JP2002072470A - Photosensitive resin composition and photosensitive film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in flexibility and resistance to the heat of soldering, developable with a dilute alkali solution and suitable for an etching resist and a cover lay and to provide a photosensitive film using the composition. SOLUTION: The photosensitive resin composition contains an imide precursor oligomer (A), a diluent (B) and a photopolymerization initiator (C). In the imide precursor obtained by reacting an epoxy resin (a) having two epoxy groups in one molecule with an ethylenically unsaturated group-containing monocarboxylic acid compound (b) and reacting the resulting unsaturated group- containing polyol compound (c) with a diamine compound (d) and a compound (e) having two acid anhydride groups in one molecule, the component (d) or (e) or each of both the components (d) and (e) contains a sulfur atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, in particular, a photosensitive resin composition suitable for forming an etching resist or a protective film (coverlay) which can be used for manufacturing a flexible printed wiring board and the like, and a photosensitive composition using the same. Sex film.

[0002]

2. Description of the Related Art Conventionally, in the production of printed wiring boards, liquid or film-shaped photosensitive resin compositions have been used. For example, as a resist for etching a copper foil of a copper-clad laminate, a printed wiring board on which wiring is formed is used for limiting a soldering position, protecting wiring, and the like.
2. Description of the Related Art Some printed wiring boards have a film shape that can be folded and incorporated into a small device such as a camera, and this is called an FPC. This FPC also requires a resist for limiting the soldering position and protecting the wiring, which is called a coverlay or a covercoat. The coverlay is formed by punching polyimide or polyester having an adhesive layer into a predetermined mold, and then by thermocompression bonding on an FPC.The cover coat is formed by printing and curing a thermosetting or photocurable ink. Formed.

In these resists used for the purpose of limiting the soldering position of the FPC and protecting the wiring, flexibility is a particularly important characteristic, and therefore, a polyimide coverlay excellent in flexibility is often used. . However, this coverlay requires an expensive mold for die cutting,
In addition, due to the manual bonding of the die-cut film and the sticking-out of the adhesive, the yield is low and the manufacturing cost is high, which is an obstacle to the expansion of the FPC market. It is difficult to respond.

Accordingly, a photosensitive resin composition for forming a highly accurate and highly reliable coverlay excellent in dimensional accuracy and resolution by a photographic development method (a method of forming an image by a phenomenon following image exposure), In particular, the appearance of a photosensitive film has been desired. For this purpose, attempts have been made to use a photosensitive resin composition for forming a solder mask. For example, photosensitive resin compositions containing an acrylic polymer and a photopolymerizable monomer as main components (JP-A-53-56018 and JP-A-54-56018).
As a photosensitive resin composition having good heat resistance, a composition mainly composed of a photosensitive epoxy resin having a chalcone group in a main chain and an epoxy resin curing agent (JP-A-54-82073) JP-A-58-62636), a composition mainly composed of a novolak-type epoxy acrylate containing an epoxy group and a photopolymerization initiator (JP-A-61-272, etc.), safety and economy As a photosensitive resin composition for forming a solder mask that can be developed with an alkaline aqueous solution, a carboxyl group-containing polymer,
Compositions comprising a monomer, a photopolymerization initiator and a thermosetting resin as main components (JP-A-48-73148, JP-A-57-73148)
178237, JP-A-58-42040,
JP-A-59-151152, etc.), but all have insufficient flexibility.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, and provides a photosensitive resin composition which is excellent in workability, excellent in flexibility, solder heat resistance and the like. To provide a photosensitive film.

[0006]

According to the present invention, there is provided (1) a method comprising reacting an epoxy resin (a) having two epoxy groups in one molecule with an ethylenically unsaturated group-containing monocarboxylic acid compound (b). In the imide precursor obtained by reacting the obtained unsaturated group-containing polyol compound (c), diamine compound (d) and compound (e) having two acid anhydride groups in one molecule, component (d) Or a photosensitive composition comprising an imide precursor oligomer (A) comprising a compound containing a sulfur atom in the molecule of component (e) or both components, a diluent (B), and a photopolymerization initiator (C). Resin composition,
(2) A diamine compound (d) is reacted with a compound (e) having two acid anhydride groups in one molecule to synthesize a terminal acid anhydride group polyamide prepolymer, and then an unsaturated group-containing polyol compound is prepared. (3) an epoxy resin having two or more epoxy groups in one molecule, (f) and an ethylenically unsaturated monocarboxylic acid compound ( b) a photosensitive resin composition according to (1), comprising an unsaturated group-containing polycarboxylic acid resin (D) which is a reaction product of a polybasic acid anhydride (g); and (4) a thermosetting component (E). And (5) laminating a layer of the photosensitive resin composition according to (1) and (3) or (4) on a support film. Photosensitive film, (6)
(1) and (3) a cured product of the photosensitive resin composition and film according to (5), (7) an article having the cured product according to (6), and (8) a printed wiring board according to (7). Related to the article.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The imide precursor oligomer (A) used in the present invention comprises an epoxy resin (a) having two epoxy groups in one molecule and an ethylenically unsaturated group-containing monocarboxylic acid compound (b). And the unsaturated group-containing polyol compound (c) obtained by reacting the compound (c) with a diamine compound (d) and a compound (e) having two acid anhydride groups in one molecule. , (D) component and / or (e) component contains a sulfur atom in the molecule).

