JP7021960B2 - Reactive polycarboxylic acid compound, active energy ray-curable resin composition using it, cured product thereof and its use - Google Patents

Description

The present invention relates to novel reactive polycarboxylic acid compounds, active energy ray-curable resin compositions containing them, cured products thereof and overcoated articles. In particular, the present invention relates to a novel reactive polycarboxylic acid compound suitable as a resist material applicable as a build-up layer of a printed wiring substrate or the like, an active energy ray-curable resin composition containing the same, and a cured product thereof.

Generally, a thermosetting resin composition is used for a build-up layer such as a printed wiring board, and the wiring is miniaturized and the build-up layer is made into multiple layers in order to reduce the size and weight of mobile devices and improve the communication speed. Wiring density is increasing.
On the other hand, a photosensitive resin composition is used to form a solder resist layer on the outermost layer of the solder resist layer of the printed wiring board in order to prevent deterioration of the wiring. For example, Patent Document 1 describes a photosensitive resin containing a binder resin obtained by further reacting a reaction product of an epoxy resin having a triglycidyl ether structure with an unsaturated group-containing carboxylic acid with a polybasic acid anhydride. The composition is described.
Further, a photosensitive resin composition containing a phenol compound as a thermosetting component is also known with the intention of improving the adhesiveness after the PCT resistance test (Patent Document 2). Further, in recent years, an alkali-developable photosensitive resin composition having good heat resistance and low dielectric loss tangent for use as a material for a build-up layer has also been developed (Patent Document 3).

Japanese Unexamined Patent Publication No. 3-100009 International Publication No. 2010/026927 Japanese Unexamined Patent Publication No. 2013-21405

However, the photosensitive resin composition described in Patent Document 1 is inferior in developability and heat-decomposability, and is not at a sufficiently satisfactory level. The use of the photosensitive resin composition of Patent Document 2 is limited to that of a protective film, and its physical performance is not sufficient. In Patent Document 3, heat resistance and heat decomposition are still insufficient. As described above, although the photosensitive resin composition has advantages such as low cost and simple manufacturing process, its physical performance is not sufficient and it is difficult to apply it to the build-up layer.
Therefore, the present invention improves the above-mentioned problems of the prior art, and is a novel reactive polycarboxylic acid compound suitable as a resist material having heat resistance, heat decomposition resistance, finely alkaline development, and applicable as a build-up layer. , It is an object of the present invention to provide an active energy ray-curable resin composition containing the same.

As a result of diligent studies to solve the above problems, the present inventors have obtained a reaction product of an epoxy resin having a specific triglycidyl ether structure and an unsaturated group-containing carboxylic acid into a specific polybasic acid anhydride. We have found that a resin composition using the reaction product of the above can solve the above-mentioned problems, and have reached the present invention.

That is, the present invention
[1] Reactivity obtained by reacting an epoxy resin (a) represented by the following formula (1) with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule. A reactive polycarboxylic acid compound (A) obtained by reacting an epoxy carboxylate compound (c) with a polybasic acid anhydride (d) represented by the following formula (2) or formula (3).

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

(R ₁ in the 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 preceding item [1].
[3] The active energy ray-curable resin composition according to the preceding item [2], which comprises a reactive compound (B) other than the reactive polycarboxylic acid compound (A).
[4] The active energy ray-curable resin composition according to the preceding item [2] or [3], which contains a photopolymerization initiator.
[5] The active energy ray-curable resin composition according to any one of [2] to [4] above, which comprises a thermosetting catalyst.
[6] The active energy ray-curable resin composition according to any one of the above items [2] to [5], which is a molding material.
[7] The active energy ray-curable resin composition according to any one of the above items [2] to [5], which is a material for forming a film.
[8] The active energy ray-curable resin composition according to any one of the above items [2] to [5], which is a resist material composition.
[9] The cured product of the active energy ray-curable resin composition according to any one of the above items [2] to [8].
[10] An article overcoated with a cured product of the active energy ray-curable resin composition according to the preceding item [9].
Regarding.

