KR101693053B1 - Flame-retardant photocurable resin composition, dry film and cured product of the same, and printed wiring board using the composition, dry film or cured product - Google Patents

Abstract

The present invention relates to a flame-retardant photo-curable resin composition capable of forming a cured film having a non-halogen composition, a low environmental load and an excellent flame retardancy, a flexible film, a dry film thereof and a cured product thereof, And a flame-retardant cured coating of the flame retardant.
The flame-retardant photocurable resin composition contains (A) an element-containing polyester which is soluble in an organic solvent, (B) a carboxyl group-containing resin and (C) a photopolymerization initiator. Preferably, the carboxyl group-containing resin (B) is a carboxyl group-containing polyurethane resin. More preferably, it further contains (D) a photopolymerizable monomer, or further contains (E) a thermosetting resin. A flame-retardant photocurable / thermosetting resin composition containing such a flame-retardant photocurable resin composition, particularly a thermosetting resin (E), can be preferably used as a solder resist.

Description

Technical Field The present invention relates to a flame-retardant photo-curing resin composition, a dry film and a cured product thereof, and a printed circuit board using the same. BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a flame-

The present invention relates to a flame-retardant photocurable resin composition that can be developed by a dilute alkaline aqueous solution, particularly a composition for a solder resist that is photo-cured by ultraviolet exposure or laser exposure, a dry film thereof and a cured product thereof, To a printed wiring board.

Conventionally, a printed wiring board and a flexible wiring board (hereinafter abbreviated as FPC) were required to have flame retardancy to be mounted on electronic equipment, and the solder resist, which is a part of these, was also required to have flame retardancy. Among them, the FPC is usually made of a polyimide substrate, and thus is a thin film unlike a printed wiring board of a glass epoxy substrate. However, since the solder resist to be applied has the same film thickness for both the printed wiring board and the FPC, the burden on the solder resist to the solder resist is relatively increased in the case of the thin FPC.

For this reason, various proposals have heretofore been made on the flame retardation of the solder resist. For example, Japanese Patent Application Laid-Open No. 2007-10794 (Patent Document 1) discloses a process for producing a polymerizable ethylenically unsaturated compound such as a halogenated aromatic ring such as (A) a binder polymer, (B) a bromophenyl group, (D) a block isocyanate compound, and (E) a phosphorus-containing compound having a phosphorus atom in the molecule, has been proposed as a flame-retardant photosensitive resin composition for an FPC . However, the use of a halogen compound such as a compound having a halogenated aromatic ring and a polymerizable unsaturated double bond is not preferable from the viewpoint of environmental load.

Japanese Patent Application Laid-Open No. 2007-10794 (claims)

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described prior art, and an object of the present invention is to provide a non-halogen composition which is excellent in flame retardancy, environmental load, flame retardancy, flexibility of a cured film, It is an object of the present invention to provide a flame-retardant photo-curable resin composition which is capable of forming a cured film having a fine pattern with excellent electroless gold plating resistance, moisture resistance, electrical insulation and the like, and particularly suitable for FPC.

It is also an object of the present invention to provide a flame retardant dry film and cured product excellent in various characteristics as described above obtained by using such a photocurable resin composition and a flame retardant cured film such as a solder resist, And a printed circuit board.

According to the present invention, there is provided a flame-retardant photocurable resin composition comprising (A) an organic solvent-soluble polyester containing an element, (B) a carboxyl group-containing resin and (C) a photopolymerization initiator do. Preferably, the carboxyl group-containing resin (B) is a carboxyl group-containing polyurethane resin.

In a preferred embodiment, it further contains (D) a photopolymerizable monomer or further contains (E) a thermosetting resin. The thermosetting resin (E) preferably includes an epoxy resin having a biphenyl skeleton. A flame-retardant photocurable / thermosetting resin composition containing such a flame-retardant photocurable resin composition, particularly a thermosetting resin (E), can be preferably used as a solder resist.

According to the present invention, there is also provided a flame-retardant photo-curable dry film obtained by applying and drying the flame-retardant photo-curable resin composition onto a carrier film, and a flame-retardant cured product obtained by curing the flame-retardant photo- curable resin composition or the dry film.

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

Since the flame-retardant photo-curable resin composition of the present invention uses an element-containing polyester and a carboxyl group-containing resin which are halogen-free organic solvent-soluble, it is possible to provide a flame- It is possible to form a cured film of a fine pattern which is rich in properties and excellent in adhesiveness to various substrates, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation and the like.

Therefore, the flame-retardant photo-curable resin composition of the present invention can be advantageously applied to the formation of a flame-retardant cured coating film of a printed wiring board, particularly, an FPC solder resist.

