KR102050126B1 - Photosensitive composition and printed circuit board having hardened layer thereof - Google Patents

Abstract

In the present invention, the photosensitive composition includes (A) a carboxyl group-containing photosensitive compound and (B) photopolymerization in order to be able to develop well on a printed wiring board, to maintain insulation for a long time, and to form a cured film having excellent mechanical strength. The photosensitive compound which contains an initiator and (C) epoxy compound, or (D) does not have a carboxyl group is further contained, The double bond equivalent of this photosensitive composition is 400 or more in the state containing no organic solvent and a filler. In another aspect, it is a photosensitive composition containing (A ') carboxyl group-containing compound, (B) photoinitiator, and (C) epoxy compound, The epoxy group of the said (C) epoxy compound of the said (A') carboxyl group-containing compound It is 1.5 equivalent or more and 4 equivalent or less with respect to 1 equivalent of carboxyl groups, and the content rate of the liquid component contained in the said photosensitive composition is 5 mass% or more and 30 mass% or less with respect to the whole component except an organic solvent and a filler.

Description

Printed wiring board which has a photosensitive composition and its hardened layer TECHNICAL FIELD

This invention relates to the printed wiring board which has a photosensitive composition and its hardened layer.

The soldering resist is formed in the printed wiring board on the base material which has a conductor layer of a circuit pattern. As a material of such a soldering resist, various photosensitive compositions are conventionally proposed. For example, Patent Document 1 discloses a photosensitive resin composition for permanent resist containing a polymer having a carboxyl group, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator.

By the way, in recent years, especially when photosensitive compositions, such as a soldering resist, are used for the printed wiring board for vehicle mounting, maintaining insulation for a long time under high temperature, high humidity environment, and the mechanical strength which a crack does not produce is calculated | required.

Japanese Patent Laid-Open No. 2005-99647 (claims)

However, in the conventional photosensitive composition, when there is much content of a photopolymerizable monomer, the problem that insulation cannot be maintained for a long time under high temperature, high humidity, or many cracks generate | occur | produced.

On the other hand, when content of a photopolymerizable monomer was reduced, since the sensitivity fell, the problem that pattern formation became difficult also occurred.

This invention is made | formed in view of the above-mentioned problem of the prior art, The basic objective is the photosensitive which can form a pattern favorably, can maintain insulation for a long time, and can form the cured film excellent in mechanical strength. It is in providing a composition.

Moreover, the objective of this invention is providing the printed wiring board with high long-term reliability which has a hardened layer of the photosensitive composition which has such the outstanding characteristic.

In order to achieve the above object, according to the first aspect of the present invention,

(A) carboxyl group-containing photosensitive compound,

(B) photoinitiator, and

(C) It is a photosensitive composition containing an epoxy compound,

There is provided a photosensitive composition, wherein the double bond equivalent of the photosensitive composition is 400 or more in a state containing no organic solvent and a filler.

In another aspect, the photosensitive composition which further contains the photosensitive compound which does not have a (D) carboxyl group other than each said component is provided.

According to a suitable aspect, the double bond equivalent of the said photosensitive composition is 400 or more and 680 or less, More preferably, it is 450 or more and 650 or less, More preferably, it is 500 or more and 650 or less in the state containing no organic solvent and a filler. Moreover, according to a suitable aspect, the content rate of (D) component in the mixed component of the said (A) carboxyl group-containing photosensitive compound and the (D) photosensitive compound which does not have a carboxyl group is 30 mass% or less. According to a more suitable aspect, the epoxy group of the (C) epoxy compound is 1.5 equivalent or more relative to 1 equivalent of the carboxyl group of the (A) carboxyl group-containing compound.

Furthermore, according to the second aspect of the present invention,

(A ') carboxyl group-containing compound,

(B) photoinitiator, and

(C) It is a photosensitive composition containing an epoxy compound,

The epoxy group of the above-mentioned (C) epoxy compound is 1.5 equivalent or more and 4 equivalents or less with respect to 1 equivalent of carboxyl group of the said (A ') carboxyl group-containing compound, and the content rate of the liquid component contained in the said photosensitive composition is the whole component except an organic solvent and a filler. It is 5 mass% or more and 30 mass% or less with respect to the photosensitive composition characterized by the above-mentioned.

According to a suitable aspect, the number of epoxy groups of the said (C) epoxy compound is two.

Moreover, according to this invention, the printed wiring board which has a hardened layer formed using the said photosensitive composition is also provided.

The photosensitive composition of the first aspect of the present invention can form a pattern satisfactorily by making the double bond equivalent of the photosensitive composition to 400 or more in a state free of an organic solvent and a filler as described above, under high temperature and high humidity. Even if it can maintain insulation for a long time, generation | occurrence | production of a crack can be suppressed. Therefore, the printed wiring board with long-term reliability can be provided by forming hardening layers, such as a soldering resist and an interlayer insulation layer, using the photosensitive composition which has such the outstanding characteristic.

Moreover, the photosensitive composition of the 2nd aspect of this invention is a photosensitive composition containing (A ') carboxyl group-containing compound, (B) photoinitiator, and (C) epoxy compound as above-mentioned, The said (C) epoxy compound The epoxy group of the compound (A ') is 1.5 equivalent or more and 4 equivalents or less with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing compound, and the content of the liquid component contained in the photosensitive composition is 5% by mass or more with respect to all components except the organic solvent and the filler. By setting it as 30 mass% or less, a pattern can be formed favorably, insulation can be maintained for a long time even under high temperature, high humidity, and generation | occurrence | production of a crack can be suppressed. Therefore, the printed wiring board with long-term reliability can be provided by forming hardening layers, such as a soldering resist and an interlayer insulation layer, using the photosensitive composition which has such the outstanding characteristic.

