KR101997412B1 - Photocurable resin composition - Google Patents

Abstract

The photocurable resin composition contains a carboxyl group-containing resin, a photopolymerization initiator, a naphthalene derivative, and / or a naphthalene derivative in order to obtain stable high resolution without occurrence of halation or undercut and to inhibit cracking during a cooling / Or naphthoquinone and derivatives thereof. Suitably, the naphthalene derivative and / or the naphthoquinone and the derivative thereof are compounds having a hydroxyl group. The above-mentioned photocurable resin composition or its dry film can be advantageously applied to the formation of a cured film such as a solder resist which is excellent in various properties such as TCT resistance and PCT resistance of a printed wiring board or a flexible printed wiring board.

Description

[0001] PHOTOCURABLE RESIN COMPOSITION [0002]

The present invention relates to a photo-curable resin composition used as a solder resist or the like of a printed wiring board, a dry film and a cured product obtained therefrom, and a printed wiring board having a cured film such as a solder resist formed by the above- .

The photo-curable resin composition can be micromachined by applying the principle of photolithography. In addition, a cured product having excellent physical properties can be obtained, and thus it is used in electronic devices, printing plates, and the like.

This photocurable resin composition includes a solvent developing type and an alkali developing type. Recently, in the viewpoint of environmental measures, an alkali development type which can be developed with a weak alkaline aqueous solution has become mainstream. For example, in the production of a printed wiring board, a production of a liquid crystal display panel, a printing plate or the like, an alkali developing type photocurable resin composition is widely used. As a characteristic required for this, for example, when used as a solder resist in the production of a printed wiring board, the cured product is required to have heat resistance capable of withstanding treatment at high temperature such as soldering.

In recent years, since solder resists have not only a high heat resistance but also cracks during a cooling / heating cycle due to progress in high density mounting and thinning of printed wiring boards and the like in accordance with the size and weight reduction, Is required. In addition, a solder resist used for a high-density mounting substrate having a fine pitch pattern for high density mounting requires a high resolution. In order to obtain a high resolution, it is necessary to enhance the contrast between the exposed portion and the unexposed portion. As a method for reducing the vulnerability of a cured product expected as an improvement in crack resistance during a cooling / heating cycle, a method using a mixture of a bisphenol-type epoxy group-containing epoxy (meth) acrylate and a novolak- (See, for example, Patent Document 1, etc.). However, with this technique, high resolution and crack resistance are not achieved at the same time.

Representative examples of conventional photocurable resin compositions include a photocurable resin composition using a carboxyl group-containing epoxy (meth) acrylate resin and (meth) acrylate monomer together with a photopolymerization initiator. By using the composition having such a constitution, necessary pattern formation is carried out after the light irradiation through the development step. However, in order to obtain a high resolution, there is a problem that it is difficult to balance the photopolymerization initiator with the carboxyl group-containing epoxy (meth) acrylate resin having photoreactive properties or the (meth) acrylate monomer. Particularly, when exposed to a dry film of a liquid type or a dry film type in a state in which a PET (polyethylene terephthalate) film is attached, the PET film is exposed in a state in which the PET film is present on the surface of the resist, There arises a problem that halation easily occurs due to the progress of the cancer reaction and thus the intended stable resolution can not be obtained. Therefore, studies have been made to obtain stable resolution by using methoquinone, hydroquinone, phenothiazine, or the like as a polymerization inhibitor, but sufficient results have not been obtained.

Japanese Patent Application Laid-Open No. 2000-109541

The present invention has been made in view of the above-described problems of the prior art, and it is an object of the present invention to provide an image forming apparatus which does not cause halation or undercut even when exposed in a state in which a film is attached to a dry film of liquid type or dry film type, And capable of suppressing the occurrence of cracks during a cooling / heating cycle.

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 photocurable resin composition as described above and a printed wiring board having a cured film such as a solder resist formed by the above- In order to solve the problem.

According to one aspect of the present invention, there is provided a photocurable resin composition characterized by containing a carboxyl group-containing resin, a photopolymerization initiator, a naphthalene derivative and / or a naphthoquinone and a derivative thereof. In a preferred embodiment, the naphthalene derivative and / or naphthoquinone and the derivative thereof are compounds having a hydroxyl group.

By such a constitution, a high resolution can be obtained, and when used in a printed wiring board or the like in a cured product thereof, the resistance to cold and heat cycles can be improved. In the photo-curable resin composition of the present invention, the carboxyl group-containing resin preferably has a photosensitive group. By having a photosensitive group, the photocuring property of the photocurable resin composition is increased and the sensitivity can be improved.

In one embodiment of the photocurable resin composition of the present invention, the photopolymerization initiator is an oxime ester-based photopolymerization initiator represented by the following general formula (I), an aminoacetophenone-based photocatalyst represented by the following general formula (II) A polymerization initiator, and at least one photopolymerization initiator selected from the group consisting of acylphosphine oxide-based photopolymerization initiators represented by the following general formula (III).

(Wherein R ¹ represents a hydrogen atom, a phenyl group (which may be substituted with 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 in the middle), 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 ² 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, (Which may have an oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (an alkyl group having 1 to 6 carbon atoms or a phenyl group R ³ and R ⁴ each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms, and R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms , Or a combination of two to form a cyclic alkyl ether group; R ⁷ and R ⁸ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, An aryl group substituted with an alkyl group or an alkoxy group, provided that one of R ⁷ and R ⁸ may represent an RC (= O) - group (wherein R is a hydrocarbon group having 1 to 20 carbon atoms).

