JP2001154351A - Photosensitive resin composition and photosensitive film using 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 aqueous alkali solution or an organic solvent and suitable for a soldering resist and a cover lay and a photosensitive film using the composition. SOLUTION: The photosensitive resin composition contains a (meth)acrylate oligomer (A), a diluent (B) and a polyamide compound (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition suitable for forming a solder resist and a protective film (cover lay) for a flexible printed wiring board which can be used for manufacturing a printed wiring board and the like, and using the same. It relates to a photosensitive 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. Some printed wiring boards are in the form of a film that can be folded and incorporated into a small device such as a camera.
It is called PC. This FPC also requires a resist to limit the soldering position and protect the wiring.
It is called a coverlay or 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 cover lay requires an expensive mold for die cutting, and the yield is low and the manufacturing cost is high due to the manual bonding of the die cut film and the protrusion of the adhesive. This is an obstacle to expansion, and it is difficult to cope with recent high density.

Therefore, 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 development 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, a photosensitive resin composition containing an acrylic polymer and a photopolymerizable monomer as main components (JP-A-53-56018, PR, JP-A-54
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 a photosensitive resin composition comprising (1) a (meth) acrylate oligomer (A), a diluent (B) and a polyamide compound (C).
(2) The photosensitive resin composition according to (1), wherein the polyamide compound (B) is a phenolic hydroxyl group-containing polyamide compound, and (3) the polyamide compound (B) is a phenolic hydroxyl group-containing polyamide compound. (1) the photosensitive resin composition according to any one of (1) to (3), which contains a photopolymerization initiator (D);
(5) (1) to (4) containing a thermosetting component (E)
The photosensitive resin composition according to any one of (1) to (6), wherein a layer of the photosensitive resin composition according to any one of (1) to (5) is laminated on a support film. Film.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The photosensitive resin composition of the present invention is a mixture containing the above (meth) acrylate oligomer (A), polyamide compound (B) and diluent (C).

A specific example of the (meth) acrylate oligomer (A) used in the present invention is epoxy (meth)
(Meth) acrylate of acrylate, polyester (meth) acrylate, polyurethane (meth) acrylate, polymer (eg, polybutadiene polymer, poly (meth) acrylate polymer, silicon polymer, etc.) Carboxyl groups such as (meth) acrylate oligomer (A1), carboxyl group-containing epoxy (meth) acrylate, carboxyl group-containing polyurethane (meth) acrylate, and carboxyl group-containing polymer (meth) acrylate Group-containing oligomers (A2) and the like can be mentioned.

More specifically, epoxy (meth) acrylate is an epoxy resin (eg, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol
Le novolak type epoxy resin, cresol novolak type epoxy resin, trisphenol methane type epoxy resin, diphenyl diglycidyl ether, copolymerization type of glycidyl methacrylate and monofunctional (meth) acrylate Epoxy resin or epoxy resin represented by the following formula (1))

[0010]

Embedded image (Two lines mean one expression)

(In the formula (1), X represents —CH ₂ — or —C
(CH3) _2- , n is an integer of 1 or more, and M represents a hydrogen atom or the following formula (G).

[0012]

Embedded image

However, when n is 1, M represents the formula (G),
When n is greater than 1, at least one of M is of the formula (G)
And the rest represent hydrogen atoms. )

A reaction product of (meth) acrylic acid and
It can be manufactured by a known method. Polyester (meth) acrylates include ethylene glycol, propylene glycol, neopentyl glycol, 3-methyl-
1,5-pentaneddiol, trimethylolpropane,
Pentaerythritol polyethoxy compounds, polyethylene glycol, polytetramethylene glycol, bisphenol A polyethoxydiol and other polyol compounds and succinic acid, adipic acid, phthalic acid, isophthalic acid,
It is a reaction product of a polyester polyol which is a reaction product of a polybasic acid such as terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or an anhydride compound thereof with (meth) acrylic acid, and is produced by a known method. Can be.