The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention not only obtains a tough cured product, but also has excellent resin physical properties even when the solvent is simply dried. ing. Further, the cured product obtained by curing the active energy ray-curable resin composition of the present invention with active energy rays such as ultraviolet rays is heat-resistant, heat-decomposable, finely alkaline-developable, and can be applied as a build-up layer. It is suitable as a possible resist material.

Hereinafter, the present invention will be described in detail.
The reactive polycarboxylic acid compound (A) of the present invention has both an epoxy resin (a) having a structure represented by the following formula (1) and an ethylenically unsaturated group and a carboxy group that can be polymerized in one molecule. The reactive epoxy carboxylate compound (c) is obtained by reacting with the carboxylic acid compound (b). Then, it can be obtained by reacting the polybasic acid anhydride (d) represented by the following formula (2) or formula (3).

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

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

The epoxy resin (a) represented by the formula (1) used in the present invention (hereinafter, also simply referred to as “epoxy resin (a)”) has various trade names, for example, TECMORE, VG-3101 (Mitsui). It is generally available as Petrochemical Co., Ltd. (trade name), NC-6000 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

In the present invention, the carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule (hereinafter, also simply referred to as “carboxylic acid compound (b)”) is directed to an active energy ray. It is intended to react in order to impart reactivity. There is no limitation as long as there is at least one ethylenically unsaturated group and one carboxyl group 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 acids, crotonic acid, α-cyanocineramic acid, cinnamic acid, or saturated or unsaturated. Examples thereof include a reaction product of a saturated dibasic acid and an unsaturated group-containing monoglycidyl compound. In the above, examples of the (meth) acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-flufurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 Semi-esters of (meth) acrylate derivatives having one hydroxyl group in the molecule and the molar reactants, half of the molar reactants of saturated or unsaturated dibasic acid and monoglycidyl (meth) acrylate derivatives Monocarboxylic acid compounds containing one carboxyl group in one molecule such as esters, (meth) acrylate derivatives having multiple hydroxyl groups in one molecule, semi-esters which are the molar reactants, saturated or unsaturated dibases Examples thereof include polycarboxylic acid compounds having a plurality of carboxyl groups in one molecule such as semi-esters which are the molar reaction products of an acid and glycidyl (meth) acrylate derivatives having a plurality of epoxy groups.

Of these, considering the stability of the reaction between the epoxy resin (a) and the carboxylic acid compound (b), the carboxylic acid compound (b) is preferably a monocarboxylic acid, and the monocarboxylic acid and the polycarboxylic acid are used. Even when used in combination, the value represented by the molar amount of monocarboxylic acid / the molar amount of polycarboxylic acid is preferably 15 or more.
Most preferably, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid can be mentioned in terms of sensitivity when made into an active energy ray-curable resin composition.

The carboxylating step for imparting reactivity to the carboxylate compound and obtaining the reactive epoxy carboxylate compound (c) will be described.

The charging ratio of the epoxy resin (a) and the carboxylic acid compound (b) in this reaction should be appropriately changed depending on the intended use. That is, when all the epoxy groups are carboxylated, the unreacted epoxy groups do not remain, so that the storage stability as the reactive epoxy carboxylate compound (c) is high. In this case, only the reactivity due to the introduced double bond will be used.

On the other hand, by reducing the amount of the carboxylic acid compound (b) charged to leave unreacted residual epoxy groups, the reactivity due to the introduced unsaturated bond and the reaction with the remaining epoxy groups, for example, the polymerization reaction with a photocation catalyst, etc. It is also possible to utilize the thermal polymerization reaction in combination. However, in this case, attention should be paid to the storage of the reactive epoxy carboxylate compound (c) and the examination of the production conditions.

In the case of producing the reactive epoxy carboxylate compound (c) in which no epoxy group remains, the carboxylic acid compound (b) is preferably 90 to 120 equivalent% with respect to 1 equivalent of the epoxy resin (a). Within this range, it is possible to manufacture under relatively stable conditions. If the amount of the carboxylic acid compound charged is larger than this, the excess carboxylic acid compound (b) remains, which is not preferable.

