the composition of the present invention. The examples include water; alcohols such as methanol, ethanol, normal-propanol , isopropanol,
normal-butanol, secondary butanol and normal-hexanol ; ketones such as acetone, methyl ethyl ketone, methyl isobuty ketone, cyclohexanone , diisobutyl ketone, cyclohexanone and
cyclopentanone; esters such as ethyl acetate, butyl acetate, normal-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, propylene glycol monomethyl ether acetate and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene and
ethylbenzene ; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene , chloroform,
1 , 1 , 1-trichloroethane , methylene chloride and
monochlorobenzene ; ethers such as tetrahydrofuran,
diethylether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, l-methoxy-2-propanol and propylene glycol monomethyl ether; dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, and sulfolane.
[0215]
<Polymerization Initiator>
The composition of the present invention may also contain a polymerization initiator. The polymerization initiator may be of a single species, or of two or more species. When two or more species are used, the total content is adjusted to the range described below. The content is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 20% by mass, and particularly 0.1% by mass to 15% by mass.
The polymerization initiator is properly selectable depending on purposes, without special limitation so long as it can initiate polymerization of the polymerizable compound with the aid of light and/or heat, and is preferably a photopolymerizable compound. When the polymerization is triggered by light, the polymerization initiator preferably shows photosensitivity over the region from ultraviolet radiation to visible light.
On the other hand, when the polymerization is triggered by heating, the polymerization initiator is preferably decomposable at 150°C to 250°C.
[0216]
The polymerization initiator preferably has at least an aromatic group, and is exemplified by acylphosphine compound, acetophenone-based compound, a-aminoketone compound, benzophenone-based compound, benzoin ether-based compound, ketal derivative compound, thioxanthone compound, oxime compound, hexaaryl biimidazole compound, trihalomethyl compound, azo compound, organic peroxide, diazonium compound, iodonium compound, sulfonium compound, azinium compound, benzoin ether-based compound, ketal derivative compound, onium salt compound, metallocene compound, organic borate compound, and disulfone compound.
From the viewpoint of sensitivity, preferable are the oxime compound, acetophenone-based compound, a-aminoketone compound, trihalomethyl compound, hexaaryl biimidazole compound and thiol compound.
Examples of the polymerization initiator preferably used in the present invention will be listed below, but not intended to limit the present invention.
[0217]
Specific examples of the acetophenone-based compound include 2, 2-diethoxyacetophenone,
p-dimethylaminoacetophenone ,
2-hydroxy-2 -methy1-1-phenyl-propane-1-one,
p-dimethylaminoacetophenone ,
4 ' -isopropyl-2-hydroxy-2-methyl-propiophenone,
1-hydroxy-eyelohexyl-phenyl-ketone ,
2-benzyl-2-dimethylamino-l- ( 4-morpholinophenyl ) -butanone, 1 , 2-tolyl-2-dimethylamino-l- ( 4 -morpholinophenyl ) -butanone , 1, 2-methyl-l- [4- (methylthio) phenyl] -2-morpholinopropanone, 1, 2-methyl-l- ( 4 -methylthiophenyl ) -2-morpholinopropane-l-on e, 2-benzyl-2-dimethylamino-l- (4-morpholinophenyl) -butanone, 1,2- (dimethylamino) -2- [ ( 4 -methylphenyl ) methyl ] -1- [4- (4-mor pholinyl ) phenyl ] -1-butanone , and
2-methyl-l- ( 4-methylthiophenyl ) -2-morpholinopropane-l-one .
[0218]
The trihalomethyl compound is more preferably an s-triazine derivative composed of at least one mono-, di-, or tri-halogen-substituted methyl group (s) bound to an s-triazine ring, exemplified by 2,4, 6-tris (monochloromethyl ) -s-triazine, 2,4, 6-tris (dichloromethyl ) -s-triazine,
2, 4, 6-tris ( trichloromethyl ) -s-triazine,
2-methyl-4, 6-bis (trichloromethyl) -s-triazine,
2—n-propyl-4 , 6-bis (trichloromethyl) -s-triazine,
2- (a, a, β-trichloroethyl ) -4, 6-bis (trichloromethyl) -s-triazi ne, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine,
2- (p-methoxyphenyl ) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3, -epoxy phenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl ) -4, 6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl ) -2, 4-butadienyl] -4, 6-bis (trichlorome thyl) -s-triazine,
2-styryl-4, 6-bis (trichloromethyl) -s-triazine,
2- (p-methoxystyryl ) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-i-propyloxystyryl ) -4, 6-bis (trichloromethyl) -s-triazin e, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine,
2- (4-naphthoxynaphthyl) -4, 6-bis (trichloromethyl) -s-triazin e, 2-phenylthio-4 , 6-bis ( trichloromethyl ) -s-triazine ,
2-benzylthio-4 , 6-bis (trichloromethyl) -s-triazine,
2, 4, 6-tris ( dibromomethyl ) -s-triazine,
2, 4, 6-tris (tribromomethyl ) -s-triazine,
2-methyl-4, 6-bis (tribromomethyl) -s-triazine, and
2-methoxy-4, 6-bis (tribromomethyl) -s-triazine.
