JP7187301B2 - Resin composition for plating resist - Google Patents

Description

The present invention relates to a resin composition for plating resist.

BACKGROUND ART Conventionally, a method of forming electrodes using a silver paste has generally been used to form electrodes for solar cells.
In recent years, a method of forming electrodes by copper plating using a plating resist has been studied in place of the conventional method of using silver paste for the purpose of reducing production costs.
For the resist that protects the base material from copper plating, a negative film is used that is cured with light and the areas that are not exposed to light are developed with alkali to form a pattern. There are heat-drying type resists that form a pattern by drying to evaporate a solvent, and resists that are cured with ultraviolet rays without using heat-drying. There are two methods for stripping the coating film, one using an organic solvent and the other using an alkaline aqueous solution as the stripping solution. Among the above, the development type resist requires many steps of pattern formation and has poor productivity. It is a resist that prints a pattern directly, and the thermal drying type has problems such as a long drying time and a large environmental load because it uses an organic solvent. In addition, the solvent peeling type uses an organic solvent for the peeling liquid, so the environmental load is large. From these facts, it is considered that a type in which a pattern is directly printed, cured with ultraviolet rays, and peeled off with an alkaline aqueous solution is preferred.

JP-A-3-031310

However, when peeling with an alkaline aqueous solution results in swelling peeling, the peeled film tends to re-adhere to the base material, the feed roll in the peel layer, and the squeeze roll. A peeling film that has reattached to the feed roll or squeeze roll tends to adhere to the base material, causing poor peeling. Therefore, it is necessary to remove the swollen and peeled coating film with a filter or the like, and it is necessary to newly install equipment for that purpose, which increases the burden of equipment costs.

In order to solve such problems, there is a need for a plating resist that can be completely dissolved in an alkaline aqueous solution instead of swelling and peeling. The plating resist is also required to prevent cracking during electroplating and to provide a cured coating film with good dryness to the touch. However, when the conventionally proposed ultraviolet curable resists are used for protection of electrolytic plating, these problems cannot be solved at the same time.

For example, in Patent Document 1, a half-ester composed of a polybasic acid anhydride and an acrylic monomer is used as a half-ester oligomer, but it swells and peels off in an alkaline aqueous solution. Moreover, the coating film cured by ultraviolet irradiation is poor in dryness to the touch and tends to stick when laminated, resulting in a marked reduction in workability. Therefore, when a half ester of polybasic acid anhydride and acrylate is used, it is possible to prevent cracks during electroplating, but the solubility in an alkaline aqueous solution and the dryness to the touch cannot be satisfied. rice field.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a plating resist resin composition that suppresses cracking during electroplating and provides a cured coating film that is excellent in solubility in an alkaline aqueous solution and dryness to the touch.

The inventors of the present invention have made intensive studies in view of the above, and found that by blending an alkali-soluble polymer, a morpholine compound having a (meth)acryloyl group, a photopolymerization initiator, and a silane-coupling-treated talc, the above problem was solved. can be solved, and the present invention has been completed.

That is, the plating resist resin composition of the present invention includes (A) an alkali-soluble polymer, (B) a morpholine compound having a (meth)acryloyl group, (C) a photopolymerization initiator, and (D) a silane coupling It is characterized by containing treated talc.

The plating resist resin composition of the present invention preferably further contains a half ester of a polybasic acid anhydride and a hydroxyalkyl (meth)acrylate monomer.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition for plating resists which suppresses the crack at the time of electroplating and can obtain the cured coating film excellent in the solubility to alkaline aqueous solution and dryness to the touch can be provided.

Hereinafter, the components contained in the resin composition for plating resist of the present invention will be described in detail. In the present specification, (meth)acryloyl group is a generic term for acryloyl group, methacryloyl group and mixtures thereof, and the same applies to other similar expressions.

