TWI420243B - A photohardenable resin composition, a dry film thereof and a hardened product, and a printed circuit board using the same - Google Patents

Description

Photocurable resin composition, dry film and cured product thereof, and printed circuit board using the same

The present invention relates to a photocurable resin composition which can be developed by a dilute aqueous alkali solution, and more particularly to a composition for a solder resist which is photocured by ultraviolet exposure or laser exposure, a dry film thereof and a cured product, and has use thereof. A printed circuit board of the hardened film formed therefrom.

Conventionally, an alkali-developing photosensitive resin composition has been used in a large amount as a solder resist for a printed circuit board. The solder resist is mainly composed of a carboxyl group-containing resin, a polyfunctional acrylate compound, a photopolymerization initiator, a thermosetting resin, or the like in order to protect the circuit of the printed circuit board. The above polyfunctional acrylate-based compound is mainly used in the form of liquid polyfunctional polyester acrylate from the viewpoint of high sensitivity and development resistance. However, when exposed, when the negative film is directly attached to the dry exposure film, the dry film is required to be dry (non-sticky). In order to improve the photocurability, a photosensitive resin composition of a liquid polyfunctional polyester acrylate is used in a large amount, and there is a problem that the dryness of the dry coating film is poor. Therefore, the amount of liquid polyfunctional polyester acrylate used is limited. In response to this, it has been proposed to use a semi-solid polyester (meth) acrylate to improve the dryness of the touch (see Patent Document 1). However, at this time, since the polyester (meth) acrylate is bifunctional, and the semi-solid shape is lowered, the sensitivity is lowered, and in order to improve the softening point of the dried coating film, there is a problem that the developability is lowered.

Further, the solder resist is used to protect the surface circuit of a printed circuit board as described above, and requires high solder heat resistance and electrical insulation. However, since the photosensitive resin is an acrylate-based compound, it is inferior in hydrophobicity and alkali resistance, and needs to be improved in terms of electrical insulation properties in which the insulation resistance value is lowered under high-temperature humidification conditions, and ion migration occurs to cause an inter-circuit short circuit. The problem.

On the other hand, Patent Document 2 discloses a carboxyl group-containing photosensitive property obtained by reacting a reaction product of an epoxy compound having two or more epoxy groups in one molecule with a monocarboxylic acid containing an unsaturated group and then reacting with a polybasic acid anhydride. The carboxyl group-containing photosensitive resin obtained by reacting a reaction product of a resin, a reaction product of a novolac type phenol resin and an epoxide with a reaction product obtained by reacting a monocarboxylic acid containing an unsaturated group with a polybasic acid anhydride, has good dryness and compactness. An example of a photosensitive composition excellent in properties. However, the carboxyl group-containing photosensitive resin obtained by reacting a reaction product of a phenolic phenol resin and an epoxide with a reaction product obtained by reacting a monocarboxylic acid containing an unsaturated group with a polybasic acid anhydride is added to a hydroxyl group produced by ring opening of an epoxide Since the unsaturated group contains a carboxylic acid and a polybasic acid anhydride, the content of the unsaturated group is reduced in order to obtain a necessary acid value, and in order to contain a large amount of unsaturated groups, the necessary acid value cannot be obtained, and the sensitivity and the display are apparent. Like the choice of the relationship.

Patent Document 1: International Publication WO 03/075095 A1 (Scope of Application)

Patent Document 2: JP-A-2003-280189 (Scope of Application)

The present invention has been made in view of the above conventional problems, and an object of the present invention is to provide a dry coating film which is excellent in touch drying property, high sensitivity, soft solder heat resistance, electroless gold resistance, moisture resistance, electrical insulation, and the like. It is excellent in the photocurable resin composition which can form a hardening film, such as a soldering agent which has high insulation resistance at the time of high temperature humidification.

Further, an object of the present invention is to provide a printed circuit comprising a dry film and a cured product excellent in the above-described properties obtained by using the photocurable resin composition, and a cured film formed by forming a solder resist or the like by the dry film and the cured product. board.

In order to achieve the above object, according to the present invention, it is possible to provide a photo-curable resin composition having an alkali-developing property, which comprises a photosensitive resin having a structure represented by the following general formula (I) (hereinafter referred to as " A photosensitive resin "), a carboxyl group-containing resin, and a photopolymerization initiator.

【化1】

(wherein R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different, and R ² represents an alkyl group selected from carbon atoms of 1 to 10, an alkylene group having a carbon number of 1 to 10, and a functional group of at least one of a group of phenyl groups, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents a hydrogen atom. Or a methyl group, p is an integer of 1 to 5, q is an integer of 3 or more, m is an integer of 1 to 4, and n is an integer of 1 to 10.

A preferred embodiment is the photocurable resin composition according to claim 1, wherein the photosensitive resin does not contain an acid and has a double bond equivalent of 200 or more and 400 or less.

Further, the photosensitive resin is a photosensitive resin obtained by reacting a compound having three or more phenolic hydroxyl groups in one molecule with a cyclic ether compound or a cyclic carbonate compound, and reacting the generated hydroxyl group with a compound having an ethylenically unsaturated group. Resin.

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

Preferably, the form further contains a thermosetting component, preferably a coloring agent. Such a photocurable resin composition, particularly a photocurable thermosetting resin composition containing a thermosetting component, is suitably used as a solder resist.

According to the present invention, it is possible to provide a photocurable dry film obtained by applying the photocurable resin composition onto a carrier film and dried, or curing the photocurable resin composition or the dry film. A cured product or a cured product obtained by photohardening, in particular, on copper, or a cured product obtained by photohardening into a pattern.

According to the present invention, it is possible to provide a printed circuit board having a cured film obtained by thermally curing the photocurable resin composition or the dry film in a pattern form.

The photocurable resin composition of the present invention is a photosensitive resin containing a structure represented by the above general formula (I), and particularly contains no acid, and has a double bond equivalent of 200 or more and 400 or less.

The photosensitive resin is obtained by reacting a compound having three or more phenolic hydroxyl groups in one molecule with a cyclic ether compound or a cyclic carbonate compound, and reacting the resulting hydroxyl group with a compound having an ethylenically unsaturated group, and drying and coating The film is excellent in dryness to the touch, high in sensitivity, soft solder heat resistance, electroless gold resistance, moisture resistance, electrical insulation, and the like, and particularly, a hardened film having high insulation resistance at high temperature and humidification can be formed. At the same time, the photosensitive resin and the carboxyl group-containing resin are contained, and the obtained photocurable resin composition can be developed by an aqueous alkali solution.

Therefore, the photocurable resin composition of the present invention can be suitably used for a hardened film of a printed circuit board or a solder resist which forms a flexible printed circuit board.

Best form for implementing the invention

Hereinafter, embodiments of the present invention will be described.

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

According to the study by the inventors of the present invention, it has been found that the dried coating film of the photocurable resin composition obtained by the photosensitive resin having the structure represented by the above general formula (I) is excellent in finger-drying property, and the cured film is The insulation resistance value under high-temperature humidification conditions is high, and there is no ion migration occurring in the case where the above-mentioned photosensitive resin is not contained, and there is no problem for a long time. In particular, a compound which does not contain the acid and has a double bond equivalent of 200 or more and 400 or less, and a compound having three or more phenolic hydroxyl groups in one molecule reacts with a cyclic ether compound or a cyclic carbonate compound to form a hydroxyl group. When the photosensitive resin obtained by reacting with the compound having an ethylenically unsaturated group was found, the sensitivity was found to be improved. More surprisingly, as the amount of the photosensitive resin used is increased, the elongation of the cured film can be improved. Therefore, the crack resistance, the softness, and the impact resistance of the hardened film are excellent, which is an unexpected effect that cannot be expected.

The photosensitive resin contains three or more structures (q≧3) represented by the above general formula (I) in one molecule. When the structure represented by the above general formula (I) is two or less in one molecule, high sensitivity cannot be achieved by one of the objects of the present invention, particularly in the case of a solder resist, the surface is harden poor, and as a result, the electricity is heated at a high temperature. Low insulation and ion migration. Similarly, a double bond equivalent of 200 or less is structurally impossible, and when it is 400 or more, high sensitivity cannot be achieved, and electrical insulating properties and ion mobility are poor. Therefore, the double bond equivalent is preferably 200 or more and 400 or less.

The photosensitive resin containing the structure represented by the above general formula (I) can be synthesized by a conventionally known method, and it is preferred to use a compound having three or more phenolic hydroxyl groups in one molecule and a cyclic ether compound or cyclic carbonic acid. The ester compound reacts to form a photosensitive resin obtained by reacting an alcoholic hydroxyl group with a compound having an ethylenically unsaturated group. In addition, when the photosensitive resin obtained by reacting the alcoholic hydroxyl group with the compound having an ethylenically unsaturated group has three or more structures represented by the above general formula (1), the alcoholic hydroxyl group may remain.