[0219]
The hexaaryl biimidazole compound is exemplified by various compounds described in the specifications of
JP-B-H6-29285, U.S. Patent No. 3,479,185, ibid. No. 4,311,783, and ibid. No. 4,622,286, specifically exemplified by
2 , 2 ' -bis ( o-chlorophenyl ) -4 , 4 ' ,5,5' -tetraphenyl biimidazole , 2, 2' -bis ( o-bromophenyl ) ) -4, 4' , 5, 5' -tetraphenyl biimidazole, 2,2' -bis ( o,p-dichlorophenyl ) -4 , ' , 5, 5' -tetraphenyl
biimidazole ,
2,2' -bis (o-chlorophenyl) -4, 4' , 5, 5' -tetra (m-methoxyphenyl ) biimidazole ,
2,2' -bis (o,o'-dichlorophenyl) -4, 4' , 5, 5' -tetraphenyl
biimidazole , 2, 2' -bis (o-nitrophenyl) -4, ' , 5, 5' -tetraphenyl biimidazole , 2 , 2 ' -bis ( o-methylphenyl ) -4 , 4 ' ,5,5' -tetraphenyl biimidazole, and
2 , 2 ' -bis ( o-trifluorophenyl ) -4 , ' , 5 , 5 ' -tetraphenyl
biimidazole .
[0220]
The oxime compound is exemplified by various compounds described in J.C.S. Perkin ll (1979)1653-1660, J.C.S. Perkin II (1979)156-162, Journal of Photopolymer Science and
Technology (1995)202-232, JP-A-2000-66385, JP-A-2000-80068 , Published Japanese Translation of PCT International
Publication for Patent Application No. 2004-534797, IRGACURE OXE 01 (1, 2-octanedione, 1- [4- (phenylthio) -,
2- (O-benzoyloxime) ] ) , IRGACURE OXE 02
(ethanone, 1- [9-ethyl-6- (2-raethylbenzoyl ) - 9H-carbazole-3-yl
1 - , 1- (O-acetyloxime) ) , both from BASF Japan Ltd., and
2- ( acetyloxyiminomethyl ) thioxanthene-9-one .
Also cyclic oxime compounds described in
JP-A-2007-231000 and JP-A-2007-322744 are preferably used.
Most preferable examples include oxime compounds having specific substituents described in JP-A-2007-269779, and oxime compounds having a thioaryl group described in
JP-A-2009-191061.
More specifically, the oxime compound is preferably a compound represented by the formula (1) below. In relation to the N-0 bond of the oxime, the oxime compound may be of (E) -isomer, or of (Z) -isomer, or of a mixture of the (E) -isomer and the (Z) -isomer.
[0221]
Chemical Formula 60]
[0222]
(In the formula (1), each of R and B independently represents a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
The monovalent substituent represented by R is preferably a monovalent non-metallic atomic group. The monovalent non-metallic atomic group is exemplified by alkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic group, alkylthiocarbonyl group, and
arylthiocarbonyl group. Each of these groups may have one or more substituents. The substituent may further be substituted by other substituent.
Examples of the substituent include halogen atom, aryloxy group, alkoxycarbonyl group or aryloxycarbonyl group, acyloxy group, acyl group, alkyl group, and aryl group.
[0223] The oxime compound may be referred, for example, to those described in paragraphs [0515] to [0538] of JP-A-2012-208494 (paragraphs [0636] to [0659] in the correspondent U.S. Patent No. 2012/0235099), the contents of which are incorporated herein by reference.
[0224]
Specific examples (C-4) to (C-13) of the oxime compounds preferably used will be listed below, but not intended to limit the present invention.
[0225]
[Chemical Formula 61]
[0226]
The oxime compound preferably has a maximum absorption wavelength in the range from 350 nm to 500 nm, more preferably from 360 nm to 480 nm, and particularly from 365 nm and 455 nm.
[0227]
The oxime compound preferably has a molar absorption coefficient in the range from 365 nmor 405 nmof 3,000 to 300,000 from the viewpoint of sensitivity, more preferably 5,000 to 300,000, and particularly 10,000 to 200,000.
The molar absorption coefficient of the compound is measurable by any of publicly known methods, and is preferably measured using, for example, a UV spectrophotometer (Carry-5 Spectrophotometer, from Varian Inc.) , and an ethyl acetate as a solvent at a concentration of 0.01 g/L.
[0228]
A compound selected from the group consisting of oxime compound, acetophenone-based compound, and acylphosphine compound is more preferable as the photopolymeri zation initiator. More specifically, for example, also
aminoacetophenone-based initiator described in
JP-A-H10-291969, acylphosphine oxide-based initiator described in Examined Japanese Patent No. 4225898, the oxime-based initiator described above, and other oxime-based initiators described in JP-A-2001-233842 are usable.
