KR20160120229A - Active energy ray curable resin composition with white color and cured product thereof, and printed wiring board - Google Patents

Abstract

Provided is a white actinic energy ray-curable resin composition capable of forming a cured product having basic characteristics including resistance to soldering heat, adhesive properties, and film hardness without performing an additional heat curing process following a photo curing process. The white actinic energy ray-curable resin composition comprises: (A) a reactive polycarbonic acid compound; (B) a reactive compound other than the reactive polycarbonic acid compound (A); (C) a photopolymerization initiator; and (D) titanium oxide, wherein the reactive polycarbonic acid compound (A) is obtained by reacting (d) a polybasic anhydride with (E) a reactant of (a) an epoxy resin represented by general formula 1, (b) an acrylic acid, and (c) a compound having at least two hydroxyl groups and at least one carboxyl group in one molecule.

Description

TECHNICAL FIELD [0001] The present invention relates to a white active energy ray-curable resin composition, a cured product thereof, and a printed wiring board. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to an active energy ray-curable resin composition suitable for a coating material for covering a conductor circuit pattern formed on a substrate such as a printed wiring board, and a coated product such as a printed wiring board coated with a cured product.

A printed wiring board is generally used to form a pattern of a conductor circuit on a substrate and to mount an electronic component by soldering on a soldering land of the circuit pattern. The circuit portion excluding the solder land is covered with the solder resist film as the permanent protective film. Thus, when soldering an electronic component to a printed wiring board, the solder is prevented from attaching to an unnecessary portion, and the circuit conductor is directly exposed to air to prevent corrosion due to oxidation or humidity.

Conventionally, in order to form a solder resist film having basic properties such as solder heat resistance and film hardness on a printed wiring board, a photo-curing step and a heat curing step are required as in Patent Document 1. First, the active energy ray-curable resin composition is applied to a printed wiring board and, if necessary, pre-dried at a temperature of about 60 to 100 DEG C to form a coated film. Next, a negative film having a light-transmitting pattern other than the land of the circuit pattern is brought into close contact with the active energy ray-curable resin composition and irradiated with an active energy ray (for example, ultraviolet rays) to be photo-cured. In addition, the non-exposed region is removed with a dilute alkaline aqueous solution to develop the coated film. Finally, the coating film is thermally cured at a temperature of about 140 to 180 DEG C to form a cured coating film of the active energy ray-curable resin composition on the printed wiring board.

However, such a conventional solder resist film forming method has a problem in that the productivity of the film-formed product is not improved because the photo-curing step and the heat curing step are performed. Further, in forming the solder resist film on the substrate with low heat resistance, there is a problem that the heat of the thermal curing process deteriorates the quality of the substrate, which is deformation of the substrate.

Patent Document 2 discloses that a resin composition containing an unsaturated group-containing polycarboxylic acid is suitable for a solder resist, but there is no mention of a white active energy ray-curable resin composition in which titanium oxide or the like is dispersed .

Japanese Patent Application Laid-Open No. 2008-257044 Japanese Patent Publication No. 2704661

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a cured product having basic properties such as solder heat resistance, adhesiveness and film hardness, The present invention provides a white active energy ray-curable resin composition capable of forming a white active energy ray-curable resin composition.

The inventors of the present invention have made intensive investigations to solve the above problems, and as a result, they found that a specific compound and a resin composition having a composition solve the above problems, and have reached the present invention.

That is,

(1) A white active energy ray-curable resin composition containing a reactive polycarboxylic acid compound (A), a reactive compound (B) other than the reactive polycarboxylic acid compound (A), a photopolymerization initiator (C) , The reactive polycarboxylic acid compound (A) is obtained by reacting an epoxy resin (a) represented by the general formula (1), a compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule, Which is a reactive polycarboxylic acid compound (A) obtained by reacting a reaction product (E) of a compound (c) having at least two hydroxyl groups and at least one carboxy group in one molecule with a polybasic acid anhydride (d) Energy ray curable resin composition comprising:

(Wherein n represents an integer of 0 to 2).

(2) The present invention also relates to a process for producing a reactive polycarboxylic acid compound (A), wherein the reactive polycarboxylic acid compound (A) comprises an epoxy resin (a) represented by the general formula (1) and a compound (A) obtained by reacting a polybasic acid anhydride (b) and a reaction product (E) of a compound (c) having at least two hydroxyl groups and at least one carboxy group in a molecule with a polybasic acid anhydride (d) , And the white active energy ray-curable resin composition described in (1) above.

(3) In the present invention, the photopolymerization initiator (C) is an acylphosphine-based photopolymerization initiator and a benzoyloxime-based photopolymerization initiator. The blending ratio of the acylphosphine-based photopolymerization initiator to the benzoyloxime-based photopolymerization initiator is 2 To 100 parts by mass of the white active energy ray-curable resin composition according to the above (1) or (2).

(4) In the present invention, the photopolymerization initiator (C) is an acylphosphine-based photopolymerization initiator and a benzoyloxime-based photopolymerization initiator, and the mixing ratio thereof is 1 to 3 parts by mass of the benzoyloxime- To 50 parts by mass of the active energy ray-curable resin composition according to the above (1) or (2).

(5) In the present invention, the photopolymerization initiator (C) is an acylphosphine-based photopolymerization initiator and a benzoyloxime-based photopolymerization initiator, and the mixing ratio thereof is 1 to 4 parts by mass of the benzoyloxime- To 10 parts by mass of the active energy ray-curable resin composition according to the above (1) or (2).