Polyurethane (meth) acrylates include alkyl polyols, polyester polyols and polyethers.
Polyol compounds having an alcoholic hydroxyl group such as terpolyol, acrylpolyol, polybutadienepolyol, phenolicpolyol, and gyriconpolyol, and 2,4- and / or 2,6-triol Range isocyanate, 4,4'-diphenylmethane diisocyanate (MDI), tolidine diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate G, xylylene diisocyanate (XDI), hydrogenated MDI, hydrogen XDI
Polyisocyanate compound such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl di (meth) acrylate
G, caprolactone-modified 2-hydroxyethyl (meth)
It is a reaction product with an ethylenically unsaturated group-containing polyhydroxy compound such as acrylate and pentaerythritol tri (meth) acrylate, and can be produced by a known method.

The (meth) acrylate of the polymer may be, for example, a reaction product of a polymer polyol such as polybutadiene polyol, silicon polyol or poly (meth) acrylate polyol with (meth) acrylic acid. And can be produced by a known method.

These (meth) acrylate oligomers
(A1) can be used alone or in combination of two or more.

The carboxyl group-containing epoxy (meth) acrylate is the same as the epoxy (meth) acrylate described above and succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-tetrahydro It is a reaction product of a polybasic anhydride such as phthalic anhydride and trimellitic anhydride, and can be produced by a known method. As a preferred carboxyl group-containing epoxy (meth) acrylate, when used for a solder resist for a flexible substrate requiring flexibility, acrylic acid is added to the epoxy resin represented by the general formula (1). The above-mentioned oligomers obtained by reacting an acid anhydride with the reacted epoxy acrylate are exemplified.

Carboxyl group-containing polyurethane (meth)
The acrylate is a polyol compound having an alcoholic hydroxyl group and pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ethertetracarboxylic dianhydride. , Diphenylsulfonetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, polybasic anhydride having at least two acid anhydride groups in a molecule such as ethylene glycol bis (anhydrotrimellitate) To prepare a carboxyl group-containing terminal alcohol compound, and then reacting the above-mentioned polyisocyanate compound to form a carboxyl group-containing terminal isocyanate-urethane prepolymer, and thereafter, the ethylenically unsaturated group-containing polymer. A reaction product obtained by reacting a hydroxy compound.

The carboxyl group-containing terminal alcohol compound is a polybasic acid anhydride having two acid anhydride groups in the molecule with respect to one equivalent of the hydroxyl group of the alcoholic hydroxyl group-containing polyol compound. Is preferably 0.5 to 0.99 equivalents (as acid anhydride equivalents). The reaction temperature of this esterification reaction is 60-150 ° C., and the reaction time is 1-1.
0 hours is preferred.

Next, a carboxyl group-containing terminal alcohol
A prepolymer is obtained by reacting the polyisocyanate compound with the polyisocyanate compound. It is preferable that 1.1 to 2.1 equivalents of the isocyanate group of the polyisocyanate compound are reacted with 1 equivalent of the hydroxyl group of the carboxyl group-containing terminal alcohol compound. The reaction temperature of the prepolymerization reaction is usually room temperature to 100 ° C, preferably 50 to 90 ° C.

The hydroxyl group of the ethylenically unsaturated group-containing polyhydroxy compound is 0.9 to 1.5 equivalents to 1 equivalent of the isocyanate group of the terminal isocyanate-urethane prepolymer thus obtained. Is preferred, and particularly preferably 1.0 to 1.1 equivalent. The reaction temperature is usually from room temperature to 100 ° C, preferably from 50 to 90 ° C.
It is. In order to prevent gelation due to radical polymerization during this reaction, it is usually preferable to add 50 to 2000 ppm of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, P-methoxyphenol, and P-benzoquinone. The resulting carboxyl group-containing urethane (meth) acrylate has a weight average molecular weight of 10
It is preferably from 100 to 100,000, and its acid value is from 20 to
200 mg KOH / g is preferred.

