KR20110039453A - 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 has a non-halogen composition, has a low environmental load, is excellent in both flame retardancy and storage stability, and is capable of forming a cured film rich in flexibility. Thereby, a printed wiring board in which a flame-retardant cured film such as solder resist is formed is provided.
A flame retardant photocurable resin composition contains (A) phosphazene compound which is liquid at room temperature, (B) carboxyl group-containing resin, and (C) photoinitiator. 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) thermosetting resin. Such a flame-retardant photocurable resin composition, especially the flame-retardant photocurable and thermosetting resin composition containing a thermosetting resin (E), can be used suitably as a soldering resist.

Description

Flame-retardant photocurable resin composition, its dry film and hardened | cured material, and the printed wiring board using these {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}

The present invention relates to a flame-retardant photocurable resin composition that can be developed by an aqueous alkali solution, in particular, a composition for soldering resists photocured by ultraviolet or laser exposure, a dry film and a cured product thereof, and a flame-retardant cured film formed by using the same. It relates to a printed wiring board having a.

Background Art Conventionally, printed wiring boards and flexible wiring boards (hereinafter, abbreviated as FPCs) have been required to be flame retardant in order to be mounted on electronic devices, and flame retardancy has also been required for solder resists which are part of them. 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 of both the printed wiring board and the FPC, the burden of flame retardation on the solder resist is relatively high in the case of the FPC of the thin film.

Therefore, various proposals have been made regarding flame retardation of a soldering resist conventionally. For example, Japanese Patent Laid-Open No. 2007-10794 (Patent Document 1) discloses polymerizable ethylenic unsaturated such as halogenated aromatic rings such as (a) a binder polymer, (b) a bromophenyl group, and a (meth) acryloyl group. A flame-retardant photosensitive resin composition for FPC containing a photopolymerizable compound having a bond in a molecule, (c) a photopolymerization initiator, (d) a block isocyanate compound and (e) a phosphorus-containing compound having a phosphorus atom in a molecule has been proposed. . However, the use of a halogen compound such as a compound having a unsaturated double bond which can be polymerized with a halogenated aromatic ring is not preferable from the viewpoint of environmental load.

In contrast, Japanese Patent Laid-Open No. 2001-75270 (Patent Document 2) discloses (a) an epoxy acrylate resin, (b) an epoxy resin, (c) a diluent, (d) a curing agent, (e) a curing accelerator, and (f) A) sensitizer, (g) phosphazene oligomer and (h) inorganic filler as essential components, and the phosphazene oligomer of (g) is contained at a ratio of 2 to 50% by weight based on the whole resin composition. In the photosensitive resin composition of Unexamined-Japanese-Patent No. 2005-283762 (patent document 3), (a) the resin component which has a (meth) acryloyl group and a carboxyl group in 1 molecule, and is soluble in a alkali solution, (b) A photosensitive composition containing a thermosetting component, (c) photoinitiator, (d) phosphazene compound and (e) diluent has been proposed. However, the phosphazene compounds exemplified in these have been found to be a phenomenon in which once dissolved in the photosensitive composition is recrystallized during storage, or a crystal is precipitated over time after the composition is applied and dried. Since there was a problem in stability as a film, only a very small amount of the phosphazene compound could be used, and the effect of flame retardancy was very low.

Japanese Patent Laid-Open No. 2007-10794 (claims) Japanese Patent Laid-Open No. 2001-75270 (claims) Japanese Patent Laid-Open No. 2005-283762 (claims)

The present invention has been made in view of the prior art as described above, has a non-halogen composition, has a low environmental load, excellent flame retardancy and storage stability, abundant flexibility of the cured film, and good adhesion to various substrates. It is an object to provide a flame-retardant photocurable resin composition which can form a fine patterned cured film excellent in solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, and the like, and particularly suitable for FPC.

Moreover, the objective of this invention is a flame-retardant dry film and hardened | cured material excellent in the various characteristics as mentioned above obtained by using such a photocurable resin composition, and a flame-retardant hardened film, such as a soldering resist, by the said dry film or hardened | cured material. It is providing the printed wiring board formed.

According to the present invention for achieving the above object, there is provided a flame-retardant photocurable resin composition comprising (A) a phosphazene compound that is liquid at room temperature, (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. In addition, "room temperature" herein means a working room temperature, generally 20 to 30 ℃, typically 25 ℃.

In a preferable embodiment, it further contains (D) a photopolymerizable monomer, or further contains (E) thermosetting resin. It is preferable that the said thermosetting resin (E) contains the epoxy resin which has a biphenyl skeleton. Such a flame-retardant photocurable resin composition, especially the flame-retardant photocurable thermosetting resin composition containing a thermosetting resin (E), can be used suitably as a soldering resist.

Moreover, according to this invention, the flame-retardant photocurable dry film obtained by apply | coating and drying the said flame-retardant photocurable resin composition on a carrier film, and the flame-retardant hardened | cured material obtained by hardening the said flame-retardant photocurable resin composition or the dry film are also provided.

Moreover, according to this invention, the printed wiring board which has a flame-retardant cured film obtained by hardening the said flame-retardant photocurable resin composition or a dry film is also provided.

The flame-retardant photocurable resin composition of the present invention uses a phosphazene derivative which is liquid at room temperature together with a carboxyl group-containing resin, so that once dissolved in the photosensitive composition is recrystallized during storage or time-lapsed after application drying. Since there is no phenomenon of precipitation of crystals, the phosphazene compound can be blended in a relatively large amount, the effect of flame retardancy is greatly increased, and the stability as a liquid composition and a dry film is excellent. Therefore, it has a non-halogen composition, has a low environmental load, excellent flame retardancy, abundant flexibility of the cured film, and excellent adhesion to various substrates, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, and the like. The cured film of a fine pattern can be formed.

Therefore, the flame-retardant photocurable resin composition of this invention can be advantageously applied to formation of a flame-retardant cured film, such as a printed wiring board, especially the soldering resist of FPC.

As mentioned above, the characteristic of the flame-retardant photocurable resin composition of this invention is that it uses the phosphazene compound (A) which is liquid at room temperature with carboxyl group-containing resin (B). As a result, there is no phenomenon in which once dissolved in the photosensitive composition is recrystallized during storage, or crystals precipitate over time after application drying, and stability as a liquid composition and a dry film is excellent.

