KR101372202B1 - Photocurable resin composition - Google Patents

Abstract

The present invention provides a photocurable resin composition capable of suppressing hygroscopicity and improving cold cycle resistance without impairing migration characteristics when used in a printed wiring board or the like in the cured product thereof. In a photocurable resin composition, carboxyl group-containing resin, a photoinitiator, a styryl group containing compound, and a maleimide compound are contained.

Description

[0001] PHOTOCURABLE RESIN COMPOSITION [0002]

TECHNICAL FIELD This invention relates to curable resin composition used as a soldering resist of a printed wiring board.

The photocurable resin composition can be microfabricated by applying the principle of the photolithography (photolithography). Moreover, since the hardened | cured material excellent in the physical property can be obtained, it is used for an electronic device, a printing plate, etc.

Although there exist a solvent developing type and an alkali developing type in this photocurable resin composition, in recent years, the alkali developing type which can be developed by the weak alkaline aqueous solution from a viewpoint of environmental measures becomes mainstream. For example, an alkali developing type photocurable resin composition is used in printed wiring board manufacture, liquid crystal display panel manufacture, or printing engraving. For example, when used as a soldering resist in the manufacture of printed wiring boards, the cured product thereof requires properties such as heat resistance that can withstand processing at high temperature conditions such as soldering, and long-term reliability such as water resistance and moisture resistance.

In recent years, high-density mounting, thinning, etc. in a printed wiring board etc. are progressing with the small size, light weight, multifunctional, and environmental correspondence of an electronic device. In particular, solder resists used for high density mounting substrates having a fine pitch pattern for high density mounting, for example, require high migration resistance and cold cycle resistance in their cured products. And accordingly, low hygroscopicity and high purity of a photocurable resin composition used as a soldering resist, ie, a decrease in water absorption and a reduction in ionic impurities in the resin composition are required.

As a photocurable resin composition which satisfies migration resistance as a hardened | cured material and cold cycle resistance to some extent, many double bonds are made to a resin skeleton using polyfunctional epoxy resin or (meth) acrylate among carboxyl group-containing epoxy (meth) acrylates. Introduced photocurable resin composition is used. By such a structure, it is thought that crosslinking density can be improved and heat resistance improvement and dimensional stability improvement are attained.

However, when a crosslinking density becomes high, since a hardened coating film becomes weak, there exists a problem that it is difficult to obtain the balance of heat resistance and a weakness reduction. The method of using a mixture of a bisphenol-type carboxyl group-containing epoxy (meth) acrylate and a novolak-type carboxyl group-containing epoxy (meth) acrylate is disclosed about weakness (for example, refer patent document 1 etc.). However, in such a method, the emphasis is placed on improving the flexibility, and there is a problem that dimensional stability and water resistance due to temperature change cannot be sufficiently obtained.

Moreover, in photocurable resin composition, it becomes possible to aim at the reduction of water absorption by improving crosslinking density using polyfunctional curable resin. However, on the other hand, the hardened | cured material becomes hard and weak, and there exists a problem of reducing cold-heat cycle resistance.

Japanese Patent Laid-Open No. 2000-109541

An object of this invention is to provide the photocurable resin composition which can suppress hygroscopicity and can improve cold-heat cycle resistance, without damaging migration characteristics when used for printed wiring boards etc. in the hardened | cured material.

In order to achieve this object, according to one aspect of the present invention, there is provided a photocurable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, a styryl group-containing compound, and a maleimide compound.

By such a structure, it becomes possible to suppress hygroscopicity and to improve cold-cycle cycle resistance, without damaging the migration resistance when used for a printed wiring board etc. in the hardened | cured material.

Moreover, in the photocurable resin composition of 1 aspect of this invention, it is preferable to contain a mercapto compound further. By such a structure, adhesiveness can be improved.

Moreover, in the photocurable resin composition of 1 aspect of this invention, it is preferable that carboxyl group-containing resin has a photosensitive group. By having a photosensitive group, the photocurability of a photocurable resin composition can increase and a sensitivity can be improved.

Furthermore, in the photocurable resin composition of 1 aspect of this invention, a photoinitiator is represented by the oxime ester photoinitiator represented by following formula (1), the aminoacetophenone type photoinitiator represented by following formula (2), and the following formula (3). It is preferable to contain at least 1 sort (s) chosen from the group which consists of an acylphosphine oxide type photoinitiator.

(Wherein R ¹ 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 group having 1 to 6 carbon atoms or a phenyl group) R ² 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 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 (alkyl group having 1 to 6 carbon atoms or phenyl Represents which may be substituted with a), R ³ and R ⁴ each independently represents an alkyl group or arylalkyl group having 1 to 12, R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Or a two-membered cyclic alkylether group, R ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, cyclohexyl group, cyclopentyl group, aryl group, or halogen atom, alkyl group or alkoxy An aryl group substituted with a group, provided that one of R ⁷ and R ⁸ represents an RC (═O) -group, where R may represent a hydrocarbon group of 1 to 20 carbon atoms

By using such a photoinitiator, a high resolution can be obtained in the resist which has a pigment at high concentration.

Moreover, in the photocurable resin composition of 1 aspect of this invention, it is preferable to contain a thermosetting component further. By containing a thermosetting component, while providing heat resistance, the tensile elongation rate of a cured film can be increased, and a crack resistance and punching resistance can be improved.

Moreover, in the photocurable resin composition of 1 aspect of this invention, a coloring agent can be contained further. By containing a colorant, it can be preferably used as a solder resist.

Moreover, according to one aspect of this invention, the dry film obtained by apply | coating and drying the photocurable resin composition mentioned above on a carrier film is provided. By using such a dry film, a resist layer can be formed easily, without apply | coating a photocurable resin composition on a base material.

Moreover, in one aspect of this invention, the photocurable resin composition or dry film mentioned above can be used as hardened | cured material obtained by photocuring by active energy ray irradiation.

In such hardened | cured material, when used for a printed wiring board etc., it becomes possible to improve cold-heat cycle resistance, without compromising migration resistance.

Moreover, in one aspect of this invention, the photocurable resin composition or its dry film mentioned above can be used as a printed wiring board which has the pattern of the hardened | cured material obtained by photocuring by active energy ray irradiation.

In such a printed wiring board, it becomes possible to improve cold cycle cycle resistance without compromising migration resistance.

In the photocurable resin composition of one aspect of the present invention, good hygroscopic cycle resistance can be obtained without inhibiting hygroscopicity and impairing migration resistance in the cured product thereof.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the electrical property and migration tolerance which were excellent in the hardened | cured material can be achieved by using together a styryl group containing compound and a maleimide compound in a photocurable resin composition, and came to complete this invention. By using together a styryl group containing compound and a maleimide compound, a crosslinking reaction advances and the water absorption of the hardened | cured material obtained from the photocurable resin composition of this embodiment can be suppressed.

Hereinafter, the photocurable resin composition of this embodiment is demonstrated in detail.

First, as carboxyl group-containing resin which comprises the photocurable resin composition of this embodiment, well-known various carboxyl group-containing resin which has a carboxyl group in a molecule | numerator can be used for the purpose of providing alkali developability. In particular, carboxyl group-containing photosensitive resin which has an ethylenically unsaturated double bond in a molecule | numerator is more preferable at the point of photocurability and developability. And it is preferable that the unsaturated double bond is derived from acrylic acid or methacrylic acid, or derivatives thereof.

As such carboxyl group-containing resin, the compound (which may be any of an oligomer and a polymer) listed below is preferable.

(1) 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.

(2) diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylol propionic acid and dimethylol butanoic acid; and polycarbonate polyols and polyether polyols. Carboxyl group-containing urethane resin by polyaddition reaction of diol compounds, such as a polyester polyol, a polyolefin polyol, an acryl polyol, a bisphenol A alkylene oxide adduct diol, a compound which has a phenolic hydroxyl group, and alcoholic hydroxyl group. .