The compound having three or more phenolic hydroxyl groups in one molecule described above is, for example, a novolac type phenol resin. The novolac type phenol resin is obtained by a condensation reaction of a phenol with formaldehyde, and usually these reactions are carried out in the presence of an acidic catalyst. The phenols used for the synthesis of the phenolic phenol resin include, for example, phenol, cresol, ethyl phenol, propanol, butanol, hexanol, octylphenol, indophenol, phenol, cumene, bisphenol A, bisphenol F, These may be used alone or in large quantities, such as dimethicone. Further, a condensate of a phenol and an aromatic aldehyde having a phenolic hydroxyl group, a poly-p-hydroxystyrene, a 1-naphthol or a condensate of 2-naphthol and an aldehyde (that is, a naphthol type phenol resin), Condensate of 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 2,3-, 2,6-, 2,7-dihydroxynaphthalene and aldehydes, single a condensate of naphthol with the above dihydroxynaphthalene and an aldehyde, a condensate of a mono- or dihydroxynaphthalene with a xylene glycol, an adduct of a mono- or dihydroxynaphthalene with a diene compound, a phenol and a bis (methoxy A condensate of a methyl group)biphenyl, etc., but is not limited thereto. In particular, the phenol resin preferably has an average phenolic number of 3 or more.

In the above-mentioned cyclic ether compound or cyclic carbonate compound, the cyclic ether compound may, for example, be ethylene oxide, propylene oxide, 1,2-butylene oxide, trimethylmethane, tetrahydrofuran or tetrahydropyran.

Further, the cyclic carbonate compound may, for example, be ethylene carbonate or propylene carbonate. Particularly preferred are ethylene oxide and propylene oxide.

The compound having an ethylenically unsaturated group is, for example, acrylic acid or methacrylic acid, and particularly preferably methacrylic acid from the viewpoint of alkali resistance or electrical insulating properties. The photosensitive resin using methacrylic acid is highly sensitive, in particular, excellent in alkali resistance and electrical properties, and can provide a cured product having a high insulation resistance value at the time of high-temperature humidification, which is an unexpected result which has not been seen in the past.

The blending amount of the photosensitive resin is, for example, suitably contained in an amount of from 1 to 100 parts by mass, preferably from 5 to 60 parts by mass, more preferably from 10 to 40 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the amount of the photosensitive resin is more than the above range, the alkali developability is lowered, and the solution is caused to develop a developing residue. On the other hand, when the amount is 1 part by mass or less, the image forming ability is affected, which is not preferable.

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

Specific examples of the carboxyl group-containing resin are preferably listed below, for example. Compound (oligomer or polymer).

(1) A copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with a compound containing an unsaturated group such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene Carboxyl containing resin.

(2) By including a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a dimethylolpropionic acid or a dimethylolbutyric acid a diol compound of a carboxyl group, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, and a bisphenol A-based alkylene oxide adduct diol, A carboxy group-containing urethane resin obtained by a polymerization addition reaction of a diol compound such as a phenolic hydroxyl group and an alcoholic hydroxyl group.

(3) by making diisocyanate with bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, dixylenol type epoxy resin Photosensitive carboxyl group obtained by polymerization addition reaction of a (meth) acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing diol compound, and a diol compound of a bifunctional epoxy resin such as a bisphenol epoxy resin A urethane resin.

(4) In the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and one or more (meth)acrylic groups in a molecule such as a hydroxyalkyl (meth) acrylate is added. A terminally (meth)acrylated photosensitive carboxyl group-containing urethane resin.

(5) In the synthesis of the resin of the above (2) or (3), a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added, and one isocyanate group and one or more are contained in the molecule ( A methyl)acrylic acid-based compound which is terminally (meth)acrylated with a carboxyl group-containing urethane resin.

(6) A photosensitive carboxyl group-containing resin obtained by reacting a bifunctional or bifunctional or higher polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to a hydroxyl group of a side chain.

(7) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin described later with epichlorohydrin, and (meth)acrylic acid, and a dibasic acid anhydride is added thereto. A photosensitive carboxyl group-containing resin of a hydroxyl group.

(8) A carboxyl group-containing polyester resin obtained by reacting a bifunctional oxetane resin described below with a dicarboxylic acid to add a dibasic acid anhydride to the produced first-order hydroxyl group.

(9) A photosensitive carboxyl group-containing resin formed by adding a compound having one epoxy group and one or more (meth)acrylic groups in one molecule to the above (1) to (8) resins.

Further, in the present specification, the (meth) acrylate is a generic term for acrylate, methacrylate, and the like, and the other similar performances are also the same.

Since the carboxyl group-containing resin has a large number of free carboxyl groups in the side chain of the backbone ‧ polymer, it can be developed by a dilute aqueous alkali solution.

Further, the acid value of the carboxyl group-containing resin is in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, alkali development is difficult, and when it is more than 200 mgKOH/g, dissolution occurs in the exposed portion by the developing liquid, so that the line becomes too fine, or sometimes the exposed portion is not The exposed portions are all dissolved and peeled off by the developing solution, and it is difficult to draw a normal photoresist pattern, which is not preferable.

Further, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, and is usually in the range of 2,000 to 150,000, preferably in the range of 5,000 to 100,000. When the weight average molecular weight is less than 2,000, there is a case where the coating film has poor tackiness (dryness of touch), and the moisture resistance of the coating film after exposure is poor, and film formation is reduced during development, and sometimes The resolution is very poor. Further, when the weight average molecular weight is more than 150,000, the development property is remarkably deteriorated, and the storage stability is not good.

The blending amount of the carboxyl group-containing resin is in the range of 20 to 60% by mass, preferably 30 to 50% by mass based on the total composition. When the compounding amount of the carboxyl group-containing resin is less than the above range, the film strength is lowered, which is not preferable. Moreover, when it is larger than the above range, the viscosity of the composition becomes high, and the coatability and the like are lowered, which is not preferable.

The use of the carboxyl group-containing resin is not limited to the above-mentioned ones, and it may be used alone or in combination of two or more.

The photopolymerization initiator is preferably an α-aminophenyl group selected from the group consisting of an oxime ester photopolymerization initiator having the group represented by the following general formula (II) and having the group represented by the following general formula (III). One or more photopolymerization initiators in a group of a ketone photopolymerization initiator and/or a mercaptophosphine oxide photopolymerization initiator having a group represented by the following formula (IV).

[Chemical 2]

(wherein R ⁶ represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (may be one or more hydroxyl groups) Substituted, the middle of the alkyl chain may have more than one oxygen atom), the cycloalkyl group having 5 to 8 carbon atoms, the alkyl alkene group having 2 to 20 carbon atoms or the benzamidine group (the alkyl group having 1 to 6 carbon atoms) Or a phenyl group); R ⁷ represents a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and an alkyl group having 1 to 20 carbon atoms (may be one or more hydroxyl groups) Substituted, may have more than one oxygen atom 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 benzhydryl group (alkane having 1 to 6 carbon atoms) Or a phenyl group); R ⁸ and R ⁹ each independently represent an alkyl group or an aralkyl group having 1 to 12 carbon atoms; and R ¹⁰ and R ¹¹ each independently represent a hydrogen atom and an alkyl group having 1 to 6 carbon atoms; a two-bonded cyclic alkyl ether group; R ¹² and R ¹³ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, and an aryl group. Or an aryl group substituted by a halogen atom, an alkyl group or an alkoxy group, but one of R ¹² and R ¹³ may represent an RC(=O)- group (wherein R is a carbon number of 1 to 20) Hydrocarbyl group).

The oxime ester-based photopolymerization initiator having the group represented by the above general formula (II) is preferably 2-(ethyl fluorenylmethyl) thioxanthene-9- represented by the following formula (V). A ketone, a compound represented by the following general formula (VI), and a compound represented by the following general formula (VII).

[化3]

【化4】

(wherein R ¹⁴ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamyl group, and an alkylene group having 2 to 12 carbon atoms; And an alkoxycarbonyl group having 2 to 12 carbon atoms (when the carbon number of the alkyl group constituting the alkoxy group is 2 or more, the alkyl group may be substituted by one or more hydroxyl groups, and the alkyl chain may have one or more oxygen atoms in the middle of the alkyl chain. , or phenoxycarbonyl; R ¹⁵ and R ¹⁷ each independently represent a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and an alkyl group having 1 to 20 carbon atoms (may be One or more hydroxy groups may be substituted, one or more oxygen atoms may be present 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 benzhydryl group (a carbon number may be used) 1 to 6 alkyl or phenyl substituted); R ¹⁶ is a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and an alkyl group having 1 to 20 carbon atoms. Substituted by one or more hydroxyl groups, having 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 benzhydryl group (carbon Number 1~6 alkyl or phenyl substituted)).

【化5】

(wherein R ¹⁸ , R ¹⁹ and R ²⁴ each independently represent an alkyl group having 1 to 12 carbon atoms, and R ²⁰ , R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a carbon number of 1 to 6; The alkyl group, the M system represents O, S or NH, and the x and y systems each independently represent an integer of 0 to 5)

Among the above oxime ester-based photopolymerization initiators, 2-(ethylhydrazinylmethyl)thioxanthene-9-one represented by the above general formula (V) and a compound represented by the formula (VI) are more preferred. . Commercially available products include CGI-325 manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE OXE01, IRGACURE OXE02, N-1919 manufactured by ADEKA Co., and the like. These oxime ester photopolymerization initiators may be used alone or in combination of two or more.

The α-aminoacetophenone photopolymerization initiator having the group represented by the general formula (III) is, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine. Acetone-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. Commercially available products include IRGACURE 907, IRGACURE 369, IRGACURE 379, and the like manufactured by Ciba Specialty Chemicals.

