KR20140047165A - Photosensitive resin composition, dry film and cured product thereof, and printed wiring board using the same - Google Patents

Abstract

The photosensitive resin composition is a photosensitive resin composition which contains at least one acrylamide group or methacrylamide group or at least one acryloyl group or methacryloyl group per molecule in a reaction product obtained by reacting a phenol resin with an alkylene oxide or a cyclocarbonate compound A carboxyl group-containing photosensitive resin obtained by reacting an isocyanate compound with a reaction product obtained by reacting a polybasic acid anhydride, and a photopolymerization initiator. In a preferred embodiment, the composition further comprises a thermosetting component. By using the photosensitive resin composition or the dry film thereof, a cured coating having a PCT resistance, HAST resistance, electroless gold plating resistance, and cold / heat shock resistance as important as a solder resist for a printed wiring board, particularly a semiconductor package can be formed.

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, a dry film and a cured product thereof, and a printed wiring board using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition that can be developed by an aqueous alkali solution, particularly a composition for a solder resist which is photo-cured by ultraviolet exposure or laser exposure, a dry film and a cured product thereof, and a printed wiring board having a cured film formed by using the same .

At present, solder resists of some commercial printed circuit boards and most industrial printed circuit boards are subjected to ultraviolet ray irradiation, ultraviolet irradiation, development, and image formation, and liquid phase development (final curing) by heat and / A solder resist is used, and from the viewpoint of environmental problems, a photo-solder resist of an alkali developing type using an aqueous alkali solution is used as a mainstream, and it is used in large quantities in the production of an actual printed wiring board. In addition, in response to the increase in the density of the printed wiring board due to the thinning and shortening of electronic devices in recent years, workability and high performance of the solder resist are also required.

However, the current alkali-developing type photo-solder resist still has a problem in terms of durability. That is, the alkali resistance, water resistance, heat resistance, and the like are lower than those of the conventional thermosetting and solvent developing type. This is because alkali-developing type photo-solder resists have a hydrophilic group as a main component in order to make it possible to develop alkali, so that chemical solution, water, water vapor and the like are easily permeated and the chemical resistance is lowered or the adhesion between the resist film and copper is lowered . As a result, alkali resistance as chemical resistance is weak. In particular, in a semiconductor package such as a ball grid array (BGA) or a chip scale package (CSP), a pressure cooker test Pressure cooker test resistance), but under such severe conditions, it is only a few hours to several hours. In addition, in the HAST test (High Accelerated Stress Test) under the condition of applying the voltage under the humidifying condition, in most cases, defects due to the occurrence of migration have been confirmed in several hours.

Further, in recent years, the temperature applied to the package tends to become extremely high, such as transition to surface mounting and use of lead-free solder in consideration of environmental problems. As a result, the temperature at the inside and the outside of the package becomes remarkably high, and the conventional liquid photosensitive resist has a problem that cracks are generated in the coating film due to thermal shock or peeled off from the substrate or the sealing material.

On the other hand, an epoxy acrylate-modified resin derived from the modification of an epoxy resin is generally used as the carboxyl group-containing resin used in the conventional solder resist. For example, Japanese Patent Application Laid-Open No. 61-243869 (Patent Document 1) discloses a photosensitive resin composition comprising a reaction product of a novolac epoxy compound and an unsaturated monobasic acid, an acid anhydride added thereto, a photopolymerization initiator, a diluent, A solder resist composition containing a compound has been reported. Japanese Unexamined Patent Publication (Kokai) No. 3-250012 (Patent Document 2) discloses a method in which (meth) acrylic acid is added to an epoxy resin obtained by reacting epichlorohydrin with the reaction product of salicylaldehyde and monovalent phenol, There is disclosed a solder resist composition comprising a photosensitive resin, a photopolymerization initiator, an organic solvent, etc. obtained by further reacting a polybasic carboxylic acid or an anhydride thereof. However, the carboxyl group-containing resin used in the conventional solder resist has poor electrical characteristics.

Japanese Patent Publication No. 61-243869 Japanese Patent Laid-Open No. 3-250012

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art as described above, and its main object is to form a cured coating having a PCT resistance, HAST resistance, electroless gold plating resistance and cold / To provide a photosensitive resin composition.

Another object of the present invention is to provide a printed wiring board comprising a dry film and a cured product excellent in various characteristics obtained by using such a photosensitive resin composition as described above and a cured film such as a solder resist formed by the dry film or the cured product .

In order to achieve the above object, according to the present invention, there is provided a reaction product obtained by reacting a phenolic resin with an alkylene oxide or a cyclocarbonate compound, with at least one acrylamide group or methacrylamide group or at least one acryloyl group There is provided an alkali developable photosensitive resin composition characterized by containing a carboxyl group-containing photosensitive resin obtained by reacting an isocyanate compound having a di- or methacryloyl group with a reaction product obtained by reacting a polybasic acid anhydride, and a photopolymerization initiator.

In a preferred embodiment, the alkylene oxide is ethylene oxide and / or propylene oxide, and the cyclocarbonate is preferably ethylene carbonate and / or propylene carbonate. Further, it is preferable that the carboxyl group-containing resin does not contain a hydroxyl group. In a preferred embodiment, the photosensitive resin composition of the present invention further contains a thermosetting component, and is preferably for a solder resist further containing a coloring agent.

According to the present invention, a photosensitive dry film obtained by applying and drying the photosensitive resin composition to a carrier film, and the photosensitive resin composition or the dry film are cured by photo-curing, preferably in a pattern of a light source with a wavelength of 350 to 410 nm A cured product obtained by photo-curing is provided.

Further, according to the present invention, there is also provided a printed wiring board having a cured coating obtained by photo-curing the photosensitive resin composition or the dry film in pattern form by irradiation of an active energy ray, preferably by direct irradiation of ultraviolet rays / RTI >

The photosensitive resin composition of the present invention is a curable resin as a main component, which is obtained by reacting a reaction product obtained by reacting a phenol resin with an alkylene oxide or a cyclocarbonate compound, with at least one acrylamide group or methacrylamide group ) Acrylamide group), or an isocyanate compound having at least one acryloyl group or methacryloyl group (hereinafter collectively referred to as a (meth) acryloyl group), reacting the obtained reaction product with a polybasic acid anhydride The photosensitive resin composition containing the carboxyl group-containing photosensitive resin is excellent in workability and developability, and in cured products thereof, high reliability can be obtained when used in, for example, a printed wiring board or a semiconductor package. In the carboxyl group-containing photosensitive resin, the unsaturated group and the carboxyl group are not present on the same chain and are located at the side chain side, respectively, so that the reactivity is excellent and the excellent alkali developability can be realized.

In the preferred embodiment of the present invention, the cured coating film obtained is further provided with heat resistance by further containing a thermosetting component.

In a preferred embodiment of the carboxyl group-containing photosensitive resin of the present invention, since the alkylene oxide is ethylene oxide and / or propylene oxide, and the cyclocarbonate is ethylene carbonate and / or propylene carbonate, the chain of the carboxyl group- The flexibility of the resulting cured coating film is improved, and the heat and shock resistance can be improved. Further, in another preferred embodiment of the present invention, since the carboxyl group-containing photosensitive resin contains no hydroxyl group, it is excellent in moisture absorption resistance and can obtain excellent PCT resistance in its cured product.

Further, by using the dry film obtained by applying and drying the above-described photosensitive resin composition of the present invention onto a carrier film, the resist layer can be easily formed without applying the curable resin composition on the substrate.

The above-mentioned photosensitive resin composition may be coated on a substrate, cured by irradiation with active energy rays and / or heating, or the above-mentioned dry film may be attached to a base material and cured It is possible to form a cured coating having a PCT resistance, HAST resistance, electroless gold plating resistance and cold / heat shock resistance which are important as a solder resist for a semiconductor package, and it is possible to obtain high reliability when used, for example, in electronic parts It becomes.

As a result of intensive investigations to solve the above problems, the present inventors have found that the above object can be achieved by using a photosensitive resin containing a carboxyl group as a starting material of a phenol resin as a curing resin as a main component of the composition , Thereby completing the present invention. The carboxyl group-containing photosensitive resin used in the present invention is excellent in flexibility and elongation due to chain extension by the addition reaction of a phenol resin with an alkylene oxide or a cyclocarbonate compound, and is excellent in flexibility and durability due to addition reaction of an alkylene oxide or a cyclocarbonate compound Addition of an isocyanate compound having at least one (meth) acrylamide group or (meth) acryloyl group in one molecule and addition of a polybasic acid anhydride to the terminal hydroxyl group, so that the unsaturated group and the carboxyl group are not present on the same side chain, It is excellent in reactivity and has excellent alkali developability due to the presence of a terminal carboxyl group remote from the main chain. The (meth) acrylamide group also has a characteristic of being superior in hydrolysis resistance as compared with a (meth) acrylate group in general. Moreover, this resin is excellent in moisture absorption resistance because it is easy to design a molecule having no hydrophilic alcoholic hydroxyl group with low reactivity. It is assumed that this point is connected to the improvement of the PCT tolerance required for the IC package. Therefore, the photosensitive resin composition of the present invention containing a carboxyl group-containing photosensitive resin, a photopolymerization initiator, a thermosetting component, a colorant and the like derived from the phenol resin obtained by the present invention is useful as a solder resist for a semiconductor package, A solder resist film having resistance, electroless gold plating resistance, and cold / heat shock resistance can be provided.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

First, the carboxyl group-containing photosensitive resin constituting the curable resin of the photosensitive resin composition of the present invention can be easily obtained by the following method.