When the epoxy group remains, the carboxylic acid compound (b) is preferably 20 to 90 equivalents based on 1 equivalent of the epoxy resin (a). If it deviates from this range, the effect of composite curing will be diminished. Of course, in this case, it is necessary to pay sufficient attention to gelation during the reaction and the stability of the reactive epoxy carboxylate compound (c) over time.

The carboxylation reaction can be carried out without a solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the carboxylating reaction.

The amount of the solvent to be used is preferably adjusted appropriately depending on the viscosity and purpose of use of the obtained resin, but is preferably used so as to have a solid content of 90 to 30% by mass, more preferably 80 to 50% by mass. Will be done.

Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and petroleum ethers and whites which are mixtures thereof. Examples thereof include ester-based solvents, ether-based solvents, and ketone-based solvents such as gasoline and solvent naphtha.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate and triethylene. Mono such as glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, or polyalkylene glycol monoalkyl ether monoacetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate. Examples thereof include polycarboxylic acid alkyl esters such as.

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

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

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

At the time of the reaction, it is preferable to use a catalyst to accelerate the reaction, and the amount of the catalyst used is the reaction in which the reactants, that is, the epoxy resin (a), the carboxylic acid compound (b), and optionally a solvent or the like are added. It is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the substance. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanate, octane. Examples thereof include known general basic catalysts such as zirconium acid acid.

Further, a thermal polymerization inhibitor can also be used. As the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene and the like are preferably used.

The end point of this reaction is the time when the acid value of the sample becomes 5 mgKOH / g or less, preferably 3 mgKOH / g or less while sampling appropriately.

The preferred molecular weight range of the reactive epoxy carboxylate compound (c) thus obtained is such that the polystyrene-equivalent weight average molecular weight in GPC is in the range of 500 to 50,000, and more preferably 1,000 to 30,000. , Particularly preferably 1000 to 10000.

If it is smaller than this molecular weight, the toughness of the cured product is not sufficiently exhibited, and if it is too large, the viscosity becomes high and coating or the like becomes difficult.

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

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

As the polybasic acid anhydride (d), a compound represented by the following formula (4) is preferable.

The reaction for adding the polybasic acid anhydride (d) can be carried out by adding the polybasic acid anhydride (d) to the carboxylating reaction solution. The amount of addition should be changed as appropriate according to the application.

The amount of the polybasic acid anhydride (d) added is, for example, the polybasic acid anhydride (d) when the reactive polycarboxylic acid compound (A) of the present invention is to be used as a resist material for developing an alkaline aqueous solution. ) Is finally obtained, and the solid acid value of the reactive polycarboxylic acid compound (A) (based on JISK5601-2-1: 1999) is preferably 40 to 120 mg · KOH / g, more preferably 60 to. It is preferable to charge a calculated value of 110 mg · KOH / g. When the solid content acid value at this time is in this range, the developability of the alkaline aqueous solution of the active energy ray-curable resin composition of the present invention is good. That is, it has good patterning properties, a wide range of control over overdevelopment, and no excess acid anhydride remains.

At the time of the reaction, it is preferable to use a catalyst to accelerate the reaction, and the amount of the catalyst used is the reactant, that is, the reactive epoxy carboxylate compound obtained from the epoxy compound (a) and the carboxylic acid compound (b). It is 0.1 to 10 parts by mass with respect to the total amount of the reaction product to which (c), the polybasic acid anhydride (d), and optionally a solvent and the like are added. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanate, octane. Examples thereof include zirconium acid acid.

The acid addition reaction can be carried out without a solvent or diluted with a solvent. 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, when the product is manufactured using a solvent in the carboxylate reaction, which is the previous step, it can be directly subjected to the acid addition reaction, which is the next step, without removing the solvent, provided that both reactions are inert. can. The solvent that can be used may be the same as that that can be used in the carboxylating reaction.

The amount of the solvent to be used is preferably adjusted appropriately depending on the viscosity and purpose of use of the obtained resin, but is preferably used so as to have a solid content of 90 to 30% by mass, more preferably 80 to 50% by mass. Be done.