[0008] Specifically, in the first reaction, two molecules per molecule
A hydroxyl group is formed by an addition reaction between the epoxy group of the epoxy resin (a) having two epoxy groups and the carboxyl group of the unsaturated group-containing monocarboxylic acid (b) to obtain the component (c). Next, the hydroxyl group of (c) and the amino group of (d) are 1
It is obtained by a compound (e) having two acid anhydride groups in the molecule by an esterification reaction and an amidation reaction.

The epoxy resin (a) having two epoxy groups in one molecule includes, for example, a diglycidyl ether compound, a diglycidyl ester compound, a diglycidylamine compound and the like.

The diglycidyl ether compound is obtained by reacting a polyol compound with epichlorohydrin by adding at least one equivalent of the former to one equivalent of the hydroxyl group. Examples of the polyol compound include bisphenol A, bisphenol F, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, resorcinol, biphenol, tetramethylbiphenol, tetraalkylbiphenol, hydrogenated bisphenol A, hydrogenated bisphenol F, tetrabromobisphenol A, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol,
Polypropylene glycol, 1,4-butanediol,
Neopentyl glycol, 1,6-hexanediol,
Examples include 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,4-hexanedimethanol, dimer acid diol, and the like.

The diglycidyl ester compound can be obtained by reacting a polycarboxyl compound with epichlorohydrin in an amount of at least one equivalent of the former carboxyl group and at least one equivalent of the latter. As polycarboxyl compounds,
For example, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendmethylenetetrahydrophthalic acid, succinic acid, maleic acid and the like can be mentioned.

The diglycidylamine compound can be obtained by reacting a polyamino compound with epichlorohydrin in an amount of 1 equivalent of the former amino group and at least 1 equivalent of the latter. Examples of the polyamino compound include aniline, o-
Toluidine and the like.

Next, examples of the unsaturated group-containing monocarboxylic acid (b) include acrylic acids, crotonic acid, α
-Cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. As acrylic acids, for example, a dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, a saturated or unsaturated dibasic anhydride and one hydroxyl group in one molecule Half esters which are an equimolar reaction product with a (meth) acrylate derivative, and half esters which are an equimolar reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl (meth) acrylate derivative are exemplified.

Examples of the saturated or unsaturated dibasic anhydride used for producing the half esters include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride. Acid, methyltetrahydrophthalic anhydride, itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride and the like. Examples of (meth) acrylate derivatives having one hydroxyl group in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate. , Glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate,
Examples thereof include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and (meth) acrylate of phenylglycidyl ether.

Further, as the saturated or unsaturated dibasic acid used for producing another half ester, for example, succinic acid, maleic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, itaconic acid, fumaric acid Examples of the acid and the like, and examples of the monoglycidyl (meth) acrylate derivatives include glycidyl (meth) acrylate.

These unsaturated group-containing monocarboxylic acids (b) can be used alone or as a mixture. A particularly preferred monocarboxylic acid is (meth) acrylic acid.

Diamine compound containing sulfur atom (d)
As 3,3'-diaminodiphenyl sulfone,
4,4'-diaminodiphenylsulfone, 4,4'-di- (3-aminophenoxy) diphenylsulfone, 4,
4'-di- (4-aminophenoxy) diphenylsulfone, 3,3'-diaminodiphenylsulfide, 4,
4'-diaminodiphenyl sulfide, 4,4'-di-
(3-aminophenoxy) diphenyl sulfide, 4,
4'-di- (4-aminophenoxy) diphenyl sulfide and the like.

When the compound (e) having two acid anhydride groups in one molecule contains a sulfur atom, a diamine compound (d) containing no sulfur atom may be used.

Examples of the diamine compound (d) containing no sulfur atom include 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 2,2-bis-
[4- (3-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] biphenyl, bis [4- (4-aminophenoxy) phenyl] methane, bis [4- (3- Aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] benzophenone, bis [4
-(4-aminophenoxy) phenyl] benzanilide, bis [4- (3-aminophenoxy) phenyl] benzanilide, 9,9-bis [4- (3-aminophenoxy) phenyl] fluorene, p-phenylenediamine, m- Phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,2-diaminocyclohexane, diaminopolysiloxane , ATBN1300 × 16 (Ube Industries, Ltd.)
D-230 (hereinafter, manufactured by San Techno Chemical Co., Ltd.), D-400, D-2000, D-4
000, ED-600, ED-900, ED-200
1, EDR-148 and the like. These can be used alone or in combination of two or more.

Containing a sulfur atom and having at least 2
Compound (e) having three acid anhydride groups includes 3,
3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and the like.

When the diamine compound (d) contains a sulfur atom, an acid anhydride compound (e) containing no sulfur atom may be used. As the acid anhydride compound (e) containing no sulfur atom, a carboxylic acid anhydride is desirable, for example, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenylethertetracarboxylic dianhydride. Anhydrous,
Examples thereof include butanetetracarboxylic dianhydride and ethylene glycol bis (anhydrotrimellitate), which can be used alone or as a mixture of two or more.