(3) bifunctional epoxy resins such as diisocyanate, 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 biphenol type epoxy resin The photosensitive carboxyl group-containing urethane resin by the polyaddition reaction of the (meth) acrylate or its partial acid anhydride modified substance, the carboxyl group-containing dialcohol compound, and a diol compound.

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

(5) Compounds having one isocyanate group and one or more (meth) acryl groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin of (2) or (3) described above. The photosensitive carboxyl group-containing urethane resin which added and terminated (meth) acrylic-acid.

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

(7) (meth) acrylic acid was reacted with a polyfunctional epoxy resin epoxidized with epichlorohydrin further to add a hydroxyl group of a bifunctional (solid) epoxy resin as described later, to which dibasic anhydride was added to the resulting hydroxyl group. Photosensitive carboxyl group-containing resin.

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

(9) A polybasic acid anhydride is added to a reaction product obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with alkylene oxides such as ethylene oxide and propylene oxide. Carboxyl group containing photosensitive resin obtained by making it react.

(10) Polybasic acid anhydride is added to the reaction product obtained by making unsaturated group containing monocarboxylic acid react with the reaction product obtained by making the compound which has a some phenolic hydroxyl group, and cyclic carbonate compounds, such as ethylene carbonate and a propylene carbonate, react in one molecule. Carboxyl group containing photosensitive resin obtained by making it react.

(11) 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 (1)-(10) mentioned above.

In addition, the term (meth) acrylate here is generically used for acrylate, methacrylate, and mixtures thereof, and the same also applies to other similar expressions below.

Since such carboxyl group-containing resin has many glass carboxyl groups in the side chain of a backbone polymer, image development by a diluted alkali aqueous solution is attained.

As for the acid value of the carboxyl group-containing resin mentioned above, 40-200 mgKOH / g is preferable. 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, so that the line becomes thinner than necessary, or in some cases, furnace It dissolves and peels off in a developing solution without distinguishing a light part and an unexposed part, and drawing of a normal resist pattern becomes difficult. And more preferably 45 to 120 mgKOH / g.

In addition, although the weight average molecular weight of carboxyl group-containing resin changes with resin skeleton, generally 2,000-150,000 are preferable. If the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coating film after exposure is bad, the film decreases at the time of image development, and the resolution may fall large. On the other hand, when a weight average molecular weight exceeds 150,000, developability may become remarkably bad and storage stability may be inferior. More preferably from 5,000 to 100,000.

It is preferable that the compounding quantity of such carboxyl group-containing resin is 20-60 mass% in all compositions. If the blending amount is less than 20 mass%, the film strength may be lowered. On the other hand, when more than 60 mass%, the viscosity of a composition becomes high and applicability | paintability etc. fall. More preferably, it is 30-50 mass%.

These carboxyl group-containing resin is not limited to what was listed, can be used, It can be used 1 type or in mixture of multiple types.

As a photoinitiator, the oxime ester type photoinitiator which has group represented by following formula (1), the (alpha)-amino acetophenone type photoinitiator which has group represented by following formula (2), and / or the acyl phosphine oxide type which has group represented by following formula (3) It is preferable to use 1 or more types of photoinitiators selected from the group which consists of a photoinitiator.

≪ Formula 1 >

(2)

(3)

(Wherein R ¹ 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 group having 1 to 6 carbon atoms or a phenyl group) R ² 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 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 (alkyl group having 1 to 6 carbon atoms or phenyl Represents which may be substituted with a), R ³ and R ⁴ each independently represents an alkyl group or arylalkyl group having 1 to 12, R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Or a two-membered cyclic alkylether group, R ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, cyclohexyl group, cyclopentyl group, aryl group, or halogen atom, alkyl group or alkoxy An aryl group substituted with a group, provided that one of R ⁷ and R ⁸ represents an RC (═O) -group, where R may represent a hydrocarbon group of 1 to 20 carbon atoms

As an oxime ester type photoinitiator which has group represented by General formula (1), Preferably, it is 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by following General formula (4), the compound represented by General formula (5), and General formula (6). The compound shown is mentioned.

(Wherein R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, and a carbon having 2 to 12 carbon atoms). An alkoxycarbonyl group (when the alkyl group constituting the alkoxyl group has two 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 R ¹⁰ and R ¹² each independently represent 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 alkyl May have one or more oxygen atoms in the middle of the chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (with 1 to 6 carbon atoms) Represents that may be substituted with kilgi or a phenyl group), R ¹¹ is a hydrogen atom, a phenyl group (having 1 to 6 carbon atoms that the alkyl group, may be substituted phenyl group or a halogen atom), an alkyl group (at least one hydroxyl group having 1 to 20 carbon atoms May be substituted with one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (alkyl group having 1 to 6 carbon atoms) Or may be substituted with a phenyl group)

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

Among the oxime ester photopolymerization initiators, the compounds represented by 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by the general formula (4) and the general formula (5) are more preferable. As a commercial item, CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02 (all are the Siba Japan company make), N-1919 (made by Adeka company), etc. are mentioned. These oxime ester-based photopolymerization initiators may be used alone or in combination of two or more.

As an α-aminoacetophenone-based photopolymerization initiator having a group represented by the formula (2), 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, and the like. As a commercial item, Irgacure 907, Irgacure 369, Irgacure 379 (all are the Siba Japan company make), etc. are mentioned.

As an acyl phosphine oxide type photoinitiator which has group represented by General formula (3), 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6- trimethyl benzoyl)-phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, etc. are mentioned. Commercially available products include Lucillin TPO (BASF), Irgacure 819 (Shiba, Japan), and the like.

It is preferable that the compounding quantity of such a photoinitiator is 0.01-30 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When the compounding quantity is less than 0.01 part by mass, the photocurability on copper is insufficient, the coating film is peeled off, and coating film properties such as chemical resistance are lowered. On the other hand, when it exceeds 30 mass parts, the light absorption in the soldering resist coating film surface of a photoinitiator will become deep, and there exists a tendency for deep-part sclerosis | hardenability to fall. More preferably 0.5 to 15 parts by mass.

Moreover, in the case of the oxime ester type photoinitiator which has group represented by General formula (1), 0.01-20 mass parts is preferable with respect to the compounding quantity with respect to 100 mass parts of carboxyl group-containing resin. When less than 0.01 mass part, the photocurability on copper is inadequate, peeling a coating film, and coating film characteristics, such as chemical-resistance, fall. Moreover, when more than 20 mass parts, light absorption in the soldering resist coating film surface of a photoinitiator becomes severe, and there exists a tendency for deep-part sclerosis | hardenability to fall. More preferably 0.01 to 5 parts by mass.

As a photoinitiator, a photoinitiator, and a sensitizer which can be used suitably for the photocurable resin composition of this embodiment, in addition, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, A xanthone compound, a tertiary amine compound, etc. are mentioned.

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

The acetophenone compound is, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone.

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

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

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

Examples of the benzophenone compound include benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl- '- propyl diphenyl sulfide.

As the tertiary amine compound, a ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (Nissocure MABP manufactured by Nippon Soda Co., Ltd.), 4,4'-diethylaminobenzophenone Dialkylaminobenzophenones such as (EAB manufactured by Hodogaya Chemical Co., Ltd.); A coumarin compound containing a dialkylamino group such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin); Ethyl 4-dimethylaminobenzoate (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylaminobenzoic acid (n- Butoxy) ethyl (Quantcure BEA by International Bio-Synthetics Co., Ltd.), isoamyl ethyl ester of p-dimethylaminobenzoic acid (Kayacure DMBI by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoic acid (Bandik ( And dialkylaminobenzoic acid esters such as Esolol 507) manufactured by Van Dyk).

