JP2001042526A - Photosensitive resin composition and production of photosensitive element, photosensitive laminated body and flexible printed circuit board using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition excellent in flame retardance, flexibility, soldering heat resistance, solvent resistance and washing resistance, having good sensitivity and resolution and capable of easily forming a fine pattern of a flexible hear resistance protective film and to produce a photosensitive element, a photosensitive laminated body and a flexible printed circuit board. SOLUTION: A photosensitive resin composition containing (a) a binder polymer containing tribromopheyl (meth)acrylate as a copolymerizable component, (b) a bisphenol A type (meth)acrylate compound, (c) a photopolymerization initiator, (d) an amino resin and (e) an aromatic phosphoric ester compound is applied on a support and dried to form the objective photosensitive element. A layer of the photosensitive resin composition is disposed on the surface of a substrate for a flexible printed circuit board to obtain the objective photosensitive laminated body. This photosensitive laminated body is imagewise irradiated with active light, the exposed part is photo-cured and the unexposed part is removed by development to form a resist pattern.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a photosensitive laminate, and a method for producing a flexible printed wiring board.

[0002]

2. Description of the Related Art In the manufacture of printed wiring boards, liquid or film-shaped photosensitive resin compositions have been conventionally used. For example, an etching resist used for etching the copper foil of a copper-clad laminate obtained by laminating a copper foil on an insulating substrate, and a solder resist used for limiting and protecting the soldering position of a printed wiring board on which wiring is formed. And the like.

[0003] A printed wiring board can be folded and incorporated into a small device such as a camera. There is a film-shaped printed wiring board generally called a flexible printed wiring board. Components are mounted on the flexible printed wiring board by soldering and protected by a solder resist. For this purpose, a polyimide film with an adhesive stamped into a predetermined mold has been laminated or printed with a printing ink composed of a heat-resistant material. The former is called coverlay and the latter is called covercoat.

[0004] The coverlay and the cover coat also serve as a protective film for wiring after soldering, and have solder heat resistance at the time of component mounting, cleaning liquid resistance after soldering, insulation, and cracking at the time of board assembly. It is necessary to have flexibility that does not enter. At present, coverlays formed by stamping a polyimide film with an adhesive satisfy these characteristics and are used most often.However, expensive molds are required for stamping, and the stamped film is manually positioned. There is a problem that the cost is high due to the bonding and bonding, and that it is difficult to form a fine pattern.

To solve these problems, Japanese Patent Application Laid-Open No. 7-2
No. 07221, JP-A-8-134390, JP-A-9-5997, etc., a liquid photosensitive resist has been proposed. However, the liquid photosensitive resist is environmentally contaminated by an organic solvent, a variation in film thickness, There are problems such as insufficient flexibility due to the filler for imparting printability. Also, Japanese Patent Application Laid-Open Nos. H5-254064 and H7-278
No. 492, etc., a film-type photosensitive coverlay has also been proposed. However, in the case of a two-layer photosensitive coverlay in which a photosensitive resist layer is provided on a polyamic acid layer, there are problems such as low resolution. is there.

[0006]

The invention according to claim 1 is excellent in flame retardancy, flexibility, solder heat resistance, solvent resistance and washing resistance, and has good sensitivity and resolution. An object of the present invention is to provide a photosensitive resin composition capable of easily forming a fine pattern of a heat-resistant protective coating. The invention according to claim 2 provides a photosensitive resin composition that exhibits the effects of the invention according to claim 1, has excellent flame retardancy, and can easily form a fine pattern of a flexible heat-resistant protective film. is there.
The invention according to claim 3 provides the photosensitive resin composition which exhibits the effects of the invention according to claim 1 or 2, furthermore has excellent flame retardancy, and can easily form a fine pattern of a flexible heat-resistant protective film. Things.

The invention described in claim 4 has the effects of the invention described in claim 1, 2 or 3, and has excellent flame retardancy, sensitivity and resolution, and can easily form a fine pattern of a flexible heat-resistant protective film. The present invention provides a photosensitive resin composition that can be used. The invention according to claim 5 has the effect of the invention according to claims 1, 2, 3 or 4, and furthermore has excellent flame retardancy and is capable of easily forming a fine pattern of a flexible heat-resistant protective film. It provides things. The invention according to claim 6 has the effects of the invention according to claim 1, 2, 3, 4 or 5, and furthermore has excellent flexibility and can easily form a fine pattern of a flexible heat-resistant protective film. The present invention provides a resin composition.

[0008] The invention of claim 7 provides the photosensitive resin composition which exhibits the effects of the invention of claim 6 and has excellent sensitivity and can easily form a fine pattern of a flexible heat-resistant protective film. It is. The invention according to claim 8 has the effects of the invention according to claim 1, 2, 3, 4, 5, 6, or 7, furthermore, has excellent flame retardancy and facilitates formation of a fine pattern of a flexible heat-resistant protective film. The present invention provides a photosensitive resin composition that can be formed. The ninth aspect of the present invention provides the first and second aspects.
The present invention provides a photosensitive resin composition exhibiting the effects of the invention described in 3, 4, 5, 6, 7, or 8, and further having excellent flame retardancy and capable of easily forming a fine pattern of a flexible heat-resistant protective film. is there.

The invention of claim 10 provides the photosensitive resin composition which has the effects of the invention of claim 9 and has excellent flame retardancy and can easily form a fine pattern of a flexible heat-resistant protective film. Is what you do. The invention according to claim 11 is the invention according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 1.
The present invention provides a photosensitive resin composition which exhibits the effects of the invention described in Item 0, has excellent flexibility, and can easily form a fine pattern of a flexible heat-resistant protective film.