(6) The present invention also provides a photoresist composition, wherein the acylphosphine-based photopolymerization initiator is 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis , 6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, and the benzoyloxime-based Wherein the photopolymerization initiator is at least one selected from the group consisting of 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], 2-propanedione- Propanedione 2-O-benzoyloxime. The present invention also relates to a white active energy ray-curable resin composition as described in (3) to (5) above.

(7) The present invention also relates to a cured product of the white active energy ray-curable resin composition according to any one of (1) to (6).

(8) The present invention also relates to a printed wiring board having a cured coating of the white active energy ray-curable resin composition according to any one of (1) to (6).

According to the embodiment of the present invention, by blending the reactive polycarboxylic acid compound (A), the heat curing step after the photo-curing step by exposure is not performed, that is, by the exposure treatment with the active energy ray, the reflectance, , A cured product excellent in various properties such as adhesion and film hardness can be obtained. Further, in the embodiment of the present invention, since a cured product excellent in the above-mentioned characteristics can be obtained without performing the heat curing step after the photo-curing step, the production efficiency of a product, for example, a printed wiring board having a cured coating, Improvement.

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in detail.

The reactive polycarboxylic acid compound (A) in the present invention is obtained by reacting the epoxy resin (a) represented by the general formula (1) with the compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule, (D) in addition to the reaction product (E) of the compound (c) having at least two hydroxyl groups and at least one carboxy group in one molecule, if necessary.

That is, the reactive polycarboxylic acid compound (A) in the present invention is obtained by reacting the reaction product (E) of the epoxy resin (a) and the compound (b) with the polybasic acid anhydride (d) Is obtained by reacting a reaction product (E) of a compound (b) and a compound (c) with a polybasic acid anhydride (d).

In the present invention, the characteristics of the present invention are exhibited by introducing an ethylenic unsaturated group and a hydroxyl group into a molecular chain by an epoxycarboxylation reaction.

The epoxy resin (a) represented by the general formula (1) in the present invention can be obtained by reacting (4 (4 (1,1-bis (p-hydroxyphenyl) , Phenol compound (PA1)) with epihalohydrin. The present epoxy resin is represented by the following representative structure:

(Wherein n represents an integer of 0 to 2).

The present epoxy resin is generally available as TECMOREVG3101L (manufactured by PRINTEC), NC-6300C (manufactured by Nippon Kayaku) and NC-6300H (manufactured by Nippon Kayaku) Compounds can be obtained by preparation.

The epoxy resin (a) used in the present invention is more preferably a solid at room temperature. In the present invention, an epoxy resin (a) having a softening point of 50 to 100 占 폚 or a melting point of 50 to 190 占 폚 is usually used, but a softening point of 60 to 100 占 폚 or a melting point of 60 to 190 占 폚 is preferable. The epoxy equivalent of 130 to 500 g / eq. Is usually used in the present invention, but is preferably 150 to 400 g / eq., More preferably 170 to 300 g / eq. When the epoxy equivalent is too small, it tends to be hard and easily tends to retreat. When the epoxy equivalent is too large, hardness hardly occurs and the glass transition point may be lowered.

Examples of the epihalohydrins used in the reaction of the phenolic compound (PA1) with epihalohydrin include epichlorohydrin,? -Methyl epichlorohydrin,? -Methyl epichlorohydrin, epibromohydrin In the present invention, epichlorohydrin which is industrially easily available is preferable. The epihalohydrin is used in an amount of usually 2 to 15 mol, preferably 4 to 10 mol, per 1 mol of the hydroxyl group of the phenol compound (PA1). The use of the remaining excess epihalohydrin may not only not only deteriorate the productivity but also lower the softening point of the epoxy resin to be produced and may not have a good effect on the toughness when the prepreg is used. When the amount of epihalohydrin is less than 2 moles, the value of n becomes large, and gelation tends to occur during the production.

In the epoxidation reaction, it is preferable to use an alkali metal hydroxide. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Further, the alkali metal hydroxide may be used as a solid or an aqueous solution thereof. For example, in the case of using an alkali metal hydroxide as an aqueous solution, an aqueous solution of an alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously flowed under reduced pressure or normal pressure, To remove water, and the epihalohydrin is continuously returned to the reaction system. In the case of using a solid, it is preferable to use a flake-shaped one because of its ease of handling and solubility. The amount of the alkali metal hydroxide to be used is generally 0.90 to 1.5 moles, preferably 1.01 to 1.25 moles, and more preferably 1.01 to 1.15 moles, per 1 mole of the hydroxyl group of the phenol compound (PA1).

In the epoxidation reaction, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride, tetramethylphosphonium chloride, tetramethylphosphonium bromide, trimethylbenzylphosphonium chloride , Triphenylbenzylphosphonium chloride, triphenylethyl bromide, and the like may be added as a catalyst. The amount of these quaternary salts to be used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol compound (PA1).

Examples of the epoxidation reaction include alcohols such as methanol, ethanol and isopropyl alcohol; ethers such as tetrahydrofuran and dioxane; aprotic polar solvents such as dimethylsulfone, dimethylsulfoxide and dimethylimidazolidinone; To conduct the reaction. From the viewpoint of the optical properties, the use of alcohols and / or ethers is preferred in the present invention.

When the alcohol or ether is used, the amount of the alcohol or ether is usually 2 to 50% by mass, preferably 4 to 20% by mass based on the amount of the epihalohydrin to be used. On the other hand, when the aprotic polar solvent is used, its amount to be used is usually 5 to 100 mass%, preferably 10 to 80 mass%, based on the amount of epihalohydrin to be used.