The imide precursor oligomer (A) used in the present invention can be synthesized, for example, as follows. In order to obtain the unsaturated group-containing polyol compound (c), the unsaturated group-containing monocarboxylic acid (b) is added in an amount of about 0.8 to 1 equivalent of the epoxy group of the epoxy resin (a).
The reaction is preferably carried out at a ratio of about 1.3 to 1.3 mol, particularly preferably about 0.9 to 1.1 mol.

Further, it is preferable to use a catalyst for accelerating the reaction. Examples of the catalyst include triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octoate, and zirconium octoate. The amount of the catalyst used is preferably 0.1 to 10% by weight based on the reaction raw material mixture. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the like. The amount used is preferably 0.01 to 0.01% based on the reaction raw material mixture.
１1% by weight. The reaction temperature is preferably 60 to 15
0 ° C. The reaction time is preferably 5 to 60 hours.

Next, the reaction of the unsaturated group-containing polyol compound (c) and the diamine compound (d) with the compound (e) having two acid anhydride groups in one molecule can be carried out simultaneously by a method of simultaneously reacting the polyamide compound and the polyamide preform. There is a method of reacting the unsaturated group-containing polyol compound (c) after synthesizing the polymer.
As a method of simultaneously reacting, assuming that the total equivalent of the hydroxyl group and the amino group of the unsaturated group-containing polyol compound (c) and the diamine compound (d) is 1 equivalent, one molecule has two acid anhydride groups in one molecule. 0.1 to 0.9 of compound (e)
The reaction is preferably performed in an equivalent amount. The reaction temperature is usually 60 to 1
The reaction time at 50 ° C. and the reaction time is preferably 1 to 10 hours, and 0.1 to 10% of a catalyst such as triethylamine may be added.

As a method of reacting the unsaturated group-containing polyol compound (c) after synthesizing the polyamide prepolymer, first, a diamine compound (d) and a compound (e) having at least two acid anhydride groups in the molecule (e) )
A terminal acid anhydride polyamide prepolymer is prepared, and then the unsaturated group-containing polyol compound (c) is reacted.

The terminal acid anhydride polyamide prepolymer is
Compound (e) having at least two acid anhydride groups in the molecule for one equivalent of the amino group of diamine compound (d)
Is preferably reacted with 1.05 to 2.0 equivalents (as acid anhydride equivalents). The reaction temperature of this amidation reaction is preferably 0 to 80 ° C., and the reaction time is preferably 1 to 10 hours.

Next, an unsaturated group-containing polyol compound (c) is reacted with the terminal acid anhydride polyamide prepolymer to obtain an oligomer (A). It is preferable to react 0.1 to 0.95 equivalent of the acid anhydride group of the terminal acid anhydride polyamide prepolymer with respect to 1 equivalent of the hydroxyl group of the unsaturated group-containing polyol compound (c). 0.8 is preferred. The reaction temperature is usually from 60 to 150C, preferably from 80 to 100C. At the time of these reactions, a reactive diluent (B-1) described later or an organic solvent (B-2) described later may be added.

Although the imide precursor oligomer (A) can be obtained by either method, the latter method is more preferable for controlling the reaction.

In the present invention, a diluent (B) is used.
Specific examples of the component (B) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol (meth) acrylate, acryloyl Acid anhydride of morpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.) and polycarboxylic acid compound (Eg, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) half ester, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) Acrylate, Methylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycene polypropoxytri (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of neopyrene glycol hydroxybivalate (for example, KAY manufactured by Nippon Kayaku Co., Ltd.
ARAD HX-220, HX-620, etc.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, mono or polyglycidyl Compounds (for example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Epoxy which is a reaction product of (meth) acrylic acid with hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, etc. Reactive diluent (B-1) such as meth) acrylate, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α
Lactones such as -acetyl-γ-butyrolactone and ε-caprolactone; dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether Ethers such as triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether and tetraethylene glycol diethyl ether; carbonates such as ethylene carbonate and propylene carbonate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone; phenol, cresol; Xylenol, etc. Phenols; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate; hydrocarbons such as toluene, xylene, diethylbenzene, cyclohexane; trichloroethane; Halogenated hydrocarbons such as tetrachloroethane and monochlorobenzene, and organic solvents such as petroleum solvents such as petroleum ether and petroleum naphtha (B-
2) and the like. The diluents may be used alone or as a mixture of two or more.

In the present invention, a photopolymerization initiator (C) is used. Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2. -Phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-
Acetophenones such as hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone And anthraquinones such as 2-amylanthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthone,
Thioxanthones such as chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-
Benzophenones such as 4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone;
Examples thereof include phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

These can be used alone or as a mixture of two or more. Further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoate It can be used in combination with an accelerator such as a benzoic acid derivative such as acid isoamyl ester.

