TWI620016B - Photosensitive composition and printed wiring board having hardened layer thereof - Google Patents

Abstract

In order to form a hardened film that can develop well, maintain insulation for a long time, and have excellent mechanical strength on a printed wiring board, the photosensitive composition contains (A) a photosensitive compound containing a carboxyl group and (B) photopolymerization. The initiator, and (C) the epoxy compound, or (D) a photosensitive compound not having a carboxyl group, and the double bond equivalent of the photosensitive composition is 400 or more in a state where it does not contain an organic solvent and a filler. In another aspect, it is a photosensitive composition containing (A ') a compound containing a carboxyl group, (B) a photopolymerization initiator, and (C) an epoxy compound, and the ring of the aforementioned (C) epoxy compound The oxygen group is 1.5 equivalents or more and 4 equivalents or less with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing compound (A ′). The content of the liquid component contained in the photosensitive composition is relative to the organic solvent and the filler. All other components are 5 mass% or more and 30 mass% or less.

Description

Photosensitive composition and printed wiring board having hardened layer thereof

The present invention relates to a photosensitive composition and a printed wiring board having a cured layer.

On a printed wiring board, a solder resist is formed on a substrate having a conductor layer of a circuit pattern. As a material of such a solder resist, various photosensitive compositions have conventionally been proposed. For example, Patent Document 1 discloses a photosensitive resin composition for a permanent resist containing a polymer having a carboxyl group, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator.

In addition, in recent years, especially when a photosensitive composition such as a solder resist is used for a printed wiring board for a vehicle, the mechanical strength required to maintain the insulation for a long time or to prevent cracks under a high temperature and high humidity environment .

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-99647 (patent application range)

However, in the conventional photosensitive composition, when the content of the photopolymerizable monomer is large, problems such as failure to maintain insulation for a long period of time under high temperature and high humidity, or occurrence of a large number of cracks have been caused.

On the other hand, when the content of the photopolymerizable monomer is reduced, the sensitivity is lowered, and the problem of pattern formation is difficult.

The present invention has been made in view of the problems of the conventional techniques described above, and its basic object is to provide a photosensitive composition that can form a pattern well, maintain long-term insulation, and form a hardened film with excellent mechanical strength. Thing.

A further object of the present invention is to provide a printed wiring board having a long-term reliability of a cured layer of a photosensitive composition having such excellent characteristics.

In order to achieve the foregoing object, according to a first aspect of the present invention, it is provided A photosensitive composition comprising (A) a photosensitive compound containing a carboxyl group, (B) a photopolymerization initiator, and (C) an epoxy compound, which is characterized in that Double bond equivalent, in the absence of organic solvents and filling In the state of the material, it is 400 or more.

In another aspect, a photosensitive composition is provided, which further comprises (D) a photosensitive compound having no carboxyl group in addition to the above-mentioned components.

According to a suitable aspect, the double bond equivalent of the photosensitive composition is 400 or more and 680 or less, more preferably 450 or more and 650 or less, and more preferably 500 or more, in a state where no organic solvent or filler is contained. Below 650. According to a more suitable aspect, the content ratio of the (D) component among the mixed components of the (A) carboxyl group-containing photosensitive compound and (D) the carboxyl group-free photosensitive compound is 30% by mass or less. According to a more suitable aspect, the epoxy group of the epoxy compound (C) is 1.5 equivalents or more with respect to 1 equivalent of the carboxyl group of the compound containing a carboxyl group (A).

Furthermore, according to a second aspect of the present invention, there is provided a photosensitive composition containing the photosensitivity of (A ') a compound containing a carboxyl group, (B) a photopolymerization initiator, and (C) an epoxy compound. Composition, characterized by The epoxy group of the (C) epoxy compound is 1.5 equivalents or more and 4 equivalents or less with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing compound (A '), and the liquid component contained in the photosensitive composition The content rate is 5 mass% or more and 30 mass% or less with respect to all components other than an organic solvent and a filler.

According to a suitable aspect, the epoxy group number of the aforementioned (C) epoxy compound Head is 2.

Furthermore, according to the present invention, there is also provided a printed wiring board having a hardened layer formed using the photosensitive composition.

As described above, the photosensitive composition of the first aspect of the present invention can form a good pattern by making the double bond equivalent of the photosensitive composition 400 or more in a state without an organic solvent and a filler. Insulation can be maintained for a long time even under high temperature and high humidity, and the occurrence of cracks can be suppressed. Therefore, by using a photosensitive composition having such excellent characteristics to form a hardened layer such as a solder resist or an interlayer insulating layer, a printed wiring board having high long-term reliability can be provided.

In addition, as described above, the photosensitive composition of the second aspect of the present invention contains (A ') a compound containing a carboxyl group, (B) a photopolymerization initiator, and (C) an epoxy compound. The composition is such that the epoxy group of the (C) epoxy compound is 1.5 equivalents or more and 4 equivalents or less with respect to 1 equivalent of the carboxyl group of the compound containing a carboxyl group (A '), and the photosensitive composition is made. The content of the liquid component contained in it is 5 mass% or more and 30 mass% or less with respect to all components other than the organic solvent and the filler. It can form a good pattern, and can maintain long even under high temperature and high humidity. It is time-insulating and suppresses the occurrence of cracks. Therefore, by using a photosensitive composition having such excellent characteristics to form a hardened layer such as a solder resist or an interlayer insulating layer, long-term reliability can be provided. Takayuki printed wiring board.

1a‧‧‧ liquid test tube

1b‧‧‧Test tube for temperature measurement

2‧‧‧marking line (A line)

3‧‧‧marking line (B line)

4a, 4b ‧‧‧ rubber stopper

5‧‧‧ thermometer

[Fig. 1] A schematic side view showing two test tubes used for liquid state determination in Examples and Comparative Examples.

According to research by the present inventors, a photosensitive composition containing (A) a photosensitive compound containing a carboxyl group, (B) a photopolymerization initiator, and (C) an epoxy compound was found, or further containing (D) When the photosensitive composition of a photosensitive compound having no carboxyl group and the double bond equivalent of the photosensitive composition is 400 or more in a state without an organic solvent and a filler, the problem of the present invention can be solved.