The phosphazene compound (A) which is liquid at room temperature contained in the flame-retardant photocurable resin composition of the present invention is a liquid or liquid viscous at 25 ° C, and preferably has the characteristics exemplified in the following conditions. desirable.

No halogens (other than ionic impurities).

-5% weight loss is 260 degreeC or more.

-A compound having a structure represented by the following formula (I).

<Formula I>

(In formula, m is an integer of 3-15, R <^1> , R <^2> is respectively independently group chosen from a C1-C6 alkyl group, an alkenyl group, and an aryl group, or a C1-C12 alkyl group, an alkenyl group, and An alkoxy group having 1 to 12 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, which may be substituted with at least one group selected from an aryl group)

In addition, the phosphazene compound represented by General formula (I) may be linear or cyclic, may be a some mixture, and may have molecular weight distribution.

In order for the phosphazene compound (A) to maintain a liquid phase at room temperature, in Formula 1, R ¹ and R ² are each independently asymmetrical or independently different substituents, and R ¹ and R ² from the viewpoint of heat resistance More preferably has at least one organic group substituted or unsubstituted phenoxy structure. In general, the smaller the number of m is, the stronger the crystallization is, but it is more soluble in a diluent to be treated as a photosensitive composition, and is often recrystallized over time in a state where the composition is cooled or dried. Therefore, liquefaction is achieved by controlling the molecular weight distribution of cyclic | annular object or linear substance, the kind of R <^1> , R <^2> , etc. in a manufacturing step. As a specific example of the phosphazene compound (A) which is liquid at room temperature, Fushimi Seiyakusho Co., Ltd., FP-366, FP-390, etc. are mentioned.

The compounding quantity of the phosphazene compound (A) which is liquid at the said room temperature is 0.5-30 mass% in the whole composition, Preferably it is 1-20 mass%.

When less than the said range, sufficient flame retardance of the hardened film obtained is not obtained and a favorable result is not obtained even in flexibility. On the other hand, when more than the said range, since the tack free performance of a coating film falls or the viscosity of a composition becomes high, it is unpreferable.

As carboxyl group-containing resin (B) contained in the flame-retardant photocurable resin composition of this invention, the well-known conventional resin compound which contains a carboxyl group in a molecule | numerator can be used. Moreover, when carboxyl group-containing photosensitive resin (B ') which has an ethylenically unsaturated double bond in a molecule | numerator is used, since it can provide photocurability and becomes an alkali developable composition, it is preferable. Moreover, it is preferable that this unsaturated double bond originates in a (meth) acrylic acid or a (meth) acrylic acid derivative. In addition, when using only the carboxyl group-containing resin which does not have an ethylenically unsaturated double bond, in order to make a composition photocurable, it is necessary to use together the photopolymerizable monomer (D) which has two or more ethylenically unsaturated groups in the molecule mentioned later. have.

As a specific example of carboxyl group-containing resin (B), the compound (it may be any of an oligomer and a polymer) listed below can be used preferably.

(1) diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid; and polycarbonate-based polyols and polyethers Carboxyl group containing by polyaddition reaction of diol compounds, such as a compound polyol, a polyester type polyol, a polyolefin type polyol, an acryl type polyol, a bisphenol A alkylene oxide adduct diol, a compound which has a phenolic hydroxyl group and an alcoholic hydroxyl group, etc. Urethane resin.

(2) bifunctional epoxy resins such as diisocyanate and bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and nonphenol type epoxy resin Photosensitive carboxyl group-containing urethane resin by the polyaddition reaction of a (meth) acrylate or its partial acid anhydride modified substance, a carboxyl group-containing dialcohol compound, and a diol compound.

(3) In the synthesis | combination of resin of said (1) or (2), the compound which has one hydroxyl group and one or more (meth) acryl groups in molecule | numerators, such as hydroxyalkyl (meth) acrylate, is added, and a terminal (meth) Acrylated carboxyl group-containing urethane resin.

(4) A compound having one isocyanate group and one or more (meth) acryl groups in a molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, is added during the synthesis of the resin (1) or (2). And terminal (meth) acrylated carboxyl group-containing urethane resin.

(5) Carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated group containing compounds, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

(6) Photosensitive carboxyl group-containing resin which made (meth) acrylic acid react with the bifunctional or more than one polyfunctional (solid) epoxy resin mentioned later, and added dibasic acid anhydride to the hydroxyl group which exists in a side chain.

(7) Containing the photosensitive carboxyl group which (meth) acrylic acid reacted with the polyfunctional epoxy resin which epoxidized the hydroxyl group of bifunctional (solid) epoxy resin further by epichlorohydrin, and added the dibasic acid anhydride to the produced hydroxyl group. Suzy.

(8) The carboxyl group-containing polyester resin which made dicarboxylic acid react with the bifunctional oxetane resin as mentioned later, and added dibasic acid anhydride to the produced | generated primary hydroxyl group.

(9) Photosensitive carboxyl group-containing resin formed by adding the compound which has one epoxy group and one or more (meth) acryl groups in 1 molecule further to resin of said (1)-(8).

Among these carboxyl group-containing resins, preferred are (X) carboxyl group-containing polyurethane resins, in particular, that the isocyanate group of the component (including diisocyanate) having an isocyanate group of the urethane resin is not directly bonded to the benzene ring in view of photosensitivity and flexibility. Preferably, (Y) the polyfunctional epoxy resin used for the synthesis | combination of the resin of said (6), (7) is a compound which has a bisphenol A structure, a bisphenol F structure, a biphenol structure, a bissilenol structure, and its hydrogenated compound In the case of, it is preferable from the viewpoint of heat resistance and flame retardancy. In addition, in another aspect, the carboxyl group-containing polyurethane resins of (1), (2), (3), and (4) and modified substances such as these (9) have a urethane bond in the main chain, so It is preferable for. Moreover, in order to make compatible characteristics, such as flexibility and solder heat resistance, the carboxyl group-containing urethane resin of said (1), (2), (3), (4), and modified | denatured material like these (9), and (5) ), (6), (7) and (8) are most preferably used in combination with a carboxyl group-containing resin and modified substances such as those (9).