The twelfth aspect of the present invention is excellent in flame retardancy, flexibility, solder heat resistance, solvent resistance, washing resistance, productivity and workability, and good sensitivity and resolution. An object of the present invention is to provide a photosensitive element capable of easily forming a fine pattern of a heat-resistant protective coating. The invention according to claim 13 is flame retardant, flexible, solder heat resistant, solvent resistant,
An object of the present invention is to provide a photosensitive laminate having excellent washing resistance, productivity and workability, excellent sensitivity and resolution, and capable of easily forming a fine pattern of a flexible heat-resistant protective film. The invention according to claim 14 is excellent in flame resistance, flexibility, solder heat resistance, solvent resistance, washing resistance, productivity and workability, and has good sensitivity and resolution, and flexible heat resistance protection. An object of the present invention is to provide a method of manufacturing a flexible printed wiring board on which a resist pattern extremely useful for forming a fine pattern of a film is formed.

[0011]

The present invention comprises (a) a binder polymer having tribromophenyl (meth) acrylate as a copolymer component, (b) a bisphenol A (meth) acrylate compound, and (c) photopolymerization initiation. Agent, (d)
The present invention relates to a photosensitive resin composition containing an amino resin and (e) an aromatic phosphate compound. The present invention also relates to the photosensitive resin composition, wherein (a) the binder polymer is a binder polymer containing tribromophenyl (meth) acrylate, (meth) acrylic acid and another vinyl monomer as a copolymer component.

The present invention also relates to the above photosensitive resin composition, wherein (a) the binder polymer is a binder polymer containing 3 to 65% by weight of tribromophenyl (meth) acrylate based on the total amount of all copolymerized components. About things.
In the present invention, (a) the binder polymer is soluble or swellable in an alkaline aqueous solution, and has an acid value of 65 to 30.
The present invention relates to the photosensitive resin composition, which is a binder polymer of 0 mgKOH / g. In addition, the present invention relates to (a) a binder polymer having a weight average molecular weight of 20,000 to 300,000.
0 relates to the photosensitive resin composition.

The present invention also relates to (b) bisphenol A
The system (meth) acrylate compound has the general formula (1)

Embedded image (Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, Y ¹ and Y ² each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are such that p + q is 4 to 40) Which is a positive integer selected so as to obtain the above photosensitive resin composition. Further, the present invention relates to the photosensitive resin composition, wherein p + q is 4 to 15 in the general formula (1). Further, the present invention relates to the photosensitive resin composition, wherein (d) the amino resin is a melamine resin.

Further, the present invention provides a method wherein (e) the aromatic phosphate compound is represented by the general formula (2):

Embedded image (Wherein R ³ represents an organic group, and Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, Number 6-1
4 aryl groups, amino groups, nitro groups, cyano groups, mercapto groups, allyl groups, alkylmercapto groups having 1 to 10 carbon atoms, hydroxyalkyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms A carboxyalkyl group, an acyl group having 1 to 10 carbon atoms in an alkyl group, and 1 to 2 carbon atoms
0 represents an alkoxy group or a group containing a heterocyclic ring, a, b,
c and d are each independently an integer of 0 to 5).

Further, the present invention provides a compound represented by the formula (2) wherein R ³ is a divalent residue obtained by removing two hydroxyl groups from dihydroxybenzene or 2,2-di (p-hydroxyphenyl) propane. The present invention relates to the above-mentioned photosensitive resin composition, which is a divalent residue excluding hydroxyl groups. The present invention further comprises (f) a repeating unit (A) composed of pentamethylene carbonate units and a repeating unit (B) composed of hexamethylene carbonate units, and the molar ratio A: B of these repeating units is 9: 1. The present invention relates to the photosensitive resin composition containing a reactant of copolycarbonate, isophorone diisocyanate and hydroxyethyl (meth) acrylate in a ratio of 1: 9.

The present invention also relates to a photosensitive element obtained by applying the above-mentioned photosensitive resin composition on a support and drying it to form a layer of the photosensitive resin composition. The present invention also relates to a photosensitive laminate having a layer of the photosensitive resin composition 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.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, the (meth) acrylic acid is
Means acrylic acid and its corresponding methacrylic acid,
(Meth) acrylate means acrylate and its corresponding methacrylate.

The photosensitive resin composition of the present invention comprises (a) a binder polymer having tribromophenyl (meth) acrylate as a copolymer component, (b) a bisphenol A (meth) acrylate compound, and (c) photopolymerization. Initiator,
It must contain (d) an amino resin and (e) an aromatic phosphate compound.

The binder polymer (a) containing tribromophenyl (meth) acrylate as a copolymer component is not particularly limited as long as tribromophenyl (meth) acrylate is used as a copolymer component. Binder polymers obtained by copolymerizing (meth) acrylate, (meth) acrylic acid and other vinyl monomers are exemplified.

Examples of the above-mentioned tribromophenyl (meth) acrylate include tribromophenyl acrylate and tribromophenyl methacrylate. Tribromophenyl acrylate is preferred. These are used alone or in combination of two or more. As the (meth) acrylic acid, for example,
Acrylic acid, methacrylic acid and the like can be mentioned, and methacrylic acid is preferable. These are used alone or in combination of two or more.

Examples of the other vinyl monomers include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate;
2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, styrene, α-styrene, vinyltoluene, N- Vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, acrylamide, acrylonitrile, methacrylonitrile, and the like. These are used alone or in combination of two or more.