The mercaptophosphine oxide-based photopolymerization initiator having the group represented by the general formula (IV) is, for example, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, bis(2,4) ,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, etc. . Commercially available products include Lucirin TPO manufactured by BASF Corporation and IRGACURE 819 manufactured by Ciba Specialty Chemicals.

The blending amount of the photopolymerization initiator is preferably from 0.01 to 30 parts by mass, preferably from 0.5 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the amount is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off, or the coating properties such as chemical resistance are lowered, which is not preferable. On the other hand, when it exceeds 30 parts by mass, the light absorption on the surface of the solder resist coating film of the photopolymerization initiator becomes severe, and the deep hardenability tends to be lowered, which is not preferable.

In the case of the oxime ester-based photopolymerization initiator having the group represented by the above formula (II), the amount thereof is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin. It is in the range of 0.01 to 5 parts by mass.

Further, it is a photopolymerization initiator, a photoinitiator, and a sensitizer used in the photocurable resin composition of the present invention, for example, a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxanthone compound. , a ketal compound, a benzophenone compound, a xanthone compound, a tertiary amine compound, and the like.

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

Specific examples of the acetophenone compound are acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1- Dichloroacetophenone.

Specific examples of the hydrazine compound are 2-methylhydrazine, 2-ethylhydrazine, 2-t-butylhydrazine, and 1-chloroindole.

Specific examples of the thioxanthone are 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

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

Specific examples of the benzophenone compound are benzophenone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzylidene group. -4'-Ethyldiphenyl sulfide 4-benzylidene-4'-propyldiphenyl sulfide.

Specific examples of the tertiary amine compound are an ethanolamine compound and a compound having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (Nissocure MABP, manufactured by Nippon Soda Co., Ltd.), 4, 4' -Diethylaminobenzophenone, 7-(diethylamino)-4-methyl-2H-1-benzopyridine, such as diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.) a dialkylamine-containing coumarin compound, 4-dimethylaminobenzoic acid ethyl ester, such as nal-2-one (7-(diethylamino)-4-methylcoumarin) Kayacure EPA), 2-dimethylaminobenzoic acid ethyl ester (Quantacure DMB manufactured by International Bio-Synthetics, Inc.), 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester (International Bio-Synthetics) Quantacure BEA), isoamyl ethyl p-dimethylaminobenzoate (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (ESolol 507, manufactured by Van Dyk Co., Ltd.) ), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

Among the above compounds, a thioxanthone compound and a tertiary amine compound are preferred. In the composition of the present invention, a thioxanthone compound is preferred from the viewpoint of deep hardenability, and among them, 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone are preferable. A thioxanthone compound such as 2-chlorothioxanthone or 2,4-diisopropylthioxanthone.

The amount of the thioxanthone compound to be added is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the carboxyl group-containing resin. When the amount of the thioxanthone compound is too large, the thick film hardenability is lowered, and the cost of the product is increased, which is not preferable.

The tertiary amine compound is preferably a compound having a dialkylaminobenzene structure, particularly preferably a dialkylaminobenzophenone compound, and a dialkylamine-containing couma bean having a maximum absorption wavelength of 350 to 410 nm. Compound. The dialkylaminobenzophenone compound is preferred because it has a low toxicity due to its 4,4'-diethylaminobenzophenone. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm is colored in the ultraviolet range because of the maximum absorption wavelength, and the colorless pigment is used as the colorless and transparent photosensitive resin composition. A colored solder resist film that reflects the color of the coloring pigment itself. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The amount of the tertiary amine compound to be added is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the amount of the tertiary amine compound is less than 0.1 part by mass, a sufficient sensitizing effect may not be obtained. In addition, when the amount is more than 20 parts by mass, the light absorption on the surface of the dry solder resist coating film of the tertiary amine compound becomes severe, and thus the deep hardenability tends to be lowered.

These photopolymerization initiators, photoinitiating aids, and sensitizers may be used singly or in combination of two or more.

The total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is preferably in the range of 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When the amount is more than 35 parts by mass, the light is absorbed and the deep curability is lowered.

In the photocurable resin composition of the present invention, in order to improve the sensitivity, a conventional N-phenylglycine, phenoxyacetic acid, sulfurized phenoxyacetic acid, mercaptothiazole or the like can be used as the chain-linking agent. Specific examples of the chain-shifting agent include a chain-linking agent having a carboxyl group such as mercapto succinic acid, mercaptoacetic acid, mercaptopropionic acid, azlaconic acid, cysteine, ortho-benzoic acid, and derivatives thereof; mercaptoethanol and mercapto a chain-shifting agent having a hydroxyl group such as propanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, Benzyl-3-mercaptopropionate, 2,2-(extended ethylene dioxide) diethane thiol, ethane thiol, 4-methyl benzene thiol, dodecyl thiol, propane thiol, Butane thiol, pentane thiol, 1-octane thiol, cyclopentane thiol, cyclohexane thiol, glycerol sulfide, 4,4-sulfurized benzene thiol, and the like.

Further, as the chain-linking agent, a heterocyclic compound having a mercapto group, for example, a mercapto-4-butyrolactone (alias: 2-mercapto-4-butyrolactone), 2-mercapto-4-methyl-4-butyl Lactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butylsulfona lactone, 2-mercapto-4-butylidene, N-methoxy-2-indenyl -4-butyrolactam, N-ethoxy-2-mercapto-4-butylidene, N-methyl-2-mercapto-4-butylidene, N-ethyl-2-mercapto- 4-butylidene, N-(2-methoxy)ethyl-2-mercapto-4-butylidene, N-(2-ethoxy)ethyl-2-mercapto-4-butene Indoleamine, 2-mercapto-5-valerolactone, 2-mercapto-5-pentalinamide, N-methyl-2-indolyl-5-pentalinamide, N-ethyl-2-mercapto-5 - Valentamamine, N-(2-methoxy)ethyl-2-mercapto-5-pentalinamide, N-(2-ethoxy)ethyl-2-indolyl-5-pentalin Amine and 2-mercapto-6-caprolactam and the like.

In particular, a heterocyclic compound having a mercapto group which does not affect the development of the photocurable resin composition, preferably mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1, 2 , 4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole. These chain-linking agents may be used alone or in combination of two or more.

In the photocurable resin composition of the present invention, a thermosetting resin may be added in order to impart heat resistance. The thermosetting component used in the present invention may be an amine resin such as melamine resin or benzoguanamine, a blocked isocyanate compound, a cyclic carbonate compound, a polyfunctional epoxy compound, a polyfunctional oxirane compound, or a sulfur. A known thermosetting resin such as an ether resin or a melamine derivative. Particularly preferred is a thermosetting component having two or more cyclic ether groups and/or a cyclic thioether group (hereinafter referred to as a cyclic (thio)ether group) in the molecule.

The thermosetting component having two or more cyclic (thio)ether groups in the molecule is any one of a cyclic ether group having 3, 4, or 5 rings in the molecule, or a cyclic thioether group, or a compound having two or more kinds of two groups, for example, a compound having at least two or more epoxy groups in a molecule, that is, a polyfunctional epoxide, a compound having at least two or more oxygen cyclobutane groups in the molecule That is, a polyfunctional oxycyclobutane compound or a compound having two or more thioether groups in the molecule, that is, a surface thioether resin.

