TW201833215A - Reactive polycarboxylic acid compound, active energy ray curable resin composition using the same, cured article of the composition and use of the cured article - Google Patents

Abstract

An object of the present invention is to provide an active energy ray curable resin composition which gives a cured film excellent in heat resistance, thermal decomposition resistance and developability. A reactive polycarboxylic acid compound (A) is obtained by reacting a reactive epoxy carboxylate compound (c) with a polybasic acid anhydride (d) represented by the following formula (2) or formula (3). The reactive epoxy carboxylate compound (c) is obtained by reacting an epoxy resin (a) represented by the following formula (1) with a carboxylic acid compound (b) having both polymerizable ethylenically unsaturated group(s) and carboxyl group(s) in one molecule. (wherein, n represents an average value and represents a value of 0 to 20) (in the formula (2), R1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).

Description

   Reactive polycarboxylic acid compound, active energy ray-curable resin composition using the same, cured product of the composition, and use of the cured product   

The present invention relates to a novel reactive polycarboxylic acid compound, an active energy ray-curable resin composition containing the compound, a cured product of the composition, and an overcoat article. In particular, the present invention relates to a novel reactive polycarboxylic acid compound suitable as a suitable photoresist material for build-up layers such as printed circuit boards, an active energy ray-curable resin composition containing the compound, and the composition.物 的 硬 物。 Hardened matter.

In general, thermosetting resin compositions are used for stacked layers of printed circuit boards and the like. In order to reduce the size and weight of portable devices and increase communication speed, miniaturization of circuits and multi-layering of stacked layers are progressing. Higher density of circuits.

On the other hand, in order to prevent deterioration of a circuit in an outermost layer of a solder resist layer of a printed circuit board, a photosensitive resin composition is used to form a solder resist layer. For example, Patent Document 1 describes a photosensitive resin composition containing a binder resin, which is a reaction product of an epoxy resin having a triglycidyl ether structure and an unsaturated carboxylic acid, and a polyacid anhydride The winner.

It is also known that a photosensitive resin composition is prepared by adding a phenol compound as a thermosetting component in an attempt to improve adhesion after a PCT resistance test (Patent Document 2). Furthermore, in recent years, an alkali-developable photosensitive resin composition has been developed, which has good heat resistance and low dielectric loss tangent and is used as a material for a build-up layer (Patent Document 3).

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Unexamined Patent Publication No. 3-100009

[Patent Document 2] International Publication No. 2010/026927

[Patent Document 3] Japanese Patent Laid-Open No. 2013-214057

However, the photosensitive resin composition described in Patent Document 1 is inferior in developability and thermal decomposition resistance, and cannot be sufficiently satisfied. The photosensitive resin composition of Patent Document 2 is limited in use to a protective film, and its physical properties are insufficient. In Patent Document 3, heat resistance and thermal decomposition resistance are still insufficient. Although such a photosensitive resin composition has advantages such as being cheap and having a simple manufacturing process, its physical properties are insufficient and it is difficult to apply it to a build-up layer.

Therefore, an object of the present invention is to provide a novel reactive polycarboxylic acid compound, which improves the problems of the above-mentioned prior art, has heat resistance, thermal decomposition resistance, and can be finely alkali-developed, and is suitable for use as a build-up layer. Suitable photoresist materials; and active energy ray-curable resin compositions containing the compound.

In order to solve the foregoing problems, the present inventors have conducted careful review and found that a resin composition can solve the foregoing problems and complete the present invention. The resin composition uses an epoxy resin having a specific triglycidyl ether structure. A reactant obtained by reacting an unsaturated carboxylic acid-containing reactant with a specific polybasic acid anhydride.

That is, the present invention relates to: [1] A reactive polycarboxylic acid compound (A) is a polymerizable ethylenic resin having an epoxy resin (a) represented by the following formula (1) and one molecule. The reactive epoxy carboxylic acid ester compound (c) obtained by reacting an unsaturated group with a carboxylic acid compound (b) of a carboxyl group reacts with a polybasic acid anhydride (d) represented by the following formula (2) or formula (3) and Winner

(In the formula, n represents the average value and the value of 0 to 20);

(R ₁ in formula (2) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).

[2] An active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) according to the above item [1], [3] The active energy ray-curable resin composition according to the above item [2] A substance containing a reactive compound (B) other than the reactive polycarboxylic acid compound (A), [4] The active energy ray-curable resin composition according to [2] or [3], and containing photopolymerization The initiator, the active energy ray-curable resin composition according to any one of [5] to [2] to [4], which contains a thermosetting catalyst, [6] to [2] to [5] The active energy ray-curable resin composition according to any one of the materials for molding, the active energy ray-curable resin composition according to any one of [7] to [2] to [5], and the film is formed Materials: [8] The active energy ray-curable resin composition according to any one of [8] to [5], a photoresist material composition, [9] A hardened material, [2] to [8] The hardened product of the active energy ray-curable resin composition according to any one of [8], and an article, which is the active energy ray-curable resin according to [9] Was cured protective coating (an overcoat) was obtained as a person.

