JP2000310853A - Photosensitive resin composition, photosensitive element using same, photosensitive laminated body, production of flexible printed circuit board and production of mounted substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure excellent electric corrosion resistance and flame resistance and to enhance circuit filling property, alkali developability, sensitivity, resolution, resistance to the heat of soldering, solvent resistance, folding endurance and shelf stability by incorporating a binder polymer, a photopolymerizable unsaturated compound having an ethylenically unsaturated group, a photopolytnerization initiator, a specified aromatic phosphoric ester and a tetrazole compound. SOLUTION: The photosensitive resin composition contains (A) a binder polymer, (B) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, (C) a photopolymerization initiator, (D) an aromatic phosphoric ester of the formula and (E) a tetrazole compound. In the formula, R1 is a divalent residue obtained by removing two hydroxyl groups from dihydroxybenzene or a divalent residue obtained by removing two hydroxyl groups from 2,2-di(p-hydroxyphenyD, Z1-Z4 are each halogen, 1-20C alkyl or the like and (m), (n), (p) and (q) are each an integer of 0-5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a photosensitive laminate, a method for producing a flexible printed wiring board, and a method for producing a mounting substrate.

[0002]

2. Description of the Related Art A liquid or film-form photosensitive resin composition has been conventionally used for producing a printed wiring board. These photosensitive resin compositions, for example, resist when etching the copper foil of the copper-clad laminate obtained by laminating the copper foil on the insulating substrate, soldering position limitation and protection of the printed wiring board on which the wiring is formed It is used as a solder resist used for the purpose.

[0003] As a printed wiring board, there is a film-shaped printed wiring board generally called a flexible printed wiring board, which can be folded and incorporated into a small device such as a camera. In order to mount components on this flexible printed wiring board, soldering is required and a solder resist is required. For this purpose, laminate the punched polyimide film with a predetermined mold with an adhesive,
Printing inks composed of heat-resistant materials have been used by printing. The former is called coverlay and the latter is called covercoat. These coverlays and covercoats also serve as a protective film for wiring after soldering, and are difficult in terms of heat resistance during soldering, insulation, flexibility that cracks are not caused by bending when assembled into the board, and safety. Long-term reliability such as flammability, prevention of circuit discoloration under high temperature and high humidity, and retention of insulation are required.

At present, coverlays formed by punching a polyimide film with an adhesive satisfy these characteristics and are used most often. However, die-cutting requires an expensive die, and punching is required. The cost is high because the positioning and bonding of the films are performed manually. In addition, there is a problem that it is difficult to form a fine pattern. To solve these problems, JP-A-7-207211, JP-A-8-134390, and JP-A-9-599.
No. 7 discloses a liquid photosensitive resist, but the liquid photosensitive resist is environmentally harmful due to an organic solvent,
There are problems such as variations in film thickness and insufficient flexibility due to a filler for imparting printability. Also, Japanese Patent Laid-Open No. 5-2
JP-A-54064 and JP-A-7-278492 disclose film-type photosensitive coverlays. In the case of a two-layer photosensitive coverlay in which a photosensitive resist layer is provided on a polyamic acid layer, Low resolution,
Other photosensitive coverlays have problems such as lack of flame retardancy.

[0005]

According to the first aspect of the present invention, the electrolytic corrosion resistance and the flame retardancy are extremely excellent, and the circuit embedding property, alkali developability, sensitivity, resolution, solder heat resistance,
An object of the present invention is to provide a photosensitive resin composition having good solvent resistance, folding resistance and storage stability. The inventions of claims 2 and 3 exhibit the effects of the invention of claim 1 and provide a photosensitive resin composition having extremely excellent solder heat resistance and flame retardancy. The invention according to claim 4 has extremely excellent electric corrosion resistance and flame retardancy, and has excellent circuit embedding properties, alkali developability, sensitivity, resolution, solder heat resistance, solvent resistance, folding resistance, storage stability and workability. It provides a photosensitive element that is good.

[0008] The invention according to claim 5 is excellent in electric corrosion resistance and flame retardancy, and has excellent circuit embedding property, alkali developability, sensitivity, resolution, solder heat resistance, solvent resistance, folding resistance,
An object of the present invention is to provide a photosensitive laminate which has excellent storage stability and workability and is extremely useful for forming a fine pattern of a flexible heat-resistant protective film. The invention according to claim 6 is extremely excellent in electric corrosion resistance and flame retardancy, and has a circuit embedding property, alkali developability, sensitivity, resolution, solder heat resistance, solvent resistance,
An object of the present invention is to provide a method for manufacturing a flexible printed wiring board having a resist pattern which is excellent in bending resistance, storage stability and workability and is extremely useful for forming a fine pattern of a flexible heat-resistant protective film. The invention according to claim 7 has extremely excellent electric corrosion resistance and flame retardancy, and has excellent circuit embedding properties, alkali developability, sensitivity, resolution, solder heat resistance,
The components are mounted on a flexible printed wiring board that has good solvent resistance, folding resistance, storage stability and workability, and a resist pattern that is extremely useful for forming a fine pattern of a flexible heat-resistant protective film. It is intended to provide a method for manufacturing a mounted substrate.

[0007]

The present invention provides (A) a binder polymer, (B) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, (C) a photopolymerization initiator, (D) a compound represented by the following general formula (I): I)

Embedded image (Wherein R ¹ is a divalent residue obtained by removing two hydroxyl groups from dihydroxybenzene or a divalent residue obtained by removing two hydroxyl groups from 2,2-di (p-hydroxyphenyl) propane) Wherein Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, amino Group, nitro group, cyano group, mercapto group, allyl group, alkyl mercapto group having 1 to 10 carbon atoms, hydroxyalkyl group having 1 to 20 carbon atoms, carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, alkyl group Represents an acyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a group containing a heterocyclic ring;
n, p and q are each independently an integer from 0 to 5), and (E) a tetrazole compound.

[0008] The present invention also relates to the photosensitive resin composition, wherein the component (A) is a binder polymer having an amide bond, an oxyalkylene skeleton and a carboxyl group. In addition, the present invention provides a method wherein the component (A) comprises (a) a dicarboxylic acid having an oxyalkylene skeleton, (b) a diisocyanate or a diamine, (c) a compound having two or more epoxy groups in one molecule, and (d) The present invention relates to the photosensitive resin composition, which is a binder polymer obtained by reacting a polycarboxylic acid monoanhydride as a reaction component.

[0009] The present invention also relates to a photosensitive element obtained by applying the above-mentioned photosensitive resin composition on a support and drying it. The present invention also relates to a photosensitive laminate having the photosensitive resin composition layer on a surface of a substrate for a flexible printed wiring board. Further, the present invention provides a flexible printed wiring, comprising irradiating the photosensitive laminate with an actinic ray in an image form, light-curing an exposed portion, and removing an unexposed portion by development to form a resist pattern. The present invention relates to a method for manufacturing a board. Further, the present invention relates to a method for manufacturing a mounting board, wherein components are mounted on a flexible printed wiring board on which a resist pattern is formed by the method for manufacturing a flexible printed wiring board.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Each component contained in the photosensitive resin composition of the present invention will be described in detail. The binder polymer as the component (A) in the present invention is not particularly limited, and examples thereof include an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, and a phenol resin. No. These can be used alone or in combination of two or more. The binder polymer as the component (A) of the present invention includes:
From the viewpoint of heat resistance and the flame retardancy of the resin itself, an amide epoxy resin is preferable, and such a resin is preferably a resin having an amide bond, an oxyalkylene skeleton, and a carboxyl group. As the resin, (a) dicarboxylic acid having an oxyalkylene skeleton, (b) diisocyanate or diamine, (c) 1
The binder polymer is preferably a compound obtained by reacting a compound having two or more epoxy groups in a molecule and (d) a polycarboxylic acid monoanhydride as reaction components.

(A) a dicarboxylic acid having an oxyalkylene skeleton, (b) a diisocyanate or a diamine,
The binder polymer obtained by reacting (c) a compound having two or more epoxy groups in one molecule and (d) a polycarboxylic acid monoanhydride as a reaction component is, for example, (a)
By reacting the component and the component (b), an amide bond is introduced into the binder polymer of the component (A), and the amide oligomer obtained by this reaction is reacted with the component (c). By obtaining a resin having a hydroxyl group generated by the reaction with the group, and reacting the hydroxyl group with the component (d), a carboxyl group can be introduced into the binder polymer of the component (A) to produce the resin.

In the above (a) dicarboxylic acid having an oxyalkylene group, the number of oxyalkylene groups in the dicarboxylic acid may be one or continuous, and in any case, the total molecular weight of the oxyalkylene group portion is as follows: 20
It is preferably from 0 to 10,000, more preferably from 500 to 5,000, and particularly preferably from 1,000 to 3,000. When the molecular weight is less than 200, the alkali developability and bending resistance of the resin obtained as the component (A) tend to decrease, and
If it exceeds 000, the heat resistance of the resin obtained as the component (A) tends to decrease.