In addition, in this specification, (meth) acrylate is a term which generically mentions acrylate, methacrylate, and a mixture thereof, and is the same also about another similar expression.

Since carboxyl group-containing resin (B) mentioned above has many free carboxyl groups in the side chain of a backbone polymer, image development by a rare alkali aqueous solution is attained.

Moreover, it is preferable that the acid value of the said carboxyl group-containing resin (B) exists in the range of 40-200 mgKOH / g, More preferably, it exists in the range of 45-120 mgKOH / g. Alkaline development becomes difficult when the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developing solution proceeds, so that the line becomes thinner than necessary or in some cases the exposed portion. It is not preferable because it dissolves and peels off with a developer without distinguishing between and unexposed portions, and drawing a normal resist pattern becomes difficult.

Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (B) changes with resin frame | skeleton, it is preferable to exist in the range of 2,000-150,000 normally, and also 5,000-100,000. When the weight average molecular weight is less than 2,000, the tack free performance of a coating film may fall, the moisture resistance of the coating film after exposure may deteriorate, the film | membrane decrease may arise at the time of image development, and the resolution may fall largely. On the other hand, when a weight average molecular weight exceeds 150,000, developability may remarkably deteriorate and storage stability may fall.

The compounding quantity of carboxyl group-containing resin (B) as mentioned above is 10-60 mass% in the whole composition, Preferably it is 20-50 mass%. When less than the said range, since coating film strength falls, it is unpreferable. On the other hand, when more than the said range, since a viscosity of a composition becomes high, applicability | paintability, etc. fall, it is not preferable.

As a photoinitiator (C) used for this invention, a well-known conventional compound can be used.

Particularly preferred photopolymerization initiators include phosphorus element-containing photopolymerization initiators, and have an effect of improving flame retardancy while being a photopolymerization initiator. As such a phosphorus element containing photoinitiator, the acyl phosphine oxide type photoinitiator which has group represented by following formula (II-1) can be used preferably.

<Formula II-1>

(In formula, R <^3> and R <^4> is respectively independently a C1-C10 linear or branched alkyl group, C1-C10 linear or branched alkoxy group, 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 ³ and R ⁴ represents an RC (= O) -group, where R may represent a hydrocarbon group of 1 to 20 carbon atoms

As an acyl phosphine oxide type photoinitiator which has group represented by the said Formula (II-1), 2,4,6-trimethyl benzoyl diphenyl phosphine oxide and bis (2,4,6- trimethyl benzoyl) -phenyl phosphine oxide And bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like. Examples of commercially available products include Lucirin TPO manufactured by BASF Corporation, Irgacure (registered trademark) 819 manufactured by Ciba Specialty Chemicals, Inc., and the like.

As another preferable phosphorus element containing photoinitiator, it is an initiator represented by following formula (II-2), As a commercial item, there exists the rucillin TPO-L by BASF Corporation.

<Formula II-2>

(Wherein R ³ has the same meaning as described above, R ⁵ and R ³ are independently a linear or branched alkyl group having 1 to 10 carbon atoms, cyclohexyl group, cyclopentyl group, aryl group, or halogen atom, An aryl group substituted with an alkyl group, and may represent an RC (= O) -group, where R represents a hydrocarbon group having 1 to 20 carbon atoms

The compounding quantity of such a phosphorus element containing photoinitiator can be selected in 1-80 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B), Preferably it is 2-50 mass parts.

As a photoinitiator which can be added other than a phosphorus element containing photoinitiator, the oxime ester system photoinitiator which has group represented by following formula (III), and the (alpha)-amino acetophenone system photoinitiator which has group represented by following formula (IV) are mentioned. .

<Formula III>

<Formula IV>

Wherein R ⁶ is a hydrogen atom, a phenyl group (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 (may be substituted with one or more hydroxyl groups, or an alkyl chain May have one or more oxygen atoms in the middle of), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (may be substituted with an alkyl or phenyl group having 1 to 6 carbon atoms) Indicates,

R ⁷ may be substituted with 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 (may be substituted with one or more hydroxyl groups, and one or more oxygen in the middle of the alkyl chain; 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 (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),

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

R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkylether group in which these two are bonded)

As an oxime ester photoinitiator which has group represented by the said Formula (III), Preferably, 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by following formula (V), the compound represented by following formula (VI), and the following The compound represented by general formula (VII) is mentioned.

(V)

<Formula VI>

(In formula, R <^12> is a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, a C2-C12 alkanoyl group, a C2-C12 thing. An alkoxycarbonyl group (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, or may have one or more oxygen atoms in the middle of the alkyl chain), or a phenoxycarbonyl group Indicate,

R ¹³ and R ¹⁵ are each independently a phenyl group (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 (may be substituted with one or more hydroxyl groups, 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 (may be substituted with an alkyl or phenyl group having 1 to 6 carbon atoms) Indicate,

R ¹⁴ is a hydrogen atom, a phenyl group (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 (may be substituted with one or more hydroxyl groups, and 1 in the middle of the alkyl chain) May have one or more oxygen atoms), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group)

<Formula VII>

(Wherein, R ¹⁶ , R ¹⁷ and R ²² each independently represent an alkyl group having 1 to 12 carbon atoms,

R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

M represents O, S or NH,

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

Among the above-mentioned oxime ester photoinitiators, 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by the formula (V) and the compound represented by the formula (VI) are more preferable. Examples of commercially available products include CGI-325 manufactured by Ciba Specialty Chemicals, Irgacure OXE01, Irgacure OXE02, and N-1919 manufactured by Adeka Corporation. These oxime ester photoinitiators can be used individually or in combination of 2 or more types.

Examples of the α-aminoacetophenone-based photopolymerization initiator having a group represented by the above formula (IV) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl ) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone, etc. are mentioned. As a commercial item, Irgacure 907, Irgacure 369, Irgacure 379 by Ciba Specialty Chemicals, etc. are mentioned.