By using such a photopolymerization initiator, it is possible to obtain high resolution even in a resist having a pigment at a high concentration.

Further, in one embodiment of the photocurable resin composition of the present invention, it is preferable to further contain a thermosetting component. By including a thermosetting component, heat resistance can be imparted, and the tensile elongation of the cured coating can be increased to improve crack resistance.

In one embodiment of the photocurable resin composition of the present invention, a colorant may further be contained. It can be preferably used as a solder resist by containing a coloring agent.

According to another aspect of the present invention, there is provided a dry film obtained by applying and drying the above-mentioned photocurable resin composition on a film. By using such a dry film, the resist layer can be easily formed without applying the photocurable resin composition on the substrate.

In one embodiment of the present invention, the above-mentioned photocurable resin composition or dry film can be used as a cured product obtained by photo-curing by irradiation with active energy rays.

When such a cured product is used in a printed wiring board or the like, it is possible to improve the resistance to cold and heat cycles.

According to another aspect of the present invention, there is provided a printed wiring board having a pattern of a cured product obtained by photo-curing the above-mentioned photo-curable resin composition or a dry film thereof with active energy ray irradiation.

In such a printed wiring board, it is possible to improve the resistance to cold and heat cycles.

According to the photocurable resin composition of the present invention, since a naphthalene derivative and / or a naphthoquinone and a derivative thereof are contained together with a carboxyl group-containing resin and a photopolymerization initiator, a film is attached to a dry film of liquid type or dry film type Halation or undercut does not occur even when exposure is carried out on the surface of the printed wiring board or the like. High hardness can be obtained, and when the cured product is used in a printed wiring board or the like, it is possible to improve the resistance to cold and heat cycles.

Therefore, the photocurable resin composition of the present invention can be advantageously applied to the formation of a cured coating film of a solder resist or the like of a printed wiring board or a flexible printed wiring board, and a stable resolution can be obtained, and a thermal cycle test (TCT ) Resistance, resistance to PCT (Pressure Cooker Test) resistance, and the like can be formed, and a highly reliable printed wiring board can be provided.

The inventors of the present invention have found that the above object can be achieved by a resin containing a carboxyl group, a photopolymerization initiator, and a photocurable resin composition containing a naphthalene derivative and / or a naphthoquinone and a derivative thereof. It came to the following.

Particularly, by using a naphthalene derivative and / or naphthoquinone and a derivative thereof, it is possible to obtain a stable high resolution that does not cause undercut or halation, and to improve crack resistance without generating a crack initiation point during a cooling / It becomes possible.

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

As the carboxyl group-containing resin constituting the photocurable resin composition of the present invention, various known carboxyl group-containing resins having a carboxyl group in the molecule may be used for the purpose of imparting alkali developability. In particular, a photosensitive resin containing a carboxyl group having an ethylenically unsaturated double bond in a molecule is preferable from the viewpoints 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) a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate and an aromatic diisocyanate, a dialcohol compound containing a carboxyl group such as dimethylolpropionic acid and dimethylolbutanoic acid and a polycarbonate polyol, a polyether polyol Containing urethane resin obtained by a mid-portion reaction of a diol compound such as a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group .

(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-mentioned (2) or (3), a compound having one hydroxyl group and at least one (meth) acryl group in a molecule such as hydroxyalkyl (meth) A photosensitive urethane resin containing an acrylated carboxyl group.

(5) In the synthesis of the resin of the above-mentioned (2) or (3), a compound having one isocyanate group and at least one (meth) acryl group in the molecule such as equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate (Meth) acrylate is added to the carboxyl group-containing photosensitive urethane resin.

(6) reacting a bifunctional or higher polyfunctional (solid) epoxy resin as described below with (meth) acrylic acid, and reacting a hydroxyl group present in the side chain with a double base such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride A carboxyl group-containing photosensitive resin to which an acid anhydride is added.

(7) a carboxyl group in which a dibasic acid anhydride is added to the resulting hydroxyl group by reacting a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a difunctional (solid) epoxy resin as described below with epichlorohydrin, Containing photosensitive resin.

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

(9) A process for producing a reaction product comprising reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with a monocarboxylic acid containing an unsaturated group, Maleic acid, maleic anhydride, maleic acid, tetrahydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride.

(10) A process for producing a reaction product comprising reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, with a monocarboxylic acid containing an unsaturated group, A carboxyl group-containing photosensitive resin.

(11) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and at least one (meth) acryl group in the molecule to the above-mentioned resins (1) to (10).

Here, the term (meth) acrylate is generically referred to as acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions below.

These carboxyl group-containing resins may be used without being limited to those listed above, and they may be used singly or in combination of plural kinds.

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

The acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200 mg KOH / g. If the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, if the amount exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line tends to be unnecessarily thin. In some cases, the resist is dissolved and peeled off without distinction between the exposed portion and the unexposed portion, It becomes difficult to render the image. And more preferably in the range of 45 to 120 mg KOH / g.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. If the weight average molecular weight is less than 2,000, the tack-free performance of the coating film may deteriorate, the moisture resistance of the coated film after exposure may be poor, and the film may be reduced during development, resulting in a significant decrease in resolution. 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. And more preferably in the range of 5,000 to 100,000.

The blending amount of such a carboxyl group-containing resin is preferably in the range of 20 to 60 mass% of the entire composition. If the blending amount is less than 20 mass%, the film strength may be lowered. On the other hand, if it is more than 60% by mass, the viscosity of the composition becomes high and the coatability and the like deteriorate. And more preferably in the range of 30 to 50 mass%.

