METHOD OF PLATING

TECHNICAL FIELD

[0001]

The present invention relates to a curable composition for plating mask, a mask material and a removing method of plating.

BACKGROUND ART

[0002]

Conventionally, methods for applying a coating on a surface of the metal substrate are known.

For example, Patent Document 1 describes a paint composition comprising (A) a monofunctional polymerizable monomer having one ethyleninc double bond in a molecule having a phenol structure; (B) a multifunctional polymerizable oligomer having eight or more ethyleninc double bonds in a molecule; and (C) a silicon-based leveling agent, as a paint composition having improved adhesiveness, abrasion resistance, and salt water resistance to the metal substrate.

PRIOR ART DOCUMENTS

Patent Documents

[0003]

Patent Document 1: JP 2014-080596 A

SUMMARY OF THE INVENTION

Problem to be Solved by the Invention

[0004]

Conventionally, plating treatment on the surface of the member is performed in order to protect the surface of the member. By plating treatment, a metal thin film (hereinafter, simply referred as “plating” or“metal plating”) is formed on the surface of the member.

[0005]

If the plating is removed from the surface of the member for processing the member, for example, a method for applying a plating removing agent is known. In this method, it is considered that the plating can be removed partially by covering a part of the plating with a mask material. However, in conventional resin materials (for example, the paint composition as described in Patent Document 1), its chemical resistance against the plating removing agent is not sufficient, and exerting the function as the mask material is difficult. Further, if metal material is used as the mask material, it has a problem that the formation of the fine pattern is difficult.

[0006] Therefore, an object of the present invention is to provide a curable composition for plating mask being capable of easily forming a mask material having improved chemical resistance against the plating removing agent in various pattern shapes. Also, an object of the present invention is to provide a mask material comprising the curable composition for plating mask as described above, and a removing method of plating using the curable composition for plating mask as described above.

MEANS FOR SOLVING THE PROBLEM

[0007]

One aspect of the present invention relates to a curable composition for plating mask, comprising a monomer ingredient containing a first monomer having a (meth)acryloyl group and an acidic functional group and a second monomer having a (meth)acryloyl group and a benzene ring; and a

photopolymerization initiator.

[0008]

Since the curable composition for plating mask comprises the first monomer and the second monomer as the monomer ingredient, the cured product has excellent adhesiveness to plating and excellent chemical resistance against the plating removing agent. Further, the curable composition for plating mask can form a mask material having a predetermined pattern by applying the composition on plating, and then curing the composition. Further, since the curable composition for plating mask can be cured by light irradiation, a mask material can be easily formed even if the base material (plating treated member) has insufficient heat resistance.

[0009]

In one aspect, the content of the first monomer may be from 5 to 40% by mass based on the total amount of the monomer ingredient.

[0010]

In one aspect, the content of the second monomer may be from 40 to 95% by mass based on the total amount of the monomer ingredient.

[0011]

In one aspect, the monomer ingredient may further contain a multifunctional monomer having two or more (meth)acryloyl groups.

[0012]

In one aspect, the content of the multifunctional monomer may be from 5 to 40% by mass based on the total amount of the monomer ingredient.

[0013]

In one aspect, the content by percentage of the acidic functional group per unit mass of the monomer ingredient may be from 0.15 to 6.0 mmol/g. [0014]

One aspect of the present invention relates to a mask material, comprising a cured product of the curable composition for plating mask as described above. The mask material has excellent adhesiveness to plating and excellent chemical resistance against the plating removing agent.

[0015]

Another aspect of the present invention relates a removing method of plating, by using the curable composition for plating mask as described above. The removing method comprises an application step for applying the curable composition for plating mask as described above on a substrate having a metal plating so as to cover a part of the metal plating; a curing step for curing the curable composition to form a covered moiety in which the metal plating is covered with the curable composition and an exposed moiety in which the metal plating is exposed; and a removing step for contacting the metal plate in the exposed moiety with a plating removing agent to remove the metal plate in the exposed moiety.

EFFECT OF THE INVENTION

[0016]

According to the present invention, provided is a curable composition for plating mask being capable of easily forming a mask material having improved chemical resistance against the plating removing agent in various pattern shapes. Also, according to the present invention, provided is a mask material comprising the curable composition for plating mask as described above, and a removing method of plating using the curable composition for plating mask as described above.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017]

The curable composition for plating mask according to this embodiment comprises a monomer ingredient and a photopolymerization initiator, and the monomer ingredient contains a first monomer having a (meth)acryloyl group and an acidic functional group and a second monomer having a

(meth)acryloyl group and a benzene ring.