1 is a schematic side view illustrating two test tubes used for liquid phase determination in Examples and Comparative Examples.

According to the studies of the present inventors, the photosensitive composition containing (A) a carboxyl group-containing photosensitive compound, (B) photoinitiator, and (C) epoxy compound, or (D) a photosensitive compound which does not have a carboxyl group, When the double bond equivalent of the said photosensitive composition is 400 or more in the state which does not contain an organic solvent and a filler, it discovered that the subject of this invention can be solved.

When the content of the photosensitive compound which does not have the 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 when the content of the photosensitive monomer is reduced, the sensitivity is lowered to form a pattern. This problem of difficulty is solved when the double bond equivalent of the total amount of the organic components in the photosensitive composition is in a specific range, that is, the double bond equivalent of the photosensitive composition is 400 or more in a state that does not contain an organic solvent and a filler. It has been found that the present invention can be completed.

Moreover, according to the research of the present inventors, it is a photosensitive composition containing (A ') carboxyl group containing compound, (B) photoinitiator, and (C) epoxy compound, The epoxy group of the said (C) epoxy compound is said (A') carboxyl group 1.5 equivalent or more and 4 equivalent or less with respect to 1 equivalent of carboxyl groups of a containing compound, and when the content rate of the liquid component contained in the said photosensitive composition is 5 mass% or more and 30 mass% or less with respect to the whole component except an organic solvent and a filler, We found that we could solve the problem. Here, determination of whether it is "liquid phase" is performed at 20 degreeC.

As described above, when the content of the photosensitive compound having no carboxyl group, i.e., the photosensitive monomer (photopolymerizable monomer) is large, the problem that insulation cannot be maintained for a long time under high temperature and high humidity tends to occur, but the photosensitive composition of the present invention contains the photosensitive monomer. Even if it does not, or it contains, even if it contains a small quantity, there is little possibility that such a problem will arise. On the other hand, when content of the photosensitive monomer is reduced, since a softening point raises generally, solubility falls and pattern formation becomes difficult, the epoxy group of the said (C) epoxy compound of the said (A ') carboxyl group-containing compound Based on 1 equivalent of carboxyl group, it was found that it can be solved when the content of the liquid component contained in the photosensitive composition is 1.5 equivalent or more and 4 equivalent or less, and 5 mass% or more and 30 mass% or less with respect to all components except the organic solvent and the filler. The present invention has been completed.

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

It is preferable that the ethylenically unsaturated double bond in the said carboxyl group-containing photosensitive compound (A) is derived from acrylic acid, methacrylic acid, or derivatives thereof.

In addition, as said carboxyl group-containing compound (A '), the well-known conventional resin compound which has a carboxyl group in a molecule | numerator can be used. As carboxyl group-containing resin, both the carboxyl group-containing resin which does not have ethylenically unsaturated double bond, and the carboxyl group-containing photosensitive resin which has ethylenically unsaturated double bond can be used, It is not limited to a specific thing, A carboxyl group-containing photosensitive resin is a sight It is more preferable in terms of chemical resistance and developability.

As a specific example of such a carboxyl group-containing photosensitive compound or a carboxyl group-containing compound, the compound (which may be any of an oligomer and a polymer) listed below is mentioned.

(1) Carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and a compound which has unsaturated double bonds, such as styrene and (alpha) -methylstyrene, and a benzene ring.

(2) To the carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated double bonds, such as styrene and (alpha) -methylstyrene, and a compound having a benzene ring, 1 or more ethylenically unsaturated groups in a molecule | numerator Carboxyl group containing photosensitive resin which makes the compound which has one epoxy group react.

(3) Aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, and bisphenol A compounds. During synthesis of the carboxyl group-containing urethane resin by the polyaddition reaction of diol compounds such as alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, in a molecule such as hydroxyalkyl (meth) acrylate The carboxyl group-containing photosensitive urethane resin which added the compound which has one hydroxyl group and one or more (meth) acryl groups, and was terminal (meth) acrylated.

(4) diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bixenol type epoxy resins; The carboxyl group-containing photosensitive urethane resin by the polyaddition reaction of the (meth) acrylate of the bifunctional epoxy resin which has a benzene ring, such as a biphenol type epoxy resin, or its partial acid anhydride modification, a carboxyl group-containing dialcohol compound, and a diol compound.

(5) A compound having one hydroxyl group and one or more (meth) acryl groups in a molecule such as hydroxyalkyl (meth) acrylate, or isophorone diisocyanate and pentaerythritol tree during the synthesis of the resin (3). The carboxyl group-containing photosensitive urethane resin which added the compound which has one isocyanate group and one or more (meth) acryl groups in a molecule | numerator, such as an equimolar reactant of an acrylate, and was terminal (meth) acrylated.

(6) (meth) acrylic acid is made to react with the bifunctional or more than one polyfunctional epoxy resin which has a benzene ring as mentioned later, and 2, such as a phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, is carried out by the hydroxyl group which exists in a side chain. Carboxyl group containing photosensitive resin which added basic acid anhydride.

(7) The hydroxyl group of the bifunctional epoxy resin which has a benzene ring as mentioned later is further reacted with (meth) acrylic acid to the polyfunctional epoxy resin epoxidized with epichlorohydrin, and the dibasic acid anhydride is added to the hydroxyl group which generate | occur | produced. Carboxyl group-containing photosensitive resin.

(8) To the polyfunctional phenolic compounds, such as novolak, cyclic ethers, such as ethylene oxide, and / or cyclic carbonates, such as a propylene carbonate, are added, the hydroxyl group obtained is partially esterified with (meth) acrylic acid, and the remainder is The carboxyl group-containing photosensitive resin which made polybasic acid anhydrides, such as maleic anhydride, tetrahydro phthalic anhydride, trimellitic anhydride, a pyromellitic dianhydride, react with a hydroxyl group.

