| WO2006054709A1 | 2006-05-26 |
| JP2003168606A | 2003-06-13 | |||
| JP2002341161A | 2002-11-27 | |||
| JP2005264347A | 2005-09-29 | |||
| JP2006068964A | 2006-03-16 | |||
| JPH01309902A | 1989-12-14 |
| CLAIMS
1. A protective film, wherein a first insulator fine particle covered with an organic thin film including a reactive functional group is mixed with a second insulator fine particle covered with an organic thin film including a reactive functional group, and coated and cured on the material surface.
2. A protective film, wherein a material surface covered with an organic thin film including a reactive functional group on the surface thereof is covalently bonded with an insulator fine particle covered with an organic thin film including a functional group, which can be reacted with the reactive functional group, through the each organic film, and cured so as to from a film.
3. The protective film according to claims 1 or 2, wherein the reactive functional group includes an epoxy group, an imino group or a chalconyl group.
4. A production method of a protective film including: a step for mixing an insulator fine particle having reactivity with a second insulator fine particle having reactivity in an organic solvent so as to form a paste; a step for coating the paste on the material surface; and a step for curing the paste.
5. The production method of a protective film according to claim 4, wherein an organic film having a functional group, which can be reacted with the first insulator particle having reactivity or the second insulator fine particle having reactivity, is pre-formed on the material surface before coating the paste. |
DESCRIPTION
PROTECTIVE FILM AND PRODUCTION METHOD THEREOF
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a protective film (so-called passivation film) having functions of leakage prevention, water resistance, moisture-proof ness and flawing prevention. More particularly, the present invention relates to a protective film using an insulator fine particle having thermal reactivity or photo-reactivity, or radical reactivity or ionic reactivity on the surface thereof.
In the present invention, the insulator fine particle mainly includes silica, alumina, and zirconia.
Description of Related Art A sputtering method, a CVD method and a sol-gel method have been conventionally used for forming a protective film having high durability with an inorganic material.
However, a specific vacuum chamber is necessary in the sputtering method and the CVD method, so that there is a problem that production cost is high. Further, high temperature is necessary for reaction in the sol-gel method, so that there is a problem that a material is restricted to one having heat-resistance.
An objective of the present invention is to provide a protective film and a production method thereof in which a material is not restricted and a vacuum chamber is not necessary, that is, to provide an insulator fine particle including an organic thin film having a reactive functional group on the surface thereof, a protective film using the insulator fine particle and a production method thereof.
SUMMARY OF THE INVENTION
Accordingly, it would be advantageous to provide a protective film, in which a first insulator fine particle covered with an organic thin film including a reactive functional group is mixed with a second insulator fine particle covered with an organic thin film including a functional group, and coated and cured on the material surface.
A second invention is a protective film, in which the material surface covered with an organic thin film including a reactive functional group on the surface thereof is covalently bonded with an insulator fine particle covered with an organic thin film including a functional group, which can be reacted with the reactive functional group, through the each organic film, and cured so as to form a film.
In this case, if the reactive functional group includes an epoxy group, an imino group or a chalconyl group, a protective film having high durability can be provided, so it is preferable.
A third invention is a production method of a protective film including: a step for mixing an insulator fine particle having a first insulator fine particle having reactivity with a second insulator fine particle having reactivity in a organic solvent so as to make a paste; a step for coating the paste on the material surface; and a step for curing the coated paste.
At this time, if an organic thin film having a functional group, which can be reacted with the first insulator particle having reactivity or the second insulator fine particle having reactivity, is pre-formed on the material surface before coating the paste, a protective film using a fine particle having high peeling resistance can be provided, so that it is preferable.
As described above, the present invention has the effect to produce and provide a protective film having high film strength and hardly including a binder component by covering the surface of a fine particle with a reactive organic thin film or monomolecular film. Further, there is the effect to provide and produce a protective film including an insulator fine particle having excellent peering resistance by covering the material surface with a reactive thin film or monomolecular film.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of the reaction of an insulator fine silica particle in Example 1 of the present invention, where the reaction is expanded to the molecular level; FIG. 1A is a view of the surface of a fine silica particle before the reaction, FIG. 1 B is a view after forming a monomolecular film containing an epoxy group, and FIG. 1C is a view after forming a monomolecular film containing an amino group; and FIG. 1 D is a cross-sectional schematic view of the state that the fine particle is formed on
the material surface as a protective film.
FIG. 2 is a cross-sectional schematic view of the state that a fine silica particle in Example 2 of the present invention is bonded and formed on the material surface as a protective film.