In particular, 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 has low toxicity and is preferable. Since the maximum absorption wavelength is in the ultraviolet region, the dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has little coloration and, of course, a colorless transparent photosensitive composition, as well as the color of the colored pigment itself using a color pigment. It becomes possible to provide the coloring soldering resist film which reflected this. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable at the point which shows the outstanding sensitizing effect with respect to the laser beam of wavelength 400-410 nm.

Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, it is preferable that a thioxanthone compound is contained from the point of deep-hardening, Especially, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, 2,4 -Thioxanthone compounds, such as diisopropyl thioxanthone, are preferable.

As a compounding quantity of such a thioxanthone compound, the ratio of 20 mass parts or less is preferable with respect to 100 mass parts of carboxyl group-containing resin. When the compounding amount exceeds 20 parts by mass, the thick film curability is lowered, which leads to an increase in the cost of the product. More preferably 10 parts by mass or less.

Moreover, as a compounding quantity of a tertiary amine compound, it is preferable that it is the ratio of 0.1-20 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When the blending amount is less than 0.1 part by mass, sufficient increase / decrease effect can not be obtained. On the other hand, when it exceeds 20 mass parts, the light absorption in the surface of the dry solder resist coating film by a tertiary amine compound will become deep, and there exists a tendency for deep-part sclerosis | hardenability to fall. More preferably 0.1 to 10 parts by mass. These photoinitiators, photoinitiation aids, and sensitizers can be used alone or as a mixture of two or more thereof.

It is preferable that the total amount of such a photoinitiator, a photoinitiator, and a sensitizer is 0.01-35 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When it exceeds 35 mass parts, there exists a tendency for deep-part sclerosis | hardenability to fall by these light absorption. On the other hand, if it is less than 0.01, the photocurability on copper will run out, a coating film will peel and a coating film characteristics, such as chemical resistance, will fall. More preferably, it is 0.01-20 mass parts. Especially as an initiator used preferably in this embodiment, when using aromatic maleimide, since ultraviolet absorption of aromatic maleimide itself is large, oxime ester is especially preferable.

N-phenylglycine, phenoxyacetic acid, thiophenoxyacetic acid, mercaptothiazole, etc. which are well-known as a chain transfer agent can be used for the photocurable resin composition of this embodiment in order to improve a sensitivity.

Examples of the chain transfer agent include mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof. These chain transfer agents may be used alone or in combination of two or more.

The styryl group containing compound used for this embodiment is used in order to provide the heat resistance of the hardened | cured material obtained by advancing a maleimide compound and hardening reaction. As such a styryl group containing compound, it may be synthesize | combined by a conventional method and may use a commercial item. As an example of the synthesis | combining method of a styryl group containing compound, mono- and polyfunctional compound and vinyl which have reaction with mono- and polyfunctional phenols and methyl styrene halide, and functional groups (for example, amino group, hydroxyl group, carboxyl group, etc.) which can react with an epoxy group And reaction with benzyl glycidyl ether.

Specific examples of the styryl group-containing compound include vinyl naphthalene, divinyl naphthalene, divinyl biphenyl, polyvinyl benzyl ether compounds obtained by reaction of polyphenols and vinyl benzyl halides, and oligophenylene ether compounds of terminal styrene (Mitsubishi Gas OPE-2St manufactured by Kagaku Co., Ltd., and a compound obtained by condensation reaction of bisphenol A with methyl styrene halide (Showa Koshi Co., Ltd. lipoxy (registered trademark) BPV-1X). These styryl group containing compounds can be used individually by 1 type or in combination of 2 or more type.

As a compounding quantity of such a styryl group containing compound, 1-50 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing resin. If the compounding quantity is less than 1 part by mass, it becomes difficult to obtain sufficient heat resistance. On the other hand, when it exceeds 50 mass parts, developability of a composition will fall and a developing residue will arise. More preferably, it is 1-25 mass parts.

As a maleimide compound used for this embodiment, it is used in order to improve heat resistance by promoting hardening reaction with a styryl compound, and / or photocuring. Such maleimide compounds include polyfunctional aliphatic / alicyclic maleimide and polyfunctional aromatic maleimide.

Examples of the polyfunctional aliphatic / alicyclic maleimide include N, N'-methylenebismaleimide, N, N'-ethylenebismaleimide, tris (hydroxyethyl) isocyanurate and aliphatic / alicyclic maleimide Maleimide ester compound of the isocyanurate frame | skeleton obtained by dehydrating esterification of carboxylic acid; Isocyanur skeleton polymaleimide, such as the maleimide urethane compound of the isocyanurate frame | skeleton obtained by urethanizing a tris (carbamate hexyl) isocyanurate and aliphatic / alicyclic maleimide alcohol; Dehydration esterification of isophoronebisurethanebis (N-ethylmaleimide), triethyleneglycolbis (maleimideethylcarbonate), aliphatic / alicyclic maleimidecarboxylic acid and various aliphatic / alicyclic polyols, or aliphatic / alicyclic maleic Aliphatic / alicyclic polymaleimide ester compounds obtained by transesterifying a midcarboxylic acid ester with various aliphatic / alicyclic polyols; Aliphatic / alicyclic polymaleimide ester compounds obtained by ether ring opening reaction of aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic polyepoxides; And aliphatic / alicyclic polymaleimide urethane compounds obtained by urethane reaction of aliphatic / alicyclic maleimide alcohol and various aliphatic / alicyclic polyisocyanates.

As a polyfunctional aromatic maleimide, Aromatic polymaleimide ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols, or transesterifying maleimide carboxylic acid ester and various aromatic polyols; Aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of maleimide carboxylic acid with various aromatic polyepoxides; Aromatic polyfunctional maleimide, such as aromatic polymaleimide urethane compounds obtained by the urethanation reaction of maleimide alcohol and various aromatic polyisocyanate, etc. are mentioned.

As such a polyfunctional aromatic maleimide, N, N '-(4,4'- diphenylmethane) bismaleimide, N, N'-2,4-tolylene bismaleimide, N, N'-, for example 2,6-tolylenebismaleimide, 1-methyl-2,4-bismaleimidebenzene, N, N'-m-phenylenebismaleimide, N, N'-p-phenylenebismaleimide, N , N'-m-toluylenebismaleimide, N, N'-4,4'-biphenylenebismaleimide, N, N'-4,4 '-[3,3'-dimethyl-biphenylene Bismaleimide, N, N'-4,4 '-[3,3'-dimethyldiphenylmethane] bismaleimide, N, N'-4,4'-[3,3'-diethyldiphenyl Methane] bismaleimide, N, N'-4,4'-diphenylmethanebismaleimide, N, N'-4,4'-diphenylpropanebismaleimide, N, N'-4,4'- Diphenyletherbismaleimide, N, N'-3,3'-diphenylsulfonbismaleimide, N, N'-4,4'-diphenylsulfonbismaleimide, 2,2-bis [4- ( 4-maleimidephenoxy) phenyl] propane, 2,2-bis [3-t-butyl-4- (4-maleimidephenoxy) phenyl] propane, 2,2- S [3-s-butyl-4- (4-maleimidephenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidephenoxy) phenyl] decane, 1,1-bis [2- Methyl-4- (4-maleimidephenoxy) -5-t-butylphenyl] -2-methylpropane, 4,4'-cyclohexylidene-bis [1- (4-maleimidephenoxy) -2 -(1,1-dimethylethyl) benzene], 4,4'-methylene-bis [1- (4-maleimidephenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4, 4'-methylene-bis [1- (4-maleimidephenoxy) -2,6-di-s-butylbenzene], 4,4'-cyclohexylidene-bis [1- (4-maleimidephenoxy C) -2-cyclohexylbenzene, 4,4'-methylenebis [1- (maleimidephenoxy) -2-nonylbenzene], 4,4 '-(1-methylethylidene) -bis [1- (Maleimide phenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4 '-(2-ethylhexylidene) -bis [1- (maleimide phenoxy) -benzene] , 4,4 '-(1-methylheptylidene) -bis [1- (maleimidephenoxy) -benzene], 4,4'-cyclohexylidene-bis [1- (maleimidephenoxy)- 3-methyl Zen], 2,2-bis [4- (4-maleimidephenoxy) phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4-maleimidephenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-maleimidephenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5-dimethyl-4- (4-maleimidephenoxy) phenyl ] Propane, 2,2-bis [3,5-dimethyl-4- (4-maleimidephenoxy) phenyl] hexafluoropropane, 2,2-bis [3-ethyl-4- (4-maleimidephenoxy Phenyl] propane, 2,2-bis [3-ethyl-4- (4-maleimidephenoxy) phenyl] hexafluoropropane, bis [3-methyl- (4-maleimidephenoxy) phenyl] methane , Bis [3,5-dimethyl- (4-maleimidephenoxy) phenyl] methane, bis [3-ethyl- (4-maleimidephenoxy) phenyl] methane, 3,8-bis [4- (4- Maleimidephenoxy) phenyl] -tricyclo [5.2.1.0 ^2,6 ] decane, 4,8-bis [4- (4-maleimidephenoxy) phenyl] -tricyclo [5.2.1.0 ^2,6 ] decane , 3,9-bis [4- (4-maleimide ) Phenyl] - tricyclo [5.2.1.0 ^2,6] decane, 4,9- bis [4- (4-maleimidophenoxy) phenyl] - tricyclo [5.2.1.0 ^2,6] decane, 1 , 8-bis [4- (4-maleimidephenoxy) phenyl] mentan, 1,8-bis [3-methyl-4- (4-maleimidephenoxy) phenyl] mentan, 1,8-bis [3 , 5-dimethyl-4- (4-maleimide phenoxy) phenyl] mentan etc. are mentioned.

