JP2009109590A - Photosensitive resin composition, photosensitive dry film, photosensitive laminated film and coverlay using those - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive dry film having a high rate of imidization, and to provide a laminated film and a resin pattern using the same. <P>SOLUTION: The photosensitive dry film uses a photosensitive resin composition to which a specific plasticizer has been added. The laminated film and resin pattern using the same are also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a photosensitive dry film, a photosensitive laminated film, and a resin pattern using them.

  In recent years, a film-like printed board called a flexible printed board (hereinafter referred to as FPC) has been gaining popularity. This board has a structure with a coverlay made of polyimide film etc. on a processed FCCL (Flexible Copper Clad Laminate), and is mainly used for devices such as mobile phones, notebook computers, digital cameras, etc. It has been. Since FPC maintains its function even when it is bent, it is an indispensable material for reducing the size and weight of equipment. Particularly, in recent years, various electronic devices have been reduced in size and weight, and the adoption of FPC for such products contributes to the reduction of the size and weight of the devices, the reduction of product cost, and the simplification of the design. ing.

  As a coverlay material provided in this FPC, a polyimide film provided with an adhesive is used from the viewpoint of bending resistance, heat resistance, and electrical insulation. However, in the case of using the polyimide film, there is a problem in terms of alignment accuracy and cost because the bonding and punching are performed manually. Therefore, various methods have been devised in which polyimide is formed by imparting photosensitivity to a polyimide precursor and forming a wiring pattern and then heating the polyimide precursor (Patent Documents 1 and 2).

However, when these polyimide precursors are made of polyimide, high temperatures of 300 ° C. or higher are required, so use them in applications where high temperatures cannot be applied, such as coverlay materials for FPCs used in electronic devices. Is difficult. Further, when the polyimide precursor is converted to polyimide, the FPC warps due to the stress accompanying the solvent removal or the ring closure reaction of the polyamic acid. When warpage occurs in the FPC, problems such as poor adhesion between the FCCL and the coverlay and an increase in driving power of an electronic device equipped with the FPC arise. Therefore, it is required to improve the warpage of the FPC having a coverlay on the copper wiring. Further, a halogen compound is blended as a flame retardant in order to make the coverlay exhibit flame retardancy, but this is not preferable from the viewpoint of environmental burden.
Patent No. 3064579 JP 2002-278061 A

  In the present invention, in view of solving the above-mentioned problems, there is no warp even when a coverlay is formed on a flexible substrate such as FCCL, and a sheet in which a photosensitive layer made of the photosensitive resin composition is formed on both sides of a support film. It aims at providing the photosensitive resin composition characterized by showing a flame retardance, the photosensitive dry film using the said photosensitive resin composition, the photosensitive laminated | multilayer film, and a resin pattern.

As a result of diligent study, the present inventor has solved the above problems by adding a specific plasticizer using a photosensitive resin composition containing a polyimide precursor. That is, the object of the present invention can be achieved by the following configuration.
1. A photosensitive resin composition comprising (A) a polyimide precursor, (B) a plasticizer represented by the following general formula (1), and (C) a photosensitive agent.

(N is an integer from 0 to 3. R ₇ and R ₈ are a single bond, an oxygen atom, and a divalent or higher organic group. X1 to X14 represent a hydrogen atom, a hydroxyl group, and a monovalent organic group, which are the same or different. Is also good.)
2. 2. The photosensitive resin composition as described in 1 above, wherein the (B) plasticizer is tris (4-hydroxyphenyl) methane.
3. The photosensitive resin composition as described in 1 or 2 above, wherein the (A) polyimide precursor is represented by the general formula (2).