DETAILED DESCRIPTION
The present invention is to provide a protective film in which a first insulator fine particle having reactivity is mixed with a second insulator fine particle having reactivity and coated and cured on the material surface, and the method includes: a step for mixing a first insulator fine particle having reactivity with a second insulator fine particle having reactivity to make a paste; a step for coating the paste on the material surface; and a step for curing the coated paste.
Further, in the present invention, an organic film having a functional group, which can be reacted with the first insulator particle having reactivity or the second insulator fine particle having reactivity, is pre-formed on the material surface before applying the mixture. Thus, the material surface covered with an organic thin film including a reactive functional group on the surface thereof is covalently bonded with an insulator fine particle covered with an organic thin film including a functional group, which can be reacted with the reactive functional group, through the each organic film, and cured so as to form a protective film.
Therefore, the present invention has the effect to produce and provide a protective film having high film strength and hardly including a binder component. Further, the present invention has the effect to produce the protective film including a insulator fine particle which has high un-peeling property. Hereinafter, the present invention will be concretely described with Examples.
However, the present invention is not limited to these examples.
In addition, although an insulator fine particle according to the present invention includes alumina, silica, zirconia and the like, the present invention will be described using a fine silica particle as a representative example. [Example 1]
First, an anhydrous silica fine particle 1 was prepared, and well dried. Then, the chemisorption liquid was prepared by the steps of: weighing 99 w.t.% of
chemicals including a reactive functional group to a functional part as a chemical adsorbent, where the reactive functional group was the chemicals including, for example, an epoxy group or an imino group at one end and an alkoxyl group at another end, that is, for example, the chemicals shown in the following chemical formulas (1) and (2); weighing 1 w.t.% of dibutyl-tin-diacetylacetonate or acetic acid which was organic acid as the silanol condensing catalyst; and solving the above-described weighed chemical materials in a mixing solvent including equivalent amounts of silicone and dimethylformamide, for example, a solvent including 50% hexamethyldisiloxane and 50% dimethylformamide, so as to have the total concentration of about 1 w.t.% (the concentration of the chemical adsorbent was preferably about 0.5 to 3%). [Formula 1]
O OCH 3
CH 2 -CHCH 2 O(CH 2 )SSi -OCH 3
OCH 3
[Formula 2]
OCH 3
H 2 N(CHa) 3 Si -OCH 3 OCH 3
The anhydrous silica fine particle was mixed and stirred in the chemisorption liquid, and reacted at a normal atmosphere (a relative humidity was 45%) for two hours. At this time, since many hydroxyl groups 2 were contained on the dangling bond of the surfaces of anhydrous silica fine particle (FIG. 1A), a -Si(OCH 3 ) group of the chemical adsorbent and the hydroxyl groups were dealcoholation-reacted (in this case, deCH 3 OH-reacted) under the existence of the silanol condensing catalyst or the organic solvent, so as to form a bond shown in the following chemical formula (3) or (4). Thereby, a chemical adsorbed monomolecular film 3 containing the epoxy group or a chemical adsorbed monomolecular film 4 containing the amino group was formed to have the film thickness of about 1 nm, where the film 3 or 4 was chemically
bonded to the whole surfaces of the fine silica particle.
In addition, when the adsorbent containing the amino group was used, the organic acid such as acetic acid or the like was preferable since a tin-based catalyst generated precipitation. Further, although the amino group contained the imino group, a pyrrole derivative, an imidazol derivative or the like could be used as a material containing the imino group except the amino group. Furthermore, by using a ketimine derivative, the amino group could be easily induced by hydrolysis after forming the film.
Then, fine silica particle were washed adding a chlorine based solvent such as chloroform or the like, so that a silica fine particle covered with a chemisorption monomolecular film having the reactive functional group on the surface thereof could be produced, where the reactive functional group was, for example, the epoxy group or the amino group. [Formula 3]
O O—
CH 2 -CHCH 2 O(CH 2 J 3 Si -O-
O—
[Formula 4]
O—
H 2 N(CH 2 J 3 Si -O- O—
The processed part had the film with thickness in a nanometer level and was remarkably thin, and the particle diameter was not damaged. In addition, when the silica particle was taken-out to the atmosphere without washing, the solvent was vaporized and the chemical adsorbent remained on the particle surface was reacted with moisture in an atmosphere, so that a silica fine particle having a remarkable-thin polymer film including the chemical adsorbent on the particle surface was obtained. The characteristic of this method was a large application area due to the
dealcoholation reaction.