The acetophenone-based initiator is commercially available as IRGACURE-907 , IRGACURE-369 and IRGACURE-379 (trade names: all from BASF Japan Ltd.). The acylphosphine -based initiator is commercially available as IRGACURE-819 and DAROCUR-TPO (trade names: the both from BASF Japan Ltd.) .
[0229]
<Surfactant>
The composition of the present invention may contain a surfactant. The . surfactant may be of a single species, or of two or more species in combination. Amount of addition of the surfactant, relative to the total mass of the composition of the present invention, is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass, and furthermore preferably 0.01 to 0.1% by mass. Various surfactants such as fluorine-containing surfactant, nonionic surfactant, cationic surfactant, anionic surfactant, silicone-based surfactant are usable.
[0230]
In particular, since the composition of the present invention is improved in liquid characteristics (especially in fluidity) when prepared as a coating liquid, by containing the fluorine-containing surfactant, so that uniformity in thickness of coating and liquid saving property may further be improved.
More specifically, when the film is formed by using a coating liquid prepared by using the composition containing the fluorine-containing surfactant, interfacial tension between the surface to be coated and the coating liquid is reduced, thereby wetting on the surface to be coated is improved, and coatability over the surface to be coated is improved. This is advantageous in view of forming, in a more appropriate manner, the film only with a small irregularity in thickness, even when a small amount of liquid is used to form a thin film of several micrometers thick or around.
[0231]
Fluorine content in the fluorine-containing surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly 7% by mass to 25% by mass. The fluorine-containing surfactant having the fluorine content adjusted to these ranges is effective in terms of uniformity in thickness of coating and liquid saving property, and is also excellent in solubility into the near infrared absorptive liquid composition.
[0232]
Examples of the fluorine-containing surfactant include Megafac F171, ditto F172, ditto F173, ditto F176, ditto F177, ditto F141, ditto F142, ditto F143, ditto F144, ditto R30, ditto F437, ditto F475, ditto F479, ditto F482, ditto F554, ditto F780, ditto F781 (all from DIC Corporation), Fluorad FC430, ditto FC431, ditto FC171 (all from Sumitomo 3M Ltd.), Surflon S-382, ditto SC-101, ditto SC-103, ditto SC-104, ditto SC-105, ditto SC1068, ditto SC-381, ditto SC-383, ditto S393, ditto KH-40 (all from Asahi Glass Co. Ltd.), PF636, PF656, PF6320, PF6520, and PF7002 (from OMNOVA Solutions Inc.).
[0233]
Specific examples of the nonionic surfactant include glycerol, trimethylolpropane , trimethylolethane and
ethoxylate and propoxylate thereof (for example, glycerol propoxylate and glycerin ethoxylate) , polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate,
polyethylene glycol distearate, sorbitan fatty acid ester
(Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 from BASF), and Solsperse 20000 (from Lubrizol Japan Ltd.).
[0234]
Specific examples of the cationic surfactant include phthalocyanine derivative (trade name: EFKA-745, from
Morishita & Co. Ltd.), organosiloxane polymer KP341 (from Shin-Etsu Chemical Co. Ltd.), (meth) acrylic acid-based (co)polymer Polyflow No.75, No.90, No.95 (from Kyoeisha Chemical Co. Ltd.), and 001 (from Yusho Co. Ltd.).
Specific examples of the anionic surfactant include 004, W005 and W017 (from Yusho Co. Ltd.).
Examples of the silicone-based surfactant include "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone DCllPA", "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", and "Toray Silicone SH8400" from Dow Corning Toray Co. Ltd.; "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460" and "TSF-4452" from Momentive Performance Materials Inc.; "KP341", "KF6001", "KF6002" from Shin-Etsu Chemical Co. Ltd.; and "BYK307", "BYK323" and "BYK330" from BYK Chemie.
[0235]
<Other Components>
In addition to the essential components and the preferable additives, other components is properly selectable for use in the near infrared absorptive liquid composition of the present invention depending on purposes, so long as the effects of the present invention are not spoiled.
Examples of the other components usable herein include binder polymer, dispersion aid, sensitizer, crosslinking agent, curing accelerator, filler, heat curing accelerator, thermal polymerization inhibitor, and plasticizer, and further include adhesion enhancer for the surface of base, and other
auxiliaries (for example, electroconductive particle , filler, defoaming agent, flame retarder, leveling agent, releasing promoter, antioxidant, perfume, surface tension modifier, and chain transfer agent).
By properly containing these components, the target near infrared cut filter is now adjustable in terms of stability, and properties such as film characteristics.
These components may be referred, for example, to paragraph [0183] and thereafter of JP-A-2012-003225, and paragraphs [0101] to [0102], paragraphs [0103] to [0104] and paragraphs [0107] to [0109] of JP-A-2008-250074 , the contents of which are incorporated herein by reference.