In addition, it was found that when the content of the photosensitive compound having no carboxyl group, that is, the photosensitive monomer (photopolymerizable monomer) is large, the insulation cannot be maintained for a long time under high temperature and high humidity, and on the other hand, the sensitivity is lowered. When the content of the monomer is decreased, the sensitivity is reduced, so it is difficult to form a pattern. The double bond equivalent of the total amount of organic components in the photosensitive composition is set to a specific range, that is, the double bond equivalent of the aforementioned photosensitive composition. In the case where the organic solvent and the filler are not contained in the case of 400 or more, it can be solved, and the present invention has been completed.

Further based on research by the present inventors, it was found that a compound containing (A ') a carboxyl group, (B) a photopolymerization initiator, and (C) A photosensitive composition of an epoxy compound, wherein the epoxy group of the (C) epoxy compound is 1.5 equivalents or more and 4 equivalents or less based on 1 equivalent of the carboxyl group of the compound containing the carboxyl group (A '); and When the content rate of the liquid component contained in this photosensitive composition is 5 mass% or more and 30 mass% or less with respect to all components other than an organic solvent and a filler, the subject of this invention can be solved. Here, the determination of "liquid state" is made at 20 ° C.

As described above, when the content of the photosensitive compound having no carboxyl group, that is, the photosensitive monomer (photopolymerizable monomer) is large, the problem that the insulation cannot be maintained for a long time under high temperature and high humidity is easily caused, but the present invention Since the photosensitive composition does not contain a photosensitive monomer or even contains a small amount, such a problem is less likely to occur. On the other hand, when the content of the photosensitive monomer is reduced, generally, the softening point increases, so the solubility decreases, and it is difficult to form a pattern. The epoxy group of the (C) epoxy compound has a higher content than the ( A ') 1 equivalent of the carboxyl group of the compound containing a carboxyl group is 1.5 equivalents or more and 4 equivalents or less, and the content of the liquid component contained in the photosensitive composition is relative to all components other than the organic solvent and the filler. In the case of 5 mass% or more and 30 mass% or less, it can be solved, and the present invention has been completed.

Hereinafter, each component of the photosensitive composition of this invention is demonstrated.

The ethylenically unsaturated double bond in the carboxyl group-containing photosensitive compound (A) is preferably one derived from acrylic acid or methacrylic acid or a derivative thereof.

On the other hand, for the compound (A ') containing a carboxyl group, A known and commonly used resin compound having a carboxyl group in the ions. As the carboxyl group-containing resin, a carboxyl group-containing resin having no ethylenically unsaturated double bond itself or a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond can be used, and is not limited to a specific one, but In terms of photocurability or development resistance, a photosensitive resin containing a carboxyl group is more preferred.

Specific examples of such a carboxyl group-containing photosensitive compound or a carboxyl group-containing compound include the following compounds (both oligomers and polymers).

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with a compound having an unsaturated double bond such as styrene and α-methylstyrene and a benzene ring.

(2) A compound having one or more ethylenically unsaturated groups and one epoxy group in the molecule, and an unsaturated carboxylic acid such as (meth) acrylic acid, and styrene and α-methylbenzene A carboxyl group-containing photosensitive resin obtained by reacting a carboxyl group-containing resin obtained by copolymerizing an unsaturated double bond such as ethylene with a benzene ring compound.

(3) Aromatic diisocyanates, diol compounds containing carboxyl groups such as dimethylolpropionic acid, dimethylolbutanoic acid, and polycarbonate-based polyols, polyether-based polyols, and polyester-based polyols Addition polymerization reaction of diol compounds such as polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups to synthesize carboxyl-containing compounds In the urethane resin, a compound having one hydroxyl group and one or more (meth) acrylic groups in the molecule such as hydroxyalkyl (meth) acrylate is added to perform terminal (meth) acrylic acid. Photosensitive urethane resin containing a carboxyl group obtained by acidification.

(4) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type (Meth) acrylates of bifunctional epoxy resins having a benzene ring, such as epoxy resins, bixylenol-type epoxy resins, bisphenol-type epoxy resins, bisphenol-type epoxy resins, etc. A carboxyl group-containing photosensitive urethane resin obtained by addition polymerization of a diol compound and a diol compound.

(5) In the resin synthesis of the above (3), a compound having one hydroxyl group and one or more (meth) acrylic acid groups in the molecule, such as hydroxyalkyl (meth) acrylate, or isophorone di, is added. Isocyanate, pentaerythritol triacrylate, and other mole compounds such as a compound having one isocyanate group and one or more (meth) acrylic acid groups in the molecule, which are obtained by terminal (meth) acrylation Photosensitive urethane resin.

(6) The (meth) acrylic acid is reacted with a bifunctional or more polyfunctional epoxy resin having a benzene ring described later, and phthalic anhydride and tetrahydrophthalic acid are added to a hydroxyl group existing in a side chain. A carboxyl group-containing photosensitive resin obtained from dibasic acid anhydrides such as dicarboxylic anhydride and hexahydrophthalic anhydride.

(7) The (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin having a benzene ring described later with epichlorohydrin, and A photosensitive resin containing a carboxyl group obtained by adding a hydroxyl group to a dibasic acid anhydride.

(8) A cyclic ether such as ethylene oxide and / or a cyclic carbonate such as propylene carbonate are added to a polyfunctional phenol compound such as novolac, and the obtained hydroxyl group is (meth) acrylic acid Partial esterification, a photosensitive resin containing a carboxyl group obtained by reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride and the like with the remaining hydroxyl groups.

(9) The epoxy resin (1) to (8) is further added with epoxy (meth) acrylate, α-methyl glycidyl (meth) acrylate, and the like having one epoxy in the molecule. A carboxyl group-containing photosensitive resin composed of a compound having one or more (meth) acrylfluorenyl groups.

In addition, in this specification, (meth) acrylic acid is a generic term for acrylate, methacrylic acid, and mixtures thereof, and other similar expressions are also the same.

As the aforementioned carboxyl group-containing photosensitive compound or carboxyl group-containing compound has a large number of carboxyl groups on the side chain of the polymer skeleton, it can be developed with a dilute aqueous alkali solution.

The acid value of the carboxyl group-containing photosensitive compound or the carboxyl group-containing compound is suitably in the range of 30 to 200 mg KOH / g, more preferably 30 to 150 mg KOH / g, and particularly preferably 45 to 120 mg KOH / g. When the acid value of the photosensitive compound containing a carboxyl group is less than 30 mgKOH / g, alkali development is difficult. On the other hand, when it exceeds 200 mgKOH / g, in order to dissolve the exposed portion caused by the developer, the line becomes narrower than necessary. Thin, depending on the situation, the exposed part and the unexposed part are dissolved and peeled by the developing solution without distinction, and it is difficult to draw a normal resist pattern, which is not good.