(1) reacting a reaction product obtained by reacting a phenolic resin with an alkylene oxide with an isocyanate compound having at least one (meth) acrylamide group in one molecule, and reacting the resultant reaction product with a polybasic acid anhydride; .

(2) a carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting a phenol resin with a cyclocarbonate compound, with an isocyanate compound having at least one (meth) acrylamide group in one molecule and reacting the obtained reaction product with a polybasic acid anhydride.

(3) a reaction product obtained by reacting a phenol resin and an alkylene oxide with an isocyanate compound having at least one (meth) acryloyl group in one molecule, and reacting the resultant reaction product with a polybasic acid anhydride; .

(4) reacting a reaction product obtained by reacting a phenolic resin with a cyclocarbonate compound, with an isocyanate compound having at least one (meth) acryloyl group in one molecule, and reacting the resultant reaction product with a polybasic acid anhydride; Suzy.

The carboxyl group-containing photosensitive resin used in the present invention uses a phenol resin as a starting material. Phenol resins with little chlorine ion impurities are readily available. Therefore, the content of the chloride ion impurity in the carboxyl group-containing photosensitive resin used in the present invention is 100 ppm or less, more preferably 50 ppm or less, and still more preferably 30 ppm or less.

The carboxyl group-containing photosensitive resin used in the present invention is also characterized in that it is a resin not containing a hydroxyl group. In general, the presence of a hydroxyl group has excellent characteristics such as improvement of adhesion by hydrogen bonding, but it is known that the moisture resistance is remarkably lowered. The carboxyl group-containing photosensitive resin of the present invention is presumed to exhibit excellent insulation reliability and PCT resistance because it is a resin that does not contain a hydroxyl group.

Further, a compound having both a cyclic ether group and an ethylenic unsaturated group in one molecule may be reacted with the carboxyl group-containing photosensitive resin obtained by the above methods (1) to (4). Such compounds include, but are not limited to, glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether or 3,4-epoxycyclohexyl Hexylmethyl methacrylate is preferred. Further, in the present specification, (meth) acrylate is generically referred to as acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

The addition amount of the compound having a cyclic ether group and an ethylenic unsaturated group in the molecule is preferably 5% to 40% by equivalent based on the carboxyl group of the carboxyl group-containing photosensitive resin. When the addition amount is less than 5% equivalent, sufficient increase in sensitivity and improvement in solder resist characteristics can not be obtained. On the other hand, if it exceeds 40% equivalent, the maximum development life is shortened and the dry- I do not. A more preferable addition amount is 10% equivalent to 30% equivalent.

Since the carboxyl group-containing photosensitive resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkaline solution becomes possible. The acid value of the carboxyl group-containing photosensitive resin is in the range of 30 to 150 mgKOH / g, and more preferably in the range of 40 to 130 mgKOH / g. When the acid value of the carboxyl group-containing photosensitive resin is less than 30 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 150 mgKOH / g, dissolution of the exposed area by the developer proceeds, The resist is dissolved and peeled off as a developing solution without distinction between the exposed portion and the unexposed portion, which makes it difficult to draw a normal resist pattern.

In addition, although the weight average molecular weight of the said carboxyl group-containing photosensitive resin changes with resin skeleton, it is preferable to exist in the range of 2,000-150,000 normally and 5,000-100,000. If the weight average molecular weight is less than 2,000, the tackfree performance may be deteriorated, the moisture resistance of the coated film after exposure may be poor, the film may be reduced during development, and the resolution may be significantly lowered. On the other hand, when a weight average molecular weight exceeds 150,000, developability may become remarkably bad and storage stability may be inferior.

The blending amount of the carboxyl group-containing photosensitive resin is preferably in the range of 20 to 60 mass%, more preferably in the range of 30 to 50 mass%, in the whole composition. When the amount is smaller than the above range, the coating film strength is lowered, which is not preferable. On the other hand, when more than the said range, since the viscosity of a composition becomes high, applicability | paintability, etc. fall, it is not preferable.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran. Of these, ethylene oxide and propylene oxide are preferable in terms of cost and supply system.

As the cyclocarbonate compound, known carbonate compounds can be used, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate. Of these, 5-membered ethylene carbonate and propylene carbonate are preferable in terms of reactivity and supply system.

These alkylene oxides or cyclocarbonate compounds may be used alone or in admixture of two or more.

The alkylene oxide or cyclocarbonate compound can be modified from a phenolic hydroxyl group to a resin having an alcoholic hydroxyl group by subjecting the phenolic hydroxyl group of the phenol resin to an addition reaction using a basic catalyst. The addition amount is preferably in the range of 0.3 to 10 moles, preferably in the range of 0.8 to 5 moles, and more preferably 1.0 to 3 moles, per 1 equivalent of the phenolic hydroxyl group. When the addition amount is less than the above range, reaction with an isocyanate compound or a polybasic acid anhydride having at least one (meth) acrylamide group or a (meth) acryloyl group in one molecule to be described later is difficult to occur and a photosensitive and dilute alkali aqueous solution The solubility of the compound of the present invention is lowered. On the other hand, when the addition amount exceeds the above range, the water resistance of the cured coating film is deteriorated by the resulting ether bond, and electric insulation property, HAST resistance, and the like are lowered.

The isocyanate compound having at least one (meth) acrylamide group in the molecule may be a compound having one isocyanate group and at least one (meth) acrylamide group in one molecule, and is not particularly limited. The isocyanate compound having a (meth) acrylamide group used in the present invention is excellent in adhesion and hydrolysis resistance, and has the same excellent reactivity as photopolymerization as (meth) acrylate. The isocyanate compound having at least one (meth) acrylamide group in the molecule used in the present invention is preferably a compound having at least one hydroxyl group and at least one (meth) acrylamide group in one molecule such as hydroxyalkyl (meth) acrylamide, , And the desired compound can be easily obtained by half-urethane formation using a diisocyanate such as isophorone diisocyanate, toluylene diisocyanate, tetramethylxylylene diisocyanate, and hexamethylene diisocyanate with little or no chlorine ion impurity . As a compound having one hydroxyl group and at least one (meth) acrylamide group in one molecule, hydroxyethyl acrylamide and the like can be given. These compounds may be used alone or in combination of two or more.

The isocyanate compound having at least one (meth) acryloyl group in the molecule may be a compound having one isocyanate group and at least one (meth) acryloyl group in one molecule, and is not particularly limited. Particularly, it is preferable to use an isocyanate compound having no chlorine ion impurity content or a very small amount as a good form. Specific examples thereof include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, bis (acryloxymethyl) ethyl isocyanate, and modified products thereof. Examples of commercially available products include Carlene MOI (methacryloyloxyethyl isocyanate), Carlens AOI (acryloyloxyethoxyethyl isocyanate), Carlens MOI-EG (methacryloyloxyethoxyethyl isocyanate (Isocyanate block body of car lens MOI), car lens MOI-BP (isocyanate block body of car lens MOI), car lens BEI (1,1-bis Methyl) ethyl isocyanate) is commercially available from Showa Denko K.K. All these trade names are registered trademarks. Further, it is also possible to use a compound having one hydroxyl group and at least one (meth) acryloyl group in one molecule and a compound having no chlorine ion impurity or having very little isophorone diisocyanate, toluylene diisocyanate, tetramethylxylene diisocyanate, A half-urethane compound with a diisocyanate such as isocyanate can also be used. Examples of the compound having one hydroxyl group and at least one (meth) acryloyl group in one molecule include 2-hydroxyethyl (meth) acrylate, pentaerythritol triacrylate and the like.

These compounds may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include methyl tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, anhydrous nadic acid, 3,6-endomethylenetetrahydrophthalic anhydride, methyl endmethylene tetrahydrophthalic anhydride, tetra Alicyclic dibasic anhydrides such as phthalic anhydride and bromo anhydride; Aliphatic or aromatic dibasic acid anhydrides such as maleic anhydride, maleic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl anhydridesuccinate, phthalic anhydride, and trimellitic anhydride, or biphenyltetracarboxylic acid dianhydride, diphenyl Aliphatic or aromatic tetracarboxylic acid dianhydrides such as tetracarboxylic acid dianhydride, ether tetracarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, anhydrous pyromellitic acid, benzophenonetetracarboxylic acid dianhydride, etc. And one or more of them may be used.