(9) In addition to the resins of the above (1) to (8), one epoxy group and at least one (meth) group in a molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. Carboxyl group containing photosensitive resin which adds the compound which has acryloyl group.

In addition, in this specification, a (meth) acrylate is a term used generically for acrylate, methacrylate, and mixtures thereof, and the same also about other similar expression.

Since the carboxyl group-containing photosensitive compound or the carboxyl group-containing compound as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a rare alkali aqueous solution is possible.

The acid value of the carboxyl group-containing photosensitive compound or the carboxyl group-containing compound is preferably in the range of 30 to 200 mgKOH / g, more preferably in the range of 30 to 150 mgKOH / g, particularly preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing photosensitive compound is less than 30 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developing solution proceeds, so that the line becomes thinner than necessary or, in some cases, the exposed portion. It is not preferable because it is dissolved and peeled off with a developer without distinction between the unexposed portion and the drawing of a normal resist pattern becomes difficult.

In addition, although the weight average molecular weight Mw (weight average molecular weight in polystyrene conversion) of the said carboxyl group-containing photosensitive compound or carboxyl group-containing compound measured by gel permeation chromatography (GPC), for example, differs according to resin skeleton, It is preferable that it is larger than 4,000 and is 150,000 or less, Furthermore, it exists in the range of 5,000 or more and 100,000 or less. If the weight average molecular weight is 4,000 or less, the adhesion-free performance may be inferior, the moisture resistance of the coating film after exposure is poor, the film decreases at the time of image development, and the resolution may fall large. On the other hand, when a weight average molecular weight exceeds 150,000, developability may remarkably worsen and it is unpreferable.

The carboxyl group-containing photosensitive compound can be used without being limited to the above-mentioned as long as it has an ethylenically unsaturated double bond in a molecule | numerator, and can also be used even if it is one type or in mixture of 2 or more types.

As a photoinitiator (B) used by this invention, at least 1 type of photoinitiator selected from the group which consists of an oxime ester photoinitiator which has an oxime ester group, the (alpha)-amino acetophenone type photoinitiator, and the acylphosphine oxide type photoinitiator. Can be used as appropriate.

As said oxime ester system photoinitiator, the photoinitiator which has two oxime ester groups in a molecule can be used suitably.

It is preferable that the compounding quantity of such an oxime ester system photoinitiator shall be 0.02-10 mass% of the whole composition amount. If it is less than 0.02 mass%, the photocurability on copper will run short, while a coating film will peel, and coating film characteristics, such as chemical-resistance, will fall. On the other hand, when it exceeds 10 mass%, there exists a tendency for the light absorption on the dry coating film surface to become severe, and deep-curing property falls.

Specifically as said (alpha)-amino acetophenone type photoinitiator, 2-methyl-1- [4- (methylthio) phenyl] -2- morpholino propane 1, 2- benzyl-2- dimethylamino-1 -(4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1 -Butanone, N, N-dimethylaminoacetophenone, etc. are mentioned.

Specifically as said acyl phosphine oxide type photoinitiator, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2,4, 6- trimethyl benzoyl)-phenylphosphine oxide, bis (2, 6-, Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like.

It is preferable that the compounding quantity of these (alpha)-amino acetophenone series photoinitiators and an acyl phosphine oxide type photoinitiators shall be 0.5-15 mass% of the composition whole quantity. If it is less than 0.5 mass%, the photocurability on copper is similarly lacking, while a coating film peels, coating film characteristics, such as chemical-resistance, fall. On the other hand, when it exceeds 15 mass%, the effect of reducing outgas is not obtained, and further, the light absorption in the dry coating film surface becomes severe, and there exists a tendency for deep-curing property to fall.

In addition, as a photoinitiator, a photoinitiator, and a sensitizer which can be used suitably for the photosensitive composition of this invention, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, 3 And higher amine compounds and xanthone compounds.

Specifically as said benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. are mentioned, for example.

Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like. Can be mentioned.

Specifically as said anthraquinone compound, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, 1-chloro anthraquinone, etc. are mentioned, for example.

Specific examples of the thioxanthone compound include 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 2,4-diisopropyl thioxanthone, and the like. Can be mentioned.

Specifically as said ketal compound, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. are mentioned, for example.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4'-methyldiphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4 -Benzoyl-4'-propyldiphenyl sulfide, etc. are mentioned.

Specifically as said tertiary amine compound, For example, an ethanolamine compound, the compound which has a dialkylaminobenzene structure, for example, 4,4'- dimethylamino benzophenone, 4,4'- diethylamino benzophenone, etc. Dialkylamino group-containing coumarins such as dialkylaminobenzophenone and 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Compound, 4-dimethylaminobenzoic acid ethyl, 2-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, p-dimethylaminobenzoic acid isoamyl ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl, etc. Can be mentioned.

Among the above photoinitiators, photoinitiators and sensitizers, thioxanthone compounds and tertiary amine compounds are preferred. In particular, it is preferable to contain a thioxanthone compound from the point of deep-hardening property. Especially, it is preferable to contain thioxanthone compounds, such as 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, and 2, 4- diisopropyl thioxanthone. Do.

As a compounding quantity of such a thioxanthone compound, it is preferable that it is 15 mass% or less of the composition whole quantity. When the compounding quantity of a thioxanthone compound exceeds 15 mass%, while thick film sclerosis | hardenability will fall, it will lead to the cost increase of a product. More preferably, it is 10 mass% or less.