Examples of the photopolymerization initiator include oxime ester-based photopolymerization initiators having a group represented by the following general formula (I),? -Aminoacetophenone-based photopolymerization initiators having a group represented by the following general formula (II) and / By using at least one photopolymerization initiator selected from the group consisting of acylphosphine oxide-based photopolymerization initiators having a group represented by the formula (III), it is possible to obtain high resolution even in resists having a high concentration of pigment.

(Wherein R ¹ represents a hydrogen atom, a phenyl group (which may be substituted with 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 ² 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, , An alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (an alkyl group having 1 to 6 carbon atoms or a phenyl group having 1 to 6 carbon atoms) , R ³ and R ⁴ each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms, and R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms And R ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom , And an aryl group substituted with an alkyl group or an alkoxy group, provided that one of R ⁷ and R ⁸ may represent an RC (= O) - group wherein R is a hydrocarbon group having 1 to 20 carbon atoms.

The oxime ester-based photopolymerization initiator having a group represented by the general formula (I) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (IV) V), and a compound represented by the following general formula (VI).

(Wherein R ⁹ 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, A carbonyl 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, may have at least one oxygen atom in the middle of the alkyl chain), or phenoxycarbonyl group , R ¹⁰ and R ¹² each independently represents a phenyl group (which may be substituted with 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 (having 1 to 6 carbon atoms), which may have one or more oxygen atoms in the middle of the chain Represents that may be substituted with an alkyl group or a phenyl group), R ¹¹ is a hydrogen atom, a phenyl group (having 1 to 6 carbon atoms that the alkyl group, may be substituted phenyl group or a halogen atom), an alkyl group (at least one hydroxyl group having 1 to 20 carbon atoms , A cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (an alkyl group having 1 to 6 carbon atoms Or a phenyl group).

(Wherein R ¹³ , R ¹⁴ and R ¹⁹ each independently represent an alkyl group having 1 to 12 carbon atoms, and R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms , M represents O, S or NH, and x and y each independently represent an integer of 0 to 5.)

Among the oxime ester-based photopolymerization initiators, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the above-mentioned general formula (IV) and a compound represented by the general formula (V) are more preferable. Commercially available products include CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02 manufactured by BASF Japan, and N-1919 manufactured by ADEKA. These oxime ester-based photopolymerization initiators may be used alone or in combination of two or more.

Examples of the? -Aminoacetophenone-based photopolymerization initiator having a group represented by the general formula (II) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoprofenon- 2- (4-methylphenyl) methyl] -1- [4- (4-methylphenyl) Morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, and the like. Commercially available products include Irgacure 907, Irgacure 369, Irgacure 379 and Irgacure 389 manufactured by BASF Japan.

As the acylphosphine oxide-based photopolymerization initiator having a group represented by the general formula (III), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lucirin TPO manufactured by BASF, Irgacure 819 manufactured by BASF Japan, and the like.

The blending amount of such photopolymerization initiator is preferably in the range of 0.01 to 30 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount is less than 0.01 part by mass, the photocurability on copper is insufficient, resulting in peeling of the coating film and deterioration of coating film properties such as chemical resistance. On the other hand, if the amount exceeds 30 parts by mass, the light absorption at the surface of the coating film of the photopolymerization initiator becomes severe, and the deep portion curability tends to be lowered. More preferably 0.5 to 15 parts by mass.

In the case of the oxime ester-based photopolymerization initiator having a group represented by the general formula (I), the blending amount thereof is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group- Wealth.

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 , Xanthone compounds, and tertiary amine compounds.

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

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

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

Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone. have.

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

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

Examples of the tertiary amine compound include an ethanolamine compound, a compound having a dialkylaminobenzene structure such as 4,4'-dimethylaminobenzophenone (Nissokyure MABP manufactured by Nippon Soda Co., Ltd.), 4,4'-diethylamino Dialkylaminobenzophenones such as benzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.); A coumarin compound containing a dialkylamino group such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin); Dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthics, Inc.), 4-dimethylaminobenzoic acid (n-dodecylaminobenzoic acid) (manufactured by Nippon Kayaku Co., (Quanta Cure BEA manufactured by International Bio-Synthics Co., Ltd.), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate And Esolol 507 manufactured by Van Dyk). Particularly, 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 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 little coloring because of its maximum absorption wavelength in the ultraviolet ray region and can be used not only for a colorless transparent photosensitive composition but also for a coloring It becomes possible to provide a solder resist film. Particularly, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable in that it exhibits an excellent increase / decrease effect on laser light having a wavelength of 400 to 410 nm.

Of these compounds, thioxanthone compounds and tertiary amine compounds are preferred. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curing. Among these, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, And thioxanthone compounds such as 2,4-diisopropylthioxanthone are preferable.

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

The amount of the tertiary amine compound is preferably from 0.1 to 20 parts by mass based on 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 coating film by the tertiary amine compound becomes serious, and the hardness at the deep portion tends to be lowered. More preferably 0.1 to 10 parts by mass. 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 35 parts by mass or less 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 due to the light absorption.

In the photocurable resin composition of the present invention, N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like known as a chain transfer agent may be used in order to improve the sensitivity. Specific examples of the chain transfer agent include, for example, mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof. These chain transfer agents may be used alone or in combination of two or more.