The compounding quantity of photoinitiator (C) as mentioned above can be chosen in 0.01-50 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B), Preferably it is 0.5-30 mass parts. If it is less than 0.01 mass part, since photocurability in copper phase is inferior and a coating film peels off or coating film properties, such as chemical resistance, fall, it is unpreferable. On the other hand, when it exceeds 50 mass parts, since the light absorption in the soldering resist coating film surface of a photoinitiator (C) becomes severe and deep-curing property tends to fall, it is unpreferable.

In addition, in the case of the oxime ester photoinitiator which has a group represented by the said Formula (III), the compounding quantity becomes like this. Preferably it is 0.01-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B), More preferably, 0.01-5 It is preferable to select in the range of mass parts.

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

As a specific example of a benzoin compound, it is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, for example.

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

As an example of an anthraquinone compound, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, and 1-chloro anthraquinone are mentioned, for example.

As a specific example of a thioxanthone compound, it is 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, 2, 4- diisopropyl thioxanthone, for example.

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

As a specific example of a benzophenone compound, for example, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyl diphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4-benzoyl -4'-propyldiphenylsulfide.

As a specific example of a tertiary amine compound, For example, an ethanolamine compound, the compound which has a dialkylaminobenzene structure, for example, 4,4'- dimethylamino benzophenone (The Nippon Soda company make, Nissocure MABP), 4,4 Dialkylaminobenzophenones such as' -diethylaminobenzophenone (manufactured by Hodogaya Chemical Co., EAB), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- Dialkylamino group-containing coumarin compounds, such as (diethylamino) -4-methylcoumarin), 4-dimethylaminobenzoate ethyl (Nippon Kayaku Co., Kayacure EPA), 2-dimethylaminobenzoate ethyl (International Bio-synthetics company Preparation, Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (International Bio-Synthetics Co., Ltd., Quantacure BEA), p-dimethylaminobenzoic acid isoamylethyl ester (Nippon Kayaku Co., Ltd.) Manufacture, Kayacure DMBI), 2-ethylhexyl 4-dimethylaminobenzoic acid (Van Dyk) Division is solrol (Esolol) 507), 4,4'- diethylamino benzophenone (a product of Hodogaya Chemical Co., Ltd., EAB) on.

Among the above compounds, thioxanthone compounds and tertiary amine compounds are preferable. It is preferable that the thioxanthone compound is contained in the composition of the present invention from the viewpoint of deep hardening, and in particular, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2 Thioxanthone compounds, such as a 4-4-isoiso thioxanthone, are preferable.

As a compounding quantity of such a thioxanthone compound, Preferably it is 20 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin (B), More preferably, the ratio of 10 mass parts or less is preferable. When the compounding quantity of a thioxanthone compound is too large, since thick film sclerosis | hardenability will fall and it will lead to the cost increase of a product, it is unpreferable.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and 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 of its low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm is less colored because the maximum absorption wavelength is in the ultraviolet region, and is a colored solder using a colorless transparent photosensitive composition as well as a color pigment to reflect the color of the color pigment itself. It is possible to provide a resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

As a compounding quantity of such a tertiary amine compound, Preferably it is 0.1-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B), More preferably, it is the ratio of 0.1-10 mass parts. When the compounding quantity of a tertiary amine compound is 0.1 mass part or less, there exists a tendency for sufficient sensitization effect to not be acquired. When it exceeds 20 mass parts, there exists a tendency for the light absorption in the surface of the dry solder resist coating film by a tertiary amine compound to become severe, and deep-curing property falls.

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

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

As a photopolymerizable monomer (D) mix | blended in order to form an image with light to the composition of this invention, a conventionally well-known (meth) acrylate monomer can be used. As a typical well-known (meth) acrylate monomer, Diacrylates of glycol, such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, propylene glycol; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or polyhydric alcohols such as ethylene oxide adducts, propylene oxide adducts or caprolactone adducts Rates; Polyhydric acrylates, such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols; And polyhydric acrylates of glycidyl ethers such as urethane acrylates, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate of the above polyalcohols. ; And melamine acrylate, and / or each methacrylate corresponding to the acrylate.

Among the (meth) acrylate monomers, phosphorus element-containing acrylate is preferred from the viewpoint of flame retardancy. For example, the phosphate type polyfunctional acrylate represented by trisacryloyl oxyethyl phosphate, or the phosphorus containing compound modified acrylate specifically, represented by following formula (VIII) is mentioned.

<Formula VIII>

Wherein R ²³ is an acrylate residue and R ²⁴ and R ²⁵ are acrylate derivatives which are organic groups other than hydrogen or halogen.

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

In order to provide heat resistance, the thermosetting resin (E) can be added to the photocurable resin composition of this invention as a thermosetting component. Especially 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. Among these, a bifunctional epoxy resin is preferable, and other than that, diisocyanate and its polyfunctional block isocyanate can also be used.

The thermosetting component (E) which has a 2 or more cyclic (thio) ether group in such a molecule | numerator is a 3, 4 or 5 member cyclic cyclic ether group, or cyclic thioether group, or any 2 or more types of 2 or more types of groups Compound having, for example, a compound having at least two or more epoxy groups in a molecule, that is, a polyfunctional epoxy compound (E-1), a compound having at least two or more oxetanyl groups in a molecule, that is, a polyfunctional oxetane compound (E -2), the compound which has 2 or more thioether group in a molecule | numerator, namely episulfide resin (E-3), etc. are mentioned.

