阅读说明：本技术 环氧丙烯酸酯树脂、碱可溶性树脂及其制造方法、硬化性与感光性树脂组合物及其硬化物 (Epoxy acrylate resin, alkali-soluble resin and method for producing the same, curable and photosensitive resin composition and cured product thereof ) 是由 宗正浩 石原一男 于 2020-09-11 设计创作，主要内容包括：本发明提供一种环氧丙烯酸酯树脂、碱可溶性树脂及其制造方法、硬化性与感光性树脂组合物及其硬化物。一种环氧丙烯酸酯树脂或碱可溶性树脂、以及在所述树脂中调配引发剂而成的硬化性树脂组合物或感光性树脂组合物。所述环氧丙烯酸酯树脂是使将二环戊二烯型酚树脂环氧化而成的树脂与(甲基)丙烯酸反应而得,所述碱可溶性树脂是使所述环氧丙烯酸酯树脂与多元羧酸类反应而得。环氧丙烯酸酯树脂由下述通式(1)表示,X为式(1a)所表示的含不饱和键的基,碱可溶性树脂中,式(1a)中的OH基的50％以上为式(3)所表示的含羧基的基。(The invention provides an epoxy acrylate resin, an alkali-soluble resin and a manufacturing method thereof, a curable and photosensitive resin composition and a cured product thereof. An epoxy acrylate resin or an alkali-soluble resin, and a curable resin composition or a photosensitive resin composition obtained by blending an initiator with the resin. The epoxy acrylate resin is obtained by reacting (meth) acrylic acid with a resin obtained by epoxidizing a dicyclopentadiene type phenol resin, and the alkali-soluble resin is obtained by reacting a polycarboxylic acid with the epoxy acrylate resin. The epoxy acrylate resin is represented by the following general formula (1), X is an unsaturated bond-containing group represented by the formula (1a), and in the alkali-soluble resin, 50% or more of OH groups in the formula (1a) are carboxyl-containing groups represented by the formula (3).)

1. An epoxy acrylate resin represented by the following general formula (1),

-CH₂-CH(OH)-CH₂-O-CO-CR²＝CH₂ (1a)

in the formula, R¹Each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group, n represents a number of 1 to 10 on the average, and X is an unsaturated bond-containing group represented by the formula (1 a); r²Represents a hydrogen atom or a methyl group.

2. An alkali-soluble resin represented by the following general formula (2) and having a carboxyl group and a polymerizable unsaturated group in the molecule,

-CH₂-CH(OL)-CH₂-O-CO-CR²＝CH₂ (2a)

-CO-M-(COOH)p (3)

in the formula, R¹Each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group, n represents a number of 1 to 10 on the average, Y represents an unsaturated bond-containing group having L represented by the formula (2a), L represents a hydrogen atom or a carboxyl group-containing group represented by the formula (3), and 50 mol% or more of L is the carboxyl group-containing group; r²Represents a hydrogen atom or a methyl group, M represents a p +1 valent carboxylic acid residue, and p is 1 or 2.

3. A curable resin composition comprising the epoxy acrylate resin according to claim 1 and a polymerization initiator.

4. A photosensitive resin composition comprising the alkali-soluble resin according to claim 2, a photopolymerizable monomer having at least one polymerizable unsaturated group, and a photopolymerization initiator.

5. A photosensitive resin composition, wherein the photosensitive resin composition according to claim 4 further contains an epoxy compound.

6. The photosensitive resin composition according to claim 4 or 5, wherein the photopolymerization initiator is contained in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the alkali-soluble resin and the photopolymerizable monomer.

7. The photosensitive resin composition according to claim 5, wherein the epoxy compound is contained in an amount of 10 to 40 parts by mass based on 100 parts by mass of the total of the alkali-soluble resin and the photopolymerizable monomer.

8. A cured product obtained by curing the curable resin composition according to claim 3.

9. A cured product obtained by curing the photosensitive resin composition according to any one of claims 4 to 7.

10. A process for producing an alkali-soluble resin, which comprises reacting an epoxy acrylate resin represented by the following general formula (11) with a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, and a tetracarboxylic acid or an acid dianhydride thereof,

in the formula, R¹R represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group²Represents a hydrogen atom or a methyl group.

11. An alkali-soluble resin having a structure represented by general formula (12) obtained by the production method according to claim 10,

-CO-M-(COOH)p (3)

in the formula, R²Represents a hydrogen atom or a methyl group, A represents a tetravalent carboxylic acid residue, L represents a carboxyl group-containing group represented by the formula (3) or a hydrogen atom, Z represents a structure represented by the formula (12a), and m is a number having an average value of 1 to 20; r¹Represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group; m represents a p +1 valent carboxylic acid residue, and p is 1 or 2.

12. A photosensitive resin composition comprising the alkali-soluble resin according to claim 11, a photopolymerizable monomer having at least two polymerizable unsaturated groups, a photopolymerization initiator and a solvent as essential components.

13. The photosensitive resin composition according to claim 12, further comprising an epoxy resin having two or more epoxy groups.

14. The photosensitive resin composition according to claim 12 or 13, wherein the photopolymerization initiator is contained in an amount of 0.1 to 30 parts by mass and the solvent is contained in an amount of 10 to 40 parts by mass, based on 100 parts by mass of the total of the alkali-soluble resin and the photopolymerizable monomer.

15. A cured product obtained by curing the photosensitive resin composition according to any one of claims 12 to 14.

Technical Field

The present invention relates to an epoxy acrylate resin, a curable resin composition using the same, an unsaturated group-containing alkali-soluble resin and a method for producing the same, a photosensitive resin composition containing the alkali-soluble resin as an essential component, and a cured product thereof. The curable resin composition, the photosensitive resin composition and the cured product thereof of the present invention can be applied to a permanent protective film such as an overcoat, an undercoat and an insulating coating for producing a circuit board; resist layers such as solder resist, plating resist, and etching resist; an insulating film for multilayering a wiring board on which a semiconductor element is mounted, a gate insulating film for a semiconductor, a photosensitive adhesive, a film for gas barrier, a sealing material for a semiconductor Light-Emitting element such as a lens or a Light Emitting Diode (LED), a top coat of paint or ink, a hard coat of plastic, a rust-proof film of metal, and the like.

Background

Solder resist inks are generally applied by screen printing as a coating film forming method in view of the use of an insulating protective film for an exposed conductor circuit of a printed wiring board or the use of preventing solder from adhering to an unnecessary solder portion of a circuit, and the cured film is required to have solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, and electrolytic corrosion resistance. These types of solder resists include both heat-curable type and ultraviolet-curable type, and epoxy resins are mainly used for the former and epoxy acrylate resins are used for the latter in many cases. In recent years, however, image formation by a photosensitive method has become the mainstream of insulating film formation using a solder resist instead of a screen printing method due to miniaturization of conductor circuit patterns of various printed wiring boards, improvement of positional accuracy, and miniaturization of mounted components. In addition, although an organic solvent has been conventionally used for developing a resist by a photolithography method, it is desirable to use a dilute aqueous alkaline solution from the viewpoint of air pollution and safety. Against this background, solder resists have a problem that conventional epoxy resins and epoxy acrylate resins suitable for screen printing are unsatisfactory.

As a countermeasure for the photosensitive method and the development with a dilute alkaline aqueous solution, for example, a phenol novolac type epoxy acrylate resin or a bisphenol a epoxy acrylate resin, or a half-esterified product produced by the reaction of the epoxy acrylate resin and an acid dianhydride, and the like are known (patent documents 1 and 2). However, when these conventional epoxy acrylate resins or acid anhydride-modified products thereof are used as resin compositions for solder resists, development properties of dilute alkaline aqueous solutions are satisfactory, but in order to stabilize physical properties, the curing temperature needs to be at least 180 ℃ or higher, and not only is the heating equipment cost high, but also, for example, when a glass epoxy substrate is used as a core substrate, the curing temperature is too high and there is a possibility that the substrate is discolored or warped. Further, the cured coating obtained from these conventional epoxy acrylate resins or their acid anhydride-modified products has a problem that solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, electrolytic corrosion resistance, or the like is insufficient.

In recent years, with the increase in density of printed wiring boards, reliability, pressure cooker resistance, and heat cycle resistance have been required for insulating layers for chip mounting boards such as build-up boards for multi-chip modules (MCM) and Chip Scale Packages (CSP), and there has been a problem that sufficient reliability cannot be exhibited even when the conventional epoxy acrylate resin or its acid anhydride-modified product is used as a resin composition for solder resists.

In addition, with the recent increase in performance and precision of electronic devices, display members, and the like, electronic components used therein are required to be downsized and densified. Further, the processability of the insulating materials used for these materials is also required to be refined and the sectional shape of the processed pattern is also required to be optimized. As an effective means for microfabrication of an insulating material, a method of patterning by exposure and development is known, in which a photosensitive resin composition is used, and various characteristics such as high sensitivity, adhesion to a substrate, reliability, heat resistance, and chemical resistance are required. In addition, various studies have been made on the use of an organic insulating material for a gate insulating film for an organic Thin Film Transistor (TFT), and there is a need to reduce the operating voltage of the organic TFT by thinning the gate insulating film. Here, in the case of an organic insulating material having a dielectric breakdown voltage of about 1MV/cm, application of a thin film having a thickness of about 0.2 μm as an insulating film is studied.