The above-mentioned polyfunctional epoxy compound is, for example, JER828, JER834, JER1001, JER1004 manufactured by Nippon Epoxy Co., Ltd., Epiclon 840 manufactured by Dainippon Ink and Chemicals, Epiclon 850, Epiclon 1050, Epiclon 2055, Epotot YD manufactured by Dongdu Chemical Co., Ltd. -011, YD-013, YD-127, YD-128, DER 317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Ltd., araldite 6071, araldite6084, araldite GY250, araldite GY260, Sumitomo of Ciba‧Specialty ‧Chemicals Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Chemical Industry Co., Ltd., AER330, AER331, AER661, AER664, etc. (all trade names) manufactured by Asahi Kasei Kogyo Co., Ltd. A type epoxy resin; JERYL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epiclon 165, Epotot YDB-400 manufactured by Dongdu Chemical Co., Ltd., YDB-500, DER542 manufactured by Dow Chemical Co., Ltd. , Araldite 8011 of Ciba‧Specialty ‧Chemicals, Sumi-epoxy ESB-400 by Sumitomo Chemical Industries Co., Ltd., ESB-700, AER by Asahi Kasei Industrial Co., Ltd. Brominated epoxy resin of 711, AER714, etc. (both trade names); JER 152, JER154, manufactured by Japan Epoxy Resin Co., Ltd., DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., and Epiclon manufactured by Dainippon Ink Chemical Industry Co., Ltd. N-730, Epiclon N-770, Epiclon N-865, Epotot YDCN-701, YDCN-704, manufactured by Dongdu Chemical Co., Ltd., araldite ECN1235, araldite ECN1273, araldite ECN1299, araldite XPY307, manufactured by Ciba‧Specialty Chemicals EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, manufactured by Sumitomo Chemical Industries, Inc., Sumi-Epoxy ESCN-195X, ESCN-220, AER ECN-235, manufactured by Asahi Kasei Kogyo Co., Ltd. , EPN-299, etc. (all are trade names) phenolic epoxy resin; Epiclon 830 manufactured by Dainippon Ink Chemical Industry Co., Ltd., JER807 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YDF-170, YDF-175 manufactured by Dongdu Chemical Co., Ltd. , YDF-2004, Ciba‧Specialty ‧ Chemicals company araldite XPY306 (all are trade names) bisphenol F-type epoxy resin; Dongdu Chemical Co., Ltd. Epotot ST-2004, ST-2007, ST-3000 (both Hydrogenation double for the name of the product) A type epoxy resin; JER604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Dongdu Chemical Co., Ltd., araldite MY720 from Ciba‧Specialty ‧Chemicals, Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. Ethylene epoxide type epoxy resin of the trade name), urethane type epoxy resin type epoxy resin of araldite CY-350 (trade name) manufactured by Ciba‧Specialty ‧ Chemicals Co., Ltd.; manufactured by Daicel Chemical Industry Co., Ltd. CELLOXID 2021, alicyclic epoxy resin manufactured by Ciba‧Specialty ‧ Chemicals Co., Ltd., CY179, etc. (all are trade names); YL-933 manufactured by Japan Epoxy Co., Ltd., TEN manufactured by Dow Chemical Co., Ltd., EPPN-501 , EPPN-502 (all are trade names) of trihydroxyphenylmethane type epoxy resin; Japan Epoxy resin company YL-6056, YX-4000, YL-6121 (all are trade names), etc. A cresol type or bisphenol type epoxy resin or a mixture of these; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink Chemical Industry Co., Ltd. ) bisphenol S type epoxy resin; Japanese epoxy tree Bisphenol A phenolic epoxy resin such as JER157S (trade name) manufactured by Ethylene Co., Ltd.; JERYL-931 manufactured by Japan Epoxy Resin Co., Ltd., araldite 163 manufactured by Ciba‧Specialty ‧ Chemicals Co., Ltd. (all are trade names) Phenol ethane type epoxy resin; araldite PT810 manufactured by Ciba‧Specialty ‧Chemicals, heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (all are trade names); Blenmer DGT manufactured by Nippon Oil & Fats Co., Ltd. Epoxy propyl phthalate resin; tetraethoxypropyl dimethyl phenol ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; ESN-190, ESN-360, and Dainippon ink manufactured by Nippon Steel Chemical Co., Ltd. A naphthalene-based epoxy resin such as HP-4032, EXA-4750, and EXA-4700 manufactured by Chemical Industry Co., Ltd.; a ring having a dicyclopentadiene skeleton such as HP-7200 or HP-7200H manufactured by Dainippon Ink and Chemicals Co., Ltd. Oxygen resin; epoxy methacrylate copolymerized epoxy resin of CP-50S, CP-50M, etc. manufactured by Nippon Oil Co., Ltd.; copolymerization of cyclohexylmaleimide and glycidyl methacrylate Epoxy resin; epoxy modified polybutadiene rubber derivative (eg Daicel PB-3600 (manufactured by Chemical Industry Co., Ltd.), CTBN modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Tosho Kasei Co., Ltd.), etc., but are not limited by these. These epoxy resins may be used alone or in combination of two or more. Among these, a phenolic epoxy resin, a heterocyclic epoxy resin, a bisphenol A epoxy resin or a mixture thereof is particularly preferred.

The above polyfunctional oxetane compound is, for example, bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetan) Alkyl methoxy)methyl]ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl) 3-oxo-oxetane methoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetane Alkyl)methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate a polyfunctional oxetane such as an ester or such an oligomer or copolymer, and an oxetane with a novolak resin, a poly(p-hydroxystyrene), a cardo type bisphenol, a cup An etherified product of a resin having a hydroxyl group such as an aromatic hydrocarbon (calixarene), a cup-containing resorcinol aromatic hydrocarbon or a sesquioxane. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

The compound having two or more cyclic thioether groups in the molecule is, for example, a bisphenol A-type thioether resin YL7000 manufactured by Nippon Epoxy Co., Ltd., or the like. Further, the same synthesis method may be employed, in which an oxygen atom of an epoxy group of a novolac type epoxy resin is substituted with a sulfur atom-containing episulfide resin.

The amount of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is preferably from 0.6 to 2.5 equivalents, more preferably from 0.8 to 2.0, per equivalent of the carboxyl group of the carboxyl group-containing resin. The range of equivalents. When the amount of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is less than 0.6 equivalent, the carboxyl group remains in the solder resist, and heat resistance, alkali resistance, electrical insulation, and the like are lowered. So it is not good. In addition, when it is more than 2.5 equivalents, the low molecular weight cyclic (thio)ether group remains in the dried coating film, which lowers the strength of the coating film and the like, which is not preferable.

In the photocurable resin composition of the present invention, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule as a thermosetting component can be added. The compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound or two or more molecules per molecule. A compound which blocks an isocyanate group, that is, a blocked isocyanate compound or the like.

As the aforementioned polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate are 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene Isocyanate, m-xylene diisocyanate and 2,4-toluene dimer. Specific examples of the aliphatic polyisocyanate are tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis(cyclohexyl isocyanate). And isophorone diisocyanate. A specific example of the alicyclic polyisocyanate is dicycloheptane triisocyanate. Further, for example, an adduct of an isocyanate compound, a biuret, and a trimeric isocyanate as exemplified above.

The blocked isocyanate group contained in the blocked isocyanate compound is a group which is temporarily inactivated by reaction of an isocyanate group with a block agent. Upon heating to a predetermined temperature, the blocker dissociates to form an isocyanate group.

The blocked isocyanate compound is an addition reaction product of an isocyanate compound and an isocyanate block agent. The isocyanate compound which can be reacted with the block agent is, for example, a trimeric isocyanate type, a biuret type, an addition molding or the like. The isocyanate compound is, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate. Specific examples of the aromatic polyisocyanate are 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene Isocyanate, m-xylene diisocyanate and 2,4-toluene dimer. Specific examples of the aliphatic polyisocyanate are tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis(cyclohexyl isocyanate). And isophorone diisocyanate. A specific example of the alicyclic polyisocyanate is dicycloheptane triisocyanate.

The isocyanate block agent is, for example, a phenolic blocker such as phenol, cresol, xylenol, chlorophenol or ethylphenol; ε-caprolactam, δ-valeroinamide, γ-butylide and β - an internal amide-based block agent such as propionamide; an active methylene-based block agent such as ethyl acetoxyacetate or acetonitrile; methanol, ethanol, propanol, butanol, pentanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, An alcohol-based block agent such as methyl lactate or ethyl lactate; a quinone blocker such as formaldehyde hydrazine, acetaldehyde oxime, acetamidine, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine or cyclohexane hydrazine; a thiol blocker such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophene, methyl thiophene or ethyl thiophene; acid amide amine such as decylamine or benzoguanamine a sulphate blocker such as succinimide succinimide or succinimide maleate; an amine blocker such as xylidine, aniline, butylamine or dibutylamine; imidazole, 2- An imidazole blocker such as ethyl imidazole; An imine blocker such as methyleneimine or propylimine.

The blocked isocyanate compound may be a commercially available product, for example, Sumijur BL3175, BL-4165, BL-1100, BL-1265, Desmojur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117 manufactured by Sumitomo Bayer urethane Co., Ltd. Desmosamu 2170, desmosamu 2265, Coronato 2512, Coronato 2513, Coronato 2520, manufactured by Mitsui Takeda Chemical Co., Ltd., B-830, B-815, B-846, B-870, B-874, B-882, manufactured by Polyurethane Industries, Japan Asahi Kasei Chemicals Corporation's TPA-B80E, 17B-60PX, E402-B80T (both trade names). Further, Sumijur BL-3175 and BL-4265 were obtained by using methyl ethyl hydrazine as a block agent.

The compound having two or more isocyanate groups or blocked isocyanate groups in one molecule may be used alone or in combination of two or more.

The compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably from 1 to 100 parts by mass, more preferably from 2 to 70, based on 100 parts by mass of the carboxyl group-containing resin. The proportion of parts by mass. When the amount of the above formulation is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable.

The thermosetting component is, for example, a melamine derivative or a benzoguanamine derivative. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, and the like. In addition, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound are obtained by making each of the hydroxyl groups The hydroxymethyl group of a melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, and a methylol urea compound is converted into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group and the like. In particular, a melamine derivative having a formaldehyde water concentration of preferably 0.2% or less is preferred for the human body or the environment.

Such commercially available products are, for example, Cymel 300 manufactured by Mitsui Cyanamide Co., Ltd., 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272. Nikalac Mx-750, same as Mx-032, same Mx-270, and Mx -280, the same Mx-290, the same Mx-706, the same Mx-708, the same Mx-40, the same Mx-31, the same Ms-11, the same Mw-30, the same Mw-30HM, the same Mw-390, the same Mw -100LM, same as Mw-750LM (above is the trade name). These thermosetting components may be used alone or in combination of two or more.

