KR101693900B1 - Photocurable resin composition, dry film and cured product of the photocurable resin composition, and printed wiring board using the photocurable resin composition, the dry film, and the cured product - Google Patents

Abstract

식 중, R¹은 수소 원자, 탄소수 1 내지 20의 유기기이며, 동일하거나 상이할 수도 있고, R²는 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 알킬렌기 및 페닐렌기로 이루어지는 군에서 선택되는 적어도 1종의 관능기를 나타내고, R³은 수소 원자 또는 탄소수 1 내지 4의 알킬기를 나타내고, R⁴는 수소 원자 또는 탄소수 1 내지 4의 알킬기를 나타내고, R⁵는 수소 원자 또는 메틸기를 나타내고, p는 1 내지 5의 정수를 나타내고, q는 3 이상의 정수를 나타내고, m은 1 내지 4의 정수를 나타내고, n은 1 내지 10의 정수를 나타낸다.The present invention relates to a photocurable resin composition capable of forming a cured coating film having excellent touch and dryness of a dried coating film, high sensitivity and flexibility, especially a high insulation resistance during high temperature humidification, a dry film thereof and a cured product thereof, And the like are formed on the printed wiring board.
The alkali developable photocurable resin composition contains a photosensitive resin having a structure represented by the following formula (I), a carboxyl group-containing resin, and a photopolymerization initiator. Preferably further contains a thermosetting component, and preferably further contains a coloring agent.
(I)

Wherein R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms and may be the same or different, and R ² is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms and a phenylene group , R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group, p Represents an integer of 1 to 5, q represents an integer of 3 or more, m represents an integer of 1 to 4, and n represents an integer of 1 to 10.

Description

TECHNICAL FIELD The present invention relates to a photocurable resin composition, a dry film and a cured product thereof, and a printed circuit board using the same. BACKGROUND ART PRODUCT}

The present invention relates to a photo-curing resin composition that can be developed by a dilute alkaline aqueous solution, particularly a composition for 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 will be.

Conventionally, the alkali developing type photosensitive resin composition is used in large quantities as solder resists for printed wiring boards. The solder resist is intended to protect circuits of a printed circuit board and is mainly composed of a carboxyl group-containing resin, a polyfunctional acrylate-based compound, a photopolymerization initiator, and a thermosetting resin. As the polyfunctional acrylate compound, a liquid polyfunctional polyester acrylate is widely used from the viewpoints of high sensitivity and resistance to development. However, in the case of the contact exposure method in which the negative film is directly applied to the dry film at the time of exposure, the dry film is required to have dry touch (tack free property). In the case of a photosensitive resin composition using a large amount of a liquid polyfunctional polyester acrylate in order to improve photo-curability, there is a problem in that the composition of the dry film is poor. Therefore, the amount of the liquid polyfunctional polyester acrylate used is limited. On the other hand, an attempt has been made to improve the dryness of a touch using a semi-solid polyester (meth) acrylate (see Patent Document 1). However, in this case, since the polyester (meth) acrylate is bifunctional and semi-solid, the sensitivity is lowered and the softening point of the dry coating film is improved.

On the other hand, the solder resist is used for protecting the surface layer circuit of the printed wiring board as described above, and high solder heat resistance and electrical insulation are required. However, since the photosensitive resin is an acrylate-based compound, its hydrophobicity and alkali resistance are inferior, and the insulation resistance value under a high-temperature humidification condition is lowered. From the viewpoint of electrical insulation, there is still a need to improve and ion migration is likely to occur, And the like.

On the other hand, Patent Document 2 discloses a photosensitive resin composition containing a carboxyl group-containing photosensitive resin obtained by reacting a reaction product of an epoxy compound having two or more epoxy groups in one molecule with a monocarboxylic acid containing an unsaturated group and a polybasic acid anhydride, There is disclosed an example of a photosensitive composition having good adhesion to touch and excellent adhesiveness by using a carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting a reaction product with a seed with a monocarboxylic acid containing an unsaturated group to a reaction product obtained by reacting a polybasic acid anhydride. However, a carboxyl group-containing photosensitive resin obtained by reacting a reaction product of a novolak-type phenolic resin and an alkylene oxide with a monocarboxylic acid containing an unsaturated group and reacting the resulting reaction product with a polybasic acid anhydride has a problem in that an alkylene oxide The content of the unsaturated group is decreased in order to obtain the necessary acid value and the required acid value is not obtained when the unsaturated group is intended to be contained in a large amount, because the unsaturated group-containing carboxylic acid and the polybasic acid anhydride are added to the hydroxyl group There was a trade-off relationship.

International Publication WO 03/075095 A1 (claims) Japanese Patent Laid-Open No. 2003-280189 (Claims)

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described prior art, and has an object of providing a dry film excellent in dry touch, excellent sensitivity and flexibility and excellent in soldering heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, Which is capable of forming a cured film such as a solder resist having a high insulation resistance at the time of use.

It is also an object of the present invention to provide a dry film and a cured product excellent in various characteristics obtained by using such a photo-curable resin composition as described above, and a printed wiring board having a cured film such as a solder resist formed by the above- And the like.

In order to achieve the above object, according to the present invention, there is provided an alkaline developer comprising a photosensitive resin (hereinafter referred to as "photosensitive resin") comprising a structure represented by the following formula (I), a carboxyl group- A photocurable resin composition is provided.

(I)

(Wherein R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different,

R ² represents at least one functional group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, and a phenylene group,

R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R ⁵ represents a hydrogen atom or a methyl group,

p represents an integer of 1 to 5, q represents an integer of 3 or more, m represents an integer of 1 to 4, and n represents an integer of 1 to 10)

In a preferred embodiment of the present invention, the photo-curable resin composition according to claim 1, which does not contain an acid of the photosensitive resin and has a double bond equivalent of 200 or more and 400 or less.

The photosensitive resin is a photosensitive resin obtained by reacting a compound having three or more phenolic hydroxyl groups in one molecule with a cyclic ether compound or cyclic carbonate compound and reacting the resultant hydroxyl group with a compound having an ethylenic unsaturated group .

In this case, the compound having three or more phenolic hydroxyl groups in the molecule is preferably a compound having a phenolic hydroxyl group having a softening point of room temperature or higher, and the compound having an ethylenically unsaturated group is preferably methacrylic acid.

In a preferred embodiment, it further contains a thermosetting component, preferably further containing a coloring agent. Such a photocurable resin composition, particularly a photocurable thermosetting resin composition containing a thermosetting component, can be preferably used as a solder resist.

According to the present invention, there can be provided a photocurable dry film obtained by applying and drying the photocurable resin composition onto a carrier film, a photocurable resin composition or a cured product obtained by curing the dry film, Or a cured product obtained by photo-curing in a pattern.

According to the present invention, there is also provided a printed wiring board characterized by having a cured coating obtained by photo-curing the photo-curable resin composition or the dry film in a patterned form, followed by thermal curing.

The photocurable resin composition of the present invention is characterized in that the photosensitive resin containing the structure represented by the above formula (I) as a photosensitive resin does not particularly contain an acid, and the double bond equivalent is 200 or more and 400 or less.