In the conventional insulating material containing a photosensitive resin composition, i-ray (365nm), which is one of line spectra of a mercury lamp, is mainly used as an exposure wavelength for performing photo-curing, by utilizing a photo-curing reaction caused by a reaction between a photoreactive alkali-soluble resin and a photopolymerization initiator. However, the i-ray is absorbed by the photosensitive resin itself or the colorant, and the light-hardening degree is decreased. In addition, if the film is thick, the absorption amount increases. Therefore, the exposed portion has a difference in the crosslinking density with respect to the film thickness direction. Thus, even if the surface of the coating film is sufficiently photo-cured, the bottom surface of the coating film is hard to photo-cure, and therefore, it is significantly difficult to cause a difference in the crosslink density between the exposed portion and the unexposed portion. Thus, it is difficult to obtain a photosensitive insulating material which has desired pattern dimensional stability, development margin (margin), pattern adhesiveness, edge shape (edge) and cross-sectional shape of the pattern and can be developed with high resolution.

In general, photosensitive resin compositions for such applications include a composition containing a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, a photopolymerization initiator, and the like, and are technically disclosed as being applicable to color filter materials. For example, patent documents 5 and 6 disclose copolymers of (meth) acrylic acid or (meth) acrylic ester having a carboxyl group, maleic anhydride, and other polymerizable monomers as binder resins. However, the disclosed copolymer is a random copolymer, and therefore, distribution of alkali dissolution rate occurs in a light irradiated portion and a light non-irradiated portion, a margin at the time of development operation is narrow, and it is difficult to obtain a pattern shape or a fine pattern with an acute angle. Particularly, in the case where a pigment is contained at a high concentration, the exposure sensitivity is significantly reduced, and a fine negative pattern cannot be obtained.

Further, patent document 3 discloses that an alkali-soluble unsaturated compound having a polymerizable unsaturated group and a carboxyl group in one molecule is effective for negative pattern formation of a color filter or the like. However, the disclosed alkali-soluble unsaturated compound is expected to be highly sensitive to the combination of the binder resin and the polyfunctional polymerizable monomer because it is insolubilized by light irradiation, but in the case of the proposed compound, since acrylic acid and acid anhydride as polymerizable unsaturated groups are arbitrarily added to hydroxyl groups of a phenol oligomer (phenol oligomer), a wide distribution is observed in the molecular weight of each molecule or the amount of carboxyl groups, and the distribution of the alkali dissolution rate of the alkali-soluble resin is widened, it is difficult to form a fine negative pattern.

Further, patent document 4 discloses multifunctionalization of an alkali-soluble resin composition in which the molecular weight of a carboxyl-containing copolymer is increased. However, since the number of polymerizable unsaturated bonds is small, the crosslinking density cannot be sufficiently obtained, and there is room for improvement in the copolymer structure such as an increase in the ratio of polymerizable unsaturated bonds in one molecule.

On the other hand, patent documents 7, 8, 9, and 10 disclose liquid resins using a reaction product of an epoxy acrylate having a bisphenol fluorene structure and an acid anhydride. However, the exemplified resin has a small molecular weight because it is a reaction product of an epoxy acrylate and an acid anhydride. Therefore, it is difficult to increase the difference in alkali solubility between the exposed portions and the unexposed portions, and a fine pattern cannot be formed.

Thus, the following compositions do not exist: low-temperature curing is possible in consideration of the restriction of heat resistance of a substrate material, manufacturing facilities, and the like, development can be performed by a photolithography method using dilute alkaline water, and solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, and electrolytic corrosion resistance required for a solder resist for a printed wiring board are sufficiently satisfied; reliability required for an insulating layer hardened film of a high-density mounting substrate such as an MCM; and a folding endurance required for a flexible display, a touch panel, or the like.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open No. Sho 61-243869

[ patent document 2] Japanese patent laid-open No. 2003-026762

[ patent document 3] Japanese patent laid-open No. Hei 4-340965

[ patent document 4] Japanese patent laid-open No. Hei 9-325494

[ patent document 5] Japanese patent laid-open No. Sho 61-213213

[ patent document 6] Japanese patent laid-open No. Hei 1-152449

[ patent document 7] Japanese patent laid-open No. Hei 4-345673

[ patent document 8] Japanese patent laid-open No. Hei 4-345608

[ patent document 9] Japanese patent laid-open No. Hei 4-355450

[ patent document 10] Japanese patent laid-open No. Hei 4-363311

Disclosure of Invention

[ problems to be solved by the invention ]

Accordingly, an object of the present invention is to provide a novel epoxy acrylate resin that can be photo-cured or thermally cured, and to provide a photosensitive resin composition that can be patterned with excellent resolution by alkali development. Further, a curable resin composition excellent in reliability such as developability, solder heat resistance, coating film hardness, adhesiveness, and chemical resistance required for a solder resist, an insulating film, or the like of a printed wiring board, and a cured product thereof are provided, and a cured film having a characteristic of exhibiting excellent chemical resistance after undergoing a processing process such as electrode formation and pressure folding resistance is provided.

[ means for solving problems ]

The present inventors have made extensive studies to solve the above problems, and as a result, they have found that a curable resin composition using an epoxyacrylate resin obtained by epoxidizing a dicyclopentadiene type phenol resin obtained by reacting a2, 6-disubstituted phenol with dicyclopentadiene is preferable for obtaining a cured product (insulating film) excellent in reliability, and that a photosensitive resin composition using an alkali-soluble resin obtained by reacting the epoxyacrylate resin with a dicarboxylic acid, a tricarboxylic acid or an acid-monoanhydride thereof is preferable for a solder resist, an insulating film or the like of a printed wiring board.

That is, the present invention is an epoxy acrylate resin represented by the following general formula (1).

[ solution 1]

-CH₂-CH(OH)-CH₂-O-CO-CR²＝CH₂(1a)

Here, R¹Each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group, n represents a number of 1 to 10 on the average, and X is an unsaturated bond-containing group represented by the formula (1 a). R²Represents a hydrogen atom or a methyl group.

The present invention also provides an alkali-soluble resin (a) represented by the following general formula (2), which has a carboxyl group and a polymerizable unsaturated group in one molecule.

[ solution 2]

-CH₂-CH(OL)-CH₂-O-CO-CR²＝CH₂ (2a)

-CO-M-(COOH)p (3)

Here, R¹Each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group, n represents a number of 1 to 10 on the average, Y represents an unsaturated bond-containing group having L represented by the formula (2a), L represents a hydrogen atom or a carboxyl group-containing group represented by the formula (3), and 50 mol% or more of L is the carboxyl group-containing group. R²Represents a hydrogen atom or a methyl group, M represents a p +1 valent carboxylic acid residue, and p is 1 or 2.

The curable resin composition of the present invention contains the epoxy acrylate resin and a polymerization initiator.

The present invention also provides a photosensitive resin composition comprising the alkali-soluble resin (a), a photopolymerizable monomer having at least one polymerizable unsaturated group, and a photopolymerization initiator. Another embodiment of the present invention relates to a cured product obtained by curing the photosensitive resin composition.

The present invention also relates to a method for producing an alkali-soluble resin (B) by reacting (a) a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, and (B) a tetracarboxylic acid or an acid dianhydride thereof with an epoxy acrylate resin represented by the following general formula (11).

[ solution 3]

In the formula, R¹R represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group²Represents a hydrogen atom or a methyl group.

Another embodiment of the present invention relates to an alkali-soluble resin having a structure represented by general formula (12), which is obtained by the production method.

[ solution 4]

-CO-M-(COOH)p (3)

In the formula, R²Represents a hydrogen atom or a methyl group, A represents a tetravalent carboxylic acid residue, L represents a substituent represented by the formula (3) or a hydrogen atom, and Z represents the formula (1)2a) In the structure, m is a number having an average value of 1 to 20.

In the formula (12a), R¹Represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group.

In the formula (3), M represents a p +1 valent carboxylic acid residue, and p is 1 or 2.

Another embodiment of the present invention is a photosensitive resin composition containing the alkali-soluble resin (B), a photopolymerizable monomer having at least two polymerizable unsaturated groups, a photopolymerization initiator, and a solvent as essential components. Another embodiment of the present invention relates to a cured product obtained by curing the photosensitive resin composition.