As the photopolymerization initiator, oxime ester-based photopolymerization initiators having oxime ester groups,? -Aminoacetophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators may be used. have.

Examples of the oxime ester-based photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02, N-1919 and NCI-831 manufactured by Ciba Japan Co., Ltd. as a commercial product. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used preferably, Specifically, the oxime ester compound which has a carbazole structure represented by a following formula is mentioned.

(Wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms) Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms, An alkoxy group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), anthryl group, pyridyl group, benzofuryl group and benzothienyl group, Ar is not present, 4, 4'-stilbene-diyl, 4, 4'-stilbene-diyl, 4, 4'-stilbene-diyl, , 2'-styrene-diyl, and n is an integer of 0 or 1.

In particular, it is preferable that X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, Ar is absent, or phenylene, naphthylene or thienylene.

The blending amount of such oxime ester-based photopolymerization initiator is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the carboxyl group-containing photosensitive resin. If the amount is less than 0.01 part by mass, the photocurability on copper is insufficient, resulting in peeling of the coating film and deterioration of coating film properties such as chemical resistance. On the other hand, if it exceeds 5 parts by mass, the light absorption at the surface of the solder resist coating film becomes severe, and the deep portion curability tends to be lowered. More preferably, it is 0.5-3 mass parts.

Specific examples of the? -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl- -1- [4- (4-morpholinyl) phenyl] -1- [2- (dimethylamino) -Butanone, N, N-dimethylaminoacetophenone, and the like. Commercially available products include Irgacure-907, Irgacure-369 and Irgacure-379 manufactured by Shiba &

Specific examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lucirin TPO manufactured by BASF, Irgacure-819 manufactured by Shiba Japan Ltd., and the like.

It is preferable that the blending amount of the? -Aminoacetophenone-based photopolymerization initiator and the acylphosphine oxide-based photopolymerization initiator is 0.01 to 15 parts by mass relative to 100 parts by mass of the carboxyl group-containing photosensitive resin. When the amount is less than 0.01 part by mass, the photocurability on copper is similarly insufficient, resulting in peeling of the coating film and deterioration of coating film properties such as chemical resistance. On the other hand, if it exceeds 15 parts by mass, the effect of reducing the outgas is not obtained, and the light absorption at the surface of the solder resist coating film becomes severe, so that the deep portion curability tends to be lowered. More preferably 0.5 to 10 parts by mass.

In addition, examples of the photopolymerization initiator, photoinitiator, and sensitizer that can be preferably used in the photocurable resin composition of the present embodiment include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, Compounds, tertiary amine compounds and xanthone compounds.

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

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

Specific examples of the anthraquinone compound include 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone.

Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and the like. .

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

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl- Benzoyl-4'-propyldiphenyl sulfide and the like.

Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure such as 4,4'-dimethylaminobenzophenone (Nissokyure MABP manufactured by Nippon Soda Co., Ltd.) , Dialkylaminobenzophenone such as 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H- Dimethylaminobenzoate (Kaya Cure EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylaminobenzoic acid ethyl (2-dimethylaminobenzoate) (Quantacure DMB manufactured by International Biosynthesis Inc.), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Biosynthesis Inc.), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylaminobenzoic acid 2-ethylhexyl (The Hodogaya Chemical Co., Ltd. Preparation EAB) (Van Dyke (Van Dyk) manufactured solrol (Esolol) 507), 4,4'- diethylamino benzophenone, and the like.

Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, it is preferable that a thioxanthone compound is contained from the point of deep-hardening property. Among them, it is preferable to include thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone .

The blending amount of the thioxanthone compound is preferably 20 parts by mass or less based on 100 parts by mass of the carboxyl group-containing photosensitive resin. If the compounding amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably 10 parts by mass or less.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable. Among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, Particularly preferred.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone has low toxicity and is preferable. Since the dialkylamino group-containing coumarin compound has a maximum absorption wavelength in the range of 350 to 410 nm in the ultraviolet region, it is possible to use a coloring pigment and a colored solder resist reflecting the color of the colored pigment itself, It becomes possible to provide a film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable at the point which shows the outstanding sensitizing effect with respect to the laser beam of wavelength 400-410 nm.

The compounding amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the carboxyl group-containing photosensitive resin. When the compounding amount of the tertiary amine compound is less than 0.1 part by mass, there is a tendency that sufficient increase or decrease effect can not be obtained. When the amount exceeds 20 parts by mass, the light absorption at the surface of the dried solder resist coating film by the tertiary amine compound becomes severe, and the deep curing property tends to be lowered. More preferably 0.1 to 10 parts by mass.

These photoinitiators, photoinitiation aids, and sensitizers can be used alone or as a mixture of two or more thereof.

The total amount of the photopolymerization initiator, photoinitiator and sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing photosensitive resin. When it exceeds 35 mass parts, there exists a tendency for deep-part sclerosis | hardenability to fall by these light absorption.

In addition, since these photopolymerization initiators, photoinitiator and sensitizer absorb specific wavelengths, the sensitivity may be lowered in some cases and may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. It is possible to increase the photoreactivity of the surface and to change the line shape and the opening of the resist to a vertical, tapered, or reverse tapered shape, and improve the processing accuracy of the line width and the opening diameter .

The photosensitive resin composition of the present invention may also contain a conventionally known carboxyl group-containing photosensitive resin for the purpose of improving photosensitivity, developability, heat resistance and electrical properties. As specific examples of the carboxyl group-containing photosensitive resin, compounds (which may be oligomers or polymers) listed below are preferable.

(1) In a molecule | numerator to carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated group containing compounds, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene, A carboxyl group-containing photosensitive resin formed by reacting a compound having at least one ethylenically unsaturated group and one epoxy group.

(2) a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate and an aromatic diisocyanate, a dialcohol compound containing a carboxyl group such as dimethylolpropionic acid and dimethylolbutanoic acid, and a polycarbonate polyol, a polyether polyol Containing urethane resin obtained by a mid-portion reaction of a diol compound such as a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group (Meth) acrylate is added to a terminal (meth) acrylate during the synthesis of a carboxyl group-containing photosensitive urethane resin, which is obtained by adding a compound having one hydroxyl group and at least one (meth)

(3) difunctional isocyanates, bifunctional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins, and biphenol type epoxy resins The carboxyl group-containing photosensitive urethane resin by the polyaddition reaction of the (meth) acrylate or its partial acid anhydride modified product of this, a carboxyl group-containing dialcohol compound, and a diol compound.

(4) In the synthesis of the resin of the above (3), a compound having one hydroxyl group and at least one (meth) acrylic group in the molecule such as hydroxyalkyl (meth) Photosensitive urethane resin.

(5) In the synthesis of the resin of the above (2) or (3), a compound having one isocyanate group and one or more (meth) acrylate groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate, (Meth) acrylate.

(6) A photosensitive resin containing a carboxyl group in which a bifunctional or higher polyfunctional (solid) epoxy resin as described below is reacted with (meth) acrylic acid and a dibasic acid anhydride is added to a hydroxyl group present in the side chain.

(7) A method in which a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, a dibasic acid anhydride is added to the resulting hydroxyl group A carboxyl group-containing photosensitive resin.

(8) A process for producing a polyfunctional phenol compound by adding a cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate to a polyfunctional phenol compound such as novolak, partially esterifying the obtained hydroxyl group with (meth) acrylic acid and reacting the remaining hydroxyl groups with a polybasic acid anhydride A carboxyl group-containing photosensitive resin.

(9) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and at least one (meth) acryl group in one molecule to the resin of the above (1) to (8).

Since the carboxyl group-containing photosensitive resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkaline solution becomes possible.

The acid value of the carboxyl group-containing photosensitive resin is in the range of 40 to 200 mgKOH / g, and more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 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 developer proceeds, It is dissolved and peeled off as a developing solution without distinction between the light portion and the unexposed portion, which makes it difficult to draw a normal resist pattern.

In addition, although the weight average molecular weight of the said carboxyl group-containing photosensitive resin changes with resin skeleton, it is preferable to exist in the range of 2,000-150,000 normally and 5,000-100,000. If the weight average molecular weight is less than 2,000, the tackfree performance may be deteriorated, the moisture resistance of the coated film after exposure may be poor, the film may be reduced during development, and the resolution may be significantly lowered. On the other hand, when a weight average molecular weight exceeds 150,000, developability may become remarkably bad and storage stability may be inferior.

The blending amount of such a carboxyl group-containing photosensitive resin is suitably in the range of 0 to 50 mass%, preferably 10 to 40 mass%, in the whole composition.

These carboxyl group-containing photosensitive resins are not limited to those listed above and may be used singly or in combination of two or more.