In the epoxidation reaction, the reaction temperature is usually from 30 to 90 캜, preferably from 35 to 80 캜. On the other hand, the reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. This reaction may be performed at atmospheric pressure or reduced pressure, and it may be reacted under a reduced-pressure condition with an azeotropic dehydration condition of water-epihalohydrin. The reactants of these epoxidation reactions can be purified by removing the epihalohydrin, solvent, etc., after the water rinse or without water rinse under heating and reduced pressure. Further, in order to further obtain an epoxy resin having less hydrolyzable halogen, the recovered reaction product is dissolved in a solvent such as toluene or methyl isobutyl ketone, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added, It is preferable that the ring-closing reaction of the by-product is carried out and the ring-opening of the halohydrin, which is a by-product, is ensured.

In this case, the amount of the alkali metal hydroxide to be used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per 1 mol of the hydroxyl group of the phenol compound (PA1) used for the epoxidation. The reaction temperature is usually from 50 to 120 캜, and the reaction time is usually from 0.5 to 2 hours.

In the epoxidation reaction, after completion of the reaction, the resulting salt is removed by filtration, water washing and the like, and the solvent is further distilled off under reduced pressure and heating to obtain an epoxy resin usable in the present invention. The thus obtained epoxy resin includes an epoxy resin added by a part of its solvent or water, and a case where halogen is not entirely ring-closed but the halogen is left.

The epoxy resin (a) which is the reaction product of the thus obtained phenol compound (PA1) and epihalohydrin is excellent in productivity and handleability and satisfies any of the following conditions for imparting high mechanical strength to the cured product .

1. The epoxy equivalent is preferably 195 to 245 g / eq., More preferably 200 to 240 g / eq.

2. In Gel Permeation Chromatography, it was confirmed that 30% by area or less of the phenol compounds (PA1) were connected to each other by epihalohydrins, 20% by area or less of the internally connected sites, and 25% Area% or less, and that of the innate is 15% or less area percent. As the remainder, the monomer of the epoxy resin (a) corresponds.

The compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule in the present invention is reacted in order to impart reactivity to an active energy ray. The ethylenic unsaturated group and the carboxy group are not limited as long as they have at least one ethylenic unsaturated group and a carboxy group, respectively. These include monocarbonic acid compounds and polycarboxylic acid compounds.

Examples of the monocarboxylic acid compound having one carboxy group in one molecule include (meth) acrylic acid, crotonic acid,? -Cyanosynnamic acid, cinnamic acid, or a monoglycidyl compound containing a saturated or unsaturated dibasic acid and an unsaturated group Reaction products. Examples of the (meth) acrylic acids in the above include (meth) acrylic acid,? -Styryl acrylic acid,? -Furfuryl acrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride, (Meth) acrylate derivatives having a hydroxyl group, semi-esters, which are in-bomb reactants, and half-esters, which are monovalent reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives.

Examples of the polycarboxylic acid compound having two or more carboxy groups in one molecule include (meth) acrylate derivatives having a plurality of hydroxyl groups in one molecule and half esters as a bimolecular reactant, glycols having a saturated or unsaturated dibasic acid and a plurality of epoxy groups And half-esters, which are reaction products of the cydyl (meth) acrylate derivative at a molar ratio.

Of these, the reaction product of (meth) acrylic acid, (meth) acrylic acid and epsilon -caprolactone, or cinnamic acid is preferable from the viewpoint of sensitivity when the active energy ray-curable resin composition is used. As the compound (b), it is preferable that the compound does not have a hydroxyl group.

The compound (c) having at least two hydroxyl groups and at least one carboxyl group in a molecule, which is used in accordance with necessity in the present invention, is reacted for the purpose of introducing a hydroxyl group into the carboxylate compound.

Specific examples of the compound (c) having at least two hydroxyl groups and at least one carboxy group in a molecule in the present invention include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylol And polyhydroxy-containing monocarboxylic acids such as valeric acid and dimethylolcaproic acid. Particularly preferred examples include dimethylolpropionic acid and the like.

Among them, in consideration of the stability of the reaction between the epoxy resin (a), the compound (b) and the compound (c), the compound (b) and the compound (c) are preferably monocarbonic acid, Even when an acid is used in combination, the value represented by the total molar amount of the monocarboxylic acid / the total molar amount of the polycarboxylic acid is preferably 15 or more.

The charging ratio of the total amount of the carbonic acid of the epoxy resin (a), the compound (b) and the compound (c) to be used in this reaction in the reaction should be appropriately changed depending on the application. That is, in the case of carboxylating all the epoxy groups, since the unreacted epoxy groups do not remain, the storage stability of the reactive epoxy carboxylate compound is high. In this case, only the reactivity due to the introduced double bond is used.

On the other hand, by deliberately reducing the amount of the carbonic acid compound to leave an unreacted residual epoxy group, the reactivity by the introduced unsaturated bond and the reaction by the remaining epoxy group, for example, the polymerization reaction by the photo cationic catalyst, Can be used in combination. In this case, however, attention should be paid to the preservation of the reactive epoxy carboxylate compound (E) and the examination of the production conditions.

When the reactive epoxy carboxylate compound (E) that does not leave an epoxy group is produced, the total amount of the compound (b) and the compound (c) to be used as needed is 90 to 120 equivalents relative to 1 equivalent of the epoxy resin (a) %. Within this range, production under relatively stable conditions is possible. If the total amount of the compound (b) and the compound (c) to be used is large, the excess amount of the compound (b) and the compound (c) remains undesirably.

When the epoxy group is intentionally left to remain, the total amount of the compound (b) and the compound (c) to be used if necessary is preferably 20 to 90 equivalent% based on 1 equivalent of the epoxy resin (a). When deviating from this range, further reaction by the epoxy group is not sufficiently progressed. In this case, it is necessary to pay enough attention to the gelation during the reaction and the stability over time of the reactive epoxy carboxylate compound (E).