[ Effect of the invention ]

According to the present invention, a novel epoxy acrylate resin which can be cured by light or heat is provided, and by containing an alkali-soluble resin which is an acid anhydride adduct of the epoxy acrylate resin, a photosensitive resin composition capable of forming a fine cured film pattern by a photolithography method can be provided. Further, according to the present invention, since the cured film pattern is low in thermal expansion, excellent in chemical resistance (alkali resistance and the like), excellent in adhesion to a substrate, heat resistance, electrical reliability and the like, a cured film pattern of a solder resist for a printed wiring board, an insulating film which needs to be subjected to photo patterning, and the like can be provided. In addition, the cured product has a low elastic modulus and excellent folding characteristics, and is useful as an insulating film for a flexible display or a touch panel.

Detailed Description

The present invention will be described in detail below. The epoxy acrylate resin of the present invention is represented by the general formula (1). In the present specification, unless otherwise specified, the epoxy acrylate resin includes an epoxy methacrylate resin.

In the general formula (1), R¹Represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or an allyl group. The alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, methylbutyl, n-pentyl, neopentyl, and neopentylA hydrocarbon group such as hexyl, dimethylbutyl, n-heptyl, methylhexyl, trimethylbutyl, n-octyl, dimethylpentyl, ethylpentyl, isooctyl, and ethylhexyl, or a cycloalkyl group having 5 to 8 carbon atoms such as cyclohexyl, cycloheptyl, cyclooctyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, and methylcycloheptyl, but is not limited thereto. From the viewpoint of ease of acquisition and reactivity when a cured product is produced, a methyl group or a phenyl group is preferable.

n is a repeating number and represents a number of 1 to 10 on the average, preferably 1.05 to 5, more preferably 1.1 to 3.5, still more preferably 1.2 to 2, and particularly preferably 1.25 to 1.5. The average value is a number average.

X is an unsaturated bond-containing group represented by the formula (1a), R²Represents a hydrogen atom or a methyl group. In formula (1a), formula (2a) and formula (3), CO is a carbonyl group (C ═ O), and may be represented by CO or OC.

The epoxy acrylate resin of the general formula (1) can be advantageously obtained by reacting an epoxy resin (a) represented by the following general formula (4) with (meth) acrylic acid. The epoxy resin is obtained by epoxidizing a dicyclopentadiene phenol resin obtained by reacting a2, 6-disubstituted phenol with dicyclopentadiene.

[ solution 5]

In the general formula (4), R¹And n and R of the formula (1)¹And n is the same. G represents a glycidyl group.

The reaction of the epoxy resin with (meth) acrylic acid can be carried out by a conventional method. For example, an epoxy group is reacted with an equimolar amount of (meth) acrylic acid. In order to react all epoxy groups with (meth) acrylic acid, (meth) acrylic acid may be used in a slightly excess amount compared to the equimolar amount of epoxy groups and carboxyl groups. The reaction temperature is usually 50 ℃ to 150 ℃ and the reaction time is usually 1 hour to 20 hours. The solvent, catalyst and other reaction conditions used in this case are not particularly limited.

The solvent is preferably one having no hydroxyl group and a boiling point higher than the reaction temperature, for example. Examples of such a solvent include: a cellosolve-based solvent containing ethyl cellosolve acetate, butyl cellosolve acetate, and the like; high boiling point ether-based or ester-based solvents including diethylene glycol dimethyl ether (diglyme), ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; ketone solvents including cyclohexanone and diisobutyl ketone; aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene.

Examples of the catalyst include: amines such as triethylamine and 1, 4-diaza [5,4,0] bicycloundecene-7; ammonium salts including tetraethylammonium bromide and triethylbenzylammonium chloride; phosphines including triphenylphosphine and tris (2, 6-dimethoxyphenyl) phosphine; and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole.

Further, hydroquinone, 4-methylquinoline, phenothiazine and the like may be added as a polymerization inhibitor when the reaction is carried out. In addition, in order to suppress the polymerization reaction due to the unsaturated bond, the reaction is carried out under a gas flow of air or the like as the case may be.

Further, as a method for producing the epoxy resin (A) as a raw material of the epoxy acrylate resin, for example, a production method described in Japanese patent laid-open No. 5-339341 can be referred to.

The epoxy resin (a) is first synthesized by reacting a2, 6-disubstituted phenol compound with dicyclopentadiene in the presence of a catalyst such as boron trifluoride-ether complex, to thereby synthesize a phenol resin represented by the following general formula (5). Then, it can be obtained by reacting the obtained phenol resin with epihalohydrin (epihalohydrin) such as epichlorohydrin to perform epoxidation.

[ solution 6]

In the general formula (5), R¹And n and R of the formula (1)¹And n is the same.

The phenol resin represented by the general formula (5) can be obtained by: dicyclopentadiene is added in an amount of preferably 0.1 to 0.2 mol, more preferably 0.1 to 0.15 mol, based on 1 mol of the 2, 6-disubstituted phenol compound, and reacted in the presence of a catalyst, and then, if necessary, the unreacted 2, 6-disubstituted phenol compound is removed.

Examples of the phenols as the raw material of the phenol resin represented by the above general formula (5) include 2, 6-dimethylphenol, 2, 6-diethylphenol, 2, 6-dipropylphenol, 2, 6-diisopropylphenol, 2, 6-di (n-butyl) phenol, 2, 6-di (tert-butyl) phenol, 2, 6-dihexylphenol, 2, 6-dicyclohexylphenol, 2, 6-diphenylphenol and the like, and 2, 6-dimethylphenol is preferable from the viewpoint of easiness of obtaining and reactivity in producing a cured product.

The acid catalyst used in the reaction of phenols with dicyclopentadiene is a lewis acid, specifically a boron trifluoride compound such as boron trifluoride, boron trifluoride-phenol complex, or boron trifluoride-ether complex; metal chlorides such as aluminum chloride, tin chloride, zinc chloride, tetrachloroethane, and ferric chloride; and organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid, among which boron trifluoride-ether complex is preferable in terms of ease of handling. The amount of the acid catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of dicyclopentadiene in the case of a boron trifluoride-ether complex.

As the reaction method, the following manner is possible: 2, 6-disubstituted phenol and a catalyst are put into a reactor, and dicyclopentadiene is dripped for 1 to 10 hours.

The reaction temperature is 50-200 ℃, and the reaction time is 1-10 hours.

After the reaction is completed, an alkali such as sodium hydroxide or potassium hydroxide is added to deactivate the catalyst, and then unreacted 2, 6-disubstituted phenol is recovered under reduced pressure.

Thereafter, in order to separate and purify the reaction product, a solvent such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, or the like is added to dissolve the reaction product, and after washing with water, the solvent is recovered under reduced pressure, whereby the desired phenol resin can be obtained.

In addition, when the reaction is carried out, a solvent such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or the like may be used depending on the need for viscosity adjustment or the like.

The epoxy resin (a) used in the present invention is obtained by reacting the phenol resin obtained by the above-mentioned method with an epihalohydrin. This reaction is carried out according to a conventional method.

For example, it can be obtained by: adding an alkali metal hydroxide such as sodium hydroxide to a mixture of a phenol resin and an epihalohydrin in an excess molar amount relative to hydroxyl groups of the phenol resin in the form of a solid or a concentrated aqueous solution, and reacting at a reaction temperature of 30 to 120 ℃ for 0.5 to 10 hours; or adding quaternary ammonium salt such as tetraethylammonium chloride and the like as a catalyst into the phenol resin and the epihalohydrin with excessive moles, reacting at the temperature of 50-150 ℃ for 1-5 hours to obtain polyhalohydrin ether (polyhalohydrin ether), adding alkali metal hydroxide such as sodium hydroxide and the like into the obtained polyhalohydrin ether in the form of solid or concentrated aqueous solution, and reacting at the temperature of 30-120 ℃ for 1-10 hours.

In the reaction, the amount of epihalohydrin used is in the range of 1 to 10 times, preferably 2 to 5 times, the molar amount of the epihalohydrin used relative to the hydroxyl groups of the phenol resin, and the amount of the alkali metal hydroxide used is in the range of 0.85 to 1.1 times, the molar amount of the alkali metal hydroxide used relative to the hydroxyl groups of the phenol resin.

The epoxy resin (a) obtained by the reaction contains unreacted epihalohydrin and a halide of an alkali metal, and therefore, the unreacted epihalohydrin is evaporated and removed from the reaction mixture, and the halide of the alkali metal is removed by a method such as extraction with water, filtration and separation, whereby the target epoxy resin (a) can be obtained.

The dicyclopentadiene type epoxy resin preferably has an epoxy equivalent (g/eq.) of 244 to 3700, more preferably 260 to 2000, and still more preferably 270 to 700.

In particular, when the phenol resin is a diphenol compound represented by the following general formula (14) which is only an n-1 isomer of the general formula (5), the obtained epoxy resin is an epoxy resin (B) represented by the following general formula (15).

[ solution 7]

In the formula, R¹And R of the general formula (1)¹Are the same meaning.

[ solution 8]

In the formula, R¹And R of the general formula (1)¹The same meaning is true, and k represents a number of 0 to 5 in average.

The epoxy resin (B) can be obtained by the same method as the epoxy resin (a) by using a phenol resin as a raw material as the diphenol compound.