When the thermosetting component having two or more cyclic (thio)ether groups in the molecule is used, it is preferred to contain a thermosetting catalyst. The thermosetting catalyst is, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl Imidazole derivatives such as 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide; benzyldimethylamine, 4-(II) Amine compounds such as methylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine A hydrazine compound such as adipic acid diamine or sebacic acid diamine; a phosphorus compound such as triphenylphosphine or the like. Further, commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all of which are trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industrial Co., Ltd., and U-CAT (registered trademark) manufactured by San-apro Co., Ltd. 3503N, U-CAT3502T (all trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CAT SA102, U-CAT 5002 (all of which are bicyclic guanidine compounds and salts thereof). It is not particularly limited thereto, and the thermosetting catalyst of the epoxy resin or the oxetane compound or the epoxy group and/or the oxetane group may be reacted with the carboxyl group, and may be used alone or in combination of two or more. Mixed use. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-ethylene can be used. Benzyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ‧ trimeric isocyanate adduct, 2,4-diamino group An S-triazine derivative such as a 6-methacryloxyethyloxy-S-triazine/trimeric isocyanate addition product, preferably used in combination as an adhesion imparting agent The compound is a thermosetting catalyst as described above.

The blending amount of the thermosetting catalyst may be a ratio of a general amount, for example, 100 parts by mass of the thermosetting component having a carboxyl group-containing resin or a cyclic (thio)ether group having two or more molecules in the molecule, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

In the photocurable resin composition of the present invention, in order to improve the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate, an adhesion promoter may be used. Specific examples include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinylmethyl-1-phenyl - triazole-2-thione, 5-amino-3-morpholinylmethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, Benzotriazole, carboxybenzotriazole, amine-containing benzotriazole, decane coupling agent, and the like.

The compound having two or more ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with an active energy ray to form a carboxyl group containing the ethylenically unsaturated group. The resin is insoluble in an aqueous alkali solution or contributes to insolubilization. Such a compound is, for example, a diacrylate of a glycol of ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol or the like; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, trihydroxyethyl a polyhydric alcohol such as a polytrimethylene isocyanate or a polyacrylate such as an ethylene oxide adduct or a propylene oxide adduct; a phenoxy acrylate, a bisphenol A diacrylate, and the like a polyacrylate such as an ethylene oxide adduct or a propylene oxide adduct; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl trimer a polyacrylate of a glycidyl ether such as an isocyanate; and a melamine acrylate and/or a methacrylate corresponding to the above acrylate.

Further, for example, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as a cresol novolac type epoxy resin with acrylic acid, or a hydroxyl group of an epoxy acrylate resin and pentaerythritol triacrylate, etc. An epoxy group-ethyl urethane compound obtained by reacting a hydroxy acrylate with an ethyl melamine compound of a diisocyanate such as isophorone diisocyanate. These epoxy acrylate-based resins do not reduce the dryness of the touch and improve the photocurability.

The compounding amount of the compound having two or more ethylenically unsaturated groups in the molecule is preferably from 5 to 100 parts by mass, more preferably from 1 to 70 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. . When the amount of the above-mentioned compounding amount is less than 5 parts by mass, the photocurability is lowered, and the alkali image after irradiation with the active energy ray is difficult to form a pattern, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the coating film becomes brittle due to a decrease in solubility in an aqueous alkali solution, which is not preferable.

The photocurable resin composition of the present invention can be formulated with a colorant. As the coloring agent, a conventional coloring agent such as red, blue, green, or yellow may be used, or any of a pigment, a dye, and a coloring matter may be used. However, in terms of reducing the environmental burden and affecting the human body, it is preferable to have no halogen.

Red colorant:

Examples of the red coloring agent include monoazo, diazo, azo lake, benzimidazolone, anthraquinone, dioxopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. For example, the following are specifically mentioned below.

Monoazo system: Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.

Diazo nitrogen system: Pigment Red 37, 38, 41.

Azo 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.

The system is: 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.

Dioxopyrrolopyrrole: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

蒽醌: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

The blue coloring agent is an anthraquinone-based or an anthraquinone-based, and the pigment is classified into a pigment (Pigment), and specifically, for example, the following color index (CI; The Society of Dyers and Colourists issued) number; 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.

For the 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 and so on. In addition to the above, a metal-substituted or unsubstituted anthraquinone compound can also be used.

Green colorant:

The green colorant also has anthraquinone, anthraquinone, and anthraquinone, specifically, for example, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like. In addition to the above, a metal-substituted or unsubstituted anthraquinone compound can also be used.

Yellow colorant:

The yellow coloring agent may be a monoazo type, a diazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type, an anthraquinone type, etc., and specifically, for example, the following.

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

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

Condensed 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 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.

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

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

Specifically, for example, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CIPigment Orange 1, CIPigment Orange 5, CIPigment Orange 13, CIPigment Orange 14, CIPigment Orange 16, CI Pigment Orange 17, CIPigment Orange 24, CIPigment Orange 34, CIPigment Orange 36, CIPigment Orange 38, CIPigment Orange 40, CIPigment Orange 43, CIPigment Orange 46, CIPigment Orange 49, CIPigment Orange 51, CI Pigment Orange 61, CIPigment Orange 63, CIPigment Orange 64, CIPigment Orange 71, CIPigment Orange 73, CIPigment Brown 23, CIPigment Brown 25, CIPigment Black 1, CIPigment Black 7, and the like.

The proportion of the above-mentioned coloring agent is not particularly limited, and is preferably from 0 to 10 parts by mass, more preferably from 0.1 to 5 parts by mass, per 100 parts by mass of the carboxyl group-containing resin.

When most of the polymer materials are oxidized, the chain oxidation is deteriorated, and the function of the polymer material is lowered. Therefore, in the photocurable resin composition of the present invention, in order to prevent oxidation, it is possible to add (1) The radical scavenger which is deactivated by the radical is generated and/or the peroxide produced by (2) is decomposed into a harmless substance, and an antioxidant such as a peroxide decomposing agent of a new radical is not produced.

As the antioxidant of the radical scavenger, specific compounds are, for example, hydroquinone, 4-tert-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t -butyl-p-cresol, 2,2-methylene-bis-(4-methyl-6-t-butanol), 1,1,3-parade (2-methyl-4-hydroxy- 5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-cis (3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1 , 3,5-glycol (3',5'-di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione An anthraquinone compound such as benzoquinone or benzopyrene, an amine compound such as bis(2,2,6,6-tetramethyl-4-piperidyl)-phthalate or phenothiazine.

The free radical supplement can be a commercially available product, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB manufactured by Asahi Kasei Co., Ltd. LA-67, ADK STAB LA-68, ADK STAB LA-87 (all of the above), IRGANOX 1010, IRGANOX 1035 IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144 by Ciba‧Specialty ‧Chemicals , TINUVIN 152, TINUVIN 292, TINUVIN 5100 (all of which are trade names).

As the antioxidant of the peroxidizing agent decomposing agent, specific compounds include, for example, a phosphorus compound such as triphenylphosphite, pentaerythritol tetralauryl sulfide propionate, dilauryl sulfide dipropionate, and distearyl 3,3. a sulfur-based compound such as '-thiodipropionate.

The peroxide decomposing agent may be a commercially available product, for example, ADK STAB TPP manufactured by Asahi Kasei Co., Ltd., Mac AO-412S manufactured by Adeka‧Agars Chemical Co., Ltd., Sumilizer TPS (both trade names) manufactured by Sumitomo Chemical Co., Ltd., and the like.

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

Since the polymer material absorbs light and causes decomposition and deterioration, the photocurable resin composition of the present invention can be used for the stabilization of ultraviolet rays, and an ultraviolet absorber can be used in addition to the above-mentioned antioxidant.

The ultraviolet absorber is, for example, a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, an amine anisate derivative, Benzomethane methane derivatives and the like. Specific benzophenone derivatives are, for example, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxy Benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, etc.; specific benzoate derivatives, such as 2-ethylhexyl water Salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzene Formate and cetyl-3,5-di-t-butyl-4-hydroxybenzoate; etc.; specific benzotriazole derivatives such as 2-(2'-hydroxy-5'- T-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5 '-Methylphenyl)-5-chlorinated benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di-t-butyl-aminophenyl)benzotriene Examples of the specific triazine derivative include hydroxyphenyltriazine, bisethylhexyloxyphenol methoxyphenyltriazine and the like.

The ultraviolet absorber may be a commercially available product such as TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN manufactured by Ciba‧Specialty ‧Chemicals 460, TINUVIN 479 (all of which are trade names) and so on.

The above-mentioned ultraviolet absorbing agent can be used alone or in combination of two or more kinds, and the molded article obtained from the photocurable resin composition of the present invention can be stabilized by using the above-mentioned antioxidant in combination.

In order to improve the physical strength and the like of the coating film, the photocurable resin composition of the present invention may be formulated with a filler as needed. As the filler, conventionally used inorganic fillers or organic fillers can be used, and in particular, barium sulfate, spherical cerium oxide and talc are preferably used. Further, in order to obtain a white appearance or flame retardancy, a metal hydroxide such as titanium oxide, metal oxide or aluminum hydroxide can be used as a bulk pigment filler. The blending amount of the filler is preferably 75% by mass or less, and more preferably 0.1 to 60% by mass or less based on the total amount of the composition. When the amount of the filler is more than 75% by mass based on the total amount of the composition, the viscosity of the insulating composition becomes high, coating and moldability are lowered, and the cured product becomes brittle, which is not preferable.

Further, in the photocurable resin composition of the present invention, an organic solvent can be used in order to synthesize the carboxyl group-containing resin or to prepare a composition, or to adjust the viscosity when applied to a substrate or a carrier film.