The ratio of the compound (b) to the compound (c) is 95: 5 to 5: 95, more preferably 95: 5 to 40: 60 is preferable. Within this range, the sensitivity to the active energy ray is good, and sufficient hydroxyl groups can be introduced to react the polybasic acid anhydride (d) to the reactive epoxy carboxylate compound (E).

The carboxylation reaction may be carried out by reacting with a solvent or by diluting with a solvent. The solvent usable here is not particularly limited as long as it is an inert solvent for the carboxylation reaction.

The amount of the solvent to be used is appropriately adjusted depending on the viscosity and application of the resin to be obtained, but is preferably 90 to 30 parts by mass, more preferably 80 to 50 parts by mass, based on 100 parts by mass of the solid content.

Specific examples thereof include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane and decane; and mixtures thereof such as petroleum ether, white gasoline, solvent naphtha Etc., ester solvents, ether solvents, ketone solvents and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as? -Butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol mono Mono or polyalkylene glycol monoalkyl ether monoamines such as ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate and butylene glycol monomethyl ether acetate; And polycarboxylic acid alkyl esters such as acetates, dialkyl glutarates, dialkyl succinates and dialkyl adipates.

Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, Glycol ethers such as glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone.

In addition, it can be carried out in a single or mixed organic solvent such as other reactive compound (B) to be described later. In this case, when the composition is used as a curable composition, it is preferable because it can be directly used as a composition.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction, and the amount of the catalyst to be used may be appropriately selected depending on the reactants, that is, the epoxy resin (a), the carbonic acid compound (b) Is usually 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the reactants to which the solvent and other components are added. The reaction temperature at that time is usually 60 to 150 占 폚, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, And basic catalysts such as zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide and zirconium oxide.

As the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl picrylhydrazine, diphenylamine, 3,5-di-t-butyl-4-hydroxytoluene and the like .

This reaction is defined as the end point when the acid value of the sample is 5 mg · KOH / g or less, preferably 3 mg · KOH / g or less while appropriately sampling.

The preferred molecular weight range of the reactive epoxy carboxylate compound (E) thus obtained is in the range of 1,000 to 50,000, more preferably 2,000 to 30,000, in terms of polystyrene equivalent weight average molecular weight in GPC.

If the molecular weight is smaller than the molecular weight, the hardness of the cured product is not sufficiently exhibited. If the molecular weight is too large, the viscosity becomes high and the coating becomes difficult.

Next, the acid addition process will be described in detail. The acid addition step is carried out for the purpose of introducing a carboxy group into the reactive epoxy carboxylate compound (E) obtained in the previous step to obtain the reactive polycarboxylic acid compound (A). That is, a carboxy group is introduced via an ester bond by addition reaction of a polybasic acid anhydride (d) to a hydroxyl group generated by the carboxylation reaction.

As specific examples of the polybasic acid anhydride (d), for example, any compound having an acid anhydride structure in the molecule can be used. However, it is preferable that the polybasic acid anhydride (d) is an anhydrous silicic anhydride, phthalic anhydride, Particularly preferred are phthalic acid, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride.

The reaction of adding the polybasic acid anhydride (d) can be carried out by adding the polybasic acid anhydride (d) to the carboxylation reaction liquid. The addition amount should be appropriately changed depending on the application.

When the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkali developing type resist, for example, the amount of the polybasic acid anhydride (d) to be added can be adjusted by adding the reactive polycarboxylic acid compound (d) (Based on JIS K5601-2-1: 1999) of 40 to 120 mg · KOH / g, and more preferably 60 to 120 mg · KOH / g. When the acid value of the solid at this time is in this range, the developability of the aqueous alkali solution of the photosensitive resin composition of the present invention is satisfactory. That is, good patterning performance and management for the phenomenon are wide, and excessive acid anhydrides do not remain.

In the reaction, it is preferable to use a catalyst in order to accelerate the reaction. The amount of the catalyst to be used is such that the amount of the catalyst obtained from the reaction product, that is, the epoxy compound (a), the carbonic acid compound (b) Is usually 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the reactive epoxy carboxylate compound (E), the polybasic acid anhydride (d), and optionally the solvent and other reactants. The reaction temperature at that time is usually 60 to 150 占 폚, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, Boron, chromium octanoate, zirconium octanoate, and the like.

The acid addition reaction may be carried out by reacting with a solvent or by diluting with a solvent. The solvent usable here is not particularly limited as far as the acid addition reaction is an inert solvent. Further, in the case where a solvent is produced by a carboxylation reaction, which is a previous step, provided that the solvent is inert to both of the two reactions, You may. Solvents which may be used are the same as those available for the carboxylation reaction.

The amount of the solvent to be used is appropriately adjusted depending on the viscosity and the purpose of the resin to be obtained, but is preferably 90 to 30 parts by mass, more preferably 80 to 50 parts by mass with respect to 100 parts by mass of the solid content.

In addition, it can be carried out in a single or mixed organic solvent such as a reactive compound (B) described later. In this case, when the composition is used as a curable composition, it is preferable because it can be directly used as a composition.

The thermal polymerization inhibitor and the like are preferably the same as those exemplified in the above carboxylation reaction.

This reaction is defined as the point where the acid value of the reactant is in the range of plus or minus 10% of the set acid value while sampling appropriately.

The weight average molecular weight of the reactive polycarboxylic acid compound (A) in terms of polystyrene in GPC is preferably in the range of 500 to 50,000, more preferably 1,000 to 20,000.