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

Further, it is preferable to use the same thermal polymerization inhibitor as the example in the carboxylation reaction.

The end point of this reaction is the point where the acid value of the reaction product falls within the range of plus or minus 10% of the set acid value while sampling as appropriate.

The preferred molecular weight range of the reactive polycarboxylic acid compound (A) thus obtained is such that the polystyrene-equivalent weight average molecular weight in GPC is in the range of 500 to 50,000, and more preferably 1,000 to 30,000. , Particularly preferably 1000 to 10000.

If it is smaller than this molecular weight, the toughness of the cured product is not sufficiently exhibited, and if it is too large, the viscosity becomes high and coating or the like becomes difficult.

Specific examples of the reactive compound (B) that 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 that are sensitive to both. Can be mentioned.

Examples of the acrylates that can be used include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, and the like.

Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, and the like. Examples thereof include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

Examples of polyfunctional (meth) acrylates include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, and ethylene glycol di (meth) acrylate. , Diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipate epoxy di (meth) acrylate, bisphenolethylene oxide di (meth) acrylate, Di (meth) acrylate hydride bisphenol ethylene oxide di (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of neopenglycol hydroxyvivariate, poly of the reaction product of dipentaerythritol and ε-caprolactone (Meta) Acrylate, Dipentaerythritol Poly (meth) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Triethylol Propanetri (Meta) Acrylate, and Ethylene Oxide Additives thereof, Pentaerythritol Tri (meth) Acrylate, and Ethylene thereof Examples thereof include an oxide adduct, a pentaerythritol tetra (meth) acrylate, and an ethylene oxide adduct dipentaerythritol hexa (meth) acrylate, and an ethylene oxide adduct thereof.

Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether and the like. Examples of styrenes include styrene, methylstyrene, ethylstyrene and the like. Examples of other vinyl compounds include triallyl isocyanurate and trimetalyl isocyanurate.

Further, as so-called reactive oligomers, a urethane acrylate having a functional group sensitive to active energy rays and a urethane bond in the same molecule, and a functional group sensitive to active energy rays and an ester bond in the same molecule. Examples thereof include polyester acrylates having both, epoxy acrylates having functional groups derived from other epoxy resins and having functional groups sensitive to active energy rays in the same molecule, and reactive oligomers in which these bonds are used in combination.

The cationic reaction type monomer is not particularly limited as long as it is a compound generally having an epoxy group. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4, -epoxycyclohexanecarboxylate (manufactured by Union Carbide). Cyracure UVR-6110 ", etc.), 3,4-Epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexenedioxide ("ELR-4206" manufactured by Union Carbide, etc.), limonendioxide (Dycel Chemical Industry) (3,4-Epoxycyclohexyl-5,5-spiro-3,4-), allylcyclohexenedioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-) Epoxy) Cyclohexane-m-dioxane, 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 and the like can be mentioned.

Of these, as the reactive compound (B), radically curable acrylates are most preferable. In the case of the cationic type, since the carboxylic acid and the epoxy group react with each other, it is necessary to make a two-component mixed type.

The reactive polycarboxylic acid compound (A) of the present invention and the other reactive compound (B) can be mixed to obtain the active energy ray-curable resin composition of the present invention. At this time, other components may be added as appropriate depending on the intended use.

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) in the composition, and 3 to 3 to 3 to 10 parts by mass of the other reactive compound (B). It contains 95 parts by mass, more preferably 3 to 90 parts by mass. If necessary, it may contain 0 to 80 parts by mass of other components.

In addition, for the purpose of adapting the active energy ray-curable resin composition of the present invention to various uses, other components may be added to the composition up to 70 parts by weight. Examples of other components include photopolymerization initiators, other additives, coloring materials, and volatile solvents added for viscosity adjustment for the purpose of imparting coating suitability. Other ingredients that may be used are illustrated below.