The dicarboxylic acid having an oxyalkylene skeleton is not particularly limited. For example, (1) Jeffamine D-2 (trade name, manufactured by Huntsman Corporation)
30, D-400, D-2000, D-4000, ED
-600, ED-900, ED-2001, EDR-1
48, bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropyl) manufactured by Koei Chemical Industry Co., Ltd.
Ethane, 1,3-bis- (3-aminopropyl) -2,
Reaction equivalence ratio of polyoxyalkylenediamine such as 2-dimethylpropane, α, ω- (3-aminopropyl) -polyethylene glycol and a known dicarboxylic acid (carboxyl group of dicarboxylic acid / amino group of polyoxyalkylenediamine) is obtained. Polyoxyalkylene amide dicarboxylic acid obtained by reacting under conditions exceeding 1, (2) polyoxyalkylene diamine and trimellitic anhydride,
Reaction equivalence ratio of cyclic tricarboxylic acid monoanhydride such as tricarballylic anhydride, maleic anhydride ricinoleic acid dehydrated product, maleic anhydride sorbic acid adduct, etc. (tricarboxylic acid monoanhydride anhydride Group / amino group of polyoxyalkylenediamine), and (3) polyoxyalkylenediimide dicarboxylic acid and pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, s -Reaction equivalence ratio of tetracarboxylic dianhydrides such as biphenyltetracarboxylic dianhydride, diphenylsulfonetetracarboxylic dianhydride, methylcyclohexenetetracarboxylic dianhydride, ethylene glycol bisanhydrotromellitate, etc. Amino group of oxyalkylenediamine / tetra The above tricarboxylic acid monoanhydride is reacted with the polyoxyalkylene imide diamine obtained by the reaction under conditions where the carboxylic acid dianhydride of the carboxylic acid exceeds 1 (an acid anhydride group of the tricarboxylic acid monoanhydride). / Amino group of polyoxyalkyleneimidodiamine) and (4) a reaction equivalence ratio of a known polyoxyalkylene diol to a known dicarboxylic acid (dicarboxylic acid) A polyoxyalkylene ester dicarboxylic acid obtained by allowing carboxyl groups / hydroxyl groups of polyoxyalkylene diol to react under a condition of more than 1;
(5) PEO acid # 4 (trade name, manufactured by Kawayan Fine Chemical Co., Ltd.)
And polyoxyethylene diglycolic acid such as 00, # 1000, and # 4000.

Among them, from the viewpoint of hydrophilicity and heat resistance of the binder polymer obtained as the component (A),
(1) polyoxyalkylene amide dicarboxylic acid,
(2) Polyoxyalkylene diimide dicarboxylic acid or (3) polyoxyalkylene polyimide carboxylic acid is preferred. These are used alone or in combination of two or more.

Either diisocyanate or diamine (b) may be used, but diisocyanate is preferred from the viewpoint of ease of production, and aromatic diisocyanate is more preferred from the viewpoint of heat resistance.

The diisocyanate includes, for example,
4,4'-diphenylmethane diisocyanate, 2,6
-Tolylene diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl ether diisocyanate, m-xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, etc. Aromatic diisocyanate compound, hexamethylene diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
Aliphatic diisocyanate compounds such as 2,4,4-trimethylhexamethylene diisocyanate and lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated 4,
4'-diphenylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-
Alicyclic diisocyanate compounds such as xylylene diisocyanate, and heterocyclic diisocyanate compounds such as 3,9-bis (3-isocyanatopropyl) -2,4,8,10-tetraspiro [5,5] undecane; Examples of the diamine include p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, and 3,3. '-Diaminodiphenylmethane, 2,
4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,
3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone,
3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 2,4'-diaminodiphenylsulfone, 2,2'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 3,
4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, 4,4'-benzophenone diamine, 3,3'-
Benzophenone diamine, 2,2'-bis [4- (4-
Aminophenoxy) phenyl] propane, 4,4'-diaminobenzanilide and the like. These are used alone or in combination of two or more.

The compound (c) having two or more epoxy groups in one molecule is not particularly limited.
Bifunctional aromatic glycidyl ether compounds such as bisphenol A epoxy resin, tetrabromobisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, naphthalene epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy Polyfunctional aromatic glycidyl ether compounds such as resin, dicyclopentadiene-phenol type epoxy resin, tetraphenylolethane type epoxy resin, polyethylene glycol type epoxy resin, polypropylene glycol type epoxy resin, neopentyl glycol type epoxy resin, dibromoneopentyl Bifunctional aliphatic glycidyl ether compounds such as glycol epoxy resin and hexanediol epoxy resin, hydrogenated bisphenol A type Bifunctional alicyclic glycidyl ether compounds such as oxy resin, polyfunctional aliphatic glycidyl ether compounds such as trimethylolpropane type epoxy resin, sorbitol type epoxy resin, glycerin type epoxy resin, and bifunctional aromatic such as diglycidyl phthalate ester Glycidyl ester compounds, bifunctional alicyclic glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester,
Bifunctional aromatic glycidylamine compounds such as N, N-diglycidylaniline, N, N-diglycidyltrifluoromethylaniline, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, , 3-bis (N, N-glycidylaminomethyl) cyclohexane, polyfunctional aromatic glycidylamine compounds such as N, N, O-triglycidyl-p-aminophenol, alicyclic diepoxy acetal, alicyclic diepoxy Bifunctional alicyclic epoxy resins such as adipate, alicyclic diepoxycarboxylate, vinylcyclohexene dioxide, bifunctional heterocyclic epoxy resins such as diglycidyl hydantoin, and polyfunctional heterocyclic epoxies such as triglycidyl isoannulate Resin, organopolysiloxane type Such bifunctional or polyfunctional silicon-containing epoxy resins such as carboxymethyl resins. From the viewpoint of controllability of the production reaction, a hydrophilic polyamide resin is preferable, a bifunctional epoxy resin is more preferable, and a bifunctional aromatic glycidyl ether is particularly preferable. Further, from the viewpoint of availability and low cost, bisphenol A type and bisphenol F type epoxy resins are preferable, and bisphenol F type epoxy resin is more preferable from the viewpoint of solubility of the obtained hydrophilic polyamide resin in an alkaline aqueous solution. These are used alone or in combination of two or more.

The polycarboxylic acid monoanhydride (d) is not particularly limited. Examples thereof include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Anhydride, methyl hexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, methyl 2-substituted butenyltetrahydrophthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride Anhydride, maleic anhydride, maleic anhydride adduct of methylcyclopentadiene, alkylated endoalkylenetetrahydrophthalic anhydride, phthalic anhydride, chlorendic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride , Tricarballylic anhydride, maleic anhydride Linoleic acid dehydration product adduct,
Examples thereof include sorbic acid adduct of maleic anhydride and trimellitic anhydride, and tetrahydrophthalic anhydride is preferred from the viewpoint of reactivity, reaction yield, and low cost. These are used alone or in combination of two or more.

The reaction equivalent ratio of (a) a dicarboxylic acid having an oxyalkylene skeleton to (b) a diisocyanate or a diamine (a carboxyl group in (a) / an isocyanate group or an amino group in (b)) is 1.03 to 2. It is preferably 1.05 to 1.7, more preferably 1.1 to 1.7.
1.5 is particularly preferred. When the reaction equivalent ratio is less than 1.03, the resulting amide oligomer is liable to be formed in which both terminals are not carboxyl groups, and the following reaction (c) with a compound having two or more epoxy groups in one molecule is not possible. When the reaction equivalent ratio exceeds 2, the dicarboxylic acid having an oxyalkylene skeleton tends to remain as an unreacted substance, and the heat resistance of the binder polymer obtained as the component (A) decreases. Tend to.

The reaction between the components (a) and (b) can be carried out in an organic solvent. The organic solvent is not particularly limited and includes, for example, lactones such as γ-butyrolactone and γ-caprolactone, carbonates such as ethylene carbonate and propylene carbonate, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ethyl acetate, and acetic acid. Esters such as n-butyl, glymes such as diglyme, triglyme and tetraglyme, hydrocarbons such as toluene, xylene and cyclohexane, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Amides such as formamide, N, N-dimethylethylene urea, N, N-
Dimethylpropylene urea, ureas such as tetramethyl urea, sulfones such as sulfolane, and the like, but from the viewpoint of low-temperature drying properties when the photosensitive resin composition is heated to form a film, lactones are the main components Is preferred. These are used alone or in combination of two or more.

The amount of the organic solvent used is 30 to 30 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b).
It is preferably 2000 parts by weight, more preferably 50 to 1000 parts by weight, and particularly preferably 70 to 400 parts by weight. If the amount of the organic solvent used is less than 30 parts by weight, the solubility is poor, and the reaction system tends to be non-uniform or highly viscous. If the amount of the organic solvent used exceeds 2,000 parts by weight, the reaction hardly proceeds. The reaction tends to be difficult to complete. Also,
The reaction temperature of the reaction between the components (a) and (b) is 100
The temperature is preferably from 300 to 300C, more preferably from 150 to 270C, and particularly preferably from 170 to 250C. If the reaction temperature is lower than 100 ° C., the reaction does not easily proceed and the reaction tends to be difficult to complete. If the reaction temperature exceeds 300 ° C., gelation or the like due to side reactions tends to occur and the reaction tends to be difficult to control.

When the amide oligomer is obtained by reacting the components (a) and (b), a part of the (a) dicarboxylic acid having an oxyalkylene group is replaced with (a ') a dicarboxylic acid containing no oxyalkylene group. It can be replaced by an acid. (A ') The dicarboxylic acid containing no oxyalkylene group is not particularly limited, and known dicarboxylic acids, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, dodecane diacid, eicosan Diacid, dimer acid, alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid,
4,4'-diphenyl ether dicarboxylic acid, 4,4 '
Aromatic dicarboxylic acids such as -diphenylsulfone dicarboxylic acid and 4,4'-benzophenone dicarboxylic acid; and dicarboxylic acids having a polycarbonate bond. The dicarboxylic acid having a polycarbonate diol bond can be synthesized by reacting a polycarbonate diol and a dicarboxylic acid under the condition that the equivalent ratio (carboxyl group of dicarboxylic acid / hydroxyl group of polycarbonate diol) exceeds 1.

When (a ') a dicarboxylic acid containing no oxyalkylene group is used, the amount of the dicarboxylic acid to be used is 5 to 9 with respect to 100 parts by weight of the total of the components (a) and (a').
0 parts by weight is preferable, 10 to 70 parts by weight is more preferable, and 20 to 50 parts by weight is particularly preferable. When the use amount of the component (a ') exceeds 90 parts by weight, the hydrophilicity of the amide oligomer component obtained is reduced, and when the amide oligomer component is used as a binder component of the photosensitive resin composition, the alkali content of the photosensitive resin composition is reduced. Developability tends to decrease, and flex resistance tends to decrease. These are used alone or in combination of two or more.