As described above, the first characteristic of the flame-retardant photocurable resin composition of the present invention is that an element-containing polyester (A) which is halogen-free organic solvent-soluble is used. The term "halogen-free" in the present specification means that a halogen compound is not actively used, except when it is incorporated as an inevitable impurity.

The element-containing polyester (A) which is soluble in an organic solvent can be obtained by reacting a phosphorus-containing carboxylic acid or its esterified product, a phosphoric acid compound, a phosphonic acid compound, a phosphorous acid compound, (See, for example, JP-A-2002-3587, JP-A-2007-204744, etc.).

Is preferably an organic solvent-soluble polyester obtained by copolymerizing a phosphorus-containing carboxylic acid represented by the following formula (I) or an ester compound thereof.

(I)

(Wherein R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group,

R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group or a hydroxy group-substituted hydrocarbon group,

l and m represent an integer of 0 to 4)

Examples of commercial products of the organic solvent-soluble element-containing polyester include Vylon (registered trademark) 237 and Vylon 337 manufactured by Toyo Bosu Co., Ltd.

These phosphorus element-containing polyesters may be a polyester polyurethane structure in which a urethane bond is partially introduced using a diisocyanate. For example, commercially available products include UR3570 manufactured by Toyobo Co., Ltd.

As the organic-solvent-soluble element-containing polyester (A), various high-molecular-weight polyester resin compounds soluble in various organic solvents for industrial use can be used and are not limited to specific ones, but those having the following properties are preferable.

(1) The weight average molecular weight is preferably in the range of 1,000 to 100,000, more preferably 5,000 to 50,000. If the weight-average molecular weight is less than 1,000, the tack-free performance of the obtained coating film may be lowered. On the other hand, if the weight average molecular weight exceeds 100,000, the solubility in various organic solvents lowers, and the developability of the obtained coating film may be markedly deteriorated.

(2) The content of phosphorus in the polyester is generally in the range of 0.3 to 20%, more preferably 1 to 5%. If it is less than 0.3%, sufficient flame retardancy may not be obtained. On the other hand, if it exceeds 20%, the flexibility and electrical characteristics of the cured coating may be markedly deteriorated.

The blending amount of the element-containing polyester (A) which is soluble in an organic solvent is 0.5 to 50 mass%, preferably 1 to 20 mass%, in the whole composition.

When the amount is smaller than the above range, sufficient flame retardancy of the obtained cured film can not be obtained and good results can not be obtained even in the flexibility. On the other hand, when the amount is larger than the above range, the tack-free performance of the coating film deteriorates or the viscosity of the composition increases, which is not preferable.

Examples of industrial various organic solvents used in the element-containing polyester (A) soluble in an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, . 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, and more preferably do not promote the hydrolysis of the high molecular weight polyester resin compound.

As the carboxyl group-containing resin (B) contained in the flame-retardant photocurable resin composition of the present invention, a known resin compound containing a carboxyl group in the molecule can be used. Use of a carboxyl group-containing photosensitive resin (B ') having an ethylenically unsaturated double bond in the molecule is preferred because it can impart light curability and an alkali developable composition. The unsaturated double bond is preferably derived from a (meth) acrylic acid or a (meth) acrylic acid derivative. When only a carboxyl group-containing water having no ethylenically unsaturated double bond is used, it is necessary to use a photopolymerizable monomer (D) having two or more ethylenically unsaturated groups in the molecule in order to make the composition photocurable have.

As specific examples of the carboxyl group-containing resin (B), compounds (any of oligomers and polymers) listed below may be preferably used.

(1) 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 polycarbonate-based polyol, Containing carboxyl groups in a diol compound such as a polyol, a polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group Urethane resin.

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

(Meth) acrylate and (meth) acrylate in the synthesis of the resin of the above (1) or (2), and adding a compound having one hydroxyl group and at least one (meth) Acrylated urethane resin containing a carboxyl group.

(4) Addition of a compound having one isocyanate group and at least one (meth) acrylate group in the molecule, such as a conformal reaction product of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin of the above (1) or (2) And a (meth) acrylated carboxyl group-containing urethane resin.

(5) A carboxyl group-containing resin obtained by copolymerizing 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.

(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) a photosensitive carboxyl group-containing compound obtained by reacting a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin to react with (meth) acrylic acid and adding a dibasic acid anhydride to the resulting hydroxyl group Suzy.

(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).