The molecular weight distribution of the obtained epoxy resin (B) can be changed by changing the charging ratio of the diphenol compound and the epihalohydrin in the epoxidation reaction, so that the closer the epihalohydrin is used to an equimolar amount to the hydroxyl group of the diphenol compound, the higher the molecular weight distribution, and the closer the epihalohydrin is used to a 20-fold molar amount to the hydroxyl group of the diphenol compound, the lower the molecular weight distribution. Further, the obtained epoxy resin can also be made to have a high molecular weight by allowing the diphenol compound to act again on the obtained epoxy resin.

However, in order to appropriately control the molecular weight of the alkali-soluble resin of the present invention, the content of k-0 mer in the general formula (15) is preferably 50% or more, more preferably 70% or more, further preferably 85% or more, and particularly preferably 95% or more. Further, k is in the range of 0 to 5, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0 to 0.5 in terms of average value. When the amount is within this range, an excessive increase in molecular weight due to addition of the acid dianhydride is easily suppressed.

In the present specification, unless otherwise specified, the dicyclopentadiene type epoxy resin refers to both the epoxy resin (a) represented by the above general formula (4) and the epoxy resin (B) represented by the above general formula (15).

The dicyclopentadiene type epoxy resin (A) is reacted with acrylic acid or methacrylic acid to produce an epoxy acrylate resin (A) represented by the general formula (1). In particular, the epoxy acrylate resin composition is distinguished from the epoxy acrylate resin (B0) represented by the general formula (11) when n is 1. When the dicyclopentadiene type epoxy resin (B) is reacted with acrylic acid or methacrylic acid, an epoxy acrylate resin (B) in which a glycidyl group is substituted with a group represented by the formula (1a) in the general formula (15) is obtained.

In the present specification, unless otherwise specified, the epoxy acrylate resin refers to all of the epoxy acrylate resin (a), the epoxy acrylate resin (B0), and the epoxy acrylate resin (B).

The epoxy acrylate resin may contain by-products derived from side reactions or by-products derived from by-products contained in the synthesis of raw materials, and may be used after purifying and removing them, or may be used in a state in which a part of the by-products remains, unless the quality or the use of the product is not impaired.

The epoxy acrylate resin can be made into a curable resin composition as described later, and can be made into a cured product.

The alkali soluble resins of the present invention are obtainable from epoxy acrylate resins. In this sense, epoxy acrylate resins are also intermediates for alkali soluble resins.

In the general formula (2), R¹N is the same as the general formula (1), Y is a group having an unsaturated bond represented by the formula (2a) and L is a hydrogen atom or a carboxyl group-containing group represented by the formula (3). Here, at least 50 mol% of L is a carboxyl group-containing group represented by the formula (3). R²The same as in formula (1a), M represents a p +1 valent carboxylic acid residue, and p is 1 or 2. Here, the carboxylic acid residue is a group generated by removing a carboxyl group or an acid anhydride group from a divalent or trivalent carboxylic acid or carboxylic acid anhydride.

L may be all the carboxyl group-containing groups represented by the formula (3), but may have both a hydrogen atom and a carboxyl group-containing group in the molecule. The carboxyl group-containing group is 50 mol% or more, preferably 70 mol% to 100 mol%, more preferably 90 mol% to 100 mol%, and still more preferably 100 mol% in all L. Since the polybasic acid groups are reactive with the base, the base-soluble resin or its polymerization reaction product (unhardened product) is rendered alkali-soluble. By changing the presence ratio of the polybasic acid groups in L, the alkali solubility can be adjusted, and the alkali developability can be optimized. Further, by changing the type of the polybasic acid group represented by the general formula (6), the resin characteristics such as alkali developability can also be changed.

The alkali-soluble resin (a) represented by the general formula (2) can be obtained by reacting the hydroxyl group of the epoxy acrylate resin (a) represented by the general formula (1) with a carboxylic acid selected from a dicarboxylic acid, a tricarboxylic acid or an anhydride thereof (acid-monoanhydride).

The carboxylic acids are exemplified by acid anhydrides since the reaction is carried out using acid anhydrides in many cases. The carboxylic acid derived from the carboxylic acid may be further substituted with a substituent such as an alkyl group, a cycloalkyl group, or an aromatic group.

As the saturated chain hydrocarbon di-or tricarboxylic acids, there are included: succinic acid monoanhydrides of succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid (oxoglutaric acid), pimelic acid, sebacic acid, suberic acid, diglycolic acid (diglycolic acid), and the like.

As the saturated cyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, there are included: acid monoanhydrides such as hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, hexahydrotrimellitic acid, and the like.

As the unsaturated di-or tricarboxylic acids, there are included: maleic acid, itaconic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid (chlorendic acid), and the like.

As the other dicarboxylic acid or tricarboxylic acid, anhydrides of phthalic acid, trimellitic acid, and the like are included. Among them, preferred is succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, or trimellitic acid anhydride, and more preferred is succinic acid, itaconic acid, or tetrahydrophthalic acid anhydride. One kind of the carboxylic acids may be used, or two or more kinds may be used in combination.

The reaction temperature for synthesizing the alkali-soluble resin (A) represented by the general formula (2) is preferably 20 to 120 ℃ and more preferably 40 to 90 ℃. The molar ratio of the epoxy acrylate resin to the carboxylic acid in this case may be selected so that the ratio of the carboxyl group-containing group in L is within the above range.

Similarly, the alkali-soluble resin (B) can be obtained by reacting the epoxy acrylate resin (B0) and the epoxy acrylate resin (B) with a carboxylic acid.

As the carboxylic acids, (a) dicarboxylic acids or tricarboxylic acids and (b) tetracarboxylic acids are used. The dicarboxylic acid or tricarboxylic acid may be a dicarboxylic acid or tricarboxylic acid, or an anhydride thereof, and is preferably an anhydride in terms of reactivity. Similarly, the tetracarboxylic acid may be a tetracarboxylic acid or an acid dianhydride thereof, and is preferably an acid dianhydride in terms of reactivity.

Examples of the (a) dicarboxylic acid, tricarboxylic acid or their anhydride include: saturated chain hydrocarbon dicarboxylic acids, saturated chain hydrocarbon tricarboxylic acids, or anhydrides thereof; saturated cyclic hydrocarbon dicarboxylic acids, saturated cyclic hydrocarbon tricarboxylic acids, or anhydrides thereof; unsaturated hydrocarbon dicarboxylic acids, unsaturated hydrocarbon tricarboxylic acids, or anhydrides thereof; aromatic hydrocarbon dicarboxylic acids, aromatic hydrocarbon tricarboxylic acids, or anhydrides thereof. Further, each hydrocarbon residue (structure excluding the carboxyl group) of the dicarboxylic acid, tricarboxylic acid or anhydride thereof may be further substituted with a substituent such as an alkyl group, a cycloalkyl group or an aromatic group.

Examples of the saturated chain hydrocarbon dicarboxylic acid or the saturated chain hydrocarbon tricarboxylic acid include: succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like. Examples of the saturated cyclic hydrocarbon dicarboxylic acid or the saturated cyclic hydrocarbon tricarboxylic acid include: hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, hexahydrotrimellitic acid, and the like. Examples of the unsaturated hydrocarbon dicarboxylic acid or unsaturated hydrocarbon tricarboxylic acid include: maleic acid, itaconic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and chlorendic acid. Examples of the aromatic hydrocarbon dicarboxylic acid or aromatic hydrocarbon tricarboxylic acid include phthalic acid, trimellitic acid, and the like. Anhydrides of the dicarboxylic acids or tricarboxylic acids may also be used. Among them, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid or their anhydrides are preferable, and succinic acid, itaconic acid, and tetrahydrophthalic acid or their anhydrides are more preferable.

Examples of the (b) tetracarboxylic acid or acid dianhydride thereof include: chain hydrocarbon tetracarboxylic acid or acid dianhydride thereof, alicyclic tetracarboxylic acid or acid dianhydride thereof, and aromatic polycarboxylic acid or acid dianhydride thereof. Each hydrocarbon residue (structure from which the carboxyl group is removed) of the tetracarboxylic acid or its acid dianhydride may be further substituted with a substituent such as an alkyl group, a cycloalkyl group, or an aromatic group.

Specific examples of the tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid. Examples of the alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornane-tetracarboxylic acid, and the like. Examples of the aromatic polycarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and the like. Acid dianhydrides of these tetracarboxylic acid compounds can also be used.

The molar ratio (a)/(b) of the dicarboxylic acid, tricarboxylic acid or anhydride thereof (a) to the tetracarboxylic acid or acid dianhydride thereof (b) used in the reaction is preferably 0.01 to 0.5, more preferably 0.02 to 0.3, and further preferably 0.03 or more and less than 0.1. If the molar ratio (a)/(b) is in the above range, an optimum molecular weight for producing a photosensitive resin composition having good photopatternability can be easily obtained. Further, the smaller the molar ratio (a)/(b), the greater the alkali solubility and the greater the molecular weight tend to be.