The photosensitive compound containing a carboxyl group or a carboxyl group For example, the weight average molecular weight Mw (polystyrene equivalent weight average molecular weight) when measured by gel permeation chromatography (GPC) is different depending on the resin skeleton, but it is preferably greater than 4,000 and less than 150,000; More preferably, it is a range of 5,000 or more and 100,000 or less. When the weight-average molecular weight is 4,000 or less, the tack-free performance may be poor, and the moisture resistance of the coating film after exposure may be poor, the film may be reduced during development, and the resolution may be significantly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, the developability may be significantly deteriorated, which is not preferable.

As long as the photosensitive compound containing a carboxyl group has an ethylenically unsaturated double bond in the molecule, it is not limited to those listed above, and may be used singly or in combination of two or more kinds.

As the photopolymerization initiator (B) used in the present invention, an oxime ester-based photopolymerization initiator having an oxime ester group, an α-aminoacetophenone-based photopolymerization initiator, and a fluorenyl phosphine oxide can be suitably used. It is a photopolymerization initiator of at least one selected from the group consisting of photopolymerization initiators.

As the oxime ester-based photopolymerization initiator, a photopolymerization initiator having two oxime ester groups in the molecule can be suitably used.

The blending amount of such an oxime ester-based photopolymerization initiator is preferably 0.02 to 10% by mass based on the total amount of the composition. If it is less than 0.02% by mass, the photo-hardenability on copper is insufficient, the coating film is peeled off, and the coating film characteristics such as chemical resistance are reduced. On the other hand, when it exceeds 10% by mass, the light absorption on the surface of the dried coating film becomes intense, and the deep hardenability tends to decrease.

Specific examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylacetone- 1, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-one, 2- (dimethylamino) -2-[(4- Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, and the like.

Specific examples of the fluorenylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzylfluorenyl oxide). ) -Phenylphosphine, bis (2,6-dimethoxybenzylfluorenyl) -2,4,4-trimethyl-pentylphosphine, and the like.

The blending amount of these α-aminoacetophenone-based photopolymerization initiators and fluorenylphosphine oxide-based photopolymerization initiators is preferably 0.5 to 15% by mass of the entire composition. If it is less than 0.5% by mass, similarly, the photocurability on copper is insufficient, the coating film is peeled off, and the coating film characteristics such as chemical resistance are reduced. On the other hand, if it exceeds 15% by mass, the effect of reducing outgassing cannot be obtained, and the light absorption on the surface of the dried coating film becomes intense, which tends to reduce deep hardenability.

Other photopolymerization initiators, photostarters, and sensitizers that can be suitably used in the photosensitive composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, and thioxanthone compounds. , Ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Specific examples of the acetophenone compound include benzene Ethyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.

Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone. Tons of ketones and so on.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

Specific examples of the benzophenone compound include benzophenone, 4-benzylfluorenyldiphenyl sulfide, 4-benzylfluorenyl-4'-methyldiphenylsulfide, and 4-benzylfluorene. -4'-ethyldiphenyl sulfide, 4-benzylfluorenyl-4'-propyldiphenyl sulfide, and the like.

Specific examples of the tertiary amine compound include ethanolamine compounds and compounds having a dialkylaminobenzene structure, such as 4,4'-dimethylaminobenzophenone and 4,4'-diethyl. Dialkylaminobenzophenones such as aminobenzophenone; 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (bis Ethylamino) -4-methylcoumarin) and other coumarin compounds containing dialkylamino groups; ethyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate Ester, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, p-dimethylaminobenzoic acid isoamylethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl Esters, etc.

Among the aforementioned photopolymerization initiators, photostarters, and sensitizers, thioxanthone compounds and tertiary amine compounds are preferred. Especially deep In terms of sclerosing property, a thioxanthone compound is preferably contained. Among them, thioxanthone compounds containing 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. For the better.

The blending amount of such a thioxanthone compound is preferably 15% by mass or less of the total amount of the composition. When the amount of the thioxanthone compound exceeds 15% by mass, the thick film hardenability is reduced, and the cost of the product is increased. It is more preferably 10% by mass or less.

The tertiary amine compound is preferably a compound having a dialkylaminobenzene structure. Among them, a dialkylaminobenzophenone compound having a maximum absorption wavelength of 350 to 450nm and containing a dialkylamine group is preferred. Coumarin compounds and coumarin ketones are particularly preferred.

The aforementioned dialkylaminobenzophenone compound is also preferred because of its low toxicity with 4,4'-diethylaminobenzophenone. The aforementioned dialkylamine group contains a coumarin compound with a maximum absorption wavelength of 350 to 410 nm and is in the ultraviolet region. Therefore, in addition to providing a light-sensitive, colorless and transparent photosensitive composition, it is also possible to provide the use of colored pigments. A pigmented hardened layer that expresses the color of the pigment itself. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The blending amount of such a tertiary amine compound is preferably 0.1 to 15% by mass based on the total amount of the composition. When the content of the tertiary amine compound is less than 0.1% by mass, there is a tendency that a sufficient sensitization effect cannot be obtained. When it exceeds 15% by mass, the light absorption on the surface of the dried coating film of the tertiary amine compound becomes intense, and the deep hardenability tends to decrease.

These photopolymerization initiators, photoinitiators and sensitizers can be used alone or as a mixture of two or more kinds.

The total amount of such a photopolymerization initiator, photoinitiator, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the aforementioned carboxyl group-containing photosensitive compound or carboxyl group-containing compound. When it exceeds 35 parts by mass, there is a tendency that the deep hardenability is reduced due to such light absorption.

In addition, these photopolymerization initiators, photoinitiators, and sensitizers absorb specific wavelengths, and therefore have lower sensitivity depending on the situation, and function as ultraviolet absorbers. However, these are not only used for the purpose of improving the sensitivity of the composition. It can absorb light of specific wavelength according to the need, improve the light reactivity of the surface, change the line shape and opening of the resist to vertical, tapered, reverse tapered, and improve the processing accuracy of line width or opening diameter.