These bismaleimide derivatives may be synthesized by a conventional method or may use a commercially available product. Among the bismaleimide derivatives in particular, those which do not contain a halogen atom in the molecule are preferable from the viewpoint of not imposing a load on the environment. These may be used singly or in combination of two or more.

As a compounding quantity of such a maleimide compound, 1-50 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing resin. If the blending amount is less than 1 part by mass, it becomes difficult to obtain sufficient heat resistance. On the other hand, when it exceeds 50 mass parts, developability of a composition will fall and a developing residue will arise. More preferably, it is 1-25 mass parts.

A mercapto compound can be added to the photocurable resin composition of this embodiment for the purpose of addition reaction and crosslinking to a vinyl group and a maleimide group. By addition of a mercapto compound, the fall of the coating-film characteristic by oxidation of a vinyl group can be prevented. In addition, in the case of a polyfunctional mercapto compound, crosslinking can be obtained, thereby improving characteristics such as PCT resistance and HAST resistance. Moreover, since these mercapto compounds function as a chain transfer agent and / or an adhesion imparting agent, the improvement of a sensitivity and the improvement of adhesiveness can also be obtained simultaneously.

Examples of such mercapto compounds include mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan , Propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

As these commercial items, for example, BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEMPIC (all manufactured by Sakai Chemical Industries, Ltd.), Kalenzu MT (registered trademark) -PE1, Kalenz MT- BD1 and Karenz (registered trademark) -NR1 (all are manufactured by Showa Denko).

Examples of the mercapto compound having a heterocycle include mercapto-4-butyrolactone (alias 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butylothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4- Butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-ballet Lolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-meth Methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzoimidazole, 2-mercaptobenzooxa Sol, 2-mercaptobenzothiazole (Accelerator M by Kawaguchi Chemical Industries, Ltd.), 2-mercapto-5-methylthio-thiadiazole, 3-mer To-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole, 2 -Mercapto-6-hexanolactam, 2,4,6-trimercapto-s-triazine (Disnet F manufactured by Sankyo Kasei Co., Ltd.), 2-dibutylamino-4,6-dimercapto-s-triazine (The Sankyo Kasei Co., Ltd. DISNET (registered trademark) DB, DISNET AF) etc. are mentioned. These mercapto compounds can use together single or 2 types or more.

As a compounding quantity of such a mercapto compound, 0.01-20 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing resin. If the compounding amount is less than 0.01 parts by mass, curing of the mercapto compound is not exhibited and no improvement in heat resistance is observed. On the other hand, when it exceeds 20 mass parts, since developing residue will arise, it is unpreferable. More preferably, it is 0.1-5 mass parts.

In order to provide heat resistance, the thermosetting component can be added to the photocurable resin composition of this embodiment. As such a thermosetting component, well-known thermosetting resins, such as an amino resin, such as a melamine resin, a benzoguanamine resin, a melamine derivative, a benzoguanamine derivative, and a cyclocarbonate compound, can be used. Especially preferred are thermosetting components having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule.

The thermosetting component which has a some cyclic (thio) ether group in such a molecule | numerator is a compound which has 2 or more of any one or 2 types of 3, 4 or 5 membered cyclic (thio) ether groups in a molecule | numerator, For example, A compound having a plurality of epoxy groups in the compound, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, namely episulfide resin, and the like. Can be.

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

As these commercial items, Cymel (registered trademark) 300, east 301, east 303, east 370, east 325, east 327, east 701, east 266, east 267, east 238, east 1141, east 272, east 202 , Copper 1156, copper 1158, copper 1123, copper 1170, copper 1174, copper UFR65, copper 300 (all manufactured by Mitsui Cyanamid, Inc.), Nikalak (registered trademark) Mx-750, copper Mx-032, copper Mx-270 , Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390 And Mw-100LM, Mw-750LM (both manufactured by Sanwa Chemical Co., Ltd.) and the like. These thermosetting components may be used alone or in combination of two or more.

It will not specifically limit, if it has a carbonate bond as a cyclic compound as a cyclocarbonate compound. As an example, the alkylene carbonate compound which has a polyfunctional structure is mentioned.