[0018]

Since the curable composition for plating mask comprises the first monomer and the second monomer as the monomer ingredient, the cured product has excellent adhesiveness to plating and excellent chemical resistance against the plating removing agent. Further, the curable composition for plating mask according to this embodiment can form easily a mask material having a predetermined pattern by applying the composition on plating, and then curing the composition. Further, since the curable composition for plating mask according to this embodiment can be cured by light irradiation, a mask material can be easily formed even if the base material (plating treated member) has insufficient heat resistance. [0019]

First Monomer

The first monomer is a monomer having a (meth)acryloyl group and an acidic functional group and being capable of copolymerizing with the second monomer.

[0020]

Examples of the acidic functional group contained in the first monomer include a carboxyl group, a sulfo group and a phosphate group. Specific examples of the first monomer include acrylic acid, methacrylic acid,’’KAYAMER PM-2” (manufactured by Nippon Kayaku Co., Ltd.),’’KAYAMER PM- 2-1” (manufactured by Nippon Kayaku Co., Ltd.), and 2-(meth)acryloyloxyethyl acid phosphonic acid.

[0021]

The content of the first monomer in the monomer ingredient may be 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more based on the total amount of the monomer ingredient. The content tends to further improve the chemical resistance against the plating removing agent. Also, the content of the first monomer in the monomer ingredient may be 40% by mass or less based on the total amount of the monomer ingredient. The content is preferably 30% by mass or less, and more preferably 25% by mass or less based on the total amount of the monomer ingredient. The content tends to further improve the adhesiveness to the plating.

[0022]

The content of the first monomer in the monomer ingredient may be adjusted so that the amount of the acidic functional group per unit mass of the monomer ingredient is from 0.15 to 6.0 mmol/g. The adjustment can provide the above described effect of the present invention significantly. The content by percentage of the acidic functional group in the monomer ingredient is more preferably 0.2 mmol/g or more, and more preferably 2 mmol/g or less.

[0023]

Second Monomer

The second monomer is a monomer having a (meth)acryloyl group and a benzene ring and being capable of copolymerizing with the first monomer.

[0024]

Example of the second monomer includes a compound represented by the following formula (1):

[0025]

[Chemical Formula 1] [0026]

In the formula (1), R ¹ represents a hydrogen atom or a methyl group; R ² represents an alkanediyl group; R ³ represents a hydrocarbon group having a benzene ring; and n represents an integer of 0 or more. When a plurality of R ² is present, the plurality of R ² may be identical or different each other.

[0027]

Preferred R ² is an alkanediyl group having a carbon number of 1 to 6, more preferably an alkanediyl group having a carbon number of 1 to 3, and further preferably an alkanediyl group having a carbon number of 2 to 3.

[0028]

The hydrocarbon group of R ³ is a group composed of carbon atoms and hydrogen atoms and having a benzene ring. Examples of the hydrocarbon group include an aryl group and an arylaklyl group.

[0029]

The aryl group may be referred as the remaining atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. Also, the arylalkyl group may be referred as the group in which a part of or all hydrogen atoms in the alkyl group is substituted with aryl group. Examples of the aromatic hydrocarbon include benzene, naphthalene and anthracene, each of which may have a substituent group. The substituent group is a hydrocarbon group. For example, the substituent group may be an alkyl group, a phenyl group, and the combination thereof (for example, an alkylphenyl group or a phenylalkyl group).

[0030]

Suitable examples of the aryl group include a phenyl group, an alkylphenyl group (for example, a tolyl group, a xylyl group, a trimethylphenyl group, and a nonylphenyl group), a biphenyl group, a phenylalkylphenyl group (for example, an a-cumylphenyl group).

[0031]

In one preferred aspect, R ² may be an unsubstituted phenyl group, or a phenyl group having at least one substituent group (a substituted phenyl group) selected from the group consisting of a phenyl group, an alkyl group and a phenylalkyl group. The alkyl group included in the substituted phenyl group is preferably an alkyl group having a carbon number of 8 to 12, more preferably an alkyl group having a carbon number of 9 (a nonyl group). Also, the phenylalkyl group included in the substituted phenyl group is preferably a phenylalkyl group having a carbon number of 8 to 12, particularly preferably a-cumyl group. The number of the substituent group included in the substituted phenyl group is preferably from 1 to 3, and more preferably 1.