In order to impart heat resistance to the photosensitive resin composition of the present invention, a thermosetting component can be added. As the thermosetting component used in the present invention, a block isocyanate compound, an amino resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, Can be used as the thermosetting resin. Among them, a preferable thermosetting component is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule. These thermosetting components having a cyclic (thio) ether group are commercially available in many kinds, and various properties can be given depending on their structure.

The thermosetting component having a plurality of cyclic (thio) ether groups in such molecules is a compound having a plurality of cyclic ether groups or cyclic thioether groups of 3, 4 or 5-membered rings in the molecule, Namely, a compound having a plurality of epoxy groups, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, .

Examples of the polyfunctional epoxy compounds include jER828, jER834, jER1001, jER1004, Epiclon 840, Epiclon 850, Epiclon 1050, Epiclon 2055, manufactured by DIC Corporation manufactured by Japan Epoxy Resin Co., DER317, DER331, DER661, and DER664 manufactured by Dow Chemical Co., Araldite 6071 and Aralid 6084 manufactured by Shiba Japan Co., , Aralidite GY250, Araldite GY260, SUMI EPOXY ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Industry Co., Ltd., AER330, AER331 and AER661 manufactured by Asahi Kasei Corporation , AER664 (all trade names), bisphenol A type epoxy resin; JERYL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152 manufactured by DIC Corporation, Epiclon 165, Epototo YDB-400, YDB-500 manufactured by Toko Kasei Co., DER542 manufactured by Dow Chemical Co., Aramidite 8011, Sumi-epoxy ESB-400 manufactured by Sumitomo Chemical Industry Co., Ltd., ESB-700, AER711 manufactured by Asahi Kasei Kogyo Co., and AER714 (all trade names); JER152, jER154 manufactured by Japan Epoxy Resin Co., DEN431, DEN438 manufactured by Dow Chemical Company, Epiclon N-730 manufactured by DIC, Epiclon N-770, Epiclon N-865, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, EPPN-201, EOCN-1025, EOCN-1025 manufactured by Nippon Kayaku Co., ESCN-220 manufactured by Sumitomo Chemical Industry Co., Ltd., AERECN-235 and ECN-299 manufactured by Asahi Chemical Industry Co., Ltd. (all trade names) Of novolak type epoxy resin; Epothilone YDF-170, YDF-175, YDF-2004 manufactured by Toko Kasei Co., Ltd., Araldite XPY306 manufactured by Shiba Japan Co., Ltd. (all trade names), Epiclon 830 manufactured by DIC Corporation, jER 807 manufactured by Japan Epoxy Resin Co., Bisphenol F type epoxy resin; Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007 and ST-3000 (trade name) manufactured by Tokuga Seisakusho; JER604 manufactured by Japan Epoxy Resin Co., Ltd., Ephoto YH-434 manufactured by Toko Kasei Co., Araldite MY720 manufactured by Shiba Japan Ltd., SUMI EPOX ELM-120 manufactured by Sumitomo Chemical Co., Ltd. A sidylamine type epoxy resin; Hidanto-type epoxy resin such as Aralidite CY-350 (trade name) manufactured by Shiba & Alicyclic epoxy resins such as Celloxide 2021 manufactured by Daicel Chemical Industries, Ltd., Araldite CY175 and CY179 manufactured by Ciba Japan Co., Ltd. (all trade names); YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T.E.N. produced by Dow Chemical Company, EPPN-501 and EPPN-502 manufactured by Nippon Kayaku Co., Ltd. (all trade names), trihydroxyphenylmethane type epoxy resin; A biscylenol type or biphenol type epoxy resin such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Japan Epoxy Resins, or a mixture thereof; Bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd. and EXA-1514 (trade name) manufactured by DIC Corporation; Bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; JERYL-931 manufactured by Japan Epoxy Resin Co., Ltd., Araldite 163 manufactured by Shiba Japan Co., Ltd. (all trade names), tetraphenylol ethane type epoxy resin; Araldite PT810 manufactured by Shiba Japan Co., Ltd., TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); Diglycidyl phthalate resins such as Blumer DGT manufactured by Nippon Oil Polymer Co., Ltd.; Tetraglycidylcylenoyl ethane resins such as ZX-1063 manufactured by Toko Chemical Co., Ltd.; Naphthalene group-containing epoxy resins such as ESN-190, ESN-360, and DIC Corporation, HP-4032, EXA-4750, and EXA-4700; Epoxy resins having a dicyclopentadiene skeleton, such as HP-7200 and HP-7200H manufactured by DIC Corporation; Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Co., Ltd.; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; And CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Tokuga Seisakusho Co., Ltd.). However, the present invention is not limited thereto. These epoxy resins may be used alone or in combination of two or more. Of these, novolak-type epoxy resins, heterocyclic epoxy resins, biquilene-type epoxy resins, and mixtures thereof are particularly preferable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (P-hydroxystyrene), cardo-type bisphenols, calixarene, calix resorcinarene, or a mixture of oxalic alcohol and novolak resin, poly And ether compounds with a hydroxyl group-containing resin such as sesquioxane. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

Examples of the episulfide resin having a plurality of cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin Co., Ltd. and the like. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used using the same synthesis method.

The amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is in the range of preferably 0.6 to 2.5 equivalents, more preferably 0.8 to 2.0 equivalents to 1 equivalent of the carboxyl group of the carboxyl group-containing photosensitive resin . When the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is less than 0.6, the carboxyl group remains in the solder resist film and the heat resistance, alkali resistance, electrical insulation, etc. are lowered. On the other hand, when the amount is more than 2.5 equivalents, a cyclic (thio) ether group having a low molecular weight remains in the dried coating film, and the strength or the like of the coating film is lowered.

Examples of other thermosetting components which can be preferably used include amino resins such as melamine derivatives and benzoguanamine derivatives. For example, methylolmelamine compounds, methylolbenzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. The alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound, and the alkoxymethylated urea compound may be used in combination with the respective methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds, and methylol urea compounds Methylol group into an alkoxymethyl group. It does not specifically limit about the kind of this alkoxy methyl group, For example, it can be set as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group. Particularly, a melamine derivative having a formalin concentration of 0.2% or less, which is human or environmentally friendly, is preferable.

These commercially available products include, for example, Cymel 300, Copper 301, Copper 303, Copper 370, Copper 325, Copper 327, Copper 701, Copper 266, Copper Copper 267, Copper Copper 238, Copper Copper 1141, Copper Copper Copper 202, 750, copper Mx-032, copper Mx-270, copper Mx-280 (manufactured by Mitsui Cyanamid Co., Ltd.), copper foil 1158, copper 1123, copper 1170, copper 1174, copper UFR65, copper 300 , Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM , And Mw-750LM (manufactured by Sanwa Chemical Co., Ltd.).

The thermosetting components may be used alone or in combination of two or more.

Further, in the photosensitive resin composition of the present invention, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be added in order to improve the curability of the composition and the toughness of the resulting cured film. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound or a compound having a plurality of blocked isocyanate groups in one molecule, i.e., a block isocyanate compound have.

As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m - xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Also, examples of the isocyanate compound, burette and isocyanurate of the isocyanate compound may be mentioned first.

The blocked isocyanate group contained in the block isocyanate compound is a group in which the isocyanate group is protected by a reaction with the blocking agent and is temporarily inactivated. When heated to a predetermined temperature, the block agent dissociates to produce an isocyanate group.

As the block isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent is used. Examples of the isocyanate compound capable of reacting with the block agent include isocyanurate type, buret type, and adduct type. As the isocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate and the alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate block agent include phenolic block agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam-based blocking agents such as? -caprolactam,? -valerolactam,? -butyrolactam and? -propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; But are not limited to, methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Alcohol-based blocking agents such as butyl acetate, diacetone alcohol, methyl lactate and ethyl lactate; Oxime block agents, such as formaldehyde, aceto aldoxin, acetoxime, methyl ethyl ketoxime, diacetyl monooxime and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol and ethyl thiophenol; Acid amide block agents such as acetic amide and benzamide; Imide block agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine blockers such as methylene imine and propylene imine, and the like.

The block isocyanate compound may be a commercially available one, for example, Sumidul BL-3175, BL-4165, BL-1100, BL-1265, Dismodules TPLS-2957, TPLS-2062, TPLS- (Trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815 (trade name, product of Sumitomo Bayer Urethane Co., Ltd.), Coronate 2512, Coronate 2513 and Coronate 2520 TPA-B80E, 17B-60PX and E402-B80T (trade names, manufactured by Asahi Kasei Chemicals Co., Ltd.), B- And the like. Further, the polymers BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a block agent.

The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be used alone or in combination of two or more.

The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is suitably from 1 to 100 parts by mass, more preferably from 2 to 70 parts by mass, per 100 parts by mass of the carboxyl group-containing photosensitive resin. When the blending amount is less than 1 part by mass, sufficient toughness of the coating film can not be obtained, which is not preferable. On the other hand, if it exceeds 100 parts by mass, the storage stability of the composition deteriorates, which is not preferable.