[(A) alkali-soluble polymer]
The plating resist resin composition of the present invention contains (A) an alkali-soluble polymer. In the present invention, examples of the alkali-soluble polymer include rosin-based resins, carboxyl group-containing acrylic copolymer resins, phenol-based resins, and cresol-based resins. Alkali-soluble polymers may be used alone or in combination of two or more. The alkali-soluble polymer may have an ethylenically unsaturated bond. Among the alkali-soluble polymers, acrylic copolymer resins containing carboxyl groups, particularly those having a weight average molecular weight in the range of 5,000 to 50,000, more preferably in the range of 7,000 to 20,000. and the acid value is preferably in the range of 50-300 mgKOH/g, more preferably 80-220 mgKOH/g. When the weight average molecular weight is 5,000 or more, the dryness to the touch of the coating film after drying is good, the workability is excellent, and the plating resistance is also improved. When the weight average molecular weight is 50,000 or less, the alkali solubility is good and the compatibility with (meth)acrylate is also good.

Examples of rosin-based resins include natural resins such as gum rosin, wood rosin, chemically modified hydrogenated rosin, polymerized rosin, rosin-modified maleic acid resin, and rosin-modified phenolic resin. The softening point of these rosin-based resins is preferably 60° C. or higher. When the temperature is 60° C. or higher, the dryness to the touch of the coating film cured with ultraviolet rays is good. The acid value is preferably in the range of 80-200 mgKOH/g. When it is 80 mgKOH/g or more, the alkali solubility is good, and when it is 200 mgKOH/g or less, the hydrophilicity is not high and the plating resistance is good.

As phenolic resins and cresol-based resins, novolac-type resins are preferable, and in the present invention, they have better alkali solubility than resol-type and other alkylphenol-type resins.

Examples of acrylic copolymer resins containing carboxyl groups include (meth)acrylic acid (hereinafter, (meth)acrylic acid means acrylic acid and methacrylic acid) copolymers, such as methyl methacrylate-methacrylic acid copolymers. Binary copolymers such as polymers, terpolymers such as styrene-2-ethylhexyl acrylate-acrylic acid copolymers, etc. Obtained by combining any (meth)acryloyl group-containing monomers copolymers.

The amount of (A) the alkali-soluble polymer is preferably 20 to 70% by mass, based on the total amount of 100% by mass of (A) the alkali-soluble polymer and (B) the morpholine compound having a (meth)acryloyl group. , more preferably 40 to 60% by mass. When it is 20% by mass or more, the viscosity does not become too low, so it is suitable for screen printing, and the alkali solubility is good. When the content is 70% by mass or less, the viscosity does not become too high and the workability is good, and the photocurability is also good.

[(B) (Meth) Morpholine Compound Having Acryloyl Group]
The plating resist resin composition of the present invention contains (B) a morpholine compound having a (meth)acryloyl group. Morpholine compounds having a (meth)acryloyl group include, for example, N-acryloylmorpholine, N-methacryloylmorpholine and the like. A morpholine compound having a (meth)acryloyl group may be used alone or in combination of two or more.

(B) The amount of the morpholine compound having a (meth)acryloyl group is a ratio in 100% by mass of the total amount of (A) the alkali-soluble polymer and (B) the morpholine compound having a (meth)acryloyl group, preferably 25 to 80% by mass, more preferably 35 to 60% by mass. When it is 25% by mass or more, the viscosity does not become too high, the workability becomes good, the photoreactivity is good, and the productivity improves. When it is 80% by mass or less, the alkali solubility becomes better, and the generation of composition residue is further suppressed.

Further, in the plating resist resin composition of the present invention, the total amount of (A) an alkali-soluble polymer and (B) a morpholine compound having a (meth)acryloyl group is preferably 20 to 80% by mass in terms of nonvolatile content. and more preferably 40 to 60% by mass. When it is 20% by mass or more, the alkali solubility is better, the generation of residue of the composition is more suppressed, the curability is good, and the work efficiency is excellent. When it is 80% by mass or less, the photocuring property is good, the working efficiency is excellent, and the occurrence of cracks due to electrolytic plating can be further suppressed.