Examples of the polyfunctional epoxy compound (E-1) include jER828, jER834, jER1001, jER1004 manufactured by Japan Epoxy Resin Co., Ltd., Epiclone 840, Epiclone 850, Epiclone 1050, manufactured by Dainippon Ink & Chemicals Co., Ltd. Epiclone 2055, Efotot YD-011, YD-013, YD-013, YD-127, YD-128 manufactured by Toto Kasei Co., Ltd., DER317, DER331, DER661, DER664, manufactured by Dow Chemical Co., Ltd. Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260, Sumitomo Ega-01, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. Bisphenol-A epoxy resins such as manufactured AER330, AER331, AER661, and AER664 (all of which are trade names); JERYL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclone 152, Epiclone 165, manufactured by Dainippon Ink Industries, Ltd., Efotot YDB-400, YDB-500, manufactured by Tohto Kasei Co., Ltd., DER542, Shiva, manufactured by Dow Chemical Co., Ltd. Brominated epoxy resins such as Araldite 8011 manufactured by Specialty Chemicals, Sumi-Epoxy ESB-400, ESB-700, manufactured by Asamihi Kasei Kogyo Co., Ltd., and AER711 and AER714 (all of which are trade names); JER152, jER154 made in Japan epoxy resin company, DEN431, DEN438 made by Dow Chemical Co., Ltd., Epiclone N-730, Epiclone N-770, Epiclone N-865, Dotogase Co., Ltd. Efotot YDCN-701, YDCN-704, Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN -1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Kagaku Kogyo Co., Ltd. Sumi-Epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo AERECN-235, ECN-299, etc. (all Novolak type epoxy resins; Araldite of epiclon 830, Japan epoxy resin company production, jER807, Toto Kasei Co., Ltd. make Epotot YDF-170, YDF-175, YDF-2004, Shiba Specialty Chemicals company make Bisphenol F-type epoxy resins, such as XPY306 (all are brand names); Hydrogenated bisphenol A epoxy resins, such as Efotot ST-2004, ST-2007, and ST-3000 (brand name) by a Toto Kasei company; Of jER604 made in Japan epoxy resin company, Etoport YH-434 made by Toto Kasei Co., Araldite MY720 made by Ciba specialty chemicals company, Sumi-epoxy ELM-120 made by Sumitomo Chemical Co., Ltd. (all brand names) Glycidylamine type epoxy resins; Hydantoin type epoxy resins, such as Araldite CY-350 (brand name) by the Ciba Specialty Chemicals company; Alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd., Araldite CY175, CY179 manufactured by Ciba Specialty Chemicals, Inc. (both trade names); Trihydroxyphenylmethane type epoxy resins such as YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T.E.N., EPPN-501, EPPN-502 manufactured by Dow Chemical Co., Ltd. (both trade names); Bixylenol type or biphenol type epoxy resins, such as YL-6056, YX-4000, and YL-6121 (all are brand names) by the Japan epoxy resin company, or mixtures thereof; Bisphenol S type epoxy resins, such as Nippon Kayaku Co., Ltd. make, EBPS-200, Asahi Denka Kogyo Co., Ltd. make, EPX-30, and EXA-1514 (brand name) by Dainippon Ink & Chemicals Co., Ltd .; Bisphenol A novolak-type epoxy resins, such as jER157S (brand name) by the Japan epoxy resin company; Tetraphenylolethane type epoxy resins such as YL-931 manufactured by Japan Epoxy Resin Co., Ltd. and Araldite 163 manufactured by Ciba Specialty Chemicals Co., Ltd. (both trade names); Heterocyclic epoxy resins such as Araldite PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (both trade names); Diglycidyl phthalate resins such as biphenyl novolak resins such as NC-3000 and NC-3100 manufactured by Nippon Kayaku Co., Ltd., Nippon Yushi Co., Ltd., Bremer DGT; Tetraglycidyl xylenoylethane resins such as those manufactured by Tohto Kasei Co., Ltd., ZX-1063; Naphthalene group-containing epoxy resins such as those manufactured by Shin-Nitetsu Chemical Co., Ltd., ESN-190, ESN-360, and Dai Nippon Ink Chemical Co., Ltd., HP-4032, EXA-4750, and EXA-4700; Epoxy resin which has dicyclopentadiene frame | skeleton, such as the Dai Nippon Ink Industries Co., Ltd. product, HP-7200, HP-7200H; Glycidyl methacrylate copolymer type epoxy resins such as Nippon Yushi Co., Ltd. product, CP-50S, CP-50M; Copolymerized epoxy resins of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., Daicel Chemical Industries, Ltd., PB-3600), CTBN-modified epoxy resins (e.g., YR-102, YR-450, manufactured by Toto Kasei Co., Ltd.), and the like. However, it is not limited to these. These epoxy resins can be used individually or in combination of 2 or more types. Among these, epoxy resins having a biphenyl skeleton such as biphenyl novolac epoxy resins are particularly preferred.

Examples of the polyfunctional oxetane compound (E-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1 , 4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3- Oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl methacrylate and oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly (p-hydroxystyrene), cardo bisphenols, calyx arenes and calyx rezo And etherates of resins having hydroxyl groups such as lecinarene or silsesquioxane. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As a compound (E-3) which has two or more cyclic thioether group in the said molecule | numerator, bisphenol-A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned, for example. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used using the same synthesis method.

The compounding quantity of the thermosetting component (E) which has a 2 or more cyclic (thio) ether group in the said molecule | numerator becomes like this. Preferably it is 0.6-2.5 equivalent, More preferably, 0.8-0.01 with respect to 1 equivalent of carboxyl group of the said carboxyl group-containing resin (B). It is in the range of 2.0 equivalent. When the compounding quantity of the thermosetting component (E) which has two or more cyclic (thio) ether group in a molecule | numerator is less than 0.6 equivalent, since a carboxyl group remains in a soldering resist film and heat resistance, alkali resistance, electrical insulation, etc. fall, it is unpreferable. . On the other hand, when it exceeds 2.5 equivalent, since the low molecular weight cyclic (thio) ether group remains in a dry coating film, since the intensity | strength of a coating film, etc. fall, it is unpreferable.

The photocurable resin composition of this invention may contain a phosphorus containing compound further as a flame retardant adjuvant. As a phosphorus containing compound, what is conventionally known as an organic phosphorus flame retardant is preferable, and there exist a phosphate ester, a condensed phosphate ester, a cyclic phosphazene compound, a phosphazene oligomer, or the compound represented by following General formula (IX).

<Formula IX>

(Wherein R ²⁶ , R ²⁷ and R ²⁸ each independently represent a substituent other than a halogen atom)

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

When using the thermosetting component (E) which has a 2 or more cyclic (thio) ether group in the said molecule, it is preferable to contain a thermosetting catalyst. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-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, 4-methyl-N, N-dimethylbenzylamine; Hydrazine compounds such as adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. Moreover, as what is marketed, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole compound) by Shikoku Kasei Kogyo Co., Ltd. Trademark) 3503N, U-CAT 3502T (all are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CAT SA102, U-CAT 5002 (all bicyclic amidine compounds and salts thereof) and the like. It is not specifically limited to these, It is preferable to accelerate reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, You may use individually or in mixture of 2 or more types. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri 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 an adduct, can be used, Preferably, the compound which also functions as these adhesive imparting agents is used together with the said thermosetting catalyst.