In the photosensitive resin composition of the present invention, an urethane formation catalyst may be added to accelerate a curing reaction between a hydroxyl group and a carboxyl group and an isocyanate group. As the urethanization catalyst, it is preferable to use at least one urethane-forming catalyst selected from the group consisting of tin catalyst, metal chloride, metal acetylacetonate salt, metal sulfate, amine compound and / or amine salt.

Examples of the tin-based catalyst include organotin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

Examples of the metal chloride include chlorides of metals such as Cr, Mn, Co, Ni, Fe, Cu, or Al, such as cobalt chloride, nickel chloride and ferric chloride.

The metal acetylacetonate salt is an acetylacetonate salt of a metal containing Cr, Mn, Co, Ni, Fe, Cu or Al, and examples thereof include cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, .

Examples of the metal sulfate include metal sulfate such as Cr, Mn, Co, Ni, Fe, Cu, or Al, and copper sulfate, for example.

Examples of the amine compound include triethylenediamine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) N, N ", N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, Aminopyridine, triazine, N'- (2-hydroxyethyl) -N, N, N'-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, (2-hydroxyethyl) -N, N ', N ", N" -tetramethyldiamine, N- N, N'-trimethyl-N '- (2-hydroxyethyl) -N, N'-tetramethyldiethylenetriamine, N- ) Propane diamine, N, N'-bis (N, N-dimethylaminopropyl) amine, bis Aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1- (2'-hydroxy Propyl imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole, 1- Imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (3'-aminopropyl) imidazole, 1- , N, N-dimethylaminopropyl-N '- (2-hydroxyethyl) imidazole, 1- (3'- (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ', N'-bis (2-hydroxypropyl) amine, (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ', N'-bis (2-hydroxypropyl) amine, melamine or / And benzoguanamine.

Examples of the amine salt include an organic acid salt-based amine salt of DBU (1,8-diaza-bicyclo [5.4.0] undecene-7).

The compounding amount of the urethanization catalyst is usually sufficient in a usual quantitative ratio, and is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10.0 parts by mass, based on 100 parts by mass of the carboxyl group-containing photosensitive resin.

When a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as imidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., U-CAT DBU, U-CATSA102, U-CAT5002 (all of bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, and may be a catalyst for accelerating the reaction between a thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group and a carboxyl group, or may be used alone or in combination have. Further, it is also possible to use at least one selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, isocyanuric acid Or an S-triazine derivative such as an adduct may be used. Preferably, a compound that also functions as such an adhesion-imparting agent is used in combination with the above-mentioned thermosetting catalyst.

The amount of these thermosetting catalysts is usually sufficient in a usual quantitative ratio, and is preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the thermosetting component having a carboxyl group-containing photosensitive resin or a plurality of cyclic (thio) Mass part, and more preferably 0.5 to 15.0 mass part.

The photosensitive resin composition of the present invention may contain a colorant. As the coloring agent, publicly known coloring agents such as red, blue, green, and yellow may be used, and any of pigments, dyes, and pigments may be used. However, it is preferable that it does not contain a halogen in terms of environmental load reduction and human influence.

Red colorant:

Examples of the red colorant include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. And the same color index (CI) issued by the Society of Dyers and Colourists).

Monoazo system: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.

Disazo system: Pigment Red 37, 38, 41.

48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.

Benzimidazolone pigments: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224, Pigment Red 174, Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, .

Diketopyrrolopyrrole-based pigments: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinacridone pigments: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

Examples of the blue colorant include a phthalocyanine type and anthraquinone type, and a pigment type is a compound classified as a pigment. Specific examples thereof include Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 Etc. may be used. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Green colorant:

Examples of the green colorant include phthalocyanine type, anthraquinone type and perylene type. Specific examples include Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20 and Solvent Green 28 . In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Yellow colorant:

Examples of the yellow colorant include a monoazo system, a disazo system, a condensed azo system, a benzimidazolone system, an isoindolinone system, and an anthraquinone system, and specific examples include the following.

Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolinone pigments: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone pigments: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 , 116, 167, 168, 169, 182, 183.

Disazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, a coloring agent such as purple, orange, brown or black may be added for the purpose of adjusting the color tone.

Illustratively, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C.I. Pigment Orange 1, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 16, C.I. Pigment Orange 17, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 51, C.I. Pigment Orange 61, C.I. Pigment Orange 63, C.I. Pigment Orange 64, C.I. Pigment Orange 71, C.I. Pigment Orange 73, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Black 1, C.I. Pigment Black 7 and so on.

Although the mixing | blending ratio of a coloring agent as above is not restrict | limited, Preferably it is 10 mass parts or less, Especially preferably, the ratio of 0.1-5 mass parts is sufficient with respect to 100 mass parts of said carboxyl group-containing photosensitive resin.

In the photosensitive resin composition of the present invention, a compound having a plurality of ethylenically unsaturated groups in the molecule may be added. A compound having a plurality of ethylenically unsaturated groups in a molecule is photo-cured by irradiation with active energy rays to insolubilize or insolubilize the carboxyl group-containing photosensitive resin in an aqueous alkali solution. Examples of such a compound include polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate and epoxy Include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol, and tris-hydroxyethylisocyanurate; and ethylene oxide adducts, propylene oxide adducts, and? -Caprolactone adducts Polyfunctional acrylates; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; The present invention is not limited to the above, and acrylates and melamine acrylates in which a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene, or a polyester polyol is directly acrylated or urethane-acrylated through a diisocyanate, And / or the respective methacrylates corresponding to the acrylate.

In addition, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolak type epoxy resin with acrylic acid, or an epoxy acrylate resin obtained by reacting a hydroxy acrylate such as pentaerythritol triacrylate with an isophorone di And an epoxy urethane acrylate compound obtained by reacting a half urethane compound of a diisocyanate such as isocyanate. Such an epoxy acrylate resin can improve the photocurability without lowering the composition of the touch and dry.

The compounding amount of the compound having a plurality of ethylenically unsaturated groups in such a molecule is preferably 5 to 100 parts by mass, more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. When the blending amount is less than 5 parts by mass, the photocurability is lowered, and pattern formation becomes difficult due to the alkali development after irradiation with active energy rays, which is not preferable. On the other hand, if it exceeds 100 parts by mass, the solubility in an aqueous alkaline solution is lowered and the coating film becomes weak, which is not preferable.

In the photosensitive resin composition of the present invention, a filler may be added if necessary in order to increase the physical strength and the like of the coating film. As such a filler, inorganic or organic fillers for publicly known generations can be used, and particularly barium sulfate, spherical silica and talc are preferably used. Further, metal hydroxide such as titanium oxide, metal oxide, and aluminum hydroxide may be used as extender pigment filler in order to obtain white appearance and flame retardancy. The blending amount of these fillers is preferably 200 parts by mass or less, more preferably 0.1 to 150 parts by mass, and particularly preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. When the blending amount of the filler exceeds 200 parts by mass, the viscosity of the composition is increased, the printing property is lowered, or the cured product becomes fragile.

The photosensitive resin composition of the present invention may use a mercapto compound as a chain transfer agent and / or an adhesion imparting agent. Examples of the mercapto compound include mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan , Propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like. Examples of commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.), car lens MT- BD1, and CALENS-NR1 (manufactured by Showa Denko K.K.).

Examples of mercapto compounds having a heterocyclic ring include mercapto-4-butyrolactone (also referred to as 2-mercapto-4-butanololide), 2-mercapto- 2-mercapto-4-butyrolactone, 2-mercapto-4-butyrolactone, 2-mercapto- 4-butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl- Mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N- Mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2- mercaptobenzothiazole, 2- 2-mercapto-6-hexanolactam, 2,4,6-trimercapto-s-triazine (manufactured by Sankyo Kasei Corporation, trade name: Disnet F), 2 -Dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd., trade name: Disnet DB), 2-anilino-4,6- dimercapto- (Trade name: Disnet AF). Further, it is also possible to use 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (Accelerator M, trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.) 1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole and the like can be preferably used. These mercapto compounds can be used individually or in combination of 2 or more types.

The blending amount of such a mercapto compound is suitably 0.01 part by mass or more and 10.0 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the above carboxyl group-containing photosensitive resin. If the amount is less than 0.01 part by mass, the effect of the mercapto compound addition is not confirmed. On the other hand, if it exceeds 10.0 parts by mass, the development failure of the photosensitive resin composition and the decrease in the drying control width may be undesirably caused.

Further, the photosensitive resin composition of the present invention may use a binder polymer for the purpose of improving tackiness and handling properties. For example, a polyester polymer, a polyurethane polymer, a polyester urethane polymer, a polyamide polymer, a polyester amide polymer, an acrylic polymer, a cellulose polymer, a polylactic acid polymer and a phenoxy polymer can be used. These binder polymers can be used alone or as a mixture of two or more thereof.