The active energy ray-curable resin composition of the present invention may further contain a photopolymerization initiator. As the photopolymerization initiator, a radical type photopolymerization initiator and a cationic photopolymerization initiator are preferable.
Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloro. Acetphenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 -Acetophenones such as on; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and the like. Thioxanthones; Ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-benzophenone such as bismethylaminobenzophenone; 2,4,6 Examples thereof include known general radical photopolymerization initiators such as phosphinoxides such as -trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

Examples of the cationic photopolymerization initiator include a diazonium salt of Lewis acid, an iodonium salt of Lewis acid, a sulfonium salt of Lewis acid, a phosphonium salt of Lewis acid, other halides, a triazine-based initiator, and a borate-based initiator. And other photoacid generators and the like.

Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Aid SI-60L / SI-80L / SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. Examples of the iodonium salt of Lewis acid include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate, and examples of the sulfonium salt of Lewis acid include triphenylsulfonium hexafluorophosphonate (CyracureUVI-6990 manufactured by UnionCarbide). , Triphenylsulfonium hexafluoroantimonate (CyracureUVI-6974 etc. manufactured by UnionCarbide) and the like, and examples of the phosphonium salt of Lewis acid include triphenylphosphonium hexafluoroantimonate and the like.

Other halides include 2,2,2-trichloro- [1-4'-(dimethylethyl) phenyl] etanone (TRIgonal PI manufactured by AKZO, etc.), 2,2-dichloro-1-4- (phenoxyphenyl). Examples thereof include etanone (Sandray 1000 manufactured by Sandoz Co., Ltd.), α, α, α-tribromomethylphenyl sulfone (BMPS manufactured by Steel Chemical Co., Ltd., etc.) and the like. Examples of the triazine-based initiator include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine (Triazine A manufactured by Panchim, etc.), 2,4. -Trichloromethyl- (4'-methoxystyryl) -6-triazine (Panchim's TriazinePMS, etc.), 2,4-trichloromethyl- (pipronyl) -6-triazine (Panchim's TriazinePP, etc.), 2,4-trichloro Methyl- (4'-methoxynaphthyl) -6-triazine (TriazineB manufactured by Panchim, etc.), 2 [2'(5-methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -s-triazine (Sanwa) Chemicals, etc.), 2 (2'-frillethylidene) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemicals, etc.) and the like.

Examples of the borate-based photopolymerization initiator include NK-3876 and NK-3881 manufactured by Nippon Photosensitizing Dye, and examples of other photoacid generators include 9-phenylaclydin and 2,2'-bis (o-chlorophenyl). ) -4,4', 5,5'-tetraphenyl-1,2-biimidazole (biimidazole manufactured by Kurokin Kasei Co., Ltd.), 2,2-azobis (2-amino-propane) dihydrochloride (Wako Pure Chemical Industries, Ltd.) V50, etc.), 2,2-azobis [2- (imidazolin-2yl) propane] dihydrochloride (VA044, etc. manufactured by Wako Junyaku Co., Ltd.), [Eta-5-2-4- (cyclopentadecyl) (1) , 2,3,4,5,6, eta)-(methylethyl) -benzene] iron (II) hexafluorophosphonate (Irgacure261, manufactured by CibaGeigy, etc.), bis (y5-cyclopentadienyl) bis [2,6 -Difluoro-3- (1H-pyri-1-yl) phenyl] Titanium (CGI-784, etc. manufactured by CibaGey) and the like can be mentioned.

In addition, an azo-based initiator such as azobisisobutyronitrile and a heat-sensitive peroxide-based radical initiator such as benzoyl peroxide may be used in combination. Further, both radical-based and cationic-based photopolymerization initiators may be used in combination. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

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

Further, the active energy ray-curable resin composition of the present invention can contain a coloring pigment. As the coloring pigment, for example, a pigment not intended for coloring, a so-called extender pigment, can also be used. For example, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like can be mentioned.

Further, the active energy ray-curable resin composition of the present invention may contain other additives, if necessary. Other additives include, for example, thermosetting catalysts such as melamine, thixotropy-imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and defoamers, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, and oxidation. An inhibitor or the like can be used.