Among these carboxyl group-containing resins, it is preferable that the isocyanate group of the carboxyl group-containing polyurethane resin (X), especially the isocyanate group of the isocyanate group-containing component of the urethane resin, is not directly bonded to the benzene ring from the viewpoint of photosensitivity and flexibility (Y) The polyfunctional epoxy resin used in the synthesis of the resins of (6) and (7) is a compound having a bisphenol A structure, a bisphenol F structure, a biphenol structure, a bis- , It is preferable from the viewpoint of heat resistance and flame retardancy. On the other side, the carboxyl group-containing polyurethane resins of the above (1), (2), (3) and (4) and the modified products such as those (9) have a urethane bond in the main chain. . In order to achieve compatibility between characteristics such as flexibility and solder heat resistance, the carboxyl group-containing urethane resin of the above-mentioned (1), (2), (3) (6), (7), (8), and modified substances such as those (9) are preferably used in combination.

Further, in the present specification, the term (meth) acrylate is generically referred to as acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin (B) 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 (B) is preferably in the range of 40 to 200 mgKOH / g, 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, And dissolves and peeled off as a developing solution without distinction between the unexposed portion and the unexposed portion, which makes it difficult to draw a normal resist pattern.

The weight average molecular weight of the carboxyl group-containing resin (B) 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. When the weight average molecular weight is less than 2,000, the tack-free performance of the coating film may be deteriorated, the moisture resistance of the coated film after exposure may deteriorate, the film may be reduced during development, and the resolution may be significantly lowered. 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 lowered.

The blending amount of the carboxyl group-containing resin (B) as described above is 10 to 60% by mass, preferably 20 to 50% by mass, in the total composition. If it is less than the above range, the coating film strength is undesirably lowered. On the other hand, if it is more than the above range, the viscosity of the composition tends to be high, and the coatability and the like are lowered.

As the photopolymerization initiator (C) used in the present invention, a known publicly known compound can be used.

As a particularly preferable photopolymerization initiator, there is a phosphorus-containing photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator having a group represented by the following general formula (II-1) can be preferably used.

≪ Formula (II-1) >

(Wherein R ⁵ and R ⁶ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy 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, provided that one of R ⁵ and R ⁶ may represent an RC (= O) - group (wherein R represents a hydrocarbon group having 1 to 20 carbon atoms)

Examples of the acylphosphine oxide-based photopolymerization initiator having a group represented by the above formula (II-1) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide , Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lucirin TPO manufactured by BASF Corporation, Irgacure (registered trademark) 819 manufactured by Ciba Specialty Chemicals, and the like.

Another preferred phosphorus-containing photopolymerization initiator is an initiator represented by the following formula (II-2), and a commercially available product is lucylline TPO-L manufactured by BASF.

≪ Formula (II-2) >

(In the formula, R ⁵ has the same meaning as defined above, R ⁷ and R ⁵ are independently C 1 -C 10 linear or branched alkyl group, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, An aryl group substituted with an alkyl group, and an RC (= O) - group (wherein R may represent a hydrocarbon group having 1 to 20 carbon atoms)

The blending amount of the phosphorus-containing photopolymerization initiator may be selected in the range of 1 to 80 parts by mass, preferably 2 to 50 parts by mass, based on 100 parts by mass of the carboxyl-containing resin (B).

As the photopolymerization initiator that can be added in addition to the phosphorus-containing photopolymerization initiator, there are oximeester-based photopolymerization initiator having a group represented by the following formula (III) and? -Aminoacetophenone-based photopolymerization initiator having a group represented by the following formula .

(III)

(Wherein R ⁸ 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) Lt; / RTI >

R ⁹ 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 atom), 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 ¹⁰ and R ¹¹ each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms,

R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two of these are bonded)

Preferred examples of the oxime ester-based photopolymerization initiator having the group represented by the above formula (III) include 2- (acetyloxyiminomethyl) thioxanthien-9-one represented by the following formula V, a compound represented by the following formula And a compound represented by the formula (VII).

(IV)

(V)

(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 a phenoxycarbonyl group And,

R ¹⁵ and R ¹⁷ 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 (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group) And,

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, (Which may have at least one oxygen atom), 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)

≪ Formula (VI)

(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,

and n and p each independently represent an integer of 0 to 5)

Among the above oxime ester-based photopolymerization initiators, 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by the above formula (V) and a compound represented by the above formula (VI) are more preferable. Commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, and N-1919 manufactured by Adeca Kabushiki Kaisha. 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 above formula (IV) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- (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.

The blending amount of the photopolymerization initiator (C) as described above can be selected from the range of 0.01 to 50 parts by mass, preferably 0.5 to 30 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (B). When the amount is less than 0.01 part by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating film properties such as chemical resistance are deteriorated. On the other hand, if it is more than 50 parts by mass, the light absorption at the surface of the solder resist coating film of the photopolymerization initiator (C) tends to be intensified and the deep portion curability tends to be lowered.