The amide oligomer obtained by reacting the components (a) and (b) is added to the amide oligomer (2) in one molecule as the component (c).
The reaction equivalent ratio of the compound having a hydroxyl group by reacting at least two epoxy groups (epoxy group equivalent of component (c) / carboxyl group equivalent of amide oligomer) is preferably from 0.5 to 3, preferably from 1.1 to 2. 5 is more preferable, and 1.2 to 2.0 is particularly preferable. If the reaction equivalent ratio is less than 0.5,
It is difficult for the binder polymer obtained as the component (A) to have a high molecular weight, and the heat resistance and the bending resistance tend to decrease. If the reaction equivalent ratio exceeds 3, gelation or the like due to a side reaction is likely to occur, and the reaction tends to be difficult to control. Also, since the bridging density increases, the bending resistance of the binder polymer obtained as the component (A) is increased. There is a tendency for sex to decrease.

The reaction of the amide oligomer and the component (c) in the step of obtaining the resin having a hydroxyl group is carried out in an organic solvent following the step of obtaining the amide oligomer. The organic solvent is not particularly limited, and for example, the organic solvent used in the step of obtaining the amide oligomer can be used as it is. When a lactone is used as a main component in the step of obtaining the amide oligomer, a low boiling N, N-dimethylformamide having a low boiling point can be used from the viewpoints of solubility and low-temperature drying properties of the binder polymer finally obtained as the component (A). It is more preferable to use in combination with amides such as. These are used alone or in combination of two or more. The amount of the organic solvent used is 30 parts by weight based on 100 parts by weight of the total amount of the amide oligomer and the component (c).
-2000 parts by weight are preferred, 50-1000 parts are more preferred, and 70-400 parts by weight are particularly preferred. If the amount of the organic solvent used is less than 30 parts by weight, the solubility is poor, and the reaction system tends to be non-uniform or highly viscous. If the amount of the organic solvent used exceeds 2000 parts by weight, the reaction proceeds. And the reaction tends to be difficult to complete.

The reaction temperature of the reaction between the amide oligomer and the component (c) in the step of obtaining the resin having a hydroxyl group is preferably 50 to 250 ° C., more preferably 100 to 200 ° C., and particularly preferably 120 to 180 ° C. If the reaction temperature is lower than 50 ° C., the reaction does not easily proceed and the reaction tends to be difficult to be completed. In addition, the resin having a hydroxyl group may have an epoxy group at the terminal, in this case, after obtaining the resin having a hydroxyl group, in order to eliminate the epoxy group of the resin having a hydroxyl group, to the resin having the hydroxyl group Preferably, a monocarboxylic acid is reacted.

The monocarboxylic acid is not particularly limited. Examples thereof include aliphatic monocarboxylic acids containing a photopolymerizable unsaturated group such as methacrylic acid and acrylic acid, formic acid, acetic acid, propionic acid, butyric acid and hexanoic acid. Examples thereof include an aromatic monocarboxylic acid such as an aliphatic monocarboxylic acid, benzoic acid, and diphenylacetic acid. Among these, a photopolymerizable unsaturated group-containing aliphatic monocarboxylic acid is preferred from the viewpoint of imparting photocurability to the resin finally obtained as the component (A). These are used alone or in combination of two or more.

When a monocarboxylic acid is reacted with a compound having a hydroxyl group, the reaction equivalent ratio of the compound having a hydroxyl group to the monocarboxylic acid (the equivalent of the carboxyl group of the monocarboxylic acid / the equivalent of the epoxy group in the compound having the hydroxyl group) is 0. .
5 to 5, preferably 0.8 to 2, more preferably 1 to
1.2 is particularly preferred. When the reaction equivalent ratio is less than 0.5, unreacted epoxy groups remain, and the storage stability of the binder polymer (A) tends to decrease. When the reaction equivalent ratio exceeds 5, unreacted monocarboxylic acid A large amount of acid remains and skin irritation tends to increase.

In the step of reacting the polyhydric carboxylic acid monoanhydride, which is the component (d), with the hydroxyl group-containing resin to obtain a hydrophilic polyamide resin, the hydroxyl group-containing resin (d)
The reaction equivalent ratio of the cyclic polycarboxylic acid monoanhydride as the component (acid anhydride group equivalent of the component (d) / hydroxyl equivalent of the compound having a hydroxyl group) is preferably from 0.1 to 1.5, more preferably from 0.3 to 1.5.
To 1, more preferably 0.6 to 0.9. When the reaction equivalent ratio is less than 0.1, the solubility of the obtained hydrophilic polyamide-based resin in an alkaline aqueous solution is poor, and when used as a binder polymer of the photosensitive resin composition, the alkali developability of the photosensitive resin composition is reduced. When the reaction equivalent ratio exceeds 1.5, the polyhydric carboxylic acid monoanhydride as the component (d) tends to remain in a large amount as an unreacted product, and the storage stability of the hydrophilic polyamide-based resin is reduced. Tends to decrease.

The reaction between the resin having a hydroxyl group and the component (d) is carried out in an organic solvent following the step of obtaining the resin having a hydroxyl group. The organic solvent is not particularly limited, and for example, the organic solvent used in the step of obtaining the amide oligomer can be used as it is. In the process of obtaining the resin having a hydroxyl group, when a mixed solvent comprising a lactone and an amide is mainly used, it is not necessary to use an additional organic solvent. These are used alone or in combination of two or more. The amount of the organic solvent used is 30 to 20 parts by weight based on 100 parts by weight of the total of the resin having a hydroxyl group and the component (d).
00 parts by weight is preferable, 50 to 1000 parts by weight is more preferable, and 70 to 400 parts by weight is particularly preferable. If the amount of the organic solvent used is less than 30 parts by weight, the solubility is poor, and the reaction system tends to be non-uniform or highly viscous. If the amount of the organic solvent used exceeds 2000 parts by weight, the reaction proceeds. And the reaction tends to be difficult to complete. The reaction temperature of the reaction between the resin having a hydroxyl group and the component (d) is 40 to 40.
250 ° C. is preferred, 60 to 200 ° C. is more preferred,
80-180 ° C is particularly preferred. The reaction temperature is 40 ° C
When the reaction temperature is less than 250 ° C., the reaction tends to be difficult to proceed and the reaction tends to be difficult to be completed.

After obtaining a hydroxyl-containing resin or a hydrophilic polyamide-based resin, photopolymerization is performed on the hydroxyl-containing resin or the hydrophilic polyamide-based resin for the purpose of imparting photocurability to the hydrophilic polyamide-based resin. The unsaturated monoisocyanate containing an unsaturated monofunctional isocyanate can be reacted, and the one thus obtained can be used as the binder polymer of the component (A). The photopolymerizable unsaturated group-containing aliphatic monoisocyanate is not particularly limited.
-Isocyanate ethyl methacrylate, methacryloyl isocyanate and the like. These can be used alone or in combination of two or more.

When an aliphatic monoisocyanate containing a photopolymerizable unsaturated group is used, a reaction equivalent ratio between a resin having a hydroxyl group or a hydrophilic polyamide resin and a monoisocyanate containing a photopolymerizable unsaturated group (containing a photopolymerizable unsaturated group) The isocyanate group of the aliphatic monoisocyanate / the compound having a hydroxyl group or the hydroxyl group of the polyamide resin) is 0.05 to 1.5.
Is preferable, 0.1-1 are more preferable, and 0.1-0.
4 is particularly preferred. When the reaction equivalent ratio is less than 0.05, photocurability is low, and when used as a binder polymer of the photosensitive resin composition, the sensitivity of the photosensitive resin composition tends to decrease. If it exceeds 0.5, the photopolymerizable unsaturated group-containing aliphatic monoisocyanate tends to remain as an unreacted product, and storage stability tends to decrease.

Each of the above-mentioned reactions may be carried out, if necessary,
A known reaction catalyst suitable for the reaction is used.

The resin having an amide bond, an oxyalkylene skeleton and a carboxyl group, which is a kind of amide epoxy resin as the binder polymer as the component (A) in the present invention obtained as described above, is, for example, a compound represented by the general formula ( II)

Embedded image (Wherein, R ⁴ represents a divalent group remaining after removing two carboxyl groups from a dicarboxylic acid having an oxyalkylene group, R ⁵ represents a diamine residue or a diisocyanate residue, and R ⁶ represents one molecule. A divalent group remaining after removing two epoxy groups from a compound having two or more epoxy groups, R ⁷ represents a hydrogen atom,

Embedded image (R ⁸ represents a residue of a polycarboxylic acid monoanhydride) or

Embedded image (R ⁹ represents an alkylene group having 1 to 6 carbon atoms or a single bond, R ¹⁰ represents a hydrogen atom or a methyl group), and s and t each independently represent an integer of 1 to 100 )
It has a chemical structure represented by

The chemical structure represented by the general formula (II) shows the chemical structure of a portion excluding the terminal of the resin, but considering the terminal, for example, the general formulas (II-1) and (II)
-2) and a chemical structure as represented by the general formula (II-3).

[0036]

Embedded image (Wherein, the definitions of R ⁴ , R ⁵ , R ⁶ , R ⁷ , s and t are the same as in the general formula (II))

The resin represented by the general formula (II-1) has epoxy groups at both ends and has a general formula (II-
The resin represented by 2) has an epoxy group at one terminal and a carboxyl group at the other terminal, and has a general formula (II-
The resin represented by 3) has a carboxyl group at both ends. The epoxy group at the end of these resins is
A part or the whole thereof may be modified by reacting a monocarboxylic acid such as methacrylic acid, acrylic acid, acetic acid, propionic acid or the like. Usually, the resin to be produced is a mixture containing these resins. From the viewpoint of heat resistance and pot life, monocarboxylic acid is added to the resin represented by (II-1) or the epoxy group at the terminal of the resin. The resin modified by the reaction is preferably contained in an amount of 20% by weight or more, and can be produced by adjusting the use ratio of each component used in the production of the resin.