The use ratio of the reactive polycarboxylic acid compound (A) in the resin composition is 5 to 70% by mass, preferably 10 to 65% by mass.

Examples of the reactive compound (B) which can be used in the present invention include so-called reactive oligomers such as radical reaction type acrylates, cationic reaction type other epoxy compounds, and vinyl compounds which are responsive to both .

Examples of the radical reactive type acrylates include monofunctional (meth) acrylates, bifunctional (meth) acrylates, trifunctional or more (meth) acrylates, urethane (meth) acrylate oligomers, ) Acrylate oligomer, epoxy (meth) acrylate oligomer and the like.

As the monofunctional (meth) acrylate, for example, acryloylmorpholine; (Meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylates such as phenoxy (meth) acrylate, phenyl (poly) ethoxy (meth) acrylate, p-cumylphenoxy Ethyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, phenylthioethyl (meth) acrylate, 2-hydroxy- (Meth) acrylate such as methoxy (meth) acrylate, and phenylphenol epoxy (meth) acrylate.

Examples of the bifunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane (Meth) acrylate, bisphenol A (poly) ethoxydi (meth) acrylate, bisphenol A (poly) propoxydi (meth) acrylate, bisphenol F Di (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of (poly) ethylene glycol di (meth) acrylate hydroxypivalic acid neopentyl glycol (for example, manufactured by Nippon Kayaku Co., , KAYARAD HX-220, HX-620, etc.).

Examples of trifunctional or higher polyfunctional (meth) acrylates include ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolooctane tri (meth) acrylate, trimethylolpropane polyethoxy tri Methylol such as trimethylolpropane (poly) propoxytri (meth) acrylate, trimethylolpropane (poly) ethoxy (poly) propoxytri (meth) acrylate; (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol polyethoxy tetra (meth) acrylate, pentaerythritol (poly) propoxy tetra Erythritol such as erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Tris [(meth) acryloyloxyethyl] isocyanurate, and caprolactone-modified tris [(meth) acryloyloxyethyl] isocyanurate; Succinic acid-modified pentaerythritol triacrylate, and succinic acid-modified dipentaerythritol pentaacrylates.

(Poly) ester (meth) acrylate oligomer include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, polyethylene glycol, 1-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl- Straight-chain or branched alkyl diols such as pentanediol, 2,4-diethyl-1,5-pentanediol and 2-butyl-2-ethyl-1,3-propanediol, (Poly) ester diol which is a reaction product of a diol compound such as bisphenol A (poly) ethoxydiol or bisphenol A (poly) propoxydiol with the dibasic acid or anhydride thereof, and (poly) Methacrylic acid, and the like.

Examples of the urethane (meth) acrylate oligomer include diol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl Glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, Butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A Polypropoxydiol) or a reaction product of these diol compounds with dibasic acids or anhydrides thereof (e.g., succinic acid, adipic acid, azelaic acid, dimeric acid, isophthalic acid, terephthalic acid, phthalic acid or anhydrides thereof) Diols, organic polyisocyanates (e.g., tetramethylene diisocyanate, hexamer Chain saturated hydrocarbon isocyanates such as isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornadiisocyanate, dicyclohexylmethane diisocyanate , Cyclic saturated hydrocarbon isocyanates such as methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate and hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3- Aromatic polyisocyanates such as rhenylene diisocyanate, rhenylene diisocyanate, pentaerythritol triisocyanate, pentaerythritol triisocyanate, pentaerythritol triisocyanate, pentaerythritol triisocyanate, (Meth) acrylate is added to the reaction system, followed by the addition of a hydroxyl group-containing It may include water.

As the epoxy (meth) acrylate oligomer, a compound having an epoxy group and a carboxylate compound of (meth) acrylic acid. Examples of the epoxy (meth) acrylate include phenol novolak type epoxy (meth) acrylate, cresol novolak type epoxy (meth) acrylate, trishydroxyphenyl methane type epoxy (meth) acrylate, dicyclopentadiene phenol type epoxy Containing epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, bisphenol F epoxy (meth) acrylate, biphenol epoxy (Meth) acrylate, glyoxylated epoxy (meth) acrylate, and heterocyclic epoxy (meth) acrylate.

Examples of vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of the styrene include styrene, methylstyrene, and ethylstyrene. Other examples of the vinyl compound include triallyl isocyanurate and trimethallyl isocyanurate.

The cationic reaction type monomer is not particularly limited as long as it is a compound having an epoxy group in general. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl- 4-epoxycyclohexane carboxylate ("Cyracure UVR-6110" manufactured by Union Carbide Company), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene (Such as "ELR-4206" manufactured by Union Carbide Corp.), limonene dioxide ("Celloxide 3000" manufactured by Daicel), allylcyclohexene dioxide, 3,4, (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate Pate ("Sara Cure UVR-6128" manufactured by Union Carbide Co., Ltd.), bis (3,4-epoxycyclohexylamine ), And the like adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethyl siloxane.

Among them, the reactive compound (B) is most preferably a monofunctional, bifunctional or trifunctional or more (meth) acrylate from the viewpoint of good polymerizability and improving strength of the resulting spacer or the like.

The reactive compound (B) of the present invention may be used alone or in combination of two or more. The proportion of the reactive compound (B) in the composition is preferably 30 to 250 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the reactive polycarboxylic acid compound (A). When the amount of the reactive compound (B) to be used is 30 to 250 parts by mass, the sensitivity of the composition and the heat resistance and elastic properties of the obtained cured product are better.