[0032]

While the upper limit of n is not particularly limited, for example, n may be 10 or less, and n is preferably 8 or less.

[0033]

As the second monomer, any commercially available product may be used. As the commercially available product, Aronix M-106, Aronix M-l 10, Aronix M-l 11, Aronix M-l 13, Aronix M-l 17 (all manufactured by TOAGOSEI CO., LTD.), NK ester A-LEN-10 (manufactured by Shin Nakamura

Chemical Co., Ltd), Light acrylate NP-4EA, Light acrylate NP-8EA (all manufactured by KYOEISHA CHEMICAL Co., LTD.), SR504, CD612, CD614 (all manufactured by Sartomer Japan),“MIRAMER Ml 64”,“MIRAMER M166” (all manufactured by Learn), KAYARAD OPP-l, KAYARAD OPP-1.5, KAYARAD OPP-2 (all manufactured by Nippon Kayaku Co., Ltd.) can be suitably used.

[0034]

The content of the second monomer in the monomer ingredient may be 40% by mass or more, preferably 50% by mass or more, and more preferably 60% by mass or more based on the total amount of the monomer ingredient. The content tends to further improve the adhesiveness to the plating. Also, the content of the first monomer in the monomer ingredient may be 95% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less based on the total amount of the monomer ingredient. The content tends to further improve the chemical resistance against the plating removing agent.

[0035]

Other Monomer

The monomer ingredient may further contain a multifunctional monomer having multiple polymerizable groups. By including the multifunctional monomer in the monomer ingredient, the curing rate of the curable composition for plating mask is increased (that is, the fast curability is improved), and the time required for curing the curable composition for plating mask can be reduced. It facilitates to apply the curable composition for plating mask to any known printing procedure, and tends to facilitate the formation of the mask material having fine pattern.

[0036]

The polymerizable group included in the multifunctional monomer is a functional group being capable of copolymerizing with the first monomer and the second monomer. Lor example, the polymerizable group may be a (meth)acryloyl group, a vinyl group, a vinylidene group, an allyl group, and a vinylether group. Among these groups, a (meth)acryloyl group is particularly preferred in terms of the excellent reactivity between the first monomer and the second monomer.

[0037]

The multifunctional monomer may have two or more polymerizable groups. The number of the polymerizable group contained in the multifunctional monomer is not particularly limited. Lor example, the number may be 3 or more, or 5 or more. In addition, the number of the polymerizable group contained in the multifunctional monomer may be, for example, 20 or less.

[0038]

The content of the multifunctional monomer in the monomer ingredient may be 5% by mass or more, preferably 7% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more based on the total amount of the monomer ingredient. It tends to obtain the curable composition for plating mask having further improved fast curability. It further decreases the tack on the surface of the mask material, and it also tends to improve the handling properties after forming the mask material. While the upper limit of the content of the multifunctional monomer in the monomer ingredient is not particularly limited, for example the content may be 40% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass. Thereby, the chemical resistance against the plating removing agent tends to be further improved.

[0039]

The monomer ingredient may further contain any other monomer other than the monomer described above. The other monomer is not particularly limited as long as the monomer can copolymerize with the first monomer and the second monomer. Examples of the other monomer include alkyl

(meth)acrylte and urethane (meth)acrylte. The content of the other monomer may be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less based on the total amount of the monomer ingredient. The monomer ingredient does not need to contain the other monomer as described above. The content of the other monomer may be 0% by mass.

[0040]

Photopolymerization Initiator

The photopolymerization initiator is not particularly limited as long as the ingredient can initiate the polymerization of the monomer ingredient by light irradiation without limitation. The type and the content of the photopolymerization initiator can be suitably selected depending on the type of the monomer ingredient and illuminated light. Also, the photopolymerization initiator can be used alone, or in combination of two or more.