Moreover, as a tertiary amine compound, the compound which has a dialkylaminobenzene structure is preferable, The dialkylamino benzophenone compound, the dialkylamino group containing coumarin compound and ketocoumarins in which the maximum absorption wavelength is 350-450 nm is especially preferable. Particularly preferred.

As said dialkylamino benzophenone compound, 4,4'- diethylamino benzophenone is preferable with low toxicity. Since the dialkylamino group-containing coumarin compound has a maximum absorption wavelength in the ultraviolet region at 350 to 410 nm, there is little coloration and colored curing that reflects the color of the color pigment itself using a color pigment as well as a colorless transparent photosensitive composition. It is possible to provide a layer. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect with respect to laser light having a wavelength of 400 to 410 nm.

As a compounding quantity of such a tertiary amine compound, it is preferable to set it as 0.1-15 mass% of the composition whole quantity. When the compounding quantity of a tertiary amine compound is less than 0.1 mass%, there exists a tendency for sufficient sensitization effect not to be acquired. When it exceeds 15 mass%, there exists a tendency for the light absorption on the surface of the dry coating film by a tertiary amine compound to become deep, and deep-curing property falls.

These photoinitiators, photoinitiator, and sensitizer can be used individually or as a mixture of 2 or more types.

It is preferable that the total amount of such a photoinitiator, a photoinitiation adjuvant, and a sensitizer is 35 mass parts or less with respect to 100 mass parts of said carboxyl group-containing photosensitive compound or carboxyl group-containing compound. When it exceeds 35 mass parts, there exists a tendency for deep-part sclerosis | hardenability to fall by these light absorption.

Moreover, since these photoinitiators, photoinitiation adjuvant, and a sensitizer absorb a specific wavelength, in some cases, a sensitivity becomes low and may act as a ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. By absorbing light of a specific wavelength as needed, it improves the photoreactivity of the surface, changes the line shape and opening of the resist into vertical, tapered, and inverse tapered, and improves the processing accuracy of the line width and the opening diameter. Can be.

As said epoxy compound (C), the polyfunctional epoxy resin which has a some epoxy group in a molecule | numerator, especially the polyfunctional epoxy resin which has a benzene ring is preferable. Specific examples of the epoxy resins include bisphenol A type epoxy resins, brominated epoxy resins, novolac type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, glycidylamine type epoxy resins, hydantoin type epoxy resins, Trihydroxyphenylmethane type epoxy resin, bixylenol type or biphenol type epoxy resin or mixtures thereof, tetraphenylolethane type epoxy resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylenoylethane resin , Naphthalene group-containing epoxy resin, epoxy resin having a dicyclopentadiene skeleton, glycidyl methacrylate copolymer type epoxy resin, further copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate, polymodified polybutadiene Rubber derivatives, CTBN modified epoxy resins, and the like. It is not. These epoxy resins can be used individually or in combination of 2 or more types.

As for the compounding quantity of the said epoxy compound, the range which becomes 1.5 equivalent or more with respect to 1 equivalent of carboxyl groups in a composition is preferable, The range which becomes 1.5 equivalent or more and 5 equivalent or less is more preferable, The range which becomes 1.5 equivalent or more and 4 equivalent or less is further more preferable. Do. When the compounding quantity of an epoxy compound is less than 1.5 equivalent, since the insulation and crack resistance of a hardened layer fall, it is unpreferable. On the other hand, when the compounding quantity of an epoxy compound exceeds 5 equivalent, since developability falls, it is not preferable.

The photosensitive composition of this invention is a hardening catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4 Imidazole derivatives such as -phenylimidazole, 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole: dicyandiamide, benzyl Amine compounds such as dimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine: adipic acid Hydrazine compounds, such as a hydrazide and a sebacic acid hydrazide: Phosphorus compounds, such as a triphenylphosphine, etc. can be further added. In particular, if it promotes reaction of the compound which has a cyclic ether group, and a carboxyl group, it is not limited to these. You may use these catalysts individually or in mixture of 2 or more types. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine and 2-vinyl-2,4-, which also function as an adhesion imparting agent Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-tri S-triazine derivatives, such as azine and isocyanuric acid adduct, can also be used, Preferably these compounds are used together with the said curing catalyst. The compounding quantity of the said curing catalyst is sufficient in a normal quantitative ratio, For example, it is 0.1-20 mass parts with respect to 100 mass parts of said carboxyl group-containing photosensitive compound or carboxyl group-containing compound, Preferably it is the ratio of 0.5-15.0 mass part.

As photosensitive compound (D) which does not have the said carboxyl group, ie, a photosensitive monomer, the compound which has 1 or more, preferably 2 or more ethylenically unsaturated double bond in a molecule | numerator can be used. A photosensitive monomer is photocured by active energy ray irradiation, and insolubilizes or insolubilizes the said carboxyl group-containing photosensitive compound in aqueous alkali solution. As such a compound, conventionally well-known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate can be used, Specifically, hydroxyalkyl acrylates, such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts thereof, propylene oxide adducts, or ε-caprolactone addition Polyvalent acrylates such as water; Polyhydric acrylates, such as ethylene oxide adduct or propylene oxide adduct of phenoxy acrylate, bisphenol A diacrylate and these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; Not limited to the above, acrylates and melamine acrylates in which polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols are directly acrylated or urethane acrylated through diisocyanates And / or each methacrylate corresponding to the said acrylate etc. are mentioned.

Moreover, hydroxyacrylates, such as pentaerythritol triacrylate, and isophorone di in the epoxy acrylate resin which made acrylic acid react with polyfunctional epoxy resins, such as a cresol novolak-type epoxy resin, and also the hydroxyl group of this epoxy acrylate resin. Epoxyurethane acrylate compounds etc. which reacted the half urethane compound of diisocyanate, such as an isocyanate, are mentioned. Such epoxy acrylate-based resin can improve photocurability without deteriorating the touch dryness.