The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention can not only obtain a tough cured product, but also have excellent resin physical properties even in a state where only the solvent is dried. In addition, the active energy ray-curable resin composition of the present invention is a hardened product obtained by hardening active energy rays such as ultraviolet rays. The hardened product has heat resistance, thermal decomposition resistance, and can be finely alkali-developed, and is suitable for use as a buildup layer. Suitable photoresist material.

Hereinafter, the present invention will be described in detail.

The reactive polycarboxylic acid compound (A) of the present invention is an epoxy resin (a) having a structure represented by the following formula (1) and a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule. The carboxylic acid compound (b) is reacted to obtain a reactive epoxy carboxylic acid ester compound (c). It can be obtained by reacting with the polybasic acid anhydride (d) represented by the following formula (2) or formula (3).

(In the formula, n represents an average value, and represents a value from 0 to 20.)

(R ₁ in formula (2) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).

The epoxy resin (a) represented by the aforementioned formula (1) (hereinafter also referred to as "epoxy resin (a)") used in the present invention can be various trade names, for example, TECMORE, VG-3101 (Mitsui Petroleum Chemical (stock), trade name), NC-6000 (manufactured by Nippon Kayaku Co., Ltd.), etc., were purchased from general sources.

In the present invention, a carboxylic acid compound (b) (hereinafter, also referred to simply as "carboxylic acid compound (b)") having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule is used to impart active energy The reactivity of the thread makes the responder. The ethylenically unsaturated group and the carboxyl group are not limited to one or more in the molecule.

Examples of the carboxylic acid compound (b) having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule include (meth) acrylic acid, butenoic acid, α-cyanocinnamic acid, cinnamic acid, or Reactants of saturated or unsaturated dibasic acids with unsaturated monoepoxypropyl compounds and the like. Examples of the above (meth) acrylics include (meth) acrylic acid, β-styryl acrylic acid, β-furan methacrylic acid, (meth) acrylic acid dimers, and saturated or unsaturated dibasic acid anhydrides and Half-esters of Moore reactants such as (meth) acrylate derivatives with one hydroxyl group in one molecule, which are saturated or unsaturated dibasic acids and (meth) acrylate monoepoxypropyl ester derivatives Mole reactants such as semi-esters, etc. Monocarboxylic compounds containing one carboxyl group in one molecule, and (meth) acrylic acid ester derivatives of saturated or unsaturated dibasic acids and multiple hydroxyl groups in one molecule Half-esters of equivalent Morse reactants, half-esters of equivalent Morse reactants, which are saturated or unsaturated dibasic acids and epoxy (meth) acrylate epoxypropyl esters having a plurality of epoxy groups Polycarboxylic acid compounds having a plurality of carboxyl groups in one molecule and the like.

Among these, when the reaction stability of the epoxy resin (a) and the carboxylic acid compound (b) is considered, the carboxylic acid compound (b) is preferably a monocarboxylic acid, and a monocarboxylic acid and a polycarboxylic acid are used in combination. In this case, the value represented by the molar amount of the monocarboxylic acid / the molar amount of the polycarboxylic acid is preferably 15 or more.

Most preferably, from the viewpoint of sensitivity as an active energy ray-curable resin composition, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid .

A carboxylic acid esterification step for giving a carboxylic acid ester compound reactivity to obtain a reactive epoxy carboxylic acid ester compound (c) will be described.

The feed ratio of the epoxy resin (a) and the carboxylic acid compound (b) in this reaction should be appropriately changed depending on the application. That is, when all epoxy groups are esterified with a carboxylic acid, since the unreacted epoxy group does not remain, the storage stability of the reactive epoxy carboxylate compound (c) is high. In this case, the reactivity by using only the introduced double bond is obtained.

On the other hand, by reducing the feed amount of the carboxylic acid compound (b) and leaving unreacted residual epoxy groups, the reactivity caused by the introduced unsaturated bonds and the residual epoxy groups can be used in combination. The reaction is, for example, a polymerization reaction and a thermal polymerization reaction caused by a photo-cation catalyst. However, at this time, attention should be paid to the preservation of the reactive epoxy carboxylic acid ester compound (c) and review of the manufacturing conditions.

