JP5604106B2 - Reactive carboxylate compound, curable resin composition using the same, and use thereof - Google Patents

Description

  The present invention relates to a phenol aralkyl type epoxy resin (a) having an excellent balance of hydroxyl group, epoxy group and softening point, one or more polymerizable ethylenically unsaturated groups and one or more polymerizable molecules in a molecule represented by acrylic acid and the like. The present invention relates to a reactive epoxycarboxylate compound (A) obtained by reacting a compound (b) having both of these carboxyl groups, and a reactive polycarboxylic acid compound (B) which is an acid-modified product thereof. These reactive epoxycarboxylate compound (A) and reactive polycarboxylic acid compound (B) have good dispersibility of the pigment, and from the resin composition containing these, a film-forming material, a solder resist, A tough cured product suitable for plating resists, color resists, color filter resists, various resists such as black matrix, and optical waveguides can be obtained.

  With the aim of reducing the size and weight of portable devices and improving communication speed, printed wiring boards are required to have high precision and high density. With this, the demand for solder resists that cover the circuit itself has become increasingly sophisticated. Performance that can withstand substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability is required more than required, and a film forming material with tougher cured material properties is required. It was.

  For these materials, a reactive polycarboxylic acid compound in which a carboxyl group is introduced with an acid anhydride for the purpose of patterning with an alkaline developer after carboxylating an epoxy resin with acrylic acid or the like is used for resist, In particular, application to solder resists is generally known (Patent Documents 1 and 2).

  Acid-modified epoxy acrylates having a phenol aralkyl type epoxy resin (for example, NC-3000 manufactured by Nippon Kayaku Co., Ltd.) as a basic skeleton are generally known as materials exhibiting high toughness after curing, and as a solder resist using the same. The use is also being studied (Patent Document 3).

  Among these, in film formation applications, particularly solder resist applications, physical properties in a state where the solvent is only volatilized after the film formation is also an important factor. Specifically, if it is more flexible than necessary at this stage, peeling or patterning film contamination occurs. In particular, in applications such as so-called dry film, this characteristic is more important because a transfer process is included.

  In order to improve toughness before and after curing, it is a general technique to use a material having a high molecular weight, but in this case, there is a problem that developability is greatly impaired.

  Furthermore, Patent Document 3 does not disclose a quantitative balance between the hydroxyl group and the epoxy group in the epoxy resin, and a suitable balance in the present invention cannot be obtained.

  In addition, an attempt to apply to black matrix resists used in liquid crystal display panels, etc., by dispersing carbon black or the like in acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin (for example, NC-3000 manufactured by Nippon Kayaku) as the basic skeleton Known (Patent Document 4).

  In this application, when coloring pigments such as carbon black are blended at a high concentration, the pigment has good affinity with the resin and the pigment is dispersed, so that good developability can be obtained even when the pigment is present at a high concentration. As shown, there is no pigment residue and development is possible. Conventional acid-modified epoxy acrylates, particularly acid-modified epoxy acrylates having a biphenyl skeleton, exhibit relatively good dispersibility, but have been required to have developability at a higher pigment concentration, that is, higher pigment dispersibility. Further, Patent Document 4 also does not disclose the quantitative balance between the hydroxyl group and the epoxy group in the epoxy resin, and the disclosed method cannot obtain a suitable balance in the present invention. Patent Document 5 describes an epoxy resin similar to the epoxy resin (a) used in the present invention, but does not describe a reactive epoxycarboxylate compound (A) and a reactive polycarboxylic acid compound (B). Absent.

Japanese Patent Publication No. 56-40329 Japanese Patent Publication No.57-45795 JP-A-11-140144 JP 2005-55814 A JP 2007-191877 A

  Although the curable resin composition using the phenol aralkyl type epoxy resin can obtain a relatively tough cured product, the present cured physical properties are not sufficient.

  Furthermore, there is a need for acid-modified epoxy acrylates that have higher dispersion in colored pigments, especially carbon black, and that have good development characteristics even at high pigment concentrations. At this time, a material having a relatively high molecular weight and appropriate developability is required.

  There is a demand for materials that have tough cured properties and good development characteristics, and also have good development characteristics even at high pigment concentrations.

  In order to solve the above-mentioned problems, the present inventors have developed an active energy ray-curable resin composition derived from an epoxy resin having a specific structure, that is, an epoxy resin containing a large amount of the structure represented by the formula (1). It has been found that a cured product can be obtained, and that the resin has excellent resin properties even when the solvent is dried. Furthermore, it has been found that it has particularly good dispersibility of colored pigments, and that it can be a resist material having good developability even at a high pigment concentration.

That is, the present invention provides a reactive epoxy carboxylate obtained by reacting the following epoxy resin (a) with a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule. Compound (A)
Formula (1)

And the following general formula (2) (in the general formula (2), Ar is represented by the general formula (3) or (4), m represents the number of substituents R and 1 to 3) N represents an average value of the number of repetitions of 1 to 10, and R represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a trifluoromethyl group, an allyl group or an aryl group, respectively. And each R may be the same or different, and Ar may be the same or different.)

An epoxy resin (a) obtained from a phenol aralkyl resin (P) having a structure shown in FIG.
(I) Epoxy resin (a) obtained by partially epoxidizing the phenol aralkyl resin (P).
(Ii) Epoxy resin (a) obtained by reacting phenol aralkyl resin (P) with phenol aralkyl type epoxy resin (E2)
About.
Furthermore, a reactive epoxycarboxylate compound (A) characterized by using an epoxy resin (a) obtained by using 1.0 to 5.0 mol of epihalohydrin with respect to 1 mol of a hydroxyl group of the phenol aralkyl resin (P). )
Furthermore, the epoxy resin (a) obtained by making it react so that the hydroxyl group of a phenol aralkyl resin (P) may be 0.01-0.3 mol with respect to 1 mol of epoxy groups of a phenol aralkyl type epoxy resin (E2). It is related with the reactive epoxy carboxylate compound (A) characterized by using.
Further, when the epoxy resin (a) has a hydroxyl group equivalent of X (g / eq.) And an epoxy equivalent of Y (g / eq.), The relationship is represented by the following formula (I).
2 ≦ (X / Y) ≦ 15 (I)
It is related with the reactive epoxycarboxylate compound (A) which satisfy | fills.
Furthermore, it is related with the reactive polycarboxylic acid compound (B) obtained by making a polybasic acid anhydride (c) react with the said carboxylate compound (A).
Furthermore, the present invention relates to an active energy ray-curable resin composition comprising the carboxylate compound (A) and / or a reactive polycarboxylic acid compound (B).
Furthermore, the present invention relates to an active energy ray-curable resin composition comprising the carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) and another reactive compound (C).
Furthermore, the present invention relates to an active energy ray-curable resin composition characterized by containing a coloring pigment in the active energy ray-curable resin composition.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a molding material.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a film forming material.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a resist material composition.
Furthermore, it is related with the hardened | cured material of the said active energy ray hardening-type resin composition.
Further, the present invention relates to an article overcoated with a cured product of the resin composition.
Further, the reactive epoxycarboxylate compound (A) is prepared by reacting the epoxy resin (a) with a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule. It relates to the manufacturing method.
Furthermore, it is related with the manufacturing method of the reactive polycarboxylic acid compound (B) which makes the said carboxylate compound (A) and polybasic acid anhydride (c) react.