The amount of the tribromophenyl (meth) acrylate to be copolymerized is 3 to 6 with respect to the total amount of the copolymerized components.
The content is preferably 5% by weight, more preferably 30 to 50% by weight. If the copolymerization amount is less than 3% by weight, the flame retardancy tends to decrease, and if it exceeds 65% by weight, the flame retardancy is obtained, but the cured coverlay tends to have low folding resistance. The copolymerization amount of the (meth) acrylic acid is preferably 10 to 45% by weight, more preferably 15 to 35% by weight, based on the total amount of the copolymerization components. If the copolymerization amount is less than 10% by weight, the development time tends to be long, and the workability tends to decrease.
If it exceeds, the adhesiveness tends to decrease. The copolymerization amount of the other vinyl monomer is preferably 25 to 87% by weight based on the total amount of the copolymerization components, and is 30 to 5% by weight.
More preferably, it is 5% by weight. When the copolymerization amount is 2
If the amount is less than 5% by weight, the flexibility tends to decrease.
If the content exceeds 10% by weight, flame retardancy and developability tend to decrease.

The binder polymer (a) containing tribromophenyl (meth) acrylate as a copolymer component is as follows:
It is preferable from the viewpoint of developability and environmental preservation that it is soluble or swellable in an aqueous alkali solution such as an aqueous solution of 1 to 3% by weight of sodium carbonate or potassium carbonate. The acid value is 65-3
00 mg KOH / g, preferably 98 to 228 mg KOH
/ g is more preferable. This acid value is 65mgKOH / g
If less than 300 mgKOH /
If it exceeds g, the development resistance of the photocured resist tends to decrease. The weight-average molecular weight (polystyrene conversion by GPC measurement) is 20,000 to 300,
000, preferably 30,000-150,
000 is more preferable. When the weight average molecular weight is less than 2,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.

The bisphenol A (meth) acrylate compound (b) is not particularly limited as long as it is a (meth) acrylate compound having a bisphenol skeleton. For example, the compound represented by the general formula (1) and the like can be used. No. In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and Y ¹ and Y ² each independently represent an alkylene group having 2 to 6 carbon atoms. The above carbon number 2
Examples of the alkylene group 6 include an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a neopentylene group, and a hexylene group, and an ethylene group is particularly preferable.

The above isopropylene group is --CH (CH ₃ )
CH ₂ — is a group represented by the formula (1)
In (Y ¹ -O)-and-(Y ² -O)-, there are two types of bonding directions: a case where the methylene group is bonded to oxygen and a case where the methylene group is not bonded to oxygen. Or two kinds of bonding directions may be mixed. Also,-
When each of the repeating units (Y ¹ -O)-and-(Y ² -O)-is 2 or more, two or more Y ¹ and two or more Y ² may be the same or different; ^{When 1} and Y ² are composed of two or more types of alkylene groups, two or more types of-(Y ¹ -O)
- and - (Y ² -O) - may exist at random or may be present blockwise.

In the general formula (1), two or more benzene rings may have one or more substituents at substitutable positions,
When it has two or more substituents, they may be the same or different. Such substituents include, for example,
Examples of Z ^{1 in} the general formula (2) described later include the groups specifically exemplified. In the general formula (1), p and q are p +
It is preferable that q is a positive integer selected to be 4 to 40, more preferably p + q is 4 to 15, and particularly preferably 5 to 13. If this number is less than 4, flexibility tends to decrease, and if it exceeds 40,
The hydrophilicity of the system tends to increase, and the adhesion at the time of development tends to decrease.

Examples of the compound represented by the general formula (1) include 2,2'-bis (4- (meth) acryloxydiethoxyphenyl) propane and 2,2'-bis (4
-(Meth) acryloxytetraethoxyphenyl) propane, 2,2'-bis (4- (meth) acryloxypentaethoxyphenyl) propane, 2,2'-bis (4-
(Meth) acryloxydiethoxyoctapropoxyphenyl) propane, 2,2'-bis (4- (meth) acryloxytriethoxyoctapropoxyphenyl) propane and the like. These are used alone or in combination of two or more. As these commercial products, for example, NK-ester BPE-500 (Shin-Nakamura Chemical Co., Ltd.)
Trade name, 2,2'-bis (4-methacryloxypolyethoxyphenyl) propane) and the like. These are used alone or in combination of two or more.

Examples of the photopolymerization initiator (c) include substituted or unsubstituted polynuclear quinones (2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone,
2,3-diphenylanthraquinone, etc.), α-ketaldonyl alcohols (benzoin, pivalone, etc.), ethers, α-hydrocarbon-substituted aromatic acyloins (α-phenyl-benzoin, α, α-diethoxyacetophenones) ), Aromatic ketones (benzophenone, 4,4'-bisdialkylaminobenzophenone such as N, N'-tetraethyl-4,4'-diaminobenzophenone, etc.),
Thioxanthones (2-methylthioxanthone, 2,4
-Diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2-ethylthioxanthone, etc.), 2-methyl-1- [4- (methylthio) phenyl] -morpholinopropan-1-one, and the like. These are used alone or in combination of two or more.

As the amino resin (d), for example,
Melamine, urea, an initial condensate obtained by reacting an aldehyde with an amino group-containing compound such as benzoguanamine is used, for example, trimethylolmelamine, tetramethylolmelamine, hexamethylolmelamine, hexamethoxymethylolmelamine, hexabutoxymethylolmelamine and the like And a melamine resin is preferable. These are used alone or in combination of two or more. These commercial products include:
For example, Cymel 300, Cymel 301, Cymel 3
03, Cymel 325, Cymel 350 (trade name, manufactured by Mitsui Cytec Co., Ltd.).

Examples of the (e) aromatic phosphate compound include compounds represented by the general formula (2). These are used alone or in combination of two or more.

R ³ in the general formula (2) represents an organic group, and represents a divalent residue obtained by removing two hydroxyl groups from dihydroxybenzene or 2,2-di (p-hydroxyphenyl) propane. It is preferably a divalent residue excluding two hydroxyl groups. Z in the general formula (2)
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, an amino group, and a nitro group. , Cyano group, mercapto group, allyl group, 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 It shows a group or a group containing a heterocyclic ring, and a, b, c and d are each independently an integer of 0 to 5.