The compounding quantity of these thermosetting catalysts is sufficient in a normal quantitative ratio, For example, it is preferable with respect to 100 mass parts of thermosetting components (E) which have two or more cyclic (thio) ether groups in a carboxyl group-containing resin (B) or a molecule | numerator. Is 0.1-20 mass parts, More preferably, it is 0.5-15.0 mass parts.

The photocurable resin composition of this invention can mix | blend a coloring agent. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from a viewpoint of reducing environmental load and an influence on a human body.

Blue colorant:

As the blue colorant, there are phthalocyanine-based and anthraquinone-based, and the pigment-based compound is classified as Pigment, specifically, the following color index (CI; issued by The Society of Dyers and Colourists) is assigned. Examples include: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

As a dye system, 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. can be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:

As the green colorant, there are phthalocyanine series, anthraquinone series, and perylene series. Similarly, 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, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:

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

Anthraquinone series: solvent yellow 163, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, pigment yellow 202.

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

Condensation azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

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

Monoazo series: 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, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone and quinacridone. It can be mentioned.

Monoazo series: 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 meter: Pigment Red 37, 38, 41.

Monoazo Lake system: Pigment Red 48: 1, 48: 2, 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 series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224 .

Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensation azo system: 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 series: 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, can also be added for the purpose of adjusting a color tone.

Specifically, 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 43, 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 There are 23 Brown, CI Pigment Brown 25, CI Pigment Black 1, and CI Pigment Black 7.

Although the mixing | blending ratio of a coloring agent as above is not restrict | limited, Preferably it is 0-10 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B), The ratio of 0.1-5 mass parts is especially preferable.

The filler of the photocurable resin composition of this invention can be mix | blended as needed in order to raise the physical strength of the coating film, etc. As such a filler, at least one selected from the group consisting of known conventional inorganic fillers and organic fillers can be used, but inorganic fillers, in particular barium sulfate, spherical silica and talc, are preferably used. Moreover, it can also be set as white resist by adding titanium oxide as a white filler. Further, in order to further impart flame retardancy, fine particles of metal oxides may be added, and specific examples thereof include aluminum hydroxide, magnesium hydroxide, boehmite, and the like. These fillers can be mix | blended individually or in combination of 2 or more types.

The compounding quantity of these fillers becomes like this. Preferably it is 300 mass parts or less, More preferably, it is 0.1-300 mass parts, Especially preferably, it is 0.1-150 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B). When the compounding quantity of a filler exceeds 300 mass parts, since the viscosity of a photocurable resin composition becomes high and printability falls or a hardened | cured material becomes weak, it is unpreferable.

Moreover, the organic solvent can be used for the photocurable resin composition of this invention for the synthesis | combination of the said carboxyl group-containing resin (B), manufacture of a composition, or viscosity adjustment for apply | coating to a board | substrate or a carrier film.

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

The photocurable resin composition of this invention is further, if necessary, thermally inhibiting inhibitors well-known and common, such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, and phenothiazine, fine-grained silica, organic bentonite Known conventional thickeners, such as montmorillonite, antifoaming agents and / or leveling agents such as silicone-based, fluorine-based, and polymer-based, silane coupling agents such as imidazole-based, thiazole-based, triazole-based additives, antioxidants, and rust-preventing agents Can be blended.

The photocurable resin composition of this invention can also be made into the form of the dry film provided with the carrier film (support) and the layer which consists of the said photocurable resin composition formed on the said carrier film.

At the time of dry film formation, the photocurable resin composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity, and a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, A film may be obtained by applying a spray coater or the like on a carrier film with a uniform thickness and drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about coating film thickness, Generally, the film thickness after drying is suitably selected in 10-150 micrometers, Preferably it is 20-60 micrometers.

A plastic film is used as a carrier film, It is preferable to use plastic films, such as polyester films, such as a polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film. Although there is no restriction | limiting in particular about the thickness of a carrier film, Usually, it selects suitably in the range of 10-150 micrometers.

After film formation on the carrier film, it is preferable to further laminate a cover film that can be peeled off the surface of the film for the purpose of further preventing dust from adhering to the surface of the film.

As a peelable cover film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, etc. can be used, for example, When peeling a cover film, it is a film | membrane and a cover film rather than the adhesive force of a film | membrane and a carrier film. It is preferable that the adhesive force of is smaller.

Moreover, the photocurable resin composition or its dry film which concerns on this invention turns into hardened | cured material by photocuring on copper. Although photocuring is possible also by an ultraviolet-ray exposure apparatus, it can also harden | cure by the laser beam whose wavelength is 350-410 nm.

Specifically, a dry film, a cured product, and a printed wiring board are formed as follows. That is, the photocurable resin composition of this invention is adjusted to the viscosity suitable for the coating method with the said organic solvent, for example, and it is immersion coating method, flow coating method, roll coating method, bar coater method, screen printing method, curtain on a base material It is apply | coated by methods, such as a coating method, and a tack free coating film can be formed by volatilizing (temporarily drying) the organic solvent contained in a composition at the temperature of about 60-100 degreeC. Moreover, after apply | coating the said composition on a carrier film, drying, and winding up as a film, it bonded on the base material so that a photocurable resin composition layer may contact a base material, and a resin insulating layer can be formed by peeling a carrier film. Thereafter, the photomask having a pattern formed by a contact type (or non-contact method) is selectively exposed with an active energy ray, and the unexposed portion is diluted with an aqueous alkali solution (for example, 0.3 to 3% aqueous solution of sodium carbonate). It develops and a resist pattern is formed. Furthermore, in the case of a composition containing a heat curing component (E), for example, two or more cyclic ethers in the carboxyl group and the molecule of the carboxyl group-containing resin (B) by heat curing at a temperature of about 140 to 180 ° C. The thermosetting component (E) which has group and / or cyclic thioether group reacts, and can form the cured coating film excellent in various characteristics, such as heat resistance, chemical-resistance, hygroscopicity, adhesiveness, and electrical characteristics. Moreover, even when it does not contain a thermosetting component (E), by heat-processing, since the ethylenically unsaturated bond remaining in the unreacted state at the time of exposure heat-polymerizes, and a coating film characteristic improves, it heats according to a purpose and a use Treatment (thermal curing) can also be performed.