This photosensitive resin is obtained by reacting a compound having three or more phenolic hydroxyl groups in a molecule with a cyclic ether compound or a cyclic carbonate compound and reacting the resultant hydroxyl group with a compound having an ethylenic unsaturated group, It is possible to form a cured film having a high insulation resistance at the time of high temperature humidification, particularly excellent in resistance to soldering heat, resistance to electroless gold plating, moisture resistance, electrical insulation and the like. Further, in order to contain a carboxyl group-containing resin together with the above photosensitive resin, the resulting photocurable resin composition can be developed with an aqueous alkali solution.

Therefore, the photo-curable resin composition of the present invention can be advantageously applied to the formation of a cured film such as a solder resist for a printed wiring board or a flexible printed wiring board.

Hereinafter, an embodiment of the present invention will be described.

As described above, a feature of the photocurable resin composition of the present invention is that a photosensitive resin containing the structure represented by the above formula (I) is used as the photosensitive resin.

According to the studies of the present inventors, it has been found that the photosensitive resin containing the structure represented by the above formula (I) contains the photosensitive resin composition of the present invention, so that the dry film of the obtained photocurable resin composition is excellent in the dry touchability and the cured film has an insulation resistance And the generation of ion migration does not have a problem over a long period of time as compared with the case where the photosensitive resin is not contained. Particularly, a cyclic ether compound or a cyclic carbonate compound is reacted with a compound which does not include its acid, has a double bond equivalent of 200 to 400 and has 3 or more phenolic hydroxyl groups in one molecule, It has been found that when a photosensitive resin obtained by reacting a compound having an ethylenically unsaturated group is used, the sensitivity is improved. Surprisingly, it has also been found that as the amount of the photosensitive resin used increases, the elongation of the cured coating is improved. For this reason, good results were obtained with respect to the resistance to cracking, flexibility and punching resistance of the cured coating, but this was unexpected and surprising.

The photosensitive resin contains three or more structures represented by the above formula (I) in one molecule (q? 3). When the number of the structure represented by the above formula (I) is less than 2 in one molecule, it is not possible to attain high sensitivity, which is one of the objects of the present invention. Particularly, in the case of solder resist, The ion migration occurred in some cases. Similarly, the double bond equivalent of 200 or less can not exist in the structure, and when it is 400 or more, high sensitivity can not be attained and further the electrical insulating property and ion migration property are deteriorated. Therefore, the double bond equivalent is preferably 200 or more and 400 or less.

The photosensitive resin comprising the structure represented by the above-mentioned formula (I) may be synthesized by a publicly known method, but it is preferable to add a compound having three or more phenolic hydroxyl groups in one molecule to a cyclic ether compound or cyclic carbonate A compound is reacted and a compound having an ethylenic unsaturated group is allowed to react with the resulting alcoholic hydroxyl group can be preferably used. When the photosensitive resin obtained by reacting a compound having an ethylenic unsaturated group with an alcoholic hydroxyl group has three or more structures represented by the above formula (1), the alcoholic hydroxyl group may remain.

Examples of the compound having three or more phenolic hydroxyl groups in the molecule include a novolac phenolic resin. The novolak type phenol resin is obtained by a condensation reaction of phenols and formaldehyde, but these reactions are usually carried out in the presence of an acidic catalyst. Examples of the phenol used in the synthesis of the novolac phenolic resin include phenol, cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, octylphenol, nonylphenol, phenylphenol, cumylphenol, bisphenol A, bisphenol F, These may be used alone or in combination. Further, condensation products of phenols with aromatic aldehydes having phenolic hydroxyl groups, condensation products of poly-p-hydroxystyrene, 1-naphthol or 2-naphthol with aldehydes (namely, naphthol type novolac resins), 1,2 -, condensates of 1,3-, 1,4-, 1,5-, 1,6-, 2,3-, 2,6-, 2,7-dihydroxynaphthalene with aldehydes, mononaphthol Condensates of dihydroxynaphthalene with aldehydes, condensates of mono or dihydroxynaphthalene with xylylene glycols, adducts of mono or dihydroxynaphthalene with diene compounds, condensation products of phenols and bis And condensates with biphenyl, but the present invention is not limited thereto. Particularly, it is preferable to use a phenol resin having an average phenol number of 3 or more.

Of the cyclic ether compound or cyclic carbonate compound, examples of the cyclic ether compound include ethylene oxide, propylene oxide, 1,2-butylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran.

Examples of the cyclic carbonate compound include ethylene carbonate and / or propylene carbonate. Especially preferred are ethylene oxide and propylene oxide.

The compound having an ethylenically unsaturated group is acrylic acid or methacrylic acid, and particularly preferable is methacrylic acid in terms of alkali resistance and electrical insulation. It has been surprisingly unexpected that the photosensitive resin using methacrylic acid has a high sensitivity, particularly excellent in alkali resistance and electrical properties, and that it has been made clear that a cured product having a high insulation resistance value during high temperature humidification is provided.

The blending amount of the photosensitive resin is suitably in the range of 1 to 100 parts by mass, preferably 5 to 60 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin containing a carboxyl group. If the blending amount of the photosensitive resin is excessively larger than the above range, the alkaline developability is lowered, and development residue tends to occur. On the other hand, when the amount is 1 part by mass or less, the image forming ability is impaired.

As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule for the purpose of imparting alkali developability can be used. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in a molecule is more preferable in terms of photocurability and resistance to development. The unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.

As specific examples of the carboxyl group-containing resin, compounds (which may be oligomers or polymers) listed below are preferable.

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene,? -Methylstyrene, lower alkyl (meth) acrylate or isobutylene.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyols, polyether Containing carboxyl groups in a diol compound such as polyol, polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, phenolic hydroxyl group and alcoholic hydroxyl group. Urethane resin.

(3) a bifunctional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a beccylenol type epoxy resin and a biphenol type epoxy resin (Meth) acrylate or a partial acid anhydride thereof, a carboxyl group-containing dialcohol compound and a diol compound.

(4) In the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and at least one (meth) acryl group in the molecule such as hydroxyalkyl (meth) A urethane resin containing a photosensitive carboxyl group.

(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 carboxyl group-containing resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin as described below with (meth) acrylic acid and adding a dibasic acid anhydride to the hydroxyl group present in the side chain.

(7) reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described below with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl group Containing photosensitive resin.

(8) A carboxyl group-containing polyester resin obtained by reacting a bifunctional oxetane resin as described below with a dicarboxylic acid, and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

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

In the present specification, (meth) acrylate is also generically referred to as acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

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

The acid value of the carboxyl group-containing 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 not preferable because it is dissolved and peeled off as a developing solution without distinction between the light portion and the unexposed portion, rendering normal resist pattern drawing difficult.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. If the weight average molecular weight is less than 2,000, the tackfree performance may deteriorate, the moisture resistance of the coated film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly decreased. On the other hand, if the weight average molecular weight exceeds 150,000, the developability may be markedly deteriorated and the storage stability may be poor.

The amount of such a carboxyl group-containing resin is suitably in the range of 20 to 60 mass%, preferably 30 to 50 mass%, in the total composition. When the blending amount of the carboxyl group-containing resin is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when it is more than the above range, the viscosity of the composition is increased, and the coating property is lowered.