Other resins that do not react to active energy rays (so-called inert polymers) include, for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, etc. Styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and modified products thereof can also be used. These are preferably used in the range of up to 40 parts by mass in the resin composition.

In particular, when the reactive polycarboxylic acid compound (A) is to be used for solder resist applications, it is preferable to use a known general epoxy resin as a resin that does not show reactivity with active energy rays. This is because the carboxyl group derived from the reactive polycarboxylic acid compound (A) remains even after the reaction and curing by the active energy rays, and as a result, the cured product is inferior in water resistance and hydrolyzability. Therefore, by using the epoxy resin, the residual carboxyl group is further carboxylated, and a stronger crosslinked structure is formed. As the known general epoxy resin, the cationic reaction type monomer can be used.

Further, for the purpose of adjusting the viscosity according to the purpose of use, a volatile solvent can be added to the resin composition in a range of up to 50 parts by mass, more preferably 35 parts by mass.

The active energy ray-curable resin composition of the present invention is easily cured by the active energy ray. Here, specific examples of the active energy beam include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and laser beams, and particle beams such as alpha rays, beta rays, and electron beams. Considering the suitable use of the present invention, ultraviolet rays, laser beams, visible rays, or electron beams are preferable.

In the present invention, the molding material is a material in which an uncured composition is placed in a mold, or a mold is pressed against the mold to form an object, and then a curing reaction is caused by active energy rays to form the uncured composition. It refers to a material used for molding by irradiating it with focal light such as a laser to cause a curing reaction.

Specific applications include a sheet molded into a flat surface, a sealing material for protecting an element, and a so-called nanoimprint material in which a finely processed "mold" is pressed against an uncured composition to perform fine molding. Further, a light emitting diode having a particularly strict thermal requirement, a peripheral encapsulating material such as a photoelectric conversion element, and the like can be mentioned as suitable applications.

In the present invention, the film-forming material is used for the purpose of covering the surface of the base material. Specific applications include ink materials such as gravure ink, flexo ink, silk screen ink, and offset ink, coating materials such as hard coat, top coat, overprint varnish, and clear coat, and various adhesives for laminating and optical disks. Adhesive materials such as agents and adhesives, solder resists, etching resists, resist materials such as resists for micromachines, and the like fall under this category. Furthermore, a so-called dry film, in which a film-forming material is temporarily applied to a peelable substrate to form a film and then bonded to the originally intended substrate to form a film, is also a film-forming material. ..

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

Of these, the introduction of the carboxyl group of the reactive polycarboxylic acid compound (A) enhances the adhesion to the substrate, so that it is preferably used for coating a plastic substrate or a metal substrate.

Furthermore, it is also preferable to use the unreacted reactive polycarboxylic acid compound (A) as an alkaline water-developable resist material composition by taking advantage of the characteristic that it is soluble in an alkaline aqueous solution.

In the present invention, the resist material composition is a film layer of the composition formed on a substrate, and then partially irradiated with active energy rays such as ultraviolet rays, and the physical characteristics of the irradiated portion and the unirradiated portion are different. Refers to an active energy ray-sensitive composition to be drawn using. Specifically, it is a composition used for the purpose of drawing by removing the irradiated portion or the unirradiated portion by dissolving it in some method, for example, a solvent or an alkaline solution.

The active energy ray-curable resin composition, which is the resist material composition of the present invention, can be applied to various materials capable of patterning, and is particularly useful for solder resist materials and interlayer insulating materials for build-up methods. Furthermore, it is also used as an optical waveguide for printed wiring boards, electric / electronic / optical substrates such as optoelectronic boards and optical boards.