As said base material, in addition to the printed wiring board and flexible printed wiring board which were previously formed in circuit, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth, an unsaturated-epoxy resin, glass Copper clad laminates of all grades (FR-4, etc.) using composite materials such as fabric / paper-epoxy resins, synthetic fiber-epoxy resins, fluorine resins, polyethylene, PPO and cyanate esters, polyimide films, PET films, glass substrates, A ceramic substrate, a wafer board, etc. can be used.

Volatilization drying performed after apply | coating the photocurable resin composition of this invention is hot air circulation type drying hot air in a dryer using IR with a hotplate, a convection oven, etc. (The thing provided with the heat source of the air heating system by steam | vapor). And a method of spraying the support to the support from the nozzle).

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

Examples of the exposure machine used for the active energy ray irradiation include a laser direct drawing device (laser direct imaging device), an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (ultra) high pressure mercury lamp, an exposure machine equipped with a mercury short arc lamp, Or a direct drawing apparatus using ultraviolet lamps, such as a (ultra) high pressure mercury lamp, can be used. In addition, as long as the laser beam in the range whose maximum wavelength is 350-410 nm is used as an active energy ray, any of a gas laser and a solid state laser may be sufficient. Moreover, although the exposure amount changes with film thickness etc., it can generally be in the range of 5-200 mJ / cm <2>, Preferably it is 5-100 mJ / cm <2>, More preferably, it is 5-50 mJ / cm <2>. As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech Co., Ltd. and Pantax Co., Ltd. can be used, and any apparatus may be used as long as it is an apparatus for oscillating laser light having a maximum wavelength of 350 to 410 nm.

The developing method may be performed by a dipping method, a shower method, a spray method, a brush method, or the like. As the developing solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines may be used. have.

[Example]

Although an Example and a comparative example are shown to the following and this invention is demonstrated concretely, of course, this invention is not limited to the following Example.

<Production of main varnish>

Formulation Examples 1-3, Comparative Formulation Examples 1-3

Each component shown in Table 1 was mix | blended in the ratio (mass part) shown in Table 1, pre-mixed with the stirrer, and kneaded with the triaxial roll mill, and the varnish of the main agent composition for soldering resists was manufactured. Here, when the dispersion degree of the obtained varnish was evaluated by the particle size measurement by the grinding meter by Eriksen company, it was 15 micrometers or less.

<Production of Hardener Varnish>

Curing agent compounding example 1, 2

Each component shown in Table 2 was mix | blended in the ratio (mass part) shown in Table 2, and pre-mixed with the stirrer, it knead | mixed with the triaxial roll mill, and the varnish of the hardening | curing agent composition for soldering resists was manufactured.

Particle Stability Over Time

The varnish of the main agent composition shown in the said Table 1 was allowed to stand for 1 week in the refrigerator set to 5 degreeC. After returning to room temperature, the varnish was apply | coated to the glass plate and the particle | grains were confirmed. The results are shown in Table 3.

<Production of Composition for Performance Evaluation>

Varnishes of the main agent composition shown in Table 1 and varnishes of the curing agent composition shown in Table 2 were blended in the proportions (mass parts) shown in Table 4 below, premixed with a stirrer, and kneaded with a triaxial roll mill to evaluate performance. The varnish of the composition was prepared.

The time-lapse particle stability of the varnish obtained by the mixing | blending ratio of Examples 1-4 and Comparative Examples 1-3 which were shown in Table 4 was carried out similarly to the evaluation of <time-long particle stability> mentioned above, and it confirmed by Examples 1-4. And Comparative Example 3 could not identify particles even after a week, but in Comparative Examples 1 and 2, particles were identified after a week.

Performance rating:

<Optimal exposure amount>

The flame-retardant photocurable resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were subjected to buff roll polishing of a circuit pattern substrate having a copper thickness of 35 μm, washed with water, dried, and then applied to the entire surface by screen printing. Dry for 30 minutes in a hot air circulating drying furnace at 80 ℃. After drying, the exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp was exposed through a step tablet (Kodak No. 2) and developed (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution). ) For 60 seconds, the optimal exposure dose was obtained when the remaining step tablet pattern was six steps.

Characteristic test:

The flame-retardant photocurable resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were all coated by screen printing on a patterned polyimide film substrate, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. The substrate was exposed to a solder resist pattern at an optimum exposure dose using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 30 wt% aqueous solution of Na ₂ CO ₃ was sprayed under a condition of 0.2 MPa spray pressure. It developed for 60 second and obtained the resist pattern. This board | substrate was heated and hardened | cured at 150 degreeC for 60 minutes. The characteristic was evaluated as follows about the obtained printed circuit board (evaluation board | substrate).

Solder Heat Resistance

The evaluation board | substrate with which the rosin type flux was apply | coated was immersed in the solder tank previously set to 260 degreeC, and the flux was wash | cleaned with denatured alcohol, and the expansion and peeling of the resist layer by visual observation were evaluated. Judgment criteria are as follows.

(Circle): Peeling is not observed even if immersion is repeated 2 or more times for 10 second.

(Triangle | delta): When it immerses twice or more for 10 second, it peels a little.

X: There exists expansion and peeling in a resist layer at the time of immersion for 10 second.

Electroless Gold Plating Resistance

After plating on the conditions of 3 micrometers of nickel and 0.03 micrometers of gold using a commercially available electroless nickel plating bath and an electroless gold plating bath, after evaluating the presence or absence of the peeling of a resist layer or the seepage of plating by tape peeling, The presence or absence of peeling of a resist layer was evaluated by tape peeling. Judgment criteria are as follows.

(Circle): Penetration and peeling are not observed.

(Triangle | delta): Although the penetration is confirmed a little after plating, it does not peel after tape peeling.

X: Penetration is observed after plating, and peeling is also observed after tape peeling.