(R ₁ is a tetravalent organic group. R ₂ and R ₃ are hydrogen or an organic group having 1 to 20 carbon atoms, and may be the same or different. R ₄ is a divalent to tetravalent organic group. R ₅ and R ₆ are each hydrogen or an organic group having 1 to 20 carbon atoms, and may be the same or different, provided that when R ₂ and R ₃ are not hydrogen, m + n> 0 and n> 0. R ₅ is hydrogen or an organic group having 1 to 20 carbon atoms, R ₆ is hydrogen, m + n ≧ 0 when at least one of R ₂ and R ₃ is hydrogen, and R ₅ and R ₆ are hydrogen. Or an organic group having 1 to 20 carbon atoms, which may be the same or different.

4). 4. The photosensitive resin composition as described in any one of 1 to 3 above, wherein the (C) photosensitive agent is a quinonediazide compound.
5). The photosensitive resin composition as described in any one of 1 to 4 above, further comprising (D) a dissolution inhibitor.
6). 6. The photosensitive resin composition as described in 5 above, wherein the (D) dissolution inhibitor is an amide compound and / or a urea compound containing a phenolic hydroxyl group.
7). 7. The photosensitive resin as described in 5 or 6 above, wherein (D) the dissolution inhibitor is at least one selected from 3′-hydroxyphenylacetanilide, 4′-hydroxyphenylacetanilide and 4-hydroxyphenylbenzamide. Composition.
8). 8. The photosensitive resin composition as described in any one of 1 to 7 above, further comprising a compound represented by the general formula (3) as the plasticizer (B).

(R ₉ to R ₁₁ are organic groups containing an ethylene glycol chain and / or a propylene glycol chain, and may be the same or different.)

9. The photosensitive resin composition according to any one of 1 to 8, further comprising (E) an organic solvent.
10. 10. The photosensitive resin composition as described in 9 above, wherein the (E) organic solvent is γ-butyrolactone.
11. 11. A photosensitive dry film comprising a layer of the photosensitive resin composition according to any one of 1 to 10 above and a support film layer.
12 12. A photosensitive laminated film, wherein the photosensitive dry film described in 11 above and a cover film are laminated.
13. The coverlay comprising the photosensitive resin composition according to any one of claims 1 to 10, wherein the polyimide precursor (A) is polyimideized.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition useful as an FPC board material which suppresses the curvature at the time of laminating and baking a photosensitive dry film thru | or a photosensitive laminated film on a board | substrate, and also has a flame retardance, A photosensitive dry film The photosensitive laminated film and the coverlay using them can be provided.

Hereinafter, the present invention will be specifically described.
The polyimide precursor and / or polyimide used in the present invention is not particularly limited as long as it is a polyimide precursor structure or a polymer having a polyimide structure, but is soluble in a solvent, warped after baking, flame retardancy. A polyimide precursor is preferable from the viewpoint of developing the polyamic acid, and polyamic acid is more preferable.
Examples of the tetracarboxylic dianhydride and diamine used as the monomer for the polyimide precursor include the following.

(A) Polyimide precursor
Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′- Biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3 , 3′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane Anhydride, bis (2,3-dicarbo Ciphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,2-bis ( 4- (4-aminophenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester, 4- (2,5-dioxotetrahydrofuran-3 -Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetra Carboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dical Xylphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxy) And benzoyloxy) phenyl) hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) -4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, and the like.

  Aliphatic tetracarboxylic dianhydrides include cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic dianhydride 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylicsan dianhydride, ethylene glycol-bis-trimellitic anhydride ester, butanediol- Bis-trimellitic anhydride ester, pentanediol-bis-trimellitic anhydride ester, bicyclo [2,2,2] oct-7-ene-2,3,5,6 tetracarboxylic dianhydride, 1,2 3,4-butanetetracarboxylic dianhydride and the like. These may be used alone or in combination of two or more.

  Of these, pyromellitic acid is used from the viewpoint of lowering the glass transition temperature (Tg) of a film obtained by baking a layer obtained by removing the solvent from the photosensitive resin composition (hereinafter referred to as photosensitive layer). Dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride , 1,1 Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4 -Dicarboxyphenyl) sulfone dianhydride, 3,3'-oxydiphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester, ethylene glycol-bis-trimellitic anhydride ester, butanediol-bis-trimellitic anhydride ester, pentanediol -Bis-trimellitic anhydride ester is preferred.