  The active energy ray-curable resin composition containing an epoxy resin having a specific structure of the present invention has excellent resin properties not only in obtaining a tough cured product but also in a state where the solvent is only dried. The cured product obtained from the active energy ray-curable resin composition of the present invention can be suitably used as a film-forming material that requires thermal and mechanical toughness.

  More preferably, it can be used for applications requiring particularly high characteristics such as solder resists for printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, and photosensitive optical waveguides.

  Furthermore, since it has high dispersibility of colored pigments such as carbon black, it can exhibit good developability even at high pigment concentrations, so that resist materials for color resists and color filters, particularly black It can be suitably used for a matrix material or the like.

  In the active energy ray-curable resin composition of the present invention, the epoxy resin (a) as an essential component has a structure in which at least phenols or naphthols are bonded with an aralkyl group as a bonding group, and the following formula (1)

It is a phenol aralkyl type epoxy resin having the structure shown in FIG.

  The epoxy resin (a) is obtained by partially epoxidizing the phenol aralkyl resin (P) (one-step method) or reacting the phenol aralkyl resin (P) with the phenol aralkyl type epoxy resin (E2) (fusion method). ) Can be obtained. The phenol aralkyl resin (P) used as a raw material is a resin having a molecular structure in which an aromatic ring is bonded to a phenol or naphthol having a substituent via a methylene bond, an ethylidene bond, a propylidene bond, or the like. Examples of the aromatic ring include phenyl, biphenyl, fluorenyl, naphthyl bishalogenomethyl, bishalogenoethyl, bishalogenopropyl; bisalkoxymethyl, bisalkoxyethyl, bisalkoxypropyl; bishydroxymethyl, bis A hydroxyethyl body, a bishydroxypropyl body, etc. can be mentioned. The phenol aralkyl resin (P) used in the present invention can be obtained by subjecting a phenol or naphthol having a substituent to a condensation reaction with the aromatic ring. In the present invention, it is preferably obtained by a condensation reaction of phenols, particularly preferably phenol and a compound having a biphenyl skeleton, and a biphenyl type phenol aralkyl resin as represented by the general formula (2) is particularly preferable.

  In the general formula (2), each R independently represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a trifluoromethyl group, an allyl group or an aryl group, or a halogen atom. Here, it is a hydrocarbon group having 1 to 15 carbon atoms, more preferably 1 to 7 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group And a chain or cyclic alkyl group such as a cycloheptyl group, an n-octyl group, and a cyclooctyl group. The aryl group preferably has 6 to 11 carbon atoms. Specifically, a phenyl group, a naphthyl group, a toluyl group, etc. are mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Among these, a hydrogen atom, a methyl group, a phenyl group or a tert-butyl group is preferable, and a hydrogen atom is particularly preferable. Although the substitution position of R is not particularly limited, the ortho position or the meta position of the hydroxyl group is independently taken. n is an average value of 1 to 10, preferably 1.0 to 5.0.

  Such a phenol aralkyl resin is also commercially available. Specifically, it is represented by Mitsui Chemicals Co., Ltd. XLC series, Meiwa Kasei Co., Ltd. MEH-7851, and the following formula (5) (Nippon Kayaku Co., Ltd.) Examples thereof include KAYAHARD GPH65 and the like.

（式中ｎは繰り返し数の平均値で１〜１０である。）

(In the formula, n is an average value of the number of repetitions and is 1 to 10.)

  The phenol aralkyl type epoxy resin (E2), which is a raw material of the epoxy resin (a) in the fusion method, is a resin having a structure in which the phenolic hydroxyl group of the phenol aralkyl resin is glycidylated and represented by the following formula (6). Compounds are preferred.

（式中ｎは繰り返し数の平均値で１〜１０である。）

(In the formula, n is an average value of the number of repetitions and is 1 to 10.)

Among them, for example, the formula (7)

（式中ｎは繰り返し数の平均値で１〜１０である。）

(In the formula, n is an average value of the number of repetitions and is 1 to 10.)

The epoxy resin represented by these is mentioned. In recent years, this epoxy resin is excellent in various properties such as flame retardancy, adhesion, and water resistance, and is particularly preferable.

  The raw material phenol aralkyl resin (P) of the epoxy resin (a) and the raw material phenol aralkyl type epoxy resin (E2) are generally synthesized by the methods described in Japanese Patent No. 3122834 and JP-A No. 2001-40053. . Specifically, 4,4′-bismethoxymethylbiphenyl and phenols are condensed under acidic conditions, or 4,4′-bishalogenomethylbiphenyl and phenols are condensed under acidic conditions; A condensation reaction of phenols may be mentioned. By reacting the obtained preferred phenol aralkyl resin with epihalohydrin, a raw material phenol aralkyl type epoxy resin, preferably a compound represented by the formula (7), is obtained. As resin represented by Formula (7), Nippon Kayaku Co., Ltd. NC-3000 and NC-3000H are mentioned as a commercial item.

Below, the manufacturing method of an epoxy resin (a) is demonstrated.
As described above, the one-step method and the fusion method can be applied to the method for producing the epoxy resin (a). However, the conventional one-step method and fusion method are intended for bifunctional epoxy resins and phenol resins. When polyfunctional is used as a raw material as in the epoxy resin (a), the polyfunctional phenol resin is used in the one-step method. It is necessary to give sufficient consideration to the reaction ratio between the polyfunctional epoxy resin and the polyfunctional phenol resin in the fusion method. Hereinafter, the epoxy resin (a) (i) and the epoxy resin (a) (ii) are distinguished from each other depending on the production method, but the same epoxy resin (a) can be obtained by using any production method.