In the case of the oxime ester-based photopolymerization initiator having the group represented by the above formula (III), 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 carboxyl group-containing resin (B) Is preferably selected in the range of from 0.1 to 10 parts by mass.

Other 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.

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

Specific examples of the acetophenone compound are, for example, 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 are, for example, 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, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure such as 4,4'-dimethylaminobenzophenone (manufactured by Nippon Soda Co., Ltd., Nisseiure MABP), 4,4 (Diethylamino) -4-methyl-2H-1-benzopyran-2-one (7-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Dimethylaminobenzoate (Kayacure EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (manufactured by International Bio-Synthesis Co., Ltd.) (Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (manufactured by International Bio-Synthesis Inc., Quanta Cure BEA), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Division is solrol (Esolol) 507), 4,4'- diethylamino benzophenone (a product of Hodogaya Chemical Co., Ltd., EAB) on.

Of the above-mentioned compounds, thioxanthone compounds and tertiary amine compounds are preferred. The composition of the present invention preferably contains a thioxanthone compound in view of deep curability, and among these, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2 , And 4-diisopropylthioxanthone are preferable.

The amount of such a thioxanthone compound 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 (B). If the compounding amount of the thioxanthone compound is too large, the curability of the thick film deteriorates, leading to an increase in the cost of the product, which is not preferable.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable. 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 is low in toxicity. A coumarin compound containing a dialkylamino group having a maximum absorption wavelength of 350 to 410 nm has little coloring because it has a maximum absorption wavelength in the ultraviolet ray region, and a colorless transparent photosensitive composition as well as a coloring pigment reflecting the color of the coloring pigment itself It becomes possible to provide a solder resist film. 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 based on 100 parts by mass of the carboxyl group-containing resin (B). When the amount of the tertiary amine compound is less than 0.1 part by mass, sufficient increase or decrease effect can not be obtained. When the amount is more than 20 parts by mass, the light absorption on 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 (B). When the amount exceeds 35 parts by mass, the deep curing property tends to be lowered due to the light absorption.

As the photopolymerizable monomer (D) to be blended for forming an image with light in the composition of the present invention, a commonly known (meth) acrylate monomer may be used. As the conventionally known (meth) acrylate monomers, 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, propylene oxide adducts or caprolactone adducts thereof, Rheology; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; And polyhydric acrylates of glycidyl ethers such as urethane acrylates, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate of the polyhydric alcohols ; And melamine acrylate, and / or the respective methacrylates corresponding to the acrylate.

Of the above (meth) acrylate monomers, phosphorus-containing acrylates are preferable from the viewpoint of flame retardancy. For example, phosphate-based polyfunctional acrylates represented by trisacryloyloxyethyl phosphate or phosphorus-containing compound modified acrylates represented by the following formula (VIII) can be given.

≪ Formula (VIII)

(Wherein R ²⁵ is an acrylate residue and R ²⁶ and R ²⁷ are an acrylate derivative which is an organic group other than hydrogen or halogen)

Such a phosphorus-containing compound modified acrylate can be synthesized generally by Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with a commonly known polyfunctional acrylate .

In the photocurable resin composition of the present invention, a thermosetting resin (E) may be added as a thermosetting component in order to impart heat resistance. Particularly preferred are thermosetting components (E) having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule. Of these, bifunctional epoxy resins are preferred, and diisocyanates and multifunctional block isocyanates thereof can also be used.

The thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule may be a thermosetting component (E) having at least two, three or four or five membered cyclic ether groups or cyclic thioether groups For example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound (E-1), a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound (E -2), a compound having two or more thioether groups in the molecule, that is, an episulfide resin (E-3), and the like.