Further, the photosensitive resin composition of the present invention can be used for the purpose of imparting flexibility and improving the fragility of a cured product. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyester amide elastomer, and an acrylic elastomer. These elastomers can be used alone or as a mixture of two or more thereof.

The organic solvent may be used in the photosensitive resin composition of the present invention for the purpose of synthesis of the carboxyl group-containing photosensitive resin, preparation of the composition, or viscosity adjustment for application to a substrate or a carrier film.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; 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 And the like; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether 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 kinds.

Generally, most of the polymeric materials are oxidized in a sequential manner when oxidization is initiated once in succession, resulting in deterioration of the function of the polymer material. In order to prevent oxidation, the photosensitive resin composition of the present invention has (1) A radical scavenger such as a radical scavenger, and / or (2) an antioxidant such as a peroxide decomposition agent which decomposes the generated peroxide into a harmless substance to prevent generation of new radicals. In particular, when the antioxidant is used in the composition using the butadiene-based elastomer used in the present invention, PCT resistance is improved, and peeling and discoloration during HAST are less effective.

Specific examples of the antioxidant that functions as a radical scavenger include hydroquinone, 4-t-butyl catechol, 2-t-butyl hydroquinone, hydroquinone monomethyl ether, 2,6- T-butyl (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'- Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione; quinone compounds such as methaquinone and benzoquinone; bis -Tetramethyl-4-piperidyl) sebacate, and phenothiazine, and the like.

Radical scavengers may be commercially available, for example, Adekastab AO-30, Adekastab AO-330, Adekastab AO-20, Adekastab LA-77, Adekastab LA-57, (Manufactured by Asahi Denka Kogyo Co., Ltd.), IRGANOX X1010, Irganox 1035, Irganox 1076, Irgacox LA-67, Adeka Staff LA- TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (trade names, manufactured by Ciba Japan KK), and the like.

Specific examples of the antioxidant that functions as a peroxide releasing agent include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetra lauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3'-thiodi And sulfur compounds such as propionate.

The release of the peroxide may be a commercially available one, and examples of the release agent include peroxides such as Adekastab TPP (product name of Asahi Denka Co., Ltd.), Mark AO-412S (trade name of Adeka Agusuga Co., Ltd.) Trade name, manufactured by Kagaku Co., Ltd.).

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

In general, since the polymer material absorbs light and causes decomposition and deterioration accordingly, a ultraviolet absorber can be used in addition to the antioxidant in the photosensitive resin composition of the present invention in order to take stabilization measures against ultraviolet rays. .

Examples of ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives. Specific examples of the benzophenone derivatives include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy- 4-dihydroxybenzophenone, and the like. Specific examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl- Hydroxybenzoate, and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, . Specific examples of the triazine derivatives include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.

Examples of ultraviolet absorbers that may be used include commercially available products such as Tinuvin PS, Tinuvin 99-2, Tinuvin 109, Tinuvin 384-2, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 400, Nubin 405, Tinuvin 460, and Tinuvin 479 (all trade names, manufactured by Shiba, Japan).

The above-mentioned ultraviolet absorber can be used alone or in combination of two or more. By using the ultraviolet absorber together with the antioxidant, the molded article obtained from the photosensitive resin composition of the present invention can be stabilized.

In the photosensitive resin composition of the present invention, an adhesion promoter may be used to improve the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate. Specific examples thereof include benzoimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi Kagaku Kogyo ) Manufacturing Accelerator M), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole- Thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

The photosensitive resin composition of the present invention may further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite and the like, if necessary. The aging stability as a thixotropic agent is preferably organic bentonite or hydrotalcite, and particularly hydrotalcite has excellent electrical properties. In addition, thermal polymerization inhibitors, defoaming agents such as silicone, fluorine, and high molecular weight and / or leveling agents, silane coupling agents such as imidazole, thiazole, and triazole, rust inhibitors, and antioxidants such as bisphenol and triazinethiol (Copper damaging agent), and the like can be compounded.

The thermal polymerization inhibitor may be used to prevent thermal polymerization or polymerization over time of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone (4-methyl-6-t-butyl-4-cresol, 2,2'-methylenebis Butylphenol), reagents with pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agents, methyl salicylate, and phenothiazine, nitroso compounds, chelates of nitroso compounds with Al And the like.

The photosensitive resin composition of the present invention can be prepared, for example, by adjusting the viscosity of the above-mentioned organic solvent to a viscosity suitable for the application method, and coating on the substrate by an immersion coating method, a flow coating method, a roll coating method, a bar coater method, , And the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 60 to 100 DEG C, whereby a tack-free coating film can be formed. Thereafter, by a contact type (or non-contact type) method, the resist film is selectively exposed to an active energy ray through a photomask having a pattern formed thereon, or directly pattern-exposed by a laser direct exposure machine, and the unexposed portion is exposed to an alkali aqueous solution For example, 0.3 to 3% aqueous sodium carbonate solution) to form a resist pattern. Further, in the case of a composition containing a thermosetting component, for example, by heating to a temperature of about 140 to 180 캜 to thermoset, the carboxyl group of the carboxyl group-containing photosensitive resin and a plurality of cyclic ether groups and / A thermosetting component having a thioether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption, adhesion, electrical properties and the like. In addition, even when the thermosetting component is not contained, since the ethylenic unsaturated bond of the photo-curing component remaining in the unreacted state during the exposure is thermally radically polymerized by heat treatment, the film property improves, (Heat curing) by heat treatment.

In addition to the printed wiring board and the flexible printed wiring board which have been formed in advance, the above substrate may be formed of a resin such as a paper-phenol resin, a paper-epoxy resin, a glass cloth-epoxy resin, a glass-polyimide, a glass cloth / (FR-4 or the like), polyimide film, PET film, glass substrate, ceramic substrate, wafer plate or the like using a composite material such as synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester Can be used.

The volatile drying after application of the photosensitive resin composition of the present invention can be carried out by a hot-air circulating drying furnace, a hot plate, a convection oven or the like (a furnace equipped with a heat source of air heating by steam, A method of contacting the support with a nozzle and a method of spraying onto the support by a nozzle).

After the photosensitive resin composition of the present invention is applied and volatilized and dried as described below, the resulting coating film is subjected to exposure (irradiation with active energy rays). An exposed part (part irradiated with an active energy ray) hardens | cures a coating film.

Examples of the exposure apparatus used for the irradiation of the active energy ray include a direct imaging apparatus (for example, a laser direct imaging apparatus for directly drawing an image with a laser by CAD data from a computer), an exposure apparatus equipped with a metal halide lamp, A direct exposure apparatus equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp can be used. As the active energy ray, either a gas laser or a solid laser may be used if laser light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure dose varies depending on the film thickness and the like, but it may be generally in the range of 5 to 200 mJ / cm ² , preferably 5 to 100 mJ / cm ² , more preferably 5 to 50 mJ / cm ² . As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech Co., Ltd. and manufactured by FANUC Corporation may be used, and any apparatus may be used as long as it is an apparatus for emitting 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 used. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, have.

The photosensitive resin composition of the present invention may be used in the form of a dry film having a solder resist layer formed by applying and drying a solder resist to a film such as polyethylene terephthalate in advance, The case where the photosensitive resin composition of this invention is used as a dry film is shown below.

The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film, which is used as needed, are laminated in this order. The solder resist layer is a layer obtained by applying and drying an alkali developable photosensitive resin composition to a carrier film or a cover film. After the solder resist layer is formed on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and the 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 mu m is used.

The solder resist layer is formed by uniformly applying an alkali developable photosensitive resin composition to a carrier film or a cover film by a blade coater, a lip coater, a comer coater, a film coater or the like to a thickness of 10 to 150 탆 and drying the same.

As the cover film, a polyethylene film, a polypropylene film or the like can be used, but it is preferable that the adhesive force to the solder resist layer is smaller than that of the carrier film.

In order to manufacture a protective film (permanent protective film) on a printed wiring board using a dry film, a cover film is peeled off, the solder resist layer and the circuit-formed substrate are superimposed and bonded together using a laminator or the like, Layer. When the exposed solder resist layer is exposed, developed and cured by heating as described above, a cured coating film can be formed. The carrier film may be peeled off either before exposure or after exposure.

<Examples>

The present invention will be described in more detail with reference to the following examples and comparative examples, but it goes without saying that the present invention is not limited to the following examples. In the following, &quot; parts &quot; and &quot;% &quot; are all based on mass unless otherwise specified.