Examples of the polyfunctional epoxy compound include jER (registered trademark) 828, jER834, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), epiclone (registered trademark) 840, epiclone 850, epiclone 1050, epiclone 2055 ( All manufactured by DIC Corporation), Efototo (registered trademark) YD-011, YD-013, YD-127, YD-128 (all manufactured by Shin-Nitetsu Chemical Co., Ltd.), DER317, DER331, DER661, DER664 ( Dow Chemical Co., Ltd.), Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260 (all from Shiva Japan), Sumiepoxy ESA-011, ESA-014, ELA-115, ELA- Bisphenol A type epoxy resins such as 128 (all manufactured by Sumitomo Chemical Industries, Ltd.), AER330, AER331, AER661, and AER664 (all manufactured by Asahi Kasei Kogyo Co., Ltd.); jERYL903 (manufactured by Mitsubishi Chemical Corporation), epiclon 152, epiclon 165 (all manufactured by DIC Corporation), Efototo YDB-400, YDB-500 (all manufactured by Shinnitetsu Chemical Co., Ltd.), DER542 (manufactured by Dow Chemical Corporation) Brominated epoxy, such as Araldite 8011 (made by Shiba Japan), Sumiepoxy ESB-400, ESB-700 (all manufactured by Sumitomo Chemical Co., Ltd.), AER711, and AER714 (all manufactured by Asahi Kasei Kogyo Co., Ltd.). Suzy; jER152, jER154 (all manufactured by Mitsubishi Chemical Corporation), DEN431, DEN438 (all manufactured by Dow Chemical Corporation), epiclon N-730, epiclon N-770, epiclon N-865 (all manufactured by DIC Corporation), Phototo YDCN-701, YDCN-704 (all manufactured by Shin-Nitetsu Chemical Co., Ltd.), Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 (all manufactured by Ciba Japan Corporation), EPPN-201 , EOCN (registered trademark) -1025, EOCN-1020, EOCN-104S, RE-306 (all manufactured by Nippon Kayaku Co., Ltd.), Sumiepoxy (registered trademark) ESCN-195X, ESCN-220 (all manufactured by Sumitomo Chemical Co., Ltd.) Novolak-type epoxy resins such as AERECN-235 and ECN-299 (all manufactured by Asahi Kasei Kogyo Co., Ltd.); Epiclone 830 (manufactured by DIC Corporation), jER807 (manufactured by Mitsubishi Chemical Corporation), Efototo YDF-170, YDF-175, YDF-2004, (all manufactured by Shin-Nitetsu Chemical Corporation) YSLV-80XY (Shin-Nitetsu Chemical Corporation) Bisphenol F-type epoxy resins, such as the said company) and Araldite XPY306 (made by Ciba Japan Corporation); Hydrogenated bisphenol A epoxy resins such as Efototo ST-2004, ST-2007, and ST-3000 (all manufactured by Shin-Nitetsu Chemical Co., Ltd.); jER604 (manufactured by Mitsubishi Chemical Corporation), Efototo YH-434 (manufactured by Shinnitetsu Chemical Industries, Ltd.), Araldite MY720 (manufactured by Shiba Japan Corporation), Sumiepoxy ELM-120 (manufactured by Sumitomo Chemical Industries, Ltd.), etc. Glycidyl amine epoxy resins; Aridite CY-350 (manufactured by Shiba, Japan); Alicyclic epoxy resins such as CELLOXIDE (registered trademark) 2021 (manufactured by Daicel Chemical Industries, Ltd.), Araldite CY175 and CY179 (all manufactured by Ciba Japan); Trihydroxyphenylmethane type epoxy resins such as YL-933 (manufactured by Mitsubishi Chemical Corporation), T.E.N., EPPN (registered trademark) -501, and EPPN-502 (all manufactured by Nippon Kayaku Co., Ltd.); A biscylenol type or biphenol type epoxy resin such as YL-6056, YX-4000, and YL-6121 (both manufactured by Mitsubishi Chemical) or a mixture thereof; Bisphenol S type epoxy resins such as EBPS-200 (manufactured by Nippon Kayakazai), EPX-30 (manufactured by Adeka) and EXA-1514 (manufactured by DIC); bisphenol A novolak type epoxy resins such as jER157S (manufactured by Mitsubishi Chemical Corporation); tetraphenylol ethane type epoxy resins such as jERYL-931 (manufactured by Mitsubishi Chemical Corporation) and Araldite 163 (manufactured by Ciba Japan); A heterocyclic epoxy resin such as ARALIDITE PT810 (manufactured by Ciba Japan KK) and TEPIC (manufactured by Nissan Chemical Industries, Ltd.); Diglycidyl phthalate resins such as Bremmer (registered trademark) DGT (manufactured by Nichi Oil Company); ZX-1063 (manufactured by Shin-Nittsu Chemical Co., Ltd.); Naphthalene group-containing epoxy resins such as ESN-190, ESN-360 (all manufactured by Shin-Nittetsu Kagaku), HP-4032, EXA-4750 and EXA-4700 (manufactured by DIC); Epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H (manufactured by DIC Corporation); Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M (manufactured by Nichisan); A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (e.g., YR-102, YR-450, manufactured by Shinnitetsu Chemical Co., Ltd.) Although these etc. are mentioned, it is not limited to these. These epoxy resins may be used alone or in combination of two or more. Of these, novolak type epoxy resins, heterocyclic epoxy resins, bisphenol A type epoxy resins, and mixtures thereof are particularly preferable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-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) methyl methacrylate, (3-ethyl-3-oxetanyl) methylmethacryl Oxetane alcohols and novolak resins, poly (p-hydroxy styrene), cardo-type bisphenols, calix arenes, and carlis resorcinarene other than polyfunctional oxetanes, such as an acrylate and these oligomers or copolymers, etc. Or an etherate with a resin having a hydroxyl group such as silsesquioxane or the like. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include a bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. 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.

Moreover, in the case of the thermosetting component which has a some cyclic (thio) ether group in a molecule | numerator, 0.6-2.5 equivalent is preferable with respect to 1 equivalent of carboxyl group of carboxyl group-containing resin. When the blending amount is less than 0.6, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, etc. are lowered. On the other hand, if it exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether groups remain in the dried coating film, so that the strength of the coated film is lowered. More preferably 0.8 to 2.0 equivalents.

Moreover, in order to improve the curability of the photosensitive resin composition and the toughness of the cured film obtained, the photocurable resin composition of this embodiment can add the compound which has several isocyanate group or blocked isocyanate group in 1 molecule as a thermosetting component. Compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule include compounds having a plurality of isocyanate groups in one molecule, that is, polyisocyanate compounds, or compounds having a plurality of blocked isocyanate groups in one molecule, that is, block isocyanate compounds. Can be.

As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.

As aromatic polyisocyanate, 4,4'- diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2, 6- tolylene diisocyanate, naphthalene-1, 5- diisocyanate, o-xylylene diisocyanate, for example. , m-xylylene diisocyanate and 2,4-tolylene dimer are mentioned.

As aliphatic polyisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4, 4- methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate are mentioned, for example.

Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Also, examples of the isocyanate compound, burette and isocyanurate of the isocyanate compound may be mentioned first.

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

As the block isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent is used. As an isocyanate compound which can react with a blocking agent, the above-mentioned polyisocyanate compound etc. are mentioned.

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

The block isocyanate compound may be commercially available, and for example, Semi-Jul (TM) BL-3175, BL-4165, BL-1100, BL-1265, Demosmod (TM) TPLS-2957, TPLS-2062, TPLS -2078, TPLS-2117, DeMotum 2170, DeMotum 2265 (all manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (all manufactured by Nippon Polyurethane Co., Ltd.), B- 830, B-815, B-846, B-870, B-874, B-882 (all manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Chemicals Co., Ltd.), etc. Can be mentioned. In addition, the schedule BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

The compound which has several isocyanate group or blocked isocyanate group in such one molecule can be used individually by 1 type or in combination of 2 or more types.

When the compounding quantity of the compound which has a some isocyanate group or a blocked isocyanate group in 1 molecule is 1-100 mass parts and compounding quantity is less than 1 mass part with respect to 100 mass parts of carboxyl group-containing resin, sufficient toughness of a coating film is not obtained. On the other hand, when it exceeds 100 parts by mass, storage stability is lowered. More preferably 2 to 70 parts by mass.

When using the thermosetting component which has a some cyclic (thio) ether group in a molecule | numerator, 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; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine.

Moreover, as a commercially available imidazole compound, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all manufactured by Shikoku Kasei Kogyo Co., Ltd.), and a block isocyanate compound of dimethylamine include U-CAT3503N, U-CAT (registered trademark) 3502T (all produced by Aprosa), a bicyclic amidine compound and salts thereof include DBU, DBN, U-CATSA (registered trademark) 102, U-CAT5002 (all manufactured by Aprosa), and the like. Can be mentioned. In particular, the present invention is not limited thereto, and may be a thermosetting catalyst of an epoxy resin or an oxetane compound, or may promote reaction of an epoxy group and / or an oxetanyl group with a carboxyl group, even if used alone or in combination of two or more thereof. Okay.

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 addition product, can be used. It is preferable to use a compound which functions as the adhesion-imparting agent together with the thermosetting catalyst.

The compounding quantity of these thermosetting catalysts is sufficient in a normal quantity ratio, For example, with respect to 100 mass parts of thermosetting components which have 2 or more cyclic (thio) ether group in carboxyl group-containing resin or molecule | numerator, Preferably it is 0.1-20 mass. Part, more preferably 0.5 to 15 parts by mass.

The photocurable resin composition of this embodiment can mix | blend a coloring agent. As a coloring agent, well-known coloring agents, such as red, blue, green, a yellow, can be used, for example, Any of a pigment, dye, and a pigment may be used. However, it is preferable that it does not contain a halogen from a viewpoint of reducing environmental load and an influence on a human body.