[0041]

Examples of the photopolymerization initiator include l-hydroxycyclohexylphenylketone, 2- methyl- 1 -(4-methylthiophenyl)-2-morpholinopropan- 1 -one, 2-benzyl -2 -dimethylamino-l -(4- morpholinophenyl)butan- 1 -one, 2, 2-dimethoxy-l ,2-diphenylethan- 1 -one, 1 -[4-(2-hydroxyethoxy)phenyl] -2-hydroxy-2-methyl-l-propan-l-one, 2 -hydroxy- 1 -[4-[4-(2-hydroxy-2-methylpropyonyl)benzyl]phenyl] - 2-methylpropan-l-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-l-[4-(4-morphol inyl)phenyl] -1- butanone, bis(2, 4, 6-trimethylbenzoyl)phenyl phosphine oxide, bis(//5-2. 4-cyclopentadien-l-yl)-bis(2, 6- difluoro-3 -( lH-pyrrole- 1 -yl)phenyl) titanium, 1 ,2-octanedione, 1 -[4-(phenylthio)-,2-(o-benzoyloxime)], ethanone, l-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,l-(o-acet yloxime), 2-hydroxy-2-methyl-l- phenylpropan-l-one, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, l-(4-isopropylphenyl)-2 -hydroxy - 2-methylpropan- 1 -one, 4-(2-hydroxyethoxy)phenyl(2 -hydroxy-2 -propyl)ketone, benzophenone, trimethylbenzophenone, methylbenzophenone, isopropyl thioxanthone, o-benzoyl benzoic acid methyl -4- phenylbenzophenone, 4-, 4’-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4’-methyldiphenyl sulfide, acrylated benzophenone, 3,3',4,4’-tetra(t-butyl peroxycarbonyl)benzophenone, 3, 3 '-dimethyl -4- methoxybenzophenone, 2, 2-dimethyl -2 -hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, Michler's ketone, 4, 4’-diethylaminobenzophenone, trimethylbenzophenone, methylbenzophenone mixture, 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2,4-dichlorothioxanthone, L-chloroform-4- propoxythioxanthone, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, L-phenyl-2- hydroxy-2-methylpropanone, 10-butyl -2 -chloroacridone, 2-ethylanthraquinone, 9,10- phenanthrenequinone, camphorquinone, oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxyphenylacetic acid, 2-(2-hydroxyethoxy)ethyl ester mixture, and 2-hydroxy 2-methyl-[4-(l- methylvinyl)phenyl] propanol oligomer. Among them, for example, 2-benzyl-2-dimethylamino-l-(4- morpholinophenyl)butan-l-one, oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2-(2 -hydroxyethoxy)ethyl ester mixture, 2-hydroxy-l-[4-[4-(2-hydroxy-2- methylpropionyl)benzyl]phenyl]-2-methylpropan-l-one, 2-hydroxy-2-methyl-[4-(l- methylvinyl)phenyl] propanol oligomer, l-hydroxycyclohexyl phenyl ketone, 2-methyl-l-(4- methylthiophenyl)-2-morpholinopropan-l-one can be more suitably used.

[0042]

Examples of the commercially available photopolymerization initiator include Omnirad 184, Omnirad907, Omnirad8l9, Omnirad369, Omnirad379, Omnirad250, Omnirad754, Omniradl27, Omnirad2595, Omniradl800, Omnirad 1870, Omniradl l73, Omnirad EDB, Omnirad EHA, Omnirad TPO (all manufactured by IGM Resins), ESACURE TZT, ESACURE KIP 150, ESACURE KIP 75LT, ESACURE KIP IT, ESACURE KIP 100F, ESACURE ONE, ESACURE KT55, ESACURE KT37, ESACURE KT046 (all manufactured by Lamberti), CN386, SR1 l24(all manufactured by Sartomer Japan Inc ), DAIDO UV-CURE #174, DAIDO UV-CURE D-177F, PHOTOCURE 50 (all manufactured by Daido Chemical Corporation).

[0043]

While the content of the photopolymerization initiator is not particularly limited, the content may be 0.1% by mass or more based on 100% by mass of the monomer ingredient. The content is preferably 0.3% by mass or more, and more preferably 0.5% by mass or more. The content of the

photopolymerization initiator may be, for example, 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less based on 100 parts by mass of the monomer ingredient.

[0044]

Other Ingredient

The curable composition for plating mask according to this embodiment may further contain any other ingredient other than the ingredient described above. Examples of the other ingredient include a fluorescent agent, a UV curing aid, a photosensitizer, an inorganic filler, an organic filler, a coupling agent, a tackifier, an anti-foaming agent, a plasticizer, an antioxidant, a polymerization inhibitor, a flame retardant, a pigment, a dye, and pigment derivatives.