[0236]
The near infrared absorptive liquid composition of the present invention has a liquid form, and is therefore readily formed into a film by a simple process such as spin coating, to thereby readily manufacture the near infrared cut filter. Accordingly, the above-described insufficient
manufacturability in the conventional near infrared cut filter may be improved.
[0237]
Applications of the near infrared absorptive liquid composition of the present invention include, but not limited to, near infrared cut filter disposed on the light receiving side of the substrate of solid state image sensing device (for example, near infrared cut filter for wafer-level lens), and near infrared cut filter disposed on the back side (on the side opposite to the light receiving side) of the substrate of solid state image sensing device, wherein application to the light-shielding film disposed on the light receiving side of the substrate of solid state image sensing device is preferable. In particular, in the present invention, the near infrared absorptive liquid composition is preferably used for forming, by coating, the film over an image sensor of solid state image sensing device. The near infrared absorptive liquid composition of the present invention preferably has a viscosity of 1 mPa-s or larger and 3,000 mPa's or smaller, more preferably 10 mPa-s or larger and 2,000 mPa-s or smaller, and furthermore preferably 100 mPa-s or larger and 1,500 raPa-s or smaller.
When the near infrared absorptive liquid composition of the present invention is used for forming the near infrared cut filter disposed on the light receiving side of the substrate of solid state image sensing device, the viscosity preferably 10 mPa-s or larger and 3,000 mPa ■ s or smaller, more preferably 500 mPa-s or larger and 1,500 mPa-s or smaller, and most preferably 700 mPa-s or larger and 1,400 mPa-s or smaller, from the viewpoint of thick film formability and uniformity of coating.
[0238]
The present invention also relates to a near infrared cut filter obtained by using the above-described near infrared absorptive liquid composition of the present invention. Such near infrared cut filter, formed by using the near infrared absorptive liquid composition of the present invention, is excellent in the light shielding performance in the near infrared region (near infrared shielding performance), excellent in the translucency in the visible light region (visible light transmittance ) , and, excellent in
weatherability such as light fastness and moisture resistance. In particular, the present invention is beneficial as the near infrared cut filter for a wavelength range from 700 to 2,500 nm.
The present invention further relates to a method of manufacturing the near infrared cut filter, having a process of coating (preferably spin coating, slit coating, screen printing, or applicator coating) the near infrared absorptive liquid composition of the present invention, on the light receiving side of the substrate of solid state image sensing device.
[0239]
In the process of forming the near infrared cut filter, first, the film is formed using the near infrared absorptive liquid composition of the present invention. The film is not specifically limited so long as it is formed while containing the near infrared absorptive liquid composition, wherein the thickness and layered structure and so forth are properly selectable depending on purposes.
[0240]
A method of forming the film is typically such as directly applying (preferably coating), on the support, the near infrared absorptive liquid composition of the present invention (the coating liquid having the solid content of the composition dissolved, emulsified or dispersed into the solvent), followed by drying.
[0241]
The support may be the substrate of solid state image sensing device, or another substrate provided on the light receiving side of the substrate of solid state image sensing device (for example, a glass substrate 30 described later) , or a layer such as a planarizing layer provided on the light receiving side of the substrate of solid state image sensing device .
The near infrared absorptive liquid composition (coating liquid) may be coated over the support by using, for example, a spin coater, slit spin coater or the like.
Conditions for drying the coated film will vary depending on species and ratio of use of the individual components and solvent, and generally at 60°C to 150°C, for 30 seconds to 15 minutes or around.
[0242]
The film thickness is properly selectable depending on purposes, without special limitation, wherein it is preferably 1 μπι to 300 μιη, more preferably 1 μν to 200 μπι, more preferably 1 μιτι to 100 μιη, furthermore preferably 1 μιη to 50 μπι, and particularly 1.0 μπι to 4.0 μπι.
[0243]
The method of manufacturing the near infrared cut filter using the near infrared absorptive liquid composition of the present invention may include other processes.
The other processes are properly selectable depending on purposes, without special limitation, and are exemplified by surface treatment of the base, preheating process (prebaking) , curing process, and postheating process (postbaking) .
[0244]
<Preheating Process, Postheating Process>
Heating temperature in the preheating process and the postheating process is generally 80°C to 200°C, and preferably
90°C to 150°C.
Heating time in the preheating process and the postheating process is generally 30 seconds to 240 seconds, and preferably 60 seconds to 180 seconds.
[0245]
<Curing Process>
The curing process is provided, as necessary, for curing the formed film. By the process, the mechanical strength of the near infrared cut filter may be improved.
The curing process is properly selectable depending on purposes, without special limitation. Preferable examples include whole exposure and whole heating. Note that the word
"exposure" in the context of the present invention is used not only for exposure by light of various wavelength, but also for exposure by electron beam, and irradiation of radioactive ray such as X-ray.