The ratio of the polymerizable unsaturated group-containing epoxy acrylate resin (c) to the carboxylic acid component (a) and the carboxylic acid component (b) in the reaction is preferably as follows: preferably, the components (c): (a) the method comprises the following steps (b) 1: 0.2-1.0: 0.01 to 1.0, preferably 1: 0.2-0.4: 0.4 to 0.8, so that the terminal of the compound becomes a carboxyl group. In this case, the reaction is preferably carried out quantitatively so that the molar ratio (c)/[ (a)/2+ (b) ] of the total amount of the acid component to the epoxy acrylate resin is 0.5 to 1.0. If the molar ratio is less than 0.5, the terminal of the alkali-soluble resin becomes an acid anhydride, and the content of unreacted acid dianhydride increases, which may reduce the stability of the alkali-soluble resin composition with time. On the other hand, when the molar ratio exceeds 1.0, the content of the hydroxyl group-containing compound containing an unreacted polymerizable unsaturated group increases, and there is a concern that the stability of the alkali-soluble resin composition with time may decrease. The molar ratio of the components (a), (b) and (c) may be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin.

From another viewpoint, preferred embodiments are: the reaction is quantitatively carried out so that the total amount of carboxyl groups (acid anhydride groups: 2 mol) in the carboxylic acid components [ (a) + (b) ] is 0.1 to 1.0 mol, preferably 0.5 to 1.0 mol, based on 1 mol of hydroxyl groups in the epoxy acrylate resin (c).

The reaction with the dicarboxylic acid, tricarboxylic acid or anhydride thereof (a) and tetracarboxylic acid or acid dianhydride thereof (b) can be carried out by heating and stirring at 90 to 130 ℃ in the presence of a catalyst such as triethylamine, tetraethylammonium bromide, triphenylphosphine, or the like.

The acid value of the alkali-soluble resin (B) produced by the above production method is preferably from 30mgKOH/g to 200mgKOH/g, more preferably from 50mgKOH/g to 150 mgKOH/g. If the acid value is less than 30mgKOH/g, residues tend to remain during alkali development, and if it exceeds 200mgKOH/g, the alkali developing solution may penetrate too quickly and a peeling phenomenon may occur.

In the above production method, the content of k ═ 0 in general formula (15) is preferably 50% or more, more preferably 70% or more, still more preferably 85% or more, and particularly preferably 95% or more, from the viewpoint of reducing the viscosity of the produced alkali-soluble resin (B). Further, k is in the range of 0 to 5, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0 to 0.5 in terms of average value.

The alkali-soluble resin (B) produced by the above production method preferably has a hydrolyzable halogen content of 0.2 mass% or less. When the content of the hydrolyzable halogen is 0.2% by mass or less, the hydrolyzable halogen is less likely to interfere with the curing reaction, and the physical properties of the cured product, particularly the insulation reliability, are less likely to be deteriorated, so that the use is preferable for applications in the electric and electronic fields. The hydrolyzable halogen content is preferably 0.1 mass% or less, and more preferably 0.05 mass% or less.

In the above production method, for example, when k is 0 in the general formula (15), the epoxy acrylate resin (B0) represented by the general formula (11) is obtained, and the alkali-soluble resin (B) having the structure represented by the general formula (12) is produced.

The alkali-soluble resin of the present invention may be the following resin: the resin composition contains not only the resin having the structure represented by the general formula (12), but also resins having different degrees of polymerization generated in each stage of the production method or resins derived therefrom.

However, the epoxy resin obtained by the above-mentioned production method may contain a component having k of 1 or more in the general formula (15). Since the epoxy acrylate resin obtained from the epoxy resin having k 1 or more contains 3 or more hydroxyl groups, it may be difficult to control the molecular weight thereof by the reaction with an acid anhydride, particularly the reaction with (b) tetracarboxylic acid or an acid dianhydride thereof. The alkali-soluble resin is represented by the following formula (17). The polymerizable unsaturated group-containing alkali-soluble resin is a mixture of oligomers having various molecular weights, and L of the following formula (17a)³L as other molecule¹Or L²Any of the above (1) is bonded, and therefore, the polymerization proceeds in a structure other than the general formula (12). However, if the content of k in the epoxy resin is in the range of 0 mer, the effect of the present invention is not affected even if the component is contained.

[ solution 9]

-CO-M-(COOH)p (3)

In the formula, R²And R of the general formula (11)²A and Z have the same meanings as those of A and Z of the formula (12), k has the same meaning as that of k of the formula (15), and L¹And L²Is a hydrogen atom, any one of the formula (17a) or the formula (3), but not all of them are hydrogen atoms. L is³L as other molecule¹Or L²Bonding is performed.

In the present specification, unless otherwise specified, the alkali-soluble resin refers to all of the alkali-soluble resin (a), the alkali-soluble resin (B0), and the alkali-soluble resin (B).

The alkali-soluble resin may be a photosensitive resin composition, and the photosensitive resin composition may be cured to form a cured product.

The epoxy acrylate resin of the present invention or the alkali-soluble resin of the present invention has two or more polymerizable unsaturated groups on average, and thus can be used as a curable resin composition.

The epoxy acrylate resin does not have alkali developability in the case of using the resin, but may have alkali developability in the case of using an alkali-soluble resin.

The curable resin composition of the present invention comprises the epoxy acrylate resin of the present invention and a polymerization initiator. The photosensitive resin composition of the present invention comprises the alkali-soluble resin of the present invention, a photopolymerizable monomer and a photopolymerization initiator.

The curable resin composition of the present invention may be used by blending a photopolymerization initiator or a radical polymerization initiator as an initiator, or may be used by blending other polyfunctional acrylates. The resin component (components of the epoxy acrylate resin and the cured resin, and no solvent) in the curable resin composition of the present invention is preferably 30 mass% or more, more preferably 50 mass% or more, and still more preferably 70 mass% or more. The resin component (components of the epoxy acrylate resin and the cured resin, and no solvent) in the curable resin composition of the present invention is preferably 30 mass% or more, more preferably 50 mass% or more, and still more preferably 70 mass% or more.

As the photopolymerization initiator, various conventional photopolymerization initiators can be used. Examples thereof include: acetophenone compounds such as acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoprophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butylbenzophenone, benzophenone compounds such as benzophenone, 2-chlorobenzophenone and p, p' -bisdimethylaminobenzophenone, benzoin ethers such as benzil (benzil), benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether, biimidazole compounds such as 2- (o-chlorophenyl) -4, 5-phenylbisimidazole, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4, 5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4, 5-diphenylbiimidazole and 2,4, 5-triarylbiimidazole, halomethyl oxadiazole compounds such as 2-trichloromethyl-5-styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3, 4-oxadiazole and 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole, 2,4, 6-tris (trichloromethyl) -1,3, 5-triazine, 2-methyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-chlorophenyl) -4, 6-bis (trichloromethyl) -1, halomethyl-s-triazine compounds such as 3, 5-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3,4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, and 2- (4-methylthiostyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -,2- (benzoyloxime), 1- (4-phenylthiophenyl) butane-1, 2-dione-2-oxime-phthalate, 1- (4-methylthiophenyl) butane-1, 2-dione-2-oxime-o-acetate, 1- (4-methylthiophenyl) butane-1-ketoxime-o-acetate and other o-acyloxime compounds, benzil dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, 2-methylthiothioxanthone, 2-isopropylthioxanthone and other sulfur compounds, 2-ethylanthraquinone, octamethylanthraquinone, 1, anthraquinones such as 2-benzoanthraquinone and 2, 3-diphenylanthraquinone, organic peroxides such as azobisisobutyronitrile, benzoyl peroxide and cumene peroxide, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. One kind of the photopolymerization initiator may be used, or two or more kinds may be used in combination. In addition, the photopolymerization initiator mentioned in the present invention is used in the meaning of containing a sensitizer.

The amount of the photopolymerization initiator used is preferably 0 to 100 parts by mass, more preferably 0.5 to 40 parts by mass, and still more preferably 1 to 10 parts by mass, based on 100 parts by mass of the epoxy acrylate resin. The amount is usually 0 to 50 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the resin composition. In the case of using a thermal polymerization initiator, a photopolymerization initiator may not be used.

Further, the photopolymerization initiator may be used together with one or more of conventional photosensitizers. Examples of the photosensitizers include: miqileine, ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, triethanolamine, triethylamine and the like. The amount of the photosensitizer used is preferably 0 to 20 parts by mass, more preferably 0.02 to 10 parts by mass, and still more preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the epoxy acrylate resin.