Particularly suitable applications include photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, and circuit boards (laminated board applications, multilayer printed wiring board applications), taking advantage of their good heat resistance and developability. Etc.), solder resist, underfill material, die bonding material, semiconductor encapsulant, fill-in-the-blank resin, component-embedded resin, etc., can be used in a wide range of applications requiring a resin composition. Among them, a resin composition for an insulating layer of a multilayer printed wiring board (a multilayer printed wiring board in which a cured product of a photosensitive resin composition is used as an insulating layer) and a resin composition for an interlayer insulating layer (a cured product of a photosensitive resin composition). It is preferable to use it for a multi-layer printed wiring board having an interlayer insulating layer) and a resin composition for plating (a multi-layer printed wiring board in which plating is formed on a cured product of a photosensitive resin composition).
Further, it can exhibit good developability even at a high pigment concentration, and can be suitably used for a color resist, a resist material for a color filter, particularly a black matrix material and the like.

Patterning using the active energy ray-curable resin composition of the present invention can be performed, for example, as follows. The composition of the present invention is applied onto a substrate with a film thickness of 0.1 to 200 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, or a spin coating method, and a coating film is applied. The coating film can be formed by drying at a temperature of usually 50 to 110 ° C, preferably 60 to 100 ° C. Then, the coating film is directly or indirectly irradiated with high-energy rays such as ultraviolet rays at an intensity of about 10 to 2000 mJ / cm ² through a photomask on which an exposure pattern is formed, and then sprayed, for example, using a developer described later. A desired pattern can be obtained by vibration immersion, paddle, brushing and the like.

The alkaline aqueous solution used for the above development includes an inorganic alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate and the like, and tetramethylammonium hydroxide. , Tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine and other organic alkaline aqueous solutions can be used. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

In addition, it is particularly preferably used for dry film applications where mechanical strength before the curing reaction by active energy rays is required. That is, because the balance between the hydroxyl group and the epoxy group of the epoxy resin (a) used in the present invention is in a specific range, the reactive carboxylate compound of the present invention has a relatively high molecular weight, but is good. It is possible to demonstrate developability.

The method for forming the film is not particularly limited, but intaglio printing method such as gravure, letterpress printing method such as flexography, stencil printing method such as silk screen, lithographic printing method such as offset, roll coater, knife coater, die coater, etc. Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating the active energy ray-curable resin composition of the present invention with active energy rays and curing it.

The article overcoated with the active energy ray-curable resin composition of the present invention is at least two layers or more obtained by forming and curing a film of the active energy ray-curable resin composition shown in the present invention on a substrate. The material consisting of the layers of is shown.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Further, in the examples, unless otherwise specified,% indicates mass%.

The softening point, epoxy equivalent, and acid value were measured under the following conditions.
1) Epoxy equivalent: Measured according to JISK7236: 2001.
2) Softening point: Measured according to JISK7234: 1986.
3) Acid value: Measured according to JISK0070: 1992 4) The measurement conditions of GPC are as follows.
Model: TOSOH HLC-8220GPC
Column: Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40 ° C.
Detector: RI (Differential Refractometer)
Molecular weight standard: Polystyrene

(Synthesis Example 1): Synthesis of Reactive Epoxy Carboxylate Compound (c) 353 g of an epoxy resin (manufactured by Mitsui Petrochemical Co., Ltd., VG-3101, epoxy equivalent 210) having a triglycidyl ether structure as the epoxy resin (a). , 122 g of acrylic acid (abbreviated as AA, Mw = 72) as the carboxylic acid compound (b), 3 g of triphenylphosphine as the catalyst, and propylene glycol monomethyl ether monoacetate as the solvent so as to have a solid content of 80%, 100. The reaction was carried out at ° C. for 24 hours to obtain a reactive epoxy carboxylate compound (c1) solution.

(Synthesis Example 2)
As the epoxy resin (a), 353 g of an epoxy resin having a triglycidyl ether structure (manufactured by Mitsui Petrochemical Co., Ltd., VG-3101, epoxy equivalent 210) was used, and methacrylic acid (abbreviated as MAA, Mw = 86) was used as the carboxylic acid compound (b). ), 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent so as to have a solid content of 80%, and react at 100 ° C. for 24 hours to prepare a reactive epoxy carboxylate compound (c2) solution. Obtained.