The exposure is preferably effected by irradiation of radioactive ray. Particularly preferable examples of the radioactive ray usable for the exposure include electron beam, and ultraviolet radiation and visible light such as KrF, ArF, g-line, h-line and i-line. Particularly, KrF, g-line, h-line and i-line are preferable.
Method of exposure include exposure using a stepper, and exposure using a high-pressure mercury lamp.
Exposure energy is preferably 5 mJ/cm 2 to 3,000 mJ/cm 2 , more preferably 10 mJ/cm 2 to 2,000 mJ/cm 2 , and most preferably
50 mJ/cm 2 to 1,000 mJ/cm 2 .
[0246]
Method of the whole exposure is exemplified by method of exposing the entire surface of the formed film. When the near infrared absorptive liquid composition contains a
polymerizable compound, curing of a polymeri zable component generated from the composition in the film is promoted, so that the film is further cured, and is improved in the mechanical strength and durability.
Apparatus for implementing the whole exposure is selectable depending on purposes, without special limitation. Preferable examples include a UV exposure apparatus typically using ultra-high pressure mercury lamp.
[0247]
Methods of whole heating process is exemplified by method of heating of the entire surface of the formed film. By the whole heating, strength of the patterned film may be enhanced.
Heating temperature in the whole heating is preferably
120°C to 250°C, and more preferably 120°C to 250°C. If the heating temperature is 120°C or above, the strength of the film may be enhanced by the heating, whereas if 250°C or below, the film may be prevented from being embrittled due to
decomposition of the components in the film.
Heating time in the whole heating is preferably 3 minutes to 180 minutes, and more preferably 5 minutes to 120 minutes.
Apparatus for implementing the whole heating is properly selectable from publicly-known apparatuses depending on purposes, without special limitation, and is exemplified by drying oven, hot plate, and IR heater.
[0248]
The present invention also relates to a camera module which includes a substrate of solid state image sensing device, and a near infrared cut filter disposed on the light receiving side of the substrate of solid state image sensing device, wherein the above-described near infrared cut filter is the near infrared cut filter of the present invention.
[0249]
The camera module according to the embodiment of the present invention will be explained below, referring to FIG. 1 and FIG. 2, but not intended to limit the present invention to the specific examples below.
Note that all constituents commonly appear in FIG. 1 and FIG. 2 will given the same reference numerals or marks.
In the description, the words "on", "above" and "upper side" are used in relation to the further side as viewed from the silicon substrate 10, whereas "under", "below" and "lower side" are used in relation to the side closer to the silicon substrate 10.
[0250]
FIG. 1 is a schematic cross sectional view illustrating a configuration of a camera module equipped with a solid state image sensing device.
A camera module 200 illustrated in FIG. 1 is connected to a circuit substrate 70 as a mounting substrate, while placing in between a solder ball 60 as a connection component.
In more details, the camera module 200 is configured to have a substrate of solid state image sensing device 100 having an image sensing device section provided on a first principal plane of a silicon substrate, a planarizing layer 46 (not illustrated in FIG. 1) provided to the first principal plane side (light receiving side) of the substrate of solid state image sensing device 100, a near infrared cut filter 42 provided on the planarizing layer 46, a glass substrate 30 (translucent substrate) provided above the near infrared cut filter 42, a lens holder 50 disposed above the glass substrate 30 and has an image sensing lens 40 housed in the inner space thereof, and a light-and-electromagnetic shield 44 disposed so as to surround the substrate of solid state image sensing device 100 and the glass substrate 30. The individual components are bonded using adhesives 20 (not illustrated in FIG. 1) and 45.
The present invention also relates to a method of manufacturing a camera module which includes a substrate of solid state image sensing device, and a near infrared cut filter disposed on the light receiving side of the substrate of solid state image sensing device. The method includes a process of forming a film by coating the near infrared absorptive liquid composition of the present invention, on the light receiving side of the substrate of solid state image sensing device.
Accordingly, in the camera module of this embodiment, the near infrared cut filter 42 is formed as a film by coating, over the planarizing layer 46, the near infrared absorptive liquid composition of the present invention. A method of forming the film by coating, to thereby manufacture the near infrared cut filter, is as described above.
The camera module 200 is configured so that incident light hv from the external is allowed to pass sequentially through the image sensing lens 40, the glass substrate 30, the near infrared cut filter 42, and the planarizing layer 46, to reach the image sensing device section on the substrate of solid state image sensing device 100.
The camera module 200 is connected to the circuit substrate 70, on the second principal plane side of the substrate of solid state image sensing device 100, through a solder ball 60 (connection component).
[0251]
FIG. 2 is an enlarged cross sectional view illustrating the substrate of solid state image sensing device 100 in FIG. 1.