When producing a reactive epoxy carboxylic acid ester compound (c) in which no epoxy group remains, the carboxylic acid compound (b) is preferably 90 to 120 equivalent% relative to 1 equivalent of the epoxy resin (a). If it is in this range, it can be manufactured under relatively stable conditions. When the feed amount of the carboxylic acid compound is more than the above range, it is not preferable because an excessive amount of the carboxylic acid compound (b) remains.

When an epoxy group is left, the carboxylic acid compound (b) is preferably 20 to 90 equivalent% relative to 1 equivalent of the epoxy resin (a). When it deviates from this range, the effect of compound hardening becomes weak. Of course, in this case, it is necessary to pay sufficient attention to the gelation during the reaction and the stability of the reactive epoxy carboxylic acid ester compound (c) over time.

The carboxylic acid esterification reaction may be a reaction without a solvent, or may be a reaction diluted with a solvent. The solvent that can be used herein is not particularly limited as long as it is a solvent that is inert to the carboxylic acid esterification reaction.

The preferable amount of the solvent should be appropriately adjusted according to the viscosity and use of the obtained resin, but it is preferably used in a manner such that the solid content content is 90 to 30% by mass, and more preferably 80 to 50% by mass.

Specific examples include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane, and decane; and mixtures thereof. Petroleum ether, white gasoline, solvent oil, etc., ester solvents, ether solvents, ketone solvents, etc.

Examples of the ester-based solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; ethylene glycol monomethyl ether acetate, and diethylene glycol monoester Methyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butane Monoalkyl ethers such as glycol monomethyl ether acetate, or polyalkylene glycol monoalkyl ether monoacetates; polycarboxylic acids such as dialkyl glutarate, dialkyl succinate, and dialkyl adipate Acid alkyl esters, etc.

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

Examples of the ketone-based solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

In addition, reactive compounds (B) (hereinafter, also simply referred to as "reactive compounds (B)") other than the reactive polycarboxylic acid compound (A) described below can be carried out alone or in a mixed organic solvent. In this case, when it is used as a curable resin composition, it is preferable because it can be directly used as a composition.

During the reaction, it is preferable to use a catalyst in order to promote the reaction. The total amount of the reactants other than the reactants, that is, the epoxy resin (a), the carboxylic acid compound (b), and the solvent added as appropriate, is 100. The catalyst is used in an amount of 0.1 to 10 parts by mass. The reaction temperature at this time is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of usable catalysts include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, Triphenylphosphine, triphenylantimony, methyltriphenylantimony, chromium octoate, zirconium octoate and other commonly known alkaline catalysts.

A thermal polymerization inhibitor may be used. Thermal polymerization inhibitors are preferably used: hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenyl picryl hydrazine, diphenylamine, 3,5 -Tertiary butyl-4 via toluene and the like.

In this reaction, the end point is set as the end point when the sample has an acid value of 5 mgKOH / g or less, and preferably 3 mgKOH / g or less, while appropriately sampling.

The preferred molecular weight range of the obtained reactive epoxy carboxylic acid ester compound (c) is a polystyrene equivalent weight average molecular weight in GPC in the range of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000. .

When the molecular weight is less than this, the toughness of the cured product cannot be sufficiently exhibited. When the molecular weight is outside the range, the viscosity becomes high, which makes coating and the like difficult.

Next, the acid addition step will be described in detail. The acid addition step is carried out for the purpose of obtaining a reactive polycarboxylic acid compound (A) by introducing a carboxyl group into the reactive epoxy carboxylic acid ester compound (c) obtained in the aforementioned step as necessary. That is, the hydroxyl group generated by the carboxylic acid esterification reaction is added to the polybasic acid anhydride (d) (hereinafter, also referred to simply as "polybasic acid anhydride (d)") represented by the above formula (2) or (3). It reacts and introduces a carboxyl group via an ester bond.

Examples of the alkyl group having 1 to 10 carbon atoms in the formula (2) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Preferred are a hydrogen atom and a methyl group.

The polybasic acid anhydride (d) is preferably a compound represented by the following formula (4).

The reaction for adding the polybasic acid anhydride (d) can be performed by adding the polybasic acid anhydride (d) to the carboxylic acid esterification reaction solution. The amount to be added can be appropriately changed depending on the application.

The amount of the polybasic acid anhydride (d) to be added is, for example, when the reactive polycarboxylic acid compound (A) of the present invention is used as a photoresist material for the development of an alkaline aqueous solution, the polybasic acid anhydride (d) is preferably used so that The solid content acid value (according to JISK5601-2-1: 1999) of the obtained reactive polycarboxylic acid compound (A) is 40 to 120 mg‧KOH / g, and more preferably 60 to 110 mg‧KOH / g. Feed in. When the solid content acid value at this time falls within this range, the developability of the alkaline aqueous solution of the active energy ray-curable resin composition of the present invention exhibits good developability. That is, the management of good patternability and excessive development is wide, and excessive acid anhydride does not remain.