[0045]

By including the photosensitizer in the curable composition for plating mask, the visibility of the cured product (i.e., the mask material) is improved, and the test the product after forming pattern can be easily performed. The type of the fluorescent agent is not particularly limited, for example, it may be benzoxazolylthiophene . [0046]

By including the UV curing aid in the curable composition for plating mask, curing by light irradiation can be easily proceeded, and the thickness of the mask material tends to thicken. The type of the UV curing aid is not particularly limited, for example, it may be secondary thiol.

[0047]

While the content of the other ingredient is not particularly limited, the content may be 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less based on 100% by mass of the monomer ingredient. The lower limit of the content of the other ingredient is not particularly limited. The content may be 0% by mass.

[0048]

The curable composition for plating mask according to this embodiment may have a viscosity at 25°C of 10,000 cps or less. The viscosity tends to facilitate its application on plating. In terms of easier formation of fine pattern by any known printing procedure, the viscosity at 25°C is preferably 5,000 cps or less, and more preferably 3,000 cps or less.

[0049]

For example, the curable composition for plating mask according to this embodiment may have a viscosity at 25 °C of 10 cps or more. The viscosity is preferably 100 cps or more. The viscosity tends to prevent the liquid dripping on the plating and to further facilitate the formation of the mask material having a predetermined pattern.

[0050]

In the specification, the viscosity of the curable composition for plating mask at 25°C shows an amount as measured by a B type viscometer according to the method of JIS K7117-1 (year version).

[0051]

The curable composition for plating mask according to this embodiment is cured by light irradiation to form the cured product. By providing the cured product on the plating, the plating under the cured product is protected from the plating removing agent. That is, the cured product of the curable composition for plating mask can be used as the mask material for protecting from chemicals such as the plating removing agent.

[0052]

Mask Material

The mask material according to this embodiment is the mask material for protecting from chemicals such as the plating removing agent, and is composed of the cured product of the curable composition for plating mask.

[0053]

In one preferred aspect, the mask material can be produced by a production method comprising an application step for applying the curable composition for plating mask on the plating; and a curing step for curing the applied curable composition to form the mask material. [0054]

In the application step, the curable composition for plating mask may be applied so as to form a predetermined pattern on the plating. The application method is not particularly limited, and any known application method can be used. Specific examples of the application method include inkjet printing, gravure printing, spray coat, and brush coating. The applied amount in the application step is not particularly limited, and the amount may be suitably changed depending on the thickness of the desired mask material.

[0055]

In the curing step, the applied curable composition for plating mask is cured to form the mask material. Curing can be performed by light irradiation. The condition of light irradiation is not particularly limited, and the condition is a range so that the curable composition for plating mask can be sufficiently cured.

[0056]

While the thickness of the mask material is not particularly limited, in terms of the further improved chemical resistance, the thickness is, for example, 0.05 pm or more, preferably 0.1 pm or more, and more preferably 0.5 pm or more. Further, in terms of the easier light curing, the thickness of the mask material is, for example, 2 mm or less, preferably 1 mm or less, and more preferably 500 pm or less.

[0057]

Removing Method of Plating

The removing method of plating according to this embodiment comprises an application step, a curing step and a removing step. The application step is a step for applying the curable composition for plating mask on a substrate having a plating (a metal plating) so as to cover a part of the metal plating. Further, the curing step is a step for curing the curable composition applied on the plating. By the curing step, a covered moiety in which the metal plating is covered with the cured product of the curable composition (i.e., the mask material) and an exposed moiety in which the metal plating is exposed are formed. The removing step is a step for contacting the metal plate in the exposed moiety with a plating removing agent to remove the metal plate in the exposed moiety.

[0058]

Hereinafter, each steps of the removing method of plating according to this embodiment will be described in detail.

[0059]

In the application step, the curable composition for plating mask is applied on a substrate having a plating (a metal plating) so as to cover a part of the metal plating. The application method is not particularly limited, for example, the application method as described above can be exemplified. Further, the applied amount in the application step is not particularly limited, and the amount may be suitably changed depending on the thickness of the desired mask material. [0060]

The substrate which is applied in the removing method of plating according to this embodiment is not particularly limited as long as the substrate has plating to be removed. For example, the substrate may be a metal material or non-metal material. The shape of the substrate is not particularly limited, for example, it may be plate, string, or rod shape.