  First, the case of the one-stage method will be described in detail. The epoxy resin (a) (i) is obtained by reacting the phenol aralkyl resin (P) with epihalohydrin in the presence of an alkali metal hydroxide. In this one-stage method, the amount of epihalohydrin and alkali metal hydroxide used is a factor that determines the rate of introduction of the structure of formula (1).

  In the reaction for obtaining the epoxy resin (a), epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin. In the present invention, epichlorohydrin which is easily available industrially is preferable. The usage-amount of epihalohydrin is 1.0-5.0 mol normally with respect to 1 mol of hydroxyl groups of raw material phenol aralkyl resin (P), Preferably it is 1.5-3.5 mol.

  Examples of the alkali metal hydroxide that can be used in the reaction include sodium hydroxide and potassium hydroxide, and solids may be used or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and further separated to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.3-2.5 mol normally with respect to 1 mol of hydroxyl groups of raw material phenol aralkyl resin, Preferably it is 0.5-2.0 mol.

  In order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol aralkyl resin.

  At this time, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

  When using alcohol, the usage-amount is 2-50 weight part normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight part. Moreover, when using an aprotic polar solvent, it is 5-100 weight part normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight part.

  The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. Furthermore, in order to make an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. The reaction can be carried out to ensure the ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per 1 mol of the hydroxyl group of the phenol aralkyl resin used for epoxidation. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin (a) (i).

  Next, the fusion method will be described in detail. This method is a method in which a phenol aralkyl type epoxy resin (E2) and a phenol aralkyl resin (P) are reacted to obtain an epoxy resin (a) (ii). In this fusion method, the ratio of the phenol aralkyl type epoxy resin (E2) and the phenol aralkyl resin (P) is a factor that determines the introduction rate of the structure of the formula (1). As the phenol aralkyl type epoxy resin (E2), a commercially available compound may be used, or the phenol aralkyl resin (P) may be epoxidized. In the case of synthesis, for example, the following method can be used.

  The phenol aralkyl type epoxy resin (E2) can be obtained by reacting the phenol aralkyl resin (P) with an epihalohydrin. As the epihalohydrin, epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin and the like can be used, and industrially easily available epichlorohydrin is preferable. The usage-amount of epihalohydrin is 2.0-20.0 mol normally with respect to 1 mol of hydroxyl groups of a phenol aralkyl resin, Preferably it is 2.5-10.0 mol.

  Examples of the alkali metal hydroxide that can be used in the reaction include sodium hydroxide, potassium hydroxide, and the like. A solid substance may be used, or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and further separated to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.9-2.5 mol normally with respect to 1 mol of hydroxyl groups of a phenol aralkyl resin, Preferably it is 0.95-2.0 mol.

  In order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol aralkyl resin.

  At this time, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

  When using alcohol, the usage-amount is 2-50 weight part normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight part. Moreover, when using an aprotic polar solvent, it is 5-100 weight part normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight part.

  The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. Furthermore, in order to make an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. The reaction can be carried out to ensure the ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the phenol aralkyl resin (P) used for epoxidation. is there. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, and the like, and the solvent is distilled off under heating and reduced pressure to obtain a phenol aralkyl type epoxy resin (E2). The epoxy resin (a) (ii) can be obtained by reacting the obtained phenol aralkyl type epoxy resin (E2) with the phenol aralkyl resin (P). Usually, it is made to react so that the hydroxyl group of a phenol aralkyl resin (P) may be 0.01-0.3 mol with respect to 1 mol of epoxy groups of a phenol aralkyl type epoxy resin (E2).

  The reaction between the phenol aralkyl type epoxy resin (E2) and the phenol aralkyl resin (P) uses a catalyst as necessary. Specific examples of catalysts that can be used include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride; quaternary phosphonium salts such as triphenylethylphosphonium chloride and triphenylphosphonium bromide; sodium hydroxide Alkali metal salts such as potassium hydroxide, potassium carbonate, cesium carbonate; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) ) Tertiary amines such as phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7; triphenylphosphine, diphenylphosphine Organic phosphines such as fin and tributylphosphine; metal compounds such as tin octylate; tetrasubstituted phosphonium / tetrasubstituted borates such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4- Examples thereof include tetraphenylboron salts such as methylimidazole / tetraphenylborate and N-methylmorpholine / tetraphenylborate. The amount used in the case of using these catalysts depends on the kind of the catalyst, but is generally 10 ppm to 30000 ppm, preferably 100 ppm to 5000 ppm, if necessary, based on the total resin amount. In this reaction, since the reaction proceeds without adding a catalyst, it is desirable to use it appropriately according to the preferred reaction temperature and amount of the reaction solvent.

  In this fusion method, the reaction can be carried out without solvent, or the reaction can be carried out by diluting with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for this reaction. In addition, in the case of producing using a solvent in the next step, carboxylation reaction, and further in the next step, acid addition reaction, the next step is performed directly without removing the solvent, provided that both reactions are inert. It can also be used for the reaction in the process.

  Specifically, for example, 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 Examples include gasoline and solvent naphtha.

  Examples of ester solvents 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 monoacetates, dialkyl glutarate, dialkyl succinate, dialkyl adipate Polycarboxylic acid alkyl esters such as And the like.

  Examples of ether solvents 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 include ethers and cyclic ethers such as tetrahydrofuran.

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

  In addition, the reaction can be carried out alone or in a mixed organic solvent such as other reactive compounds (C) described later. In this case, when used as a curable composition, it can be used directly as a composition, which is preferable.

  The usage-amount of a solvent is 0-300 weight part with respect to the total resin weight, Preferably it is 0-100 weight part.

  The reaction temperature and reaction time must be appropriately selected depending on the resin concentration and the amount of catalyst, and cannot be generally defined, but the reaction time is usually 1 to 200 hours, preferably 1 to 100 hours. It is preferable that the reaction time is short from the viewpoint of productivity. Moreover, reaction temperature is 0-250 degreeC normally, Preferably it is 30-200 degreeC.

  After completion of the reaction, the epoxy resin solution obtained using the solvent can be adjusted as it is, and can proceed to the next carboxylation step as a solution containing the epoxy resin (a) (ii). . If necessary, the catalyst or the like may be removed by washing with water and the like, and the solvent may be distilled off under reduced pressure under heating to isolate the epoxy resin (a) (ii) and proceed to the next step.

  One of the epoxy resins (a) used in the present invention can be represented by the following formula (10).

(In the formula, j, k, and l are average values of the number of repetitions, and 0 ≦ j ≦ 39, 0 ≦ k ≦ 39, and 0 ≦ l ≦ 39.)