Examples of the polyfunctional epoxy compound (E-1) include jER828, jER834, jER1001, jER1004 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 840 manufactured by Dainippon Ink and Chemicals, Inc., Epiclon 850, Epiclon 1050, Epiclon 2055, Eptothets YD-011, YD-013, YD-127 and YD-128 manufactured by Dot Chemical Industries, DER317, DER331, DER661 and DER664 manufactured by Dow Chemical Co., Aralidite 6071, Araldite 6084, Araldite GY250, Araldite GY260, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Bisphenol A type epoxy resins such as AER330, AER331, AER661 and AER664 (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd.; JERYL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152 manufactured by Dainippon Ink and Chemicals, Inc., Epiclon 165, Epitot YDB-400, YDB-500 manufactured by Tokto Kasei 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, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 manufactured by Ciba Specialty Chemicals, EPPN-201, EOCN manufactured by Nippon Kayaku Co., Ltd., EOCN 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., Eportot YDF-170, YDF-175, YDF-2004 manufactured by Tokuga Seisaku Co., Ltd., Araldite manufactured by Ciba Specialty Chemicals, Bisphenol F type epoxy resin such as XPY306 (all trade names); Hydrogenated bisphenol A type epoxy resins such as Epotot ST-2004, ST-2007 and ST-3000 (trade name) manufactured by Tokuga Seisakusho; JER604 manufactured by Japan Epoxy Resin Co., Ltd., Eportot YH-434 manufactured by Toko Kasei Co., Araldite MY720 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Glycidylamine type epoxy resins; A hidanto-type epoxy resin such as Aralidite CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Alicyclic epoxy resins such as Celloxide 2021 manufactured by Daicel Chemical Industries, Ltd., Araldite 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 resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., and EXA-1514 (trade name) 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.; YL-931 manufactured by Japan Epoxy Resin Co., Ltd., Araldite 163 manufactured by Ciba Specialty Chemicals, Inc. (all trade names), tetraphenylol ethane type epoxy resin; Araldite PT810 manufactured by Ciba Specialty Chemicals Inc., TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); Biphenyl novolac resins such as NC-3000 and NC-3100 manufactured by Nippon Kayaku Co., Ltd., diglycidyl phthalate resins such as Bremer DGT manufactured by Nippon Oil and Fats Co., Ltd., Tetraglycidylcyloyl ethane resins such as ZX-1063 manufactured by Tokto Kasei Co., Ltd.; Epoxy resins containing naphthalene groups such as ESN-190, ESN-360, Dainippon Ink and Chemicals, Inc., HP-4032, EXA-4750 and EXA-4700 manufactured by Shinnitetsuga Chemical Co., 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 (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (e.g., YR-102 and YR-450 manufactured by Tokuga Seisakusho Co., Ltd.) But are not limited to these. These epoxy resins may be used alone or in combination of two or more. Among them, an epoxy resin having a biphenyl skeleton such as biphenyl novolak type epoxy resin is particularly preferable.

Examples of the polyfunctional oxetane compound (E-2) 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-ethyl-3-oxetanyl) methyl acrylate, In addition to polyfunctional oxetanes such as methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, poly (p-hydroxystyrene), cardo type bisphenols, calixarene, And ether compounds of a resin having a hydroxyl group such as ricin arene, silsesquioxane and the like. Other than these, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate may be mentioned.

Examples of the compound (E-3) having at least two cyclic thioether groups in the molecule include a bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd. 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 (E) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents, more preferably 0.8 to 3.0 equivalents based on 1 equivalent of the carboxyl group of the carboxyl group-containing resin (B) 2.0 equivalents. When the compounding amount of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is less than 0.6 equivalent, the carboxyl group remains in the solder resist film and the heat resistance, alkali resistance, . On the other hand, if it exceeds 2.5 equivalents, a low molecular weight cyclic (thio) ether group remains in the dried coating film, and the strength or the like of the coating film is lowered.

The photocurable resin composition of the present invention may further contain a phosphorus-containing compound as a flame-retardant auxiliary. The phosphorus-containing compound is preferably an organic phosphorus-based flame retardant which is publicly known and is preferably a phosphoric acid ester and a condensed phosphoric acid ester, a cyclic phosphazene compound, a phosphazene oligomer or a compound represented by the following formula (IX).

<Formula IX>

(Wherein R ²⁸ , R ²⁹ and R ³⁰ each independently represent a substituent other than a halogen atom)

Commercially available products of the compound of formula (IX) include HCA, SANKO-220, M-ESTER and HCA-HQ.

When a thermosetting component (E) having two or more 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 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Dicyandiamide; Amine compounds such as benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; Hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., U-CAT DBU, U-CAT SA102, U-CAT 5002 (both bicyclic amidine compounds and salts thereof), and the like can be given as examples of the isocyanate compound (trade name) 3503N and U-CAT 3502T (all trade names of block isocyanate compounds of dimethylamine). But are not limited to these, and it is preferable to accelerate the reaction of the epoxy resin and the oxetane compound with a thermosetting catalyst, or between the epoxy group and / or the oxetanyl group and the carboxyl group, and 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 S-triazine derivatives such as adducts can be used, and compounds which function also as these adhesion-imparting agents are preferably used in combination with the above-mentioned thermosetting catalyst.

The compounding amount of these thermosetting catalysts is usually sufficient in a usual quantitative ratio and is preferably in the range of, for example, 100 parts by mass of the carboxyl-containing resin (B) or the thermosetting component (E) having at least two cyclic (thio) Is 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

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

Blue colorant:

As a blue colorant, there are a phthalocyanine type and an anthraquinone type, and a pigment type is a compound classified as a pigment, specifically, a color index (CI) issued by The Society of Dyers and Colourists , Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

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

Green colorant:

Examples of the green colorant include phthalocyanine type, anthraquinone type and perylene type. 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. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Yellow colorant:

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. Specific examples of the yellow colorant 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.