In the present invention, a diluent (B) is used. Specific examples of the diluent (B) include, for example, alcohols such as methanol, ethanol and isopropanol; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; lactones such as γ-butyrolactone and γ-valerolactone; ethers such as 1,4-dioxane and tetrahydrofuran; ethylene carbonate, propylene carbonate and the like Phenols such as phenol, cresol and xylen; butyl cellosolve acetate and carbitol
Luacetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate
And glycol derivatives such as dipropylene glycol monomethyl ether; alicyclic hydrocarbons such as cyclohexanone and cyclohexane; and organic solvents such as petroleum solvents such as petroleum ether and petroleum naphtha; ) Acrylates, phenoxyethyl (meth) acrylates,
Acryloyl morpholine, bisphenol A polyethoxydi (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaeryth Litol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, dipentaerythritol penta and hexa (meth) Examples thereof include photopolymerizable monomers such as acrylate.
One or more of these diluents may be added.

In the present invention, a polyamide compound (C) is used. Specific examples of the polyamide compound (C) can be easily produced by a condensation reaction of a dicarboxylic acid which is an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid with a diamine compound which is an aliphatic diamine or an aromatic diamine. Examples of the polyamide compound that can be preferably used include a phenolic hydroxyl group-containing aromatic polyamide resin. The phenolic hydroxyl group-containing aromatic polyamide resin is a phenolic hydroxyl group-containing aromatic polyamide oligomer compound obtained by a condensation reaction of a dicarboxylic acid having a phenolic hydroxyl group with a diamine component, or a phenolic hydroxyl group-containing aromatic polyamide resin and a carboxyl group at both terminals. A block copolymer, which is a reaction product of a polybutadiene / acrylonitrile containing copolymer, and the like can be given. Specifically, for example, JP-A-8-143661, JP-A-9-32412
0, JP-A-9-176485, JP-A-6-2991
It can be obtained by the method described in, for example, JP-A No. 33, and has a skeleton structure represented by the following formulas (2) and (3).

[0025]

Embedded image (4 lines mean one expression)

(Where x, y, z, l, m and n are average polymerization degrees, respectively; x = 3 to 7, y = 1 to 4,
z = 5 to 15, 1 + m = 2 to 200, and m /
(M + n) ≧ 0.04. )

[0027]

Embedded image (Two lines mean one expression)

(In the formula (3), R represents a divalent organic group,
R _{1 and} R ₂ each represent at least one group selected from the group consisting of a methyl group, an ethyl group and an isopropyl group;
Represents an integer, b represents 1 or 2, a + c = 1, 0 ≦ a ≦
0.1,10 ≦ d ≦ 10000. )

The block copolymer represented by the above formula (2) is a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both ends and a polybutadiene / acrylonitrile copolymer having carboxyl groups at both ends. And obtained by reacting

The amino terminus is used at both ends used as a raw material.
The phenolic hydroxyl group-containing aromatic polyamide oligomer compound having a hydroxyl group is synthesized by polycondensation of an aromatic diamine component and an aromatic dicarboxylic acid component. By mixing an aromatic diamine having a hydroxyl group or an aromatic dicarboxylic acid into the aromatic diamine component or the aromatic dicarboxylic acid component, a phenolic hydroxyl group-containing aromatic polyamide oligomer compound can be produced. The formation of aminoallyl groups at both ends of the oligomer compound can be easily achieved by subjecting the aromatic diamine component to a polycondensation reaction in excess of the aromatic dicarboxylic acid component. Blocking of the phenolic hydroxyl group-containing aromatic polyamide oligomer compound having both terminal amino aryl groups thus synthesized with the carboxy group-containing polybutadiene / acrylonitrile copolymer is similarly performed by the above-mentioned condensation polymerization. Can be synthesized. This polycondensation can be carried out by a conventionally known method. That is, the above-mentioned direct dehydration polycondensation polymerization method between the carboxyl group and the amino group, a polymerization method in which the carboxyl group is acid chlorided with thionyl chloride or the like and then reacted with an amine, and a polycondensation catalyst using a phosphite and pyridine are used. Synthetic methods are preferred.