[0061]

The type of the plating formed on the substrate is not particularly limited. Examples of the type of the plating include silver plating, nickel plating, copper plating, copper alloy plating, gold plating, and tin plating.

[0062]

In the curing step, the curable composition for plating mask which is applied on the plating is cured to form the mask material. The covered moiety which is covered with the mask material does not affect by the plating removing agent in the removing step as described below, and is maintained on the substrate because the plating is protected by the mask material. The exposed moiety which is not covered with the mask material is removed from the substrate by the plating removing agent in the removing step as described below.

[0063]

Curing of the curable composition for plating mask can be performed by light irradiation. The condition of light irradiation is not particularly limited, and the condition is a range so that the curable composition for plating mask can be sufficiently cured. The thickness of the mask material formed by curing is not particularly limited, for example, it may be the thickness as described above.

[0064]

In the removing step, the plating in the exposed moiety is removed by the plating removing agent. In the removing step, the plating removing agent may contact with the covered moiety. In the covered moiety, the mask material is formed on the plating, and thereby the plating and the plating removing agent are not contacted directly, and the plating is not removed. Further, in this embodiment, since the mask material has high adhesiveness to the plating and high chemical resistance against the plating removing agent, the base plating is prevented from affecting the adverse effect due to the peeling of the mask material.

[0065]

The type of the plating removing agent may be suitably selected depending on the type of the plating. Examples of the plating removing agent include Enstrip S liquid, Melstrip N-950, Melstrip-NH- 841, Melstrip TL-3400, Melstrip HN-844, Melstrip FIN-980, Enstrip TL cone liquid, Enstrip TL-105, Enstrip-TL-l06, Enstrip TL-142 cone., Agrip 940, Melstrip A-965, Enstrip AU-78M, Melstrip AU-3160, Melstrip AU-3170, Enstrip Q-592 (manufactured by Meltex Inc.), SVAC H-150, SVAC H-150PN (manufactured by SASAKI CHEMICAL CO., LTD.), New Rip Master #1219, Rip Master Plus, Rip Master NRP- 100, Rip Master -10, Rip Master NRP-20, Rip Master NRP-01, Rip Master HANDA, and Rip Master AL-KK (manufactured by Kizai Corporation). [0066]

In the removing step, the plating removing agent may contact with the plating at a predetermined processing temperature for a predetermined processing time. The processing temperature is not particularly limited, for example, it may be from 0 to 90°C or from 15 to 50°C. Further, the processing time is not particularly limited, for example, it may be from 5 sec to 10 min, or from 10 sec to 5 min.

[0067]

In the removing method according of this embodiment, by the removing step, a composite member comprising an exposed moiety in which the metal plating is removed to expose the surface of the member and a laminate moiety in which the plating and the mask material are laminated on the surface of the member is formed.

[0068]

In this embodiment, the composite member itself can be used as the product, can be used after removing the mask material from the laminate moiety as the product, can be used after further treatment of the exposed moiety (e.g., metal vaporization or plating treatment) as the product, or can be used after further treatment of the exposed moiety and then removing the mask material from the laminate moiety as the product.

[0069]

As one preferred aspect, for example, a wire saw (a coping saw) can be produced by applying the removing method as described above to a wire with the plating treatment, removing a part of the plating in predetermined pattern, and forming a new plating layer containing abrasive grains on the exposed moiety in which the plating was removed.

EXAMPLES

[0070]

The present invention will be described more specifically below using examples, but the present invention is not intended to be limited to the examples.

[0071]

Example 1

Raw materials as described in Table 1 were subsequently mixed to obtain a curable composition for plating mask (hereinafter also referred to as an application liquid).

[0072]

The resulting application liquid was applied on a brass substrate (manufactured by IWATA MFG.CO., LTD., SIM plate dimensions of cut material, material: brass, thickness: 0.15 mm) using meyer bar No. 8. Then, UV ray was irradiated by using UV ray irradiator (H-bulb, DRS model, Fusion UV System Inc.) at a dose of 900 mJ/cm ² ten times to form a mask material. The resulting mask materials were evaluated according to the following method. The results are shown in Table 1. [0073]

Surface Condition

The surface of the mask material was touched, and then the presence or absence of its tack was confirmed. When there was no tack, it was evaluated as A, and when there was a tack, it was evaluated as B.