The hydrogen atom of the benzene ring in the above residue is a halogen atom, an alkyl group having 1 to 20 carbon atoms,
10 cycloalkyl groups, aryl groups having 6 to 14 carbon atoms, amino groups, nitro groups, cyano groups, mercapto groups, allyl groups, alkyl mercapto groups having 1 to 10 carbon atoms, hydroxyalkyl groups having 1 to 20 carbon atoms, A carboxyalkyl group having 1 to 10 carbon atoms in an alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, a group containing an alkoxy group or heterocycle having 1 to 20 carbon atoms, an alkoxyalkyl having 1 to 3 carbon atoms One or more substituents such as a group may be substituted.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine and astatine.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, nonadecyl And an icosyl group. 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 include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group and a phenanthryl group. ,
It may be substituted with a cyano group, a mercapto group, an allyl group, an alkyl group having 1 to 20 carbon atoms, or the like. The carbon number 1
Examples of the alkyl mercapto group of No. 10 include a methyl mercapto group, an ethyl mercapto group, and a propyl mercapto group. Examples of the hydroxyalkyl group having 1 to 20 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxyisopropyl group, and a hydroxybutyl group.

Examples of the carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group and a carboxybutyl group. Examples of the acyl group having 1 to 10 carbon atoms in the alkyl group 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 include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the group containing a heterocyclic ring include a furyl group, a thienyl group, a pyrrolyl group,
Examples include a thiazolyl group, an indolyl group, and a quinolyl group.

From the viewpoints of ease of production and availability, the general formula (3)

Embedded image (Wherein, R ³ has the same meaning as R ³ in Formula (2), and R ⁴ and R ⁵ each independently represent a hydrogen atom or a carbon atom
To 4) are preferred.

R ⁴ and R ⁵ in the general formula (3) 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 ⁴ and R ⁵ is an alkyl group having 1 to 4 carbon atoms.

General formula (3) used as component (e)
Examples of the aromatic phosphate represented by
³ is a divalent residue obtained by removing two hydroxy groups from 2,2'-di (p-hydroxyphenyl) propane;
⁴ Compounds methyl group and R ⁵ is a hydrogen atom, a divalent residue obtained by removing R ³ is 2,2-di (p- hydroxyphenyl) two hydroxyl groups from propane, R ⁴
A compound wherein R ⁵ is a methyl group; a compound wherein R ³ is a divalent residue obtained by removing two hydroxyl groups from m-dihydroxybenzene; R ⁴ is a methyl group and R ⁵ is a hydrogen atom; ³ is a divalent residue obtained by removing two hydroxyl groups from m-hydroxybenzene, and a compound in which R ⁴ and R ⁵ are methyl groups. The aromatic phosphate ester represented by the general formula (2) used as the component (e) can be obtained from Daihachi Chemical Industry Co., Ltd. under the trade names PX200, C
It is available as R-747 and the like.

The photosensitive resin composition of the present invention may further comprise (f) a repeating unit (A) composed of pentamethylene carbonate units and a repeating unit (B) composed of hexamethylene carbonate units, if necessary. And a reactant of copolycarbonate, isophorone diisocyanate and hydroxyethyl (meth) acrylate in which the molar ratio A: B of these repeating units is from 9: 1 to 1: 9.

The above copolycarbonate can be synthesized, for example, by reacting a predetermined polyol with phosgene while adjusting the molecular weight. Generally, the copolycarbonate preferably has a number average molecular weight of 600 to 1,000, and more preferably 700 to 900. If the molar ratio (A) :( B) of this copolycarbonate is out of the above range, gelation may occur, which is not preferable. The molar ratio (A) :( B) of the copolycarbonate is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, and preferably 5: 5. Particularly preferred.

The above copolycarbonates may be added, for example, with isophorone diisocyanate and hydroxyethyl (meth)
By reacting the acrylate, the component (f) can be obtained. The amount of isophorone diisocyanate used in this reaction is usually slightly larger than the molar amount of copolycarbonate used. This reaction is generally performed as follows. The copolycarbonate and a slight excess of isophorone diisocyanate are mixed, a catalyst such as dibutyltin dilaurate is added, and the mixture is reacted at 60 to 120 ° C. Next, hydroxy (meth) acrylate is reacted with the terminal isocyanate group of the synthesized urethane oligomer. This reaction is carried out in the presence of paramethoxyphenol and di-tert-butyl-hydroxy-toluene in a proportion of 2 to 2.4 mol of hydroxyethyl (meth) acrylate to 60 to 9 mol per mol of urethane oligomer.
The reaction is performed at 0 ° C. For example, by confirming the disappearance of the isocyanate group in the infrared absorption spectrum,
Check the end point of the reaction.

As the component (f), for example, urethane acrylate oligomer UF-800 manufactured by Kyoeisha Chemical Co., Ltd.
1, UF-8002, UF-8003 and the like are commercially available, and UF-8003 is particularly preferred. From now on, all are methyl ethyl ketone solutions. These are used alone or in combination of two or more.

The amount of the component (a) in the present invention is as follows:
The amount is preferably 30 to 70 parts by weight, more preferably 35 to 50 parts by weight, based on 100 parts by weight of the total of the components (a), (b) and (f). When the compounding amount is less than 30 parts by weight, there is a tendency that the alkali developability is reduced, and when the photosensitive element is used, the photosensitive resin composition layer is softened and problems such as exudation from the end of the film tend to occur. If it exceeds, the sensitivity and the solder heat resistance tend to decrease.

The amount of the component (b) in the present invention is as follows:
10 to 100 parts by weight based on 100 parts by weight of the total amount of component (a)
Parts by weight, more preferably 30 to 60 parts by weight. If the amount is less than 10 parts by weight, the flexibility after soldering tends to be insufficient.
If the amount exceeds 0 parts by weight, flexibility tends to decrease.