  Specific examples of the diamine include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4 ′. -Diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4 ' -Diaminobiphenyl, 3,7-diamino-dimethylbenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4′-diaminodiphenylsulfone, 4,4′-diaminobenzanilide, 1, n-bis (4-aminophenyl) Noxy) alkane, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-amino) Phenyl) fluorene, 5 (6) -amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4- Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2- Bis (4-aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 4,6-dihydroxy-1,3-phenylenediamine, 3, 3′-dihydroxy-4,4′-diaminobiphenyl, 1,4-bis (4-aminophenoxy) pentane, 1,5-bis (4′-aminophenoxy) pentane, bis (γ-aminopropyl) tetramethyldi Siloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, diamino represented by formula (4) Examples thereof include siloxane compounds. These may be used alone or in combination of two or more.

(R is an integer of 2 to 12)
Among these, from the viewpoint of lowering Tg, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-dianobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,7-diamino-dimethylbenzothiophene-5,5 -Dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminobenzanilide 1, n-bis (4-aminophenoxy) alkane, 1,3-bis (4-aminophenoxy) -2,2-dimethyl Lopan, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 5 (6) -amino-1- (4-aminomethyl) -1 , 3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4 '-Bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl ] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,6-dihydroxy-1,3-phenylenediamine, 3,3′-dihydroxy-4, '-Diaminobiphenyl, 1,4-bis (4-aminophenoxy) pentane, 1,5-bis (4'-aminophenoxy) pentane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis ( Gamma-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, and a diamine represented by formula (4) are preferred.

(R is an integer of 2 to 12)
The Tg of the photosensitive layer obtained by removing the solvent of the photosensitive resin composition of the present invention is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, and further preferably 100 ° C. or lower. By setting the Tg to 120 ° C. or less, it is possible to remove the stress associated with solvent removal, and to reduce the warpage of the support film and a film composed of the photosensitive layer (hereinafter referred to as photosensitive dry film).

When synthesizing a polyimide precursor, a polymer terminal may be sealed with a monofunctional acid anhydride, a monofunctional carboxylic acid, or a monofunctional amine as necessary.
Moreover, it is also possible to esterify a part of carboxyl group of the polyimide precursor used for this invention using well-known compounds, such as an alcohol compound, and a method.
The polyimide which can be used for this invention is compoundable by a well-known method using the compound similar to the tetracarboxylic dianhydride and diamine which were used with the polyimide precursor.

(B) Plasticizer The (B) plasticizer used in the present invention reduces the warpage of the sheet composed of the film after baking and the substrate, and the photosensitive layer composed of the photosensitive resin composition on both sides of the support film. From the viewpoint of the flame retardancy of the formed sheet, the compound represented by the general formula (1) is preferable.

(N is an integer of 0 or more. R ₇ and R ₈ are a single bond, an oxygen atom, and a divalent or higher organic group. X ₁
From X ₁₄ represents a hydrogen atom, a hydroxyl group, an organic group, it may be the same or different, respectively. )

  Specifically, dihydroxydiphenylmethane, 4,4′-dioxyphenol, 1,4-bis- (3-hydroxyphenoxy) -benzene, 1,3-bis- (4-hydroxyphenoxy) -benzene, 1,5 -Binuclear body such as -bis- (o-hydroxyphenoxy) -3-oxapentane, α, α'-bis- (4-hydroxyphenyl) -1,4-diisopropylbenzene, tris (4-hydroxyphenyl) methane, And trinuclear bodies such as tris (4-hydroxyphenyl) ethane and 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl} phenol. These phenol compounds may be used alone or in combination of two or more.

The compound represented by the general formula (3) can be used together with the general formula (1) for the plasticizer (B) used in the present invention.