Red colorant:

Examples of the red colorant include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. &Lt; / RTI &gt;

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.

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

Illustratively, pigments such as Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black 7, and the like.

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 (B).

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, at least one selected from the group consisting of an inorganic filler and an organic filler for a publicly known tube can be used, and inorganic fillers, particularly barium sulfate, spherical silica and talc, are preferably used. A white resist can also be obtained by adding titanium oxide as a white filler. In order to further impart flame retardancy, metal oxide fine particles may be added, and specific examples thereof include aluminum hydroxide, magnesium hydroxide, and boehmite. These fillers may be used alone or in combination of two or more.

The blending amount of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, particularly preferably 0.1 to 150 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (B). When the blending amount of the filler exceeds 300 parts by mass, the viscosity of the photo-curable resin composition becomes high and the printability is deteriorated or the cured product becomes weak.

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

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether And the like; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents are used alone or as a mixture of two or more kinds.

The photo-curable resin composition of the present invention can further contain, if necessary, a known thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, and phenothiazine, fine silica, organic bentonite , Montmorillonite and the like, antifoaming agents and / or leveling agents such as silicone, fluorine and polymeric agents, silane coupling agents such as imidazole, thiazole and triazole, antioxidants and rust inhibitors Can be blended.

The photo-curable resin composition of the present invention may be in the form of a dry film having a carrier film (support) and a layer comprising the photo-curable resin composition formed on the carrier film.

In the case of dry film formation, the photocurable resin composition of the present invention is diluted with the above organic solvent, adjusted to an appropriate viscosity, and then subjected to heat treatment such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, Spray coater or the like to a uniform thickness on the carrier film and dried at a temperature of usually 50 to 130 DEG C for 1 to 30 minutes to obtain a film. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 占 퐉, preferably 20 to 60 占 퐉 in film thickness after drying.

As the carrier film, a plastic film is used, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 mu m.

It is preferable to laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film after the film is formed on the carrier film.

As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. When the cover film is peeled off, It is preferable that the adhesive force of the adhesive agent is smaller.

Further, the photocurable resin composition or the dry film thereof according to the present invention is cured by being photo-cured on copper. The photo-curing may be performed by an ultraviolet exposure apparatus, but it may be cured by laser light having a wavelength of 350 to 410 nm.

Specifically, a dry film, a cured product, and a printed wiring board are formed as follows. That is, the photocurable resin composition of the present invention can be prepared by, for example, adjusting the viscosity with a suitable viscosity for the coating method with the above-mentioned organic solvent, and coating the substrate with a coating composition such as an immersion coating method, a flow coating method, a roll coating method, a bar coater method, Coating method or the like, and the organic solvent contained in the composition is volatilized (temporarily dried) at a temperature of about 60 to 100 ° C to form a tack-free coating film. The resin insulating layer can be formed by applying the composition on a carrier film, drying and winding the film as a film, bonding the photocurable resin composition layer on the substrate so as to contact the substrate, and peeling the carrier film. Thereafter, the resist film is selectively exposed to an active energy ray through a photomask having a pattern formed by a contact type (or noncontact type), and the unexposed portion is exposed with a dilute alkaline aqueous solution (for example, a 0.3 to 3% aqueous solution of sodium carbonate) And developed to form a resist pattern. Further, in the case of a composition containing the thermosetting component (E), for example, by heating to a temperature of about 140 to 180 ° C to thermoset, the carboxyl group of the carboxyl-containing resin (B) Curable component (E) having a cyclic thioether group and / or a cyclic thioether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption, adhesion, electrical properties and the like. In addition, even when the thermosetting component (E) is not contained, since the ethylenic unsaturated bonds remaining in the unreacted state during thermal exposure are subjected to thermal radical polymerization and the film properties are improved, (Heat curing) may be performed.

As the above substrate, in addition to a printed circuit board or a flexible printed circuit board formed in advance, a substrate made of a resin such as a paper-phenol resin, a paper-epoxy resin, a glass cloth-epoxy resin, a glass-polyimide, a glass cloth / (FR-4 and the like), polyimide film, PET film, glass substrate, glass substrate, and the like using all kinds of composites such as cloth / paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, A ceramic substrate, a wafer plate, or the like can be used.