The photosensitive compound which does not have the above carboxyl group is a compound whose weight average molecular weight Mw by GPC measurement is 4000 or less, for example.

In addition, the compounding quantity of the photosensitive compound which does not have a carboxyl group is 30 mass% or less, Preferably it is 1 mass% or more and 10 mass% or less of all the photosensitive components (photosensitive compound which does not have a carboxyl group-containing photosensitive compound + carboxyl group), More preferably, 1 mass% or more and 5 mass% or less are suitable.

The photosensitive composition of this invention can contain a well-known conventional mercapto compound and an adhesion promoter, in order to improve adhesiveness with base materials, such as a polyimide, as needed. Examples of the mercapto compound include 2-mercaptopropionic acid, trimethylolpropane tris (2-thiopropionate), 2-mercaptoethanol, 2-aminothiophenol, 3-mercapto-1,2,4-triazole, Mercapto group containing silane coupling agents, such as 3-mercapto- propyl trimethoxysilane, etc. are mentioned. As an adhesion promoter, for example, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl- 1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzo Triazole, carboxybenzotriazole, amino group-containing benzotriazole, vinyltriazine and the like. These may be used independently, respectively and may be used in combination of 2 or more type. As for the compounding quantity, the range of 10 mass parts or less per 100 mass parts of said carboxyl group-containing photosensitive compound or carboxyl group-containing compound is suitable. When the compounding quantity of these compounds exceeds the said range, since the epoxy group of the said epoxy compound required for a crosslinking reaction is consumed (reacts with an epoxy group), and a crosslinking density falls, it is unpreferable.

Since most of the high molecular material is once oxidized, oxidative deterioration occurs in sequence, resulting in deterioration of the function of the high molecular material. Thus, in order to prevent oxidation in the photosensitive composition of the present invention, (1) the generated radicals are invalidated. (2) An antioxidant such as a peroxide decomposing agent which decomposes the generated radical scavenging agent and / or (2) the generated peroxide into a harmless substance and prevents generation of new radicals can be added.

As antioxidant which acts as a radical trapping agent, for example, hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2 , 2-methylene-bis (4-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'-di-t-butyl-4 Phenol-based compounds such as -hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone-based compounds such as metoquinone and benzoquinone, bis (2,2,6, And amine compounds such as 6-tetramethyl-4-piperidyl) -sebacate and phenothiazine.

As antioxidant which acts as a peroxide decomposer, For example, phosphorus compounds, such as a triphenyl phosphite, pentaerythritol tetralauryl thio propionate, a dilauryl thiodipropionate, distearyl 3,3'- tee Sulfur type compounds, such as an odys propionate, etc. are mentioned.

Such antioxidant can be used individually by 1 type or in combination of 2 or more types.

The photosensitive composition of this invention can use a ultraviolet absorber other than the said antioxidant.

Examples of such ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives.

The above-mentioned ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, and can be stabilized the molding obtained from the photosensitive composition of this invention by using together with antioxidant.

Moreover, in the photosensitive composition of this invention, other additives other than the said component can also be added unless the effect of this invention is impaired. As the additive, known conventional thickeners, antifoaming agents and / or leveling agents such as silicone-based, fluorine-based and polymer-based, known coloring agents such as phthalocyanine-blue, phthalocyanine-green, disazo yellow, titanium oxide, carbon black, naphthalene black and the like Can be mentioned. If necessary, silane coupling agents, plasticizers, foaming agents, flame retardants, antistatic agents, anti-aging agents, antibacterial and anti-corrosive agents, and the like can be added, such as known conventional thermal polymerization inhibitors, imidazole-based, thiazole-based, and triazole-based compounds. have.

[Filler]

The photosensitive composition of this invention may further contain at least 1 sort (s) of filler chosen from the group which consists of an inorganic filler and an organic filler for the purpose of improving characteristics, such as adhesiveness, hardness, heat resistance, etc. as needed. Examples of the inorganic fillers include barium sulfate, calcium carbonate, barium titanate, silicon oxide, amorphous silica, talc, clay, hydrotalcite, neuburgh silica particles, mica powder, and the like. The organic fillers include silicon powder, nylon powder, Fluorine powder and the like. In addition, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, a metal oxide, and aluminum hydroxide can be used as the extender pigment filler. Among the fillers, silica is particularly excellent in low hygroscopicity and low volume expandability. Silica, regardless of melting and crystallinity, may be a mixture thereof, but silica is preferably surface-treated with a coupling agent or the like because the electrical insulation can be improved. In addition, fiber fillers, such as organic bentonite, montmorillonite, glass fiber, carbon fiber, and boron nitride fiber, etc. are mentioned as said filler.

The average particle diameter (D ₅₀₎ of the filler is preferably 25㎛ or less, more preferably 10㎛ or less, and more preferably not more than 3㎛. Here, the particle size of the D ₅₀ is, US (Mie) obtained by using a laser diffraction scattering type particle size distribution measurement method based on scattering theory volume cumulative 50%. More specifically, it can measure by making a particle size distribution of microparticles | fine-particles by a laser diffraction scattering type particle size distribution measuring device, and making the median diameter into the average particle diameter. The measurement sample can use preferably what disperse | distributed microparticles in water by the ultrasonic wave. As a laser diffraction type particle size distribution measuring apparatus, LA-500 made by Horiba, Ltd. can be used. As for the compounding quantity of these inorganic and / or organic fillers, 300 mass parts or less are suitable per 100 mass parts of said carboxyl group-containing photosensitive compound or carboxyl group-containing compound, Preferably it is the ratio of 5-150 mass parts. When the compounding quantity of a filler exceeds the said ratio, the corrosion resistance of a cured film falls and it is unpreferable.