(R ₉ to R ₁₁ are organic groups containing an ethylene glycol chain and / or a propylene glycol chain, which may be the same or different.)
Specific examples include compounds represented by general formula (5) and general formula (6), but are not limited thereto.

(N is an integer greater than or equal to 0)

(N is an integer greater than or equal to 0)
These compounds may be used alone or in combination of two or more.
Moreover, you may use combining the compound represented by General formula (5) and General formula (6).

(C) Photosensitizer (C) The photosensitizer used in the present invention is preferably a compound that generates an acid upon irradiation with actinic rays. Of these, quinonediazide compounds are preferred. For example, those described in US Pat. No. 2,797,213, 3669658 can be used. Among these, an ester compound of a phenol compound and 1,2-naphthoquinone-2-diazide-4-sulfonic acid or 1,2-naphthoquinone-2-diazide-5-sulfonic acid is preferable. These may be used alone or in combination of two or more.

  The blending amount of the (C) photosensitizer used in the present invention is preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the (A) polyimide precursor. The blending amount of the photosensitive agent is preferably 5 parts by weight or more from the viewpoint of sensitivity and 30 parts by weight or less from the viewpoint of light absorption.

(D) Dissolution inhibitor The photosensitive resin composition of the present invention may contain a dissolution inhibitor for the purpose of suppressing the solubility of the polyimide precursor in an alkaline developer. The dissolution inhibitor that can be used in the present invention refers to a compound that forms a hydrogen bond with the carboxyl group of the polyimide precursor. When the carboxyl group of the polyimide precursor is hydrogen-bonded with the dissolution inhibitor, it is shielded from the developer, and dissolution can be suppressed.

Examples of the compound having a group capable of hydrogen bonding with a carboxyl group include a carboxylic acid compound, a carboxylic acid ester compound, an amide compound, and a urea compound. An amide compound and a urea compound are preferable from the viewpoint of the effect of inhibiting dissolution in an alkaline aqueous solution and storage stability.
Examples of the amide compound include N, N-diethylacetamide, N, N-diisopropylformamide, N, N-dimethylbutyramide, N, N-dibutylacetamide, N, N-dipropylacetamide, N, N-dibutylformamide. N, N-diethylpropionamide, N, N-dimethylpropionamide, N, N′-dimethoxy-N, N′-dimethyloxamide, N-methyl-ε-caprolactam, 4-hydroxyphenylbenzamide, salicylamide, salicylanilide , Acetanilide, 2′-hydroxyphenylacetanilide, 3′-hydroxyphenylacetanilide, 4′-hydroxyphenylacetanilide.

Among these, an amide compound containing an aromatic hydroxyl group is more preferable from the viewpoints of lowering the Tg of the photosensitive layer and the film obtained by baking the photosensitive layer, increasing the sensitivity of the photosensitive layer, and increasing the residual film ratio. Specific examples include 4-hydroxyphenylbenzamide, 3′-hydroxyphenylacetanilide, and 4′-hydroxyphenylacetanilide. These may be used alone or in combination of two or more.
Examples of the urea compound include 1,3-dimethylurea, tetramethylurea, tetraethylurea, 1,3-diphenylurea, and 3-hydroxyphenylurea. Among these, a urea compound containing an aromatic hydroxyl group is more preferable from the viewpoint of increasing sensitivity, increasing the residual film ratio, reducing the Tg of the photosensitive layer and the film obtained by baking the photosensitive layer. Specific examples include 3-hydroxyphenylurea. These may be used alone or in combination of two or more.