The photocurable resin composition of the present invention can be produced by using a naphthalene derivative and / or a naphthoquinone and a derivative thereof, and when exposed in a state of attaching a PET film to a dry film of liquid type or dry film type, Stable resolution can be obtained regardless of the time for peeling the PET film without causing halation. This is because the naphthalene derivative and / or naphthoquinone and its derivative have an effect of slowing the rate of the photoreaction under oxygen evasion unlike phenothiazine and hydroquinone, which are general polymerization inhibitors (that is, acting as a polymerization inhibitor under oxygen escape) ), It is considered that the speed of the surface hardening is suppressed and uniformly hardened in the thickness direction.

Of the naphthalene derivatives and / or naphthoquinone and derivatives thereof used in the present invention, examples of the naphthalene derivative include ammonium 1,4-dihydroxy-2-naphthalenesulfonate and 4-methoxy-1-naphthol. Examples of the naphthoquinone and derivatives thereof include 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, and anthrone.

Examples of commercially available naphthalene derivatives include KenoPower (registered trademark) WSI, Keno Power MNT (all manufactured by Kawasaki Kasei Kogyo Co., Ltd.) and 4-methoxy-1-naphthol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) .

Examples of commercial products of naphthoquinone and its derivatives include KenoPower (registered trademark) NQI, KenoPower LSN, KenoPower ATR (all manufactured by Kawasaki Chemical), 1,4-naphthoquinone, 2- 1,4-naphthoquinone, and anthrone (both manufactured by Tokyo Kasei Kogyo Co., Ltd.).

The blending amount of the naphthalene derivative and / or naphthoquinone and the derivative thereof is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin. When the blending amount of the naphthalene derivative and / or the naphthoquinone and the derivative thereof is less than 0.01 part by mass, the resolution is not stabilized and halation or undercut occurs, and high resolution can not be obtained. On the other hand, when it exceeds 20 parts by mass, the coating film characteristics such as electroless gold plating resistance are deteriorated due to the deterioration of the photocurability. And more preferably 0.05 to 10 parts by mass.

In the photocurable resin composition of the present invention, a thermosetting component can be added to impart heat resistance. Examples of the thermosetting component used in the present invention include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives and benzoguanamine derivatives, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, A known thermosetting resin such as episulfide resin can be used. Particularly preferred are thermosetting components having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule.

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

Examples of the polyfunctional epoxy compound include jER 828, jER 834, jER 1001, jER 1004 (all manufactured by Mitsubishi Chemical), Epiclon 840, Epiclon 850, Epiclon 1050 YD-013, YD-127, YD-128 (all manufactured by Shinnitetsu Chemical), DER 317, DER 331, DER 661, DER 664 (all manufactured by Dow Chemical Company), Araldite 6071, Araldite 6084, Araldite GY250 and Araldite GY260 (both manufactured by BASF Japan), Sumi Epoxy ESA-011, ESA-014, ELA Bisphenol A type epoxy resin of AER 330, AER 331, AER 661, AER 664, etc. (all manufactured by Asahi Kasei Kogyo Co., Ltd.); (all manufactured by Shin-Etsu Chemical Co., Ltd.), DER 542 (manufactured by Dow Chemical Co., Ltd.), EPCLON 165 Brominated epoxy resin such as Araldite 8011 (manufactured by BASF Japan), Sumi epoxy ESB-400, ESB-700 (all manufactured by Sumitomo Chemical Co., Ltd.), AER 711 and AER 714 (all manufactured by Asahi Kasei Corporation) ; DER 431, DEN 438 (all manufactured by Dow Chemical Company), Epiclon N-730, Epiclon N-770 and Epiclon N-865 (all manufactured by DIC) Araldite ECN1273, Araldite ECN1299, Araldite XPY307 (both manufactured by BASF Japan), EPPN-701, YDCN-701 and YDCN- 201, EOCN (registered trademark) -1025, EOCN-1020, EOCN-104S, RE-306 (all manufactured by Nippon Kayaku Co., Ltd.), Sumi Epoxy ESCN- 195X, ESCN- -235, and ECN-299 (both manufactured by Asahi Kasei Corporation); (All manufactured by Shin-Etsu Chemical Co., Ltd.), Araldite XPY306 (manufactured by BASF Japan Co., Ltd.), Epiclone 830 (manufactured by DIC Corporation), jER 807 (manufactured by Mitsubishi Chemical Corporation), Eptotol YDF-170, YDF- Bisphenol F type epoxy resin, e.g. Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007, and ST-3000 (all manufactured by Shinnitsu Tetsu Chemicals); (manufactured by Sumitomo Chemical Co., Ltd.), JER 604 (manufactured by Mitsubishi Chemical Corporation), Epitoto YH-434 (manufactured by Shinnitetsu Chemical Co., Ltd.), Araldite MY720 Glycidylamine type epoxy resin; Heidantoin-type epoxy resins such as Aralydite CY-350 (manufactured by BASF Japan); Alicyclic epoxy resins such as CELLOXIDE (registered trademark) 2021 (manufactured by Daicel Chemical Industries, Ltd.), Araldite CY175 and CY179 (all manufactured by BASF Japan); Trihydroxyphenylmethane type epoxy resins such as YL-933 (manufactured by Mitsubishi Chemical Corporation), T. E. N., EPPN (registered trademark) -501, and EPPN-502 (all available from Nippon Kayaku Co., Ltd.); A biscylenol type or biphenol type epoxy resin such as YL-6056, YX-4000, and YL-6121 (both manufactured by Mitsubishi Chemical) or a mixture thereof; Bisphenol S type epoxy resins such as EBPS-200 (manufactured by Nippon Kayakazai), EPX-30 (manufactured by Adeka) and EXA-1514 (manufactured by DIC); bisphenol A novolak type epoxy resins such as jER 157S (manufactured by Mitsubishi Chemical Corporation); tetraphenylol ethane type epoxy resins such as jERYL-931 (manufactured by Mitsubishi Chemical Corporation) and Araldite 163 (manufactured by BASF Japan); Heterocyclic epoxy resins such as ARALIDITE PT810 (manufactured by BASF Japan) and TEPIC (manufactured by Nissan Chemical Industries, Ltd.); Diglycidyl phthalate resins such as Bremmer (registered trademark) DGT (manufactured by Nichisan); Tetraglycidylsilane ethyl resin such as ZX-1063 (manufactured by Shinnittsu Chemical Co., Ltd.); Naphthalene group-containing epoxy resins such as ESN-190, ESN-360 (all manufactured by Shin-Nittetsu Kagaku), HP-4032, EXA-4750 and EXA-4700 (manufactured by DIC); An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H (manufactured by DIC); Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M (manufactured by Nichi- Co.); A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN modified epoxy resins (e.g., YR-102 and YR-450 manufactured by Shinnittsu Chemical Co., , But the present invention is not limited thereto. These epoxy resins may be used alone or in combination of two or more. Of these, novolak type epoxy resins, heterocyclic epoxy resins, 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 polyfunctional oxetanes such as methacrylates and oligomers or copolymers thereof, oxetane alcohol and novolac resins, poly (p-hydroxystyrene), cardo type bisphenols, calixarene, calix resorcin Isocyanuric acid, isophorone diisocyanate, isophorone diisocyanate, isophorone diisocyanate, isophorone diisocyanate, isophorone diisocyanate, Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. An episulfide resin in which an oxygen atom of the epoxy group of the novolak type epoxy resin is replaced with a sulfur atom can also be used by using the same synthesis method.

The amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents based on 1 equivalent of the carboxyl group of the carboxyl group-containing resin. When the blending amount is less than 0.6, a carboxyl group remains in the solder resist film to deteriorate heat resistance, alkali resistance, electrical insulation, and the like. On the other hand, if it exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether groups remain in the dried coating film, so that the strength of the coated film is lowered. More preferably 0.8 to 2.0 equivalents.

Other thermosetting components include amino resins such as melamine derivatives and benzoguanamine derivatives. For example, methylolmelamine compounds, methylolbenzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. The alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound, and the alkoxymethylated urea compound may be 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 is desirable for human body or environment.

These commercially available products include, for example, CYMEL (registered trademark) 300, Copper 301, Copper 303, Copper 370, Copper 325, Copper 327, Copper 701, Copper 266, Copper Copper 267, Copper Copper 238, Copper Copper 1141, Mx-032, Mx-032, Mx-032, Mx-032, Mx-032, Mx-032, Mx-032, Mx- -270, Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw -390, Mw-100LM, and Mw-750LM (both manufactured by Sanwa Chemical Co., Ltd.). These thermosetting components may be used alone or in combination of two or more.

To the curable resin composition of the present invention, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be added in order to improve the hardenability and toughness of the resulting cured product. Examples of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule thereof include a polyisocyanate compound and a block isocyanate compound. In addition, the blocked isocyanate group is a group in which an isocyanate group is protected by a reaction with a blocking agent and is temporarily inactivated, and when heated to a predetermined temperature, the blocking agent dissociates to form an isocyanate group.

As such a 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, and examples of the above-mentioned isocyanate compound adduct, burette and isocyanurate are exemplified.

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 the above-mentioned polyisocyanate compounds and the like.

Isocyanate block agents include, for example, 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, methyl thiophenol and ethyl thiophenol; 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, for example, Sumitra TM BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TM (registered trademark) TPLS-2957, TPLS- (All manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate (registered trademark) 2512, Coronate 2513 and Coronate 2520 (all manufactured by Nippon Polyurethane Industry Co., Ltd.) B-880, B-815, B-846, B-870, B-874 and B-882 (all manufactured by Mitsui Takeda Chemical Co.), TPA-B80E, 17B-60PX and E402-B80T (all manufactured by Asahi Chemical Industry Co., Ltd.) and the like. Further, SMILDIR BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a block agent. These compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be used singly or in combination of two or more.

The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass with respect to 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. On the other hand, when it exceeds 100 parts by mass, storage stability is lowered. More preferably 2 to 70 parts by mass.

When a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4- Imidazole derivatives such as phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; 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 of which are trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd. and U-CAT DBU, U-CATSA102, and U-CAT5002 (both trade names of bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, and it may be a thermosetting catalyst of an epoxy resin or an oxetane compound, or a catalyst capable of accelerating a reaction between an epoxy group and / or an oxetanyl group and a carboxyl group, . 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 And S-triazine derivatives such as adducts may be used. Preferably, a compound that also functions as such an adhesion-imparting agent is used in combination with a thermosetting catalyst.

The compounding amount of these thermosetting catalysts is usually sufficient in the usual quantitative ratio, and is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, More preferably 0.5 to 15.0 parts by mass.

A colorant may be added to the photo-curable resin composition of the present invention. As the coloring agent, known coloring agents such as red, blue, green, and yellow may be used, and any of pigments, dyes, and pigments may be used. However, from the viewpoint of the environmental load reduction and the effect on the human body, it is preferable that no halogen is contained.