  When the phenol aralkyl resin (P) used in the present invention is monofunctional (in the case of j = 0 in the formula (10)), the epoxy resin (a) has a linear structure, but is polyfunctional (0 <When j ≦ 39), the epoxy resin (a) has a branched structure. In the case of polyfunctionality, a branched chain may be further generated from the branched chain, resulting in a complicated structure.

  As another thing of the epoxy resin (a) used by this invention, following formula (8)

(Wherein k and l are the same as in formula (10)).

  The sum of the average number of repetitions, the value indicated by (k + 2j + l) or (k + l) can be infinitely large because it is derived from the phenol aralkyl resin used as the raw material (average number n of the number of repetitions is 1 to 10). Preferably, both (k + 2j + 1) or (k + 1) are 2-40 as an average value, more preferably 2-30. When it is larger than 2, the effect of the hydroxyl group of the present invention is effectively exhibited, and when it is smaller than 40, preferably smaller than 30, the viscosity of the uncured state is in a suitable range.

  Specific examples of the compound represented by formula (8) include formula (9)

(Wherein, k and l are the same as those in formula (8)), but are not limited thereto.

In the present invention, the hydroxyl equivalent of the epoxy resin (a) is X (the epoxy equivalent of the corresponding epoxy resin and the epoxy group in the epoxy resin (a) are reacted with an equivalent amount of phenol to open the epoxy group. Then, the value calculated from the hydroxyl equivalent (based on JIS K 0070: 1992. Unit: g / eq.), The epoxy equivalent of the epoxy resin is Y (based on JIS K-7236: 2001. Unit: g / eq.). ), The epoxy resin (a) satisfying the following formula (I) is preferable. Hereinafter, (X / Y) = α.
2 ≦ (X / Y) ≦ 15 (I)

X, Y and j, k, and l have the following relationship.
X = (Molecular weight of epoxy resin) / (j + l)
Y = (Molecular weight of epoxy resin) / (j + k + 1)
Therefore, j, k, and l have the relationship of α value and the following formula (II).
(J + k + 1) / (j + 1) = X / Y = α Formula (II)

  In the epoxy resin (a) used in the present invention, the balance between the epoxy equivalent and the hydroxyl equivalent is important. That is, the ratio of the epoxy group and the hydroxyl group contained in the molecule is an important parameter.

  The bond of the formula (1) is a structure obtained when an epoxy resin reacts with a phenol compound or an alcohol compound. Generally, it is a bond formed when a high molecular weight grade, for example, solid bisphenol A type epoxy resin (or phenoxy resin) is synthesized, and this method is also called a one-step method or a fusion method (Advanced method or two-step method). (See pages 24-25 and 30-31, edited by Hiroshi Kakiuchi). The epoxy resin (a) is a compound using this one-stage method or fusion method. In the present invention, either the one-stage method or the fusion method may be used. However, since the by-product tends to increase when synthesized by the one-stage method, it is preferable to use the fusion method.

  In the epoxy carboxylate compound (A) or the reactive polycarboxylic acid compound (B) of the present invention, the amount of the bond containing a hydroxyl group such as the formula (1) contained in the molecular skeleton of the epoxy resin (a) However, in the case of an alkali development type solder resist, for example, it contributes to physical properties such as developability and sensitivity. The presence of a large number of hydroxyl groups in the molecular chain brings about a pseudo-crosslinking effect due to the hydroxyl groups. However, when there are too many bonding modes, the concentration of epoxy groups in the molecular skeleton is reduced, which causes a problem in curability. Therefore, the ratio between the hydroxyl equivalent and the epoxy group becomes important. In addition, the softening point contributes to tackiness, but not only that, it contributes to the functional group density of the epoxy equivalent and hydroxyl equivalent, and also contributes to developability during alkali development. Therefore, it is a problem whether the softening point is too large or too small. As the molecular weight and epoxy value increase, the softening point increases. That is, the balance of epoxy equivalent, hydroxyl equivalent, and molecular weight (softening point) is important.

  When the value of X / Y exceeds 15, the effect of the structure (1) is not sufficiently exhibited, and characteristics such as good developability, toughness of the cured product, and pigment dispersibility are not exhibited. On the other hand, when it is less than 2, the reactive site cannot be sufficiently introduced in the carboxylation reaction, and sufficient curability cannot be exhibited. When the epoxy resin (a) is polyfunctional, if it is less than 2, there is a high possibility that the epoxy resin (a) is gelled, and the problem in the present invention cannot be solved. In addition, it is guessed that the effect of structure (1) is the interaction between the polymer chain by a hydroxyl group, or a polymer and a pigment. A more preferable range of X / Y is a range of 3 to 10.

  Next, the carboxylation step for the purpose of giving the carboxylate compound reactivity and obtaining the reactive carboxylate compound (A) will be described.

  In this reaction, a reactive carboxylate compound (A) is obtained by reacting the obtained epoxy resin (a) with a compound (b) having both a polymerizable ethylenically unsaturated group and one or more carboxyl groups. .

  The compound (b) shown here is reacted for imparting reactivity to active energy rays. Specific examples include (meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. In the above, examples of the acrylic acid include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 molecule. Half-esters that are (meth) acrylate derivatives having one hydroxyl group and equimolar reactants, half-esters that are equimolar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, etc. Monocarboxylic acid compound containing one carboxyl group in one molecule, (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule and half-esters which are equimolar reactants, saturated or unsaturated dibasic acid and plural Carboxyl group in one molecule such as half-esters that are equimolar reaction products with glycidyl (meth) acrylate derivatives having an epoxy group of And polycarboxylic acid compounds having a plurality of.

  Of these, considering the stability of the reaction between the epoxy resin (a) and the carboxylic acid compound (b), (b) is preferably a monocarboxylic acid, even when the monocarboxylic acid and the polycarboxylic acid are 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 is used from the viewpoint of sensitivity when an active energy ray-curable resin composition is used.

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

  On the other hand, by reducing the charged amount of the carboxylic acid compound and leaving the unreacted residual epoxy group, the reactivity due to the introduced unsaturated bond and the reaction due to the remaining epoxy group, for example, the polymerization reaction or thermal polymerization reaction by the photocationic catalyst. Can be used in combination. In this case, however, attention should be paid to the storage of the reactive carboxylate compound and the examination of the production conditions.