In the present invention, an unsaturated group-containing polycarboxylic acid resin (D) may be used. The unsaturated group-containing polycarboxylic acid resin (D) includes an epoxy resin (f) having two or more epoxy groups in one molecule, an ethylenically unsaturated group-containing monocarboxylic acid compound (b), and a polybasic anhydride. (G).

Examples of the epoxy resin (f) having two or more epoxy groups in one molecule include bisphenol type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, and trisphenol methane. Ethers such as epoxy resin, brominated epoxy resin, biphenyl-type epoxy resin, biphenol-type epoxy resin; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate Alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate, tetrahydric Phthalic acid diglycidyl ester,
Glycidyl esters such as dimer acid glycidyl ester; glycidylamines such as tetraglycidyldiaminophenylmethane; heterocyclic epoxy resins such as triglycidyl isocyanurate; Epicoat series (Epicoat 1009, 1031: Yuka Shell Epoxy Co., Ltd.)
Manufactured), Epicron series (Epiclon N-3050,
N-7050: manufactured by Dainippon Ink and Chemicals, Inc.), DE
R series (DER-642U, DER-673MF:
Bisphenol A type epoxy resins such as Dow Chemical Co., Ltd.) and YDF series (YDF-2004, 200
7: manufactured by Toto Kasei Co., Ltd.) and an epoxy resin obtained by reacting an alcoholic hydroxyl group of a bisphenol F type epoxy resin with an epihalohydrin such as epichlorohydrin.

The reaction between the alcoholic hydroxyl group of the epoxy resin and epihalohydrin is preferably carried out in the presence of dimethyl sulfoxide. The amount of epihalohydrin used is determined based on the amount of alcoholic hydroxyl group 1 in the starting epoxy compound.
What is necessary is just to use 1 equivalent or more with respect to equivalent. However, when the amount exceeds 15 equivalents to 1 equivalent of the alcoholic hydroxyl group, the effect of increasing the amount is almost negligible, but the volumetric efficiency deteriorates.

In carrying out the reaction, an alkali metal hydroxide is used. As the alkali metal hydroxide, for example, caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, but caustic soda is preferable. It is sufficient to use approximately 1 equivalent of the alkali metal hydroxide with respect to 1 equivalent of the alcoholic hydroxyl group to be epoxidized in the raw material epoxy compound. When the total amount of the alcoholic hydroxyl groups of the starting epoxy compound is epoxidized, an excess amount may be used. However, if the amount exceeds 2 equivalents relative to 1 equivalent of the alcoholic hydroxyl groups, the polymer tends to be slightly polymerized.

The reaction temperature is preferably from 30 to 100 ° C.
When the reaction temperature is lower than 30 ° C., the reaction becomes slow and a long-time reaction is required. If the reaction temperature exceeds 100 ° C., many side reactions occur, which is not preferable. After completion of the reaction, excess epihalohydrin and dimethyl sulfoxide are distilled off under reduced pressure, and then the resulting resin is dissolved in an organic solvent, and a dehydrohalogenation reaction can be performed with an alkali metal hydroxide.

The epoxy resin (f) is reacted with the ethylenically unsaturated group-containing monocarboxylic acid compound (b) to obtain an epoxy (meth) acrylate compound. It is preferable to react 0.3 to 1.2 equivalents of the total amount of the carboxyl group of the component (b) with one equivalent of the epoxy group of the epoxy resin, and more preferably 0.9 to 1.05 equivalents. At the time of reaction or after completion of the reaction, one or more of the diluents (b) can be used.

Furthermore, a catalyst can be used to promote the reaction. Examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, triphenylstilbin, triphenylphosphine and the like. The amount used is preferably 0.1 to 10% by weight, more preferably 0.3 to 5% by weight, based on the reaction raw material mixture.

During the reaction, a polymerization inhibitor is preferably used to prevent polymerization of the ethylenically unsaturated group. Examples of the polymerization inhibitor include methoquinone, hydroquinone, methylhydroquinone, phenothiazine and the like. The amount used is preferably from 0.01 to 1% by weight, more preferably from 0.05 to 0.5% by weight, based on the reaction raw material mixture. The reaction temperature is 60-150 ° C, and furthermore, 8
0-120 ° C is preferred. The reaction time is preferably 5 to 60 hours.

Next, a polybasic acid anhydride (g) is reacted. Examples of the polybasic acid anhydride (g) include succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyl-
Examples thereof include tetrahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride. The amount of the polybasic anhydride (g) used per 0.05 equivalent of the hydroxyl group in the epoxy (meth) acrylate is 0.05 to 1.0 per equivalent of the hydroxyl group.
It is preferable to react at zero equivalent. The reaction temperature is 60 to 1
50 ° C, more preferably 80 to 100 ° C.