As the aromatic diamine used in the production of the above-mentioned phenolic hydroxyl group-containing aromatic polyamide oligomer compound, m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4'-diaminodiphenyl Ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether
Ter, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-
Diaminodiphenylthioether, 3,3′-diaminodiphenylthioether, 3,3′-dimethyl-4,
4'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4 '
-Diaminobenzophenone, 3,3'-diaminophenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylthioether, 2,2'-bis (3-aminophenyl) propane, 2,2 ' -Bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone, benzidine, 3,3'-dimethylbenzidine, 3,
3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, 2,2'-bis (3-
Aminophenoxyphenyl) propane, 2,2′-bis (4-aminophenoxyphenyl) propane, 1,3-
Bis (4-aminophenoxyphenyl) benzene, 1,
3-bis (3-aminophenoxyphenyl) propane,
4,4 ′-(p-phenylenediisopropylidene) bisaniline and the like, and these may be used alone or in combination of two or more.

The dicarboxylic acids used for producing the phenolic hydroxyl group-containing aromatic polyamide oligomer compound of the present invention include, for example, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-oxydibenzoic acid , 4,
4'-biphenyldicarboxylic acid, 3,3'-methylene dibenzoic acid, 4,4'-methylene dibenzoic acid, 4,4'-
Thiodibenzoic acid, 3,3′-carbonyldibenzoic acid,
4,4′-carbonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 1,5-naphthalenedicarboxylic acid,
Examples thereof include 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,2-naphthalenedicarboxylic acid, but are not limited thereto.

Further, as the hydroxyl group-containing aromatic dicarboxylic acid or hydroxyl group-containing aromatic diamine used for introducing a phenolic hydroxyl group into the polyamide compound of the present invention, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid, 3-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 3,
3'-dihydroxy-4,4'-dianiline, 3,2-
Bis (3'-amino-4-hydroxyphenyl) propane, 2,4-dihydroxy-1,5-diaminobenzene, 5-hydroxy-1,3-diaminobenzene and the like can be used.

A block formed from a phenolic hydroxyl group-containing aromatic polyamide oligomer compound having an amino alcohol group at both terminal groups and a polybutadiene / acrylonitrile copolymer containing both terminal carboxyl groups used in the present invention. The copolymer is represented by the structure of the formula (2). Considering physical properties such as strength and elastic modulus of the obtained copolymer, the average degree of polymerization x, y, l, m and n are as follows. x = 3 ~
7, y = 1 to 4, z = 5 to 15, l + m = integer of 2 to 200, and a copolymer in which m / (m + 1) ≧ 0.04 is preferable.

Specific examples of the dicarboxylic acid having a phenolic hydroxyl group which can be used for obtaining the phenolic hydroxyl group-containing aromatic polyamide oligomer compound represented by the above formula (3) include the above-mentioned hydroxyl group-containing aromatic compounds. Examples thereof include dicarboxylic acids, and the above-mentioned dicarboxylic acids having no phenolic hydroxyl group may be used in combination. The skeleton of the dicarboxylic acid having no phenolic hydroxyl group except for the carboxyl group corresponds to R in the formula (2).

Specific examples of the diamine component having a diaminodiphenylmethane skeleton having an alkyl group that can be used in obtaining the compound represented by the formula (3) include bis (4-amino-3-methylphenyl) methane and Screw (4
-Amino-3,5-dimethylphenyl) methane, bis (4-amino-3-ethylphenyl) methane, bis (4
-Amino-3,5-diethylphenyl) methane, bis (4-amino-3-propylphenyl) methane, bis (4-amino-3,5-dipropylphenyl) methane,
Bis (4-amino-3-isopropylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane and the like can be mentioned.