The radical polymerization initiator is preferably blended for thermal polymerization, but may not be blended when only photo-curing is performed. Preferred radical polymerization initiators include, for example: conventional peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl carbonate peroxide, di-2-ethylhexyl carbonate peroxide and t-butylperoxypropionate, and azo compounds such as 1,1' -azobiscyclohexane-1-carbonylnitrile, 2' -azobis- (2, 4-dimethylvaleronitrile), 2' -azobis- (4-methoxy-2, 4-dimethylvaleronitrile), 2' -azobis- (methyl isobutyrate), α -azobis- (isobutyronitrile) and 4,4' -azobis- (4-cyanovaleric acid). The amount of the thermal polymerization initiator used is preferably 0 to 100 parts by mass, more preferably 0.02 to 60 parts by mass, and still more preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the epoxy acrylate resin. The amount of the curable resin composition of the present invention is preferably 0 to 50 parts by mass, and more preferably 0.01 to 30 parts by mass, based on 100 parts by mass of the curable resin composition of the present invention.

The photosensitive resin composition of the present invention preferably contains 30 mass% or more of (a) the alkali-soluble resin, more preferably 50 mass% or more, in the solid content from which the solvent has been removed (the solid content includes a monomer which becomes a solid content after curing).

In order to exhibit the characteristics as a photosensitive resin composition, the following components (a) to (C) are preferably contained as essential components, and more preferably, the component (D) is further contained. In particular, when the component (a) is the alkali-soluble resin (B0), the alkali-soluble resin (B), or both, the component (B) preferably has at least two polymerizable unsaturated groups and preferably contains the component (S).

(A) An alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule;

(B) a photopolymerizable monomer having at least one polymerizable unsaturated group;

(C) a photopolymerization initiator;

(D) an epoxy resin;

(S) solvent

Examples of the photopolymerizable monomer as the component (B) include: examples of the hydroxyl group-containing monomer include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, including ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, ethylene glycol di (meth) acrylate, and the like, (meth) acrylates such as sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa (meth) acrylate, polyhydric alcohols such as pentaerythritol and dipentaerythritol, vinylbenzyl ether compounds of polyhydric phenols such as phenol novolak, and addition polymers of divinyl compounds such as divinylbenzene. When it is necessary to form a crosslinked structure between molecules of the alkali-soluble resin, it is preferable to use a photopolymerizable monomer having two or more polymerizable unsaturated groups, and it is more preferable to use a photopolymerizable monomer having three or more polymerizable unsaturated groups. Further, one kind of the compound may be used, or two or more kinds may be used in combination. The component (B) preferably has no free carboxyl group.

The blending ratio [ (A)/(B) ] (mass ratio) of the component (B) to the component (A) is preferably 20/80-95/5, more preferably 20/80-90/10, and even more preferably 40/60-80/20. Here, if the blending ratio of the alkali-soluble resin is small, the cured product after the photo-curing reaction becomes brittle. Further, since the acid value of the coating film is low, solubility of an unexposed portion in an alkali developing solution is lowered, and thus, there is a problem that an edge of a pattern is shaken and is not sharp. Conversely, if the blending ratio of the alkali-soluble resin is greater than the above range, the proportion of the photoreactive functional group in the resin is small, and thus the formation of a crosslinked structure by the photo-curing reaction may be insufficient. In addition, when the acid value of the resin component is too high, the solubility of the exposed portion in the alkali developing solution becomes high, and therefore the following problems may occur: the formed pattern is thinner than the target line width, and pattern deletion and the like are likely to occur.

The photopolymerization initiator (C) may be the same photopolymerization initiator as mentioned in the description of the curable resin composition of the present invention. As the (C) photopolymerization initiator, a compound which does not act as a photopolymerization initiator or a sensitizer by itself but can increase the capability of the photopolymerization initiator or the sensitizer by combined use may be added. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine which are effective when used in combination with benzophenone.

The amount of the photopolymerization initiator to be added is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 25 parts by mass, even more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, based on 100 parts by mass of the total amount of the alkali-soluble resin (a) and the photopolymerizable monomer (B). Here, if the amount of the photopolymerization initiator added is too small, the rate of photopolymerization becomes slow and sufficient sensitivity cannot be obtained, and if the amount of the photopolymerization initiator added is too large, the sensitivity becomes too strong and the pattern line width becomes thick with respect to the pattern mask, and faithful to the line width of the mask cannot be reproduced or halation (shading) which is a state where the tapered shape (the shape in the film thickness direction of the developed pattern cross section) becomes unclear and the edge is easily generated. Further, when exposed to high temperature in the subsequent process, decomposition gas may be generated.

In addition, examples of the (D) epoxy resin include: phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, bisphenol fluorene type epoxy resin, glycidyl ether of polyhydric alcohol, glycidyl ester of polycarboxylic acid, polymer containing glycidyl (meth) acrylate as a unit, epoxy resins such as alicyclic epoxy resins, epoxidized polybutadiene (for example, "Nissan (NISSO) -PB. JP-100", manufactured by Nissan Kaida Co., Ltd.), epoxy resins having a silicone skeleton, phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate, and the like. When it is necessary to increase the crosslinking density of the alkali-soluble resin, a compound having at least two or more epoxy groups is preferable. The epoxy resin preferably has an epoxy equivalent of 100-300 g/eq and a number average molecular weight of 100-5000. (D) The component (A) may be used alone or in combination of two or more. When it is necessary to increase the crosslinking density of the alkali-soluble resin, an epoxy resin having at least two or more epoxy groups is preferable.

When the epoxy resin (D) is used, the amount of the epoxy resin (D) added is preferably in the range of 10 to 40 parts by mass based on 100 parts by mass of the total of the components (a) and (B). Here, as one purpose of adding the epoxy resin, there is a case where the amount of carboxyl groups remaining when the cured film is formed after patterning is reduced in order to improve the reliability of the cured film, and in this purpose, if the amount of the epoxy resin used is less than 10 parts by mass, there is a possibility that the moisture resistance reliability when used as an insulating film cannot be secured. In addition, when the amount of the epoxy resin used is more than 40 parts by mass, the amount of the photosensitive group of the resin component in the photosensitive resin composition decreases, and there is a possibility that sensitivity for patterning cannot be sufficiently obtained.

When the photosensitive resin composition of the present invention is used for insulating material applications, etc., it is preferable to use a (S) solvent. Examples of the (S) solvent include: alcohols such as methanol, ethanol, N-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, 3-hydroxy-2-butanone, diacetone alcohol and the like, terpenes such as α -terpineol or β -terpineol and the like, ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone and the like, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene and the like, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and the like, glycol ethers such as ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate and the like, Cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and other acetates. These are dissolved and mixed singly or in combination to prepare a homogeneous solution composition.

In addition, various additives such as a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant may be optionally blended in the photosensitive resin composition of the present invention.

As the hardening accelerator, for example, there can be used conventional compounds known as a hardening accelerator, a hardening catalyst, a latent hardening agent, and the like generally used for an epoxy resin, including: tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, lewis acids, organometallic compounds, imidazoles, diazabicyclo compounds, and the like.

Examples of the thermal polymerization inhibitor and the antioxidant include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butyl catechol, phenothiazine (phenothiazine), a hindered phenol compound, a phosphorus heat stabilizer, and the like.

Examples of plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like.

Examples of the filler include: glass fibers, silica, mica, alumina, and the like.

Examples of the defoaming agent and the leveling agent include silicone compounds, fluorine compounds, and acrylic compounds.

Examples of coupling agents include: and silane coupling agents such as vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane and 3-ureidopropyltriethoxysilane.

Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and the like.

The photosensitive resin composition of the present invention preferably contains 70 mass% or more, preferably 80 mass% or more, and more preferably 90 mass% or more of the total of (a) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) an epoxy resin in a solid content other than the (S) solvent (the solid content contains a monomer which becomes a solid content after curing). The amount of the solvent varies depending on the target viscosity, but is preferably 10 to 80% by mass relative to the total amount.

The photosensitive resin composition can be applied to a substrate or the like, dried, and hardened by irradiating (exposing) with light (including ultraviolet rays, radiation, and the like) to form a hardened material (coating film). At this time, a portion to which light is irradiated and a portion to which light is not irradiated are provided using a photomask or the like, only the portion to which light is irradiated is cured, and the other portion is dissolved with an alkaline solution, thereby obtaining a cured product (coating film) of a desired pattern.

As for each step of the film forming method by coating and drying of the photosensitive resin composition, specifically exemplified is a method of applying the photosensitive resin composition to a substrate by any of a conventional solution dipping method, a spray method, a method using a roll coater, a land coater (blade coater), a slit coater, a spin coater, and the like.

The photosensitive resin composition is applied to a desired thickness by the above method, and then the solvent is removed (prebaking) to form a film. The prebaking is performed by heating with an oven, a hot plate, or the like, vacuum drying, or a combination thereof. The heating temperature and heating time of the prebaking may be suitably selected depending on the solvent to be used, and are preferably, for example, from 1 minute to 10 minutes at 80 ℃ to 120 ℃.

As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, g-ray, i-ray, X-ray, or the like can be used, and the wavelength of the radiation is preferably in the range of 250nm to 450 nm.