[(C) Photoinitiator]
The plating resist resin composition of the present invention contains (C) a photopolymerization initiator. Examples of photopolymerization initiators include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2, 6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-( 2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6- bisacylphosphine oxides such as trimethylbenzoyl)-phenylphosphine oxide (Omnirad 819 manufactured by IGM); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4, 6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (OMnirad TPO H manufactured by IGM) monoacylphosphine oxides such as; Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropane- hydroxyacetophenones such as 1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methyl Benzophenones such as benzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone; cetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4- Acetophenones such as morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; Thioxanthones such as thioxanthone and 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, etc. ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate and p-dimethylbenzoic acid ethyl ester; -octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -,1-(0-acetyloxime) and other oxime esters; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) )phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrr-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2-nitro Fluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like can be mentioned. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type. Particularly preferred initiators include 2,2′-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins) and the like as benzyl methyl ketal-based radical polymerization initiators. -Hydroxyalkylphenone-based radical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name Omnirad 1173, registered trademark of IGM Resins) and the like, and acylphosphine oxide-based Examples of radical polymerization initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name OmniradTPO H, manufactured by IGM Resins), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (trade name name Omnirad 819, manufactured by IGM Resins) and the like.

(C) The amount of the photopolymerization initiator compounded in the plating resist resin composition of the present invention is 1 to 15% by mass, more preferably 2 to 7% by mass, in terms of non-volatile matter. When the compounding amount is 1% by mass or more, the curability is good and peeling does not occur during plating. When the compounding amount is 15% by mass or less, the degree of polymerization is good, and in this case also peeling does not occur during plating.

[(D) Silane coupling-treated talc]
The plating resist resin composition of the present invention contains (D) silane-coupling-treated talc. Although the method for preparing the silane-coupling-treated talc is not particularly limited, surface treatment agents include silane-based coupling agents such as vinylsilane-based coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, and mercaptosilane-based coupling agents. It can be adjusted using a coupling agent, an organosilazane compound, or the like. Vinylsilane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxysilane, methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxysilane. and propyltriethoxysilane. Aminosilane-based coupling agents include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-2-(aminoethyl)aminopropyltrimethoxysilane, and the like. mentioned. Epoxysilane coupling agents include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl)ethyltri methoxysilane and the like. The mercaptosilane-based coupling agent includes merkatopropyltrimethoxysilane, merkatopropyltriethoxysilane, and the like. Other silane coupling agents such as methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, imidazolesilane, and triazinesilane can also be used. Organosilazane compounds include hexamethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane and the like.

Among surface treatment agents, silane-based coupling agents are preferred, vinylsilane-based coupling agents are more preferred, and methacryloxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl More preferred are methacryloxysilane coupling agents such as methyldiethoxysilane and 3-methacryloxypropyltriethoxysilane.

(D) The silane-coupling-treated talc may be commercially available talc, such as talc obtained by treating Micro Ace K1 manufactured by Nippon Talc Co., Ltd. with a vinylsilane coupling agent. good.

(D) The average primary particle size of the silane-coupling-treated talc is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm.

(D) Silane-coupling-treated talc may be used alone or in combination of two or more. (D) The content of silane-coupling-treated talc in the plating resist resin composition of the present invention is 20 to 70% by mass, preferably 30 to 60% by mass, in terms of non-volatile content. When it is 20% by mass or more, the crack prevention effect becomes better. When it is 70% by mass or less, it is easier to dissolve in the peeling process and less likely to leave a residue.

(Half ester of polybasic acid anhydride and hydroxyalkyl (meth)acrylate monomer)
The resin composition for a plating resist of the present invention preferably contains a half ester of a polybasic acid anhydride and a hydroxyalkyl (meth)acrylate monomer. It is more suppressed, and the peeling residue can be reduced.

As the half ester of a polybasic acid anhydride and a hydroxyalkyl (meth)acrylate monomer, commonly known ones that can be used in resist compositions may be used. Here, the half ester is premised to be synthesized with 1 mol of (meth)acrylate monomer per 1 mol of polybasic acid anhydride, but the (meth)acrylate monomer may be used in excess. . Examples of polybasic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, maleic anhydride, succinic anhydride, dodececylsuccinic anhydride, hymic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Examples of hydroxyalkyl (meth)acrylate monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, 1,6- Hexanediol mono(meth)acrylate, diethylene glycol mono(methyl)acrylate and the like can be mentioned. The half ester may be used singly or in combination of two or more.