In order to promote the reaction, a catalyst is preferably used in the reaction. The reactive epoxy carboxylate compound (c) and the polybasic acid anhydride (c) obtained from the epoxy resin (a) and the carboxylic acid compound (b) are preferred to the reactants. d) 100 parts by mass of the total amount of reactants other than the solvent to be added, and the usage amount of the catalyst is 0.1 to 10 parts by mass. The reaction temperature at this time is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of usable catalysts include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, Triphenylphosphine, triphenylantimony, methyltriphenylantimony, chromium octoate, zirconium octoate, etc.

The present acid addition reaction can be carried out without a solvent or diluted with a solvent to carry out the reaction. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the acid addition reaction. In addition, in the case of using a solvent for the carboxylic acid esterification reaction in the previous step for production, it is possible to directly supply the acid addition reaction to the next step without removing the solvent under the condition that both reactions are inert. The solvent that can be used may be the same as those capable of being used in the carboxylic acid esterification reaction.

The preferred amount of the solvent should be appropriately adjusted according to the viscosity and use of the obtained resin, and it is preferably used in a manner such that the solid content content is 90 to 30% by mass, and more preferably 80 to 50% by mass.

In addition, the aforementioned reactive compound (B) and the like may be performed alone or in a mixed organic solvent. In this case, when it is used as a curable resin 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 carboxylic acid esterification reaction.

In this reaction, the end point is set as the end point when the acid value of the reactant is within a range of plus or minus 10% of the set acid value while taking a sample appropriately.

The preferred molecular weight range of the thus obtained reactive polycarboxylic acid compound (A) is a polystyrene-equivalent weight average molecular weight in the GPC range of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000.

When the molecular weight is less than this, the toughness of the cured product cannot be sufficiently exhibited. When the molecular weight is outside the range, the viscosity becomes high, which makes coating and the like difficult.

Specific examples of the reactive compound (B) that can be used in the present invention include radically reactive acrylates, cation-reactive other epoxy compounds, and vinyl compounds that sense both. So-called reactive oligomers.

Examples of usable acrylates include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, and urethane acrylates.

Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, and polyethylene glycol (formaldehyde). (Meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenylethyl (meth) acrylate, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, (methyl Group) benzyl acrylate, tetrahydrofuran methyl (meth) acrylate, and the like.

Examples of polyfunctional (meth) acrylates include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and nonanediol di (Meth) acrylate, ethylene glycol di (meth) acrylate, ethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, ginsyl (meth) acryl group Oxyethyl triisocyanate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol epoxy Ethane di (meth) acrylate, bisphenol di (meth) acrylate, ε-caprolactone adduct of hydroxytrimethylacetate neopentyl glycol, di (meth) acrylate, dineopent Poly (meth) acrylates of reactants of tetraol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, trihydroxyethyl Propane tri (meth) acrylate and its ethylene oxide adduct; neopentyl tetraol tri (meth) acrylate and its ethylene oxide adduct; neopentaerythritol tetra (meth) Acrylate and its ethylene oxide Adducts; dipentaerythritol hexa (meth) acrylate, and ethylene oxide adducts thereof.

Examples of usable 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 styrenes include styrene, methylstyrene, and ethylstyrene. Examples of other ethylene compounds include triallyl trimer isocyanate, trimethylallyl trimer isocyanate, and the like.

Examples of the reactive oligomers include urethane acrylates having a functional group that can sense active energy rays and urethane bonds in the same molecule, and similarly sensible in the same molecule. The functional groups of the active energy ray and the ester acrylate polyester acrylate, other epoxy acrylates derived from the epoxy resin and having the functional group that can sense the active energy ray in the same molecule, these bonds are used in combination Reactive oligomers, etc.

The cation-reactive monomer is generally not particularly limited as long as it is a compound having an epoxy group. Examples include: glycidyl (meth) acrylate, methylglycidyl ether, ethylglycidyl ether, butylglycidyl ether, bisphenol A diglycidyl ether, 3 1,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("CYRACURE UVR-6110", etc., manufactured by Union Carbide), 3,4-epoxycyclohexylethyl- 3,4-epoxy cyclohexane carboxylate, vinyl cyclohexene dioxide ("ELR-4206" manufactured by Union Carbide, etc.), limonene dioxide ("CELLOXIDE 3000" manufactured by Daicel Chemical Industries, etc.) ), Allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-epoxypropane, 2- (3,4-epoxycyclohexyl-5,5- Spiro-3,4-epoxy) cyclohexane-m-di Alkane, bis (3,4-epoxycyclohexyl) adipate ("CYRACURE UVR-6128" manufactured by Union Carbide, etc.), bis (3,4-epoxycyclohexylmethyl) adipate , Bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, etc. .