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

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.

Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, and Pigment Blue 15: Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Pigment Blue 15, Pigment Blue 16, Pigment Blue 60, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, and the like. In addition to these, metal substituted or unsubstituted phthalocyanine compounds may also be used.

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

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 examples thereof include the following.

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

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

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

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

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

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

In addition, coloring agents such as purple, orange, green, and black may be added for the purpose of adjusting the color tone. Concretely, it is possible to use pigments such as Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, Pigment Orange 1, Pigment Orange 5, Pigment Orange 13, Pigment Orange 14, 16, Pigment Orange 17, Pigment Orange 24, Pigment Orange 34, Pigment Orange 36, Pigment Orange 38, Pigment Orange 40, Pigment Orange 43, Pigment Orange 46, Pigment Orange 49, Pigment Orange 51, Pigment Orange 61, Pigment Orange 63, Pigment Orange 64, Pigment Orange 71, Pigment Orange 73, Pigment Brown 23, Pigment Brown 25, Pigment Black 1, Pigment Black 7 have.

The mixing ratio of such a colorant is not particularly limited, but is preferably 10 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. If it exceeds 10 parts by mass, the deep curing property may be remarkably deteriorated. More preferably 0.1 to 5 parts by mass.

The compound having a plurality of ethylenically unsaturated groups in the molecule used in the photo-curable resin composition of the present invention is photo-cured by irradiation with active energy rays to insolubilize the carboxyl group-containing resin having an ethylenic unsaturated group in a dilute aqueous alkali solution, Or insolubilization.

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; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; And methacrylates corresponding to melamine acrylate and / or acrylate.

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

The compounding amount of the compound having a plurality of ethylenically unsaturated groups in such molecules is preferably 5 to 100 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 5 parts by mass, the photocurability is lowered, and pattern formation becomes difficult due to the alkali development after irradiation with active energy rays. On the other hand, if it exceeds 100 parts by mass, the solubility in a dilute alkaline aqueous solution decreases and the coating film becomes weak. More preferably 1 to 70 parts by mass.

In the photo-curable resin composition of the present invention, a filler may be added as needed in order to increase the physical strength and the like of the coating film. As such a filler, known inorganic or organic fillers can be used, and in particular, barium sulfate, spherical silica, hydrotalcite and talc are preferably used. Further, metal hydroxide such as titanium oxide, metal oxide, and aluminum hydroxide may be used as extender pigment filler in order to obtain white appearance and flame retardancy. The blending amount of the filler is preferably 75% by mass or less 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 increases, the coating and the formability are lowered, and the cured product becomes fragile. And more preferably from 0.1 to 60 mass%.

The photo-curable resin composition of the present invention can be used for the synthesis of a carboxyl group-containing resin, for the production of a 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 contain, if necessary, known heat polymerization inhibitors, known thickeners such as fine silica, organic bentonite and montmorillonite, antifoaming agents and / or leveling agents such as silicone, fluorine, and high molecular weight, , Thiazole-based, and triazole-based silane coupling agents, antioxidants, rust inhibitors, and the like.

The thermal polymerization inhibitor can 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- Phenol, cuprous chloride, phenothiazine, chloranil, naphthylamine,? -Naphthol, 2,6-di-t-butyl-4-cresol, 2,2'- butylphenol), reactants such as pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agents, methyl salicylate, phenothiazine, nitroso compounds, Chelate, and the like.

In the photo-curable resin composition of the present invention, an adhesion promoter may be used to improve interlayer adhesiveness or adhesion between the resin insulating layer and the substrate to be formed. Examples of such adhesion promoters include, for example, benzoimidazole, benzoxazole, benzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, Methyl-thiazole-2-thione, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

The photocurable resin composition of the present invention having such a constitution as described above may be prepared in a predetermined composition and then adjusted to a viscosity suitable for a coating method using, for example, an organic solvent, and then a coating method such as an immersion coating method, a flow coating method, Method, a bar coater method, a screen printing method, a curtain coating method or the like.

Then, the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 60 to 100 캜 to form a coat-free coating film (resin insulating layer). At this time, the volatile drying can be carried out by a hot air circulating drying furnace, an IR, a hot plate, a convection oven or the like (a method in which hot air in a dryer is countercurrently contacted with a heat source using an air heating method by steam, ) Can be used.

It is also possible to form a resin insulating layer by forming a dry film with the photo-curable resin composition and bonding it to a substrate.

The dry film has a structure in which, for example, a carrier film such as polyethylene terephthalate, a resin insulating layer such as a solder resist layer, and a peelable cover film which is used as needed are laminated in this order.

The resin insulating layer is a layer obtained by applying and drying a photocurable resin composition onto a carrier film or a cover film. Such a resin insulating layer is formed by uniformly applying a photocurable resin composition of the present invention to a carrier film with a thickness of 10 to 150 mu m by using a blade coater, a lip coater, a comer coater, a film coater or the like and drying the same. Then, a cover film is further laminated as necessary to form a dry film. At this time, it is also possible to apply the photocurable resin composition to a cover film, dry it, and then laminate the carrier film.

As the carrier film, for example, a thermoplastic film such as a polyester film having a thickness of 2 to 150 mu m is used.

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

When a cover film is used in such a dry film, the resin film is peeled off, the resin insulating layer and the base material are superimposed, and the base film is joined with a laminator or the like to form a resin insulating layer on the base material. The carrier film may be peeled off before or after exposure, which will be described later.