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

Examples of the photopolymerization initiator include an oxime ester-based photopolymerization initiator having a group represented by the following formula (II), an? -Aminoacetophenone-based photopolymerization initiator having a group represented by the following formula (III), and / It is preferable to use at least one photopolymerization initiator selected from the group consisting of acylphosphine oxide-based photopolymerization initiators.

≪

(III)

(IV)

(Wherein R ⁶ represents a hydrogen atom, a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with at least one hydroxyl group, A cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group)

R ⁷ represents a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with at least one hydroxyl group, A cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group)

R ⁸ and R ⁹ each independently represent an alkyl or arylalkyl group having 1 to 12 carbon atoms,

R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cyclic alkyl ether group having two bonded thereto,

R ¹² and R ¹³ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, with the proviso that R ¹² And R ¹³ May represent an RC (= O) - group (wherein R may represent a hydrocarbon group having 1 to 20 carbon atoms)

Examples of the oxime ester-based photopolymerization initiator having the group represented by the above formula (II) include 2- (acetyloxyiminomethyl) thioxanthin-9-one represented by the following formula V, a compound represented by the following formula Include compounds represented by the following formula (VII).

(V)

≪ Formula (VI)

(Wherein R ¹⁴ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, An alkoxycarbonyl group (when the number of carbon atoms of the alkyl group constituting the alkoxyl group is 2 or more, the alkyl group may be substituted with at least one hydroxyl group, or may have at least one oxygen atom in the middle of the alkyl chain) or phenoxycarbonyl group,

R ¹⁵ and R ¹⁷ are each independently a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with at least one hydroxyl group, (Which may have one or more oxygen atoms), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group)

R ¹⁶ represents a hydrogen atom, a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with at least one hydroxyl group, A cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group)

(VII)

(Wherein R ¹⁸ , R ¹⁹ and R ²⁴ each independently represent an alkyl group having 1 to 12 carbon atoms,

R ²⁰ , R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

M represents O, S or NH,

x and y each independently represent an integer of 0 to 5)

Of the above oxime ester-based photopolymerization initiators, 2- (acetyloxyiminomethyl) thioxanthin-9-one represented by the above formula (V) and a compound represented by the formula (VI) are more preferable. Commercially available products include CGI-325, Irgacure-OXE01, Irgacure-OXE02, and N-1919 manufactured by ADEKA, which are manufactured by Ciba Specialty Chemicals. These oxime ester-based photopolymerization initiators may be used alone or in combination of two or more.

As the? -Aminoacetophenone-based photopolymerization initiator having the group represented by the above formula (III), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoprofenon- (Dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinophenyl) ) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone, and the like. Commercially available products include Irgacure-907, Irgacure-369 and Irgacure-379 manufactured by Ciba Specialty Chemicals.

Examples of the acylphosphine oxide-based photopolymerization initiator having a group represented by the formula (IV) 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 Lucilin TPO manufactured by BASF, Irgacure-819 manufactured by Ciba Specialty Chemicals, and the like.

The blending amount of such a photopolymerization initiator is suitably in the range of 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. If the blending amount of the photopolymerization initiator 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 is more than 30 parts by mass, the light absorption at the surface of the solder resist coating film of the photopolymerization initiator tends to become severe, and the deep curing property tends to be lowered.

In the case of the oxime ester-based photopolymerization initiator having the group represented by the above formula (II), its blending amount is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the above- Range is preferred.

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

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

Specific examples of the acetophenone compound are 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 and 2,4-diisopropylthioxanthone.

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

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

Specific examples of the tertiary amine compound include an ethanolamine compound, a compound having a dialkylaminobenzene structure such as 4,4'-dimethylaminobenzophenone (Nisseiura MABP manufactured by Nippon Soda Co., Ltd.), 4,4'- Dialkylaminobenzophenones such as diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran- Dimethylaminobenzoate (Kaya Cure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (manufactured by International Bio-Synthesis Co., Ltd., (KANACURE DMBI, manufactured by Nippon Kayaku Co., Ltd.), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylaminobenzoic acid 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk Co., Ltd., Eso lol) 507), and 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

Of the above-mentioned compounds, thioxanthone compounds and tertiary amine compounds are preferred. In the composition of the present invention, it is preferable that the thioxanthone compound is contained in view of deep curing property. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, And thioxanthone compounds such as 2,4-diisopropylthioxanthone are preferable.

The amount of the thioxanthone compound to be added is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the carboxyl group-containing resin. If the compounding amount of the thioxanthone compound is too large, the thick film curing property is lowered, leading to an increase in cost of the product, which is not preferable.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because it has low toxicity. A coumarin compound containing a dialkylamino group having a maximum absorption wavelength in the range of 350 to 410 nm has a maximum absorption wavelength in the region of ultraviolet rays and therefore has a small coloration and a colorless transparent photosensitive composition as well as a coloring pigment, It is possible to provide a colored solder resist film which is reflected. Particularly, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent increase / decrease effect on laser light having a wavelength of 400 to 410 nm.

The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing 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. On the other hand, 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 portion curing property tends to be lowered.

These photopolymerization initiators, photoinitiators and sensitizers may be used alone or in admixture of two or more.

The total amount of the photopolymerization initiator, photoinitiator and sensitizer is preferably in the range of not more than 35 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount exceeds 35 parts by mass, the deep curing property tends to be lowered by these light absorption.

In the photo-curing resin composition of the present invention, N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as a chain transfer agent for improving the sensitivity. Specific examples of the chain transfer agent include chain transfer agents having a carboxyl group such as mercapto succinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; A chain transfer agent having a hydroxyl group such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropane diol, mercaptobutanediol, hydroxybenzene thiol and derivatives thereof; Methyl-3-mercaptopropionate, 2,2- (ethylene dioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan Butanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

Examples of the heterocyclic compound having a mercapto group functioning as a chain transfer agent include mercapto-4-butyrolactone (alias: 2-mercapto-4-butanololide), 2-mercapto- 4-butyrolactone, 2-mercapto-4-butyrolactone, 2-mercapto-4-butyrolactone, 2- 2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) 2-mercapto-5-valerolactone, N-methyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl- -Hexanolactam, and the like.

Particularly, as a heterocyclic compound having a mercapto group which is a chain transfer agent which does not impair the developability of the photocurable resin composition, mercapto benzothiazole, 3-mercapto-4-methyl-4H- 5-methyl-1,3,4-thiadiazole-2-thiol, and 1-phenyl-5-mercapto-1H-tetrazole are preferable. These chain transfer agents may be used alone or in combination of two or more.

A thermosetting resin can be added to the photo-curable resin composition of the present invention to impart heat resistance. Examples of the thermosetting component used in the present invention include amine resins such as melamine resin and benzoguanamine resin, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives A thermosetting resin for known purpose can be used. Particularly preferred are thermosetting components having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

The thermosetting component having at least two cyclic (thio) ether groups in the molecule is a compound having at least two, three or four or five membered cyclic ether groups or cyclic thioether groups in the molecule, For example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having two or more thioether groups in the molecule , An episulfide resin, and the like.