The substrate of solid state image sensing device 100 is configured to have a silicon substrate 10 as a base, image sensing devices 12, an insulating interlayer 13, a base layer 14, a red color filter 15R, a green color filter 15G, a blue color filter 15B, an overcoat 16, microlenses 17, a
light-shielding film 18, an insulating film 22, a metal electrode 23, a solder resist layer 24, an internal electrode 26, and a device surface electrode 27.
Note that the solder resist layer 24 is omissible.
[0252]
First, the configuration of the substrate of solid state image sensing device 100 will be explained mainly on the first principal plane side thereof.
As illustrated in FIG. 2, on the first principal plane side of the silicon substrate 10, which is a base of the substrate of solid state image sensing device 100, provided is the image sensing device section having a plurality of image sensing devices 12 such as CCDs or CMOSs arranged therein in a two dimensional manner.
In the image sensing device section, the insulating interlayer 13 is formed over the image sensing devices 12, and the base layer 14 is formed over the insulating interlayer 13. Over the base layer 14, there are provided the red color filter 15R, the green color filter 15G and the blue color filter 15B (in some cases, collectively referred to as "color filter 15", hereinafter) so as to be respectively corresponded to the image sensing devices 12.
Ill An unillustrated light-shielding film may be provided to the boundaries of the red color filter 15R, the green color filter 15G, and the blue color filter 15B, and to the periphery of the image sensing device section. The light-shielding film may be manufactured, for example, by using a publicly known black color resist.
The overcoat 16 is formed over the color filter 15, and the microlenses 17 are formed over the overcoat 16 so as to be respectively corresponded to the image sensing devices 12 (color filter 15) .
On the microlenses 17, provided is the planarizing layer
46.
[0253]
On the periphery of the image sensing device section on the first principal plane side, there are provided a peripheral circuit (not illustrated) and the internal electrode 26, wherein the internal electrode 26 is electrically connected through the peripheral circuit to the image sensing devices 12.
Further over the internal electrode 26, the device surface electrode 27 is formed while placing in between the insulating interlayer 13. In the insulating interlayer 13 laid between the internal electrode 26 and the device surface electrode 27, there is formed a contact plug (not illustrated) for electrically connecting these electrodes. The device surface electrode 27 is used for applying voltage and reading signals through the contact plug and the internal electrode 26.
Over the device surface electrode 27, the base layer 14 is formed. Over the base layer 14, the overcoat 16 is formed. The base layer 14 and the overcoat 16 are opened above the device surface electrode 27 to form a pad opening, in which a part of the device surface electrode 27 exposes.
[0254]
The configuration on the first principal plane side of the substrate of solid state image sensing device 100 was described above. In place of providing the near infrared cut filter 42 over the planarizing layer 46, the near infrared cut filter may alternatively be provided over the microlenses 17, between the base layer 14 and the color filter 15, or, between the color filter 15 and the overcoat 16. In particular, it is preferably provided within 2 mm (more preferably within 1 mm) away from the surface of the microlenses 17. By providing the near infrared cut filter at this position, the process of forming thereof may be simplified, unnecessary near infrared radiation into the microlenses may thoroughly be eliminated, and thereby the near infrared shielding performance may further be improved.
On the first principal plane side of the substrate of solid state image sensing device 100, the adhesive 20 is provided on the periphery of the image sensing device section, and with the aid of the adhesive 20, the substrate of solid state image sensing device 100 and the glass substrate 30 are bonded.
The silicon substrate 10 has a through-hole formed therein so as to extend therethrough, and in the through-hole which extends through the silicon substrate 10, a through-hole electrode as a part of the metal electrode 23 is provided. With the aid of the through-hole electrode, the image sensing device section and the circuit substrate 70 are electrically connected .
[0255]
Next, the configuration of the substrate of solid state image sensing device 100 will be explained mainly on the second principal plane side thereof.
On the second principal plane side, the insulating film 22 is formed so as to extend over the second principal plane and the inner wall of the through-hole.
On the insulating film 22, there is provided the metal electrode 23 patterned so as to extend from a region on the second principal plane of the silicon substrate 10 to the inside of the through-hole. The metal electrode 23 is an electrode for connecting the image sensing device section in the substrate of solid state image sensing device 100 and the circuit substrate 70.
The through-hole electrode is a portion of the metal electrode 23 formed in the through-hole. The through-hole electrode extends through a part of the silicon substrate 10 and the insulating interlayer to reach the lower side of the internal electrode 26, and is electrically connected to the internal electrode 26.
Further on the second principal plane side, there is provided a solder resist layer 24 (protective insulating film) formed so as to cover the second principal plane having the metal electrode 23 formed thereon, and has an opening which allows a part of the metal electrode 23 to expose therein.
Further on the second principal plane side, there is provided a light-shielding film 18 formed so as to cover the second principal plane having the solder resist layer 24 formed thereon, and has an opening which allows a part of the metal electrode 23 to expose therein.
While the light-shielding film 18 illustrated in FIG. 2 is patterned so as to cover a part of the metal electrode 23, and to allow the residual part to expose, it may alternatively be patterned so as to allow the entire portion of the metal electrode 23 to expose (the same will also apply to the patterning of the solder resist layer 24).