When the amide compound is used as the (D) dissolution inhibitor that can be used in the present invention, (A) 0.1 mol to 1.5 mol of the dissolution inhibitory effect is expressed with respect to 1 mol of the carboxyl group of the polyimide precursor. It is preferable to mix | blend and it is more preferable to mix | blend 0.15-1.0 mol.
In the case of using a urea compound, the (D) dissolution inhibitor used in the present invention is preferably 0.1 mol to 1.5 mol from the viewpoint of the dissolution inhibition effect with respect to 1 mol of the carboxyl group of the (A) polyimide precursor. From the viewpoint of the dissolution inhibiting effect and the mechanical properties of polyimide obtained by baking after alkali development, it is more preferable to add 0.15 to 0.5 mol.
Moreover, when using both an amide compound and a urea compound, the total amount of an amide compound and a urea compound is 0.1 mol-1 with respect to 1 mol of carboxyl groups of the (A) polyimide precursor from a viewpoint of a dissolution inhibitory effect. A range of .5 mol is preferred.

(E) Organic solvent The organic solvent (E) that can be used in the present invention is preferably an ester compound such as γ-butyrolactone or ethyl lactate or an ether compound such as tetrahydrofuran from the viewpoint of solubility in an alkaline developer. These organic solvents may be used alone or in combination of two or more. The organic solvent that can be used in the present invention is preferably 120 to 900 parts by weight with respect to 100 parts by weight of the polyimide precursor.

  In the organic solvent used in the present invention, a solvent having a boiling point lower than that of γ-butyrolactone can be blended as necessary. By blending a low boiling point solvent, foaming during drying can be suppressed.

  Specific examples of the low boiling point solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl alcohol, isopropyl alcohol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and hexylene glycol. Alcohols, 1,4-dioxane, trioxane, diethyl acetal, 1,2-dioxolane, ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, anisole, ethyl acetate, methyl benzoate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monopropyl ether acetate, ethylene glycol diacetate, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diacetate and other esters, n -Hydrocarbons such as heptane, n-octane, cyclohexane, benzene, toluene, xylene, ethylbenzene and diethylbenzene.

(F) Crosslinking agent In this invention, a crosslinking agent can be mix | blended in order to improve the mechanical physical property of the film after baking. As the crosslinking agent, a tetracarboxylic acid compound or a tetracarboxylic acid ester compound represented by formula (7), a polyamic acid compound or a carboxyl group-containing polyamic acid ester compound represented by formula (8) is preferable.

(R ₁₂ is a tetravalent organic group, and R _{13 to} R ₁₆ are hydrogen or an organic group having 1 to 20 carbon atoms, which may be the same or different.)

(R ₁₇ , R ₁₉ and R ₂₁ are tetravalent organic groups which may be the same or different. R ₁₈ and R ₂₀ are divalent to tetravalent organic groups which are the same or different. R _{22 to} R ₂₈ are hydrogen or an organic group having 1 to 20 carbon atoms, and may be the same or different, and p is an integer of 0 to 100.)

The blending amount of the (F) crosslinking agent that can be used in the present invention is 0.1 mol to 1. mol in terms of the expression of the crosslinking effect with respect to the number of moles of residual amino groups of the polyamic acid or carboxyl group-containing polyamic acid ester. 5 mol is preferable, and 0.5 mol to 1.1 mol is more preferable.
The amount of residual amino groups can be calculated using high performance liquid chromatography.

(G) Thermal base generator The photosensitive resin composition of the present invention can contain a thermal base generator, if necessary. A thermal base generator is a compound that generates a base by heating. For example, a base such as an amine is protected with an acid chloride compound, which is protected with a dicarbonate compound, which forms a salt structure with an acid such as a sulfonic acid. Thereby, it is stable without exhibiting basicity at room temperature, and can be a thermal base generator that generates a base by deprotection by heating.

By blending the thermal base generator, the temperature of the heat imidization after development of the photosensitive layer obtained by removing the solvent of the photosensitive resin composition can be made relatively low.
Specific examples of the thermal base generator include U-CAT (registered trademark) SA810, U-CAT SA831, U-CAT SA841, U-CAT SA851 (trade name, manufactured by San Apro), N- (isopropoxycarbonyl). -2,6-dimethylpiperidine, N- (tert-butoxycarbonyl) -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine, 1,3-bis (4-aminophenoxy) Examples include compounds in which both amines of benzene are protected with dibutyl dicarbonate.