Such organic solvents are, for example, 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, and carbitol , glycol carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate An ester of dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol butyl ether acetate, or the like; an alcohol such as ethanol, propanol, ethylene glycol or propylene glycol; octane An aliphatic hydrocarbon such as decane; a petroleum solvent such as petroleum ether, naphtha, hydrogenated naphtha or solvent oil. This organic solvent may be used singly or in combination of two or more.

The photocurable resin composition of the present invention may be formulated with conventionally known thermal polymerization inhibitors, fine powdered cerium oxide, organic bentonite, montmorillonite, etc., known as tackifiers, polyfluorene oxides, and fluorine. A known additive such as a defoaming agent and/or a flat agent such as a polymer or a polymer, a decane coupling agent such as an imidazole-based compound, a thiazole-based or a triazole-based compound, an antioxidant, and a rust preventive agent.

The above thermal polymerization inhibitor is used to prevent thermal polymerization or polymerization of a polymerizable compound. Thermal polymerization inhibitors are, for example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrophenol, 2-hydroxybenzophenone, 4-methoxy 2-hydroxybenzophenone, copper chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-Asia Methyl bis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactants, salicylic acid a methyl ester, a phenothiazine, a nitroso compound, a chelating agent of a nitroso compound and A1, and the like.

The photocurable resin composition of the present invention is adjusted to a viscosity suitable for the coating method by the above organic solvent, for example, by a dip coating method, a flow coating method, a roll coating method, a bar coating method, or screen printing. A method such as a curtain coating method is applied to a substrate, and the organic solvent contained in the composition is volatilized and dried (pre-dried) at a temperature of about 60 to 100 ° C to form a non-sticky form. Coating film. Further, the composition is applied onto a carrier film, dried, and attached to a substrate in the form of a film to form a resin insulating layer.

Then, by contact (or non-contact), by forming a pattern of the mask, by selective exposure of the active energy line, or by direct exposure of the laser exposure machine, the unexposed part is thinned An aqueous alkali solution (for example, 0.3 to 3 wt% aqueous sodium carbonate solution) is developed to form a photoresist pattern. Further, for example, it is thermally cured by heating to a temperature of about 140 to 180 ° C to thermally cure the carboxyl group of the carboxyl group-containing resin and two or more cyclic ether groups and/or cyclic thioether groups in the molecule. The component reacts to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties.

The above substrate may be made of paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimine, glass cloth, in addition to a printed circuit board or a flexible printed circuit board in which a circuit is formed in advance. / non-woven fabric - epoxy resin, glass cloth / paper - epoxy resin, synthetic fiber - epoxy resin, fluororesin, polyethylene, PPO, cyanate ester and other composite materials (FR-4, etc.) Plywood, polyimide film, PET film, glass substrate, ceramic substrate, wafer board, etc.

The volatilization drying which is carried out after applying the photocurable resin composition of the present invention can be carried out by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a conveyor belt oven or the like (using a heat source having a heating method by steam air) The method of countercurrent contact of the hot air in the dryer or the method of blowing the nozzle on the support is performed.

The photocurable resin composition of the present invention is applied as described below, and after volatilization and drying, the obtained coating film is exposed (irradiation of active energy rays). The coating film exposure portion (the portion irradiated by the active energy ray) is hardened.

The exposure machine used for the active energy ray irradiation can be equipped with a direct drawing device (for example, a laser direct imaging device that directly images an image by laser data of a computer), an exposure machine equipped with a metal halide lamp, and the like. An (extra) high-pressure mercury lamp exposure machine, an exposure machine equipped with a mercury short-arc light lamp, or a direct drawing device using an ultraviolet lamp such as a (super) high-pressure mercury lamp. The active energy ray may be any one of a gas laser or a solid laser as long as it uses laser light having a maximum wavelength of 350 to 410 nm. Further, the exposure amount varies depending on the film thickness and the like, and is generally 5 to 200 mJ/cm ² , preferably 5 to 100 mJ/cm ² , and more preferably 5 to 50 mJ/cm ² . As the direct drawing device, for example, a device manufactured by Orbotech Co., Ltd., a Pentax company, or the like can be used, and any device can be used as long as it can oscillate laser light having a maximum wavelength of 350 to 410 nm.

Examples of the development method include a dipping method, a rinsing method, a spraying method, a brushing method, and the like. The developing solution may be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia or an amine. An aqueous alkali solution.

The photocurable resin composition of the present invention may have a solder resist layer formed by applying a solder resist to a film such as polyparaphenylate or a film formed by drying, in addition to a method of directly applying a liquid to a substrate. The form of the dry film is used. When the photocurable resin composition of the present invention is used as a dry film, it is as follows.

The dry film has a structure in which a carrier film, a solder resist layer, and a peelable protective film which are used as necessary are laminated. The solder resist layer is a layer obtained by applying an alkali developable photocurable resin composition to a carrier film or a protective film and drying the composition. After the solder resist layer is formed on the carrier film, the protective film is laminated thereon or a solder resist layer is formed on the protective film, and when the laminate is laminated to the carrier film, a dry film can be obtained.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm can be used.

In the solder resist layer, the alkali-developable photocurable resin composition is uniformly applied to a thickness of 10 to 150 μm using a knife coater, a lip coater, a twin roll coater, a film coater, or the like. A carrier film or a protective film is formed by drying.

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

When a protective film (permanent protective film) is formed on a printed circuit board by using a dry film, the protective film is peeled off, and then overlapped with the solder resist layer and the substrate on which the circuit is formed, and laminated using a laminator or the like to form a substrate on the circuit. A solder resist layer is formed thereon. When the solder resist layer after the formation is subjected to exposure, development, and heat curing in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off before or after exposure.

Example

The invention will be specifically described below by way of examples and comparative examples, but the invention is not limited to the following examples. In the following, "parts" and "%" are quality benchmarks unless otherwise stated.

Photosensitive resin synthesis example 1:

In a pressure cooker equipped with a thermometer, a nitrogen gas introduction device, an epoxide introduction device, and a stirring device, 106 parts of a novolac type phenol resin (manufactured by Showa Polymer Co., Ltd., hydroxyl equivalent 106) and 2.6 parts of a 50% sodium hydroxide aqueous solution were charged. 100 parts of toluene/methyl isobutyl ketone (mass ratio = 2/1), nitrogen substitution in the system while stirring, followed by heating and heating, and slowly introducing propylene oxide 60 at 150 ° C and 8 kg / cm ² The reaction was carried out in portions. The reaction was continued for about 4 hours until the gauge pressure was 0.0 kg/cm ^{2 and} then cooled to room temperature. To the reaction solution, 3.3 parts of a 36% aqueous hydrochloric acid solution was added and neutralized with sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and the solvent was removed by an evaporator to obtain an epoxide adduct of a phenolic phenol resin having a hydroxyl equivalent of 164 g/eq. This is a hydroxyl group of 1 equivalent average addition epoxide 1 mole.

164 parts of the epoxide adduct of the obtained novolac type phenol resin, 86 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 parts of hydroquinone monomethyl ether, and 100 parts of toluene were placed in a mixer and a thermometer. In the reactor in which the air was blown into the tube, the mixture was stirred while being blown in air, and reacted at 110 ° C for 6 hours. The water formed by the reaction was in the form of an azeotropic mixture with toluene, and after the distillation was started, the mixture was further reacted for 5 hours and cooled to room temperature. The obtained reaction solution was washed with a 5% sodium chloride aqueous solution, and the toluene was distilled off using an evaporator, and carbitol acetate was added to obtain a phenolic type PO addition methacrylate resin solution having a nonvolatile content of 70% ( Double bond equivalent 250g / eq ‧ acid price 0). This is called A-1 varnish.

Photosensitive resin synthesis example 2:

164 parts of an epoxide adduct of a novolac type phenol resin obtained in Synthesis Example 1, 72 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 parts of hydroquinone monomethyl ether, and 100 parts of toluene were placed in a mixer and a thermometer. In the reactor in which the air was blown into the tube, the mixture was stirred while being blown in air, and reacted at 90 ° C for 12 hours. The water formed by the reaction was in the form of an azeotropic mixture with toluene, and after the distillation was started, the mixture was further reacted for 5 hours and cooled to room temperature. The obtained reaction solution was washed with a 5% sodium chloride aqueous solution, and the toluene was distilled off using an evaporator, and carbitol acetate was added to obtain a phenolic type PO addition acrylate resin solution having a nonvolatile content of 70% (double bond) Equivalent 236g / eq ‧ acid value 0). This is called A-2 varnish.

Photosensitive resin synthesis example 3:

In a pressure cooker equipped with a thermometer, a nitrogen gas introduction device, an epoxide introduction device, and a stirring device, 106 parts of a novolac type phenol resin (manufactured by Showa Polymer Co., Ltd., hydroxyl equivalent 106) and 2.6 parts of a 50% sodium hydroxide aqueous solution were charged. And 100 parts of toluene/methyl isobutyl ketone (mass ratio = 2/1), nitrogen substitution in the system while stirring, followed by heating and heating, and slowly introducing ethylene oxide at 150 ° C, 8 kg / cm ² 50 parts were reacted. The reaction was continued for about 4 hours until the gauge pressure was 0.0 kg/cm ^{2 and} then cooled to room temperature. To the reaction solution, 3.3 parts of a 36% aqueous hydrochloric acid solution was added and neutralized with sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and the solvent was removed by an evaporator to obtain an epoxide adduct of a phenolic phenol resin having a hydroxyl equivalent of 150 g/eq. This is a hydroxyl group of 1 equivalent average addition epoxide 1 mole.