[0074]

Immersion Test 1 (Acidic Solution)

The brass substrate in which the mask material was formed was immersed in 2% hydrochloric acid at 25°C for 90 sec. After immersion, the presence or the absence of the mask material peeling was confirmed. When there was no mask material peeling and its adhesiveness to the substrate was maintained, it was evaluated as A. When there was no mask material peeling, but the mask material was softened, it was evaluated as B. When there was a mask material peeling, it was evaluated as C.

[0075]

Immersion Test 2 (Basic Solution)

The brass substrate in which the mask material was formed was immersed in an basic solution (Metal cleaner 373, manufactured by ATOTECH, pH 12.35) at 25°C for 90 sec. After immersion, the presence or the absence of the mask material peeling was confirmed. When there was no mask material peeling and its adhesiveness to the substrate was maintained, it was evaluated as A. When there was no mask material peeling, but the mask material was softened, it was evaluated as B. When there was a mask material peeling, it was evaluated as C.

[0076]

Immersion Test 3 (Plating Removing Agent)

The brass substrate in which the mask material was formed was immersed in a plating removing agent (Melstrip CU-3940, manufactured by Meltex Inc.) at 25°C for 90 sec. After immersion, the presence or the absence of the mask material peeling was confirmed. When there was no mask material peeling and its adhesiveness to the substrate was maintained, it was evaluated as A. When there was no mask material peeling, but the mask material was softened, it was evaluated as B. When there was a mask material peeling, it was evaluated as C.

[0077]

Adhesion Test

By a cross-cut method according to JIS K 5600, the adhesiveness of the base material was evaluated. More specifically, the mask material was cut into a 5x5 lattice shape of each 1 mm, and then an adhesive tape (manufactured by NITTO DENKO CORPORATION) was adhered to the mask material. The adhered adhesive tape was peeled. When the mask material peeling was not occurred, it was evaluated as A. When the peeling was occurred, it was evaluated as C. [0078]

Examples 2-9

The curable compositions for plating mask were prepared as similar as in Example 1, except that raw materials were changed as described in Table 1 or Table 2. The resulting curable compositions for plating mask were then used to form mask materials as similar as in Example 1, and then to evaluate them. The results are shown in Table 1 or Table 2.

[0079]

Comparative Examples 1 to 3

The curable compositions for plating mask were prepared as similar as in Example 1, except that raw materials were changed as described in Table 3. The resulting curable compositions for plating mask were then used to form mask materials as similar as in Example 1, and then to evaluate them. The results are shown in Table 3. In Comparative Example 3, the compositions were not cured, and could not form the mask material.

[0080]

In the Table,“Amount of acidic functional group” refers to the percentage of the acidic functional group per unit mass of the monomer ingredient in the curable composition for plating mask.

[0081]

In the Table,“PM-21” refers to“KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.);“M-l 13” refers to Aronix M-l 13 (manufactured by TOAGOSEI CO., LTD.);“M-l 11” refers to Aronix M-l 11 (manufactured by TOAGOSEI CO., LTD.);“CN2302” refers to CN2303 (manufactured by Sartomer);“DPHA” refers to dipentaerythritol hexaacrylate (manufactured by Sartomer);“D1173” refers to Omnirad 1173 (manufactured by IGM Resins);“TPO” refers to“Omnirad TPO (manufactured by IGM Resins);“PE1” refers to“Karenz MT PE1 (manufactured by SHOWA DENKO K.K.); and “UVITEX” refers to UVITEX OB (manufactured by BASF).

[0082] [Table 1]

[0083] [Table 2]

[0084]

[Table 3]

[0085]

Examples 10-13

The curable compositions for plating mask were prepared as similar as in Example 1, except that raw materials were changed as described in Table 4. The resulting curable compositions for plating mask were then used to form mask materials as similar as in Example 1, and then to evaluate them. The results are shown in Table 4.

[0086]

In the Table,“tack-free pass” shows how many UV ray was irradiated by which the number of irradiation out of 10 times until the tack on the mask material was eliminated. Smaller the number, it is considered that the curable composition for plating mask has excellent fast curability. In Examples 10 and 11, after UV was irradiated ten times, the tack was not eliminated. [0087] [Table 4]