(Example 1, Comparative Example 1): Preparation of Reactive Polycarboxylic Acid Compound (A) Table 1 shows 593 g of the obtained reactive epoxycarboxylate compound (c) solution as polybasic acid anhydride (d). The compound, amount (g), and propylene glycol monomethyl ether monoacetate so as to have a solid content of 65% as a solvent are added, heated to 100 ° C., and then subjected to an acid addition reaction to cause a reactive polycarboxylic acid compound (A). ) A solution was obtained. 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 acid value (mg · KOH / g): The measurement was performed as a solution and converted to the value in solid content.

(Example 2, Comparative Example 2): Preparation of resist material composition 54.44 g of the reactive polycarboxylic acid compound (A) obtained in Example 1 was used, and HX-220 (B) was used as the other reactive compound (B). Product name: 3.54 g of diacrylate monomer manufactured by Nippon Kayaku Co., Ltd., 4.72 g of Irgacure 907 (manufactured by Ciba Speciality Chemicals) as a photopolymerization initiator, and Kayacure DETX-S (Nippon Kayaku Co., Ltd.) ), 0.47 g, GTR-1800 (manufactured by Nippon Kayaku) as a curing agent component, 1.05 g of melamine as a thermosetting catalyst, and 20.95 g of methyl ethyl ketone as a concentration adjusting solvent, and use a bead mill. The mixture was kneaded and uniformly dispersed to obtain a resist material resin composition.
The obtained composition was uniformly applied to a copper foil film to be a support film by a roll coating method, and passed through a hot air drying furnace having a temperature of 70 ° C. to form a resin layer having a thickness of 30 μm. After that, spray development was performed with a 1% aqueous sodium carbonate solution, and the time until complete development, the so-called break time, was used as the evaluation of developability (unit: seconds).

From the above results, the resist material composition using the reactive polycarboxylic acid compound (A) of the present invention has good developability.

(Example 3 and Comparative Example 3): Evaluation of thermostable decomposition resistance 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 propylene. After adding 2.4 g of glycol monomethyl ether monoacetate, uniformly applying it to a polyimide film, passing it through a hot air drying furnace at a temperature of 80 ° C. to form a resin layer having a thickness of 20 μm, an ultraviolet exposure device (ORC Manufacturing Co., Ltd.) , Model HMW-680GW) to obtain a cured product. The produced cured product is cut out with a width of 5 mm. After that, it was set in a viscoelasticity measuring device RSA-G2 manufactured by TA instruments, and the frequency was 10 Hz and the temperature rising rate was 2 ° C./min in an air atmosphere. The tan δ was measured with Tg, and the temperature at the maximum value of tan δ was defined as Tg.
In addition, the temperature at which the weight of the prepared sample 3 mg was reduced by 5% was measured using TGA / DSC1 manufactured by METTLER in an air flow of 100 ml per minute.

From the above results, the active energy ray-curable resin composition using the reactive polycarboxylic acid compound (A) of the present invention is superior in heat resistance and heat decomposability as compared with the comparative resin composition. You can see that.

Claims (10)

Reactive epoxy carboxylate obtained by reacting an epoxy resin (a) represented by the following formula (1) with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule. A reactive polycarboxylic acid compound (A) obtained by reacting compound (c) with a polybasic acid anhydride (d) represented by the following formula (2) or formula (3).

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

(R ₁ in the formula (2) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) according to claim 1. The active energy ray-curable resin composition according to claim 2, which comprises a reactive compound (B) other than the reactive polycarboxylic acid compound (A). The active energy ray-curable resin composition according to claim 2 or 3, which comprises a photopolymerization initiator. The active energy ray-curable resin composition according to any one of claims 2 to 4, which comprises a thermosetting catalyst. The active energy ray-curable resin composition according to any one of claims 2 to 5, which is a molding material. The active energy ray-curable resin composition according to any one of claims 2 to 5, which is a material for forming a film. The active energy ray-curable resin composition according to any one of claims 2 to 5, which is a resist material composition. The cured product of the active energy ray-curable resin composition according to any one of claims 2 to 8. An article overcoated with a cured product of the active energy ray-curable resin composition according to claim 9.