The weight average molecular weight of the component (A) is tack,
From the viewpoints of solder heat resistance, solvent resistance, folding resistance, adhesion, coating workability, etc., it is preferably from 10,000 to 500,000, more preferably from 20,000 to 200,000, It is particularly preferred that it is 30,000 to 100,000. The weight-average molecular weight was measured by gel permeation chromatography, and lithium bromide monohydrate and phosphoric acid were prepared as buffering agents so that the concentrations became 0.03 mol / l and 0.06 mol / l, respectively. It is calculated as a polystyrene equivalent value from a calibration curve prepared using standard polystyrene, using an equal volume mixed solvent eluent of dimethylformamide (DMF) and tetrahydrofuran (THF).

As the photopolymerizable unsaturated compound having an ethylenically unsaturated group as the component (B) in the present invention, known compounds can be used without any particular limitation. For example, α, β- Compounds obtained by reacting unsaturated carboxylic acids, 2,2-bis (4- (acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-
(Methacryloxypolyethoxy) phenyl) propane,
A compound obtained by reacting an α, β-unsaturated carboxylic acid with a glycidyl group-containing compound, a urethane monomer, nonylphenyldioxylene acrylate, nonylphenyldioxylene methacrylate, γ-chloro-β-hydroxypropyl-β′-acryloyloxy Ethyl-o-phthalate, γ-chloro-β-hydroxypropyl-β ′
-Methacryloyloxyethyl-o-phthalate, β-
Hydroxyethyl-β'-acryloyloxyethyl-
o-phthalate, β-hydroxyethyl-β′-methacryloyloxyethyl-o-phthalate, alkyl acrylate, alkyl methacrylate and the like.

Examples of the polyhydric alcohol include polyethylene glycol diacrylate having 2 to 14 ethylene groups, polyethylene glycol dimethacrylate having 2 to 14 ethylene groups, trimethylolpropane diacrylate, and trimethylol. The number of propane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, the number of propylene groups is 2 to 14 Polypropylene glycol diacrylate, polypropylene glycol dimethacrylate having 2 to 14 propylene groups, dipen Erythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexa methacrylate. Examples of the α, β-unsaturated carboxylic acid include acrylic acid and methacrylic acid.

Examples of the 2,2-bis (4- (acryloxypolyethoxy) phenyl) propane include, for example,
2,2-bis (4- (acryloxydiethoxy) phenyl) propane, 2,2-bis (4- (acryloxytriethoxy) phenyl) propane, 2,2-bis (4-
(Acryloxypentaethoxy) phenyl) propane,
2,2-bis (4- (acryloxydecaethoxy) phenyl) and the like. Examples of the 2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane and 2,2-bis (4- ( Methacryloxytriethoxy) phenyl) propane, 2,
2-bis (4- (methacryloxypentaethoxy) phenyl) propane, 2,2-bis (4- (methacryloxydecaethoxy) phenyl) propane, and the like.
2-Bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE-500 (Shin-Nakamura Chemical Co., Ltd.)
It is commercially available as (product name).

Examples of the glycidyl group-containing compound include, for example, trimethylolpropane triglycidyl ether triacrylate, trimethylolpropane triglycidyl ether trimethacrylate, 2,2-bis (4-
Acryloxy-2-hydroxy-propyloxy) phenyl, 2,2-bis (4-methacryloxy-2-hydroxy-propyloxy) phenyl and the like can be used. Examples of the urethane monomer include addition of an acrylic monomer having an OH group at the β-position or a methacrylic monomer corresponding thereto, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Reactant, tris (methacryloxytetraethylene glycol isocyanate hexamethylene isocyanurate, E
O-modified urethane dimethacrylate, EO, PO-modified urethane dimethacrylate and the like. EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. Also, PO
Represents propylene oxide, and the PO-modified compound has a propylene oxide group block structure.

Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. From the standpoint of folding resistance as a flexible printed wiring board, 2,2-bis (4
-(Dimethacryloxypolyethoxy) phenyl) propane is preferred. These compounds can be used alone or in combination of two or more.

Further, as the photopolymerization initiator which is the component (C) in the present invention, for example, benzophenone, N,
N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,
4'-diaminobenzophenone, 4-methoxy-4'-
Aromatic ketones such as dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-ethylanthraquinone, and phenanthrenequinone; benzoin methyl ether;
Benzoin ether compounds such as benzoin ethyl ether and benzoin phenyl ether, methyl benzoin,
Benzoin compounds such as ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, 2,2'-bis (o
-Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer,
-(O-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer,
-(O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,
5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- ( 2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2-
2,4,5-triarylimidazole dimer such as (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-
Acridine derivatives such as bis (9,9'-acridinyl) heptane; N-phenylglycine; These are used alone or in combination of two or more.

In the general formula (I), which is the component (D) in the present invention, R ¹ is a divalent residue obtained by removing two hydroxyl groups from dihydroxybenzene or 2,2-
Di (p-hydroxyphenyl) propane is a divalent residue obtained by removing two hydroxyl groups, and the hydrogen atom of the benzene ring in these residues is a halogen atom, a carbon atom having 1 to 1 carbon atoms.
20 alkyl groups, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 14 carbon atoms, amino groups, nitro groups, cyano groups, mercapto groups, allyl groups, having 1 to 1 carbon atoms
0 alkylmercapto group, hydroxyalkyl group having 1 to 20 carbon atoms, carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, acyl group having 1 to 10 carbon atoms in the alkyl group, alkoxy having 1 to 20 carbon atoms Group or a group containing a heterocycle, a substituent such as an alkoxyalkyl group having 1 to 3 carbon atoms, and 1
May be substituted. When R ¹ is, for example, a divalent residue obtained by removing two hydroxyl groups from an aliphatic dialcohol, hydrolysis resistance is small and electric corrosion resistance is poor. Further, when m, n, p and q in the general formula (I) are each 2 or more, two or more Z ¹ , two or more Z ² , and two or more Z
^Three and two or more Z ⁴ may be the same or different.

The halogen atom of Z ¹ , Z ² , Z ³ and Z ^{4 in} the general formula (I) is, for example, fluorine, chlorine,
Bromine, iodine, astatine and the like can be mentioned. Examples of the alkyl group having 1 to 20 carbon atoms of Z ¹ , Z ² , Z ³ and Z ^{4 in} the general formula (I) include, for example, methyl group, ethyl group, n-
Propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl Octadecyl group, nonadecyl group, icosyl group and the like. Z ¹ , Z ² , Z ³ and Z ^{4 in the} general formula (I)
Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Examples of the aryl group having 6 to 14 carbon atoms of Z ¹ , Z ² , Z ³ and Z ^{4 in} the general formula (I) include, for example,
Phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group and the like, halogen atom, amino group, nitro group, cyano group, mercapto group, allyl group, alkyl having 1 to 20 carbon atoms It may be substituted with a group or the like. Z ¹ in the general formula (I),
Examples of the alkyl mercapto group having 1 to 10 carbon atoms of Z ² , Z ³ and Z ⁴ include a methyl mercapto group, an ethyl mercapto group, and a propyl mercapto group. In formula (I), Z ¹ , Z ² , Z ³ and Z ^{4 each} have 1 to 1 carbon atoms.
Examples of the hydroxyalkyl group of 20 include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxyisopropyl group, a hydroxybutyl group and the like.

In formula (I), examples of the carboxyalkyl group having 1 to 10 carbon atoms in the alkyl groups Z ¹ , Z ² , Z ³ and Z ⁴ include, for example, carboxymethyl group, carboxyethyl group and carboxyethyl group. Examples include a propyl group and a carboxybutyl group. In the general formula (I), Z ¹ , Z ² ,
Examples of the acyl group having 1 to 10 carbon atoms in the alkyl group of Z ³ and Z ⁴ include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a pivaloyl group. . Examples of the alkoxy group having 1 to 20 carbon atoms of Z ¹ , Z ² , Z ³ and Z ^{4 in} the general formula (I) include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. Examples of the group containing a heterocyclic ring of Z ¹ , Z ² , Z ³ and Z ^{4 in} the general formula (I) include a furyl group, a thienyl group, a pyrrolyl group, a thiazolyl group, an indolyl group, a quinolyl group and the like. Can be

From the viewpoint of ease of production, availability, etc.,
General formula (III)

Embedded image (Wherein, R ¹ has the same meaning as R ¹ in formula (I), and R ² and R ³ each independently represent a hydrogen atom or a carbon atom having 1 to 1 carbon atoms.)
And an aromatic phosphate ester represented by the following formula:

R ² and R ³ in the general formula (III) each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, from the viewpoint of availability. A methyl group is preferred. From the viewpoints of flame retardancy, folding resistance, hydrolysis resistance, electrolytic corrosion resistance, etc.,
More preferably, at least one of R ² and R ³ is an alkyl group having 1 to 4 carbon atoms.

The formula (II) used as the component (D)
As the aromatic phosphoric acid ester represented by I), for example, a divalent residue obtained by removing two hydroxyl groups wherein R ¹ is 2,2'-di (p- hydroxyphenyl) propane, R ² Is a methyl group and R ³ is a hydrogen atom,
R ¹ is a divalent residue obtained by removing two hydroxyl groups from 2,2'-di (p- hydroxyphenyl) propane, compound R ² and R ³ are methyl groups, R ¹ is m- A divalent residue obtained by removing two hydroxyl groups from dihydroxybenzene, a compound in which R ² is a methyl group and R ³ is a hydrogen atom, and R ¹ is a compound obtained by removing two hydroxyl groups from m-dihydroxybenzene. Compounds which are divalent residues and in which R ² and R ³ are methyl groups are exemplified. The aromatic phosphate represented by the general formula (III) used as the component (D) is available from Daihachi Chemical Industry Co., Ltd. under the trade names PX200, CR-747 and the like.