In the present invention, it is preferable to use a thermosetting component (E) as a curing system component in addition to the components described above.
By using this, a material for a printed wiring board having excellent solder heat resistance and electrical characteristics can be obtained. The thermosetting component (E) used in the present invention includes an imide precursor oligomer (A) and an unsaturated group-containing polycarboxylic acid resin (D).
What is necessary is just to have a functional group which thermally cures in the molecule, and it is not particularly limited. Examples thereof include an epoxy resin, a melamine compound, a urea compound, an oxazoline compound, a phenol compound, and a dihydrobenzoxazine ring-containing compound. Can be mentioned. Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, trisphenolmethane type epoxy resin, brominated epoxy resin, and biquilenol type. Glycidyl ethers such as epoxy resins and biphenol type epoxy resins; 3,
4-epoxy-6-methylcyclohexylmethyl-3,
4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4
Alicyclic epoxy resins such as epoxycyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate and glycidyl dimer; tetraglycidyl Glycidylamines such as diaminodiphenylmethane; and heterocyclic epoxy resins such as triglycidyl isocyanurate. Among them, an epoxy resin having a melting point of 50 ° C. or more is preferable because a tack-free photopolymerizable film can be formed after drying.

Examples of the melamine compound include melamine and a melamine resin which is a polycondensate of melamine and formalin. Examples of the urea compound include urea and urea resins which are polycondensates of urea and formalin.

Examples of the oxazoline compound include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 5-methyl-2-phenyl-2-oxazoline,
2,4-diphenyloxazoline and the like.

Examples of the phenol compound include phenol, cresol, chilenol, catechol, resorcin, hydroquinone, pyrogallol, resol and the like.

As the dihydrobenzoxazine ring-containing compound, for example, a mixture of 1 equivalent of a hydroxyl group of a compound having a phenolic hydroxyl group and about 1 equivalent of an amino group of a primary amine is dissolved in 1 to 5 mol of formaldehyde heated to 70 ° C. or more. 70-110 ° C, preferably 90-100
The reaction can be carried out at a temperature of 120 ° C. for 20 to 120 minutes, followed by drying under reduced pressure at a temperature of 120 ° C. or lower. It is preferable that all the phenolic hydroxyl groups of the compound having a phenolic hydroxyl group react with the primary amine and formaldehyde to form a dihydrobenzoxazine ring. The compound having a phenolic hydroxyl group is not particularly limited, and examples thereof include compounds such as bisphenol A, bisphenol F, biphenol, trisphenol, and tetraphenol, and phenol resins. Examples of the phenolic resin include a novolak resin obtained by reacting a phenolic compound such as a monovalent phenolic compound such as phenol or an alkylphenol such as xylenol, t-butylphenol and octylphenol, a polyhydric phenol compound such as resorcinol and bisphenol A with formaldehyde. Alternatively, there are a resol resin, a phenol-modified xylene resin, a melamine phenol resin, and a polybutadiene-modified phenol resin. 1
The secondary amine is not particularly limited, and examples thereof include methylamine, cyclohexylamine, aniline, and substituted aniline. Formaldehyde may be used in the form of formalin or polyformaldehyde.

The dihydrobenzoxazine ring-containing compound can be prepared by a known method (for example, DE 2217099).
No. H. Ishida, J. et al. Polym. Sci. , P
artA32, 1121 (1994)).

Among these thermosetting components (E), epoxy resins are particularly preferred because of their excellent reactivity with the carboxyl groups in the components (A) and (D) and good adhesion to copper. .

When an epoxy resin is used as the thermosetting component (E), it is preferable to use a curing accelerator for the epoxy resin in order to accelerate the reaction with the carboxyl group in the component (A). Specific examples of the epoxy resin curing accelerator include 2-methylimidazole and 2-methylimidazole.
Ethyl-3-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-
Imidazole compounds such as undecyl imidazole; melamine, guanamine, acetoguanamine, benzoguanamine, ethyldiaminotriazine, 2,4-diaminotriazine, 2,4-diamino-6-tolyltriazine;
Triazine derivatives such as 2,4-diamino-6-xylyltriazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, pyridine, m-
Tertiary amines such as aminophenol; polyphenols and the like. These curing accelerators can be used alone or in combination.

In the present invention, various additives and the like can be further added as needed. As various additives,
For example, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay,
Thixotropic agents such as Aerosil, phthalocyanine blue, phthalocyanine green, coloring agents such as titanium oxide, silicone, fluorine-based leveling agents and defoamers, dyes, hydroquinone, p-methoxyphenol,
And polymerization inhibitors such as hydroquinone monotyl ether.

In the photosensitive resin composition of the present invention, the proportion of each component used is (A) 20 to 96% by weight, (B)
The component is preferably 3 to 50% by weight, the component (C) 1 to 30% by weight, more preferably the component (A) 40 to 90% by weight, the component (B) 5 to 40% by weight, and the component (C) 5 to 20% by weight. . When the component (D) is used, 0 to 0 of the component (A) component use ratio.
It is preferable to replace 80% by weight, more preferably 10 to 50% by weight, with the component (D). When the component (E) is used, the functional group of the thermosetting component (E) is preferably 0.2 to 3 per carboxyl group in the component (A) or the components (A) and (D). The ratio which becomes 0.0 equivalent is preferable. Above all, a ratio of 1.0 to 1.5 equivalents is preferred from the viewpoint of excellent solder heat resistance and electrical characteristics when formed into a printed wiring board.

The photosensitive resin composition and the photosensitive film of the present invention are obtained by dissolving, mixing, mixing the components (A), (B), (C), (D), (E) and various additives. It can be prepared and manufactured by kneading.