The volatile drying performed after applying the photocurable resin composition of the present invention can be carried out by a hot-air circulating drying furnace, a hot plate, a convection oven or the like (a furnace equipped with a heat source of air heating by steam, Or a method of atomizing the support from a nozzle) can be used.

As described above, after the photocurable resin composition of the present invention is applied and volatilized and dried, the resulting coating film is exposed (irradiation of active energy rays). The coating film cures the exposed portion (the portion irradiated with the active energy ray).

Examples of the exposure device used for the active energy ray irradiation include a laser direct imaging device (laser direct imaging device), an exposure device equipped with a metal halide lamp, an exposure device equipped with a (high) pressure mercury lamp, an exposure device 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. If a laser beam having a maximum wavelength in the range of 350 to 410 nm is used as the active energy ray, it may be a gas laser or a solid laser. The exposure dose varies depending on the film thickness and the like, but it can be generally set within a range of 5 to 200 mJ / cm 2, preferably 5 to 100 mJ / cm 2, more preferably 5 to 50 mJ / cm 2. As the direct drawing apparatus, for example, 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.

The developing method can be carried out by a dipping method, a shower method, a spraying method, a brushing method or the like. As the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, have.

[Example]

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.

Examples 1 to 3, Comparative Examples 1 and 2

Each component shown in Table 1 was compounded in the ratio (mass part) shown in Table 1, preliminarily mixed with a stirrer, and then kneaded by a three-roll mill to prepare a photocurable and thermosetting resin composition for solder resist. Here, the degree of dispersion of the obtained photo-curable / thermosetting resin composition was evaluated by particle size measurement by a grid meter manufactured by Eric Sansa and found to be 15 占 퐉 or less.

Performance evaluation:

<Optimum exposure dose>

A circuit pattern substrate having a copper thickness of 35 占 퐉 was buffed and polished, washed with water, and then coated on the entire surface by a screen printing method to form a photocurable thermosetting resin composition of each of the examples and the comparative examples. And dried in a circulating drying furnace for 30 minutes. After drying, the film was exposed through a step tablet (Kodak No. 2) using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp and developed (30 ° C, 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution ) Was performed for 60 seconds, the remaining exposure amount of the step tablet was 6, and the optimum exposure amount was set.

Characteristic test:

The composition of each of the above Examples and Comparative Examples was coated on the patterned polyimide film substrate by screen printing, dried at 80 DEG C for 30 minutes, and allowed to cool to room temperature. The substrate was exposed to a solder resist pattern at an optimal exposure dose using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 캜 was sprayed under a pressure of 0.2 MPa And development was carried out for 60 seconds to obtain a resist pattern. The substrate was cured by heating at 150 DEG 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 soldering tank 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 by visual inspection were evaluated. The criteria are as follows.

○: No peeling was observed even if the immersion for 10 seconds was repeated twice or more.

△: slightly peeled if the immersion for 10 seconds was repeated twice or more.

×: Expansion and peeling were observed in the resist layer at one time of immersion for 10 seconds.

<Electroless gold plating resistance>

Plating was carried out using a commercially available electroless nickel plating bath and electroless gold plating bath under the conditions of nickel of 3 탆 and gold of 0.03 탆 and the presence or absence of peeling of the resist layer or permeation of the plating was evaluated by tape filling , And the presence or absence of peeling of the resist layer was evaluated by tape peeling. The criteria are as follows.

◎: Seeping and peeling were not observed.

○: Seeping after plating is slightly confirmed, but not peeled off after tape peeling.

?: Very slight seeping was observed after plating, and peeling was observed after tape peeling.

X: Peeling occurred after plating.

<Electrical Characteristics>

An evaluation board was prepared using the interdigital electrode B coupon of IPC B-25 in place of the copper foil substrate under the above-described conditions. A bias voltage of DC 100 V was applied to this interdigital electrode, The presence or absence of migration after 1,000 hours was confirmed. The criteria are as follows.

?: No change observed at all.

Δ: Very slight change.

X: Migration has occurred.

<Acid resistance>

The evaluation substrate was immersed in a 10 vol% H ₂ SO ₄ aqueous solution at room temperature for 30 minutes to confirm seepage, elution of the coating film, peeling by tape peeling. The criteria are as follows.

○: No seeping, leaching, peeling.

△: Seeping, leaching or peeling was confirmed a little.

X: Seeping, leaching or peeling was largely confirmed.