Among them, the reactive compound (B) is preferably a radical-curable acrylate. In the case of the cationic type, the carboxylic acid must react with the epoxy group, so it must be a two-liquid mixed type.

The reactive polycarboxylic acid compound (A) of the present invention is mixed with a reactive compound (B) other than (A) to obtain an active energy ray-curable resin composition of the present invention. In this case, other components may be appropriately added depending on the application.

The active energy ray-curable resin composition of the present invention contains 97 to 5 parts by mass, preferably 87 to 10 parts by mass of the reactive polycarboxylic acid compound (A), and other reactive compounds (B) 3. To 95 parts by mass, and more preferably 3 to 90 parts by mass. It may contain other components from 0 to 80 parts by mass as required.

In addition, for the purpose of making the active energy ray-curable resin composition of the present invention suitable for various uses, other components may be added to the composition with an upper limit of 70 parts by weight. Examples of the other components include a photopolymerization initiator, other additives, a coloring material, and a volatile solvent for viscosity adjustment added for the purpose of imparting applicability and the like. The following illustrates other ingredients that can be used.

The active energy ray-curable resin composition of the present invention may further contain a photopolymerization initiator. The photopolymerization initiator is preferably a radical photopolymerization initiator or a cationic photopolymerization initiator.

Examples of the radical type photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and the like; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetone Acetophenones such as benzene, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-propane-1-one; 2- Anthraquinones such as ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-pentylanthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthone , 2-chlorothioxanthone and other thioxanthones; acetophenone ketals, benzyl dimethyl ketal and other ketals; benzophenone, 4-benzylmethyl-4'-methyl Diphenyl sulfides, benzophenones such as 4,4'-bis (methylamino) benzophenone; 2,4,6-trimethylbenzylidene diphenylphosphine oxide, Phosphine oxides such as bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide and other conventionally known radical-type photopolymerization initiators.

Examples of the cationic photopolymerization initiator include diazonium salts of Lewis acids, phosphonium salts of Lewis acids, phosphonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, and Based initiators, borate based initiators, and other photoacid generators.

Examples of the diazonium salt of the Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sanxin Chemical Industry Co., Ltd. SUN-AID SI-60L / SI-80L / SI-100L, etc.); Examples of phosphonium salts of Lewis acids include diphenylsulfonium hexafluorophosphonate, diphenylsulfonium hexafluoroantimonate, etc .; Lewis acids Examples of the sulfonium salts include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990, manufactured by UnionCarbide, etc.), triphenylsulfonium hexafluoroantimonate (Cyracure UVI-6974, manufactured by UnionCarbide, etc.), and the like; Examples of the phosphonium salt include triphenylphosphonium hexafluoroantimonate and the like.

Other halides include 2,2,2-trichloro- [1-4 '-(dimethylethyl) phenyl] ethanone (TrigonalPI, etc., manufactured by AKZO), 2,2-dichloro-1- 4- (phenoxyphenyl) ethanone (Sandray 1000, manufactured by Sandoz, etc.), α, α, α-tribromomethylphenylphosphonium (BMPS, etc. manufactured by Iron Manufacturing Co., Ltd.), and the like. three Examples of system initiators: 2,4,6-ginseng (trichloromethyl) -tris , 2,4-trichloromethyl- (4'-methoxyphenyl) -6-tri (TriazineA, etc., manufactured by Panchim), 2,4-trichloromethyl- (4'-methoxystyryl) -6-tri (TriazinePMS, etc., manufactured by Panchim), 2,4-trichloromethyl- (piperyl) -6-tri (TriazinePP, etc., manufactured by Panchim), 2,4-trichloromethyl- (4'-methoxynaphthyl) -6-tri (TriazineB, etc., manufactured by Panchim), 2 [2 '(5-methylfuryl) ethylene] -4, 6-bis (trichloromethyl) -s-tri (Manufactured by Sanwa Chemical Co., Ltd.), 2 (2'-furanylethylene) -4, 6-bis (trichloromethyl) -s-tri (Manufactured by Sanwa Chemical Co., Ltd.).

Examples of boric acid ester-based photopolymerization initiators include NK-3876 and NK-3881 made by Japan Photosensitive Pigment; other photoacid generators include 9-phenylacridine, 2,2'-bis (o- (Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2-biimidazole (biimidazole produced by Kurojin Kasei Co., Ltd.), 2,2-azobis (2-amino-propane) Dihydrochloride (V50 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-Azobis [2- (imidazolin-2yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [η- 5-2-4- (cyclopentadecyl) (1,2,3,4,5,6, η)-(methylethyl) -benzene] iron (II) hexafluorophosphonate (CibaGeigy) (Irgacure 261, etc.), bis (y5-cyclopentadienyl) bis [2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl] titanium (CGI-784, etc., manufactured by CibaGeigy) .