Examples of the polyfunctional epoxy compounds include jER828, jER834, jER1001, jER1004 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 840, Epiclon 850, Epiclon 1050, Epiclon 2055, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664 manufactured by Dow Chemical Company, Araldide 6071 manufactured by Ciba Specialty Chemicals Inc. Epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Ltd., AER330 manufactured by Asahi Kasei Corporation, , AER331, AER661, AER664 (all trade names), bisphenol A type epoxy resin; JERYL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152 manufactured by Dainippon Ink and Chemicals, Inc., Epiclon 165, Epototo YDB-400, YDB-500 manufactured by Dotogasei Co., DER542 manufactured by Dow Chemical Co., Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., AER711 and AER714 manufactured by Asahi Chemical Industry Co., Ltd. (all trade names), brominated epoxy resin; JER152, jER154 manufactured by Japan Epoxy Resin Co., Ltd., DEN431 and DEN438 manufactured by Dow Chemical Company, Epiclon N-730 manufactured by Dainippon Ink and Chemicals, Inc., Epiclon N-770, Epiclon N-865, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201 manufactured by Nippon Kayaku Co., Ltd., EOCN (trade name) manufactured by Nippon Kayaku Co., Epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industry Co., Ltd., AERECN-235 and ECN-299 manufactured by Asahi Chemical Industry Co., Ltd. Novolac-type epoxy resin; Epiclon 830 manufactured by Dainippon Ink and Chemicals, Inc., jER 807 manufactured by Japan Epoxy Resin Co., Ltd., Epototo YDF-170, YDF-175, YDF-2004 manufactured by Tokto Kasei Co., Araldide XPY306 manufactured by Ciba Specialty Chemicals, Bisphenol F type epoxy resin (all trade names); Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007 and ST-3000 (all trade names) manufactured by Tokuga Seisakusho; JER604 manufactured by Japan Epoxy Resin Co., Ltd., Ephoto YH-434 manufactured by Toko Kasei Co., Araldide MY720 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Glycidylamine type epoxy resins; A hindered phenolic epoxy resin such as Araldide CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Alicyclic epoxy resins such as Celllock 2021 manufactured by Daicel Chemical Industries, Ltd., Araldides CY175 and CY179 manufactured by Ciba Specialty Chemicals, Inc. (all trade names); YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T.E.N. produced by Dow Chemical Co., EPPN-501, EPPN-502 (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., and EXA-1514 (all trade names) manufactured by Dainippon Ink and Chemicals, Inc.; 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., Araldide 163 manufactured by Ciba Specialty Chemicals Co., Ltd. (all trade names), tetraphenylol ethane type epoxy resin; Cycloaliphatic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals Inc., 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.; Epoxy resin containing naphthalene group such as ESN-190, ESN-360 manufactured by Shinnitetsu Chemical Co., Ltd., HP-4032, EXA-4750 and EXA-4700 manufactured by Dainippon Ink and Chemicals, Incorporated; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink and Chemicals, Incorporated; 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; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.) and CTBN-modified epoxy resins (e.g., YR-102 and YR-450 manufactured by Tokuga Seisakusho Co., Ltd.) , But are 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, bisphenol A type epoxy resins, and mixtures thereof are particularly preferable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ (3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [ (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, In addition to the polyfunctional oxetanes such as oligomers and copolymers thereof, oxetane alcohol and novolac resin, poly (p-hydroxystyrene), cardo type bisphenols, calixarene, calix resorcinarene, 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 compound having two or more cyclic thioether groups in the molecule include a bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., An episulfide resin in which the oxygen atom of the epoxy group of the novolac epoxy resin is substituted with a sulfur atom can also be used by using the same synthetic method.

The blending amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is preferably in the range of 0.6 to 2.5 equivalents, more preferably 0.8 to 2.0 equivalents, based on 1 equivalent of the carboxyl group of the carboxyl group-containing resin It is suitable. When the blending amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is less than 0.6, the carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulating properties and the like 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.

In the photocurable resin composition of the present invention, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule as a thermosetting component can be added. Such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound or a compound having two or more blocked isocyanate groups in one molecule, i.e., a block isocyanate compound .

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. Examples of the above-mentioned isocyanate compounds include adduct, burette and isocyanurate.

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 blocking 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 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.

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-based blocking agents such as formaldehyde scavengers, acetal aldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol and ethylthiophenol; Acid amide type block agents such as acetic acid amide, benzamide and the like; 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, and examples thereof include Sumidor BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS B-815, B-815, and B-815 manufactured by Mitsui Takeda Chemical Co., Ltd. were mixed in a mortar, a mortar, a mortar, a mortar, 846, B-870, B-874, B-882 and TPA-B80E, 17B-60PX and E402-B80T (all trade names) manufactured by Asahi Kasei Chemicals Corporation. Further, SMILDIR BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a block agent.

The above-mentioned compounds having two or more 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 two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass, based on 100 parts by mass of the carboxyl group-containing 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 is lowered, which is not preferable.

Examples of the thermosetting component include melamine derivatives, benzoguanamine derivatives, and the like. 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 prepared by reacting the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound, and methylol urea compound Is converted into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a 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, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141 750, copper Mx-032, copper Mx-270 (trade name) manufactured by Sanwa Chemical Co., Ltd., , Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM and Mw-390 , Copper Mw-100LM, copper Mw-750LM (trade name, trade name). The thermosetting components may be used alone or in combination of two or more.

When a thermosetting component having at least two 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 sol, 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 the products 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 it is possible to accelerate the reaction between the epoxy resin and the thermosetting catalyst of the oxetane compound, or between the epoxy group and / or the oxetanyl group and the carboxyl group, or they may be used alone or in combination of two or more . 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 mass parts per 100 parts by mass of the thermosetting component having two or more cyclic (thio) ether groups in the carboxyl group- More preferably 0.5 to 15.0 parts by mass.

In the photocurable resin composition of the present invention, an adhesion promoter may be used to improve the adhesiveness between the layers or the adhesion between the photosensitive resin layer and the substrate. Specific examples thereof include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinomethyl-1 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, Sol, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent, and the like.

The compound having two or more ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photo-cured by irradiation with active energy rays to insolubilize the ethylenically unsaturated group-containing carboxyl group-containing resin in an aqueous alkali solution, It is to help insolubility. Such compounds include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol and tris-hydroxyethylisocyanurate; or polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts thereof; Polyfunctional acrylates such as phenoxy acrylate, bisphenol A diacrylate and 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; And melamine acrylate and / or 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 a hydroxyl acrylate such as pentaerythritol triacrylate and an isophorone And an epoxy urethane acrylate compound obtained by reacting a half-urethane compound of a diisocyanate such as a diisocyanate. Such an epoxy acrylate resin can improve photo-curability without deteriorating the touch-dry composition.

The compounding amount of the compound having two or more ethylenically unsaturated groups in the molecule is preferably 5 to 100 parts by mass, more preferably 1 to 70 parts by mass based on 100 parts by mass of the carboxyl-containing resin. When the blending amount is less than 5 parts by mass, the photocurability is lowered, and pattern formation becomes difficult due to 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.