Then, the equivalent amounts of the fine silica particles 5 and 6 respectively covered with the chemisorption monomolecular films containing the epoxy group or the amino group were taken, and fully mixed in isopropyl alcohol to a paste. After that, the paste was coated on a glass substrate 7 and heated at about 50 to 100 degree C. As a result, the epoxy group and the amino group were added by the reaction shown in the following chemical formula (5) so as to bond and solidify the silica fine particles, and then, a protective film 8 which was strong even though not containing a binder could be formed. [Formula 5]
O
/ \ -(CH 2 )CH-CH 2 + H 2 NCH 2 -
► - (CH 2 )CHCH 2 -NHCH 2 -
OH
[Example 2]
An organic thin film 9 containing an epoxy or amino group as a reactive functional group was pre-formed on the surface of the glass substrate 7 by the similar method in Example 1 , and the coated film was formed like that in Example 1. Then, the organic thin film on the surface of the silica fine particle was reacted with the organic thin film on the substrate surface, so as to form a protective film IfJ including the fine silica particle having high peering resistance strength. (FIG. 2)
In addition, in the above-described Example 1 , the chemicals shown in the formulas (1) and (2) were used as the chemical adsorbent including the reactive group. However, in addition to the above-described adsorbents, the chemicals shown in the following (1) to (16) could be used.
(1) (CH 2 OCH)CH 2 O(CH2)7Si(OCH3)3
(2) (CH 2 OCH)CH2θ(CH2)iiSi(OCH 3 )3 (3) (CH 2 CHOCH(CH2)2)CH(CH2)2Si(OCH 3 )3
(4) (CH 2 CHOCH(CH 2 )2)CH(CH2)4Si(OCH 3 )3
(5) (CH 2 CHOCH(CH2)2)CH(CH2)6Si(OCH 3 )3
(6) (CH 2 OCH)CH2O(CH2)7Si(OC 2 H 5 )3
(7) (CH 2 OCH)CH 2 O(CH 2 )Ii Si(OC 2 Hs) 3
(8) (CH 2 CHOCH(CH2)2)CH(CH 2 ) 2 Si(OC 2 H 5 )3
(9) (CH 2 CHOCH(CH 2 ) 2 )CH(CH 2 )4Si(OC 2 H 5 )3 (10) (CH 2 CHOCH(CH 2 ) 2 )CH(CH 2 )6Si(OC 2 H5)3
(11) H 2 N(CH 2 ) 5 Si(OCH 3 ) 3
(12) H 2 N(CH 2 ) 7 Si(OCH 3 ) 3
(13) H 2 N(CH2)9Si(OCH 3 )3
(14) H 2 N(CH 2 ) S Si(OC 2 Hs) 3 (15) H 2 N(CH 2 ) 7 Si(OC 2 H5)3
(16) H 2 N(CH 2 ) 9 Si(OC 2 H5) 3
In these formulas, a (CH 2 OCH) group is a functional group shown in the following formula (6), and a (CH 2 CHOCH(CH 2 ) 2 )CH group is a functional group shown in the following formula (7). [Formula 6]
O CH 2 -CH -
[Formula 7]
O- — CH-CH 2
\ / \
CH CH
\ /
CH 2 -CH 2
Further, the chemicals shown in the following (21) to (26) could be used as the chemical adsorbent containing an energy beam reactive functional group, where the energy beam was light or electron beam. In this case, it was not necessary to mix two kinds of reactive fine particles, and only one kind was coated, and the energy beam such as light or electron beam was irradiated so as to cure the particle.
(21) CH≡C-C≡C-(CH 2 )i 5 SiCI 3
(22) CH=C-C=C-(CH 2 )2Si(CH3)2(CH 2 )i5SiCl3
(23) CH≡C-C≡C-(CH 2 )2Si(CH3)2(CH 2 )9SiCl3
(24) (C 6 H5)(CH)2CO(C 6 H4)O(CH2)6OSi(OCH3)3 (25) (C 6 H5)(CH) 2 CO(C6H4)O(CH 2 ) 6 OSi(OC 2 H5)3
(26) (C 6 H 5 )CO(CH)2(C6H4)O(CH2)6θSi(OCH3) 3
In this formulas, (C 6 H 5 )CO(CH) 2 (C 6 H 4 ) shows the chalconyl group. In addition, in Example 1 , as the silanol condensing catalyst, a metal carboxylate, a metal carboxylate ester, a metal carboxylate polymer, a metal carboxylate chelate, a titanic acid ester, a titanic acid ester chelate and the like can be used. More particularly, the followings can be used, that is, stannous acetic acid, dibutyltin dilaurate, dibutyltin dioctanate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctanate, dioctyltin diacetate, stannous dioctanate, lead naphthenate, cobalt naphthenate, iron 2- ethylhexenoate, a dioctyltin bisoctylthioglycolate ester, a dioctyltin maleate ester, a dibutyltin maleate polymer, a dimethyltin mercapto propionate polymer, dibutyltin bisacetyl acetate, dioctyltin bisacetyl laurate, tetrabutyl titanate, tetranonyl titanate, and a bis(acetylacetonyl)dipropyl titanate.