In addition, an azo-based initiator such as azobisisobutyronitrile, and a thermally-sensitive peroxide-based radical initiator such as benzoylperoxide may be used in combination. Moreover, you may use together a radical type and a cationic type photoinitiator. The photopolymerization initiator may be used singly or in combination of two or more kinds.

Among these, in consideration of the characteristics of the reactive polycarboxylic acid compound (A) of the present invention, a radical photopolymerization initiator is particularly preferred.

The active energy ray-curable resin composition of the present invention may contain a colored pigment. As the coloring pigment, for example, a so-called extender pigment that is not intended for coloring can also be used. Examples thereof include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silicon dioxide, and clay.

Furthermore, the active energy ray-curable resin composition of the present invention may contain other additives as required. Other additives include, for example, thermosetting catalysts such as melamine, thixotropy imparting agents such as aerosil, polysiloxane-based, fluorine-based leveling agents or defoamers, hydroquinone, and hydroquinone Polymerization inhibitors such as phenol monomethyl ether, stabilizers, antioxidants, etc.

Other resins (so-called inert polymers) that do not show reactivity to active energy rays include other epoxy resins, phenol resins, urethane resins, polyester resins, ketone-formaldehyde resins, and cresol resins. , Xylene resin, diallyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and modified products thereof. These are preferably used in a range of 40 parts by mass in the resin composition.

In particular, when a reactive polycarboxylic acid compound (A) is used for solder resist applications, it is preferable to use a generally known epoxy resin as a resin that does not exhibit reactivity to active energy rays. This is because the carboxyl group derived from the reactive polycarboxylic acid compound (A) remains after hardening through the active energy ray reaction. As a result, the hardened product has poor water resistance or hydrodegradability. Therefore, the remaining carboxyl group is further carboxylated with an epoxy resin to form a stronger crosslinked structure. The generally known epoxy resin may use the aforementioned cationic reactive monomer.

In addition, depending on the purpose of use, and for the purpose of adjusting viscosity, a volatile solvent in a range of 50 parts by mass, more preferably 35 parts by mass, may be added to the resin composition.

The active energy ray-curable resin composition of the present invention is easily hardened by the active energy ray. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and laser rays, particle rays such as alpha rays, beta rays, and electron rays. When considering the preferred use of the present invention, among these, ultraviolet rays, laser rays, visible rays, or electron rays are preferred.

The molding material in the present invention refers to a person who can use an unhardened composition to be put into a mold, or press the mold to form an object, and then be formed by a hardening reaction caused by active energy rays. A material used in applications where the composition irradiates focal light, such as laser, and causes a curing reaction and molding.

Specific applications include flat sheets, sealing materials to protect components, micro-pressing a "mold" that has been micro-machined on an unhardened composition, so-called nano-imprinting, and thermal requirements. Particularly suitable are suitable applications such as peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements.

The material for forming a film in the present invention refers to a person who is used for the purpose of covering the surface of a substrate. Specific uses include: gravure printing ink, flexographic printing ink, screen sieve printing ink, lithographic printing ink and other printing ink materials; hard coating, top coating, overprint varnish, clear coating, etc. Coating materials; various other adhesives for lamination and optical discs, adhesives, and other adhesive materials; solder resists, etching resists, and resist materials such as micro-machine resists and other suitable applications. In addition, the film-forming material is temporarily applied to a peelable substrate to form a film, and then the film is adhered to the substrate which is the original purpose to form a film. The so-called dry film also conforms to the film-forming material.

The cured product obtained by irradiating the photosensitive resin composition of the present invention with active energy rays is also included, and a multilayer material having the cured product layer is also included.

Among them, the introduction of the carboxyl group of the reactive polycarboxylic acid compound (A) is preferably used for the purpose of covering a plastic substrate or a metal substrate because the adhesiveness to the substrate is improved.

Furthermore, it is also preferable to use an unreacted reactive polycarboxylic acid compound (A) as a soluble compound in an alkaline aqueous solution, and to use it as a basic water-developing photoresist material composition.

In the present invention, the photoresist material composition refers to an active energy ray that is formed by forming a coating layer of the composition on a substrate and then partially irradiating active energy rays such as ultraviolet rays to draw the physical properties of the irradiated and unirradiated parts Inductive composition. Specifically, a composition used for the purpose of dissolving and removing an irradiated portion or an unirradiated portion by, for example, a solvent or an alkaline solution, etc., and drawing it.