  When manufacturing the reactive carboxylate compound (A) which does not leave an epoxy group, it is preferable that a carboxylic acid compound (b) is 90-120 equivalent% with respect to 1 equivalent of epoxy resins (a). Within this range, it is possible to manufacture under relatively stable conditions. When the amount of the carboxylic acid compound charged is larger than this, an excess of the carboxylic acid compound (b) remains, which is not preferable.

  Moreover, when leaving an epoxy group, it is preferable that a carboxylic acid compound (b) is 20-90 equivalent% with respect to 1 equivalent of epoxy resins (a). When deviating from this range, the effect of the composite curing is reduced. Of course, in this case, sufficient attention must be paid to gelation during the reaction and stability with time of the carboxylate compound (A).

  Carboxylation reaction can also be made to react without solvent, or can be 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 carboxylation reaction.

  The preferred amount of solvent used should be adjusted as appropriate according to the viscosity and intended use of the resin obtained, but is preferably 90 to 30 parts by weight, more preferably 80 to 50 parts by weight based on the solid content. used.

  Specifically, for example, 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 Examples include gasoline, solvent naphtha, ester solvents, ether solvents, ketone solvents, and the like.

  Examples of ester solvents 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 monoacetates, dialkyl glutarate, dialkyl succinate, dialkyl adipate Polycarboxylic acid alkyl esters such as And the like.

  Examples of ether solvents 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 include ethers and cyclic ethers such as tetrahydrofuran.

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

  In addition, the reaction can be performed in a single or mixed organic solvent such as other reactive compounds (C) described later. In this case, when used as a curable composition, it can be used directly as a composition, which is preferable.

  In the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is a reaction with the reaction product, that is, the epoxy compound (a), the carboxylic acid compound (b), and optionally a solvent or the like added. It is 0.1-10 weight part with respect to the total amount of a thing. 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 octoate, octane. Examples thereof include known general basic catalysts such as zirconium acid.

  Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene and the like as a thermal polymerization inhibitor.

  The end point of this reaction is the time when the acid value of the sample is 1 mgKOH / g or less, preferably 0.5 mgKOH / g or less, while sampling appropriately.

  As a preferable molecular weight range of the reactive carboxylate compound (A) thus obtained, the polystyrene-equivalent weight average molecular weight in GPC is in the range of 5,000 to 30,000, more preferably 6,000 to 20,000. is there.

  When the molecular weight is smaller than this, the toughness of the cured product is not sufficiently exhibited, and when it is larger than this, 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 performed for the purpose of obtaining a reactive polycarboxylic acid (B) by introducing a carboxyl group into the reactive carboxylate compound obtained in the previous step as necessary. That is, a carboxyl group is introduced through an ester bond by adding a polybasic acid anhydride (c) to a hydroxyl group generated by a carboxylation reaction.

  As specific examples of the polybasic acid anhydride (c), for example, any compound having an acid anhydride structure in the molecule can be used, but it is excellent in alkaline aqueous solution developability, heat resistance, hydrolysis resistance and the like. Succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride Is particularly preferred.

  The reaction for adding the polybasic acid anhydride (c) can be performed by adding the polybasic acid anhydride (c) to the carboxylation reaction solution. The amount added should be changed as appropriate according to the application.

  For example, when the polycarboxylic acid compound (B) of the present invention is used as an alkali development type resist, the polybasic acid anhydride (c) is finally added. The resulting reactive polycarboxylic acid compound (B) has a solid acid value (based on JIS K5601-2-1: 1999) of 40 to 120 mg · KOH / g, more preferably 60 to 110 mg · KOH / g. It is preferable to charge the calculated value. When the solid content acid value at this time is within this range, the aqueous alkaline resin developability of the photosensitive resin composition of the present invention exhibits good developability. That is, good patternability and a wide control range for over-development are possible, and no excess acid anhydride remains.

  During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is the amount of the reactant, that is, the carboxylate compound obtained from the epoxy compound (a), the carboxylic acid compound (b), and the like. It is 0.1-10 weight part with respect to the total amount of the reaction material which added the basic acid anhydride (c) and the solvent etc. depending on the case. 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 octoate, octane. Examples include zirconium acid.

  This acid addition reaction can be reacted with no 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, in the case of producing using a solvent in the carboxylation reaction that is the previous step, it may be subjected directly to the acid addition reaction that is the next step without removing the solvent, provided that both reactions are inert. it can. The solvent that can be used may be the same as that used in the carboxylation reaction.

  The preferred amount of solvent used should be adjusted as appropriate according to the viscosity and intended use of the resin obtained, but is preferably 90 to 30 parts by weight, more preferably 80 to 50 parts by weight based on the solid content. Used.

  In addition, the reaction can be performed in a single or mixed organic solvent such as the reactive compound (C). In this case, when used as a curable composition, it can be used directly as a composition, which is preferable.

  Moreover, it is preferable to use the thing similar to the illustration in the said carboxylation reaction as a thermal-polymerization inhibitor.

  In this reaction, the end point is determined when the acid value of the reaction product is within a range of plus or minus 10% of the set acid value while appropriately sampling.

  Specific examples of the reactive compound (C) that can be used in the present invention include so-called reactive oligomers such as radical-reactive acrylates, cation-reactive other epoxy compounds, and vinyl compounds sensitive to both. Can be mentioned.

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

  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, Examples include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

  As polyfunctional (meth) acrylates, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, Diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogen Ε-Caprola of bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and neopent glycol hydroxybivalate Tone adduct di (meth) acrylate, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, trimethylolpropane tri (meth) acrylate, triethylolpropane tri ( (Meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and its ethylene oxide adduct, etc. Is mentioned.

  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, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  Furthermore, as so-called reactive oligomers, urethane acrylate having a functional group capable of acting on active energy rays and a urethane bond in the same molecule, and similarly a functional group capable of acting on active energy rays and an ester bond in the same molecule. Examples thereof include polyester acrylate, epoxy acrylate derived from an epoxy resin, and epoxy acrylate having a functional group capable of acting on active energy rays in the same molecule, and a reactive oligomer in which these bonds are used in combination.

  The cation reactive monomer is not particularly limited as long as it is generally a compound 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) "Syracure UVR-6110" etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as "ELR-4206" manufactured by Union Carbide), limonene dioxide (Daicel Chemical) “Celoxide 3000” manufactured by Kogyo Co., Ltd.), allyl cyclohexylene dioxide, 3,4, -epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxy Cycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide), bis (3 4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane and the like.

  Of these, the reactive compound (C) is most preferably an acrylate that is radically curable. In the case of the cation type, the carboxylic acid and the epoxy react with each other, so that a two-component mixed type is required.