As the photopolymerization initiator (C) of the present invention, an active species capable of initiating polymerization of a reactive compound (B) other than the reactive polycarboxylic acid compound (A) and the reactive polycarboxylic acid compound (A) ≪ / RTI > Examples of the photopolymerization initiator (C) include acylphosphine compounds, benzoyloxime compounds, acetophenone compounds, and imidazole compounds.

Among them, the use of a combination of an acylphosphine compound and a benzoyloxime compound as a photopolymerization initiator can provide a cured product having excellent properties such as reflectance, solder heat resistance, adhesion, and film hardness, even if the heat- Can be obtained.

The acylphosphine-based photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having an acylphosphine structure, and examples thereof include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6- (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide and the like Acylphosphine oxide compounds.

The benzoyloxime-based photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having a benzoyloxime structure, and examples thereof include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime) 2-propanedione-2-O-benzoyloxime, and 1-phenyl-1,2-propanedione-2-O-benzoyloxime.

The mixing ratio of the acylphosphine-based photopolymerization initiator to the benzoyloxime-based photopolymerization initiator is not particularly limited. For example, the lower limit of the amount of the acylphosphine-based photopolymerization initiator to the 1 part by mass of the benzoyloxime- , It is more preferably 3 parts by mass from the viewpoint of sufficiently performing internal hardening and further improving adhesion, and particularly preferably 4 parts by mass from the viewpoint of reliably preventing the decrease of the reflectance of the cured product. On the other hand, the upper limit of the amount of the acylphosphine-based photopolymerization initiator to 1 part by mass of the benzoyloxime-based photopolymerization initiator is preferably 100 parts by mass in order to reliably improve solder heat resistance and adhesion, More preferably 50 parts by mass, and particularly preferably 10 parts by mass in view of further improving balance between solder heat resistance and adhesion.

That is, the compounding ratio of the acylphosphine-based photopolymerization initiator and the benzoyloxime-based photopolymerization initiator is usually about 2 to 100 parts by mass, preferably about 3 to 50 parts by mass, relative to 1 part by mass of the benzoyloxime-based photopolymerization initiator Mass part, particularly preferably about 4 to 10 mass part.

The total amount of the acylphosphine-based photopolymerization initiator and the benzoyloxime-based photopolymerization initiator is not particularly limited. For example, the lower limit of the total amount is preferably 100 to 100 parts by mass of the reactive polycarboxylic acid compound (A) 1 part by mass is preferable from the viewpoint of improving the mechanical strength of the cured product and 2 parts by mass is particularly preferable from the viewpoint of improvement of heat resistance. On the other hand, the upper limit value thereof is preferably 30 parts by mass from the viewpoint of suppressing the decrease in reflectance due to discoloration due to oxidative decomposition of the photopolymerization initiator, and particularly preferably 20 parts by mass from the viewpoint of adhesion with the substrate.

That is, the total amount of the acylphosphine-based photopolymerization initiator and the benzoyloxime-based photopolymerization initiator is preferably from 1 to 30 parts by mass, more preferably from 2 to 20 parts by mass, per 100 parts by mass of the reactive polycarboxylic acid compound (A) Particularly preferred.

Titanium oxide (D) is an artificial titanium oxide and rutile titanium oxide having a rutile crystal structure, which are blended for whitening a cured product such as a coating film. Of these, rutile titanium oxide is preferred in terms of whiteness. TR-700 "," TR-750 "," TR-840 "manufactured by Fuji Titanium Industry Co., Ltd.," R CR-90 "," CR-60 "," CR-80 "," CR-90 " KR-270 "," KR-310 "and" KR-380 "manufactured by Titan Kogyo Co., Ltd., and the like. These may be used alone or in combination of two or more.

The blending amount of the titanium oxide (D) is not particularly limited, but is preferably about 30 to 200 parts by mass, particularly preferably about 30 to 200 parts by mass, from the viewpoint of balance of whiteness and strength of the cured product relative to 100 parts by mass of the reactive polycarboxylic acid compound (A) Is about 50 to 150 parts by mass.

The white active energy ray-curable resin composition of the present invention may contain various additives, for example, antifoaming agents, dispersants, solvents, extender pigments and the like, as appropriate, in addition to the above components.

As the defoaming agent, known defoaming agents can be used, and examples thereof include silicon, hydrocarbon, acrylic and the like. Examples of the dispersing agent include silane coupling agents, titanate coupling agents and alumina coupling agents.

The solvent is for controlling the viscosity and dryness of the white active energy ray-curable resin composition, and examples thereof include ketones such as methyl ethyl ketone and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol, cyclohexane Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, petroleum solvents such as petroleum ether and petroleum naphtha, cellosolve such as cellosolve and butyl cellosolve, carbitol, butyl carbitol and the like Carbitol, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate and butyl carbitol acetate. These may be used alone or in combination of two or more.

The extender pigment is for auxiliary enhancement of the mechanical strength of a cured product (for example, a coated solder resist film), and examples thereof include silica, barium sulfate, alumina, aluminum hydroxide, talc, mica and the like .

Further, in the present invention, the active energy ray-curable resin composition is colored with white by using titanium oxide. However, depending on the application, it is possible to appropriately add a blue colorant, a yellow colorant, A coloring agent or the like may be added. Specific examples of colorants other than white include inorganic pigments such as phthalocyanine pigments such as phthalocyanine green and phthalocyanine blue, organic pigments such as anthraquinone pigments and azo pigments, and carbon black.

The method for producing the active energy ray-curable resin composition of the present invention is not limited to a specific method. For example, the above components may be blended at a predetermined ratio, and then the mixture may be kneaded at room temperature in a three- Or kneading means such as a super mixer, a planetary mixer or the like. Further, before kneading or mixing, if necessary, pre-kneading or premixing may be performed.