As the developer suitable for the alkali development, for example, an aqueous solution of sodium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, or the like can be used. The developer can be appropriately selected depending on the characteristics of the resin layer, and it is also effective to add a surfactant as needed. The developing temperature is preferably 20 to 35 ℃, and a fine image can be formed precisely using a commercially available developing machine, ultrasonic cleaner, or the like. Further, water washing is generally performed after the alkali development. As the developing method, a shower developing method, a spray developing method, a dip (dip) developing method, a dip (paddle) developing method, or the like can be applied.

After the development in the above-mentioned manner, heat treatment (post-baking) is performed at 180 to 250 ℃ for 20 to 100 minutes. The baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. The post-baking is performed by heating with an oven, a hot plate, or the like, as in the pre-baking.

The patterned coating film of the present invention is formed through each step by photolithography. Then, polymerization or curing (both may be collectively referred to as curing) is completed by heat, thereby forming a cured film such as an insulating film having a desired pattern. The curing temperature in this case is preferably 160 ℃ to 250 ℃.

The photosensitive resin composition of the present invention has a higher number of polymerizable unsaturated groups per molecule than conventional ones, and therefore, the photo-curability is improved, and the crosslink density after curing can be increased without increasing the amount of the photopolymerization initiator. That is, when ultraviolet light or electron beams are irradiated to a thick film, the hardened portion is hardened to the bottom, and thus the difference in solubility between the exposed portion and the unexposed portion with respect to an alkali developing solution becomes large, whereby the dimensional stability of a pattern, the developing margin, and the pattern adhesion are improved, and a pattern can be formed with high resolution. Further, even in the case of a thin film, the residual film amount at the exposed portion can be greatly improved and peeling at the time of development can be suppressed by increasing the sensitivity.

The photosensitive resin composition of the present invention can be used very effectively for a solder resist for producing a circuit board, a plating resist, an etching resist, or an insulating film for forming a multilayer wiring board on which a semiconductor element is mounted, a gate insulating film of a semiconductor, a photosensitive adhesive (particularly, an adhesive which requires heat adhesion performance after patterning by photolithography), and the like.

The cured product can also be used for a solder resist layer, a resist layer such as a plating resist layer or an etching resist layer, an interlayer insulating layer of a multilayer printed wiring board or the like, a film for gas barrier, a sealing material for semiconductor light-emitting elements such as a lens and a light-emitting diode (LED), a top coat of paint or ink, a hard coat of plastics, a rust-proof film of metals, and the like.

[ examples ]

The present invention will be specifically described below based on examples, but the present invention is not limited thereto. In the examples, "part" means part by mass and "%" means% by mass unless otherwise specified. Unless otherwise specified, evaluation of the resins in these examples was carried out as follows.

[ solid content concentration ]

The solid content concentration is determined by impregnating a glass filter with (1g) of a resin solution, a photosensitive resin composition, or the like (mass: w0(g) was weighed and the mass [ W2(g) ] of the resultant was calculated from the following equation using the mass [ W1(g) ] of the resultant mixture heated at 160 ℃ for 2 hours.

Solid content concentration (%) < 100 × (W2-W0)/(W1-W0)

[ acid value ]

The measurement was carried out in accordance with Japanese Industrial Standard (JIS) K0070. Specifically, the resin solution was dissolved in dioxane, and titration was performed with a 0.1N-KOH aqueous solution using a potential difference titration apparatus ("COM-1600" manufactured by yokoku corporation), and the amount of KOH required per 1g of the solid content was defined as the acid value.

[ molecular weight ]

The molecular weight was measured by Gel Permeation Chromatography (GPC) ("HLC-8220 GPC", manufactured by Tosoh Co., Ltd., column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuperH-5000 (1) (manufactured by Tosoh Co., Ltd.), solvent: tetrahydrofuran, temperature: 40 ℃ C., speed: 0.6mL/min), and a value obtained as a conversion value of standard polystyrene ("PS-Oligomer Kit (PS-Oligomer Kit)" manufactured by Tosoh Co., Ltd.) was defined as the weight average molecular weight (Mw).

[ relative dielectric constant, dielectric loss tangent ]

The value of 1GHz after storage in a room at 23 ℃ and 50% humidity after absolute drying was measured by a cavity resonance method (vector network analyzer (VNA) E8363B (Agilent Technology), cavity resonator perturbation method dielectric constant measurement apparatus (manufactured by kanto electronic application development)).

[ film thickness ]

The cured film was measured using a stylus type step shape measuring apparatus (manufactured by Kotian (KLA-Tencor) (Strand., P-10)).

[ contact Property ]

The film of the glass substrate with the cured film was cut with cross cuts so as to form at least 100 mesh shapes, and then a peel test was performed using cellophane tape (cellophane tape), and the state of the mesh was visually evaluated.

Very good: no peeling was observed at all

O: slight peeling was observed in the coating film

And (delta): peeling was observed on a part of the coating film

X: the film was almost peeled off

[ alkali resistance ]

The glass substrate with the cured film was immersed in a solution of a mixed solution of 30 parts by weight of 2-aminoethanol and 70 parts by weight of glycol ether, which was maintained at 80 ℃, and after 10 minutes, the substrate was lifted up, washed with pure water and dried to prepare a sample in which a chemical was immersed, and the adhesion was evaluated.

[ acid resistance ]

The glass substrate with the cured film was immersed in a solution of aqua regia (hydrochloric acid: nitric acid: 7: 3) maintained at 50 ℃, taken out after 10 minutes, washed with pure water and dried to prepare a sample in which a chemical was immersed, and the adhesion was evaluated.

[ bending test ]

The photosensitive resin composition was applied onto a 125mm × 125mm glass substrate with a release film attached thereto so that the film thickness after post-baking became 30 μm using a spin coater, and prebaked at 110 ℃ for 5 minutes to prepare a resist filmAnd (4) coating the board. Thereafter, the resultant was patterned using a photomask for pattern formation at 500W/cm²The high-pressure mercury lamp (2) is irradiated with ultraviolet rays having a wavelength of 365nm to cause a photo-curing reaction at the exposed portion. Then, the plate after the exposure was developed for 30 seconds from the time when the development of the pattern was started by the 0.8% tetramethylammonium hydroxide (TMAH) aqueous solution and the 23 ℃ shower development, and further, the unexposed portion of the coating film was removed by spray water washing. Thereafter, a heat curing treatment was performed at 230 ℃ for 30 minutes using a hot air dryer, and the obtained pattern was peeled from the release film to obtain a test film. The obtained test film was folded in half, and then the top of the fold was spread upward. This test was repeated and evaluated as many times as cracks or breaks were observed.

The materials used are abbreviated as follows.

E1: 2, 6-xylenol-dicyclopentadiene type epoxy resin (YDDP-100, epoxy equivalent 271g/eq, manufactured by Nichika chemical & materials Co., Ltd.)

E2: phenol novolac type epoxy resin (YDPN-638 epoxy equivalent 177g/eq, manufactured by Nippon iron Chemicals & materials Co., Ltd.)

E3: bisphenol A type liquid epoxy resin (YD-127, epoxy equivalent 182g/eq, manufactured by Nichika & materials Co., Ltd.)

E4: cresol novolak type epoxy resin (YDCN-700-3, manufactured by Nichika & materials Co., Ltd., YDCN-700-3, epoxy equivalent 203g/eq., softening point 73 ℃ C.)

BPDA: 3,3',4,4' -biphenyltetracarboxylic dianhydride

THPA: 1,2,3, 6-tetrahydrophthalic anhydride

TPP: triphenylphosphine

HQ: hydroquinone

TEAB: tetraethylammonium bromide

PGMEA: propylene glycol monomethyl ether acetate

R1: epoxy acrylate resin obtained in example 1

HR 1: epoxy acrylate resin obtained in comparative example 1

HR 2: epoxy acrylate resin obtained in comparative example 3

A1: alkali-soluble resin obtained in example 2

A2: alkali-soluble resin obtained in example 3

HA 1: alkali-soluble resin obtained in comparative example 2

HA 2: alkali-soluble resin obtained in comparative example 3

HA 3: alkali-soluble resin obtained in comparative example 4

HA 4: a68.9% PGMEA solution of a cresol novolak-type acid-modified epoxy acrylate resin (CCR-1172, manufactured by Nippon chemical Co., Ltd.)

B1: dipentaerythritol hexaacrylate

C1: photopolymerization initiator (Irgacure 184, manufactured by BASF corporation)

C2: photopolymerization initiator (4,4' -bis (dimethylamino) benzophenone (miilerone))

Example 1

In a reaction vessel equipped with a stirrer, a temperature adjusting device, a reflux condenser and an air introducing device, 271 parts of E1 was dissolved in 61 parts of PGMEA, and 72 parts of acrylic acid, 3.5 parts of TPP and 0.1 part of HQ were added thereto, and after reacting at 110 ℃ for 8 hours while blowing air, 285 parts of PGMEA was added to obtain a PGMEA solution of an epoxy acrylate resin (R1). The solid content concentration of the obtained resin solution was 50%.