The condensation reaction includes triphenyl phosphite, tri-o-tolyl phosphite, tri-m-tolyl phosphite, di-m-tolyl phosphite, tri-p-tolyl phosphite, Di-p-tolyl phosphate, di-o-chlorophenyl phosphite, tri-o-chlorophenyl phosphite, di-phosphite
a phosphite such as p-chlorophenyl and pyridine;
2-picoline, 3-picoline, 4-picoline, 2,4-
It is preferably carried out in the presence of a pyridine derivative such as lutidine, 2,6-lutidine or 3,5-lutidine, and in an amide solvent such as N-methylpyrrolidone or dimethylacetamide.

Further, the above-mentioned polyamide compound containing a (meth) acryloyl group in the molecule can also be used in the present invention.

(A) to (A) contained in the resin composition of the present invention.
The amount of the component (C) is from 5 to 80% in the composition.
% By weight, particularly preferably 10 to 70% by weight.
The component (B) is preferably 3 to 80% by weight, particularly 5 to 70% by weight.
% By weight is preferred. The component (C) is preferably from 1 to 50% by weight, particularly preferably from 5 to 30% by weight.

In the present invention, a photopolymerization initiator (D) may be used. Examples of the photopolymerization initiator (D) include benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; acetophenone, 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone,
Acetophenones such as 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one;
Anthraquinones such as 2-ethylanthraquinone, 2-tert-butyl-anthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; acetophenone Ketals such as dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4,4
Benzophenones such as -bismethylaminobenzophenone; and 2,4,6-trimethylbenzoyldiphenylphosphine 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-dimethylamino It can be used in combination with an accelerator such as a benzoic acid derivative such as benzoic acid isoamyl ester.

The photopolymerization initiator (D) is used in an amount of 0.5 to 20 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the total weight of the components (A), (B) and (C). A ratio of 15 parts by weight is preferable.

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. As the thermosetting component (E) used in the present invention, although not particularly specified, for example, epoxy resin, melamine compound,
Urea compounds, oxazoline compounds, phenol compounds and the like can be mentioned. As the epoxy resin, specifically, bisphenol A type epoxy resin, bisphenol-
Epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, trisphenol methane epoxy resin, brominated epoxy resin, biquinolol epoxy resin, biphenol epoxy resin, etc. Glycidyl ethers of 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,
Alicyclic epoxy resins such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate, diglycidyl tetrahydrophthalate, dimer Glycidyl esters such as acid glycidyl ester; glycidylamines such as tetraglycidyldiaminodiphenylmethane; and heterocyclic epoxy resins such as triglycidyl isocyanurate. Above all, melting point is 50 ℃
The above epoxy resin is preferable because it can form a tack-free photopolymerizable film 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, and resole.

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

Further, in the present invention, the (meth) acrylate oligomer (A), the diluent (B), the polyamide compound (C), the photopolymerization initiator (D) and the thermosetting component (E) Further various additives as needed, for example,
Fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, and clay; and thixotropic agents such as aerosil; phthalocyanine blue;
Coloring agents such as phthalocyanine lines and titanium oxide, silicones, fluorine-based leveling agents and defoamers; polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether are added for the purpose of improving the performance of the composition. You can do it.

The component (E) as described above may be previously mixed with the resin composition, but it is preferable to use the component (E) before mixing it on a printed wiring board. That is,
It is preferable to mix them in a two-part type of a curing agent solution mainly composed of the components (A) and (C), and to mix them before use.

The resin composition of the present invention can be used in a liquid state as an insulating material between layers of an electronic component, or as a solder for printed wiring boards.
It is useful as a resist ink such as a resist. The resin composition of the present invention can be used as a film-shaped photosensitive film. It 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, etc., and 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. Further, the thickness of these polymer films is preferably from 5 to 100 μm, more preferably from 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.

The method for producing the photosensitive resin composition and the photosensitive film of the present invention includes (A) component, (B) component,
Component (C), photopolymerization initiator (D) and thermosetting component (E)
Alternatively, a resin composition can be prepared by dissolving, mixing, and kneading various additives.