  It is possible to obtain the active energy ray-curable resin composition of the present invention by mixing the carboxylate compound (A) or the reactive polycarboxylic acid compound (B) of the present invention with another reactive compound (C). it can. At this time, you may add another component suitably according to a use.

  The active energy ray-curable resin composition of the present invention contains 97 to 5 parts by weight, preferably 87 to 10 parts by weight of the carboxylate compound (A) and / or the reactive polycarboxylic acid compound (B) in the composition. 3 to 95 parts by weight of the reactive compound (C), more preferably 3 to 90 parts by weight. If necessary, other components may be contained in an amount of 0 to 80 parts by weight.

  The carboxylate compound (A) or the reactive polycarboxylic acid compound (B) in the active energy ray-curable resin composition of the present invention can be appropriately used depending on the application. For example, in the case of a so-called solvent development type in which a pattern is formed by a printing method or an unreacted site is washed away by a solvent or the like without developing even in the same solder resist application, a carboxylate compound (A) is used and alkaline water is used. In the case of developing by using a reactive polycarboxylic acid compound (B). In general, the reactive polycarboxylic acid compound (B) is often used for this application from the viewpoint that the alkaline water development type can easily form a fine pattern. Of course, there is no problem even if (A) and (B) are used in combination.

  The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. 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. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  The colored pigment used in the present invention is used for using the active energy ray resin composition of the present invention as a coloring material. Since 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, particularly excellent dispersibility of the pigment, that is, dispersibility is exhibited.

  Although this mechanism is not clear, since the dispersion proceeds well, the pigment concentration can be increased as a result, and in a composition that requires development, the dispersion is in a more favorable state. Good patterning characteristics are exhibited, and there are few development residues in the development and dissolution area, which is preferable.

  Examples of the color pigment include organic pigments such as phthalocyanine, azo, and quinacridone, carbon black, and inorganic pigments such as titanium oxide. Of these, carbon black is most preferred because of its high dispersibility.

  In the present invention, the molding material refers to a material in which an uncured composition is put into a mold or an object is molded by pressing the mold and then a curing reaction is caused by active energy rays, or a laser is applied to the uncured composition. It refers to a material used for the purpose of irradiating a focused light or the like to cause a curing reaction to form.

  Specific applications include a sheet formed into a flat shape, a sealing material for protecting the element, a so-called nanoimprint material that performs fine molding by pressing a "mold" that has been micro-processed into an uncured composition, Furthermore, particularly suitable applications include peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements, which have particularly severe thermal requirements.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives. Such materials include adhesive materials such as adhesives and adhesives, and resist materials such as solder resists, etching resists, and micromachine resists. Furthermore, a film-forming material is temporarily applied to a peelable substrate to form a film, and then a so-called dry film in which a film is formed by being bonded to the originally intended substrate also corresponds to the film-forming material. .

  Among these, the introduction of the carboxyl group of the reactive polycarboxylic acid compound (B) increases the adhesion to the substrate, and therefore, it is preferably used as an application for coating a plastic substrate or a metal substrate.

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

  In the present invention, the resist material composition is formed by forming a film layer of the composition on a substrate, and then partially irradiating active energy rays such as ultraviolet rays, and the physical difference between irradiated and unirradiated parts. This refers to an active energy ray-sensitive composition that is intended to be drawn using. Specifically, it is a composition used for the purpose of removing the irradiated part or the unirradiated part by dissolving the irradiated part or unirradiated part with, for example, a solvent or an alkaline solution and drawing.

  The active energy ray-curable resin composition for resists of the present invention can be applied to various materials that can be patterned, and is particularly useful for solder resist materials, interlayer insulating materials for build-up methods, and optical waveguides. It is also used for printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates.

  As a particularly suitable application, taking advantage of the property that a tough cured product can be obtained, making use of a permanent resist application such as a solder resist, and the property of good pigment dispersibility, printing inks, color filters, etc. The use of a color resist, particularly a black matrix resist is preferred.

  In addition, it is particularly suitably used as a dry film application that requires mechanical strength before the curing reaction with active energy rays. That is, since the balance of the hydroxyl group and 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 excellent. Developability can be exhibited.

  There are no particular restrictions on the method for forming the film, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater, 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 and curing the active energy ray-curable resin composition of the present invention with active energy rays.

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

  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 a photopolymerization initiator, other additives, a coloring material, and a volatile solvent added for viscosity adjustment for the purpose of imparting coating suitability. Examples of other components that can be used are shown below.

  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, 2,2-diethoxy 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholino-propan-1-one; ant such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Quinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide A general radical type photoinitiator is mentioned.

  As cationic photopolymerization initiators, Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine-based initiator, borate-based initiator, And other photoacid generators.

  Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Shine SI-60L / SI-80L / SI-100L, etc., manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. Examples of Lewis acid iodonium salts include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of Lewis acid sulfonium salts include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide). Etc.), triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide) and the like. Is, as a phosphonium salt of a Lewis acid, triphenyl phosphonium hexafluoroantimonate, and the like.

  Other halides include 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (Trigonal PI, etc., manufactured by AKZO), 2.2-dichloro-1--4- (phenoxyphenyl). ) Etanone (Sandray 1000 manufactured by Sandoz, etc.), α, α, α-tribromomethylphenylsulfone (BMPS manufactured by Steel Manufacturing Chemical Co., Ltd.) and the like. Examples of triazine-based initiators include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine (such as Triazine A manufactured by Panchi), 2, 4-trichloromethyl- (4′-methoxystyryl) -6-triazine (such as Triazine PMS manufactured by Panchim), 2,4-trichloromethyl- (pipronyl) -6-triazine (such as Triazine PP manufactured by Panchim), 2, 4-trichloromethyl- (4′-methoxynaphthyl) -6-triazine (Triazine B, etc., manufactured by Panchi), 2 [2 ′ (5-methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -s- Triazine (manufactured by Sanwa Chemical Co., Ltd.), 2 (2'-furylethyl) Redene) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.) and the like.

  Examples of the borate photopolymerization initiator include NK-3876 and NK-3881 manufactured by Nippon Photosensitive Dye, and other photoacid generators include 9-phenylacridine, 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) V50 etc. manufactured by the company), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [eta-5-2-4- (cyclopentadecyl) (1 , 2,3,4,5,6, eta)-(methylethyl) -benzene] iron (II) hexafluorophosphonate (Irgacure 261, etc., manufactured by Ciba Geigy), bis y5- cyclopentadienyl) bis [2,6-difluoro-3-(1H-pyr-1-yl) phenyl] titanium (Ciba Geigy Corp. CGI-784, etc.) and the like.