150 parts of the epoxide adduct of the obtained novolac type phenol resin, 86 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 part of hydroquinone monomethyl ether, and 100 parts of toluene were placed in a mixer and a thermometer. In the reactor in which the air was blown into the tube, the mixture was stirred while being blown in air, and reacted at 110 ° C for 6 hours. The water formed by the reaction was in the form of an azeotropic mixture with toluene, and after the distillation was started, the mixture was further reacted for 5 hours and cooled to room temperature. The obtained reaction solution was washed with a 5% sodium chloride aqueous solution, and the toluene was distilled off using an evaporator, and carbitol acetate was added to obtain a phenolic EO addition methacrylate resin solution having a nonvolatile content of 70% ( Double bond equivalent 236g / eq ‧ acid price 0). This is called A-3 varnish.

Comparative Synthesis Example 1:

In a pressure cooker equipped with a thermometer, a nitrogen gas introduction device, an epoxide introduction device, and a stirring device, 94 parts of a monofunctional phenol compound (hydroxyl equivalent 94), 2.6 parts of a 50% aqueous sodium hydroxide solution, and toluene/methyl isobutyl ketone were charged. (mass ratio = 2/1) 100 parts, nitrogen substitution in the system was carried out while stirring, and then the temperature was raised by heating, and 50 parts of ethylene oxide was gradually introduced at 150 ° C and 8 kg / cm ² to carry out a reaction. The reaction was continued for about 4 hours until the gauge pressure was 0.0 kg/cm ^{2 and} then cooled to room temperature. To the reaction solution, 3.3 parts of a 36% aqueous hydrochloric acid solution was added and neutralized with sodium hydroxide. This neutralized reaction product was diluted with toluene, washed with water three times, and the solvent was removed by an evaporator to obtain an epoxide adduct of a phenol compound having a hydroxyl equivalent of 138 g/eq. This is a hydroxyl group of 1 equivalent average addition epoxide 1 mole.

138 parts of the obtained phenol compound epoxide adduct, 86 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 parts of hydroquinone monomethyl ether, and 100 parts of toluene were placed in a mixer, a thermometer, and air. The reactor was blown into the tube, stirred while blowing air, and reacted at 110 ° C for 6 hours. The water formed by the reaction was in the form of an azeotropic mixture with toluene, and after the distillation was started, the mixture was further reacted for 5 hours and cooled to room temperature. The obtained reaction solution was washed with a 5% sodium chloride aqueous solution, and the toluene was distilled off using an evaporator, and carbitol acetate was added to obtain a 70% non-volatile EO addition methacrylate resin solution (double bond) Equivalent 224g / eq ‧ acid price 0). This is called A-4 varnish.

Synthesis example of carboxyl group-containing resin (B-1):

A cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C) was introduced into a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube. Epoxy equivalent 220) 660 g, carbitol acetate 421.3 g and solvent naphtha 180.6 g, heated to 90 ° C, stirred and dissolved. Subsequently, the mixture was temporarily cooled to 60 ° C, and 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of methylhydroquinone were added, and the mixture was reacted at 100 ° C for 12 hours to obtain a reaction product having an acid value of 0.2 mgKOH/g. 241.7 g of tetrahydrophthalic anhydride was added thereto, and the mixture was heated to 90 ° C for 6 hours. Thereby, a carboxylic acid resin-containing solution having an acid value of 50 mgKOH/g, a double bond equivalent (g weight of the unsaturated group per 1 mol of the resin) 400, and a weight average molecular weight of 7,000 was obtained. Hereinafter, the solution containing the carboxylic acid resin is referred to as B-1 varnish.

Synthesis example of carboxyl group-containing resin (B-3):

In a pressure cooker equipped with a thermometer, a nitrogen gas introduction device, an epoxide introduction device, and a stirring device, a phenolic cresol resin (manufactured by Showa Polymer Co., Ltd., trade name "Shonol CRG951", OH equivalent: 119.4) 119.4 g was charged. 1.19 g of potassium hydroxide and 119.4 g of toluene were mixed with nitrogen while stirring, and then heated to raise the temperature. Then, 63.8 g of propylene oxide was slowly added dropwise, and the reaction was carried out at 125 to 132 ° C and 0 to 4.8 kg/cm ² for 16 hours. Then, it was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain an epoxy of a novolak type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. Propane reaction solution. This is an epoxide having an average of 1.08 moles per 10,000 equivalents of phenolic hydroxyl groups. 293.0 g of the epoxide reaction solution of the obtained novolac 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 placed in a mixer, a thermometer, and an air blow. The reactor was introduced into the tube, and air was blown at a rate of 10 ml/min, and the reaction was carried out at 110 ° C for 12 hours while stirring. 12.6 g of water was distilled off by means of an azeotropic mixture of water and toluene formed by the reaction. Then, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, followed by washing with water. Then, toluene was replaced with 118.1 g of diethylene glycol monoethyl ether acetate using an evaporator while distilling off to obtain a novolac type acrylate resin solution. Next, 332.5 g of the obtained novolac type acrylate resin solution and 1.22 g of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min. Further, 60.8 g of tetrahydrophthalic anhydride was slowly added thereto while stirring, and the reaction was carried out at 95 to 101 ° C for 6 hours. A carboxyl group-containing photosensitive resin having an acid value of 88 mg KOH/g and a nonvolatile content of 71% was obtained. Hereinafter, the reaction solution is referred to as varnish B-3.

Examples 1 to 15 and Comparative Examples 1 to 5

The resin solution of each of the following synthesis examples was used, and the components shown in Table 1 and the ratios (mass parts) shown in Table 1 were blended, premixed with a stirrer, and kneaded by a three-roll mill to prepare a photosensitive resin for the solder resist. Things. Here, the dispersion of the obtained photosensitive resin composition was measured by a pelletizer manufactured by Erichsen Co., Ltd., and when it was evaluated, it was measured to be 15 μm or less.

Remarks

^*1 : NKester BPE-900 (manufactured by Shin-Nakamura Chemical Co., Ltd.) Ethylene oxide-modified bifunctional acrylate containing bisphenol A skeleton (double bond equivalent ‧‧‧556)

^*2 : KAYARAD DPCA-60 (Nippon Chemical Co., Ltd.) (double bond equivalent ‧‧‧210)

^*3 : Dipentaerythritol hexaacrylate (DPHA: Nippon Chemical Co., Ltd.) (double bond equivalent ‧‧‧108)

^*4 : Syclomer P (ACA) 320 (Daicel Chemical Industry Co., Ltd.)

^*5 : ZFR-1124 (Nippon Chemical Co., Ltd.)

^*6 : ZCR-1601H (Nippon Chemical Co., Ltd.)

^*7 : SPV-1000L (Showa Polymer Co., Ltd.)

^*8 : 2-methyl-1-(4-methylphenylthio)-2-morpholinopropan-1-one (IRGACURE 90 Ciba‧Specialty‧Chemicals)

^*9 : 2-(ethoxycarbonylmethyl) thioxanthene-9-one

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

^*11 : Dimethyl phenol type epoxy resin (YX-4000; made by Japan Epoxy Resin Co., Ltd.)

^*12 : CIPigment Blue 15:3

^*13 : CIPigment Yellow 147

^*14 : Barium sulfate (B-30: 堺Chemical (share) system)

^*15 : Dipropylene glycol monomethyl ether

^*16 : Block isocyanate (Asahi Kasei Chemicals Co., Ltd.)

^*17 : Methyl melamine resin (made by Sanhe Chemical Co., Ltd.)

^*18 : Antioxidant (Ciba‧Specialty‧Chemicals)

Performance evaluation: <Optimum exposure>

The circuit pattern substrate having a copper thickness of 35 μm was polished by a buff roll, washed with water, and dried, and then subjected to full-coating of the photocurable thermosetting resin of the foregoing examples and comparative examples by screen printing. The material was dried in a hot air circulating drying oven at 80 ° C for 60 minutes. After drying, exposure was carried out by a stage (optical density) exposure meter (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development was performed for 60 seconds (30 ° C, 0.2 MPa, 1 wt%). In the case of Na ₂ CO ₃ aqueous solution), the pattern of the remaining stage exposure meter is the optimum exposure amount in the case of 7 stages.

<finger dryness>

The photocurable thermosetting resin composition described in Table 1 was applied to the copper foil substrate on which the pattern was formed by screen printing, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes, and allowed to cool to room. temperature. The PET film was pressed against the substrate, and then the state of bonding of the film when the negative film was peeled off was evaluated.

◎: When the film was peeled off, there was no resistance at all, and there was no trace on the coating film.

○: When the film was peeled off, there was no resistance at all, but there was a slight trace on the coating film.

△: When the film was peeled off, there was only a slight resistance, and there was a slight trace on the coating film.

×: When the film was peeled off, there was resistance and there was a clear trace on the coating film.