The amount of the component (c) in the present invention is as follows:
(A) 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the component.
It is preferably 0.1 parts by weight, more preferably 0.1 to 10 parts by weight. If the amount is less than 0.1 part by weight, the sensitivity tends to be insufficient, and if it exceeds 20 parts by weight, the pattern shape tends to be poor.

The amount of the component (d) in the present invention is as follows:
The amount is preferably from 3 to 20 parts by weight, more preferably from 5 to 15 parts by weight, based on 100 parts by weight of the total amount of the component (a). If the amount is less than 3 parts by weight, solder heat resistance and flame retardancy tend to be insufficient, and if it exceeds 20 parts by weight, flexibility tends to decrease.

In the present invention, the amount of the component (e) is
(A) 15 to 150 parts by weight based on 100 parts by weight of the total amount of the components.
It is preferable to set it as a weight part, and it is more preferable that it is 30-130 weight part. If the amount is less than 15 parts by weight, the flame retardancy tends to decrease. If the amount exceeds 150 parts by weight, the tack tends to increase and the workability tends to increase.

The amount of the component (e) used as required in the present invention is preferably 20 to 120 parts by weight based on 100 parts by weight of the total amount of the component (a).
More preferably, it is 30 to 100 parts by weight. If the amount is less than 20 parts by weight, flexibility tends to be insufficient, and if it exceeds 120 parts by weight, developability tends to decrease.

The photosensitive resin composition of the present invention may contain a dye such as malachite green or Victoria Pure Blue, a photochromic agent such as tribromophenylsulfone or leucocrystal violet, a thermochromic inhibitor, if necessary. p
-Plasticizers such as toluenesulfonamide, pigments, fillers,
Antifoaming agent, flame retardant, stabilizer, adhesion promoter such as 2-amino-5-mercapto-1,3,5-thiadiazole, leveling agent, release accelerator, antioxidant, fragrance, imaging agent, thermal crosslinking An agent or the like can be contained in an amount of about 0.01 to 20 parts by weight based on 100 parts by weight of the total of the components (a) and (b). These are used alone or in combination of two or more.

If necessary, the photosensitive resin composition of the present invention may contain a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether or the like. And a solution having a solid content of about 30 to 60% by weight. Further, the photosensitive resin composition of the present invention is not particularly limited, but a metal surface, for example, copper, a copper-based alloy, nickel, chromium, iron, an iron-based alloy such as stainless steel,
Preferably, it is applied as a liquid resist on the surface of copper, a copper-based alloy, or an iron-based alloy, dried and then coated with a protective film, if necessary, or used in the form of a photosensitive element.

The thickness of the layer of the photosensitive resin composition varies depending on the application, but is preferably from 1 to 100 μm, more preferably from 20 to 60 μm, after drying. If it is less than 1 μm, coating tends to be industrially difficult, and if it exceeds 100 μm, the effect of the present invention tends to be small and sensitivity tends to be insufficient. When using a liquid resist coated with a protective film, an inert polyolefin film such as polyethylene or polypropylene is used as the protective film.From the viewpoint of the peelability from the photosensitive resin composition layer, the polyethylene film is used. Is preferred.

The photosensitive element is used as a support
It can be obtained by applying and drying a photosensitive resin composition on a polymer film made of polyethylene terephthalate, polypropylene, polyethylene, polyester or the like.
The coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater. In addition, drying is 80
It can be performed at about 150 ° C. for about 5 to 30 minutes. Since these polymer films must be removable later from the layer of the photosensitive resin composition, they may have been subjected to a surface treatment that makes removal impossible, or may be a material. Not be. The thickness of these polymer films is preferably 1 to 100 μm, and 1 to 30 μm.
m is more preferable. If the thickness is less than 1 μm, the mechanical strength tends to decrease, and problems such as breakage of the polymer film during coating tend to occur. If the thickness exceeds 30 μm, the resolution tends to decrease and the price tends to increase. . In addition, one of these polymer films is laminated on both sides of the photosensitive resin composition layer as a protective film of the photosensitive resin composition, and the other is used as a support film of the photosensitive resin composition layer. Is also good.

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

In producing a resist pattern using the photosensitive element, if the above-mentioned protective film is present, the protective film is removed and a circuit is formed while heating the layer of the photosensitive resin composition. And a method of obtaining a photosensitive laminated body by pressure bonding to a substrate for use. From the viewpoint of adhesiveness and followability, it is preferable to laminate under reduced pressure. The surface to be laminated is usually a metal surface, but is not particularly limited. The heating temperature of the layer of the photosensitive resin composition is preferably from 70 to 130 ° C.,
It is preferably 1 × 10 ⁵ to 1 × 10 ⁶ Pa, and 4 × 1
The pressure is preferably reduced to 0 ³ Pa or less, but there is no particular limitation on these conditions. In addition, if the layer of the photosensitive resin composition is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the circuit forming substrate in advance, but in order to further improve the lamination property, the circuit forming substrate is formed. A pre-heat treatment of the substrate for use can also be performed.

The photosensitive laminate in which the layering of the photosensitive resin composition is completed in this way is irradiated with actinic rays imagewise through a negative or positive mask pattern called an artwork. At this time, when the polymer film present on the photosensitive laminate is transparent, the active light beam may be irradiated as it is, and when it is opaque, it is necessary to remove it naturally. From the viewpoint of protecting the layer of the photosensitive resin composition, the polymer film is transparent, and it is preferable to irradiate the active film through the polymer film while leaving the polymer film remaining. As a light source of the actinic ray, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet rays is used. In addition, those that effectively emit visible light, such as a flood light bulb for photography and a sun lamp, are also used. Since the sensitivity of the photopolymerization initiator contained in the layer of the photosensitive resin composition is usually maximum in the ultraviolet region,
In this case, it is preferable to use an active light source that effectively emits ultraviolet rays.