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

  Other additives include, for example, thermosetting catalysts such as melamine, thixotropy imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, oxidation An inhibitor or the like can be used.

  Further, as other pigment materials, for example, those not intended for coloring, so-called extender pigments can be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like.

  In addition to this, as resins not showing reactivity to active energy rays (so-called inert polymers), for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, Styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the resin composition in the range of up to 40 parts by weight.

  In particular, when the reactive polycarboxylic acid compound (B) 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 to active energy rays. This is because the carboxyl group derived from (B) remains even after being reacted and cured by active energy rays, and as a result, the cured product is inferior in water resistance and hydrolyzability. Therefore, by using an epoxy resin, the remaining carboxyl group is further carboxylated to form a stronger cross-linked structure. The cation-reactive monomer can be used as the known general epoxy resin.

  Depending on the purpose of use, for the purpose of adjusting the viscosity, a volatile solvent may be added to the resin composition in a range of 50 parts by weight, more preferably up to 35 parts by weight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Moreover, unless otherwise indicated in an Example, a part shows a weight part.

The softening point and epoxy equivalent were measured under the following conditions.
1) Epoxy equivalent: Measured by a method according to JIS K-7236: 2001.
2) Hydroxyl equivalent: measured by a method according to JIS K 0070: 1992 after reacting an epoxy equivalent of the corresponding epoxy resin with an epoxy group in the epoxy resin and an equivalent amount of acetic acid to open the epoxy group. It calculated from the obtained hydroxyl equivalent.
3) Softening point: Measured by a method according to JIS K-7234: 1986.
4) GPC measurement conditions are as follows.
Model: TOSOH HLC-8220GPC
Column: Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml / min. 40 ° C
Detector: Differential refractometer Molecular weight standard: Polystyrene

Synthesis Example 1: Synthesis of epoxy resin Phenol-biphenyl novolac type epoxy resin (Nippon Kayaku Co., Ltd.) as an epoxy resin of the above formula (8) while purging nitrogen in a flask equipped with a stirrer, a reflux condenser, and a stirring device. NC-3000H, epoxy equivalent 288 g / eq., Softening point 70 ° C., compound represented by formula (7), n≈3) 576 g, phenol-aralkyl resin, phenol-biphenyl novolac resin (KAYAHARD, manufactured by Nippon Kayaku Co., Ltd.) GPH65 hydroxyl group equivalent 197 g / eq., Compound represented by formula (5), n≈2) is charged in the amount shown in Table 1, and methyl isobutyl ketone (MIBK) as a solvent is added in a solid content of 60 parts by weight. Prepared. After uniformly dissolving at 70 ° C., 0.5 g of triphenylphosphine was added and stirred at 100 ° C. for 20 hours. After completion of the reaction, oxygen purge was performed to oxidize triphenylphosphine to obtain an epoxy resin (a) resin solution.
Further, the solvent was removed from the obtained resin solution by drying under reduced pressure to obtain an epoxy resin (a). The epoxy equivalent, hydroxyl equivalent, and softening point (sp) were measured and summarized in the table. Further, α (X / Y in formula (I)) was determined from this value.

Note WPE: Epoxy equivalent (g / eq) = Y
OHV: hydroxyl equivalent (g / eq) = X
sp: Softening point (° C)
In Table 1, the molar ratio of GPH-65 indicates the molar ratio of the hydroxyl group to the epoxy group of NC-3000H.
Further, Comparative Example Synthesis Example 1-1 showed data of NC-3000H itself.
The α value shown for gelation in Comparative Synthesis Example 1-2 could not be measured, and was shown as a calculated value. It can be seen that when the α value is less than 2, it is not suitable for the present invention.

Example 1 Preparation of Carboxylate Compound (A) The epoxy resin (a) prepared in Synthesis Example 1-1, 1-2, 1-3, 1-4 was described in the table, and one or more polymerizations in the molecule. Acrylic acid (abbreviation AA, Mw = 72) is listed in the table as a compound (b) having both an ethylenically unsaturated group and one or more carboxyl groups, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether mono as a solvent Acetate was added to a solid content of 80% and reacted at 100 ° C. for 24 hours to obtain a carboxylate compound (A) solution.

Comparative Example 1: Preparation of carboxylate compounds to be compared NC-3000H (manufactured by Nippon Kayaku Co., Ltd.) is described in Table 2, each having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule. As compound (b), acrylic acid (abbreviation AA, Mw = 72) was added in the amount shown in Table 2, 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%. It was made to react for 24 hours and the carboxylate compound (A) solution was obtained.

Example 2: Preparation of reactive polycarboxylic acid compound (B) Tetrahydrophthalic anhydride (abbreviated as THPA) was added as polybasic acid anhydride (c) to 299 g of the carboxylate compound (A) solution obtained in Example 1. After adding propylene glycol monomethyl ether monoacetate as described in Table 3 and a solid content of 65 parts by weight as a solvent and heating to 100 ° C., an acid addition reaction is performed to obtain a reactive polycarboxylic acid compound (B) solution. It was.

Example 3: Preparation of composition for hard coat 20 g of reactive carboxylate compound (A) synthesized in Examples 1 and 2, 4 g of dipentaerythritol hexaacrylate which is a radical curable monomer (C), UV reaction As a mold initiator, 1.5 g of Irgacure 184 was dissolved by heating.
Further, this was coated on a polycarbonate plate by a hand applicator so as to have a film thickness of 20 microns at the time of drying, and solvent drying was carried out in an electric oven at 80 ° C. for 30 minutes. After drying, an ultraviolet-ray exposure apparatus (manufactured by Oak Seisakusho) equipped with a high-pressure mercury lamp was irradiated with an ultraviolet ray with an irradiation dose of 1000 mJ and cured to obtain an article overcoated with the resin composition.
The hardness of the coating film of the article overcoated with this resin composition was measured according to JIS K5600-5-4: 1999, and an impact test was conducted according to ISO6272-1: 2002.

  From the above results, in the case of (A) using the epoxy resin (a) having an α value exceeding 10, it is clear that the curability is good but the impact resistance is inferior. is there. This is presumably because the hydroxyl group contained in the epoxy resin (a) serving as the basic skeleton exhibits impact resistance.