The photo-curable resin composition of the present invention may contain a colorant. As the coloring agent, known coloring agents such as red, blue, green, and yellow can 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 a monoazo system, a disazo system, an azo lake system, a benzimidazolone system, a perylene system, a diketopyrrolopyrrole system, a condensed azo system, an anthraquinone system and a quinacridone system, .

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:

The blue colorant includes a phthalocyanine pigment and an anthraquinone pigment. The pigment pigment is classified into a pigment, specifically, a color index (CI) such as the following Society of Diamonds and Colors Dyers and Colourists) numbers: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pure Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

The dye system is 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. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28 and the like can be used have. 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.

Other coloring agents such as purple, orange, brown, and 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.

The mixing ratio of the colorant as described above is not particularly limited, but is preferably 0 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin.

Most of the polymer materials are oxidatively deteriorated successively one after another at the beginning of oxidation, resulting in deterioration of the function of the polymer material. Therefore, in order to prevent oxidation of the photo-curing resin composition of the present invention, (1) And / or (2) an antioxidant such as a peroxide decomposition agent that decomposes the generated peroxide into a harmless substance and prevents generation of new radicals.

Specific examples of the antioxidant that functions as a radical supplement include hydroquinone, 4-tert-butyl catechol, 2-t-butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1, 3-tris , 3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'- Phenol-based compounds such as 4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, , 6-tetramethyl-4-piperidyl) sebacate, phenothiazine, and the like.

Radical supplements may be those commercially available, for example, adekastab AO-30, adekastab AO-330, adekastab AO-20, adekastab LA-77, Adekastab LA-57, Adekastab LA-67, Adekastab LA-68, Adekastab LA-87 (all trade names), Irganox 1010, Ciba Specialty Chemicals Inc., 1035, Irganox 1076, Irganox 1135, Tinuvin 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292 and Tinuvin 5100 (all trade names).

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'- And sulfur compounds such as thiodipropionate.

The release of the peroxide may be commercially available, for example, adekastab TPP manufactured by Asahi Denka Co., Ltd., Mark AO-412S manufactured by Adeka Argussagaku Co., Ltd., and Smiliger TPS manufactured by Sumitomo Chemical Co., Ltd. Trade name).

The above antioxidants may be used alone or in combination of two or more.

Since the polymer material absorbs light and causes degradation and deterioration thereof, the photo-curing resin composition of the present invention can use an ultraviolet absorber in addition to the above-mentioned antioxidant in order to take measures against stabilization against ultraviolet rays.

Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives. Examples of specific benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- Dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone; Examples of specific benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert- butylphenyl- -4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole; Specific examples of the triazine derivatives include hydroxyphenyltriazine, bisethylhexyloxyphenol methoxyphenyltriazine, and the like.

Examples of the ultraviolet absorber include commercially available products such as Tinuvin PS manufactured by Ciba Specialty Chemicals, Tinuvin 99-2, Tinuvin 109, Tinuvin 384-2, Tinuvin 900, Tinuvin 928, Tinuvin 928, 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, and Tinuvin 479 (all trade names).

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

The photo-curable resin composition of the present invention may contain a filler as necessary in order to increase the physical strength and the like of the coating film. As such a filler, an inorganic or organic filler for known purpose can be used, but barium sulfate, spherical silica and talc are particularly 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 the filler is preferably 75% by mass or less, more preferably 0.1 to 60% by mass of the total amount of the composition. When the blending amount of the filler exceeds 75 mass% of the total amount of the composition, the viscosity of the insulating composition becomes high, and the coating and the formability are lowered, and the cured product becomes weak.

The photo-curing resin composition of the present invention can be used for the synthesis of the carboxyl group-containing resin or for the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film.

Examples of the organic solvent 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.

The photo-curable resin composition of the present invention may further contain a heat polymerization inhibitor, a known polymerization inhibitor, a known thickener such as fine silica, organic bentonite, and montmorillonite, a defoaming agent such as silicone, fluorine, , Silane coupling agents such as imidazole-based, thiazole-based, and triazole-based additives, antioxidants, rust inhibitors, and the like.

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-butyl catechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone (4-methyl-6-t-butyl-4-cresol, 2,2'-methylenebis Butylphenol), reagents such as pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agents, methyl salicylate and phenothiazine, nitroso compounds, chelates of nitroso compounds and Al .

The photo-curable resin composition of the present invention can be prepared by, for example, adjusting the viscosity with a suitable viscosity for the application method with the above-mentioned organic solvent, and coating on the substrate by an immersion coating method, a flow coating method, a roll coating method, a bar coater method, Method, and the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 60 to 100 ° C, whereby a tack-free coating film can be formed. The resin insulating layer can be formed by applying the above composition onto a carrier film, drying it, and then winding it up as a film and bonding it to the base material.

Thereafter, the resist film is directly pattern-exposed by an exposure light or a laser direct exposure machine through a photomask having a pattern formed thereon by a contact type (or non-contact method) selectively, and the unexposed portion is exposed to an alkali solution 0.3 to 3 wt% aqueous sodium carbonate solution) to form a resist pattern. Further, the thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in the molecule reacts with the carboxyl group of the carboxyl group-containing resin by heating to a temperature of, for example, about 140 to 180 ° C, , A cured coating film excellent in various properties such as chemical resistance, hygroscopicity, adhesion, electrical properties and the like can be formed.

In addition to a printed circuit board or a flexible printed circuit board previously formed in a circuit, the substrate may be formed of a resin such as a paper-phenol resin, a paper-epoxy resin, a glass-epoxy resin, a glass-polyimide, a glass / nonwoven- Polybutylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, polyimide film, PET film, glass substrate, ceramic substrate, and wafer plate using composite materials such as resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, Etc. may be used.

The volatile drying after application of the photocurable resin composition of the present invention can be carried out by a hot-air circulation type drying furnace, a hot plate, a convection oven or the like (hot air in a dryer using a heat- A method of countercurrent contact with the support and a method of spraying the support from the nozzle).

The photocurable resin composition of the present invention is applied as follows, volatilized and dried, and then the resulting coating film is exposed (irradiated with active energy rays). The coating film cures the exposed portion (the portion irradiated with the active energy ray).

Examples of the exposure apparatus used for irradiating the active energy ray include a direct imaging apparatus (for example, a laser direct imaging apparatus that draws an image with a laser directly by CAD data from a computer), an exposure apparatus equipped with a metal halide lamp, An exposure apparatus equipped with a mercury lamp, an exposure apparatus equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (second) 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 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 writing apparatus, for example, a product manufactured by Nippon Orbotech Co., Ltd. or 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.

Examples of the developing method include a dipping method, a shower method, a spraying method, a brushing method, and the like. As the developing solution, an alkali aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, Can be used.

The photo-curing 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, in addition to a method of directly applying the composition in a liquid state. The case where the photocurable resin composition of the present 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 developing photocurable 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 photocurable 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, the cover film is peeled off, the solder resist layer and the circuit-formed base material are superimposed and bonded together by using a laminator or the like, Thereby forming a resist layer. When the exposed solder resist layer is exposed, developed, and heat cured as described above, a cured coating film can be formed. The carrier film can be peeled off either before 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, "parts" and "%" are on a mass basis unless otherwise specified.