Alternatively, the solder resist layer 24 is omissible, and the light-shielding film 18 may be provided directly on the second principal plane having the metal electrode 23 formed thereon .
On the exposed portion of the metal electrode 23, there is provided a solder ball 60 as a connection component, and through the solder ball 60, the metal electrode 23 of the substrate of solid state image sensing device 100 and an unillustrated connection electrode of the circuit substrate 70 are electrically connected.
[0256]
The substrate of solid state image sensing device 100 configured as explained above may be manufactured by any of publicly known methods described, for example, in paragraphs [0033] to [0068] of JP-A-2009-158863 , and in paragraphs [0036] to [0065] of JP-A-2009-99591.
[0257]
One embodiment of the camera module has been explained above referring to FIG. 1 and FIG. 2, with no intention of limiting such one embodiment to that illustrated in FIG. 1 and FIG. 2.
[Example]
[0258]
The present invention will further be detailed below referring to Examples. Materials, amount of use, ratio, details of processes, procedures of process and so forth described in Examples below may be modified arbitrarily, without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed to be limited by Examples below. In Examples, wording of "part (s) " used for describing the amount of use means "part(s) by weight", unless otherwise specifically stated.
[0259]
Abbreviations used in the Examples are listed below:
MO-A: KARAYAD DPHA (from Nippon Kayaku Co. Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate )
MO-B: RP-1040 (pentaerythritol polyethoxytetraacrylate ) (from Nippon Kayaku Co. Ltd.)
MO-C: A-DPH-12E (dipentaerythritol polyethoxyhexaacrylate ) (from Shin-Nakamura Chemical Co. Ltd.)
MO-D: Cyclomer ACA230AA ( acyl-modified acrylate ) (from Daicel Corporation )
MO-E: MX2-RD-F8 (acrylic polymer) (from Nippon Shokubai Co. Ltd. )
MO-F: methacrylic acid (138-10805, from Wako Pure Chemical Industries Ltd.)
MO-G: EHPE-3150 (epoxy resin, from Daicel Chemical Industries, Ltd.)
MO-H: JER157S65 (epoxy resin, from Japan Epoxy Resin Co. Ltd. ) ADD-A: F-781 (from DIC Corporation; surfactant)
ADD-B: R-30 (from DIC Corporation; surfactant)
I-A: OXE-01 (from BASF Japan Ltd.)
I-B: OXE-02 (from BASF Japan Ltd.)
I-C: Percumyl D (from NOF Corporation)
P-l: polymer composed of benzyl methacrylate and methacrylic acid with a molar ratio of 80:20 (Mw=30,000); binder)
PGMEA: propylene glycol monomethyl ether acetate PGME : propylene glycol monomethyl ether
CYH: cyclohexanone
[0260]
(Compound A and Method of Preparing the Same)
Five grams of anhydrous copper benzoate and 7 g of
(methacryloyloxy) ethyl phosphate (from Johoku Chemical Co. Ltd.) were dissolved into 25 cc of acetone, and the mixture was allowed to react at room temperature for 3 hours under stirring. The obtained reaction product was dropped into a hexane solvent, and a precipitate was collected by filtration, then dried, to obtain the target product.
[0261]
(Compound B and Method of Preparing the Same)
The target product was obtained in the same way as Compound A, except that bis [ (2-methacryloyloxy) ethyl] phosphate (from Johoku Chemical Co. Ltd.) was used in place of (methacryloyloxy) ethyl phosphate.
[0262]
(Compound C and Method of Preparing the Same)
The target product was obtained in the same way as
Compound A, except that Phosmer PP (from Unichemical Co. Ltd.) was used in place of (methacryloyloxy) ethyl phosphate.
[0263]
(Compound D)
EPOLIGHT 1178 (diimonium dye, from Epolin, Inc.) was used.
[0264]
(Compound E)
The target product was obtained in the same way as Compound A, except that diphenyl phosphate was used in place of (methacryloyloxy) ethyl phosphate.
[0265]
(Example 1)
The compounds below were mixed to prepare a near infrared absorptive liquid composition of Example 1.
■ Compound A (copper phosphate compound) 10 parts by mass
■ MO-A (polymerizable compound) 9.98 parts by mass
■ Cyclohexanone (solvent) 80 parts by mass
■ Add-A (surfactant) 0.02 parts by mass [0266]
The near infrared absorptive liquid compositions of the individual Examples and the Comparative Examples were prepared based on the compositions same as that of Example 1, except that species of the copper phosphate compound, polymeri zable compound, polymerization initiator, solvent and various additives were selected as listed in Table below. For the compositions added with the polymerization initiator, ratio of the polymeri zable compound was adjusted to 9.88 parts by mass, and ratio of the polymerization initiator was adjusted to 0.1 parts by mass. The mark in the cells of table indicates absence of the material.