Next, a method of using the white active energy ray-curable resin composition of the present invention will be described. Here, the case where the white active energy ray-curable resin composition of the present invention is applied as a solder resist film on a circuit substrate will be described as an example.

The white active energy ray-curable resin composition of the present invention thus obtained is applied to a printed wiring board having a circuit pattern formed by etching a copper foil, for example, by screen printing, spray coater, bar coater, applicator, blade coater, A knife coater, a roll coater, a gravure coater or the like, using a known coating method. After coating, a tack-free coating film may be formed by preliminary drying at a temperature of about 60 to 80 DEG C for about 15 to 60 minutes to volatilize the solvent in the white active energy ray-curable resin composition, if necessary. A negative active film having a light-transmitting pattern other than a land of a circuit pattern is brought into close contact with a white active energy ray-curable resin composition applied by a known coating method, and an active energy ray (for example, , Ultraviolet ray) is irradiated to photocure the coating film. Next, a desired solder resist film can be formed on the printed wiring board by developing the coating film by removing the non-exposed region corresponding to the land with a dilute alkaline aqueous solution. As the above developing method, a spray method, a shower method, or the like is used, and a dilute aqueous alkali solution to be used is not particularly limited, and for example, an aqueous solution of sodium carbonate of 0.5 to 5% is exemplified. When it is not necessary to develop the coating film, the white active energy ray-curable resin composition may be photo-cured without using a negative film.

Electronic parts are soldered to a circuit board coated with the solder resist film thus obtained by a classification soldering method, a reflow soldering method, or the like, thereby forming an electronic circuit unit.

A cured product and a cured film of the photo-cured white active energy ray-curable resin composition and a circuit board or printed wiring board having the cured product or the cured film are also included in the present invention.

(Example)

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In Examples, " part " means mass part and "% " means mass%, unless otherwise specified.

The softening point, the epoxy equivalent, and the acid value were measured under the following conditions.

1) Epoxy equivalent: Measured by the method according to JIS K7236: 2001.

2) Softening point: Measured by the method according to JIS K7234: 1986.

3) Acid value: Measured by the method according to JISK0070: 1992

Examples 1-1 to 1-3

[Preparation of reactive polycarboxylic acid compound (A)] [

N = 0 (64%), n = 1 (23%), n = 2 or more (13%) of the epoxy resin (a) (abbreviated AA, Mw = 72) as the compound (b) and the amount of dimethylolpropionic acid (abbreviated as DMPA, Mw = 134) as the compound (c) are shown in Table 1 Was added to the medium. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content became 80% by mass of the reaction solution and reacted at 100 ° C for 24 hours to obtain a solution of a reactive epoxy carboxylate compound (E) . And the solid content (AV: mg · KOH / g) of 5 or less was used as the reaction end point. The acid value measurement was carried out in the reaction solution and converted to the acid value as a solid content.

Then, tetrahydrophthalic anhydride (abbreviated as THPA) was added as a polybasic acid anhydride (d) to the reactive epoxy carboxylate compound (E) solution and propylene glycol monomethyl ether monoacetate (THPA) so as to have a solid content of 65% , And the mixture was heated to 100 占 폚, followed by acid addition reaction to obtain a solution of the reactive polycarboxylic acid compound (A). The solid acid value (AV: mg · KOH / g) is shown in Table 1.

Comparative Examples 1-1 and 1-2

[Preparation of comparative reactive polycarboxylic acid compound]

The epoxy resin was changed from the epoxy resin (a) of Examples 1-1 to 1-3 to the amount of cresol novolak epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 200 g / eq. , A carboxylate compound solution was obtained in the same manner as in Examples 1-1 to 1-3.

Subsequently, in the same manner as in Examples 1-1 to 1-3, a comparative reactive polycarboxylic acid compound solution was obtained. The solid acid value (AV: mg · KOH / g) is shown in Table 1.

Comparative Example 1-3

[Preparation of reactive polycarboxylic acid compound having no comparative aromatic ring]

Liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen-introducing tube was charged with 900 g of diethylene glycol dimethyl ether as a solvent and 80 g of t-butyl-peroxy-2-ethylhexanoate 21.4 g of PERBUTYL (registered trademark) manufactured by Nippon Oil and Fats Co., Ltd.) was added and heated to 90 占 폚. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (PLACCEL FM1 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Was added dropwise over 3 hours with 21.4 g of bis (4-t-butylcyclohexyl) peroxydicarbonate (PEROYL TCP manufactured by Nippon Oil and Fats Co., Ltd.) and further added for 6 hours to obtain a carboxy group- To obtain a copolymer resin. The reaction was carried out in a nitrogen atmosphere.

Subsequently, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (CYCLOMER A200 manufactured by Daicel Co., Ltd.), 3.6 g of dimethylbenzylamine as a ring opening catalyst, 1.5 g of a polymerization inhibitor , 1.80 g of hydroquinone monomethyl ether was added and heated to 100 占 폚 and stirred to carry out the ring-opening addition reaction of epoxy. After 16 hours, a solution containing 65% by mass (solid content) of a carboxy group-containing resin having an acid value of solid content of 108.9 mgKOH / g and a weight average molecular weight of 25,000 and no aromatic ring was obtained.

<Preparation of composition of the present invention>

The components shown in the following Table 2 were compounded in the mixing ratios shown in Table 2 below and mixed and dispersed at room temperature using a three-roll mill to prepare Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 A white active energy ray-curable resin composition was prepared.

Details of each component used in Examples and Comparative Examples are shown.