Next, the prepared resin composition was uniformly applied on the polymer film of the support film,
The solvent can be removed by heating and / or blowing with hot air to form a dry film. The thickness of the dried film is not particularly limited, and is preferably 10 to 100 μm.
It is more preferable that the thickness be 60 μm.

The photosensitive film of the present invention comprising two layers of the photosensitive layer and the polymer film thus obtained is rolled as it is or by further laminating a protective film on the other surface of the photosensitive layer. It can be wound up and stored.

The photosensitive resin composition and the photosensitive film of the present invention can be used as paints, coating agents, adhesives and other triads as well as the above-mentioned applications.

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 pressure-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 completed in lamination is
It is imagewise exposed to actinic light using a negative or positive film. 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 protection of the photosensitive layer, the polymer film is transparent, and it is preferable to expose the polymer film while leaving the polymer film remaining. As the active light, a known active light source can be used, and examples thereof include light generated from carbon arc, mercury vapor arc, xenon arc, and the like.
Since the sensitivity of the photopolymerization initiator contained in the photosensitive layer is usually maximum in the ultraviolet region, the active light source in this case is preferably one that effectively emits ultraviolet light.

Next, after exposure, if a polymer film is present on the photosensitive layer, it is removed, and then a carboxyl group-containing (meth) acrylate oligomer is obtained as (meth) acrylate oligomer (A). When-is used, an unexposed portion can be removed and developed by a known method such as spraying, rocking immersion and brushing using an aqueous alkali solution. As the base of the alkaline aqueous solution, for example, alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium or sodium or potassium carbonate or bicarbonate, potassium phosphate, sodium phosphate and the like Examples thereof include alkali metal phosphates, alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and among them, an aqueous solution of sodium carbonate is preferable. The pH of the aqueous alkali solution used for development is preferably 9 to 11. The developing temperature can be adjusted according to the developability of the photosensitive layer. Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating the development, and the like can be mixed in the alkaline aqueous solution. Further, if necessary, development can be carried out using only organic solvents.

Further, after the development, ultraviolet irradiation or heating by a high-pressure mercury lamp can be performed for the purpose of improving solder heat resistance, chemical resistance and the like as a cover of the FPC. The irradiation amount of ultraviolet rays is 0.2 to 10 J / cm 2
It is preferable that at the time of this irradiation, 60 to 150
It is preferred to involve heating at ° C. The heating temperature during heating is preferably 100 to 170 ° C.
Either the irradiation of the ultraviolet rays or the heating may be performed first. After the characteristics of the cover-lay are given in this way,
Mounting (soldering) of components such as LSIs, and mounting to devices such as cameras.

[0059]

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 of carboxyl group-containing epoxy (meth) acrylate (A)) Synthesis Example 1 In the above general formula (1), X is -CH2-, M is a hydrogen atom, and the average degree of polymerization n is 6 Bisphenol F which is 0.2
After dissolving 380 parts of an epoxy compound of the type (epoxy equivalent: 950 g / eq, softening point: 85 ° C.) and 925 parts of epichlorohydrin in 462.5 parts of dimethyl sulfoxide, 60.9 parts of 98.5% NaOH (70%) was stirred at 70 ° C. (0.5 mol) was added over 100 minutes. After the addition, the reaction was further performed at 70 ° C. for 3 hours. After the completion of the reaction, 250 parts of water was added and washed. After oil-water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered by distillation under reduced pressure from the oil layer, and then dimethyl sulfoxide was distilled off.
The reaction product containing by-produced salt is treated with methyl isobutyl ketone 75
0 parts, and further add 10 parts of 30% NaOH,
The reaction was performed at 0 ° C. for 1 hour. After the reaction is completed, add 2 parts with 200 parts of water.
Washing was performed once. After oil-water separation, methyl isobutyl ketone was recovered by distillation from the oil layer, and the epoxy equivalent was 310 g / e.
q, an epoxy resin (a) having a softening point of 69 ° C. was obtained. When the obtained epoxy resin (a) was calculated from the epoxy equivalent, about 5 out of 6.2 alcoholic hydroxyl groups in the starting material bisphenol F type epoxy compound were epoxidized. . This epoxy resin (a) 3
Charge 10 parts and 251 parts of carbitol acetate,
The mixture was heated and stirred at 90 ° C. and dissolved. 60 ° C.
And cooled to 60 parts of acrylic acid, dimer acid (acid value (m
gKOH / g) = 196) 97 parts, methylhydroquinone 0.8 parts and triphenylphosphine 2.5 parts were added,
The mixture was heated and dissolved at 80 ° C., and reacted at 98 ° C. for 35 hours to obtain an epoxy acrylate having an acid value of 0.5 mg KOH / g and a solid content of 65%. Then, 718.5 parts of this epoxy acrylate, 100 parts of succinic anhydride,
54 parts of luacetate was charged and reacted at 90 ° C. for 6 hours.
Carboxyl group-containing epoxy acrylate having an acid value of 99 mg KOH / g and a solid content of 65% (A-1)
I got