In the present invention, a flame retardant other than the aromatic phosphate represented by the general formula (I) used as the component (D), such as FG Hamiha 7000 and FG Hamiha (trade names, manufactured by Teijin Chemicals Ltd.) 7500, FG Hamiha 810
0, FG Hamiha 3600, FG Hamiha 3200, FG Hamiha 3100, FG Hamiha 3000, FG Hamiha 200
A halogen-based flame retardant such as TAIC-6B (trade name, manufactured by Nippon Kasei) may be used in an amount of 50 parts by weight or less based on 100 parts by weight of the component (D). Further, a flame retardant aid such as antimony trioxide, antimony pentoxide, barium borate, and aluminum hydroxide may be added in an amount of 50 parts by weight or less based on 100 parts by weight of the component (D).

The tetrazole compound used as the component (E) in the present invention includes, for example, 1H-tetrazole, 5,5'-bis-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H -5-substituted-1H-tetrazole such as -tetrazole, 5-amino-1H-tetrazole, 5-mercapto-1H-tetrazole, 1-methyl-1H-tetrazole, 1-phenyl-1H-tetrazole, 1-amino-1H-tetrazole , 1-substituted-1H-tetrazole such as 1-mercapto-1H-tetrazole, 1-phenyl-5-methyl-1
H-tetrazole, 1-phenyl-5-amino-1H-
Tetrazole, 1-phenyl-5-mercapto-1H-
Monosubstituted-5-substituted-1H-tetrazole such as tetrazole; From the viewpoint of preventing oxidation of copper, 1H-tetrazole and 5-substituted-1H-tetrazole are more preferable.

The amount of component (A) used is from 20 to 9 parts per 100 parts by weight of the total of components (A) and (B).
It is preferably 5 parts by weight, more preferably 30 to 90 parts by weight, and particularly preferably 40 to 90 parts by weight. When the amount of the component (A) is less than 20 parts by weight, the film forming property of the photosensitive element tends to decrease. When a coverlay is formed by thermocompression bonding on the surface of the wiring board on which the wiring is formed, circuit coverage and solder heat resistance tend to decrease.

The amount of component (B) used is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, based on 100 parts by weight of the total of components (A) and (B). More preferably, it is particularly preferably 10 to 60 parts by weight. When the use amount of the component (B) is less than 5 parts by weight, the sensitivity as the photosensitive resin composition is low, and when the photosensitive element is formed, the coverlay is formed by thermocompression bonding to the surface of the flexible printed wiring board on which the wiring is formed. The circuit coverage tends to decrease, and if it exceeds 80 parts by weight, the photosensitive resin composition layer when formed into a photosensitive element tends to seep out from the side due to the flow, and storage stability tends to decrease.

Component (C) is used in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the total of components (A) and (B).
The amount is preferably 0 parts by weight, more preferably 0.05 to 10 parts by weight. The amount of the component (C) is 0.
If the amount is less than 01 parts by weight, sufficient sensitivity tends to be difficult to obtain,
If the amount exceeds 20 parts by weight, light absorption on the exposed surface of the photosensitive resin composition tends to increase, and the internal light curing tends to be insufficient.

The amount of component (D) used is preferably 1 to 50 parts by weight, and more preferably 5 to 45 parts by weight, based on 100 parts by weight of the total of components (A) and (B). More preferred. If the amount of the component (D) is less than 1 part by weight, sufficient flame retardancy tends to be difficult to obtain, and if it exceeds 50 parts by weight, photocuring tends to be insufficient.

Component (E) is used in an amount of 0.01 to 1 with respect to 100 parts by weight of the total of components (A) and (B).
It is preferably 0 parts by weight, more preferably 0.05 to 5 parts by weight. (E) The amount of the component used is 0.0
When the amount is less than 1 part by weight, the discoloration of the conductor and the moisture resistance and insulation resistance tend to decrease.

Further, polyvinylpyrrolidone may be added to the photosensitive resin composition of the present invention from the viewpoint of tack properties and edge fusion prevention. Examples of the polyvinylpyrrolidone include Polypyrrolidone K-120 (trade name, manufactured by IPS). The weight average molecular weight of polyvinylpyrrolidone is 10,000 to 3,000,000.
It is preferred that The amount of polyvinylpyrrolidone used is preferably 1 to 20 parts by weight based on 100 parts by weight of the total of components (A), (B), (C), (D) and (E). If the amount is less than 10 parts by weight, the effect of reducing tack and edge fusion tends to be small, and if it exceeds 20 parts by weight, heat resistance and substrate embedding properties tend to be reduced.

Further, a plasticizer may be added to the photosensitive resin composition of the present invention. The plasticizer to be used is not particularly limited. For example, p-toluenesulfonic acid amide, toluenesulfone-N-ethylamide, p-toluenesulfone-N-cyclohexylamide, di (2-ethylxyl) phthalate, dibutyl phthalate , Dinonyl phthalate, di (2-ethylxyl) adipate, dibutyl adipate, dibutyl sebacate (2-ethylxyl), dibutyl sebacate, tributyl acetylcitrate, azelaic acid (2-ethylxyl), dibutyl azelate, tributyl phosphate Examples include phenyl, tricresyl phosphate, diethylene glycol monolate, epoxy fatty acid ester, methoxycyclolated methyl stearate, tri (2-ethylxyl) trimellitate, and trialkyl trimellitate. Further, p-toluenesulfonic acid amide is preferred from the viewpoint of the resist shape, the obtained resin, and the compatibility with polyvinylpyrrolidone. The amount of plasticizer used is
The amount is preferably 1 to 20 parts by weight, preferably less than 1 part by weight, based on 100 parts by weight of the total of the components (A), (B), (C), (D) and (E). The effect of imparting properties tends to be small, and if it exceeds 20 parts by weight, the heat resistance tends to decrease.

It is preferable to use a thermal crosslinking agent in combination with the photosensitive resin composition of the present invention from the viewpoint of solvent resistance. Examples of the thermal crosslinking agent include a melamine compound and a block-type polyisocyanate compound. Examples of the melamine compound include hexamethoxymethylmelamine and American Cyanamid.
benzoguanamine, such as Cymel (registered trademark) 1123, 1125, manufactured by Mitsui Toatsu Cymel Co., Ltd., and glycoluril resin Cymel (registered trademark) 1170, 1171;
1172, urea-based resin Beetle (registered trademark) 6
0, 65, 80 and the like. Examples of the block type polyisocyanate compound include Coronates 2513, 2507 and 251 manufactured by Nippon Polyurethane Industry Co., Ltd.
5, 2512, Death Module BL3175, BL4165 manufactured by Sumitomo Bayer Urethane Co., Ltd., and the like. The amount of the thermal cross-linking agent used is the above-mentioned component (A), component (B),
The total amount of the components (C), (D) and (E) is preferably 1 to 30 parts by weight, preferably 1 to 30 parts by weight.
If less than parts by weight, the effect of improving solvent resistance tends to be small,
If it exceeds 30 parts by weight, photocurability and thermal stability tend to decrease.

The photosensitive resin composition of the present invention may contain, if necessary, a dye, a color former, a thermochromic inhibitor, a pigment, a filler, a defoamer, a stabilizer, an adhesion promoter, a leveling agent. , 2 parts by weight of a peeling accelerator, an antioxidant, a fragrance, an imaging agent, etc. based on 100 parts by weight of the total of the components (A), (B), (C), (D) and (E). Parts by weight or less.

Examples of the above dyes include fuchsin, auramine base, chalcosid green S, paramagenta, crystal violet, methyl orange, night blue 2B, Victoria blue, malachite green,
Basic Blue 20, Iozing Green, Night Green B, Trivarosan, New Magenta, Acid Violet RRH, Red Violet 5RS, Ethyl Violet, Methylene Blue, New Methylene Blue GG, Phthalocyanine Green, Diamond Green, Rhodamine B and the like. Examples of the color former include tribromomethylphenyl sulfone, leuco crystal violet, and the like. Examples of the thermal color-developing agent include glycidyl ether compounds such as polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and bisphenol A-PO 2-mol addition diglycidyl ether.

Examples of the pigments include phthalocyanine pigments such as phthalocyanine blue, quinacridone pigments such as indanthrene blue, phthalocyanine green, halogenated phthalocyanine, dioxazine violet, and quinacridone red; pyrrolo-pyrrole pigments; and anthraquinone pigments. , Berylen pigment, carbon, titanium carbon, iron oxide, azo black pigment, titanium white, silica, talc, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, precipitated barium carbonate, barium titanate, etc. Is mentioned. Examples of the filler include silica, calcium carbonate, calcium silicate, magnesium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, clay, barium sulfate, barium titanate, titanium oxide, zinc oxide, magnesium oxide, and silicon oxide. , Aluminum oxide, aluminum hydroxide, mica powder, inorganic fillers such as magnetic iron oxide, carbon black, melamine resin, phenol resin, urea resin, polystyrene resin, urea-formalin resin, styrene-methacrylic acid copolymer, styrene- Organic fillers such as butadiene copolymer and hollow plastic pigment are exemplified.

Examples of the antifoaming agent include a silicon compound, a fluorine compound, a polymer compound and a hydrocarbon compound. Examples of the stabilizer include p
-Hydroxyaromatic compounds such as methoxyphenol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, phenylbenzoquinone, p
-Toluquinone, quinones such as p-xyloquinone, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine, amines such as phenyl-α-naphthylamine, phenothiazine, heterocyclic compounds such as pyridine, nitrobenzene, dinitrobenzene, chloranil,
Arylforce fight, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,
2'-methylenebis (4-methyl-6-tert-butylphenol), cuprous chloride and the like.