Resin Synthesis Example 1

120 parts of novolac cresol resin (OH equivalent: 120), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate were charged into a reaction kettle, and the mixture was heated to 150 to 160 DEG C while stirring to initiate the reaction And then the reaction was continued at 200 to 220 ° C for about 2 hours. Carbon dioxide gas was generated at the same time as the reaction progressed. Thereafter, the mixture was cooled to room temperature to obtain a propylene carbonate reaction product of a novolak type cresol resin having a hydroxyl group equivalent of 182.2 g / eq. This was equivalent to an average addition of 1.08 mole of propylene oxide per equivalent of phenolic hydroxyl group.

The reaction product was dissolved in 270 parts of diethylene glycol monoethyl ether acetate, and then 135.0 parts of half urethane in which isophorone diisocyanate and hydroxyethyl acrylamide were reacted at a molar ratio of 1: 1 was reacted at 75 ° C for 4 hours. Further, 91.2 parts of tetrahydrophthalic anhydride was gradually added and the reaction was carried out at 95 ° C for about 5 hours. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 61% and a solid acid value of 81.3 mgKOH / g. This is called Resin Solution A-1.

Resin Synthesis Example 2

119.4 parts of novolac cresol resin (trade name: "SCORNOL CRG951", OH equivalent: 119.4), manufactured by Showa Kobunshi Co., Ltd.) was added to an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device and a stirring device, 1.19 parts of potassium hydroxide and 119.4 parts of toluene were charged, and the system was purged with nitrogen while stirring, and the mixture was heated and heated. Next, slowly added 63.8 parts of propylene oxide, and reacted for 16 hours at 125 to 132 ℃, 0 to 4.8 kg / cm ^2. Thereafter, the reaction solution was cooled to room temperature. To the reaction solution, 1.56 parts of 89% phosphoric acid was added and mixed to neutralize the potassium hydroxide. To the reaction mixture was added a propylene oxide reaction solution of a novolac cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / &Lt; / RTI &gt; It was found that an average of 1.08 mole of alkylene oxide per 1 equivalent of phenolic hydroxyl group was added.

293.0 parts of the alkylene oxide reaction solution 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 fed into a reactor equipped with a stirrer, a thermometer and an air blowing tube, ml / minute and reacted at 110 DEG C for 12 hours while stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 parts of water were spilled out. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off by replacing toluene with 118.1 parts of diethylene glycol monoethyl ether acetate to obtain an novolak type acrylate resin solution. Next, 332.5 parts of the obtained novolak type acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, blowing air at a rate of 10 ml / min, 60.8 parts of tetrahydrophthalic anhydride was slowly added, and the mixture was reacted at 95 to 101 ° C for 6 hours. A photosensitive resin having a carboxyl group of an acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. This is designated as resin solution A-2.

Resin Synthesis Example 3

120 parts of novolac cresol resin (OH equivalent: 120), 0.6 part of triphenylphosphine and 112 parts of propylene carbonate were charged into a reaction kettle, and the mixture was heated to 150 to 160 DEG C while stirring to initiate the reaction And then the reaction was continued at 200 to 220 ° C for about 2 hours. Carbon dioxide gas was generated at the same time as the reaction progressed. Then, it cooled to room temperature and obtained the propylene carbonate reaction product of the novolak-type cresol resin whose hydroxyl equivalent is 182.2 g / eq. This was equivalent to an average addition of 1.08 mole of propylene oxide per equivalent of phenolic hydroxyl group.

Next, the reaction product was dissolved in 270 parts of diethylene glycol monoethyl ether acetate, and then 208.1 parts of half urethane in which isophorone diisocyanate and pentaerythritol triacrylate were previously reacted at a molar ratio of 1: 1 was reacted at 75 ° C for 4 hours. Further, 91.2 parts of tetrahydrophthalic anhydride was gradually added and the reaction was carried out at 95 ° C for about 5 hours. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 64.4% and a solid acid value of 68.9 mgKOH / g. This is designated as Resin Solution A-3.

Comparative Synthesis Example 1

EPICLON N-695 manufactured by DIC Corporation, softening point: 95 占 폚, epoxy equivalent: 214, average number of functional groups: 7.6) was added to 600 parts of diethylene glycol monoethyl ether acetate, (Total number of aromatic rings: 5.0 moles), 360 parts of acrylic acid (5.0 moles) and 1.5 parts of hydroquinone were charged and stirred at 100 DEG C to dissolve uniformly. Then, 4.3 parts of triphenylphosphine was added, and the mixture was heated to 110 DEG C for 2 hours, heated to 120 DEG C, and further reacted for 12 hours. 415 parts of an aromatic hydrocarbon (Solvesso 150) and 456.0 parts (3.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction solution and reacted at 110 DEG C for 4 hours. After cooling, the mixture was allowed to have a solid content of 89 mgKOH / g and a solid content of 65 % Of a resin solution. This is called resin solution R-1.

Comparative Synthesis Example 2

925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide were dissolved in 400 parts of bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 DEG C, and then 81.2 parts of 98.5% NaOH was added thereto at 70 DEG C over 100 minutes with stirring. After the addition, the reaction was further carried out at 70 DEG C for 3 hours. Subsequently, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide was distilled off under reduced pressure to dissolve the reaction product containing the by-product salt and dimethyl sulfoxide in 750 parts of methyl isobutyl ketone, and further, 30% NaOH And the mixture was reacted at 70 DEG C for 1 hour. After completion of the reaction, water was washed twice with 200 parts of water. After water separation, methyl isobutyl ketone was distilled off from the oil layer to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 캜.

2900 parts (10 equivalents) of epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone and 1950 parts of carbitol acetate were added and heated to 90 DEG C and stirred to dissolve the reaction mixture. Subsequently, the reaction solution was cooled to 60 占 폚, 16.7 parts of triphenylphosphine was added, heated to 100 占 폚, and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Subsequently, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were added thereto, and the mixture was heated to 95 DEG C and reacted for about 6 hours to obtain a resin solution having a solid content of 100 mgKOH / g and a solid content of 65% . This is called resin solution R-2.

Examples 1 to 6 and Comparative Examples 1 and 2

Using the resin solution of the above synthesis example, the various components shown in Table 1 were mixed together at the ratio (parts by mass) shown in Table 1, premixed in a stirrer, and kneaded with a three-roll mill to obtain a photosensitive resin composition for a solder resist . The degree of dispersion of the obtained photosensitive resin composition was evaluated by particle size measurement by a grindmeter manufactured by Ericensa and found to be 15 占 퐉 or less.

Performance evaluation:

<Optimum exposure dose>

Each of the photosensitive resin compositions of the examples and the comparative examples was buffed to a thickness of 35 mu m on a circuit pattern substrate having a copper thickness of 35 mu m and then washed with water and then dried and then applied onto the entire surface by screen printing to obtain a hot- Lt; / RTI &gt; for 60 minutes. After drying, the resist film was exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and was exposed to development (30 ° C, 0.2 MPa, 1 wt% sodium carbonate aqueous solution) When the pattern of the step tablet is 7, the optimum exposure amount is set.

<Developability>

Each of the photosensitive resin compositions of the above Examples and Comparative Examples was coated on a copper beta substrate by a screen printing method so as to have a film thickness after drying of about 25 占 퐉 and dried in a hot air circulation type drying furnace at 80 占 폚 for 30 minutes. After drying, development was carried out with a 1 wt% sodium carbonate aqueous solution, and the time until the dry coating film was removed was measured by a stop watch.

<Maximum developing life>

Each of the photosensitive resin compositions of the above Examples and Comparative Examples was applied on the entire surface by screen printing on a patterned copper foil substrate, dried at 80 占 폚, taken out for 20 minutes to 80 minutes for 10 minutes, and then cooled to room temperature. The substrate was developed with a 1 wt% sodium carbonate aqueous solution at 30 DEG C under a spray pressure of 0.2 MPa for 90 seconds, and the maximum allowable drying time at which no residue remained was regarded as the maximum developing life.

<Tachung>

Each photosensitive resin composition of the said Example and the comparative example was apply | coated whole surface by the screen printing on the patterned copper foil board | substrate, it was made to dry for 30 minutes by 80 degreeC hot-air circulation drying furnace, and it cooled to room temperature. The substrate was struck with a PET negative film, pressed under a reduced pressure condition for 1 minute by ORC (HMW-GW20), and then the film was peeled off when the film was peeled off was evaluated according to the following criteria .

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

△: When the film is peeled off, there is a little resistance, and a trace remains on the film.

X: When the film was peeled, there was resistance, and there was a clear trace on the film.

Characteristic test:

Each of the photosensitive resin compositions of the above Examples and Comparative Examples was applied on the entire surface by screen printing on the patterned copper foil substrate, dried at 80 캜 for 30 minutes, and then allowed to cool to room temperature. The substrate was exposed to a solder resist pattern at an optimum exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp, and developed for 90 seconds under the condition of a 1 wt% sodium carbonate aqueous solution at 30 DEG C and a spray pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under the conditions of an integrated exposure dose of 1000 mJ / cm ² in a UV conveyer, and then cured by heating at 150 ° C for 60 minutes. The properties of the obtained printed board (evaluation board) were evaluated as follows.