Examples of the substrate on which a coating film is formed or a dry film is bonded include paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine, (FR-4 and the like), other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, and the like can be used as the material of the laminated plates for high frequency circuits using cyanate ester or the like have.

In addition, the photoresist is selectively exposed to an active energy ray through a photomask having a pattern formed by a contact (or noncontact) method, or directly pattern-exposed by a laser direct exposure apparatus.

Examples of the exposure apparatus used for irradiation with active energy rays include a direct drawing 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 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, it is preferable to use laser light having a wavelength in the range of 350 to 410 nm. By setting the maximum wavelength within this range, it is possible to efficiently generate radicals from the photoinitiator. Any gas laser or solid laser may be used as long as the laser light in this range 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 imaging apparatus, for example, those manufactured by Nippon Denshoku Kogyo Co., Ltd. and manufactured by FANUC Corporation may be used, and any apparatus may be used as long as it is an apparatus for emitting laser light having a wavelength of 350 to 410 nm.

The unexposed portion is then developed with a dilute aqueous alkali solution (for example, a 0.3 to 3 wt.% Aqueous solution of sodium carbonate) to obtain a cured product ( Pattern).

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

When a thermosetting component is added, for example, by heating to a temperature of about 140 to 180 DEG C to thermoset, the carboxyl group of the carboxyl-containing resin and, for example, a plurality of cyclic ether groups and / or cyclic thioether groups Cured product having excellent properties such as heat resistance, chemical resistance, hygroscopicity, adhesion, electrical properties, and the like can be formed.

As described above, the photocurable resin composition of the present invention contains a carboxyl group-containing resin, a photopolymerization initiator, a naphthalene derivative and / or naphthoquinone and a derivative thereof, It is possible to satisfy the resolution and the reliability such as the cold and heat cycle resistance. By using such a cured product as a printed wiring board or the like, high reliability can be obtained.

Example

EXAMPLES The present invention will be described in detail with reference to the following examples and comparative examples, but it goes without saying that the present invention is not limited to these examples. In the following, "part (s) " and"% "are all mass standards unless otherwise specified.

Examples 1 to 11 and Comparative Examples 1 to 3

(Mass parts) shown in Table 1, premixed with a stirrer, and kneaded by a three-roll mill to prepare a photosensitive resin composition for a solder resist. Here, the degree of dispersion of the obtained photosensitive resin composition was evaluated by particle size measurement by a grindmeter manufactured by Ericensa and found to be 15 탆 or less.

Performance evaluation:

<Optimum exposure dose>

The circuit pattern substrate having a copper thickness of 35 mu m was buffed and polished, washed with water, and then dried. The photosensitive resin compositions of the examples and comparative examples were applied to the entire surface by a screen printing method, Lt; / RTI &gt; for 60 minutes. After drying, the resist film was exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high pressure mercury lamp (short arc lamp), and developed (30 ° C, 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution ) Was performed for 60 seconds, the optimum exposure amount was set to 7 when the remaining step tablet pattern was single.

<Developability>

The photosensitive resin compositions of the examples and comparative examples were coated on the front copper substrate by screen printing to a thickness of about 25 mu m after drying and dried in a hot air circulation type drying oven at 80 DEG C for 30 minutes. After drying, development was carried out with a 1 wt% Na ₂ CO ₃ aqueous solution, and the time until the dry coating film was removed was measured by a stopwatch.

Characteristic evaluation:

&Lt; Production of liquid type substrate &

The photosensitive resin compositions of the examples and comparative examples were coated on the entire surface of the patterned copper foil substrate so as to have a film thickness of 20 mu m after being dried by screen printing, dried at 80 DEG C for 30 minutes, and cooled to room temperature. PET film (FB-50: 16 占 퐉, manufactured by Toray Industries, Inc.) was attached to the obtained substrate and pressed using a vacuum laminator (MVLP (registered trademark) -500, , And a degree of vacuum of 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer. The substrate was exposed to a solder resist pattern at an optimum exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the adhered PET film was peeled off after 10 minutes. Thereafter, development was carried out for 60 seconds at a spray pressure of 0.2 MPa in a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C 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 캜 for 60 minutes. The properties of the obtained printed board (evaluation board) were evaluated as follows.

&Lt; Production of dry film type substrate &

Each of the photosensitive resin compositions of the examples and comparative examples was appropriately diluted with methyl ethyl ketone and then applied to a PET film (FB-50: 16 탆 by Dores Inc.) so that the film thickness after drying was 20 탆 by using an applicator And dried at 80 DEG C for 30 minutes to obtain a dry film. After buffing the substrate with the circuit formed thereon, the obtained dry film was subjected to a heat treatment under the conditions of a pressure of 0.8 MPa, 70 DEG C for 1 minute and a degree of vacuum of 133.3 Pa using a vacuum laminator (MVLP (registered trademark) -500, To obtain a substrate (unexposed substrate) having an unexposed solder resist layer. The substrate was exposed to a solder resist pattern at an optimum exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the PET film was peeled off after 10 minutes. Thereafter, development was carried out for 60 seconds at a spray pressure of 0.2 MPa in a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C 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 캜 for 60 minutes. The properties of the obtained printed board (evaluation board) were evaluated as follows.