The half ester may be a half ester having a structure obtained by subjecting a polybasic acid anhydride and a hydroxyalkyl (meth)acrylate monomer to a normal esterification reaction. It may be a half ester obtained using a basic acid.

The amount of the half ester compounded in the plating resist resin composition of the present invention is 10 to 60% by mass, more preferably 15 to 50% by mass, in terms of non-volatile matter. When the amount is 10% by mass or more, the curability is good, and penetration of the plating solution into the coating film is suppressed. When it is 60% by mass or less, the solubility at the time of peeling is excellent, the stickiness of the cured coating film is suppressed, and the workability is improved.

(Photoreactive monomer)
The resin composition for a plating resist of the present invention may contain a photoreactive monomer, as long as the above problems can be solved. As the photoreactive monomer, any resin that is cured by irradiation with active energy rays may be used, and in the present invention, compounds having one or more ethylenically unsaturated bonds in the molecule are particularly preferably used. A photoreactive monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

The photoreactive monomer is preferably a reactive diluent, and is preferably a photopolymerizable monomer having at least one (meth)acryloyl group and at least one carboxylic acid group in one molecule. Specifically, (meth)acrylate monomers and bifunctional unsaturated compounds such as polyethylene glycol (meth)acrylate and polypropylene glycol (meth)acrylate are preferred. The resin composition for a plating resist of the present invention preferably does not contain a trifunctional or higher (meth)acrylate as a photoreactive monomer, so that the plating resist film can be easily dissolved in an alkaline aqueous solution in the stripping step. It is possible to suppress the peeling residue more easily.

The amount of the photoreactive monomer compounded in the plating resist resin composition of the present invention is preferably 1 to 30% by mass, more preferably 2 to 15%, in terms of non-volatile matter. A blending of 1% by mass or more provides a dilution effect, and the viscosity can be adjusted to be suitable for preferable screen printing. Within 30% by mass, a viscosity suitable for screen printing can be maintained.

(thixotropic agent)
The plating resist resin composition of the present invention may contain a thixotropic agent other than the silane-coupling-treated talc. A thixotropic agent has the effect of imparting thixotropic behavior when added to a resin composition. The thixotropic behavior is behavior in which the viscosity decreases when shear stress is applied to the resin composition, and the viscosity increases when the stress is removed. Thixotropic behavior helps prevent settling of fillers and pigments when incorporated. Thixotropic agents may be used singly or in combination of two or more.

Examples of the thixotropic agent include inorganic thixotropic agents and organic thixotropic agents.
As the inorganic thixotropic agent, silica, particularly ultrafine silica having a primary particle size of 5 to 50 nm and a specific surface area of 30 m ² /g or more is preferred. Specific examples of ultrafine silica include AEROSIL 90, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 255, AEROSIL 300, AEROSIL 380, AEROSIL RY50, AEROSIL RY200, AEROSIL RX200, AEROSIL R540, Tosoh Silica manufactured by Nippon Aerosil Co., Ltd. Nipsil L-250, Nipsil L-300, Nipsil E-200A, Nipsil E-220A, Nipsil N-300A manufactured by the company. The content of the ultrafine silica powder in the plating resist resin composition of the present invention is preferably 1 to 15% by mass, more preferably 2 to 5% by mass, in terms of non-volatile matter. When the content is 1% by mass or more, the thixotropy is improved, and the pattern reproducibility is improved. When the content is 15% by mass or less, the thixotropy is not too high, the defoaming property is good, the leveling is good, pinholes and blurring are less likely to occur, and the pattern reproducibility is good.

Other inorganic thixotropic agents include clay minerals such as bentonites. Specific examples of clay minerals include Esben, Esben E, Esben WX, Esben C, Esben W manufactured by Hojun Co., Ltd., Orben, Orben A, and Orben P manufactured by Shiraishi Kogyo Co., Ltd., and the like.