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone and quinacridone. For example, the following color index (CI) issued by The Society of Dyers and Colourists is attached.

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.

As a blue coloring agent, there are phthalocyanine series and anthraquinone series, for example, 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, dye system, for example, 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 and the like can be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Examples of the green colorant include, for example, phthalocyanine series, anthraquinone series, and perylene series, and 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, a metal substituted or unsubstituted phthalocyanine compound can also be used.

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

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

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

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

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

In addition, a coloring agent such as purple, orange, brown or black may be added for the purpose of adjusting the color tone. Specifically, pigment violet 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, pigment orange 1, pigment orange 5, pigment orange 13, pigment orange 14, pigment orange 16 , Pigment Orange 17, Pigment Orange 24, Pigment Orange 34, Pigment Orange 36, Pigment Orange 38, Pigment Orange 40, Pigment Orange 43, Pigment Orange 46, Pigment Orange 49, Pigment Orange 51 Pigment Orange 61, Pigment Orange 63, Pigment Orange 64, Pigment Orange 71, Pigment Orange 73, Pigment Brown 23, Pigment Brown 25, Pigment Black 1, Pigment Black 7 and the like.

Although the compounding ratio of such a coloring agent does not have a restriction | limiting in particular, Preferably it is 10 mass parts or less, Especially preferably, the ratio of 0.1-5 mass parts is enough with respect to 100 mass parts of carboxyl group-containing resin.

Moreover, in order to insolubilize or insolubilize an ethylenically unsaturated group containing carboxyl group-containing resin to aqueous alkali solution, the compound which has several ethylenically unsaturated group can also be added to the photocurable resin composition of this embodiment. As such a compound, Diacrylates of glycol, such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, propylene glycol; Polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or ethyl acetate adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; And melamine acrylate, and / or each methacrylate corresponding to the acrylate.

Moreover, hydroxyacrylates, such as pentaerythritol triacrylate, and isophorone in the epoxy acrylate resin which made acrylic acid react with polyfunctional epoxy resins, such as a cresol novolak-type epoxy resin, and the hydroxyl group of this epoxy acrylate resin. Epoxy urethane acrylate compounds etc. which reacted the half urethane compound of diisocyanate, such as diisocyanate, are mentioned. Such epoxy acrylate-based resin can improve photocurability without deteriorating the touch dryness.

As for the compounding quantity of the compound which has some ethylenically unsaturated group in such a molecule | numerator, the ratio of 5-100 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing resin. When the compounding quantity is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult due to alkali development after active energy ray irradiation. On the other hand, if it exceeds 100 parts by mass, the solubility in an aqueous alkali solution is lowered and the coating film becomes weak. More preferably, it is 10-70 mass parts.

In order to raise the physical strength of the coating film, etc. of the photocurable resin composition of this embodiment, a filler can be mix | blended as needed. Known inorganic or organic fillers can be used as such fillers, but barium sulfate, spherical silica, hydrotalcite and talc are particularly preferred. Moreover, in order to obtain a white appearance and flame retardance, metal hydroxides, such as titanium oxide, a metal oxide, and aluminum hydroxide, can also be used as a extender pigment filler.

It is preferable that the compounding quantity of such a filler is 75 mass% or less of the whole composition. When the compounding quantity of a filler exceeds 75 mass% of the whole composition, the viscosity of an insulating composition will become high, applicability | paintability and moldability will fall, and hardened | cured material will become weak. And more preferably from 0.1 to 60 mass%.

Moreover, the organic solvent can be used for the photocurable resin composition of this embodiment for the synthesis | combination of carboxyl group-containing resin, 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, petroleum solvents and the like. 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 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.

Since most of the high molecular material is oxidized once, oxidation deterioration occurs in sequence, and the function of the high molecular material is degraded. Therefore, the radicals generated in the photocurable resin composition of the present embodiment are invalidated to prevent oxidation. Radical supplements and / or antioxidants, such as peroxide decomposers, which decompose the generated peroxides into harmless substances to prevent the generation of new radicals.

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

The radical supplement may be commercially available, for example, adecastab (registered trademark) AO-30, adecastab AO-330, adecastab AO-20, adecastab LA-77, adecastab LA-57 , Adecastab LA-67, Adecastab LA-68, Adecastab LA-87 (all manufactured by Adeca), Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (all are the Siba Japan company make), etc. are mentioned.

As antioxidant which functions as a peroxide decomposition agent, For example, phosphorus compounds, such as a triphenyl phosphite, pentaerythritol tetralauryl thio propionate, a dilauryl thio dipropionate, distearyl-3,3'- Sulfur type compounds, such as thiodipropionate, etc. are mentioned.

A peroxide decomposer may be commercially available, for example, Adecas tab TPP (made by Adeka Co.), Mark AO-412S (made by Adeka Agus Kagaku Co., Ltd.), Smallizer (registered trademark) TPS (Sumitomo Kagaku) Company) etc. are mentioned. These antioxidant can be used individually by 1 type or in combination of 2 or more types.

In addition, since the polymer material absorbs light and causes decomposition and deterioration accordingly, the photocurable resin composition of the present embodiment can use a ultraviolet absorber in addition to the antioxidant described above in order to take stabilization measures against ultraviolet rays. have.

As such a ultraviolet absorber, 2-hydroxy-4- methoxy- benzophenone- 2-hydroxy-4- methoxy benzophenone, 2-hydroxy-4- n-octoxy benzophenone, 2, 2, for example Benzophenone derivatives such as' -dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone; Butyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and hexa Benzoate derivatives such as decyl-3,5-di-t-butyl-4-hydroxybenzoate; Benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- Benzotriazole derivatives such as (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole; Triazine derivatives such as hydroxyphenyltriazine and bis (ethylhexyloxyphenol) methoxyphenyltriazine; Cinnamate derivatives such as methyl-2,4-diisopropylcinnamate and 2-ethylhexyl-p-methoxycinnamate; Anthranilate derivatives such as methyl anthranilate, phenyl anthranilate and benzyl anthranilate; and dibenzoylmethane derivatives such as t-butylmethoxydibenzoylmethane.

As a ultraviolet absorber, it may be commercially available, for example, tinuvin PS, tinubin 99-2, tinubin 109, tinubin 384-2, tinubin 900, tinubin 928, tinubin 1130, tinubin 400, tinubin 405, tinuvin 460, tinuvin 479 (all are the Siba Japan Corporation), etc. are mentioned.

Such an ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, and can be stabilized the molding obtained from the photocurable resin composition of this embodiment by using together with antioxidant.

As needed, the photocurable resin composition of the present invention may be a known thickener such as finely divided silica, organic bentonite, montmorillonite, antifoaming agents and / or leveling agents, such as silicon-based, fluorine-based, and polymer-based, imidazole-based, thiazole-based, and triazole-based compounds. Known additives such as silane coupling agents, antioxidants, rust inhibitors and the like can be blended.

Moreover, in order to prevent thermal superposition | polymerization or time-lapse superposition | polymerization of the polymeric compound contained in the photocurable resin composition in this embodiment, a polymerization inhibitor can be used.

As such a thermal polymerization inhibitor, for example, 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydride Roxybenzophenone, cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis (4-methyl- 6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactants, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and Al And chelate with.

An adhesion promoter can be used for the photocurable resin composition of this embodiment in order to improve adhesiveness between layers or adhesiveness of the photosensitive resin layer and a base material. Examples of such adhesion promoters include benzoimidazole, benzoxazole, benzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, and 5-amino-3-morpholinomethyl-thia Sol-2-thione, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

The photocurable resin composition of this embodiment comprised in this way is manufactured by predetermined composition, and is adjusted to the viscosity suitable for the application | coating method with an organic solvent, for example, and it is immersion coating method, flow coating method, roll coating on a base material. It is applied by a method such as a method, a bar coater method, a screen printing method and a curtain coating method.