The obtained resin solution was distilled off under reduced pressure to remove the solvent, 100 parts of the obtained solid content was put in a fluororesin mold, 1 part of dicumyl peroxide was added, and the mixture was heated in an oven at 100 ℃ for 30 minutes and at 170 ℃ for 1 hour to harden the solid content, thereby obtaining a hardened product. Using the cured product thus obtained, test pieces having a thickness of 0.2mm and 0.2 cm. times.10 cm were prepared, and the relative dielectric constant and the dielectric loss tangent were measured, and the results are shown in Table 1.

Comparative example 1

In the same apparatus as in example 1, 177 parts of E2 were dissolved in 44 parts of PGMEA, and 72 parts of acrylic acid, 3.5 parts of TPP, and 0.1 part of HQ were added thereto, and reacted at 110 ℃ for 8 hours while blowing air, and then 208 parts of PGMEA was added thereto, thereby obtaining a PGMEA solution of an epoxy acrylate resin (HR 1). The solid content concentration of the obtained resin solution was 50%. In the same manner as in example 1, test pieces were prepared, and the relative permittivity and the dielectric loss tangent were measured, and the results are shown in table 1.

[ Table 1]

	Example 1	Comparative example 1
			Resin composition	R1	HR1
Relative dielectric constant	3.0	3.4
			Dielectric loss tangent	0.015	0.021

Example 2

In the same apparatus as in example 1, 450 parts of a 50% PGMEA solution of R1, 98 parts of THPA, 1.8 parts of TEAB, and 40 parts of PGMEA were charged, and stirred at 120 to 125 ℃ for 6 hours to obtain an alkali-soluble resin solution (a 1). The resin solution thus obtained had a solid content concentration of 55%, an acid value (in terms of solid content) of 113mgKOH/g, and a molecular weight (Mw) of 890.

40.5 parts of A1, 12.5 parts of B1, 1.3 parts of C1, 0.2 part of C2, 6.3 parts of E4 and 39.2 parts of PGMEA were blended to obtain a photosensitive resin composition.

The obtained photosensitive resin composition was applied onto a 125mm × 125mm glass substrate by using a spin coater so that the film thickness after post baking became 30 μm, and pre-baked at 110 ℃ for 5 minutes to prepare a coated plate. Thereafter, the molten steel was used at 500W/cm²The high-pressure mercury lamp (2) is irradiated with ultraviolet rays having a wavelength of 365nm to perform a photo-curing reaction of the entire surface exposure. Then, the plate after the exposure was treated with a 0.8% tetramethylammonium hydroxide (TMAH) aqueous solution and spray development at 23 ℃ for 60 seconds, and further subjected to spray water washing. Thereafter, the glass substrate with the cured film was heat-cured at 230 ℃ for 30 minutes using a hot air dryer. The obtained glass substrate with a cured film was subjected to adhesion, alkali resistance and acid resistance tests, and the results are shown in table 2.

Comparative example 2

In the same apparatus as in example 1, 450 parts of HR1 50% PGMEA solution, 135 parts of THPA, 1.8 parts of TEAB and 70 parts of PGMEA were charged and stirred at 120 to 125 ℃ for 6 hours to obtain an alkali-soluble resin solution (HA 1). The resin solution thus obtained had a solid content concentration of 55%, an acid value (in terms of solid content) of 138mgKOH/g, and a molecular weight (Mw) of 1450.

A photosensitive resin composition and a glass substrate with a cured film were obtained in the same manner as in example 2, except that 43.3 parts of HA1 was used instead of 40.5 parts of a1 and PGMEA was changed to 36.4 parts. The same test as in example 2 was performed on the obtained glass substrate with a cured film, and the results are shown in table 2.

Comparative example 3

In the same apparatus as in example 1, 182 parts of E3 was dissolved in 45 parts of PGMEA, and 72 parts of acrylic acid, 3.5 parts of TPP, and 0.1 part of HQ were added thereto, and reacted at 110 ℃ for 8 hours while blowing air, and then 212 parts of PGMEA was added thereto, to obtain a PGMEA solution of an epoxy acrylate resin (HR 2). The solid content concentration of the obtained resin solution was 50%.

The obtained resin solution 291 parts, dimethylolpropionic acid 4.0 parts, 1, 6-hexanediol 11.8 parts, and PGMEA 84 parts were charged, and the temperature was raised to 45 ℃. Subsequently, 61.8 parts of isophorone diisocyanate was added dropwise while paying attention to the temperature. After the dropwise addition, the mixture was stirred at 75 to 80 ℃ for 6 hours. Further, 21 parts of THPA was charged and stirred at 90 to 95 ℃ for 6 hours to obtain an alkali-soluble resin solution (HA 2). The resin solution thus obtained had a solid content concentration of 66%, an acid value (in terms of solid content) of 38.4mgKOH/g, and a molecular weight (Mw) of 12220.

A photosensitive resin composition and a glass substrate with a cured film were obtained in the same manner as in example 2, except that 43.8 parts of HA2 was used instead of 40.5 parts of a1 and PGMEA was changed to 35.9 parts. The same test as in example 2 was performed on the obtained glass substrate with a cured film, and the results are shown in table 2.

[ Table 2]

As shown in table 2, it is understood that the photosensitive resin composition containing an alkali-soluble resin prepared in example 2 and the cured product thereof exhibit good results with respect to adhesion, alkali resistance and acid resistance.

Example 3

A reaction vessel equipped with a stirrer, a temperature controller, a reflux condenser and an air-introducing device was charged with 450 parts of R1 50% PGMEA solution, 49 parts of BPDA, 25 parts of THPA, 0.69 part of TEAB and 20 parts of PGMEA, and the mixture was stirred at 120 to 125 ℃ for 6 hours to obtain an alkali-soluble resin (A2). The resin thus obtained had a solid content of 55%, an acid value (in terms of solid content) of 92mgKOH/g, and a molecular weight (Mw) of 3500.

Comparative example 4

The same apparatus as in example 1 was charged with 291 parts of HR2 in 50% PGMEA, 4 parts of dimethylolpropionic acid, 11.8 parts of 1, 6-hexanediol and 84 parts of PGMEA, and the temperature was raised to 45 ℃. Then, 61.8 parts of isophorone diisocyanate was added dropwise while paying attention to the temperature in the flask. After the completion of the dropwise addition, the mixture was stirred at 75 to 80 ℃ for 6 hours. Further, 21 parts of THPA was charged and stirred at 90 to 95 ℃ for 6 hours to obtain an alkali-soluble resin solution (HA 3). The resin thus obtained had a solid content concentration of 66.5%, an acid value (in terms of solid content) of 38.4mgKOH/g, and a molecular weight (Mw) of 12220.

The photosensitive resin compositions of example 4 and comparative examples 5 to 6 were prepared by blending the above blending components at the ratios shown in Table 3. All numerical values in table 3 indicate parts by mass.

[ Table 3]

Composition (I)	Example 4	Comparative example 5	Comparative example 6
				A2	38.9
HA3		43.8
				HA4			42.3
B1	12.5	12.5	12.5
				C1	1.3	1.3	1.3
C2	0.2	0.2	0.2
				PGMEA	27.6	35.9	37.4
E4	6.3	6.3	6.3

The photosensitive resin compositions shown in Table 3 were applied onto a 125mm × 125mm glass substrate using a spin coater so that the film thickness after post baking was 30 μm, and prebaked at 110 ℃ for 5 minutes to prepare coated plates. Thereafter, the resultant was patterned using a photomask for pattern formation at 500W/cm²The high-pressure mercury lamp (2) is irradiated with ultraviolet rays having a wavelength of 365nm to cause a photo-curing reaction at the exposed portion. Then, the exposed plate was developed with a 0.8% aqueous tetramethylammonium hydroxide (TMAH) solution and sprayed at 23 ℃ to develop a patternAfter the lapse of 30 seconds, the film was developed and further subjected to spray water washing to remove the unexposed portion of the coating film. Thereafter, the cured film of example 4 and comparative examples 5 to 6 was obtained by heat-curing treatment at 230 ℃ for 30 minutes using a hot air dryer.

[ Table 4]

	Example 4	Comparative example 5	Comparative example 6
				Film thickness (mum)	30.2	30.1	30.1
Adhesion Property	◎	◎	◎
				Alkali resistance	◎	×	〇
Acid resistance	◎	×	〇
				Bending test (times)	5	5	2

From the results of example 4 and comparative examples 5 to 6, it is understood that when the alkali-soluble resin of the present invention or the photosensitive resin composition containing the same is used, a cured film having excellent reliability such as pressure folding resistance can be produced while patterning having excellent resolution is performed by alkali development.

The curable resin composition, the photosensitive resin composition and the cured product thereof of the present invention can be suitably used for a solder resist, a plating resist, an etching resist for producing a circuit board, an insulating film for multilayering a wiring board on which a semiconductor element is mounted, a gate insulating film of a semiconductor, a photosensitive adhesive, and the like.