[Organic Solvent]

In the photosensitive composition of this invention, an organic solvent can be used in order to melt | dissolve or disperse the said carboxyl group-containing photosensitive compound and an epoxy compound easily, or to adjust to the viscosity suitable for coating. Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, Ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as these; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate and methyl 2-hydroxyisobutyrate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents are used alone or as a mixture of two or more thereof. The compounding quantity of an organic solvent can be set suitably according to a desired viscosity.

The photosensitive composition of this invention is adjusted to the viscosity suitable for the application | coating method with the said organic solvent, for example, and can be dip-coated, a flow-coating method, a roll-coating method, a bar coater method, a screen printing method, a curtain coating method, etc. on a base material. By apply | coating by the method of, and volatile-drying (temporary drying) the organic solvent contained in a composition at the temperature of about 60-100 degreeC, a non-tacky coating film can be formed. Moreover, a dry coating film can be formed by apply | coating the said composition on a carrier film, drying, and a thing wound up as a film on a base material. Thereafter, by contact type (or non-contact method), the pattern is exposed directly by an active energy ray through a photomask on which a pattern is formed, or by direct pattern exposure by a laser direct exposure machine, and the unexposed portion is diluted with an aqueous alkali solution (for example, 0.3). To 3% by mass aqueous solution of sodium carbonate) to form a resist pattern. In addition, by using a high pressure mercury lamp or the like, ultraviolet rays can be irradiated so as to have an integrated exposure amount of 500 to 2000 mJ / cm ² , followed by final curing. In addition, for example, by heating to a temperature of about 140 to 180 ° C and thermosetting, the carboxyl group-containing photosensitive compound or the carboxyl group of the carboxyl group-containing compound reacts with the epoxy group of the epoxy compound, heat resistance, chemical resistance, hygroscopicity, adhesion, electrical The cured coating film excellent in various characteristics, such as a characteristic, can be formed.

Examples of the substrate include paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / nonwoven fabric-epoxy resin, glass cloth / paper-epoxy, in addition to a printed wiring board or a flexible printed wiring board formed in advance. Copper clad laminates of all grades (FR-4, etc.) using composite materials such as resins, synthetic fiber-epoxy resins, fluororesins, polyethylene, PPO, cyanate esters, polyimide films, PET films, glass substrates, ceramic substrates, wafer boards Etc. can be used.

Volatilization drying after applying the photosensitive composition of this invention is a hot-air circulation type drying furnace, and it uses a IR with a hotplate, a convection oven, etc. (The thing provided with the heat source of the air heating system by steam is counter-current. And a method of spraying from the nozzle to the support).

As mentioned above, after apply | coating the photosensitive composition of this invention and carrying out volatilization drying, exposure (irradiation of an active energy ray) is performed with respect to the obtained dry coating film. An exposed part (part irradiated with an active energy ray) hardens | cures a dry coating film.

As an exposure machine used for the said active energy ray irradiation, a direct drawing apparatus (for example, the laser direct imaging apparatus which draws an image with a laser directly by CAD data from a computer), the exposure machine equipped with the metal halide lamp, (super) high pressure mercury A direct drawing apparatus using ultraviolet lamps such as an exposure machine equipped with a lamp, an exposure machine equipped with a mercury short arc lamp, or a (ultra) high pressure mercury lamp can be used. As the active energy ray, any one of a gas laser and a solid state laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. Moreover, although the exposure amount changes with film thickness etc., it can generally be in the range of 5-800mJ / cm <^2> , Preferably it is 5-700mJ / cm <^2> . As the direct drawing device, for example, those made by Nippon Orbotech Co., Ltd., Oak Co., Ltd. can be used, and any device may be used as long as the device emits laser light having a maximum wavelength of 350 to 410 nm.

As the developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be performed. As a developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines or the like can be used. Can be.

The photosensitive composition of the present invention can be used in the form of a dry film having a dry coating film formed by applying and drying the photosensitive composition to a film such as polyethylene terephthalate in advance, in addition to the method of directly applying the substrate to a liquid phase. The case where the photosensitive composition of this invention is used as a dry film is shown below.

A dry film has a structure which the carrier film, the dry coating film, and the peelable cover film used as needed are laminated | stacked in this order. A dry coating film is a layer obtained by apply | coating and drying alkali developable photosensitive composition to a carrier film or a cover film, for example. After forming a dry coating film in a carrier film, a cover film is laminated | stacked on it, or a dry coating film is formed in a cover film, and this laminated body is laminated | stacked on a carrier film, and a dry film is obtained.

As a carrier film, thermoplastic films, such as a polyester film of 2-150 micrometers thickness, are used.

The dry coating film is formed by uniformly applying an alkali developable photosensitive composition to a carrier film or cover film with a blade coater, a lip coater, a comma coater, a film coater and the like at a thickness of 10 to 150 µm and drying it.

Although a polyethylene film, a polypropylene film, etc. can be used as a cover film, It is preferable that adhesive force with a dry coating film is smaller than a carrier film.

In order to produce a protective film (permanent protective film) on a printed wiring board using a dry film, a cover film is peeled off, the dry coating film and the circuit-formed substrate are piled up, it is matched using a laminator, etc., and a dry coating film is formed on the circuit-formed substrate. do. With respect to the formed dry coating film, when it exposes, develops, and heat-cures like the above, a hardened layer can be formed. The carrier film may be peeled off at any time before or after exposure.