Photosensitive resin Synthesis Example 1:

Into an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device and a stirrer, 106 parts of a novolak type phenol resin (manufactured by Showa Kobunshi Kabushiki Kaisha, hydroxyl equivalent 106), 2.6 parts of a 50% sodium hydroxide aqueous solution, / Methyl isobutyl ketone (mass ratio = 2/1) were charged, and the inside of the system was purged with nitrogen while stirring. Subsequently, the temperature was elevated by heating, and 60 parts of propylene oxide was gradually introduced at 150 占 폚 and 8 kg / cm2. The reaction was continued for about 4 hours until the gauge pressure became 0.0 kg / cm &lt; 2 &gt;, followed by cooling to room temperature. To the reaction solution, 3.3 parts of 36% hydrochloric acid aqueous solution was added and mixed, and sodium hydroxide was neutralized. This neutralization reaction product was diluted with toluene, washed with water three times, and then stripped with an evaporator to obtain an alkylene oxide adduct of a novolak type phenol resin having a hydroxyl group equivalent of 164 g / eq. Which means that an alkylene oxide is added in an average of 1 mole per 1 equivalent of hydroxyl groups.

164 parts of the obtained alkylene oxide adduct of novolak type phenolic resin, 86 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 part of hydroquinone monomethyl ether and 100 parts of toluene were placed in a reactor equipped with a stirrer, a thermometer, The mixture was stirred while blowing air, and reacted at 110 ° C for 6 hours. After the water produced by the reaction started to flow out as an azeotropic mixture with toluene, the reaction was continued for another 5 hours and then cooled to room temperature. The resultant reaction solution was washed with a 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and carbitol acetate was added to obtain a methacrylate resin solution having a novolak type PO of nonvolatile content of 70% (double bond equivalent weight: 250 g / eq. This is referred to as A-1 vanishing.

Photosensitive resin Synthesis Example 2:

164 parts of the alkylene oxide adduct of the novolak type phenol resin obtained in Synthesis Example 1, 72 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 part of hydroquinone monomethyl ether and 100 parts of toluene were placed in a flask equipped with a stirrer, And the mixture was stirred while blowing air and reacted at 90 DEG C for 12 hours. After the water produced by the reaction started to flow out as an azeotropic mixture with toluene, the reaction was continued for another 5 hours and then cooled to room temperature. The resulting reaction solution was washed with an aqueous 5% NaCl solution, toluene was distilled off using an evaporator, and carvolylacetate was added to obtain a novolak type PO-added acrylate resin solution having a nonvolatile content of 70% (double bond equivalent weight 236 g / eq. This is referred to as A-2 vanishing.

Photosensitive resin Synthesis Example 3:

Into an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device and a stirrer, 106 parts of a novolak type phenol resin (manufactured by Showa Kobunshi Kabushiki Kaisha, hydroxyl equivalent 106), 2.6 parts of a 50% sodium hydroxide aqueous solution, / Methyl isobutyl ketone (mass ratio = 2/1) were charged, and the inside of the system was purged with nitrogen with stirring. Subsequently, the temperature was elevated by heating, and 50 parts of ethylene oxide was slowly introduced at 150 占 폚 and 8 kg / cm2. The reaction was continued for about 4 hours until the gauge pressure became 0.0 kg / cm &lt; 2 &gt;, followed by cooling to room temperature. To the reaction solution, 3.3 parts of 36% hydrochloric acid aqueous solution was added and mixed, and sodium hydroxide was neutralized. This neutralization reaction product was diluted with toluene, washed with water three times, and removed with an evaporator to obtain an alkylene oxide adduct of a novolak type phenol resin having a hydroxyl group equivalent of 150 g / eq. Which means that the alkylene oxide is added in an average of 1 mole per 1 equivalent of the hydroxyl group.

150 parts of the obtained alkylene oxide adduct of novolak type phenol resin, 86 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 part of hydroquinone monomethyl ether and 100 parts of toluene were placed in a reactor equipped with a stirrer, a thermometer, The mixture was stirred while blowing air, and reacted at 110 ° C for 6 hours. After the water produced by the reaction started to flow out as an azeotropic mixture with toluene, the reaction was continued for another 5 hours and then cooled to room temperature. The resultant reaction solution was washed with a 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and carvitol acetate was added to obtain a methacrylate resin solution having a novolak-type EO added with a nonvolatile content of 70% (double bond equivalent: 236 g / eq. This is called A-3 vanishing.

Comparative Synthesis Example 1:

94 parts of a monofunctional phenol compound (hydroxyl equivalent: 94), 2.6 parts of a 50% aqueous solution of sodium hydroxide, 2.6 parts of toluene / methyl isobutyl ketone (mass ratio = 2 / 1) was charged, and the inside of the system was purged with nitrogen with stirring. Subsequently, the temperature was elevated by heating, and 50 parts of ethylene oxide was gradually introduced at 150 占 폚 and 8 kg / cm2. The reaction was continued for about 4 hours until the gauge pressure became 0.0 kg / cm &lt; 2 &gt;, followed by cooling to room temperature. To the reaction solution, 3.3 parts of 36% hydrochloric acid aqueous solution was added and mixed, and sodium hydroxide was neutralized. This neutralization reaction product was diluted with toluene, washed with water three times, and then stripped with an evaporator to obtain an alkylene oxide adduct of a phenol compound having a hydroxyl group equivalent of 138 g / eq. Which means that an alkylene oxide is added in an average of 1 mole per 1 equivalent of hydroxyl groups.

138 parts of the alkylene oxide adduct of the obtained phenol compound, 86 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 part of hydroquinone monomethyl ether and 100 parts of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, The mixture was stirred while blowing air and reacted at 110 DEG C for 6 hours. After the water produced by the reaction started to flow out as an azeotropic mixture with toluene, the reaction was continued for another 5 hours and then cooled to room temperature. The obtained reaction solution was washed with a 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and carbitol acetate was added to obtain a methacrylate resin solution with EO addition of 70% of nonvolatile matter (double bond equivalent: 224 g / eq. Acid value 0). This is called A-4 vanishing.

Synthesis Example of Carboxyl Group-Containing Resin (B-1)

A cresol novolac epoxy resin (EOCN-104S, manufactured by Nippon Kayaku Co., Ltd.) having a softening point of 92 占 폚 and an epoxy equivalent of 220 占 퐉 was added to a 2 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen- ), 421.3 g of carbitol acetate and 180.6 g of solvent naphtha were introduced and dissolved by heating at 90 占 폚 and stirring. Then, the reaction mixture was cooled to 60 deg. C, and 216 g of acrylic acid, 4.0 g of triphenylphosphine and 1.3 g of methylhydroquinone were added and reacted at 100 DEG C for 12 hours to obtain a reaction product having an acid value of 0.2 mgKOH / g. Thereto was added 241.7 g of tetrahydrophthalic anhydride, heated to 90 ° C, and reacted for 6 hours. Thus, a solution of a carboxyl group-containing resin having an acid value of 50 mg KOH / g, a double bond equivalent (g weight of the resin per one mole of the unsaturated group) of 400, and a weight average molecular weight of 7,000 was obtained. Hereinafter, this solution of the carboxyl group-containing resin is referred to as B-1 varnish.