Organic thixotropic agents include vegetable oils containing carboxylic acids, synthetic oils, amides obtained by reacting polymers with amines, hydrogenated oils obtained by hydrogenating vegetable oils, and polar There are polyethylene oxide type, polyester type, polyether type, fluorine type, surfactant type, etc. into which a group is introduced, and there is also a composite system in which two or more of these are used in combination. Specific examples of the organic thixotropic agent include talen 2000, talen 2450, talen 7200, talen 7500, talen 8700, talen 8900, talen KY-2000, talen M-1021B, flowon RCM-210, and flownon manufactured by Kyoeisha Chemical Co., Ltd. SH-290, Flownon SA-300, DISPARLON 3600, DISPARLON 3900, DISPARLON 4200, DISPARLON 4401, DISPARLON 6500, DISPARLON 6810, DISPARLON 6900 manufactured by Kusumoto Chemicals, BYK-405, BYK-410, BYK-411 manufactured by BYK-Chemie , BYK-430, BYK-431 and the like.

(Other additives)
In addition, the plating resist resin composition of the present invention may contain other known and commonly used additives in the field of resists. Other additives include, for example, coupling agents, surface tension modifiers, surfactants, matting agents, thermal polymerization inhibitors, antioxidants, rust preventives, inorganic fillers, organic fillers, and for adjusting film properties. polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, waxes, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and other known and commonly used coloring agents, antifoaming agents such as silicone-based, fluorine-based, and polymer-based antifoaming agents and leveling agents. Such additives may be blended by appropriately adjusting the amount used within a range in which the desired effects of the additives can be obtained without impairing the effects of the present invention.

The resin composition for a plating resist of the present invention may contain an organic solvent within a range that does not impair the effects of the present invention, but from the viewpoint of photocurability, it preferably does not contain an organic solvent. It is 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0% by mass in the resin composition for use.

The resin composition for plating resist of the present invention may be one-component or two-component or more.

The method of forming a plating resist film using the plating resist resin composition of the present invention is not particularly limited. A patterned plating resist may be formed.

A plating resist film formed from the resin composition for plating resist of the present invention is soluble in a dilute alkaline aqueous solution, and can be easily removed with a known remover such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. The concentration of alkaline substances such as sodium hydroxide is, for example, 1 to 5 mass %.

The plating resist formed from the resin composition for plating resist of the present invention is not particularly limited, and examples thereof include plating resists for forming electrodes of solar cells, plating resists for printed wiring boards, and the like. Moreover, the plating treatment to which the plating resist formed from the resin composition for plating resist is exposed is not particularly limited.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following, "parts" and "%" are based on mass unless otherwise specified.

(Preparation of resin composition)
After blending the respective components shown in Examples and Comparative Examples shown in Table 1 below, they were mixed by stirring. After that, the mixture was kneaded twice with three rolls to prepare a resin composition.

(Preparation of test substrate)
A 400-mesh stainless bias screen was used to print on a copper-clad laminate that had been buffed after acid treatment. The coating thickness at that time was 12 μm. Using a UV irradiator with a metal halide lamp as a light source, the coating film was cured with a light intensity of 1000 mJ/cm ² .

(dry to the touch)
After curing, the coating films cooled to room temperature were laminated together, a load of 1 kg was applied, and the degree of adhesion after standing for 6 hours was confirmed.
Evaluation method:
◯: There was no abnormality in the coating film even when it was separated.
Δ: The coating film left marks when it was separated.
x: The coating film was peeled off when separated.

(Printability)
The bleeding width was measured at a portion with a resolution line width of 100 μm.
⊚: Less than 30% ◯: Bleeding width is 30 to 50%.
x: Bleeding width is over 50%.

(Evaluation after electrolytic plating)
After electrolytic copper sulfate plating, the appearance of the coating film was visually confirmed, and the presence or absence of cracks on the resist coating film was confirmed with an optical microscope.
Electrolytic copper sulfate plating conditions:
Solution temperature 30°C, processing time 30 minutes Plating solution resistance:
⊚: No peeling by tape peeling.
O: No abnormality in appearance.
x: Permeation of the plating solution into the resist coating film.
Crack resistance:
◯: No cracks occurred.
Δ: Cracks occurred only on the surface of the coating film. It did not reach the copper surface under the paint film.
x: Cracks reaching the copper surface under the coating film occurred.