The active energy ray-curable resin composition of the present invention, which is a photoresist material composition, can be applied to various materials that can be patterned, such as interlayer insulation materials for solder resist materials and stacking methods, and can also be used in Electrical / electronic / optical substrates such as printed circuit boards, optoelectronic substrates, or optical substrates as optical waveguides.

As a particularly suitable application, it can be used in insulating resin sheets such as photosensitive films, photosensitive films with a support, and prepregs, as well as circuit boards (multilayer boards) due to the characteristics of good heat resistance and developability. Applications, such as multilayer printed circuit board applications), solder resists, underfill materials, die bonding materials, semiconductor sealing materials, filler resins, parts resins and other resin compositions are necessary for a wide range use. Among these, a resin composition for an insulating layer of a multilayer printed circuit board (a multilayer printed circuit board using a cured product of a photosensitive resin composition as an insulating layer), and a resin composition for an interlayer insulating layer (a composition of a photosensitive resin) The hardened product of the product is used as a multilayer printed circuit board as an interlayer insulating layer), and a resin composition for plating formation (a multilayer printed circuit board formed by plating on a cured product of a photosensitive resin composition).

Furthermore, it can exhibit good developability even at high pigment concentrations, and can also be applied to photoresist materials for color photoresists and color filters, especially black matrix materials.

The patterning system using the active-energy-ray-curable resin composition of this invention can be performed as follows, for example. The composition of the present invention is coated on the substrate with a film thickness of 0.1 to 200 μm by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, or a spin coating method. The coating film is dried at a temperature of usually 50 to 110 ° C, preferably 60 to 100 ° C, to form a coating film. Thereafter, the coating film is directly or indirectly irradiated with high energy rays, such as ultraviolet rays, through a photomask formed with an exposure pattern at an intensity of usually about 10 to 2000 mJ / cm ^2. Using a developing solution described later, for example, spraying, shaking, dipping, Paddle brushing to obtain the desired pattern.

The alkaline aqueous solution used for the above development can be used: potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate and other inorganic alkaline aqueous solutions; or tetramethyl hydroxide Organic alkaline aqueous solutions such as ammonium, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and ginsylethanolamine. The aqueous solution may further contain an organic solvent, a buffering agent, a dissolving agent, a dye or a pigment.

In addition, it is particularly suitable for use as a dry film that requires mechanical strength before the hardening reaction by active energy ray. That is, since the balance of the hydroxyl group and the epoxy group of the epoxy resin (a) used in the present invention is within a specific range, the reactive carboxylic acid ester compound of the present invention can exhibit its advantages even though it has a relatively high molecular weight. Good developability.

The method of film formation is not particularly limited, and can be arbitrarily adopted: gravure printing methods such as gravure, letterpress printing methods such as flexographic printing, stencil printing methods such as screen printing, lithographic printing methods such as lithography, roller coating, knife coating, Various coating methods such as mold coating, curtain coating, and spin coating.

The cured product of the active energy ray-curable resin composition of the present invention refers to a person who irradiates the active energy ray-curable resin composition of the present invention with an active energy ray to harden.

The article obtained by subjecting the active energy ray-curable resin composition of the present invention to a protective coating means that the active energy ray-curable resin composition of the present invention is formed on a substrate and hardened to have at least two Material above the layer.

    [Example]    

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited by these examples. In the examples, unless otherwise specified,% represents mass%.

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

1) Epoxy equivalent: measured according to the method of JIS K 7236: 2001.

2) Softening point: Measured in accordance with JIS K 7234: 1986.

3) Acid value: Measured according to JIS K 0070: 1992.

4) The measurement conditions of GPC are as follows.

Model: TOSOH HLC-8220GPC

Column: Super HZM-N

Eluent: THF (tetrahydrofuran); 0.35ml / min, 40 ° C

Detector: Detector: Differential Refractometer

Molecular weight standard: polystyrene

(Synthesis example 1): Synthesis of reactive epoxy carboxylic acid ester compound (c)

Addition: 353 g of epoxy resin (a) epoxy resin having a triglycidyl ether structure (manufactured by Mitsui Petrochemical Co., Ltd., VG-3101, epoxy equivalent 210), acrylic acid as a carboxylic acid compound (b) (Referred to as AA, Mw = 72) 122 g, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent was added so as to have a solid content content of 80%, and reacted at 100 ° C for 24 hours A solution of a reactive epoxy carboxylic acid ester compound (c1) was obtained.

(Synthesis example 2)

Addition: 353 g of epoxy resin (a) epoxy resin having a triglycidyl ether structure (manufactured by Mitsui Petrochemical Co., Ltd., VG-3101, epoxy equivalent 210), and carboxylic acid compound (b) 146 g of acrylic acid (MAA for short, Mw = 86) and 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent was added so as to have a solid content content of 80%, and the reaction was performed at 100 ° C. In 24 hours, a reactive epoxy carboxylic acid ester compound (c2) was obtained.