<resolution>

The circuit pattern substrate having a line/pitch of 300/300 μm and a copper thickness of 35 μm was subjected to a polishing roll polishing, and after being washed with water and dried, the photocurable thermosetting resin of the examples and the comparative examples was applied by screen printing. The material was dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, exposure is performed using an exposure apparatus equipped with a high pressure mercury lamp (short arc lamp). The exposed circular type is used for a glass dry plate in which a line of 20/30/40/50/60/70/80/90/100 μm is drawn at the pitch portion. The exposure amount is a state in which the active energy ray is irradiated in a state in which the photosensitive resin composition has an optimum exposure amount. After the exposure, development was carried out by a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C, and a pattern was drawn, and a hardened coating film was obtained by thermal hardening at 150 ° C for 60 minutes.

The minimum residual line (resolution) of the cured coating film of the obtained photosensitive resin composition for a solder resist was determined using an optical microscope adjusted to 200 times.

<Tensile modulus, tensile strength (tensile failure strength), elongation (tensile failure extension)>

The composition of each of the above-described composition examples and comparative composition examples was applied onto a water-washed and dried PTFE (polytetrafluoroethylene) plate by screen printing, and dried at 80 ° C for 30 minutes using a hot air circulating drying oven. After cooling to room temperature, it was exposed to an appropriate exposure amount, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 2 kg/cm ² for 60 seconds. This substrate was irradiated with ultraviolet rays under the conditions of a cumulative exposure amount of 1000 mJ/cm ^{2 in} a UV transfer furnace, and then dried at 150 ° C for 60 minutes using a hot air circulating drying oven. After cooling this to room temperature, the cured coating film was peeled off from the PTFE sheet to obtain an evaluation sample.

The tensile modulus, the tensile strength (tensile breaking strength), and the elongation (tensile failure elongation) of the above-mentioned evaluation samples were measured by a tensile-compression tester (manufactured by Shimadzu Corporation).

<softness>

The composition of each of the above Examples and Comparative Examples was applied by screen printing on a water-dried polyimide material (thickness: 25 μm), and dried at 80 ° C for 30 minutes using a hot air circulating drying oven. After cooling to room temperature, exposure was carried out at an appropriate exposure amount 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 subjected to a pressure of 2 kg/cm ² for 60 seconds. . This substrate was irradiated with ultraviolet rays under the conditions of a cumulative exposure amount of 1000 mJ/cm ^{2 in} a UV transfer furnace, and then cured by heating at 150 ° C for 60 minutes to obtain a folding resistance test and a sample for soft test.

The method of processing the obtained cured film into a film-shaped test piece having a width of 10 mm and a length of 90 mm was placed on the electronic scale, and the other side was bent, and the film was 3 mm apart. The maximum load applied by the electronic scale is used as the rebound force and evaluated on the basis of the following criteria.

○: less than 10g

△: 10~ less than 30g

×: 30g or more

Feature test:

The composition of each of the above examples and comparative examples was applied by a screen printing method to a copper foil substrate on which a pattern was formed, and the film thickness after drying was 20 μm, dried at 80 ° C for 30 minutes, and left to cool. temperature. For this substrate, an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) was used to expose the solder resist pattern with an appropriate exposure amount, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C was subjected to a spray pressure of 2 kg/cm ² for 60 seconds. Visualization, obtaining a photoresist pattern. This substrate was irradiated with ultraviolet rays under the conditions of a cumulative exposure amount of 1000 mJ/cm ^{2 in} a UV transfer furnace, and then cured by heating at 150 ° C for 60 minutes. The following characteristics were evaluated for the obtained printed substrate (evaluation substrate).

<Welding heat resistance>

The evaluation substrate coated with the rosin-based co-solvent was immersed in a solder bath set at 260 ° C in advance, and the auxiliary solvent was washed with a modified alcohol, and then the expansion and peeling of the photoresist layer were visually evaluated. The judgment criteria are as follows.

◎: No peeling was observed even if the immersion was repeated for 6 or more times for 10 seconds.

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

△: When immersed for 10 times or more for 10 seconds, it was slightly peeled off.

X: When immersed for 10 seconds within 3 times, the photoresist layer was swollen and peeled off.

<electroless gold plating resistance>

Electroless nickel plating bath and electroless gold plating bath of a commercial product were used, and plating was performed under the conditions of 0.5 μm of nickel and 0.03 μm of gold, and the peeling of the photoresist layer or the infiltration of the plating layer was evaluated by tape peeling. The peeling of the photoresist layer was evaluated by tape peeling. The judgment criteria are as follows.

◎: No penetration or peeling.

○: After plating, there was slight penetration, but the tape was not peeled off after peeling off.

△: After plating, only a slight infiltration occurred, and after peeling off the tape, there was peeling off.

×: Peeling after plating.

<Electrical characteristics>

The copper foil substrate was replaced by a comb-shaped electrode pattern with a line and a pitch of 50/50 μm, and an evaluation substrate was prepared under the above conditions. A bias voltage of DC 10 V was applied to the comb-shaped electrode, and 100 in the tank was measured at 130 ° C and 85% RH. Insulation resistance value after hours. The measurement voltage was carried out at DC 10V.

<Alkaline resistance>

The evaluation substrate was immersed in a 10 wt% aqueous NaOH solution at 50 ° C for 30 minutes to carry out infiltration or dissolution of the coating film, and peeling was confirmed by tape peeling. The criteria for determination are as follows.

○: no penetration or dissolution, no peeling.

△: Slightly infiltrated, dissolved or peeled off.

×: There is infiltration, dissolution or significant peeling.

<Dry film production>

The photosensitive resin compositions for the solder resists of Example 1 and Comparative Example 1 were each appropriately diluted with methyl ethyl ketone, and then applied to a PET film (FB-50: 16 μm manufactured by Toray Industries, Inc.) using a coater to dry. The film thickness after the film was 20 μm, and dried at 80 ° C for 30 minutes to obtain a dry film.

<Substrate production>

After the substrate on which the circuit was formed was polished and polished, the dry film produced by the above method was vacuum laminator (MVLP-500 manufactured by Nihon Seiki Co., Ltd.) at a pressure of 0.8 MPa, 70 ° C, 1 minute, and a vacuum degree of 133.3. The conditions of Pa were subjected to heat lamination to obtain a substrate (unexposed substrate) having an unexposed solder resist layer.

The evaluation results are shown in Table 2.

As shown in the above Table 2, in the cases of Examples 1 to 15 of the present invention, the touch drying property was not lowered as compared with Comparative Examples 1 to 5, and high sensitivity was achieved, and the obtained hardened film had excellent flexibility. . In particular, the examples using the photosensitive resin A-1 in which propylene oxide and methacrylic acid are added to the novolac type phenol resin are excellent in solder heat resistance, electroless gold plating resistance, and electrical properties, and can be used as alkali-developing photohardening. The resin composition is used.

On the other hand, in the case of Comparative Examples 1 and 2 in which A-4 and A-5 having a number of cores of 3 or less were used, the dryness of the touch, the heat resistance of soldering, and the electrical characteristics were inferior.

Industrial use

As described above, the present invention can provide a photocurable resin composition having a dry touch coating film which is excellent in dry touch property, high in sensitivity and soft, and particularly capable of forming a hardened film having high insulation resistance at high temperature and humidification, and a dry film thereof. A cured circuit and a printed circuit board formed by forming a hardened film such as a solder resist.

Claims (9)

An alkali-developable photocurable resin composition characterized by comprising a photosensitive resin having a structure represented by the following general formula (I), a carboxyl group-containing resin, and a photopolymerization initiator; (wherein R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different, and R ² represents at least one selected from the group consisting of an alkylene group having 1 to 10 carbon atoms and a phenyl group. a functional group, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group, and p represents a group 1~ An integer of 5, q represents an integer of 3 or more, m represents an integer of 1 to 4, and n represents an integer of 1 to 10). The photocurable resin composition according to claim 1, wherein the photosensitive resin does not contain an acid and has a double bond equivalent of 200 or more and 400 or less. The photocurable resin composition of the first aspect of the invention, wherein the photosensitive resin is a compound having three or more phenolic hydroxyl groups in one molecule. A photosensitive resin obtained by reacting a hydroxyl group with a cyclic ether compound or a cyclic carbonate compound to react with a compound having an ethylenically unsaturated group. The photocurable resin composition of claim 3, wherein the compound having three or more phenolic hydroxyl groups in one molecule has a softening point at room temperature or higher. The photocurable resin composition of the first aspect of the patent application, which further contains a thermosetting component. A photocurable dry film which is obtained by applying a photocurable resin composition according to any one of claims 1 to 5 to a film and drying it. A cured product characterized in that the photocurable resin composition according to any one of claims 1 to 5 is applied onto a substrate, and the photocurable resin composition is applied onto the film. The dried dry film is laminated on a substrate, and the formed dried coating film is photohardened on copper. A cured product characterized in that the photocurable resin composition according to any one of claims 1 to 5 is applied onto a substrate, and the photocurable resin composition is applied onto the film. The dried dry film is laminated on a substrate, and the formed dried coating film is photohardened into a pattern. A printed circuit board characterized in that the photocurable resin composition according to any one of claims 1 to 5 is applied onto a substrate to be dried or the photocurable resin composition is applied to the printed circuit board. On the film, dried The obtained dry film was laminated on a substrate, and the formed dried coating film was photohardened into a pattern, and then the hardened film obtained by heat curing was performed.