The aforementioned epoxy compound (C) is preferably a polyfunctional epoxy resin having a plurality of epoxy groups in the molecule, and particularly preferably a polyfunctional epoxy resin having a benzene ring. Specific examples of the epoxy resin include bisphenol A epoxy resin, brominated epoxy resin, novolac epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, and propylene oxide. Amine type epoxy resin, allantoin type epoxy resin, trihydroxyphenylmethane type epoxy resin, bixylenol type or bisphenol type epoxy resin or a mixture thereof, tetraphenol ethane type ring Oxygen resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylylene ethane resin, naphthyl-containing epoxy resin, dicyclopentadiene skeleton Epoxy resin, epoxy propylene methacrylate copolymerization epoxy resin, further copolymerized epoxy resin of cyclohexyl maleimide and propylene methacrylate, epoxy modified polybutadiene Rubber Gum derivatives, CTBN modified epoxy resins, etc. are not limited to these. These epoxy resins can be used alone or in combination of two or more.

The blending amount of the aforementioned epoxy compound is preferably in the range of 1.5 equivalents or more relative to 1 equivalent of the carboxyl group in the composition; more preferably in the range of 1.5 equivalents or more and 5 equivalents or less; more preferably in the range of 1.5 equivalents or more, 4 Range below equivalent. When the blending amount of the epoxy compound is less than 1.5 equivalents, the insulation properties and crack resistance of the hardened layer are reduced, so it is not good. On the other hand, if the blending amount of the epoxy compound exceeds 5 equivalents, the developability is lowered, which is not preferable.

The photosensitive composition of the present invention may further include, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 -Cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, and other imidazole derivatives; dicyandiamide, benzyldimethyl Amine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-di Amine compounds such as methylbenzylamine; hydrazine compounds such as hydrazine adipate and hydrazine sebacate; phosphorus compounds such as triphenylphosphine and the like are used as hardening catalysts. In particular, as long as it promotes a reaction between a compound having a cyclic ether group and a carboxyl group, it is not limited thereto. These catalysts can be used alone or in combination of two or more. In addition, guanamine, eguanidamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-tri, which also functions as an adhesion-imparting agent, can also be used. Azine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Trimeric isocyanate adduct, 2,4-diamino-6-methacryl methoxyethyl-S-triazine. S-triazine derivatives such as trimeric isocyanate adducts, These compounds are preferably used in combination with the aforementioned hardening catalyst. The blending amount of the hardening catalyst is a ratio of a normal amount. For example, it is 0.1 to 20 parts by mass, and preferably 0.5 to 15.0 with respect to 100 parts by mass of the aforementioned carboxyl group-containing photosensitive compound or carboxyl group-containing compound. The proportion by mass.

As the photosensitive compound (D) having no carboxyl group, that is, a photosensitive monomer, a compound having one or more, preferably two or more ethylenically unsaturated double bonds in the molecule can be used. The photosensitive single system is light-hardened by irradiation with active energy rays, so that the aforementioned photosensitive compound containing a carboxyl group is insoluble in an alkaline aqueous solution, or assists an insoluble person. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, (meth) ) Acrylic epoxy esters, specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, Diacrylates of glycol ethers such as propylene glycol; N, N-dimethylacrylamide, N-methylmethacrylamide, N, N-dimethylaminopropylacrylamide, etc. Amines; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, and other amine alkyl acrylates; hexanediol, trimethylolpropane, pentaerythritol, diamine Polyols such as pentaerythritol, ginsyl-hydroxyethyltrimeric isocyanate, etc., or polyvalent acrylates such as ethylene oxide adduct, propylene oxide adduct, or ε-caprolactone adduct; Polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and phenolic ethylene oxide adducts or propylene oxide adducts thereof; glycerol Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl trimer Polyvalent acrylates of glycidyl ether such as isocyanate; not limited to the above, examples include polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, polyester polyols and the like Acrylates and melamine acrylates which are directly acrylated or urethane acrylated through diisocyanate, and / or each methacrylate corresponding to the acrylate, and the like.

Further examples thereof include an acrylic epoxy resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and isophorone di. An epoxy urethane acrylate compound and the like obtained by reacting a diisocyanate half urethane compound such as isocyanate with the hydroxyl group of the acrylic epoxy resin. Such an acrylic epoxy resin can improve the photo-hardening property without reducing the touch dryness.

The photosensitive compound having no carboxyl group as described above is, for example, a compound having a weight average molecular weight Mw4000 or less measured by GPC.

The blending amount of the photosensitive compound having no carboxyl group is 30% by mass or less of the total photosensitive components (the photosensitive compound containing a carboxyl group and the photosensitive compound having no carboxyl group); preferably 1% by mass or more, 10 Mass% or less; more preferably 1 mass% or more and 5 mass% or less is appropriate.

The photosensitive composition of the present invention may contain a well-known and commonly used mercapto compound or an adhesion promoter in order to improve the adhesion to a substrate such as polyimide, if necessary. Examples of the mercapto compound include 2-mercaptopropionic acid, trimethylolpropane (2-thiopropionate), 2-mercaptoethanol, and 2-mercaptoethanol. Mercapto-containing silane coupling agents such as aminothiophenol, 3-mercapto-1,2,4-triazole, and 3-mercapto-propyltrimethoxysilane. Examples of adhesion promoters include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and 3-morpholinylmethyl- 1-phenyl-triazole-2-thione, 5-amino-3-morpholinylmethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, Tetrazole, benzotriazole, carboxybenzotriazole, amine-containing benzotriazole, vinyltriazine, and the like. These can be used individually or in combination of 2 or more types. The blending amount thereof is preferably in a range of 10 parts by mass or less per 100 parts by mass of the aforementioned carboxyl group-containing photosensitive compound or carboxyl group-containing compound. When the compounding amount of these compounds exceeds the above-mentioned range, the epoxy group of the aforementioned epoxy compound necessary for the cross-linking reaction (reacts with the epoxy group) is consumed, and the cross-linking density is lowered, which is not preferable.

In many polymer materials, once oxidation begins, oxidative degradation will continue to occur continuously, resulting in a decrease in the function of the polymer material. Therefore, in order to prevent oxidation in the photosensitive composition of the present invention, free radicals generated by (1) may be added. An antioxidant such as a deactivated radical scavenger or / and a peroxide decomposer which decomposes the peroxide generated in (2) into a harmless substance so that no new radical is generated.