The volatilization drying after application is hot air circulation drying, IR, hot plate, convection oven, etc. Spraying)) at a temperature of about 60 to 100 ° C.

Moreover, a resin insulating layer can also be formed by forming a dry film with a photocurable resin composition, and bonding this on a base material.

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

A resin insulating layer is a layer obtained by apply | coating and drying a photocurable resin composition to a carrier film or a cover film. Such a resin insulating layer is formed by uniformly applying the photocurable resin composition of the present embodiment to a carrier film at a thickness of 10 to 150 µm with a blade coater, a lip coater, a coater, a film coater, or the like, and drying it. And a dry film is formed by laminating | stacking a cover film as needed further. At this time, after apply | coating a photocurable resin composition to a cover film and drying, you may laminate | stack a carrier film.

As a carrier film, thermoplastic films, such as a polyester film with a thickness of 2-150 micrometers, are used, for example.

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

When a cover film is used using such a dry film, this is peeled off, a resin insulating layer is formed on a base material by laminating | stacking a resin insulating layer and a base material, and bonding using a laminator etc .. Further, the carrier film can be peeled off before or after exposure, which will be described later.

At this time, as a base material on which a coating film is formed or a dry film is bonded, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven fabric epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine, polyethylene, PPO ㆍ By using copper clad laminate for high frequency circuit using cyanate ester etc., copper clad laminate of all grades (FR-4, etc.), other polyimide film, PET film, glass substrate, ceramic substrate, wafer board, etc. have.

In addition, by contact type (or non-contact method), pattern exposure is performed directly by an active energy ray or by direct exposure by a laser direct exposure machine through the photomask in which the pattern was formed.

As an exposure machine used for active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device which draws images directly with a laser by CAD data from a computer), an exposure machine equipped with a metal halide lamp, a (ultra) high pressure mercury lamp A direct drawing device using an ultraviolet light lamp such as a mounted exposure machine, an exposure machine equipped with a mercury short arc lamp, or a (ultra) high pressure mercury lamp can be used.

As an active energy ray, it is preferable to use the laser beam whose wavelength is 350-410 nm. By making wavelength into this range, radical can be produced efficiently from a photoinitiator. If the laser beam of this range is used, it may be either a gas laser or a solid state laser. Moreover, although the exposure amount changes with film thickness etc., it is generally 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. may be used, and any apparatus may be used as long as the apparatus emits laser light having a wavelength of 350 to 410 nm.

And, this way, by exposing, to cure the exposed portion (irradiated portion by the active energy ray), and developed with a dilute alkali aqueous solution of the exposed area (e.g., 0.3 to 3 wt.% Na ₂ CO ₃ aqueous solution) , Hardened | cured material (pattern) is formed.

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

Moreover, when it contains a thermosetting component, for example, by heating to a temperature of about 140-180 degreeC and thermosetting, the carboxyl group of carboxyl group-containing resin and the thermosetting component which has several cyclic (thio) ether group in a molecule | numerator react. Thus, a cured product excellent in various properties such as heat resistance, chemical resistance, hygroscopicity, adhesion, and electrical properties can be formed.

<Examples>

Although an Example and a comparative example are shown to the following and demonstrated concretely, of course, this invention is not limited to these Examples. In addition, below "part" and "%" are a mass reference | standard unless there is particular rejection.

[Synthesis of carboxyl group-containing resin (A-1)]

In an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device, and a stirring device, 119.4 g of a novolak-type cresol resin (Showa Kobunshi Co., Ltd., brand name "Shonol CRG951", OH equivalent: 119.4), potassium hydroxide 1.19 g and toluene 119.4g were thrown in, the inside of a system was substituted by nitrogen, stirring, and it heated up.

Next, 63.8 g of propylene oxide was slowly added dropwise and reacted at 125 to 132 ° C and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added and mixed with the reaction solution to neutralize potassium hydroxide, and a propylene oxide reaction of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. A solution was obtained. It was found that an average of 1.08 mole of alkylene oxide per 1 equivalent of phenolic hydroxyl group was added.

293.0 g of the alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air blown pipe, Was blown at a rate of 10 ml / min and reacted at 110 ° C for 12 hours while stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 g of water flowed out. Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized in 35.35 g of an aqueous 15% sodium hydroxide solution, followed by washing with water.

Thereafter, toluene was distilled off while replacing toluene with 118.1 g of diethylene glycol monoethyl ether acetate in an evaporator to obtain a novolac acrylate resin solution. Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air blown tube, and the air was blown at a rate of 10 ml / min, while stirring. 60.8 g of tetrahydrophthalic anhydride was added gradually, and it was made to react at 95-101 degreeC for 6 hours. A photosensitive resin having a carboxyl group of an acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. Hereinafter, this reaction solution is called resin solution A-1.

[Synthesis of carboxyl group-containing resin (A-2)]

1070 g (glycidyl) to orthocresol novolak-type epoxy resin (DIC Corporation make, EPICLON N-695, softening point 95 degreeC, epoxy equivalent 214, average functional number 7.6) to 600 g of diethylene glycol monoethyl ether acetate Radix (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were thrown in, and it heated and stirred at 100 degreeC, and melt | dissolved uniformly.

Subsequently, 4.3 g of triphenylphosphines were thrown in, and it heated at 110 degreeC, after reaction for 2 hours, it heated up at 120 degreeC and reacted for 12 hours further. 415 g of aromatic hydrocarbon (Solvso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction liquid, and it reacted at 110 degreeC for 4 hours, and after cooling, solid acid value 89 mgKOH / g, solid content 65 % Resin solution was obtained. This is designated as resin solution A-2.

After using these resin solutions A-1, A-2 and commercially available resin solutions A-3 and A-4, it mix | blends with the various components and ratio (mass part) shown in Table 1, and after pre-mixing in a stirrer, It knead | mixed with the triaxial roll mill and manufactured the photocurable resin composition for soldering resists. Here, when the dispersion degree of the obtained resin composition was evaluated by the particle size measurement by the Eriksen company grinder, it was 15 micrometers or less.

Remarks

* 1: ZFR-1401H (solid content: 65.0%, solid acid value: 100 Nippon Kayaku Co., Ltd. make)

* 2: ZCR-1601H (solid content: 65.0%, solid acid value: 100 Nippon Kayaku Co., Ltd. make)

* 3: 2-Methyl-1- (4-methylthiophenyl) -2-morpholino propane-1-one (IRGACURE 907 by Ciba Japan Corporation)

* 4: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] 1,1- (O-acetyl oxime) (Ilgacure from Ciba Japan Corporation) OXE02)

* 5: Compound obtained by condensation reaction of bisphenol A with halogenated methyl styrene (manufactured by Showa Chemical Industries, Ltd .: Repoxy BPV-1X)

* 6: oligophenylene ether compound of terminal styrene (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

* 7: bismaleimide compound (MIA-200 by DIC Corporation)

* 8: 4,4'- diphenylmethane bismaleimide (BMI-1000H by Daiwa Kasei Kogyo Co., Ltd.)

* 9: 3,3'- dimethyl-5,5'-diethyl-4,4'- diphenylmethane bismaleimide (BMI-5100 by Daiwa Kasei Kogyo Co., Ltd.)

* 10: 1,6-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH manufactured by Yamato Kasei Kogyo Co., Ltd.)

* 11: 2,4,6-trimercapto-s-triazine (Disnet F manufactured by Sankyo Kasei Co., Ltd.)

* 12: 1, 4-bis (3-mercapto butyryloxy) butane (Carens MTBD1 by Showa Denko Co., Ltd.)

* 13: 2-mercaptobenzothiazole (Kawaguchi Chemical Industries, Ltd. accelerator M)

* 14: Polybutadiene skeleton epoxy resin (PB3600 by Daicel Chemical Industries, Ltd.)