<Flammability>

The composition of each of the examples and the comparative examples was applied to a polyimide film (Capton 100H) having a thickness of 25 탆 by screen printing, dried at 80 캜 for 20 minutes, and cooled to room temperature. Further, the back side was similarly coated on the entire surface by screen printing, dried at 80 DEG C for 20 minutes, and cooled to room temperature to obtain a double-side coated substrate. A solder resist was exposed to the entire surface at an optimum exposure dose using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp mounted on the substrate, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 캜 was sprayed under a pressure of 0.2 MPa Development was carried out for 60 seconds, and thermal curing was carried out at 150 캜 for 60 minutes to obtain an evaluation sample. This flame retardancy evaluation sample was subjected to a thin film vertical burning test according to the UL94 standard. The evaluation is expressed as VTM-0 or VTM-1 based on the UL94 standard.

<Flexibility>

The composition of each of the examples and the comparative examples was applied to a 25 탆 polyimide film (Capton 100H) by screen printing, dried at 80 캜 for 30 minutes, and cooled to room temperature to obtain a one side coated substrate. A solder resist was exposed to the entire surface at an optimum exposure dose using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp mounted on the substrate, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 캜 was sprayed under a pressure of 0.2 MPa Development was carried out for 60 seconds, and thermal curing was carried out at 150 占 폚 for 60 minutes. The resulting sample was repeatedly bent 180 degrees by folding the joint with the solder resist as an outer side several times, and the state of occurrence of cracks in the coating film at this time was visually observed with an optical microscope of magnification 200 to evaluate the number of times that no crack occurred Respectively.

The results of each of the above evaluation tests are shown collectively in Table 2.

As shown in Table 2, in the case of Examples 1 to 3 using the photo-curable and thermosetting resin composition containing the organic solvent-soluble polyester containing the organic solvent of the present invention, the obtained cured film had excellent flame retardancy and flexibility , The solder heat resistance, the electroless gold plating resistance, the electrical characteristics, and the acid resistance, but Comparative Example 2 using the photo-curable / thermosetting resin composition containing no element-containing polyester which is soluble in an organic solvent did not have flame retardancy. On the other hand, in the case of Comparative Example 1 using a photo-curing / thermosetting resin composition containing a phosphorus-containing flame retardant that is common in place of an element-containing polyester which is soluble in an organic solvent, there is no problem in flame retardancy but the flexibility is deteriorated. The characteristics were not enough.

Example 4

The photocurable and thermosetting resin composition prepared in the same manner as in Example 1 was diluted with methyl ethyl ketone and applied on a carrier film and dried by heating to form a resin composition layer having a thickness of 20 占 퐉. Lt; / RTI &gt; Further, a cover film was bonded thereon to obtain a dry film. Thereafter, the cover film was peeled off and bonded to the patterned polyimide substrate using a laminator. (HMW-680-GW20) equipped with a metal halide lamp mounted thereon was used to expose a solder resist pattern at an optimal exposure dose, and the carrier film was peeled off. Thereafter, a 1 wt% Na ₂ CO ₃ aqueous solution And a spray pressure of 0.2 MPa for 60 seconds to obtain a substrate having a resist pattern formed thereon. Thereafter, heating and curing were carried out for 60 minutes with a hot air dryer at 150 캜 to prepare a test substrate. The test substrates having the obtained cured coatings were subjected to the evaluation tests of the respective characteristics in the same manner as the above-mentioned test method and evaluation method.

There was no problem with the handling properties of the obtained dry film, and the characteristics of the obtained dry film were almost equivalent to those of Example 1. [

Claims (9)

(A) an element-containing polyester which is soluble in an organic solvent, (B) a carboxyl group-containing resin and (C) a photopolymerization initiator,
Wherein the blending amount of the organic solvent-soluble element-containing polyester (A) is 0.5 to 50 mass% in the whole composition. The flame-retardant photocurable resin composition according to claim 1, further comprising (D) a photopolymerizable monomer. The flame-retardant photocurable resin composition according to claim 1, further comprising (E) a thermosetting resin. The flame-retardant photocurable resin composition according to claim 3, wherein the thermosetting resin (E) comprises an epoxy resin having a biphenyl skeleton. The flame-retardant photocurable resin composition according to claim 1, wherein the carboxyl group-containing resin (B) is a carboxyl group-containing polyurethane resin. The flame-retardant photocurable resin composition according to any one of claims 1 to 5, which is a solder resist. A flame-retardant photo-curable dry film obtained by applying and drying the flame-retardant photo-curable resin composition according to any one of claims 1 to 5 on a carrier film. A flame-retardant cured product obtained by curing a flame-retardant photo-curable resin composition according to any one of claims 1 to 5 or a dry film obtained by applying and drying the flame-retardant photo-curable resin composition on a carrier film. A flame-retardant photo-curable resin composition according to any one of claims 1 to 5 or a flame-retardant photo-curable resin composition obtained by coating a dry film obtained by applying and drying the flame-retardant photo-curable resin composition onto a carrier film, Wiring board.