Examples of the antioxidant acting as a free radical recovery agent include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, and 2,6-di- t-butyl-p-cresol, 2,2-methylene-bis (4-methyl-6-t-butylphenol), 1,1,3-ginseng (2-methyl-4-hydroxy -5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-para (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-ginseng (3 ', 5'-di-t-butyl-4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, etc. Phenol-based; quinone-based compounds such as methylquinone, benzoquinone; bis (2,2,6,6-tetramethyl-4-piperidinyl) -sebacate, amine-based compounds such as phenothiazine, etc. .

Examples of the antioxidant acting as a peroxide decomposing agent include phosphorus-based compounds such as triphenylphosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, and distearate. Sulfur compounds such as 3,3'-thiodipropionate and the like.

These antioxidants can be used alone or in combination of two or more.

In the photosensitive composition of the present invention, an ultraviolet absorber can be used in addition to the above-mentioned antioxidant.

Examples of such ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, and anthranilic acid. Ester derivatives, dibenzyl fluorenylmethane derivatives, and the like.

The aforementioned ultraviolet absorbers can be used singly or in combination of two or more. By using them in combination with an antioxidant, the formed article obtained from the photosensitive composition of the present invention can be stabilized.

Further, in the photosensitive composition of the present invention, additives other than the aforementioned components may be added as long as the effects of the present invention are not impaired. Examples of the additives include well-known and commonly used thickeners, polysiloxane-based, fluorine-based, polymer-based defoamers and / or leveling agents, phthalocyanine blue, phthalocyanine green, disazo yellow, titanium oxide, Carbon black, naphthalene black) and the like. Further, a known and commonly used thermal polymerization inhibitor may be added according to need; silane coupling agents such as imidazole, thiazole, and triazole; plasticizers, foaming agents, flame retardants, antistatic agents, anti-aging agents, Antibacterial. Mildew, etc.

[filler]

The photosensitive composition of the present invention may further contain at least one kind of filler selected from the group consisting of an inorganic filler and an organic filler for the purpose of improving characteristics such as adhesion, hardness, and heat resistance as needed. Examples of the inorganic filler include barium sulfate, calcium carbonate, barium titanate, silicon oxide, amorphous silicon dioxide, talc, clay, hydrotalcite, Neuburger silica particles, mica powder, and the like, and organic fillers include silicon powder. , Nylon powder, fluorine powder, etc. Furthermore, in order to obtain a white appearance or flame retardancy, a metal hydroxide such as titanium oxide, metal oxide, aluminum hydroxide, or the like may be used as a pigment extender filler. Among the above fillers, silicon dioxide is particularly excellent in low hygroscopicity and low volume expansion. Regardless of the melting and crystallinity, silicon dioxide can also be a mixture of these, especially in the case of surface-treated silicon dioxide, such as a coupling agent, which can improve electrical insulation and is therefore preferred. Other examples of the filler include fiber-reinforced materials such as organic bentonite, montmorillonite, glass fibers, carbon fibers, and boron nitride fibers.

The average particle diameter (D ₅₀ ) of the filler is 25 μm or less, more preferably 10 μm or less, and even more preferably 3 μm or less. Here, D ₅₀ means a particle diameter of 50% of a volume integral obtained by using a Mie scattering theory and a laser diffraction scattering particle size distribution measurement method. More specifically, the particle size distribution of the microparticles can be prepared by using a laser diffraction scattering type particle size distribution measuring device on the basis of volume, and the number diameter can be used as the average particle diameter for measurement. As the measurement sample, it is preferable to use a method in which fine particles are dispersed in water by ultrasonic waves. As the laser diffraction type particle size distribution measuring device, LA-500 manufactured by Horiba, etc. can be used. The blending amount of these inorganic and / or organic fillers is preferably 300 parts by mass or less per 100 parts by mass of the aforementioned carboxyl group-containing photosensitive compound or carboxyl group-containing compound, and is preferably a proportion of 5 to 150 parts by mass. . When the blending amount of the filler exceeds the above-mentioned ratio, the folding resistance of the hardened film is reduced, which is not preferable.

[Organic solvents]

In the photosensitive composition of the present invention, an organic solvent may be used in order to make the aforementioned carboxyl group-containing photosensitive compound or epoxy compound easily dissolve or disperse, or to adjust the viscosity suitable for coating. Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ether ethers, glycol ether ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; and celluloid, methylcellulose, and butyl Cellusof, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Glycol ether ethers; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, 2- Esters of methyl isobutyrate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; octane, decane And other aliphatic hydrocarbons; petroleum-based solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent petroleum brain. Such an organic solvent can be used alone or as a mixture of two or more kinds. The blending amount of the organic solvent can be appropriately set according to the desired viscosity.

The photosensitive composition of the present invention can be adjusted to a viscosity suitable for, for example, the aforementioned method of coating with an organic solvent, and the substrate may be subjected to a dip coating method, a shower coating method, a roll coating method, a rod coating method, It is applied by screen printing method, curtain coating method, etc., and the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of about 60 to 100 ° C to form an anti-adhesive coating film. In addition, a dry coating film can be formed by applying the composition to a carrier film and drying it, and then attaching it as a film to a substrate by a winder. Then, by contact (or non-contact), a patterned mask is used to selectively expose with active energy rays or direct pattern exposure with a laser direct exposure machine, and expose the unexposed part with a dilute alkali aqueous solution ( For example, 0.3 ~ 3 mass% sodium carbonate aqueous solution) is developed to form a resist pattern. Further, a high pressure mercury lamp, etc. may be used to totalizer exposure amount became 500 ~ 2000mJ / cm ² of ultraviolet rays irradiated, to finish hardening. In addition, by heating to a temperature of, for example, about 140 to 180 ° C., the film may be cured by heat to react the carboxyl group containing the carboxyl group or the carboxyl group-containing compound with the epoxy group epoxy group to form heat resistance and chemical resistance. Hardened coating film with excellent properties including moisture resistance, moisture resistance, adhesion, and electrical properties.

The substrate can be a paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyurethane, in addition to a printed wiring board or a flexible printed wiring board with a circuit formed in advance. Imine, glass Glass cloth / non-fiber cloth-epoxy resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin. Polyethylene. PPO. Copper foil laminates, polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, etc. of all grades of composite materials such as cyanate esters (FR-4, etc.).

Volatile drying performed after coating the photosensitive composition of the present invention can use a hot-air circulation type drying oven, IR furnace, heating plate, convection oven, etc. (using a heat source with air heating method of steam to make hot air in the dryer The method of countercurrent contact and the method of blowing the support from a nozzle).