Further, as a solvent of the film forming solution, even when the chemisorption liquid was alkoxysilane-based or chlorosilane-based, organic chlorine-based solvents not including water a hydrocarbon-based solvent, a fluorocarbon-based solvent, a silicone-based solvent, or a mixture of those can be used. In addition, when the solvent is evaporated so as to increase the particulate concentration without washing, it is preferable that a boiling point of the solvent is about 50 to 250 degree C. More particularly, a organic chlorine-based solvent, non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzene, isoparaffin, normalparaffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethylsilicone, phenylsilicone, alkyl-modified silicone, polyether silicone, dimethylformaldehyde, and the like can be used. Further, when the adsorbent is based on alkoxysilane and the solvent is evaporated so as to form the organic film, an alcohol-based solvent such as methanol, ethanol, propanol or the like, or a mixture of those can be used in addition to the above-described solvents.
Further, as the fluorocarbon-based solvent, a fluorocarbon-based solvent,
Fluorinate (produced by 3M Corporation), Aflude (produced by Asahi Glass Co., Ltd.) and the like can be used. In addition, these solvents can be used independently, or can be used by mixing two or more kinds if these can be well mixed. Further, the organic chlorine-based solvent such as chloroform can be added.
On the other hand, instead of the above-described silanol condensing solvent, when the ketimine compound, organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, the aminoalkylalkoxy silane compound were used, the processing time could be shortened to about 1/2 to 2/3 although having the same concentration.
Further, when the silanol condensing catalyst was used by mixing with the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, the aminoalkylalkoxy silane compound although the mixing rate could be within the range of 1:9 to 9:1 , a mixing rate of about 1 :1 was ordinarily preferable), the processing time could be shortened several times further (up to about 30 minutes), and the time for forming the film could be shortened to several.
For example, when the process was carried out under the same conditions except H3 which was the ketimine compound produced by Japan Epoxy Resin Corporation was used instead of the dibutyltin oxide which was the silanol catalyst, approximately similar results could be obtained although the reaction time could be shortened to about one hour.
Further, when the process was carried out under the same conditions except a mixture (having the mixing ratio of 1 :1) of H3 which was the ketimine compound produced by Japan Epoxy Resin Corporation and the dibutyltin bisacetyl acetonate which was the silanol catalyst was used instead of the silanol catalyst, approximately similar results could be obtained although the reaction time could be shortened to about 30 minutes.
Therefore, it was clear that the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxy silane compound had higher activity than the silanol condensing catalyst.
Furthermore, when the silanol condensing catalyst was used by mixing with one of the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxy silane compound, the reactivity became further higher. In addition, in this case, the ketimine compound used in the present invention was not limited especially. For example, the followings could be used, that is, 2,5,8-triaza-1 ,8-nonadien, 3,11 -dimethyl-4,7, 10-triaza-3, 10-tridecadien,
2 , 10-d imethyl-3, 6 , 9-triaza-2 , 9-u ndecad ien , 2,4,12,14-tetramethyl-5,8, 11 -triaza-4, 11 -pentadecadien, 2,4,15,17-tetramethyl-5 ,8,11 ,14-tetraaza-4 , 14-octadecad ien ,
2,4,20,22-tetramethyl-5,12,19-triaza-4,19-trieicosadien, and the like.
Further, the organic acid used in the present invention was not limited especially. For example, formic acid, acetic acid, propionic acid, butyric acid, malonic acid or the like could be used, and approximately similar results could be obtained.
In the above-described two examples, the fine silica particle was used. However, the present invention can be applied to any fine particles if these are an insulator fine particle containing active hydrogen such as hydrogen in a hydroxyl group on the surface thereof. Further, the present invention can be applied to an organic insulator fine particle containing active hydrogen such as a hydroxyl group on the surface thereof.
Further, the present invention can be used to all applications using a conventional inorganic protective film formed using the sputtering method, the CVD method or the sol-gel method. More particularly, the inorganic protective film is a protective film on the surface of a semiconductor substrate, a protective film on the surface of a wiring substrate, a protective film on the surface of each kinds of a metal product, a protective film on the surface of a glasses lens, a protective film on the surface of a building material, and a protective film on the surface of an applied film.