(Synthesis Example of Polyamide Compound (C) Represented by Formula (2)) Synthesis Example 2 Phenolic hydroxyl group-containing aromatic polyamide-polybutadiene / acrylonitrile block copolymer (hereinafter referred to as BPA)
M, synthesis of phenolic hydroxyl groups contained in the aromatic polyamide portion of 14 mol%) 19.93 g (120 mmol) of isophthalic acid, 3,
30.63 g (153 mmol) of 4'-oxydianiline, 3.64 (20 mmol) of 5-hydroxyisophthalic acid, 3.9 g of lithium chloride, and 12.3 g of calcium chloride.
1 g, 240 ml of N-methyl-2-pyrrolidone,
Pour 54 ml of pyridine into a 1-liter four-necked round-bottomed flask, stir and dissolve, add 74 g of triphenyl phosphite and react at 90 ° C. for 4 hours to obtain a phenolic hydroxyl group-containing aroma. A group III polyamide oligomer was produced. A polybutadiene / acrylonitrile copolymer having carboxyl groups at both ends (Hycar CT
BN, BF Goodrich. The acrylonitrile component contained in the polybutadiene acrylonitrile part is 17
A solution prepared by dissolving 48 g of N-methyl-pyrrolidone in 240 ml is added,
After further reacting for 4 hours, the reaction solution was cooled to room temperature, and the reaction solution was poured into 20 liters of methanol, and the content of the polybutadiene / acrylonitrile copolymer used in the present invention was 5%.
An aromatic polyamide-polybutadiene / acrylonitrile block copolymer containing about 14 mol% of a phenolic hydroxyl group of 0 wt% was deposited. The polymer thus obtained was further purified by washing with methanol and refluxing methanol. The intrinsic viscosity of this polymer was 0.85 dL / g (dimethylacetamide, 30 ° C.). An infrared spectrum of the polymer powder was measured by a diffuse reflection method.
At 856-2975 cm-1, absorption based on the CH bond of the butadiene moiety was observed, and at 2245 cm-1 absorption based on the nitrile group was observed.

Example 1 A photosensitive resin composition containing the materials shown in Table 1 was 25 μm
Was applied evenly on a polyethylene terephthalate film having a thickness of 5 mm and dried to remove the solvent. The thickness of the photosensitive layer after drying was 50 μm. Next, the photosensitive laminate was obtained by laminating a polyethylene film as a protective film on the photosensitive layer.

Table 1 Materials Compounding amount (parts by weight) Carboxyl group-containing epoxy acrylate (A-1) obtained in Synthesis Example 1 115.4 Polyamide compound (BPAM) obtained in Synthesis Example 2 15 KAYARAD DPHA (Japan) A mixture of dipentaerythritol penta and hexaacrylate manufactured by Kayaku Co., Ltd.) 10 Diethylaminobenzophenone 0.1 Benzophenone 5.0 Hexamethoxymelamine 10.0 Victoria Pure-0.2 Methyl ethyl ketone 45 γ-butyrolactone 45

Separately, the copper surface of an FPC substrate (trade name, F30VC125RC11, manufactured by Nikkan Kogyo Co., Ltd.) in which a 35 μm thick copper foil was laminated on a polyimide substrate was polished with an abrasive brush, washed with water, and dried. The photosensitive film was laminated on this substrate (23 ° C.) using a vacuum laminator.