Moreover, although the photosensitive composition of this invention is suitable as a permanent film material of a printed wiring board, it is especially suitable as a soldering resist material and an interlayer insulation material.

EXAMPLE

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, of course, this invention is not limited to the following Example. In addition, below, "%" and "part" are mass references | standards unless there is particular notice.

Synthesis Example 1

119.4 parts of novolak-type cresol resin (trade name "Shonol CRG951", OH equivalence: 119.4) by Showa Kobunshi Kabushiki Kaisha in an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device. 1.19 parts and 119.4 parts of toluene were thrown in, the inside of the system was nitrogen-substituted and stirred, and it heated up. Next, 63.8 parts of propylene oxides were dripped gradually, and it was made to react at 125-132 degreeC and 0-4.8 kg / cm <^2> for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added and mixed with the reaction solution to neutralize potassium hydroxide, and the propylene oxide of the novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. A solution of the addition reactant was obtained. This was an average of about 1.08 mol of alkylene oxide added per equivalent of phenolic hydroxyl group.

293.0 parts of the solution of the alkylene oxide addition reaction product of the obtained novolak-type 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 introduced into a reactor equipped with a stirrer, a thermometer, and an air suction tube, and air was supplied. It was blown at a rate of 10 ml / min and reacted at 110 ° C for 12 hours while stirring. As for the water produced | generated by reaction, 12.6 parts of water flowed out as an azeotropic mixture with toluene. Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts of 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while replacing toluene with 118.1 parts of diethylene glycol monoethyl ether acetate, to obtain a novolac acrylate resin solution. Subsequently, 332.5 parts of the obtained novolak-type acrylate resin solution, 0.8 part of chromium naphthenate, and 0.4 part of lithium naphthenate were introduced into a reactor equipped with a stirrer, a thermometer, and an air suction tube, and the air was blown at a rate of 10 ml / min, followed by stirring. 60.8 parts of tetrahydrophthalic anhydride were added gradually, making it react at 95-101 degreeC for 6 hours, and taken out after cooling. Thus obtained carboxyl group-containing photosensitive compound was 70.9% of non volatile matter and 82.1 mgKOH / g of solid content acid values.

Examples 1 to 9 and Comparative Examples 1 to 3

Each component was mix | blended in the ratio shown in Table 1 and Table 2, and after stirring, it disperse | distributed with the triaxial roll mill and obtained the photosensitive composition.

The acid value, epoxy equivalent, and double bond equivalent in the said Table 1 and Table 2 were measured with the following method.

<Measurement of Acid Value for Total Amount of Organic Components>

The photosensitive composition was dried at 70 degreeC for 24 hours, the organic solvent was removed, and solid content was obtained. Acetone was added to the solid to dissolve and disperse, and the filler was separated from the solid by a centrifugal separator. The acid value was measured according to JIS K2501 using the organic component which separated the filler. The acid value obtained in this way is an acid value with respect to the organic component total amount.

<Measurement method of epoxy equivalent to total amount of organic components>

In the same manner as in the case of measuring the acid value, an organic component obtained by separating the filler was obtained. Using this organic component, the first equivalent was measured according to JIS K7236.

On the other hand, except having not used tetraethylammonium bromide, the 2nd equivalent was measured similarly to the measuring method of 1st equivalent.

The 2nd equivalent was subtracted from the 1st equivalent, and "epoxy equivalent with respect to the organic component total amount" was computed.

<Measurement method of double bond equivalent>

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

The 1st equivalent was subtracted from the 3rd equivalent, and "double bond equivalent with respect to the organic component total amount" was computed.

<Method of Determining Liquid Components>

The determination of the liquid phase was carried out in accordance with Attachment No. 2 "Method of Confirming Liquid Phase" of the Directive on the Test and Properties of Dangerous Goods (1989 Autonomous Directive No. 1).

(1) device

Constant temperature water bath: Agitator, heater, thermometer, thermostat (with temperature control at ± 0.1 ° C) and having a depth of at least 150 mm.

In addition, in the determination of a liquid component, all about 22 liters of tap water were made into a low temperature constant temperature water bath (combination of Yamato Kagaku Co., Ltd. low temperature constant temperature water tank (model BU300) and an input thermostat thermomate (model BF500)). Into the model BU300, the power supply of the thermomate (model BF500) attached thereto was turned on and set to the set temperature (20 ° C), and the water temperature was finely adjusted to the set temperature ± 0.1 ° C by the thermomate (model BF500). Any device that can be adjusted can be used.

examiner:

As a test tube, as shown in FIG. 1, it is a flat bottom cylindrical transparent glass of internal diameter 30mm and height 120mm, marking marks 2 and 3 are attached to the part of 55mm and 85mm height from a pipe bottom, respectively, The entrance of the test tube is sealed with a rubber stopper 4b having the same size as the test tube 1a for the liquid phase determination test tube 1a sealed with the rubber stopper 4a, and a perforated rubber stopper for inserting and supporting the thermometer in the center. , The test tube 1b for temperature measurement in which the thermometer 5 is inserted into the rubber stopper 4b is used. Hereinafter, the marking line of 55 mm in height from the pipe bottom is called "A line", and the marking line of 85 mm in height from the pipe bottom is called "B line".

As the thermometer 5, although the thing for the freezing point measurement (SOP-58 scale range 20-50 degreeC) prescribed | regulated to JIS B7410 (1982) "glass thermometer for oil tests" is used, the temperature range of 0-50 degreeC can be measured. All you can do is.