The photosensitive composition of the present invention is applied in the above manner, and after evaporation and drying, the obtained dried coating film is exposed (irradiation of active energy rays). The exposed part (the part irradiated with active energy rays) of the dried coating film is hardened.

The exposure machine used for the above-mentioned active energy ray irradiation can use a direct drawing device (for example, a laser direct imaging device that directly draws an image by laser using CAD data from a computer), an exposure machine equipped with a metal halide lamp, and a ( Ultra-high-pressure mercury lamp exposure machine, exposure machine equipped with mercury short-arc lamp, or direct-drawing device of ultraviolet light using (ultra-high-pressure mercury lamp). As long as the active energy ray uses laser light having a maximum wavelength in the range of 350 to 410 nm, both gas lasers and solid lasers can be used. In addition, although the exposure amount varies depending on the film thickness and the like, it may be generally within a range of 5 to 800 mJ / cm ² , and preferably within a range of 5 to 700 mJ / cm ² . The direct drawing device may be, for example, manufactured by Orbotech Corporation, ORC Corporation, etc. Any device may be used as long as the device oscillates laser light having a maximum wavelength of 350 to 410 nm.

As the development method, a dipping method, a spray method, a spray method, a brush method, or the like can be used, and the developing solution can be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. Of alkaline aqueous solution.

The photosensitive composition of the present invention may have a method in which the photosensitive composition is directly applied to a substrate in a liquid state, and the photosensitive composition may be dried in advance by coating the photosensitive composition on a film such as polyethylene terephthalate. It is used in the form of a dry film of a coating film. The case where the photosensitive composition of the present invention is used as a dry film is as follows.

The dry film is a structure having a carrier film, a dry coating film, and a peelable coating film used in order, which are laminated. The dry coating film is a layer obtained by applying, for example, an alkali developable photosensitive composition to a carrier film or a coating film and drying it. After the carrier film is formed into a dry coating film, a coating film is laminated thereon, or a dry coating film is formed on the coating film, and this laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm can be used.

Dry coating film is used to make the alkali-developable photosensitive composition equal to the carrier film or coating by using a doctor blade coater, lip coater, comma coater, or film coater. It is formed by uniformly coating and drying at a thickness of 10 to 150 μm.

As the film, a polyethylene film, a polypropylene film, or the like can be used, and the adhesion force with the dried coating film is preferably smaller than that of the carrier film.

Use a dry film to make a protective film (permanent protective film) on a printed wiring board. The film is peeled off, the dry coating film is overlapped with the substrate on which the circuit is formed, and the substrate is formed using a laminator and the like. A dry coating film is formed on the material. A hardened layer can be formed by exposing, developing, and heating and curing the formed dry coating film in the same manner as described above. The carrier film can be peeled off before or after exposure.

Furthermore, the photosensitive composition of the present invention is suitable as a material for a permanent film of a printed wiring board, and among them, it is particularly suitable as a material for a solder resist and an interlayer insulating material.

[Example]

Hereinafter, examples and comparative examples are shown to specifically explain the present invention, but the present invention is not limited to the following examples. In addition, the "%" and "parts" described below are all based on quality unless otherwise specified.

Synthesis Example 1

In an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, a novolac cresol resin (trade name "Shonol CRG951", OH equivalent weight: 119.4) manufactured by Showa Polymer Co., Ltd. 119.4 Parts, potassium hydroxide 1.19 parts, and toluene 119.4 parts. While stirring, the nitrogen in the system was replaced, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide was slowly dropped, and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. After that, it was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. Solution of propylene oxide addition reactant. This is a phenolic hydroxyl group with an average addition of about 1.08 moles of alkylene oxide per equivalent.

293.0 parts of a solution of the alkylene oxide addition reaction product of the obtained novolac cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were placed in a mixer, a thermometer, Air was blown into the reactor of the tube, and air was blown in at a rate of 10 ml / min, while stirring, while reacting at 110 ° C for 12 hours. The water produced by the reaction was distilled as 12.6 parts of water as an azeotropic mixture with toluene. After that, it was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts of a 15% sodium hydroxide aqueous solution, followed by washing with water. Thereafter, toluene was replaced with an evaporator by 118.1 parts of diethylene glycol monoethyl ether acetate and distilled off to obtain a novolac type acrylate resin solution. Next, 332.5 parts of the obtained novolak-type acrylate resin solution, 0.8 parts of chromium naphthenate, and 0.4 parts of lithium naphthenate were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at While blowing in at a speed, while stirring, slowly add 60.8 parts of tetrahydrophthalic anhydride, react at 95-101 ° C for 6 hours, and take it out after cooling. The carboxyl group-containing photosensitive compound thus obtained had a nonvolatile content of 70.9% and a solid content acid value of 82.1 mgKOH / g.

Examples 1 to 9 and Comparative Examples 1 to 3

Each component was blended in the ratios shown in Tables 1 and 2, and after stirring, it was dispersed with a three-roll mill to obtain a photosensitive composition.

The acid values, epoxy equivalents, and double bond equivalents in the aforementioned Tables 1 and 2 were measured as follows.

<Measurement method of acid value with respect to total organic component>

The photosensitive composition was dried at 70 ° C for 24 hours to remove organic solvents. Agent to obtain a solid content. Acetone was added to the solid content to dissolve / disperse it, and the filler was separated from the solid content by a centrifugal separator. Using the separated organic components of the filler, the acid value was measured in accordance with JIS K2501. The acid value obtained in this way is the acid value relative to the total amount of organic components.

<Method for measuring epoxy equivalent with respect to total organic component>

In the same manner as in the case of measuring the acid value, an isolated organic component of the filler was obtained. Using this organic component, the first equivalent was measured in accordance with JIS K7236.

On the other hand, the second equivalent was measured in the same manner as the method for measuring the first equivalent except that tetraethylammonium bromide was not used.

Subtract the second equivalent from the first equivalent to calculate the "epoxy equivalent to the total amount of organic components."

<Method for measuring double bond equivalent>

In the same manner as in the case of measuring the acid value, an isolated organic component of the filler was obtained. After reacting morpholine with this organic component, acetic anhydride is added to react with unreacted morpholine. The third equivalent was calculated by titrating the reactant between the organic component and morpholine with perchloric acid.

Subtract the 1st equivalent from the 3rd equivalent to obtain the "double bond equivalent with respect to the total amount of organic components".