Example 4: Preparation of dry film type resist composition 54.44 g of the reactive polycarboxylic acid compound (B) obtained in Example 2 and HX-220 (trade name: Nippon Chemical Co., Ltd.) as the other reactive compound (C) Yakugure 907 (manufactured by Nippon Kayaku Co., Ltd.) 0 .47 g, 14.83 g of GTR-1800 (manufactured by Nippon Kayaku) as the curing component, 1.05 g of melamine as the thermosetting catalyst, and 20.95 g of methyl ethyl ketone as the concentration adjusting solvent, kneaded with a bead mill and uniformly dispersed A resist resin composition was obtained.
The obtained composition was uniformly applied to a polyethylene terephthalate film as a support film by a roll coating method, passed through a hot air drying furnace at a temperature of 70 ° C., and a resin layer having a thickness of 30 μm was formed. A polyethylene film to be a protective film was attached to obtain a dry film. The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 μm, polyimide film thickness: 25 μm) using a heating roll at a temperature of 80 ° C., and a resin layer was attached to the entire surface of the substrate while peeling off the protective film.

  Next, in order to estimate the mask on which the circuit pattern was drawn and sensitivity using an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW), Kodak Step Tablet No. 2 was irradiated with ultraviolet rays. Then, the film on a dry film was peeled and the peeling state was confirmed. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin on the non-irradiated part of the ultraviolet rays. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction in a hot air drier at 150 ° C. for 60 minutes to obtain a cured film.

Evaluation of peelability The peelability was determined by the ease of the film to be peeled after completion of exposure.
○ +: It peels off very cleanly at the interface.
○: It peels cleanly at the interface.
(Triangle | delta): If it peels carefully, it can peel.
Δ-: Cannot be peeled off unless peeled off very carefully.
X: There exists a part which aggregates and peels partially (or the whole surface).

Sensitivity evaluation Sensitivity was determined based on how many density portions remained in the exposed portion that passed through the step tablet during development. The higher the number of steps (value), the higher sensitivity is determined in the dark part of the tablet (unit: step).

Evaluation of developability The developability was evaluated based on the so-called break time (unit: second) until the pattern shape portion was completely developed when developing the exposed portion that passed through the pattern mask.

Curability evaluation Curability evaluation was shown by pencil hardness of the cured film after heating at 150 ° C.
The evaluation method was based on JIS K5600-5-4: 1999.

  As apparent from the above results, when the value of α is too large (Comparative Example 4-1), the peelability of the dry film is poor.

Example 5: Evaluation of pigment dispersibility 20 g of the reactive polycarboxylic acid compound (B) obtained in Example 2 and DPHA (trade name: Nippon Kayaku Co., Ltd., acrylate single as the other reactive compound (C) 5.0 g, propylene glycol monomethyl ether acetate 10 g as an organic solvent, and Mitsubishi carbon black MA-100: 10 g as a color pigment were mixed and stirred. 35 g of glass beads were put therein and dispersed for 1 hour with a paint shaker.
The dispersion after the dispersion was coated on a polyethylene terephthalate film with a wire bar coater # 2, and dried for 10 minutes with a hot air dryer at 80 ° C.
The gloss of the coating film surface after drying was measured using a 60 ° reflection gloss meter to evaluate the dispersibility of the carbon black. At this time, a higher measured gloss value indicates better pigment dispersibility.

  As is clear from the above results, when the α value of the epoxy resin (a) serving as the basic skeleton of the reactive polycarboxylic acid (B) in the present invention exceeds 10, it is clear that the dispersibility of the carbon black is inferior. became.

  As the active energy ray-curable resin of the present invention, as a material having both curability and toughness, a hard coat material, a resist material that can be developed with an alkali, and an application that exhibits good pigment dispersibility have been shown. A curable printing ink, a color resist, particularly a material having both resist suitability such as pigment dispersibility and developability, can be particularly preferably used for a black matrix for LCD.

Claims (12)

In the following epoxy resin (a) and one or more polymerizable in the molecule ethylenically unsaturated group and a compound having both one or more carboxyl groups (b) and reactive epoxy obtained by reacting a carboxylate compound (A) There,
Formula (1)

And the following general formula (2) (in the general formula (2), Ar is represented by the general formula (3) or (4), m represents the number of substituents R and 1 to 3) N represents an average value of the number of repetitions of 1 to 10, and R represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a trifluoromethyl group, an allyl group or an aryl group, respectively. And each R may be the same or different, and Ar may be the same or different.)

An epoxy resin (a) obtained from a phenol aralkyl resin (P) having a structure shown in FIG.
(I) Epoxy resin (a) obtained by partially epoxidizing the phenol aralkyl resin (P).
(Ii) an epoxy resin (a) obtained by reacting a phenol aralkyl resin (P) with a phenol aralkyl type epoxy resin (E2) ;
When the epoxy resin (a) is represented by the following formula (I) when the hydroxyl group equivalent of the epoxy resin (a) is X (g / eq.) And the epoxy equivalent is Y (g / eq.):
2 ≦ (X / Y) ≦ 15 (I)
And the softening point of the epoxy resin (a) is 75 to 105 ° C.
Reactive epoxycarboxylate compound (A).   The reactive epoxy carboxy according to claim 1, wherein an epoxy resin (a) obtained by using 1.0 to 5.0 mol of epihalohydrin is used with respect to 1 mol of a hydroxyl group of the phenol aralkyl resin (P). Rate compound (A).   An epoxy resin (a) obtained by reacting 1 mol of the epoxy group of the phenol aralkyl type epoxy resin (E2) so that the hydroxyl group of the phenol aralkyl resin (P) is 0.01 to 0.3 mol is used. The reactive epoxycarboxylate compound (A) according to claim 1. A reactive polycarboxylic acid compound (B) obtained by reacting the carboxylate compound (A) according to any one of claims 1 to 3 with a polybasic acid anhydride (c). An active energy ray-curable resin composition comprising the carboxylate compound (A) according to any one of claims 1 to 3 and / or the reactive polycarboxylic acid compound (B) according to claim 4 . The active energy ray-curable resin composition according to claim 5, further comprising a reactive compound (C) other than (A) and (B). Furthermore, a coloring pigment is contained, The active energy ray hardening-type resin composition of Claim 5 or Claim 6 characterized by the above-mentioned. The active energy ray-curable resin composition according to any one of claims 5 to 7 , which is a molding material. The active energy ray-curable resin composition according to any one of claims 5 to 8 , which is a film forming material. The active energy ray-curable resin composition according to any one of claims 5 to 9 , which is a resist material composition. A cured product of the active energy ray-curable resin composition according to any one of claims 5 to 10 . An article overcoated with a cured product obtained by curing the resin composition according to any one of claims 5 to 10 .