<Acid resistance>

The evaluation substrate was immersed in a 10 wt% HCl aqueous solution at room temperature for 30 minutes to visually confirm seepage and elution of the coating film, and peeling by tape peeling was confirmed. The criteria are as follows.

○: Change is not recognized.

△: Very little change.

X: The coating film has swelling or swelling or dropping.

<Alkali resistance>

The evaluation substrate was immersed in a 10 wt% aqueous solution of NaOH at room temperature for 30 minutes to confirm the seepage and the elution of the coating film visually and peeling by tape peeling was confirmed. The criteria are as follows.

○: Change is not recognized.

△: Very little change.

X: The coating film has swelling or swelling or dropping.

&Lt; Soldering heat resistance &

The evaluation substrate on which the rosin-based flux was applied was immersed in a solder bath set at 260 占 폚 in advance, and the flux was washed with denatured alcohol, and then the expansion and exfoliation of the resist layer were visually evaluated. The criteria are as follows.

○: peeling is not recognized even if immersion for 10 seconds is repeated 3 times or more.

?: Slightly peeled if the immersion for 10 seconds was repeated 3 times or more.

X: Expansion and peeling occurred in the resist layer within 3 times of immersion for 10 seconds.

<Electroless gold plating resistance>

Plating was carried out using a commercially available electroless nickel plating bath and electroless gold plating bath under the conditions of nickel of 5 占 퐉 and gold of 0.05 占 퐉 and the peeling of the resist layer or the impregnation of the plating was evaluated by tape peeling , And the peeling of the resist layer was evaluated by tape peeling. The criteria are as follows.

(Double-circle): No seepage and peeling are seen.

(Circle): Although it penetrates a little after plating, it does not peel after tape peeling.

(Triangle | delta): Very slight seepage after plating and peeling is also seen after tape peeling.

X: Peeling occurred after plating.

<PCT Resistance>

The evaluation substrate on which the solder resist cured coating film was formed was treated for 168 hours under conditions of 121 占 폚, saturation and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by Espec Corporation) Respectively. The criteria are as follows.

○: No swelling, peeling, discoloration, or elution.

?: A little swelling, peeling, discoloration, elution.

X: Expansion, peeling, discoloration, and a lot of dissolution appear.

<Cold shock resistance>

An evaluation board having a solder resist cured coating film on which a removal pattern and a removal pattern were formed was prepared. The obtained evaluation substrate was subjected to an immunity test for 1000 cycles in one cycle at -55 DEG C / 30 minutes to 150 DEG C / 30 minutes in a cold / impact tester (manufactured by ETK Corp.). After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged based on the following criteria.

◎: Cracking rate less than 20%.

?: Cracking rate of 20 to 40%.

?: Crack generation rate of 40 to 60%.

×: Crack generation rate of 60% or more.

<HAST attribute>

A solder resist cured coating film was formed on a BT substrate on which interdigital electrodes (line / space = 30 占 퐉 / 30 占 퐉) were formed to prepare an evaluation substrate. The evaluation substrate was placed in a high-temperature and high-humidity bath under an atmosphere at 130 캜 and a humidity of 85%, charged at a voltage of 5 V, and subjected to a HAST test in the bath for 168 hours. The in-house insulation resistance value at the elapsed time of 168 hours was evaluated according to the following criteria.

○: 10 ⁸ Ω or more

?: 10 ⁶ to 10 ⁸ ?

×: Less than 10 ⁶ Ω

The results of the above evaluation test are shown in Table 2 below.

Examples 7 to 12 and Comparative Examples 3 and 4

Each of the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 and 2 prepared by the formulations shown in Table 1 was diluted with methyl ethyl ketone and applied on a PET film and dried at 80 DEG C for 30 minutes to obtain a photosensitive resin composition having a thickness of 20 mu m Thereby forming a photosensitive resin composition layer. Further, a cover film was laminated thereon to produce a dry film, which were Examples 7 to 12 and Comparative Examples 3 and 4, respectively.

<Dry Film Evaluation>

The cover film of the dry film obtained as described above was peeled off, the film was laminated to the patterned copper foil substrate, and then exposed in the same conditions as the substrate used for evaluating the coating film properties of Examples 1 to 6 above. After the exposure, the carrier film was peeled off and developed for 90 seconds under the conditions of a 1 wt% sodium carbonate aqueous solution at 30 캜 and a spray pressure of 0.2 MPa to obtain a resist pattern. Thereafter, the substrate was irradiated with ultraviolet rays under the condition of an integrated exposure dose of 1000 mJ / cm ² in a UV conveyer, and the substrate was further heated and cured in a hot air drier at 150 ° C for 60 minutes to prepare a test substrate. The test substrate having the obtained cured coating was subjected to the evaluation test of each characteristic by the above-described test method and evaluation method. The results are shown in Table 3.

Examples 13 to 18 and Comparative Examples 5 and 6

Using the resin solution of the above-mentioned synthesis example, the various components shown in Table 4 were combined with the ratios (parts by mass) shown in Table 4, premixed in a stirrer, and kneaded by a three-roll mill to obtain a photosensitive resin composition for a solder resist . The degree of dispersion of the obtained photosensitive resin composition was evaluated by particle size measurement by a grindmeter manufactured by Ericensa and found to be 15 占 퐉 or less.

Performance evaluation:

Using the respective photosensitive resin compositions of the examples and the comparative examples, the optimum exposure amount, developability, maximum development life, and tackiness were tested by the above-described test method and evaluation method in the same manner as in Examples 1 to 6 above.

Using the photosensitive resin compositions of Examples and Comparative Examples, an evaluation substrate was prepared in the same manner as in the characteristic tests of Examples 1 to 6 above. The evaluation board having the cured coating thus obtained was subjected to the evaluation tests of the acid resistance, alkali resistance, solder heat resistance, electroless gold plating resistance, PCT resistance and HAST characteristics by the above-described test method and evaluation method.

The results of the above evaluation test are shown in Table 5 below.

Examples 19 to 24 and Comparative Examples 7 and 8

Each of the photosensitive resin compositions of Examples 13 to 18 and Comparative Examples 5 and 6 prepared by the prescriptions shown in Table 4 was diluted with methyl ethyl ketone and applied on a PET film and dried at 80 DEG C for 30 minutes to obtain a photosensitive resin composition having a thickness of 20 mu m Thereby forming a photosensitive resin composition layer. Further, a cover film was laminated thereon to prepare a dry film, which were Examples 19 to 24 and Comparative Examples 7 and 8, respectively.

<Dry Film Evaluation>

The cover film of the dry film obtained as described above was peeled off, the film was thermally laminated on the patterned copper foil substrate, and then exposed in the same conditions as the substrate used for evaluating the coating film characteristics of Examples 1 to 6 above. After the exposure, the carrier film was peeled off and developed for 90 seconds under the conditions of a 1 wt% sodium carbonate aqueous solution at 30 캜 and a spray pressure of 0.2 MPa to obtain a resist pattern. Thereafter, the substrate was irradiated with ultraviolet rays under the condition of an integrated exposure dose of 1000 mJ / cm ² in a UV conveyer, and the substrate was further heated and cured in a hot air drier at 150 ° C for 60 minutes to prepare a test substrate. The test substrate having the obtained cured coating was subjected to the evaluation test of each characteristic by the above-described test method and evaluation method. The results are shown in Table 6.

From the results of Tables 2 and 3 and Tables 5 and 6, it can be seen that the photosensitive resin composition of the present invention provides a photosensitive resin composition having PCT resistance, cold shock resistance, and electrical characteristics (HAST characteristic) required for a solder resist for an IC package .

The photosensitive resin composition or the dry film thereof of the present invention can be advantageously applied to the formation of a cured coating film of a solder resist or the like of a printed wiring board or a flexible printed wiring board. In particular, the solder resist for a semiconductor package is excellent in PCT resistance, HAST resistance, A cured coating having gold plating resistance and cold / heat shock resistance can be formed.

Claims (4)

One or more acrylamide groups or methacrylamide groups or one in a molecule to a reaction product obtained by reacting a phenol resin with 1.1 to 3 moles of an alkylene oxide or a cyclocarbonate compound per equivalent of phenolic hydroxyl group of the phenol resin. An alkali developable photosensitive resin composition comprising a carboxyl group-containing photosensitive resin obtained by reacting an isocyanate compound having two or more acryloyl groups or methacryloyl groups, and reacting the resulting reaction product with a polybasic anhydride, and a photopolymerization initiator. . A photosensitive dry film obtained by applying and drying the photosensitive resin composition according to claim 1 onto a film. A cured product obtained by photo-curing or heat-curing the photosensitive resin composition according to the above-mentioned 1, or a dry film obtained by applying and drying the photosensitive resin composition on a film. A printed wiring board having the cured product according to claim 3.