Examples of the adhesion-imparting agent include an imidazole compound, a thiazole compound, a triazole compound, and a silane coupling agent. Examples of the leveling agent include a silicon-based compound, a fluorine-based compound, a polymer-based compound, and an acryl copolymer. Examples of the antioxidant include, for example, a salicylic acid-based compound, a benzophenone-based compound, an ultraviolet absorber such as a benzotriazole-based compound, a metal deactivator,
Examples include radical reaction inhibitors such as phenolic compounds and amine compounds, and peroxide decomposers such as sulfur compounds and phosphorus compounds.

The photosensitive resin composition of the present invention can be used as a photosensitive element by coating it on a support film and drying it. As the support, a polymer film, for example, a film made of polyethylene terephthalate, polypropylene, polyethylene or the like is used, and a polyethylene terephthalate film is preferable. Since these polymer films must be removable from the photosensitive resin composition layer later, they must not have been subjected to a surface treatment so as not to be removable or be made of a material. The thickness of these polymer films is usually 5 to 1
It is 00 μm, preferably 10 to 30 μm. One of these polymer films may be laminated on both surfaces of the photosensitive resin composition layer as a support film for the photosensitive resin composition layer, and the other as a protective film for the photosensitive resin composition layer. Further, the protective film of the photosensitive resin composition layer may be subjected to a matting treatment.

The photosensitive resin composition of the present invention may contain, if necessary, methanol, ethanol, n-propanol, i-
Aliphatic alcohols such as propanol, n-butanol, n-pentanol and hexanol, hydrocarbons such as benzyl alcohol and cyclohexane, diacetone alcohol, 3-methoxy-1-butanol, acetone, methyl ethyl ketone, methyl propyl ketone and diethyl Ketone, methyl isobutyl ketone, methyl pentyl ketone,
Methylhexyl ketone, ethyl butyl ketone, dibutyl ketone, cyclopentanone, cyclohexanone, γ-butyrolactone, 3-hydroxy-2-butanone, 4-hydroxy-2-pentanone, 6-hydroxy-2-hexanone, ethylene glycol, diethylene glycol,
Triethylene glycol, tetraethylene glycol,
Propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, methyl cellosolve Ethylene glycol alkyl ethers such as acetate and ethyl cellosolve acetate and their acetates, diethylene glycol monoalkyl ethers and their acetate diethylene glycol dialkyl ethers, triethylene glycol alkyl ethers, propylene glycol alkyl ethers and their acetates, dipropylene Glycol alkyl ethers, carboxylic acid esters such as toluene, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and ethyl butyrate Dissolved in a solvent such as dimethylformamide, dimethylsulfoxide, dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, methyl benzoate, ethyl benzoate, propylene carbonate or a mixture thereof to obtain a solid content of 30 to 60.
It can be applied as a solution of about weight%.

Next, the photosensitive resin composition is uniformly applied on the polymer film as the support film layer, and the solvent is removed by heating or blowing with hot air to form a dry film. The thickness of the dried film is not limited, and is usually 10 to 10
0 μm, preferably 20 to 60 μm.

The photosensitive element of the present invention comprising the two layers of the photosensitive resin composition layer and the polymer film obtained as described above may be used as it is or may be used on the other surface of the photosensitive resin composition layer. The protective film is further laminated, wound up in a roll shape and stored.

In producing a photoresist image using the photosensitive element of the present invention, if the protective film is present, the protective film is removed and the substrate is heated while heating the photosensitive resin composition layer. To form a photosensitive laminate having a photosensitive resin composition layer on the surface. More preferably, the layers are laminated under reduced pressure.
The surface to be laminated is usually a substrate for a flexible printed wiring board on which wiring is formed by etching or the like, but there is no particular limitation. Heating and pressure bonding of the photosensitive resin composition layer are usually performed at 70 to 130 ° C., and pressure bonding pressure of 1 × 10 ⁵ to 1 × 10 ^6.
The reaction is performed under reduced pressure of 4 × 10 ³ Pa or less, but there is no limitation on these conditions. When the photosensitive element of the present invention is used, if the photosensitive resin composition layer is heated as described above, it is not necessary to pre-heat the substrate in advance. In order to further improve the lamination property, a pre-heat treatment of the substrate can be performed.

The photosensitive laminate in which the lamination of the photosensitive resin composition has been completed in this manner is then imagewise exposed to active light using a negative film or a positive film. At this time, if the polymer film present on the photosensitive resin composition layer is transparent, it may be exposed as it is, and if it is opaque, it is necessary to remove it. From the standpoint of protecting the photosensitive resin composition layer, the polymer film is transparent, and it is preferable to expose the polymer film while leaving the polymer film remaining. The active light is a known active light source, for example,
Light generated from a carbon arc, a mercury vapor arc, a xenon arc or the like is used. Since the sensitivity of the photoinitiator contained in the photosensitive resin composition layer is usually maximum in the ultraviolet region, it is preferable that the active light source should emit ultraviolet light effectively.

The layer of the photosensitive resin composition imagewise exposed to active light can be heated after exposure to induce or promote bridging of the exposed portion. Next, after exposure, if a polymer film is present on the photosensitive resin composition layer, it is removed by a known method such as spraying, rocking immersion, brushing, scraping and the like after removing the polymer film. The exposed portion is removed and development is performed. As the developing solution, for example, a known developing solution such as an alkaline aqueous solution and a surfactant aqueous solution is used.

Examples of the base of the alkaline aqueous solution include alkali hydroxides such as hydroxides such as lithium, sodium and potassium, carbonates such as lithium, sodium and potassium or alkali carbonates such as bicarbonate and potassium phosphate. , Alkali metal phosphates such as sodium phosphate,
Alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used. As the alkaline aqueous solution, a dilute solution of 0.1 to 5% by weight of sodium carbonate, a dilute solution of 0.1 to 5% by weight of potassium carbonate, 0.1
A diluted solution of sodium hydroxide of 5 to 5% by weight, a diluted solution of sodium tetraborate of 0.1 to 5% by weight, and the like are preferable. The pH of the alkaline aqueous solution used for development is preferably 9-11.
The temperature is adjusted according to the developability of the photosensitive resin composition layer. For example, a surfactant, an antifoaming agent, a small amount of an organic solvent, and the like may be added to the alkaline aqueous solution.

The surfactant in the surfactant aqueous solution is not particularly limited. For example, an anionic surfactant, a cationic surfactant, a nonionic surfactant (nonionic surfactant) or the like may be used. You can also.

Examples of the anionic surfactant include sodium lauryl alcohol sulfate, sodium oleyl alcohol sulfate, sodium lauryl sulfate, ammonium lauryl sulfate and sodium dodecylbenzenesulfonate. Examples of the cationic surfactant include: For example, stearylamine hydrochloride, lauryltrimethylammonium chloride, alkylbenzenedimethylammonium chloride and the like can be mentioned. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene allyl ether, and polyoxyethylene alkyl allyl. Ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, glycerin Fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkyl amines and the like, in particular, polyoxyethylene allyl ether of a nonionic surfactant, polyoxyethylene alkyl allyl ethers, such as polyoxyethylene derivatives.

The concentration of the surfactant is 0.01 to 1
The content is preferably 5% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 5% by weight.

After development, ultraviolet irradiation or heating by a high-pressure mercury lamp is performed for the purpose of improving solder heat resistance, chemical resistance and the like. The irradiation amount of ultraviolet rays is generally about 0.2 to 10 J / cm ² , and it is more preferable that the irradiation is accompanied by heat of 60 to 150 ° C. The heating is performed at a temperature in the range of 100 to 170 ° C. for about 15 to 90 minutes. Either of the ultraviolet irradiation and the heating may be performed first.

The flexible printed wiring board on which the coverlay has been formed in this manner is then mounted with components such as LSI, diode, transistor, monolithic IC, VLSI, etc. by soldering or the like to form a mounting board.
This is mounted on a small device such as a camera device.

[0080]

The present invention will be described below in detail with reference to examples. “Parts” in the following examples means “parts by weight” unless otherwise specified.

Synthesis Example 1 [Synthesis of dicarboxylic acid having oxyalkylene group] Polyoxypropylene diamine (trade name, manufactured by Heinzmann Corporation) was placed in a flask equipped with a stirrer, thermometer, cooling tube, distilling tube, and nitrogen gas introducing tube. , Jeffamine D-2000, average molecular weight 2000) 2000 parts by weight,
384 parts by weight of trimellitic anhydride was charged, and the temperature was raised to 200 ° C. over 1 hour while distilling off by-produced condensed water with toluene in the course of nitrogen gas aeration.
After keeping the temperature at the same temperature for 2 hours to complete the dehydration imidization reaction, the mixture was cooled to obtain a polyoxyalkylenediamine derivative (polyoxyalkylenediimide dicarboxylic acid).

Synthesis Example 2 [Synthesis of dicarboxylic acid having oxyalkylene group] In a flask equipped with a stirrer, a thermometer, a cooling tube, a distilling tube, and a nitrogen gas introducing tube, poly (oxyethylene oxypropylene) diamine (Heinz) was added. Man Corporation's trade name, Jeffamine ED-2001, average molecular weight 20
2,000 parts by weight and 384 parts by weight of trimellitic anhydride were charged, and heated to 200 ° C. over 1 hour while azeotropically distilling off by-product condensed water with toluene under nitrogen gas aeration. Warmed. After keeping the temperature at the same temperature for 2 hours to complete the dehydration imidization reaction, the mixture was cooled to obtain a polyoxyalkylenediimide dicarboxylic acid.

Synthesis Example 3 [Synthesis of dicarboxylic acid having oxyalkylene group] α, ω- (3-aminopropyl)-was placed in a flask equipped with a stirrer, thermometer, cooling tube, distilling tube and nitrogen gas introducing tube.
Polyethylene glycol (trade name, manufactured by Koei Chemical Industry Co., Ltd.
PEGPA-1000, average molecular weight 1100) 1922
A part by weight and 76 parts by weight of trimellitic anhydride were charged, and the temperature was raised to 200 ° C. over 1 hour while distilling off by-produced condensed water with toluene in the middle under nitrogen gas aeration. After keeping the temperature at the same temperature for 3 hours to complete the dehydration imidization reaction, the mixture was cooled to obtain a polyoxyalkylenediimide dicarboxylic acid.