&Lt; Reactive Compound (B) >

B-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

&Lt; Photopolymerization initiator (C) >

C-1: Acylphosphine-based photopolymerization initiator

Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819, manufactured by BASF)

C-2: benzoyloxime-based photopolymerization initiator

- (4- (phenylthio) -2- (O-benzoyloxime)) (IRGACURE OXE 01, BASF)

<Titanium oxide (D)>

D-1: rutile titanium oxide (CR-80, manufactured by Ishihara Industries Co., Ltd.)

<Preparation of Test Specimen>

A printed circuit board on which a circuit pattern was formed on a copper-clad laminate (FR-4, thickness 1.6 mm, conductor thickness 35 μm) was buffed (polished) or buffing I did it. Then, the compositions of the present invention of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 were applied to a printed wiring board by a screen printing method, respectively. Thereafter, the prepared printed wiring board was dried in a hot air circulation type drying furnace at 80 DEG C for 30 minutes. (Photo-curing step) of ultraviolet rays (wavelength: 300 to 400 nm) was exposed to a coating film of a printed wiring board after drying (photo-curing step) with an exposure apparatus (OAK Manufacturing Corporation, type HMW-680GW) To form a cured coating film, and a test piece was produced. The thickness of the cured coating film was 15 to 20 占 퐉.

<Evaluation>

The compositions of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 and test pieces formed from the coatings were evaluated as follows. The evaluation results are shown in Table 3.

(1) Reflectance

Using a spectrophotometer U-3310H (manufactured by Hitachi, Ltd., φ60 mm integral sphere), the reflectance at 450 nm of a test piece coated with a cured coating film was measured.

(2) Light fastness

The obtained test piece was further irradiated with super-UV (90 mW) light for 24 hours to accelerate the deterioration, and then the color change was measured using a spectrophotometer U-3310H (manufactured by Hitachi, Respectively. ? E * ab represents a change in color. The smaller this value is, the smaller the change in color is.

(3) Solder heat resistance

The cured coating film of the test piece was immersed in a solder bath of 260 DEG C for 10 seconds in accordance with the test method of JIS C-6481, followed by peeling test (peeling test) with a cellophane tape to make one cycle, The state was visually observed and evaluated according to the following criteria.

?: No change in coating film was confirmed even after 2 cycles of repetition.

?: Change was observed in the coating film after repeating two cycles.

X: Peeling was confirmed in the coating film after one cycle repetition.

(4) Adhesion

(10 x 10) cross cuts of 1 mm were formed on the test piece in accordance with JIS K-5600-5-6, and a peeling test (peeling test) with a cellophane tape was carried out. The peeling state of the cross- , And the number of grid patterns not separated from the substrate among the 100 crosscuts was measured.

(5) Film hardness

According to the test method of JIS K-5600-5-4, a pencil of 3B to 9H, which had been ground so that the end of the core was flat, was pressed against the cured coating film on the copper foil of the test piece at an angle of 45 DEG, The hardness of the pencil which did not occur was recorded.

As apparent from the above results, the white active energy ray-curable compositions containing the reactive polycarboxylic acid compound (A) of the present invention of Examples 2-1 to 2-3 were comparative examples 2-1 to 2- 3, the reflectance, the light resistance and the solder heat resistance were good, and the adhesion and the film hardness were excellent. Examples 2-1 and 2-2 which also used DMPA (compound (c)) for the preparation of the reactive polycarboxylic acid compound (A) were prepared in the same manner as in Example 2-3 , It was found that they exhibited better adhesion.

The white active energy ray-curable resin composition of the present invention can obtain a cured product having excellent reflectance, solder heat resistance, adhesiveness, and film hardness without a thermal curing step after the photo-curing step. For example, Resist film, and coverlay.

Claims (6)

1. A white active energy ray-curable resin composition comprising a reactive polycarbonate compound (A), a reactive compound (B) other than the reactive polycarbonate compound (A), a photopolymerization initiator (C), and titanium oxide (D) Wherein the carbonic acid compound (A) is at least one compound selected from the group consisting of an epoxy resin (a) represented by the general formula (1), a compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxy group in a molecule, Which is a reactive polycarboxylic acid compound (A) obtained by reacting a reaction product (E) of a compound (c) having at least two hydroxyl groups and at least one carboxy group with a polybasic acid anhydride (d) Resin composition:

(Wherein n represents an integer of 0 to 2). The method according to claim 1,
Wherein the reactive polycarboxylic acid compound (A) is at least one compound selected from the group consisting of an epoxy resin (a) represented by the general formula (1), a compound (b) having at least one polymerizable ethylenic unsaturated group and at least one carboxyl group in one molecule, Wherein the reactive polycarboxylic acid compound (A) is obtained by reacting a reaction product (E) of a compound (c) having at least two hydroxyl groups and at least one carboxyl group with a polybasic acid anhydride (d). 3. The method according to claim 1 or 2,
The photopolymerization initiator (C) is an acylphosphine-based photopolymerization initiator and a benzoyloxime-based photopolymerization initiator. The blending ratio of the acylphosphine-based photopolymerization initiator to the benzoyloxime-based photopolymerization initiator is preferably from 2 to 100 parts by mass, Curable resin composition. The method of claim 3,
Wherein the acylphosphine-based photopolymerization initiator is 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethylbenzoyl) , 4,4-trimethyl-pentylphosphine oxide and (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, and the benzoyloxime-based photopolymerization initiator is at least one selected from the group consisting of 1,2-octane 2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-O-benzoyl Oxime. &Lt; / RTI &gt; A cured product of the white active energy ray-curable resin composition according to claim 1. A printed wiring board having the cured coating of the white active energy ray-curable resin composition according to claim 1.