* 15: bisphenol-type epoxy resin (YSLV-80XY by Shin-Nitetsu Chemical Co., Ltd.)

* 16: Block isocyanate (TPA-B80E by Asahi Kasei Chemicals Co., Ltd.)

* 17: Methylated melamine resin (Mw-100LM by Sanwa Chemical Co., Ltd.)

* 18: antioxidant (made by Shiba Japan)

* 19: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

* 20: B-30 (manufactured by Sakai Chemical Industries, Ltd.)

* 21: C.I. Pigment Blue 15: 3

* 22: C.I. Pigment Yellow 147

* 23: dipropylene glycol monomethyl ether

Performance rating:

<Optimum exposure dose>

After the buff roll polishing, the compositions of each of the examples and the comparative examples shown in Table 1 were applied to the entire surface by screen printing, respectively, to a circuit pattern substrate having a thickness of 35 占 퐉 and dried copper. It was dried in a drying furnace for 60 minutes.

After drying, an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) was used for exposure through a step tablet (Kodak No. 2), followed by development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution). ) Was performed at 60 seconds, and the optimum exposure dose was determined when the remaining step tablet pattern was seven stages.

<Developability>

The composition of the Example and comparative example of Table 1 was apply | coated so that it might become about 25 micrometers after drying by the screen printing method on the copper front substrate, and it dried for 30 minutes in the hot air circulation type drying furnace of 80 degreeC. After drying, image development was performed with the 1 mass% sodium carbonate aqueous solution, and time until the dry coating film was removed was measured with the stopwatch.

Characteristic test:

The composition of each Example and the comparative example of Table 1 is apply | coated whole surface so that the film thickness after drying may be set to 20 micrometers by screen printing on the patterned copper foil board | substrate, it is made to dry at 80 degreeC for 30 minutes, and is cooled to room temperature. The substrate was exposed to a solder resist pattern at an optimum exposure dose using an exposure apparatus equipped with a high pressure mercury lamp (short arc lamp), and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed at a spray pressure of 2 kg / cm ² . It developed for 60 second and obtained the resist pattern.

This board | substrate was irradiated with the ultraviolet-ray on the conditions of accumulated exposure amount 1000mJ / cm <^2> by UV conveyor, and it heated at 170 degreeC for 60 minutes, and hardened | cured. The properties of the obtained printed board (evaluation board) were evaluated as follows.

Electroless Gold Plating

After plating on the conditions of 0.5 micrometer of nickel and 0.03 micrometer of gold using the electroless nickel plating bath and the electroless gold plating bath of a commercial item, after evaluating the presence or absence of the peeling of the resist layer or the plating permeation by peeling a tape, The presence or absence of peeling of the resist layer was evaluated by peeling a tape. The criteria are as follows.

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

 (Circle): Slight permeation is confirmed after plating, but it does not peel after tape peeling.

 (Triangle | delta): Only a slight permeation is seen after plating, and peeling is also seen after tape peeling.

 X: Peeling occurred after plating.

<Insulation after humidification test (HAST)>

The composition of each Example and the comparative example of Table 1 was apply | coated to the board | substrate with which the comb-shaped electrode (line / space = 50 micrometer / 50 micrometer) was formed, and it exposed and developed, and was thermosetted, and the evaluation board | substrate was produced. This evaluation board | substrate was put into the high temperature high humidity tank in the atmosphere of 130 degreeC, and humidity of 85%, the voltage was charged at 5V, and the HAST (Highly Accelerated Stress Test) was done for 192 hours. Electrical insulation after HAST was measured.

<TCT immunity>

The evaluation board | substrate with which the composition of each Example and comparative example of Table 1 was apply | coated to the board | substrate with a 2 mm copper line pattern, exposed, and developed, and then thermosetted and the resist pattern of 3 mm square was formed on the copper line. Was produced. This evaluation board | substrate was put into the cold heat cycle machine which temperature cycle is performed between -65 degreeC and 150 degreeC, and TCT (Thermal Cycle Test) was done. And the external appearance at 600 cycles, 800 cycles, and 1000 cycles was observed.

(Double-circle): No abnormality in 1000 cycles.

○: No abnormality at 800 cycles, cracking at 1000 cycles.

(Triangle | delta): No abnormality in 600 cycles, and a crack generate | occur | produced in 800 cycles.

X: The crack generate | occur | produced in 600 cycles.

<PCT Resistance>

The evaluation board | substrate which formed the hardened | cured material (hardened film) of the composition of each Example and comparative example of Table 1 was 121 degreeC, saturation, 0.2 using PCT apparatus (HAST system TPC-412MD made by SPECK Corporation). Under the conditions of MPa, 168, 192 hours PCT (Pressure Cooker Test) was performed. And the state of the coating film after a process was evaluated. The criteria are as follows.

(Double-circle): No expansion, peeling, discoloration, and elution for 192 hours.

(Circle): No expansion, peeling, discoloration, and elution for 168 hours.

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

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

Dry Film Evaluation:

The evaluation board | substrate was produced by the method shown below about the photosensitive resin composition of Example 1 and the comparative example 1, and it evaluated similarly.

<Dry Film Production>

After properly diluting the photocurable resin compositions of Example 1 and Comparative Example 1 with methyl ethyl ketone, respectively, and using an applicator, a PET film (FB-50 manufactured by Toray Industries, Inc.) so that the film thickness after drying might be 20 µm. 16 µm) and dried at 80 ° C. for 30 minutes to obtain a dry film.

<Substrate Fabrication>

After buffing the circuit-formed substrate, and using the vacuum laminator (MVLP (registered trademark) -500 manufactured by Meiki Seisakusho Co., Ltd.), the dry film produced by the above method was pressurized: 0.8 MPa, 70 DEG C, 1 minute, Vacuum degree: It heat-laminated on the conditions of 133.3 Pa, and obtained the board | substrate (unexposed board | substrate) which has an unexposed soldering resist layer.

The evaluation results are shown in Table 2.

As shown in Table 2, in Examples 1 to 8 using the styryl group-containing compound and the maleimide compound, favorable HAST, TCT resistance and PCT resistance were obtained without lowering photocurability in comparison with Comparative Examples 1 to 4. I could see. In particular, in Example (Example 1, 2, 6-8) which contains A-1 as carboxyl group-containing resin, it turned out that it is excellent in insulation reliability and is useful as a soldering resist.

On the other hand, in Comparative Examples 2-4 which do not use the maleimide compound, TCT resistance and PCT resistance were inferior, and it was a coating film which is weak with respect to the obtained cured coating film. Moreover, in the case of the comparative example 1 which does not use the styryl group containing compound and the maleimide compound, TCT resistance and PCT resistance fell further, and the sensitivity fell and the electrical property fell.

Claims (5)

Containing a carboxyl group-containing resin, a photopolymerization initiator, a vinylphenyl group-containing compound, and a maleimide compound,
The said vinylphenyl group containing compound hardens-reacts with the said maleimide compound, The photocurable resin composition characterized by the above-mentioned. The photocurable resin composition according to claim 1, comprising a mercapto compound. It is obtained by apply | coating and drying the photocurable resin composition of Claim 1 or 2 on a film, The dry film characterized by the above-mentioned. The dry coating film obtained by apply | coating and drying the photocurable resin composition of Claim 1 or 2 to a base material, or the coating film obtained by laminating | stacking the dry film obtained by apply | coating and drying the said photocurable resin composition on a film to an active energy Cured product obtained by photocuring by irradiation of a line. The dry coating film obtained by apply | coating and drying the photocurable resin composition of Claim 1 or 2 to a base material, or the coating film obtained by laminating | stacking the dry film obtained by apply | coating and drying the said photocurable resin composition on a film to an active energy It has a pattern of the hardened | cured material obtained by photocuring by irradiation of a line, The printed wiring board characterized by the above-mentioned.