Synthesis Example 4 [Synthesis of Component (A)] In a flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas inlet pipe, 643 parts by weight of the polyoxyalkylenediimide dicarboxylic acid obtained in Synthesis Example 1 was added.
Adipic acid 49 parts by weight, sebacic acid 68 parts by weight, isophthalic acid 55 parts by weight, terephthalic acid 55 parts by weight, dimer acid 2 parts by weight, 4,4'-diphenylmethane diisocyanate 63 parts by weight, tolylene diisocyanate (2,4-
176 parts by weight of isomer / 2,6-isomer = 80/20 mol%) and 1200 parts by weight of γ-butyrolactone were charged,
The temperature was raised to 200 ° C. over 1.5 hours under a nitrogen gas flow while exhausting the carbon dioxide gas that was being replicated out of the system.
After keeping the temperature at the same temperature for 3 hours to complete the decarboxylation amidation reaction, the mixture was cooled to 130 ° C. to obtain a solution of the amide oligomer.

Next, 298 parts by weight of Epomic R140P (trade name, bisphenol A type epoxy resin, manufactured by Mitsui Petrochemical Industry Co., Ltd.) and N, N-dimethylformamide 4
Then, the mixture was kept at the same temperature for 1.5 hours to complete the hydroxyethyl esterification reaction.
Then, a solution of a resin having a hydroxyl group was obtained. Next, the nitrogen gas ventilation was switched to dry air ventilation,
58 parts by weight of methacrylic acid, 6 parts by weight of methquinone and 20 parts by weight of N, N-dimethylbenzylamine were added to a solution of a resin having a hydroxyl group kept at 115 ° C. and kept at the same temperature for 1.5 hours. To complete the epoxy group capping reaction. Subsequently, 217 parts by weight of tetrahydrophthalic anhydride was added while maintaining the temperature at 115 ° C, and the temperature was maintained at the same temperature for 2 hours to complete the half-esterification reaction.
After cooling to 70 ° C., 25 parts by weight of 2-isocyanateethyl methacrylate was further added, and the mixture was kept at the same temperature for 1.5 hours to complete the photopolymerizable unsaturated group introduction reaction. A hydrophilic polyamide-based resin (hereinafter referred to as A-1) having an acid value of 50 KOHmg / g in solid content was obtained.

Synthesis Example 5 Synthesis of Component (A) In Synthesis Example 4, the dicarboxylic acid having an oxyalkylene group obtained in Synthesis Example 1 was synthesized.
Was replaced with the dicarboxylic acid having an oxyalkylene group obtained in the above, and 298 parts by weight of Epomic R140P was added to 17
217 parts of tetrahydrophthalic anhydride instead of 9 parts by weight.
A hydrophilic polyamide resin having a solid content acid value of 36 KOHmg / g (hereinafter, referred to as “Synthesis Example 4”) was prepared in the same manner as in Synthesis Example 4 except that the weight was changed to 130 parts by weight and 25 parts by weight of 2-isocyanateethyl methacrylate was changed to 15 parts by weight. A-2).

Synthesis Example 6 [Synthesis of Component (A)] 296 parts by weight of the hydrophilic dicarboxylic acid having an oxyalkylene group obtained in Synthesis Example 3 in a flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas inlet pipe. , Adipic acid 14 parts by weight, sebacic acid 19 parts by weight, isophthalic acid 15 parts by weight, dimer acid 1.1 parts by weight, 4,
20 parts by weight of 4'-diphenylmethane diisocyanate,
Tolylene diisocyanate (2,4-isomer / 2,6-
55 parts by weight of isomer = 80/20 mol%) and 489 parts by weight of γ-butyrolactone were charged, and while carbon dioxide gas produced as a by-product was exhausted to the outside of the system under nitrogen gas aeration, 1.
The temperature was raised to 200 ° C. over 5 hours. After keeping the temperature at the same temperature for 3 hours to complete the decarboxylation amidation reaction, the solution was cooled to 130 ° C. to obtain a solution of the amide oligomer.

Next, 2 parts by weight of EPOMIC R301 (trade name of bisphenol A type epoxy resin manufactured by Mitsui Petrochemical Industries, Ltd.) and Epototh YDF-2001 (Toto Kasei) were added to a solution of the polyamide intermediate kept at 130 ° C.
280 parts by weight (trade name, manufactured by Co., Ltd., bisphenol F type resin) and 773 parts by weight of N, N-dimethylformamide were added, and the mixture was kept at the same temperature for 2.5 hours to complete the hydroxyethyl esterification reaction. The solution was cooled to 115 ° C. to obtain a solution of a resin having a hydroxyl group. Next, nitrogen gas ventilation was switched to dry air ventilation, and 13 parts by weight of methacrylic acid, 0.09 part by weight of methquinone and N, N were added to a solution of a hydroxyl group-containing resin kept at 115 ° C.
9 parts by weight of dimethylbenzylamine were added, and the mixture was kept at the same temperature for 3 hours to complete the epoxy group-capping reaction. Subsequently, while keeping the temperature at 115 ° C., tetrahydrophthalic anhydride 18
3 parts by weight were added, and the mixture was kept at the same temperature for 1 hour to complete the half-esterification reaction, thereby obtaining a hydrophilic polyamide-based resin having an acid value of 77 KOH mg / g (hereinafter referred to as A-3).

Examples 1 to 5 and Comparative Examples 1 and 2 The respective materials shown in Table 1 were mixed to prepare a solution of the photosensitive resin composition.

[0090]

[Table 1]

The materials used in the examples and comparative examples are shown below. * 1: A urethane acrylate compound synthesized by reacting 2 mol of trimethylhexamethylene diisocyanate with 1 mol of cyclohexanedimethanol and further reacting with 2 mol of 2-hydroxyethyl methacrylate. * 2: In the general formula (III), R ¹ is 2,2-di (p
-Hydroxyphenyl) propane is a divalent residue obtained by removing two hydroxyl groups, R ² is a methyl group, and R ³ is a hydrogen atom. * 3: In the above formula (III) , R ¹ is a divalent residue obtained by removing two hydroxyl groups from m-dihydroxybenzene, and R ² and R ³ are methyl groups * 4:

Embedded image

The obtained solution of the photosensitive resin composition was added to 20 μm.
m on a polyethylene terephthalate film with a thickness of 80 m and a hot air convection dryer at 80-110 ° C for about 1 hour.
After drying for 0 minutes, the solvent was removed. The dried film thickness of the photosensitive resin composition layer was 50 μm. On the photosensitive resin composition layer, a polyethylene film having a thickness of 25 μm was further adhered as a protective film to obtain a photosensitive element of the present invention.

The obtained photosensitive element has a circuit embedding property, solder heat resistance after resist formation, folding resistance, flame retardancy,
Storage stability and electric corrosion resistance The evaluation was performed by the following methods, and the results are shown in Table 2.

(1) Circuit embedding property A copper foil of a flexible printed wiring board substrate (trade name: F30VC125RC11, manufactured by Nickan Industry Co., Ltd.) in which a 35 μm thick copper foil is laminated on a polyimide base material is etched according to a conventional method. Space (μm) = 165/16
5, 318/318, 636/636, using a continuous vacuum laminator (trade name: VLM-1 type, manufactured by Hitachi Chemical Co., Ltd.) on a flexible printed wiring board on which three test pattern copper circuits were formed. Shoe temperature 120 ° C,
The photosensitive element was laminated at a laminating speed of 0.5 m / s, a pressure of 4000 Pa or less, and a pressure of 3.0 × 10 ⁵ Pa while peeling off the polyethylene film.

Subsequently, the three test pattern portions are visually observed with a stereoscopic microscope to check for the presence of bubbles or the like around the copper circuit. The three test pattern portions are cut out, and the copper circuit section is observed by epoxy casting. A sample was prepared, and the follow-up situation of the coverlay around the copper circuit was checked with an electron microscope to determine the circuit embedding property. The evaluation criteria are as follows. Good: No residual bubbles and no gap around the copper circuit. Bad: Residual bubbles or a gap around the copper circuit.

(2) Photosensitive Characteristics (Alkali Developability, Sensitivity and Resolution) Copper surface of a flexible printed wiring board substrate (F30VC125RC11, manufactured by Nickan Industry Co., Ltd.) in which a 35 μm thick copper foil is laminated on a polyimide substrate. Was polished with an abrasive brush, washed with water and dried. A continuous vacuum laminator (Hitachi Chemical Industry)
(VLM-1 type, manufactured by Co., Ltd.), a heat shoe temperature of 120 ° C., a laminating speed of 0.5 m / min, and a pressure of 4.
The photosensitive elements were laminated at a pressure of 0 × 10 ³ Pa or less and a pressure of 3.0 × 10 ⁵ Pa while peeling off the polyethylene film.

Next, Kodak Step Tablet No. 2 (manufactured by Eastman Kodak Co., Ltd., 21-step step tablet) was brought into close contact with the polyethylene terephthalate film of the obtained sample, and HMW manufactured by Oak Manufacturing Co., Ltd.
A predetermined amount of light was exposed using a -201GX type exposure machine, and a 1% by weight aqueous solution of sodium carbonate was sprayed as a developing solution at 30 ° C. for 120 seconds, and the exposure required to obtain eight step tablets was determined as the sensitivity. .

Further, a photo tool (Kodak Step Tablet No. 2 and line / space (μm) = 30/3)
A photo tool having a negative pattern of 0 to 250/250 (resolution) and line / space (μm) = 30/400 to 250/400 (adhesion)) is adhered onto the polyethylene terephthalate film of the obtained sample. Then, exposure was carried out at an exposure amount capable of obtaining eight steps of step tablets, and the smallest resolution at which a rectangular resist shape was obtained when developed and the value of the line / space of the adhesive pattern were taken as the resolution.