<Method for judging liquid components>

The determination of the liquid state is based on the "Confirmation of liquid state" according to the provincial ordinance (Provincial Decree No. 1 of the Heisei year of the first year) on the test of dangerous substances and properties. Law.

(1) Device

Use a constant temperature water tank: agitator, heater, thermometer, automatic temperature regulator (those with a temperature control of ± 0.1 ℃) and a depth of 150mm or more.

For the determination of liquid components, a combination of a low-temperature thermostatic water tank (type BU300) manufactured by Yamato Scientific Co., Ltd. and a thermostat thermostat (type BF500) was used to add approximately 22 liters of tap water to the low-temperature thermostatic water tank (type BU300). ), Turn on the assembled Thermomate (type BF500) power supply, set the set temperature (20 ° C), and finely adjust the water temperature to the set temperature ± 0.1 ° C with Thermomate (type BF500), but as long as it is a device that can be adjusted the same Can be used.

Test tube:

As shown in Figure 1, the test tube is made of a flat-bottomed cylindrical transparent glass with an inner diameter of 30mm and a height of 120mm. The heights of 55mm and 85mm from the bottom of the tube are marked with lines 2, 3, and the test tube mouth The test tube 1a for determining the liquid state is sealed with a rubber stopper 4a; and the same size and in the same manner are marked with a rubber stopper 4b for inserting / supporting a thermometer hole in the center to seal the test tube opening, and The rubber stopper 4b is inserted into the temperature measurement test tube 1b of the thermometer 5. In the following, the line with a height of 55mm from the bottom of the tube is referred to as the "A line" and the line with a height of 85mm from the bottom of the tube is referred to as "B line".

Thermometer 5 is used for measuring the freezing point (SOP-58 scale range 20 ~ 50 ℃) specified in JIS B7410 (1982) "Glass Thermometer for Petroleum Testing", but those who can measure the temperature range of 0 ~ 50 ℃ Just fine.

(2) Test execution sequence

Samples that have been left for more than 24 hours at an atmospheric pressure of 20 ± 5 ° C are placed in the test tube 1a for determining the liquid state shown in Fig. 1 (a) and the test tube 1b for temperature measurement shown in Fig. 1 (b). Up to the A line. Place two test tubes 1a, 1b upright and place them in a low temperature thermostatic water tank so that the B line is below the water surface. Make the lower end of the thermometer below 30mm of the A line.

After the sample temperature reaches the set temperature of 20 ± 0.1 ° C, it is maintained for 10 minutes. After 10 minutes, take out the liquid test tube 1a from the low-temperature constant temperature water tank, immediately level it down on a horizontal test bench, and use a horse watch to measure the time at which the liquid tip in the test tube moves from line A to line B recording. At the set temperature, the sample is judged to be liquid when the measurement time is within 90 seconds, and it is judged to be solid when it is longer than 90 seconds.

For each photosensitive composition, a test substrate was prepared in the following manner, and the following characteristics were evaluated. The results are shown in Tables 3 and 4.

<Manufacture of test substrate>

Using a screen printing method, a 100-mesh polyester screen was used for the photosensitive composition to form a thickness of 20 to 30 μm on the entire surface of a printed wiring board on which a copper pattern was formed, and a coating film was applied. After drying in a hot air dryer at 80 ° C for 60 minutes, the negative film with a resist pattern was adhered to the coating film, and an ultraviolet exposure device (ORC Manufacturing Co., Ltd., type HMW-680GW) was used, and the exposure amount was 500 mJ / cm ² Of ultraviolet. Next, it was developed with a 1% sodium carbonate aqueous solution at a spray pressure of 2.5 kg / cm ² for 60 seconds. Thereafter, the substrate was irradiated with ultraviolet rays by a high-pressure mercury lamp so that the cumulative exposure amount became 1000 mJ / cm ² , and then cured at 160 ° C. for 1 hour to obtain an evaluation substrate.

The tests of insulation, cracking, pattern formation (developing properties) and adhesion were performed as follows.

<Insulation resistance in PCBT>

Using the comb electrode B specimen of IPCB-25, an evaluation substrate was prepared under the above conditions. A bias voltage of 30 VDC was applied to the comb electrode. A PCT device (HAST YSTEM TPC-412MD, manufactured by ESPEC Corporation) was used at 121 ° C and humidity. 97% of conditions, the time required to reduce the resistance value to 1.0 × 10 ⁷ Ω or less was measured. A situation that requires more than 300 hours can be evaluated as good.

<TCT corner crack>

The aforementioned photosensitive composition was coated on a substrate having a copper wire pattern of 2 mm, and exposed and developed in the same manner as above, followed by ultraviolet irradiation and thermal curing. Seven copper resists of 3 mm square size were formed on the copper wire. Type evaluation substrate. Place this evaluation substrate between -65 ° C and 150 ° C The hot and cold cycle machine that performs temperature cycling performs TCT (Thermal Cycle Test). In addition, the appearance at 1,000 cycles was observed, and the number of cracks was counted. A case where the number of cracks is 30/68 or less can be evaluated as good. In addition, the value of the denominator "68" means 4 corners (4) x 17 corners of a 3mm square resist pattern, a total of 68 corners, and the value of the numerator "30" indicates the number of cracks.

<Pattern formation>

Use a magnifying glass to visually determine the state after exposure and development. The results are shown in Tables 3 and 4. In Examples 1 to 9 and Comparative Examples 1 to 3, patterns can be formed.

<Adhesiveness>

The photosensitive composition was coated on the entire surface of the patterned copper foil substrate by screen printing, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. A PET negative film was brought into contact with this substrate, and pressed under a reduced pressure condition of ORC (HMW-GW20) for 1 minute, and then the state of the film after the negative film was peeled off was evaluated.

Good: When the film is peeled off, there is no resistance and no trace remains on the coating film.

Defective: When the film is peeled off, it has resistance, leaving traces on the coating film.

As shown in Table 3, the patterns can be formed well in Examples 1 to 9, and the insulation can be maintained for a long time even under high temperature and high humidity, and the occurrence of cracks can be suppressed. However, as shown in Table 4, in Comparative Examples 1 to 3 in which the double bond equivalent of the entire composition was less than 400 after the filler was removed from the photosensitive composition, the insulation could not be maintained for a long time under high temperature and high humidity, and cracks occurred. Also many.

[Industrial availability]

The curable resin composition or the dry film of the present invention is suitable as a material for a permanent coating of a printed wiring board, and among them, it is particularly advantageous to be used as a material for a solder resist and an interlayer insulating material.