Next, after the exposure, if a support is present on the layer of the photosensitive resin composition of the photosensitive laminate, the support is removed and then a developing solution such as an aqueous alkaline solution is used. For example, the unexposed portion is removed and developed by a known method such as spraying, rocking immersion, brushing, and scraping to develop a resist pattern. As a developer,
A safe and stable one having good operability, such as an alkaline aqueous solution, is used. As the base of the alkaline aqueous solution, for example, lithium, alkali hydroxide such as sodium or potassium hydroxide, lithium, sodium,
Examples thereof include alkali carbonates such as potassium or ammonium carbonate or bicarbonate, alkali metal phosphates such as potassium phosphate and sodium phosphate, and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate.

The alkaline aqueous solution used for development includes a dilute solution of 0.1 to 5% by weight of sodium carbonate,
Dilute solution of 0.1-5% by weight potassium carbonate, 0.1-5%
Weight% dilute solution of sodium hydroxide, 0.1-5% by weight
A dilute solution of sodium tetraborate or the like is preferred. The pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11, and the temperature is adjusted in accordance with the developability of the photosensitive resin composition layer. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. Development methods include a dip method and a spray method, and a high-pressure spray method is most suitable for improving resolution.

After development, it is preferable to perform ultraviolet irradiation or heating by a high-pressure mercury lamp for the purpose of improving solder heat resistance, chemical resistance and the like. UV irradiation dose is 0.2 to 10
J / cm ² is generally used.
More preferably with 50 ° C. heat. Heating is 100 ~
This is performed at a temperature of about 170 ° C. for about 15 to 90 minutes. Either the irradiation of the ultraviolet rays or the heating may be performed first. The flexible printed wiring board on which the coverlay is formed in this manner is then mounted with components such as LSI, diode, transistor, monolithic IC, and VLSI by soldering or the like, and is used as a mounting board, which is a small-sized camera device or the like. Attached to equipment.

[0059]

EXAMPLES [Synthesis of Binder Polymer] A mixture of 70 g of methyl cellosolve and 50 g of toluene was placed in a 300 ml separable flask under a nitrogen atmosphere and heated to 80 ° C. while stirring. After keeping it warm for 30 minutes, 50 g of tribromophenyl acrylate, 22 methacrylic acid
g, methyl methacrylate 25 g, methyl acrylate
1 g, tetrahydrofurfuryl acrylate 1 g, toluene 24 g, azobisisobutyronitrile 0.2 g
Was dropped into the separable flask for 3 hours to cause a reaction. Then, 10 g of methyl cellosolve,
After adding a mixture of 10 g of toluene and keeping the temperature for 3 hours, a solution prepared by dissolving 0.4 g of azobisisobutyronitrile in 10 g of methyl cellosolve and 10 g of toluene was added, and the temperature was further kept for 4 hours. Thereafter, the mixture was cooled to obtain a binder polymer solution A (solid content, 35% by weight). Table 1 shows the weight average molecular weight of the obtained polymer.

The binder polymer solution B shown in Table 1
The synthesis was performed in the same manner as the binder polymer solution A except that the amounts of copolymerization and the components of C, D and E were changed. Table 1 shows the weight average molecular weight of the obtained polymer.
Shown in

[0061]

[Table 1]

Examples 1 to 3 and Comparative Examples 1 to 4 The materials shown in Table 2 were blended to obtain solutions.

[0063]

[Table 2]

The component (a) shown in Table 3 was added to this solution.
(B), (d), (e) and (f) were blended to prepare a solution of the photosensitive resin composition. The unit of the amount in Table 3 represents parts by weight (solid content).

[0065]

[Table 3]

The solution of the photosensitive resin composition obtained was
The resulting solution was uniformly coated on a polyethylene terephthalate film having a thickness of m and dried with a hot air convection dryer at 100 ° C. for 10 minutes to remove the solvent. The thickness of the photosensitive resin composition layer after drying was 50 μm. A polyethylene film having a thickness of about 25 μm was further adhered on the photosensitive resin composition layer as a protective film to obtain a photosensitive element of the present invention.

The photosensitive characteristics of the obtained photosensitive element, solder heat resistance after forming the resist, folding resistance and flame retardancy were evaluated by the following methods, and the results are shown in Table 4.

(1) Photosensitive Characteristics A substrate for a flexible printed board in which a 35 μm thick copper foil is laminated on a polyimide substrate (trade name: F, manufactured by Nickan Kogyo Co., Ltd.)
The copper surface of 30VC125RC11) was polished with an abrasive brush, washed with water and dried. A continuous vacuum laminator (manufactured by Hitachi Chemical Co., Ltd.)
Using the product name VLM-1), heat shoe temperature 10
The photosensitive element was laminated at 0 ° C., a laminating speed of 1.0 m / s, a pressure of 4,000 Pa or less, and a pressure of 2.94 × 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 adhered onto the polyethylene terephthalate film of the sample obtained after being left at room temperature for 1 hour or more. A predetermined amount of light was exposed using an HMW-201GX type exposure machine manufactured by Oak Manufacturing Co., Ltd., and unexposed portions were removed by spraying a 1% by weight aqueous solution of sodium carbonate at 30 ° C. The sensitivity was defined as the amount of exposure necessary to obtain eight step tablets.

A photo tool (Kodak Step Tablet No. 2, 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 brought into close contact with the polyethylene terephthalate film of the obtained sample. The exposure was carried out at an exposure amount capable of obtaining eight steps of step tablets, and the line / space value of the smallest resolution pattern capable of obtaining a rectangular resist shape when developed was defined as the resolution.