Synthesis Example of Carboxyl Group-Containing Resin (B-3)

119.4 g of a novolac cresol resin (trade name: "SCORNOL CRG951", trade name, manufactured by Showa Kobunshi Co., Ltd., OH equivalent: 119.4) was added to an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device, 1.19 g of potassium and 119.4 g of toluene, and the system was purged with nitrogen while stirring, and the temperature was raised by heating. Subsequently, 63.8 g of propylene oxide was slowly added dropwise, and the reaction was carried out at 125 to 132 占 폚 and 0 to 4.8 kg / cm2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize the potassium hydroxide, and a propylene oxide reaction solution of a novolak type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / &Lt; / RTI &gt; This means that the average of the alkylene oxides per 1.0 equivalent of the phenolic hydroxyl group was 1.08 mol. 293.0 g of the alkylene oxide reaction solution of the obtained novolak type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were fed into a reactor equipped with a stirrer, a thermometer and an air blowing tube, 10 mL / min, and reacted at 110 DEG C for 12 hours with stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 g of water was spilled out. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off by replacing the toluene with 118.1 g of diethylene glycol monoethyl ether acetate to obtain an novolak type acrylate resin solution. Subsequently, 332.5 g of the obtained novolak type acrylate resin solution and 1.22 g of triphenylphosphine were charged 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 g of tetrahydrophthalic anhydride was slowly added thereto, and the reaction was carried out 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. Hereinafter, this reaction solution is referred to as a varnish B-3.

Examples 1 to 15 and Comparative Examples 1 to 5:

Using the resin solutions of the respective synthesis examples, the various components shown in Table 1 were compounded in the proportions (parts by mass) shown in Table 1, preliminarily mixed with a stirrer, kneaded with a three-roll mill, To prepare a resin composition. Here, the degree of dispersion of the obtained photosensitive resin composition was evaluated by particle size measurement by a grindmeter manufactured by Ericensen, and found to be 15 占 퐉 or less.

Remarks

^{* 1} : NK ester BPE-900 (Shin-Nakamura Chemical Industry Co., Ltd.) Bisphenol A skeleton-containing ethylene oxide modified bifunctional acrylate (double bond equivalent: 556)

^{* 2} : Kayalad DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.) (double bond equivalent: 210)

^{* 3} : dipentaerythritol hexaacrylate (DPHA: manufactured by Nippon Kayaku Co., Ltd.) (double bond equivalent: 108)

^{* 4} : Cyclomer-P (ACA) 320 (manufactured by Daicel Chemical Industries, Ltd.)

^{* 5} : ZFR-1124 (manufactured by Nippon Kayaku Co., Ltd.)

^{* 6} : ZCR-1601H (manufactured by Nippon Kayaku Co., Ltd.)

^{* 7} : SPV-1000L (manufactured by Showa Kobunshi Co., Ltd.)

^{* 8} : 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure-90 manufactured by Ciba Specialty Chemicals)

^{* 9} : 2- (Acetyloxyiminomethyl) thiooxanthen-9-one

^{* 10} : phenol novolak type epoxy resin (DEN438: manufactured by Dow Chemical)

^{* 11} : Vicilsilene type epoxy resin (YX-4000: manufactured by Japan Epoxy Resin Co., Ltd.)

^{* 12} : CI Pigment Blue 15: 3

^{* 13} : CI Pigment Yellow 147

^{* 14} : Barium sulfate (B-30, manufactured by Sakai Chemical Industry Co., Ltd.)

^{* 15} : Dipropylene glycol monomethyl ether

^{* 16} : Block isocyanate (manufactured by Asahi Kasei Chemicals Co., Ltd.)

^{* 17} : methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd.)

^{* 18} : Antioxidant (manufactured by Ciba Specialty Chemicals)

Performance evaluation:

<Optimum exposure dose>

The photocurable thermosetting resin compositions of the above Examples and Comparative Examples were buffed to a thickness of 35 占 퐉 on a circuit pattern substrate having a copper foil thickness of 35 占 퐉, washed with water, and then dried and applied on the entire surface by screen printing. Dry 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 (short arc lamp), developed (30 ° C, 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) The optimal exposure amount was set to 7 when the pattern of the remaining step tablet was 7 times.

<Touch-up Drying>

The photocurable thermosetting resin compositions shown in Table 1 were coated on the entire surface by screen printing on the patterned copper foil substrates, dried in a hot air circulating type drying furnace at 80 캜 for 30 minutes, and cooled to room temperature. A PET film was pressed on this substrate, and then the state of adhesion of the film when the negative film was peeled off was evaluated.

&Amp; cir &amp; &amp; cir &amp;: There is no resistance at all when peeling off the film, and no trace remains on the film.

○: There is no resistance at the time of peeling off the film, but a trace remains on the film.

DELTA: There is a little resistance when peeling off the film, and a trace remains on the film.

X: There is resistance when peeling off the film, and there is a clear trace on the film.

<Resolution>

The photocurable thermosetting resin compositions of the examples and the comparative examples were buffed, polished with a line / space of 300/300 占 퐉 and a copper thickness of 35 占 퐉, buffed, washed, screened and then dried at 80 占 폚 In a hot-air circulation type drying furnace for 30 minutes. After drying, exposure was performed using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). In the exposure pattern, a glass photographic photosensitive plate for drawing a line of 20/30/40/50/60/70/80/90/100 μm was used in the space portion. The amount of exposure was irradiated with an active energy ray so as to obtain an optimum exposure amount of the photosensitive resin composition. After exposure, development was carried out with an aqueous solution of 1 wt% Na ₂ CO ₃ at 30 ° C to form a pattern, and thermal curing was performed at 150 ° C for 60 minutes to obtain a cured coating film.

(Resolution) obtained by adjusting the minimum remaining line of the cured coating film of the obtained photosensitive resin composition for a solder resist to 200 times.

<Tensile Modulus, Tensile Strength (Tensile Fracture Strength), Elongation (Tensile Fracture Elongation)>

The PTFE (polytetrafluoroethylene) plate previously washed with water and dried was coated with the composition of each of the above composition examples and comparative composition by screen printing, and dried in a hot air circulation type drying oven at 80 DEG C for 30 minutes. After cooling it to room temperature, exposed to an appropriate exposure amount, and a 1 wt% Na ₂ CO ₃ aqueous solution for 30 ℃ was performed for 60 seconds under the conditions of the developing spray pressure 2 kg / ㎠. This substrate was irradiated with ultraviolet rays under the condition of an integrated exposure dose of 1000 mJ / cm 2 in a UV conveyer, and then cured in a hot air circulation type drying furnace at 150 ° C for 60 minutes. After cooling to room temperature, the cured coating film was peeled from the PTFE plate to obtain an evaluation sample.

The tensile modulus, tensile strength (tensile break strength) and elongation (tensile break strength) of the evaluation sample were measured by a tensile-compression tester (Shimadzu Corporation).