Claims (6)

A photosensitive composition containing (A) a photosensitive compound containing a carboxyl group, (B) a photopolymerization initiator, and (C) an epoxy compound, characterized in that the photosensitive composition The double bond equivalent is 450 or more and 646 or less in the state of not containing an organic solvent and a filler. The epoxy group of the (C) epoxy compound is equivalent to the carboxyl group of the (A) carboxyl group-containing photosensitive compound , Which is 1.84 equivalents or more and 4 equivalents or less, and the (A) carboxyl group-containing photosensitive compound includes any one of the following (2) to (9): (2) The molecule has at least one ethylenic compound. A compound containing a saturated group and an epoxy group, and a carboxyl group-containing photosensitive resin obtained by reacting a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid with a compound having an unsaturated double bond and a benzene ring; (3) In the addition polymerization reaction of aromatic diisocyanate, carboxyl group-containing diol compound and diol compound to synthesize carboxyl group-containing urethane resin, add 1 hydroxyl group and 1 in the molecule The above (meth) acrylic group compound is a photosensitive urethane resin containing carboxyl group obtained by terminal (meth) acrylic esterification; (4) diisocyanate and bifunctional ring with benzene ring (Meth) acrylic acid esters of oxygen resins or their partial anhydride modified products, carboxyl group-containing diol compounds and diol compounds obtained by the addition polymerization reaction of carboxyl group-containing photosensitive urethane resins; (5) Addition polymerization reaction of aromatic diisocyanate, carboxyl group-containing diol compound and diol compound to synthesize carboxyl group-containing carbamate resin, adding one isocyanate group and one or more (methyl ) Acrylic-based compound, a carboxyl group-containing photosensitive urethane resin obtained by terminal (meth) acrylic esterification; (6) (Meth) acrylic acid and a bifunctional benzene ring or more The reaction of a multifunctional epoxy resin to add a dibasic acid anhydride to the hydroxyl group present in the side chain to obtain a photosensitive resin containing a carboxyl group; The hydroxyl group of the oxygen resin is further reacted with epichlorohydrin to obtain a multifunctional epoxy resin, and a carboxyl group-containing photosensitive resin is obtained by adding a dibasic acid anhydride to the generated hydroxyl group; (8 ) Adding cyclic ether and / or cyclic carbonate to the multifunctional phenol compound, partially esterifying the resulting hydroxyl group with (meth) acrylic acid, and reacting the polyhydric anhydride with the remaining hydroxyl group Carboxyl photosensitive resin; and (9) The resin as described in (3) to (8) above is further added with a compound having one epoxy group and more than one (meth) acryloyl group in the molecule Photosensitive resin containing carboxyl groups. For example, the photosensitive composition of claim 1 further contains (D) a photosensitive compound having no carboxyl group, and (D) is a compound having one or more ethylenically unsaturated double bonds in the molecule. The photosensitive composition as claimed in Item 2 of the patent application, wherein the (D) photosensitive compound without a carboxyl group in the mixed component of the aforementioned (A) photosensitive compound containing a carboxyl group and the aforementioned (D) photosensitive compound without a carboxyl group The content rate of the sexual compound is 30% by mass or less. A photosensitive composition comprising (A ') a carboxyl group-containing compound, (B) a photopolymerization initiator, and (C) an epoxy compound, which is characterized in that the aforementioned (A') contains a carboxyl group The compound includes any of the following (1) to (9): (1) obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with a compound having an unsaturated double bond and a benzene ring Resins containing carboxyl groups; (2) Compounds that have more than one ethylenically unsaturated group and one epoxy group in the molecule, and compounds that have unsaturated double bonds and benzene rings by making unsaturated carboxylic acids The carboxyl group-containing photosensitive resin obtained by reacting the carboxyl group-containing resin obtained by copolymerization; (3) Addition polymerization reaction of aromatic diisocyanate, carboxyl group-containing diol compound and diol compound to synthesize carboxyl group-containing amine In the urethane resin, a compound having one hydroxyl group and one or more (meth) acrylic groups in the molecule is added to obtain a carboxyl group-containing photosensitive amine group obtained by esterifying the terminal (meth) acrylate Formate resin; (4) Addition polymerization of diisocyanate, (meth) acrylate with bifunctional epoxy resin having benzene ring or partial acid anhydride modification, diol compound containing carboxyl group and diol compound The resulting carboxyl group-containing photosensitive urethane resin; (5) Addition polymerization reaction of aromatic diisocyanate, carboxyl group-containing diol compound and diol compound to synthesize carboxyl group-containing urethane group Among the resins, a compound containing a carboxyl group-containing photosensitive urethane resin obtained by adding a compound having one isocyanate group and one or more (meth) acrylic groups in the molecule for terminal (meth) acrylate esterification; (6) A carboxyl group-containing photosensitive resin obtained by reacting (meth) acrylic acid with a bifunctional or more multifunctional epoxy resin having a benzene ring to add a dibasic acid anhydride to the hydroxyl group present in the side chain ; (7) reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin having a benzene ring with epichlorohydrin, and reacting with the generated hydrogen A photosensitive resin containing a carboxyl group obtained by adding an oxygen group to a dibasic acid anhydride; (8) Adding a cyclic ether and / or cyclic carbonate to a multifunctional phenol compound, and converting the resulting hydroxyl group to (methyl) Acrylic acid partially esterified to make polyacid anhydride react with the remaining hydroxyl group to obtain a carboxyl group-containing photosensitive resin; and (9) The above resins (1), (3) to (8) are further added to the molecular weight A carboxyl group-containing photosensitive resin composed of a compound having one epoxy group and one or more (meth) acryloyl groups; the epoxy group of the aforementioned (C) epoxy compound contains more than the aforementioned (A ') The equivalent of the carboxyl group of the carboxyl compound is 1.84 equivalents or more and 4 equivalents or less, and the content of the liquid component contained in the photosensitive composition is 5 mass% or more relative to all components except the organic solvent and the filler 30% by mass or less, the double bond equivalent of the photosensitive composition is 450 or more and 646 or less in the state of not containing organic solvents and fillers. For example, in the photosensitive composition of claim 4, the number of epoxy groups of the aforementioned (C) epoxy compound is 2. A printed wiring board is characterized by having a hardened layer formed using the photosensitive composition as described in any one of patent application items 1 to 5.