The photosensitive film of the present invention can be produced by laminating a layer of the photosensitive resin composition of the present invention on a support film. Examples of the support include a polymer film, for example, a film made of polyethylene terephthalate, polypropylene, polyethylene and the like. Among them, a polyethylene terephthalate film is preferable. Since these polymer films must be removed from the photosensitive layer later, they must not be surface-treated or made of a material that cannot be removed. The thickness of these polymer films is 5 to 100.
μm, more preferably 10 to 30 μm. These polymer films can be laminated on both sides of the photosensitive layer as a support film for one photosensitive layer and another as a protective film for the photosensitive layer.

Next, the prepared photosensitive resin composition was
After uniformly coated on the polymer film of the support film, the solvent can be removed by heating and / or blowing with hot air to form a dried film. The thickness of the dry film is
There is no particular limitation, and the thickness is preferably 10 to 100 μm, and more preferably 20 to 60 μm.

The photosensitive film of the present invention comprising two layers, the photosensitive layer and the polymer film, obtained as described above, may be used as it is or by further laminating a protective film on the other surface of the photosensitive layer to form a roll. It can be wound up and stored.

The photosensitive resin composition and the photosensitive film of the present invention are particularly useful as resists such as etching resists and solder resists for flexible printed wiring boards, and can also be used as paints, coating agents, adhesives and the like. .

The printed wiring board of the present invention can be obtained, for example, as follows. That is, when a liquid resin composition is used, the present invention is applied to a substrate for printed wiring with a film thickness of 5 to 160 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, and a curtain coating method. By applying the resin composition of the above, and drying the coating film at a temperature of 60 to 110 ° C, preferably 60 to 100 ° C,
A tack-free coating film can be formed. Thereafter, a photomask on which an exposure pattern such as a negative film is formed is brought into direct contact with the coating film (or placed on the coating film without being in contact with the coating film), and irradiated with ultraviolet rays at an intensity of about 10 to 2000 mJ / cm ² , The unexposed portion is developed using a developing solution described later, for example, by spraying, rocking immersion, brushing, scrubbing, or the like. Then, if necessary, further irradiate ultraviolet rays, then 100 to 200 ° C., preferably 140 ° C.
A print with a permanent protective film that excels in flexibility by performing heat treatment at a temperature of up to 180 ° C. and satisfies various characteristics such as heat resistance, solvent resistance, acid resistance, adhesion, and electrical characteristics of the resist film. A wiring board is obtained.

Examples of the organic solvent used for the development include halogens such as trichloroethane, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; 1,4-dioxane and tetrahydrofuran. Ethers such as methyl ethyl ketone,
Ketones such as methyl isobutyl ketone; lactones such as γ-butyrolactone; glycol derivatives such as butyl cellosolve acetate, carbitol acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; alicyclic hydrocarbons such as cyclohexanone and cyclohexanol; And petroleum solvents such as petroleum ether and petroleum naphtha, water and alkaline aqueous solutions include alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines. Can be used.

As a method for producing a photoresist image using the photosensitive film of the present invention, when the protective film is present, the protective film is removed and then the photosensitive layer is press-bonded to the substrate while heating. By doing so, they can be laminated. At this time, it is preferable that the layers are stacked under reduced pressure. The surface to be laminated is not particularly limited, and is preferably an FPC on which wiring is formed by etching or the like. The heating temperature of the photosensitive layer is not particularly limited,
The temperature is preferably set to 90 to 130 ° C. The pressure for pressing is not particularly limited, and it is preferable that the pressing be performed under reduced pressure. The photosensitive layer thus laminated is brought into direct contact with a photomask on which an exposure pattern such as a negative film is formed (or placed on the coating in a state where it is not in contact with the film), and is irradiated with ultraviolet rays at 10 to 2000 mJ / cm. ^Two
Irradiate with moderate intensity. At this time, if the polymer film present on the photosensitive layer is transparent, it can be exposed as it is, but if it is opaque, it needs to be removed.
From the viewpoint of protecting the photosensitive layer, the polymer film is transparent, and it is preferable to expose the polymer film while leaving the polymer film remaining. As an irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, a laser beam or the like can be used as the active light for exposure.

Next, after exposure, if a polymer film is present on the photosensitive layer, the polymer film is removed, and then, using the above-mentioned developer, a known method such as spraying, rocking immersion, or brushing is used. Thus, the unexposed portion can be removed and development can be performed. Then, if necessary, further irradiate ultraviolet rays, then 100 to 200 ° C., preferably 140 to 18
By performing a heat treatment at a temperature of 0 ° C., the flexibility is excellent, and the heat resistance, solvent resistance, acid resistance, adhesion,
A printed wiring board having a permanent protective film satisfying various characteristics such as electric characteristics can be obtained.

[0060]

The present invention will be described below with reference to examples. It goes without saying that the present invention is not limited to the following examples. In the following, “parts” means “parts by weight” unless otherwise specified.