(Example 1, Comparative Example 1): Preparation of reactive polycarboxylic acid compound (A)

To 593 g of the obtained reactive epoxycarboxylic acid ester compound (c) solution, the compound described in Table 1 as the polybasic acid anhydride (d) and the amount (g) were added so that the solid content content was 65%. Propylene glycol monomethyl ether monoacetate was added as a solvent, and after heating at 100 ° C, an acid addition reaction was performed to obtain a solution of a reactive polycarboxylic acid compound (A). The solid acid value (AV: mgKOH / g) and weight average molecular weight of the obtained reactive polycarboxylic acid compound (A) are shown in Table 1. Solid content acid value (mg‧KOH / g): The measurement is measured by a solution and converted into a solid content value.

(Example 2, Comparative Example 2): Preparation of a photoresist material composition

Addition: 54.44 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 and 3.54 g of HX-220 (a trade name: a diacrylate monomer made by Nippon Kayaku Co., Ltd.) as another reactive compound (B) 4.72 g of Irgacure 907 (produced by Ciba Seika) as a photopolymerization initiator and 0.47 g of Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.); GTR-1800 (Nippon Kayaku) as a hardener component 14.83 g, 1.05 g of melamine as a thermosetting catalyst, and 20.95 g of methyl ethyl ketone as a concentration-adjusting solvent were kneaded with a bead mill to uniformly disperse to obtain a photoresist resin composition.

The obtained composition was uniformly coated on a copper foil film serving as a support film by a roll coating method, and passed through a hot-air drying furnace at a temperature of 70 ° C to form a resin layer having a thickness of 30 µm. After that, the development was performed by spray development with a 1% sodium carbonate aqueous solution to complete development, that is, with a break time to evaluate the developability (unit: second).

From the above results, it is understood that the photoresist material composition using the reactive polycarboxylic acid compound (A) of the present invention has good developability.

(Example 3 and Comparative Example 3): Evaluation of thermal decomposition resistance

Addition: 24.8 g of the reactive polycarboxylic acid compound (A) obtained in Example 1, 0.5 g of Irgacure 184 as a photopolymerization initiator, and 2.4 g of propylene glycol monomethyl ether monoacetate were uniformly coated on polyfluorene The amine film was passed through a hot-air drying oven at a temperature of 80 ° C to form a resin layer having a thickness of 20 µm, and then exposed with an ultraviolet exposure device (ORC Manufacturing Co., Ltd., model HMW-680GW) to obtain a cured product. The produced hardened product was cut to a width of 5 mm. Thereafter, it was installed in a viscoelasticity measuring device RSA-G2 made by TA instruments, and tan δ was measured in an air environment at a frequency of 10 Hz and a heating rate of 2 ° C./min, and the temperature of the maximum value of tan δ was set to Tg.

In addition, 3 mg of the prepared sample was measured at a temperature of 5% weight reduction using a TGA / DSC1 manufactured by METTLER in an air flow of 100 ml per minute.

From the above results, it can be seen that the active energy ray-curable resin composition using the reactive polycarboxylic acid compound (A) of the present invention has superior heat resistance and thermal decomposition resistance than the comparative resin composition.

Claims (10)

A reactive polycarboxylic acid compound (A) is an epoxy resin (a) represented by the following formula (1) and a carboxylic acid compound having a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule ( b) a reactive epoxy carboxylic acid ester compound (c) obtained by the reaction, which is obtained by reacting with a polybasic acid anhydride (d) represented by the following formula (2) or formula (3); In the formula, n represents an average value, and represents a value from 0 to 20; R ₁ in formula (2) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.     An active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) described in item 1 of the patent application scope.         The active energy ray-curable resin composition according to item 2 of the scope of application for a patent contains a reactive compound (B) other than the reactive polycarboxylic acid compound (A).         The active energy ray-curable resin composition according to item 2 or 3 of the scope of patent application, which contains a photopolymerization initiator.         The active energy ray-curable resin composition according to any one of claims 2 to 4 of the patent application scope, which contains a thermosetting catalyst.         The active energy ray-curable resin composition according to any one of claims 2 to 5 of the scope of patent application, which is a molding material.         The active energy ray-curable resin composition according to any one of claims 2 to 5 of the scope of patent application, which is a material for forming a film.         The active energy ray-curable resin composition according to any one of claims 2 to 5 of the scope of patent application, which is a photoresist material composition.         A hardened product is a hardened product of the active energy ray-curable resin composition according to any one of claims 2 to 8.         An article is a protective coating made of a hardened product of the active energy ray-curable resin composition described in item 9 of the scope of patent application.