(2) Test procedure

A-line is placed in a test tube 1a for liquid phase determination (1) shown in FIG. 1 (a) and a temperature measurement test tube (1b) shown in FIG. 1 (b), respectively. Put it in. Two test tubes 1a and 1b are placed upright in a low temperature constant temperature bath so that the B line is below the surface of the water. The thermometer is such that its lower end is 30 mm below 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, the test tube 1a for the liquid phase determination was taken out from the low temperature constant temperature bath, immediately fell horizontally on a horizontal test bench, and the time when the tip of the liquid level in the test tube moved from line A to line B was measured with a stopwatch. Record it. The sample determines that the time measured at the set temperature is within 90 seconds, that the liquid phase and the solid phase exceed 90 seconds.

About each photosensitive composition, the test board | substrate was produced as follows and the following characteristic evaluation was performed. The results are shown in Tables 3 and 4.

<Production of Test Board>

The photosensitive composition was apply | coated whole surface to the printed wiring board in which the copper pattern was formed so that it might become 20-30 micrometers thickness using the 100-mesh polyester screen by the screen printing method, and a coating film was used for 80 degreeC hot air dryer. After drying for 60 minutes, the negative film having a resist pattern was brought into close contact with the coating film, and was irradiated with ultraviolet light having an exposure dose of 500 mJ / cm ² using an ultraviolet exposure apparatus (Ok Seisakusho Co., Ltd., HMW-680GW). Subsequently, it developed with the spray pressure of 2.5 kg / cm <^2> for 60 second with the 1% sodium carbonate aqueous solution. Thereafter, the substrate was irradiated with ultraviolet rays so as to have an integrated exposure amount of 1000 mJ / cm ² with a high pressure mercury lamp, and finally cured. The substrate was heated at 160 ° C. for 1 hour to be post-cured to obtain an evaluation substrate.

Insulation, cracking, pattern formation (development) and adhesiveness were tested as follows.

Insulation Resistance in PCBT

The evaluation board | substrate was produced on the conditions mentioned above using the comb-shaped electrode B coupon of IPCB-25, the bias voltage of DC30V was applied to this comb-shaped electrode, and the PCT apparatus (HAST YSTEM TPC-412MD by an spec) is used. The process was performed under conditions of 121 ° C. and a humidity of 97%, and the time when the resistance value was lowered to 1.0 × 10 ⁷ Ω or less was measured. When 300 hours or more are required, it can evaluate as favorable.

<TCT Corner Crack>

The photosensitive composition was applied to a substrate on which a 2 mm copper line pattern was formed, exposed and developed in the same manner as above, and then irradiated with ultraviolet rays and thermoset to form an evaluation substrate on which 17 resist patterns of 3 mm on each side were formed on the copper line. Produced. This evaluation board | substrate was put into the cold heat cycle machine which temperature cycle is performed between -65 degreeC and 150 degreeC, and TCT (Thermal Cycle Test) was done. Then, the appearance at 1000 cycles was observed, and the number of cracks was calculated. When the number of cracks is 30/68 or less, it can be evaluated as good. In addition, the numerical value "68" of a denominator is four edge | corners (4 pieces) x 17 pieces of the resist pattern of 3 mm each side, and it means 68 edges, and the numerical value "30" of a molecule | numerator shows the generation number of a crack.

<Pattern formability>

The state after exposure and image development was visually determined with a magnifying glass. As a result, as in Tables 3 and 4, in Examples 1 to 9 and Comparative Examples 1 to 3, formation of patterns was possible.

<Adhesiveness>

The photosensitive composition was apply | coated whole surface by the screen printing on the patterned copper foil board | substrate, respectively, it dried for 30 minutes in 80 degreeC hot-air circulation type drying furnace, and cooled to room temperature. The negative film made from PET was put on this board | substrate, and it crimped | bonded by ORC company (HMW-GW20) for 1 minute under reduced pressure conditions, and the sticking state of the film at the time of peeling a negative film after that was evaluated.

Good: When peeling off a film, there is no resistance and a mark is not left in a coating film.

Poor: There is resistance when peeling off the film and marks on the coating film.

As shown in Table 3, in Examples 1 to 9, a pattern could be formed satisfactorily, insulation could be maintained for a long time even under high temperature, high humidity, and generation | occurrence | production of a crack was suppressed. However, as shown in Table 4, in Comparative Examples 1 to 3 having a double bond equivalent weight of the whole composition excluding the filler from the photosensitive composition, which was less than 400, insulation was not maintained for a long time under high temperature and high humidity, and there were many cracks.

Although the curable resin composition or its dry film of this invention is suitable as a permanent film material of a printed wiring board, it can use it especially advantageously as a soldering resist material and an interlayer insulation material.

1a Test tube for liquid phase determination
1b temperature test tube
2 mark (A line)
3 mark (B line)
4a, 4b rubber stopper
5 thermometer

Claims (7)

(A) carboxyl group-containing photosensitive compound,
(B) photoinitiator, and
(C) epoxy compound
Containing,
(D) It is a photosensitive composition which can further contain the photosensitive compound which does not have a carboxyl group,
The double bond equivalent of the said photosensitive composition is 400 or more and 680 or less in the state containing no organic solvent and a filler,
The content rate of the liquid component contained in the said photosensitive composition is 5 mass% or more and 30 mass% or less with respect to the all components except the organic solvent and a filler,
(D) The compounding quantity of the photosensitive compound which does not have a carboxyl group is 0-10 mass% with respect to the whole photosensitive component (photosensitive compound which does not have a carboxyl group-containing photosensitive compound + carboxyl group),
The epoxy group of the said (C) epoxy compound is 1.5 equivalent or more and 4 equivalent or less with respect to 1 equivalent of carboxyl groups of the said (A) carboxyl group-containing compound, The photosensitive composition characterized by the above-mentioned. It has a hardened layer formed using the photosensitive composition of Claim 1, The printed wiring board characterized by the above-mentioned. delete delete delete delete delete

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