Synthesis Example 1 (Synthesis of Unsaturated Group-Containing Polyol Compound (c)) A mixture of bisphenol A epoxy resin and bisphenol F epoxy resin (product name: ZX- 1059, manufactured by Toto Kasei Co., Ltd.), 168.2 g, acrylic acid 72.06 g, triphenylphosphine 1.2 g, and methoxyphenol 0.24 g were charged, and the mixture was heated to 60 ° C. and dissolved.
C. for 24 hours to obtain an unsaturated group-containing polyol compound (c-1) having an acid value of 0.3 mgKOH / g.

Synthesis Example 2 (Synthesis of imide precursor oligomer (A)) A round bottom flask equipped with a stirring device and a condenser was charged with 3,
716 g of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride (product name: Ricacid DSDA, manufactured by Shin Nippon Rika Co., Ltd., acid value: 627 mg KOH / g), γ
-Butyrolactone (477.3 g) was charged and dissolved, and 248.2 g of 3,3'-diaminophenylsulfone (product name: DAS, manufactured by Konishi Chemical Industry Co., Ltd.) was added at room temperature to γ.
-A solution dissolved in 165.5 g of butyrolactone was slowly added dropwise. After the dropwise addition, the mixture was reacted at 40 ° C. for 5 hours to obtain a polyamide prepolymer having a solid content acid value of 349.1 mgKOH / g. Thereafter, 961 g of the unsaturated group-containing polyol compound (c-1) obtained in Synthesis Example 1 and 640.7 g of γ-butyrolactone were charged and reacted at 90 ° C. for 10 hours, and the solid acid value was 116.6 mgKOH / g, An oligomer (A-1) having a content of 60% was obtained.

Synthesis Example 3 (Synthesis of Unsaturated Group-Containing Polycarboxylic Acid Resin (D)) A bisphenol F type epoxy resin (epoxy equivalent: 310 g /
(eq, softening point: 69 ° C), 310 g, and 251 g of carbitol acetate were charged and dissolved by heating at 90 ° C with stirring. The obtained solution was cooled to 60 ° C., added with 60 g of acrylic acid, 97 g of dimer acid, 0.8 g of methylhydroquinone, and 2.5 g of triphenylphosphine, heated and dissolved at 80 ° C., reacted at 98 ° C. for 35 hours, and solidified. 0.3 m
An epoxy acrylate having gKOH / g and a solid content of 65% was obtained. Then, the epoxy acrylate 718.5
g, succinic anhydride 100 g, carbitol acetate 5
4 g, and reacted at 90 ° C. for 6 hours.
An unsaturated group-containing polycarboxylic acid resin (D-1) having 9 mgKOH / g and a solid content of 65% was obtained.

Examples and Comparative Examples A photosensitive resin composition containing the materials shown in Table 1 was applied to a printed circuit board (a laminate of an imide film and a copper foil) by screen printing and dried at 80 ° C. for 20 minutes. .
Thereafter, a negative film is applied to the substrate, and the substrate is irradiated with ultraviolet rays at an integrated exposure amount of 500 mJ / cm ² using an exposure machine according to a predetermined pattern, and the organic solvent or 1 wt% Na 2 C
The test substrate was prepared by developing with an O3 aqueous solution and heat curing at 150 ° C. for 50 minutes. With respect to the obtained test substrate, characteristics such as alkali developability, solder heat resistance, flexibility, heat deterioration resistance, and electroless gold plating resistance were evaluated.

Table 1 Compounding amount (parts by weight) Example Comparative example 12 3 1 A-1 160 160 83 D-1 78 154 DPCA-60 * 1 30 30 30 30 DETX-S * 2 1.0 1.0 1.0 1.0 Irg907 * 3 10 10 10 10 γ-butyrolactone 40 40 40 40 YX-4000 * 4 40 40 40 Developability ○ ○ ○ ○ Solder heat resistance ○ ○ ○ ○ Flexibility ○ ○ ○ × Heat deterioration ○ ○ ○ × Electroless gold plating resistance ○ ○ ○ ○

Note) * 1: DPCA-60; manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA-60 (ε- of dipentaerythritol
* 2: DETX-S; KAYACU manufactured by Nippon Kayaku Co., Ltd.
RE DETX-S (diethylthioxanthone) * 3: Irg907; manufactured by Ciba Specialty Chemicals, Irgacure 907 (2-methyl-1 [4
-(Methylthio) phenyl] -2-morpholinopropan-1-one) * 4: YX-4000; manufactured by Yuka Shell Epoxy Co., Ltd.
Biphenyl type epoxy resin

(Developability) The coating film was dried at 80 ° C. for 60 minutes, and the developability by spray development with a 1% aqueous solution of sodium carbonate at 30 ° C. was evaluated.・: No residue is visually observed. ×: There is a residue visually.

(Solder Heat Resistance) A rosin-based flux was applied to a test substrate, immersed in molten solder at 260 ° C. for 10 seconds, and evaluated by the state of the cured film when peeled off with a cellophane adhesive tape. ○ ・ ・ ・ ・ ・ ・ No abnormality. ×: There is peeling.

(Flexibility) Judgment was made in a state where the test board was solidly bent at 180 degrees. ○ ・ ・ ・ ・ ・ ・ No cracks. △ ・ ・ ・ ・ Slight cracks. C: Cracks were formed in the bent portion and the cured film was separated.