(3) Solder heat resistance In the same manner as in the above (2), a test negative mask was brought into close contact with a sample of polyethylene terephthalate film obtained by laminating a photosensitive element on a substrate for a flexible printed wiring board. Was exposed at a selected exposure amount, and allowed to stand at room temperature for 1 hour. Thereafter, the polyethylene terephthalate film was peeled off, spray-developed with the same developer and developing conditions as in (2), and dried at 80 ° C. for 10 minutes. Then, ultraviolet irradiation of 1 J / cm ² was performed using an ultraviolet irradiation apparatus manufactured by Oak Manufacturing Co., Ltd., and a heating treatment was further performed at 150 ° C. for 60 minutes to obtain a flexible printed wiring board on which a coverlay was formed. Next, after applying a rosin-based flux MH-820V (manufactured by Tamura Kaken Co., Ltd.), it was immersed in a 260 ° C. solder bath for 30 seconds to perform a soldering process. After such an operation, the occurrence of cracks in the coverlay, and the situation of lifting and peeling of the coverlay from the substrate were visually evaluated according to the following criteria. Good: No crack, floating or peeling occurred. Bad: Crack, floating or peeling occurred.

(4) Solvent resistance The flexible printed wiring board on which the coverlay was formed by the same operation as in (3) above was immersed in methyl ethyl ketone and isopropyl alcohol for 15 minutes at room temperature, and then the coverlay was lifted from the substrate. The state of peeling was visually evaluated according to the following criteria. Good: No lifting or peeling occurred. Bad: Floating or peeling occurred.

(5) Folding Resistance A coverlay was formed on the substrate for a flexible printed wiring board obtained by the same operation as in (3), and the sample subjected to the soldering treatment was bent 180 ° by bending and bending. The state of occurrence of cracks in the cover lay at that time was visually evaluated according to the following criteria. Good: No cracks occurred. Bad: Cracks occurred.

(6) Flame Retardant Flexible Printed Wiring Board (Nikkan Industry Co., Ltd.)
Vacuum laminator (trade name: VLM-1 manufactured by Hitachi Chemical Co., Ltd.) on a polyimide substrate with an adhesive obtained by etching a copper foil (trade name: F30VC125RC11 manufactured by Hitachi Chemical Co., Ltd.)
The photosensitive element at a heat shoe temperature of 120 ° C., a laminating speed of 0.5 m / min, an air pressure of 4.0 × 10 ³ Pa or less, and a pressure of 3.0 × 10 ⁵ Pa while peeling off the polyethylene film. The layers were laminated and exposed so as to obtain eight steps of step tablets. After leaving at room temperature for 1 hour, the polyethylene terephthalate film of the sample was peeled off, spray-developed with the same developing solution and developing conditions as in (2), and dried at 80 ° C. for 10 minutes. Next, ultraviolet ray irradiation of 1 J / cm ² was performed using an ultraviolet ray irradiator manufactured by Oak Manufacturing Co., Ltd., and heat treatment was performed at 150 ° C. for 60 minutes to obtain a sample plate on which a coverlay was formed. The flame retardancy of the obtained sample plate was evaluated according to UL94 standard.

(7) Storage stability A 90 m-long photosensitive element wound in a roll is stored at a temperature of 23 ° C. and a humidity of 60%, and the appearance of exudation of the photosensitive layer from the side of the roll is observed for 6 months. It was visually evaluated according to the following criteria over the interval. Good: No exudation of the photosensitive layer even after 6 months. Bad: Excess of exudation of the photosensitive layer within 6 months.

(8) Corrosion resistance The copper foil of a flexible printed wiring board substrate (trade name: F30VC125RC11, manufactured by Nickan Kogyo Co., Ltd.) obtained by laminating a 35 μm thick copper foil on a polyimide substrate was etched in a conventional manner to obtain a line / space. (Μm) = 165/16
5, 318/318, 636/636 Three test pattern IPC multi-purpose test pattern (I
A flexible printed wiring board on which PC-B-25) is formed is prepared. Polish the copper surface with an abrasive brush, wash with water,
Dried. A continuous vacuum laminator (manufactured by Hitachi Chemical Co., Ltd., trade name V
LM-1 type), the photosensitive element was formed of a polyethylene film at a heat shoe temperature of 120 ° C., a laminating speed of 0.5 m / min, an air pressure of 4.0 × 10 ³ Pa or less, and a pressure of 3.0 × 10 ⁵ Pa. Were peeled off and laminated.

A test negative mask was brought into close contact with the polyethylene terephthalate film of the sample in which the photosensitive element was laminated on the substrate for the flexible printed wiring board, and the exposure was performed with an exposure amount capable of obtaining eight step tablets. After leaving at room temperature for 1 hour, the polyethylene terephthalate film of the sample was peeled off, spray-developed with the same developing solution and developing conditions as in (2), and dried at 80 ° C. for 10 minutes. Subsequently, ultraviolet irradiation of 1 J / cm ² was performed using an ultraviolet irradiation apparatus manufactured by Oak Manufacturing Co., Ltd.
Heat treatment was performed for 0 minutes to obtain a flexible printed wiring board on which a coverlay was formed. Solder wires to the flexible printed wiring board with this coverlay,
A voltage of 100 V was applied under the conditions of 85 ° C. and 85% RH. After a lapse of 500 hours, the sample was taken out, the appearance of the substrate and the dentite were visually observed and observed with a microscope of about 100 times, and the electrical resistance was evaluated by measuring the insulation resistance value.

[0106]

[Table 2]

[0107]

According to the present invention, the photosensitive resin composition according to the present invention has extremely excellent corrosion resistance and flame retardancy, and has good circuit embedding properties.
It has good alkali developability, sensitivity, resolution, solder heat resistance, solvent resistance, folding resistance and storage stability, and is extremely suitable for use as a liquid resist and photosensitive element. The photosensitive resin compositions according to claims 2 and 3 exhibit the effects of the invention according to claim 1, exhibit extremely excellent solder heat resistance and flame retardancy, and are extremely suitable for use as liquid resists and photosensitive elements. It is. The photosensitive element according to claim 4 is extremely excellent in corrosion resistance and flame retardancy, and has good circuit embedding, alkali developability, sensitivity, resolution, solder heat resistance, solvent resistance, folding resistance, storage stability and workability. Since it has good flexibility, it is extremely useful for forming a fine pattern of a flexible heat-resistant protective film.

The photosensitive laminate according to the fifth aspect is extremely excellent in electric corrosion resistance and flame retardancy, and is also excellent in circuit embedding, alkali developability, sensitivity, resolution, solder heat resistance, solvent resistance, folding resistance, and storage. Since it has good stability and workability, it is extremely useful for forming a fine pattern of a flexible heat-resistant protective film. The method for producing a flexible printed wiring board according to claim 6 is extremely useful for forming a fine pattern of a flexible heat-resistant protective film, is extremely excellent in electrolytic corrosion resistance and flame retardancy, and has circuit embedding properties, alkali developability, and sensitivity. This is a method for producing a flexible printed wiring board on which a resist pattern having good resolution, solder heat resistance, solvent resistance, folding resistance, storage stability and workability is formed. The method for manufacturing a mounting board according to claim 7 is extremely useful for forming a fine pattern of a flexible heat-resistant protective film, and has extremely excellent electrolytic corrosion resistance and flame retardancy;
And circuit embedding, alkali developability, sensitivity, resolution,
A method for manufacturing a mounting substrate, comprising mounting components on a flexible printed wiring board on which a resist pattern having good solder heat resistance, solvent resistance, folding resistance, storage stability and workability is excellent. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/28 H05K 3/28 DF term (Reference) 2H025 AA01 AA02 AA04 AA10 AA13 AA20 AB11 AB15 AC01 AD01 BC13 BC31 CB23 CB41 CB42 CB43 CC05 CC06 CC20 DA19 FA17 FA39 4J011 QA13 QA14 QA22 QA23 QA24 QA33 QA35 QB19 QB23 QB24 RA06 RA08 RA10 RA11 RA12 SA21 SA31 TA02 TA08 TA10 UA01 VA01 WA01 5E314 AA27 FF16 AB13 GG15 CB15

Claims (7)

[Claims] 1. A binder polymer, (B) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, (C)
Photopolymerization initiator (D) The following general formula (I) (Wherein R ¹ is a divalent residue obtained by removing two hydroxyl groups from dihydroxybenzene or a divalent residue obtained by removing two hydroxyl groups from 2,2-di (p-hydroxyphenyl) propane) Wherein Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, amino Group, nitro group, cyano group, mercapto group, allyl group, alkyl mercapto group having 1 to 10 carbon atoms, hydroxyalkyl group having 1 to 20 carbon atoms, carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, alkyl group Represents an acyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a group containing a heterocyclic ring;
n, p and q are each independently an integer of 0 to 5), and (E) a tetrazole compound. 2. The photosensitive resin composition according to claim 1, wherein the component (A) is a binder polymer having an amide bond, an oxyalkylene skeleton and a carboxyl group. 3. Component (A) is: (a) a dicarboxylic acid having an oxyalkylene skeleton, (b) a diisocyanate or a diamine, (c) a compound having two or more epoxy groups in one molecule, and (d) a polyisocyanate. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a binder polymer obtained by reacting a monocarboxylic acid monoanhydride as a reaction component. 4. A photosensitive element obtained by applying and drying the photosensitive resin composition according to claim 1, 2 or 3 on a support. 5. A photosensitive laminate having the photosensitive resin composition layer according to claim 1, on a surface of a substrate for a flexible printed wiring board. 6. A resist pattern is formed by irradiating the photosensitive laminate according to claim 5 with actinic rays in an image form, light-curing an exposed portion, and removing an unexposed portion by development. Manufacturing method for flexible printed wiring boards. 7. A method of manufacturing a flexible printed wiring board according to claim 6, wherein components are mounted on the flexible printed wiring board on which the resist pattern is formed.