<Flexibility>

The composition of each of the above Examples and Comparative Examples was applied to a cap toning material (thickness 25 mu m) previously washed and dried by a screen printing method and dried at 80 DEG C for 30 minutes in a hot air circulation type drying furnace. After cooling it to room temperature, it was exposed at an appropriate exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and a 1 wt% aqueous solution of Na ₂ CO ₃ at 30 ° C was sprayed at a spray pressure of 60 kg / A short-time development was carried out. 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 heated at 150 캜 for 60 minutes to be cured to obtain an evaluation sample for bending resistance test and flexibility test.

One side of a film-like test piece produced by processing the obtained cured film with a width of 10 mm and a length of 90 mm was placed on an electronic balance and the other side was bent so that the maximum load applied to the electronic scale The repulsive force was evaluated by the following criteria.

○: less than 10 g

DELTA: 10 to 30 g or less

×: 30 g or more

Characteristic test:

The compositions of the above Examples and Comparative Examples were coated on the entire surface of the patterned copper foil substrate so that the film thickness after drying in the screen printing was 20 占 퐉, dried at 80 占 폚 for 30 minutes, and then cooled to room temperature. A solder resist pattern was exposed at an optimum exposure dose using an exposure apparatus having a high-pressure mercury lamp (short arc lamp) mounted on this substrate, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 캜 was sprayed at 60 Followed by development for a second time 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.

&Lt; Soldering heat resistance &

The evaluation substrate coated with the rosin-based flux 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 peeling of the resist layer were visually evaluated. The criteria are as follows.

&Amp; cir &amp;: Peeling was not confirmed even if immersion for 10 seconds was repeated 6 times or more.

?: Peeling is not confirmed even if immersion for 10 seconds is repeated 3 times or more.

?: When the immersion for 10 seconds is repeated 3 times or more, it slightly peels off.

占 There is expansion and peeling in the resist layer within 3 times of immersion for 10 seconds.

<Electroless gold plating resistance>

The electroless nickel plating bath and the electroless gold plating bath of a commercially available product were used to perform plating under the conditions of nickel of 0.5 탆 and gold of 0.03 탆 and the presence or absence of peeling of the resist layer and the penetration of the plating were evaluated by tape peeling Thereafter, the peeling of the resist layer was evaluated by tape peeling. The criteria are as follows.

◎: Seeping and peeling are not seen.

?: A little seeping was confirmed after plating, but peeling was not observed after tape peeling.

B: Only a slight penetration is seen after plating, and peeling is seen after tape peeling.

X: Peeling occurs after plating.

<Electrical Characteristics>

An evaluation substrate was fabricated using the interdigital electrode pattern of line / space = 50/50 占 퐉 instead of the copper foil substrate under the above-described conditions. A bias voltage of DC 10 V was applied to this interdigital electrode, The insulation resistance value after the elapse of time was measured in the bath. The measurement voltage was 10 V DC.

<Alkali resistance>

The evaluation substrate was immersed in a 10 wt% NaOH aqueous solution at 50 캜 for 30 minutes to confirm seeping, elution of the coating film, and further peeling by tape peeling. The criteria are as follows.

○: Seeping, elution, no peeling.

B: Permeation, elution, or peeling is slightly confirmed.

X: Sealing, elution, or peeling is largely confirmed.

<Dry Film Production>

Each of the photosensitive resin compositions for solder resists of Example 1 and Comparative Example 1 was appropriately diluted with methyl ethyl ketone, and then a PET film (FB-50 manufactured by Toray Co., Ltd., having a thickness of 16 탆 ), And dried at 80 DEG C for 30 minutes to obtain a dry film.

<Substrate Fabrication>

After the circuit-formed substrate was buffed, the dry film produced by the above-mentioned method was pressed using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho) at a pressure of 0.8 MPa, 70 DEG C for 1 minute, and a degree of vacuum of 133.3 Pa (Unexposed substrate) having an unexposed solder resist layer was obtained.

The evaluation results are shown in Table 2 below.

As shown in Table 2, in Examples 1 to 15 of the present invention, it was found that the sensitivity was improved without lowering the touch dry composition as compared with Comparative Examples 1 to 5, and the obtained cured coating had excellent flexibility . Particularly, in the examples using the photosensitive resin A-1 in which propylene oxide and methacrylic acid were added to the novolak type phenolic resin, they were excellent in solder heat resistance, electroless gold plating resistance and electrical characteristics, and were useful as an alkali developable photo- Was recognized.

On the other hand, in the case of Comparative Examples 1 and 2 using A-4 and A-5 having a number of nuclei of 3 or less, the touch-to-dry composition, solder heat resistance and electrical characteristics were poor.

As described above, a photocurable resin composition capable of forming a cured film having excellent dry touchability, high sensitivity and flexibility, and particularly high insulation resistance at high temperature humidification, a dry film thereof, and a cured product thereof It is possible to provide a printed wiring board in which a cured film such as solder resist is formed.

Claims (11)

An alkaline developing photocurable resin composition comprising a photosensitive resin having a structure represented by the following formula (I) and not containing an acid, which is not a calixarene structure, a carboxyl group-containing resin, and a photopolymerization initiator.
(I)

(Wherein R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different,
R ² represents at least one functional group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms and a phenylene group,
R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ⁵ represents a hydrogen atom or a methyl group,
p represents an integer of 1 to 5, q represents an integer of 3 or more,
m represents an integer of 1 to 4, and n represents an integer of 1 to 10) The photocurable resin composition according to claim 1, wherein the photosensitive resin has a double bond equivalent of 200 or more and 400 or less. The photosensitive resin composition according to claim 1, wherein the photosensitive resin has a structure in which a cyclic ether compound or a cyclic carbonate compound is reacted with a compound having not less than 3 phenolic hydroxyl groups in one molecule, Is a photosensitive resin obtained by reacting a compound having a group represented by the formula 4. The photocurable resin composition according to claim 3, wherein the compound having at least three phenolic hydroxyl groups in a molecule, not the above-mentioned calixarene structure, is a compound having a phenolic hydroxyl group having a softening point of room temperature or higher. The photocurable resin composition according to claim 3, wherein the compound having an ethylenically unsaturated group is methacrylic acid. The photo-curable resin composition according to any one of claims 1 to 4, which is a photo-curable thermosetting resin composition further containing a thermosetting component. The photocurable resin composition according to any one of claims 1 to 5, which is a solder resist further containing a colorant. A photocurable dry film obtained by applying and drying the photocurable resin composition according to any one of claims 1 to 5 onto a carrier film. A cured product obtained by photo-curing a photocurable resin composition according to any one of claims 1 to 5 or a photo-curable dry film obtained by applying and drying the photo-curable resin composition to a carrier film. A cured product obtained by photocuring a photocurable resin composition according to any one of claims 1 to 5 or a photocurable dry film obtained by applying and drying the photocurable resin composition to a carrier film in the form of a pattern. A photo-curable resin composition according to any one of claims 1 to 5, or a photo-curable dry film obtained by applying and drying the photo-curable resin composition to a carrier film, And the resulting cured coating film.