(Heat-Resistant Deterioration Resistance) The test substrate was left at 125 ° C. for 5 days, and was evaluated in a state of 180 ° solid bending. ○ ・ ・ ・ ・ ・ ・ No cracks. △ ・ ・ ・ ・ Slight cracks. C: Cracks were formed in the bent portion and the cured film was separated.

(Electroless Gold Plating Resistance) The gold plating was performed on the test substrate as described below, and the state was determined by peeling with a cellophane adhesive tape. ○ ・ ・ ・ ・ ・ ・ No abnormality. Δ: Some peeling was observed. ×: No peeling.

Electroless gold plating method: A test substrate was subjected to an acidic degreasing solution at 30 ° C. (Metex, manufactured by Nippon MacDermid Co., Ltd.).
(5% aqueous solution of L-5B) for 3 minutes to degrease, then dipped in running water for 3 minutes and washed with water. Next, the test substrate was placed in a 14.3 wt% ammonium persulfate aqueous solution at room temperature for 3 hours.
Then, it was immersed in running water for 3 minutes and then washed with water. After the test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute, it was immersed in running water for 30 seconds to 1 minute and washed with water. Next, the test substrate was immersed in a 30 ° C. catalyst solution (a 10 vol% aqueous solution of a metal plate activator 350 manufactured by Meltex Co., Ltd.) for 7 minutes to give a catalyst, and then a 3 vol% aqueous solution in running water, pH 4.0.
6) for 20 minutes to perform electroless nickel plating. After the test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute, it was immersed in running water for 30 seconds to 1 minute and washed with water. Next, the test substrate was placed in a 95 ° C. gold plating solution (aqueous solution of 15 vol% of Aurolectroles UP and 3 vol% of potassium gold cyanide, manufactured by Meltex Co., Ltd., pH 6).
After immersion in electroless gold plating for 3 minutes, immersion in running water for 3 minutes and washing with water, and immersion in warm water at 60 ° C. for 3 minutes and washing with hot water. After sufficient washing with water, the water was thoroughly removed, dried, and a test substrate plated with electroless gold was obtained.

As is clear from the above results, the photosensitive resin composition of the present invention shows good alkali developability, or has poor heat resistance, flexibility, heat deterioration resistance and electroless gold plating resistance. Provides excellent cured film.

[0074]

The photosensitive resin composition of the present invention has good workability, excellent flexibility and excellent solder heat resistance, and is suitable for an etching resist for FPC and a photosensitive film for coverlay.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08F 299/02 C08F 299/02 C08G 73/12 C08G 73/12 G03F 7/004 501 G03F 7/004 501 512 7 / 028 7/028 H05K 3/28 H05K 3/28 DF term (reference) 2H025 AA00 AA10 AB11 AB15 AD01 BC32 BC42 BC69 BJ10 CA01 CA27 CA35 CC03 CC20 FA03 FA17 4J011 PA33 PA35 PA43 PA83 PA85 PA86 PB30 PC02 QA23 QA13 QA23 QA22 QB18 RA10 RA11 RA12 SA02 SA04 SA06 SA07 SA15 SA16 SA22 SA25 SA32. SA71 SB01 SB03 TA22 TB01 UA121 UA122 UA131 UA132 UA151 UA171 UA231 UA261 UA761 UA762 UB011 UB012 UB021 UB121 UB122 UB131 UB141 UB151 UB152 UB172 UB221 UB281 UB291 UB292 UB402 VA021 VA031A04AB12A031A041A031 1 DD06 DD07 FF06 FF19 GG10 GG14

Claims (8)

[Claims] 1. An unsaturated group-containing polyol compound (c) obtained by reacting an epoxy resin (a) having two epoxy groups in one molecule with an ethylenically unsaturated group-containing monocarboxylic acid compound (b). An imide precursor obtained by reacting a diamine compound (d) with a compound (e) having two acid anhydride groups in one molecule, the component (d), the component (e), or both components. Imide precursor oligomer (A) comprising a compound containing a sulfur atom in the molecule
And a diluent (B) and a photopolymerization initiator (C). 2. A diamine compound (d) is reacted with a compound (e) having two acid anhydride groups in one molecule to synthesize an acid anhydride group-containing polyamide prepolymer, and thereafter, an unsaturated group-containing polyol. A method for producing an imide precursor oligomer (A), which comprises reacting a compound (c). 3. A reaction product of an epoxy resin having two or more epoxy groups in one molecule, (f), an ethylenically unsaturated monocarboxylic acid compound (b) and a polybasic anhydride (g). The photosensitive resin composition according to claim 1, which contains a certain unsaturated group-containing polycarboxylic acid resin (D). 4. The photosensitive resin composition according to claim 1, further comprising a thermosetting component (E). 5. A photosensitive film obtained by laminating a layer of the photosensitive resin composition according to claim 1 on a support film. 6. A cured product of the photosensitive resin composition and film according to claim 1. 7. An article having the cured product according to claim 6. 8. The article according to claim 7, which is a printed wiring board.