[Table 8]
Copper Polymerizable Polymerization Solvent Surfactant Exposure phosphate compound initiator done? compound
Example 1 Compound A MO-A - CyH Add-A -
Example 2 Compound A MO-A I-A CyH Add-A Yes
Example 3 Compound A MO-B l-A PGMEA Add-A -
Example 4 Compound A MO-C CyH/ Add-A
PGMEA
(50/50)
Example 5 Compound A MO-D - PGMEA Add-B Yes
Example 6 Compound B MO-E I-B CyH - Yes
Example 7 Compound C MO-A/MO-D l-C CyH/ Add-B - (50/50) PGME
Example 8 Compound A MO-F - CyH Add-B -
Example 9 Compound A MO-G I-A PGMEA Add-A -
Example 10 Compound A MO-H CyH/ Add-A
PGMEA
(50/50)
Example 11 Compound E MO-A - CyH Add-A -
Comparative Compound D MO-A - PGMEA Add-A - Example 1
Comparative Compound A - I-A CyH P-1 Yes Example 2 Add-A "Exposure done?" in Table indicates that whether the exposure took place or not, in the process of manufacturing the near infrared cut filter.
[0267]
The thus-obtained near infrared absorptive liquid compositions were evaluated as follows.
[0268]
[Methods of Evaluation]
<Evaluation of Near Infrared Absorptive Liquid Composition> (Manufacture of Near Infrared Cut Filter)
Each of the near infrared absorptive liquid compositions of the individual Examples and Comparative Examples was spin-coated using a spin coater (Mikasa Spin Coater 1H-D7 from Mikasa Co . Ltd . ; at 340 rpm) over a glass substrate, and prebaked at 100°C for 120 seconds. Next, as shown in Table, parts of samples were subjected to the whole exposure at 2000 mJ/cm 2 , using an i-line stepper. Then all samples were heated on a hot plate at 180°C for 180 seconds, to thereby obtain the near infrared cut filters.
[0269]
(Evaluation of Near Infrared Shielding Performance)
Transmittance at 900 nm of the thus-obtained near infrared cut filters was measured using a spectrophotometer U-4100 (from Hitachi High-Technologies Corporation). A minimum value of transmittance (%) at 1,000 nm in the near infrared region was used as an index of shielding performance. A transmittance in the near infrared region of 5% or smaller may be understood as an index of good near infrared shielding performance for practical use.
[0270]
(Evaluation of Heat Resistance)
Each of the substrates of Examples and Comparative Examples was further heated on the hot plate at 220°C for 3 minutes. Before and after the heat resistance test, a maximum absorbance (AbsXmax) in the wavelength range from 700 nm to 1,400 nm, and the minimum absorbance (AbsAmin) in the wavelength range from 400 nm to 700 nm of each near infrared cut filter were measured using a spectrophotometer U-4100 (from Hitachi High-Technologies Corporation) , and an absorbance ratio represented by "AbsXmax/AbsXmin" was determined. Rate of change of absorbance ratio represented by | (absorbance ratio before test-absorbance ratio after test) | /absorbance ratio before test χ 100 (%) was evaluated according to the criteria below :
A: rate of change of absorbance ratio≤2%;
B: 2%<rate of change of absorbance ratio≤4%;
C: 4%<rate of change of absorbance ratio≤7%; and D: 7%<rate of change of absorbance ratio.
[0271]
[Table 9]
[0272]
As is clear from Table, the near infrared absorptive liquid compositions each containing the copper phosphate compound, the compound having a polymerizable group, and 50 to 80% by mass of a solvent, were found to be excellent in the near infrared shielding performance and heat resistance.
[0273]
It was confirmed from the results that, by using the near infrared absorptive liquid composition of the present invention, the near infrared cut filter excellent in all of the near infrared shielding performance, light fastness and heat resistance may be obtained.
Since the near infrared absorptive liquid composition of the present invention is a liquid, so that the near infrared cut filter may readily be manufactured by a simple process such as forming the film by spin coating, and thereby an insufficient manufacturability of the conventional near infrared cut filter may be improved.
Having described above, the near infrared absorptive liquid composition of the present invention is suitable for manufacturing a camera module having a substrate of solid state image sensing device, and the near infrared cut filter disposed on the light receiving side of the substrate of solid state image sensing device.
[0274]
The present disclosure relates to the subject matter contained in Japanese Patent Application No. 037239/2013 filed on February 27, 2013 and Japanese Patent Application No. 106450/2012 filed on May 8, 2012, which are expressly incorporated herein by reference in their entirety. All the publications referred to in the present specification are also expressly incorporated herein by reference in their entirety.
The foregoing description of preferred embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or to limit the invention to the precise form disclosed. The description was selected to best explain the principles of the invention and their practical application to enable others skilled in the art to best utilize the invention in various embodiments and various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention not be limited by the specification, but be defined claims set forth below.
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