Next, the obtained sample is
Using a one-step tablet and a negative film of a linear line having a line / space of 150 μm / 150 μm, exposure was performed at 200 mJ / cm ² , and then left at room temperature for 30 minutes. Next, spray development was performed at 30 ° C. for 100 seconds using a 1% aqueous solution of sodium carbonate. Here, the number of remaining step tablets is measured, and the results are shown in Table 3.
It was shown to. Next, a heat treatment was performed at 150 ° C. for 45 minutes, and further, ultraviolet irradiation at ³ J / cm ² was performed to obtain a coverlay.

The sample was placed at 180 ° for flexibility evaluation.
And observe the cover layer for cracks and other abnormalities. Then, check the rosin crack MH-820V
(Trade name, manufactured by Tamura Kaken Co., Ltd.), soldered at 260 ° C. for 10 seconds, observed for abnormalities such as blistering as solder heat resistance, and then evaluated for flexibility. For this reason, it was bent at 180 °, and the cover lay was observed for abnormalities such as cracks. Table 3 shows the above evaluation results.

Example 2 and Comparative Examples 1 to 3 Photosensitive films were laminated in the same manner as in Example 1 except that the composition used in Example 1 was changed to the composition shown in Table 2. Processed and evaluated. The results are summarized in Table 3.

Table 2 Materials Example Comparative Example 2 12 Carboxyl group-containing epoxy acrylate (A-1) obtained in Synthesis Example 1 115.4 115.4 115.4 Polyamide compound obtained in Synthesis Example 2 ( BPAM) 15 KAYARAD DPHA 25 Ditrimethylolpropane tetraacrylate 10 25 Diethylaminobenzophenone 0.1 0.1 0.1 Benzophenone 5.0 5.0 5.0 Hexamethoxymelamine 10.0 10.0 10.0 Victoria Pureable-0.2 0.2 0.2 Methyl ethyl ketone 45 45 45 γ-butyrolactone 45 45 45

Table 3 Number of Steps Remaining Solder Heat Resistance Bendability (180 ° C.) (260 ° C., 10 seconds) Before Soldering After Soldering Example 19 Good Good Good 〃 29 Cracking 〃 29 〃 Cracking Cracking

As is evident from Table 3, when the photosensitive resin composition of the present invention is used, it is possible to obtain a good coverlay in both solder heat resistance and bending property (flexibility).

[0071]

The photosensitive resin composition of the present invention has good workability, excellent flexibility and excellent solder heat resistance, and is suitable for solder resists, inks for coverlay, and photosensitive films.

Continuation of the front page F term (reference) 2H025 AA10 AA13 AB11 AB15 AC01 AD01 BC13 BC32 BC42 BC74 BC85 CA00 CB24 CB45 CC03 FA17 5E314 AA27 AA33 AA38 CC01 CC15 GG08 GG26

Claims (6)

[Claims] (1) a (meth) acrylate oligomer (A),
A photosensitive resin composition containing a diluent (B) and a polyamide compound (C). 2. The photosensitive resin composition according to claim 1, wherein the (meth) acrylate oligomer (A) is a carboxyl group-containing (meth) acrylate oligomer. 3. The photosensitive resin composition according to claim 1, wherein the polyamide compound (B) is a phenolic hydroxyl group-containing polyamide compound. 4. The photosensitive resin composition according to claim 1, further comprising a photopolymerization initiator (D). 5. The photosensitive resin composition according to claim 1, further comprising a thermosetting component (E). 6. A photosensitive film obtained by laminating a layer of the photosensitive resin composition according to claim 1 on a support film.