(2) Solder heat resistance In the same manner as in (1) above, 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 flexible printed board substrate, and the number of step tablets was eight. Exposure was performed at the obtained exposure amount. After leaving at room temperature for 1 hour, the polyethylene terephthalate film of the sample was peeled off, unexposed portions were removed by spraying a 1% by weight aqueous solution of sodium carbonate at 30 ° C., and then developed, and then dried at 80 ° C. for 10 minutes.
Next, using a Toshiba UV irradiator manufactured by Toshiba Electric Materials Co., Ltd., UV irradiation of 1 J / cm ² was performed.
Heating was performed for 5 minutes to obtain a flexible printed board on which a coverlay was formed.

Next, a rosin flux MH-820 was used.
After applying V (manufactured by Tamura Kaken Co., Ltd.), it was immersed in a solder bath at 260 ° C. for 30 seconds to perform a soldering treatment. After such an operation, the occurrence of cracks in the coverlay and the situation of floating and peeling of the coverlay from the substrate were visually evaluated according to the following criteria. Good: No cracks, lifting and peeling occurred. Bad: Cracks, lifting and peeling occurred.

(3) Solvent resistance The flexible printed circuit board on which the coverlay was formed by the same operation as in (2) above was immersed in methyl ethyl ketone and isopropyl alcohol for 10 minutes at room temperature, and then the coverlay was lifted off and peeled from the substrate. Was visually evaluated according to the following criteria. Good: No lifting or peeling occurred Bad: Lifting or peeling occurred

(4) Folding resistance A coverlay was formed on the substrate for a flexible printed board obtained by the same operation as in (2), and the sample subjected to the soldering treatment was bent 180 ° by bending and bending. The occurrence of cracks in the coverlay was visually evaluated according to the following criteria. Good: No cracks occurred. Bad: Cracks occurred.

(5) Flame-retardant substrate for flexible printed board (manufactured by Nickan Industry Co., Ltd.)
Using a vacuum laminator (trade name: VLM-1 type, manufactured by Hitachi Chemical Co., Ltd.), a heat shoe temperature of 120 ° C. and a laminating speed were applied to the polyimide base material with the adhesive obtained by etching the copper foil of trade name F30VC125RC11). 1.0
m / s, atmospheric pressure 4,000 Pa or less, pressure bonding pressure 2.94 × 10 ⁵
The photosensitive element was laminated at a pressure of Pa (3 kgf / cm ² ) while peeling off the polyethylene film, and exposed so that the number of step tablets was 8 steps. After leaving at room temperature for 1 hour, the polyethylene terephthalate film of the sample was peeled off, and an unexposed portion was removed by spraying a 1% by weight aqueous solution of sodium carbonate at 30 ° C., followed by development.
Dry at 80 ° C. for 10 minutes. Next, using a Toshiba UV irradiator manufactured by Toshiba Electric Materials Co., Ltd., UV irradiation at 1 J / cm ² was performed, and a heat treatment was further performed at 150 ° C. for 45 minutes to prepare a substrate for evaluation of flame retardancy. This evaluation board is used by Underw
The flame retardancy was evaluated according to the apparatus and method (VTM method) based on the flame retardancy test standard UL94 of polymer materials of riters Laboratories Inc. (hereinafter abbreviated as UL). Table 4 shows the results.

[0076]

[Table 4]

As is evident from Table 4, the use of the photosensitive resin composition and the photosensitive element of the present invention makes it possible to obtain good solder heat resistance and folding resistance and a flame retardancy of 9%.
A coverlay for a flexible printed wiring board which is 4VTM-1 (UL standard) or 94VTM-0 (UL standard) is obtained.

[0078]

The photosensitive resin composition according to the first aspect is excellent in flame retardancy, flexibility, solder heat resistance, solvent resistance and washing resistance, and has good sensitivity and resolution. A fine pattern of the heat-resistant protective film can be easily formed. The photosensitive resin composition according to the second aspect has the effects of the invention according to the first aspect, further has excellent flame retardancy, and can easily form a fine pattern of a flexible heat-resistant protective film. The photosensitive resin composition according to the third aspect exhibits the effects of the invention according to the first or second aspect, further has excellent flame retardancy, and can easily form a fine pattern of a flexible heat-resistant protective film.

The photosensitive resin composition according to the fourth aspect has the effects of the invention according to the first, second or third aspect, and furthermore has excellent flame retardancy, sensitivity and resolution, and a fine pattern of a flexible heat-resistant protective film. Can be easily formed. The photosensitive resin composition according to the fifth aspect has the effects of the invention according to the first, second, third or fourth aspect, further has excellent flame retardancy, and can easily form a fine pattern of a flexible heat-resistant protective film. . The photosensitive resin composition according to the sixth aspect has the effects of the invention according to the first, second, third, fourth, or fifth aspect, further has excellent flexibility, and can easily form a fine pattern of a flexible heat-resistant protective film. Can be formed.

The photosensitive resin composition according to the seventh aspect has the effects of the invention according to the sixth aspect, is further excellent in sensitivity, and can easily form a fine pattern of a flexible heat-resistant protective film.
The photosensitive resin composition according to claim 8 is characterized in that:
The effects of the invention described in 3, 4, 5, 6, or 7 are exhibited, and further, the flame retardancy is excellent, and the fine pattern of the flexible heat-resistant protective film can be easily formed. The photosensitive resin composition according to the ninth aspect has the effects of the invention according to the first, second, third, fourth, fifth, sixth, seventh, and eighth aspects, and further has excellent flame retardancy and a flexible heat-resistant protective coating. Can be easily formed.

The photosensitive resin composition according to the tenth aspect has the effects of the invention according to the ninth aspect, and further has excellent flame retardancy,
A fine pattern of a flexible heat-resistant protective film can be easily formed. The photosensitive resin composition according to claim 11,
The effects of the invention described in 2, 3, 4, 5, 6, 7, 8, 9 or 10 are exhibited, the flexibility is excellent, and the fine pattern of the flexible heat-resistant protective film can be easily formed.