<Electrical characteristic>

The evaluation board | substrate was produced on the conditions mentioned above using the comb-shaped electrode B coupon of IPC B-25 instead of the copper foil board | substrate, the bias voltage of DC100V is applied to this comb-shaped electrode, and 85 degreeC, 85% RH constant temperature and humidity tank The resistance value and the presence or absence of migration after 1,000 hours was confirmed at. Judgment criteria are as follows.

◎: Insulation resistance value after humidification 10 ¹² Ω or more, no copper migration.

(Circle): The insulation resistance value after humidification is less than 10 ¹² ohms, 10 ⁹ ohms or more, and there is no migration of copper.

(Triangle | delta): The insulation resistance value after humidification is 10 ⁹ ohms or more, and there exists copper migration.

X: Insulation resistance value after humidification 10 ⁸ ohms or less, copper migration exists.

<Flammability>

The compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were front-coated with a 25 μm thick polyimide film (Kapton 100H) or a 12.5 μm thick polyimide film (Kapton 50H) by screen printing, and 20 at 80 ° C. Dry for a minute and allow to cool to room temperature. Moreover, the back surface was similarly apply | coated by screen printing, it dried for 20 minutes at 80 degreeC, and cooled to room temperature, and obtained the double-coated board | substrate. The substrate is exposed to the entire surface of the solder resist using an exposure apparatus equipped with a metal halide lamp (HMW-680-GW20) at an optimum exposure dose, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa. The image development was performed for 60 second, it thermosetted at 150 degreeC for 60 minutes, and it was set as the evaluation sample. The thin material vertical combustion test based on UL94 standard was done about this flame retardance sample. Evaluation is expressed as VTM-0 or VTM-1 based on the UL94 specification.

<Flexibility>

The composition of each Example and the comparative example was apply | coated completely by screen printing to the 25-micrometer polyimide film (Kapton 100H), dried at 80 degreeC for 30 minutes, cooled to room temperature, and obtained the single-side coating substrate. The substrate is exposed to the entire surface of the solder resist using an exposure apparatus equipped with a metal halide lamp (HMW-680-GW20) at an optimum exposure dose, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa. The image development was performed for 60 second, and thermosetting was performed for 60 minutes at 150 degreeC. The solder resist of the obtained sample was repeatedly subjected to 180 ° bending by seam folding as the outside, and the crack occurrence state in the coating film at this time was observed by visual observation and an optical microscope with a magnification of 200, and the number of times the crack did not occur was evaluated. It was.

Table 5 shows the results of the above evaluation tests.

As is clear from the results shown in Tables 3 and 5, the flame-retardant photocurable resin compositions of Examples 1 to 4 of the present invention not only have excellent storage stability, but also solder heat resistance, electroless gold plating resistance, electrical properties, and flame retardancy. , Flexibility was excellent. On the other hand, in the case of the flame-retardant photocurable resin compositions of Comparative Examples 1 and 2 using phenoxyphosphazene having high solid crystallinity at room temperature, there are no problems in solder heat resistance, electroless gold plating resistance, electrical properties, flame retardancy, but storage stability, In the case of the comparative example 3 using the phenolic hydroxyl group containing phenoxy phosphazene, flexibility fell, although the particle stability was excellent over time, electroless gold plating resistance, electrical property, flame retardance, and flexibility fell.

Examples 5-8

The flame-retardant photocurable resin composition prepared according to Examples 1 to 4 shown in Table 4 was diluted with methyl ethyl ketone and coated on a carrier film, and dried by heating to form a photosensitive resin composition layer having a thickness of 20 µm, and a cover film thereon. Was bonded together to obtain a dry film. Then, the cover film was peeled off and the film was bonded to the patterned polyimide film board | substrate using a laminator. Using a metal halide lamp is equipped with an exposure apparatus (HMW-680-GW20) in the substrate to expose a solder resist pattern by the optimal exposure amount, and then peeling the carrier film, a 1 wt% Na ₂ CO ₃ aqueous solution for 30 ℃ It developed for 60 second under the conditions of a spray pressure of 0.2 MPa, and obtained the resist pattern. Then, it heat-hardened for 60 minutes with the 150 degreeC hot air dryer, and produced the test board | substrate. About the test board | substrate which has the obtained hardened film, the evaluation test of each characteristic was done similarly to the above-mentioned test method and evaluation method. The results were equivalent to Examples 1-4.

In addition, evaluation of particle stability with time in the dry film state was performed as follows.

That is, the flame-retardant photocurable resin composition prepared according to Example 1 and Comparative Example 1 shown in Table 4 was diluted with methyl ethyl ketone, coated on a carrier film, and dried under heat to form a photosensitive resin composition layer having a thickness of 20 μm. The cover film was bonded on it and the dry film was manufactured. With respect to the manufactured dry film, the particles were not found in the dry film obtained from the composition of Example 1 when stored for one week at 5 ° C. in the same manner as in the evaluation of <permanent particle stability> described above. Particles were confirmed in the dry film.

Claims (9)

The flame-retardant photocurable resin composition containing (A) phosphazene compound which is liquid at room temperature, (B) carboxyl group-containing resin, and (C) photoinitiator. The flame retardant photocurable resin composition according to claim 1, further comprising (D) a photopolymerizable monomer. The flame-retardant photocurable resin composition of Claim 1 which further contains (E) thermosetting resin. The flame-retardant photocurable resin composition of Claim 3 in which the said thermosetting resin (E) contains the epoxy resin which has a biphenyl frame | 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 of any one of Claims 1-5 which is a soldering resist. The flame-retardant photocurable dry film obtained by apply | coating and drying the flame-retardant photocurable resin composition in any one of Claims 1-5 on a carrier film. The flame-retardant hardened | cured material obtained by hardening the dry film obtained by apply | coating and drying the flame-retardant photocurable resin composition or the said flame-retardant photocurable resin composition on a carrier film in any one of Claims 1-5. It has a flame-retardant cured film obtained by hardening | curing the dry-film obtained by apply | coating and drying the flame-retardant photocurable resin composition or the said flame-retardant photocurable resin composition on a carrier film in any one of Claims 1-5. Wiring board.