(Confirmation of peeling state)
The test substrate was immersed in a 3% sodium hydroxide aqueous solution heated to 50° C. for 30 seconds to check the peeling state.
○: dissolved.
x: Swelling.

(Confirmation of peeling residue)
After the test substrate was immersed in a 3% sodium hydroxide aqueous solution heated to 50°C for 30 seconds, it was washed with water at a pressure of 0.1 MPa for 20 seconds, dried at 60°C for 1 minute, and then impregnated with alcohol. It was visually confirmed whether the resist residue adhered to the wiping paper.
⊚: Detachment was possible with no residue after immersion in sodium hydroxide for 20 seconds.
◯: No peeling residue.
Δ: Peeling residue is 50% or less of the printed area.
x: Peeling residue is present in 50% or more of the printed area.

*1: Styrene, acrylic acid copolymer resin (Joncryl 67 manufactured by BASF Japan)
*2: Phenol novolac resin (BRG-557 manufactured by Aica Kogyo Co., Ltd.)
*3: Half ester of polybasic acid anhydride with hydroxyalkyl (meth)acrylate (HOA-MPL manufactured by Kyoeisha Chemical Co., Ltd.)
*4: Acryloylmorpholine (ACMO manufactured by KJ Chemical Co.)
* 5: 2-Hydroxyethyl methacrylate (Light ester HO-250 manufactured by Kyoeisha Chemical Co., Ltd.)
* 6: Dimethyl polysiloxane (KS-66 manufactured by Shin-Etsu Chemical Co., Ltd.)
*7: Carbon black (black colorant)
* 8: Photoinitiator (OMNIRAD 651 manufactured by IGM)
*9: Thixotropic agent (Nippon Aerosil #200 (fine powder silica))
*10: Silane coupling-treated talc (Spectra K manufactured by Powdex)
*11: Untreated talc (Micro Ace K-1 manufactured by Fuji Talc Co., Ltd.)

As shown in the table above, the plating resist resin composition of the present invention includes (A) an alkali-soluble polymer, (B) a morpholine compound having a (meth)acryloyl group, (C) a photopolymerization initiator, and (D) A plating resist film formed using a plating resist resin composition containing silane-coupling-treated talc has excellent dryness to the touch, suppresses cracking during electroplating, and is completely soluble in an alkaline aqueous solution. It can be seen that the resist film can be peeled off without any residue. On the other hand, in the plating resist film formed using the resin composition of Comparative Example 1, cracks were generated during electroplating, and residues were generated during alkaline aqueous solution treatment. The plating resist film formed using the resin composition of Comparative Example 2 was swollen and peeled, and a peeled residue was also produced.

Claims (3)

(A) an alkali-soluble polymer, (B) a morpholine compound having a (meth)acryloyl group, (C) a photopolymerization initiator, and (D) a plating resist comprising silane-coupling-treated talc An ultraviolet curable resin composition for
The (A) alkali-soluble polymer includes at least one of a rosin-based resin, an acrylic copolymer resin containing a carboxyl group, a phenol-based resin, and a cresol-based resin,
The total amount of the (A) alkali-soluble polymer and (B) the (meth)acryloyl group-containing morpholine compound in terms of non-volatile content in the ultraviolet-curable resin composition for plating resist is 20 to 80 mass. % and
The amount of the (B) morpholine compound having a (meth)acryloyl group is the total amount of the (A) alkali-soluble polymer and the (B) morpholine compound having a (meth)acryloyl group in a ratio of 100% by mass. , 25 to 80% by mass of an ultraviolet curable resin composition for a plating resist . The plating according to claim 1, wherein the amount of (D) silane-coupling-treated talc is 20 to 70% by mass in terms of nonvolatile content in the ultraviolet-curable resin composition for plating resist. UV-curable resin composition for resist. 3. The UV-curable resin composition for a plating resist according to claim 1 , further comprising a polybasic acid anhydride and a half ester of a hydroxyalkyl (meth)acrylate monomer.