The photosensitive element according to the twelfth aspect has flame retardancy, flexibility, solder heat resistance, solvent resistance, washing resistance,
It is excellent in productivity and workability, good in sensitivity and resolution, and can easily form a fine pattern of a flexible heat-resistant protective film. The photosensitive laminate according to claim 13 is flame-retardant,
Flexibility, solder heat resistance, solvent resistance, washing resistance, excellent productivity and workability, and good sensitivity and resolution,
A fine pattern of a flexible heat-resistant protective film can be easily formed. The method for producing a flexible printed wiring board according to claim 14, wherein the flame-retardant, flexible, solder heat-resistant, solvent-resistant,
A resist pattern which is excellent in washing resistance, productivity and workability, has good sensitivity and resolution, and is extremely useful for forming a fine pattern of a flexible heat-resistant protective film can be formed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/107 C08K 5/107 5E314 5/521 5/521 C08L 33/16 C08L 33/16 61/20 61 / 20 61/28 61/28 75/16 75/16 G03F 7/004 501 G03F 7/004 501 7/027 502 7/027 502 H05K 3/28 H05K 3/28 D (72) Inventor Katsunori Tsuchiya Ibaraki 4-13-1, Higashimachi, Hitachi City Hitachi Chemical Co., Ltd. Yamazaki Office (72) Inventor Naoki Sasahara 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Office F-term (reference) 2H025 AA00 AA01 AA02 AA06 AA10 AA13 AB15 AC01 AD01 BC13 BC43 BC65 BC66 BC81 BC83 CB13 CB14 CB41 CB55 CC05 CC17 CC20 4J002 BG081 CC163 CC183 CC193 CH052 CK054 EE038 EE058 EH076 EU187 EV238 EV308 EW 308 308 GP03 4J011 PA46 PA69 PA85 PA95 PB29 PC02 QB16 QB24 SA06 SA21 SA25 SA32 SA34 SA63 SA64 SA75 UA01 4J027 AA02 AC03 AC04 AC06 AG12 AG24 CA25 CA27 CA34 CA35 CA36 CC05 CD10 4J100 AB02Q AB04Q AJ02R AL03Q AL04QAL08 BC08 A08Q08A08Q08P DA01 DA29 JA37 5E314 AA27 AA33 CC01 DD06 DD07 FF06 GG10 GG14 GG26

Claims (14)

[Claims] 1. A binder polymer comprising (a) tribromophenyl (meth) acrylate as a copolymer component,
(B) bisphenol A (meth) acrylate compound, (c) photopolymerization initiator, (d) amino resin, and (e)
A photosensitive resin composition containing an aromatic phosphate compound. 2. The photosensitive resin composition according to claim 1, wherein (a) the binder polymer is a binder polymer containing tribromophenyl (meth) acrylate, (meth) acrylic acid and another vinyl monomer as a copolymer component. . 3. The photosensitive material according to claim 1, wherein (a) the binder polymer is a binder polymer containing 3 to 65% by weight of tribromophenyl (meth) acrylate based on the total amount of all copolymerized components. Resin composition. 4. The binder polymer (a) is soluble or swellable in an aqueous alkali solution and has an acid value of 65 to 300.
4. The photosensitive resin composition according to claim 1, which is a binder polymer of mgKOH / g. 5. The method according to claim 1, wherein (a) the binder polymer has a weight average molecular weight of 20,000 to 300,000.
5. The photosensitive resin composition according to 2, 3 or 4. 6. A compound (b) comprising a bisphenol A (meth) acrylate compound represented by the general formula (1): (Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, Y ¹ and Y ² each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are such that p + q is 4 to 40) The photosensitive resin composition according to claim 1, 2, 3, 4, or 5, which is a compound represented by the following formula: 7. The photosensitive resin composition according to claim 6, wherein p + q is 4 to 15 in the general formula (1). 8. The photosensitive resin composition according to claim 1, wherein (d) the amino resin is a melamine resin. 9. The (e) aromatic phosphate compound is
General formula (2) (Wherein R ³ represents an organic group, and Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, Number 6-1
4 aryl groups, amino groups, nitro groups, cyano groups, mercapto groups, allyl groups, alkylmercapto groups having 1 to 10 carbon atoms, hydroxyalkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 10 carbon atoms A carboxyalkyl group, an acyl group having 1 to 10 carbon atoms in an alkyl group, and 1 to 2 carbon atoms
0 represents an alkoxy group or a group containing a heterocyclic ring, a, b,
c and d are each independently an integer of 0 to 5).
The photosensitive resin composition as described in the above. 10. In the general formula (2), R ³ is a divalent residue obtained by removing two hydroxyl groups from dihydroxybenzene or two hydroxyl groups from 2,2-di (p-hydroxyphenyl) propane. The photosensitive resin composition according to claim 9, which is a divalent residue excluding 11. It further comprises (f) a repeating unit (A) consisting of pentamethylene carbonate units and a repeating unit (B) consisting of hexamethylene carbonate units, and the molar ratio A: B of these repeating units is 9: 1 to 1: 1. 1:
9. A reaction product of a copolycarbonate, isophorone diisocyanate and hydroxyethyl (meth) acrylate, which is 9, 2, 3, 4, 5, 6, 7, 8,
11. The photosensitive resin composition according to 9 or 10. 12. The method of claim 1, 2, 3, 4, 5, 6, 7,
A photosensitive element comprising the photosensitive resin composition according to 8, 9, 10 or 11, which is coated on a support and dried to form a layer of the photosensitive resin composition. 13. The flexible printed wiring board substrate according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 1, or 1.
12. A photosensitive laminate having a layer of the photosensitive resin composition according to 0 or 11. 14. A resist pattern is formed by irradiating the photosensitive laminate according to claim 13 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.