&Lt; Resolution stability >

The photosensitive resin compositions of Example 1 and Comparative Example 1 were coated on the entire surface of a patterned copper foil substrate so as to have a thickness of 20 탆 after being dried by screen printing and dried in a hot air circulation type drying furnace at 80 캜 for 30 minutes. The exposure was performed at 100 mJ / cm ² using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the time for peeling the PET film was 5 to 60 minutes. Thereafter, development was carried out with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C for 60 seconds to form a pattern, and ultraviolet irradiation was carried out under the conditions of an integrated exposure dose of 1000 mJ / cm ² in a UV conveyer, The cured coating film was obtained by curing. The length of the opening bottom portion of the opening design value of 80 占 퐉 in the cured coating film of the obtained photosensitive resin composition for a solder resist was measured. The criteria are as follows.

G: The opening bottom of 80 탆 design pitch is 60 탆 or more and 80 탆 or less, and undercut and halation are not generated.

H: Halation occurred. The opening bottom portion is at least 40 탆 and less than 60 탆.

A: Undercut occurred. The opening bottom portion is larger than 80 탆 and smaller than 100 탆.

<Resolution>

An evaluation board was produced under the above-described substrate production conditions. The length of the opening bottom portion of the opening design value of 80 占 퐉 in the cured coating film of the obtained photosensitive resin composition for a solder resist was measured. The criteria are as follows.

G: The opening bottom of 80 탆 design pitch is 60 탆 or more and 80 탆 or less, and undercut and halation are not generated.

H: Halation occurred. The opening bottom portion is at least 40 탆 and less than 60 탆.

A: Undercut occurred. The opening bottom portion is larger than 80 탆 and smaller than 100 탆.

&Lt; Soldering heat resistance &

The evaluation substrate on which the rosin flux was applied was immersed in a solder bath set at 260 占 폚 in advance, and the flux was washed with denatured alcohol, and then evaluated for the swelling and peeling of the resist layer by visual inspection. The criteria are as follows.

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

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

DELTA: Repeated immersion for 10 seconds at least three times results in slight detachment.

X: The resist layer was swollen and peeled within 3 times of immersion for 10 seconds.

<Domestic delivery gold plated castle>

Plating was carried out using a commercially available electroless nickel plating bath and electroless gold plating bath under the conditions of nickel 0.5 탆 and gold 0.03 탆 and the peeling of the resist layer or the impregnation of the plating was evaluated by a tape fill, Layer was peeled off. The criteria are as follows.

◎: Seeping and peeling are not seen.

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

B: Seeping slightly after plating, peeling after tape peeling is also seen.

X: Peeling occurs after plating.

<Tolerance of TCT>

A photosensitive resin composition was coated on a substrate having a copper line pattern of 2 mm formed thereon, exposed and developed, and thermally cured to prepare an evaluation substrate on which a resist pattern with a width of 3 mm was formed on a copper line. The evaluation substrate was placed in a cooling / heating cycle in which a temperature cycle was performed between -65 DEG C and 150 DEG C, and TCT was performed. Then, the appearance at 600 cycles, 800 cycles, and 1000 cycles was observed.

A: No abnormality in 1000 cycles.

?: No abnormality in 800 cycles, but cracks occurred in 1000 cycles.

?: No abnormality in 600 cycles, but cracking occurred in 800 cycles.

×: Crack occurred in 600 cycles.

<PCT Resistance>

The evaluation substrate on which the solder resist cured coating film was formed was subjected to PCT for 168 hours and 192 hours at 121 占 폚 and saturation at 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by Espec Co., Ltd.). The state of the coated film after the PCT was evaluated. The criteria are as follows.

⊚: 192 hours No swelling, peeling, discoloration, or elution.

○: 168 hours No swelling, peeling, discoloration, elution.

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

X: A lot of swelling, peeling, discoloration, and dissolution are observed.

The evaluation results of the resolution stability (post exposure stability) are shown in Table 2, and the evaluation results of the other properties are shown in Table 3.

As shown in Table 2, in Example 1 using a naphthalene derivative and / or naphthoquinone and a derivative thereof, it was found that good resolution was obtained regardless of the time for peeling the PET film as compared with Comparative Example 1 .

As shown in Table 3, in Examples 1 to 11 using naphthalene derivatives and / or naphthoquinone and derivatives thereof, excellent resolution, TCT resistance and PCT resistance were obtained as compared with Comparative Examples 1 to 3 Able to know.

On the other hand, in Comparative Example 2 in which naphthalene derivatives and / or naphthoquinone and derivatives thereof were not used in comparison with Example 3, the halation was largely caused. When the PET film was peeled after 10 minutes from the exposure, , Peeling of the coating film occurred, and solder heat resistance, internal electrolytic gold plating resistance, TCT resistance and PCT resistance were lowered. In comparison with Example 1, in Comparative Example 1 in which naphthalene derivative and / or naphthoquinone and its derivative were not used, and in Comparative Example 3 in which phenothiazine was used in place of the naphthalene derivative and / or naphthoquinone and its derivative, TCT resistance was similarly lowered, But the resolution was not stabilized and the halation occurred, and the peeling occurred in the PCT after 168 hours elapsed.

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

Claims (5)

A carboxyl group-containing resin,
A photopolymerization initiator,
Wherein the solder resist composition comprises at least one of 4-methoxy-1-naphthol, 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, And a step of exposing the film in a state where the film is attached to the dry film. The solder resist composition according to claim 1, which is used in the solder resist forming method. A dry film obtained by applying and drying the solder resist composition according to claim 2 on a film. A dry film obtained by applying and drying the solder resist composition according to claim 2 on a substrate or a dry film obtained by applying and drying the solder resist composition on a film is laminated to a substrate to form a coating film, By weight. A printed wiring board characterized by having the pattern of the cured product according to claim 4.