  N- (isopropoxycarbonyl) -2,6-dimethylpiperidine, N- (tert-butoxycarbonyl) from the viewpoints of storage stability of photosensitive resin composition, stability by solvent removal, alkali solubility, and ion migration A compound in which both amines of -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine, and 1,3-bis (4-aminophenoxy) benzene are protected with dibutyl dicarbonate is preferable. The compounds are described, for example, in Chemistry Letters Vol. 34, no. 10 (2005).

  (G) The blending amount of the thermal base generator is preferably 1 to 30 parts by weight, and more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the alkali-soluble resin, from the viewpoint of promoting imidization and developing performance.

In the photosensitive resin composition of the present invention, for the purpose of improving the wettability with the support film, alcohols such as ethanol, 2-propanol and ethylene glycol, ethyl lactate, methyl benzoate and ethylene glycol mono Esters such as propyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as n-butyl ether, tetrahydrofuran and dioxane, glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monoethyl ether I can do it.
In the photosensitive resin composition of the present invention, an imidazole compound, a triazole compound, a tetrazole compound, and a sulfide compound can be blended as necessary. By blending these compounds, the adhesion to the copper substrate can be improved.

(Production of photosensitive dry film)
It is possible to produce a photosensitive dry film using the photosensitive resin composition of the present invention. The photosensitive dry film is obtained by applying the photosensitive resin composition to a support film and drying the solvent. As the support film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene / cyclodecene copolymer (trade name: APEL, manufactured by Mitsui Chemicals) and the like can be used. The thickness of the carrier film is usually from 15 to 100 μm, preferably from 15 to 75 μm, in consideration of coatability, adhesion, rollability, toughness, cost and the like.

The photosensitive resin composition can be applied to the above support film using a known method such as a reverse roll coater, a gravure roll coater, a comma coater, a lip coater, or a slot die coater.
Drying of the solvent can be performed at a temperature of 50 to 120 ° C. with a dryer using hot air drying, far infrared rays, or near infrared rays. The thickness of the photosensitive layer obtained by solvent removal is preferably 5 to 100 μm, more preferably 5 to 50 μm. The film thickness is preferably 5 μm or more from the viewpoint of insulation reliability, and preferably 100 μm or less from the viewpoint of obtaining a good line image.

A cover film can be laminated on the photosensitive dry film to form a photosensitive laminated film. By laminating the cover film, adhesion of the photosensitive layer to the support film can be prevented. As the cover film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene / cyclodecene copolymer (product name: APEL, manufactured by Mitsui Chemicals) can be used.
The photosensitive resin composition of the present invention can be used as a coverlay. A coverlay refers to a protective film that protects wiring formed on a silicon wafer, a copper clad laminate, an FPC, or the like.

(Coverlay production)
A photosensitive dry film can be produced from the photosensitive resin composition of the present invention, and a coverlay can be formed on the FPC. For example, it can be formed by the following steps.

1. A step of laminating a photosensitive dry film composed of the photosensitive resin composition of the present invention on a circuit-formed surface such as FPC to form a photosensitive layer.
The photosensitive dry film is superposed on a circuit-formed surface such as FPC, and heated to 40 to 120 ° C., preferably 60 to 110 ° C. by a known method such as flat lamination, roll lamination, or vacuum press. The photosensitive layer can be laminated by laminating at a pressure of 2 to 4 MPa. At this time, when the photosensitive dry film is a photosensitive laminated film in which a cover film is laminated, the cover film is peeled off before lamination. By setting the temperature at which lamination is possible to 40 ° C or higher, there is no need to take time and labor when aligning before lamination, and by setting it to 120 ° C or lower, imidization does not proceed too much, allowing for a sufficient laminating time and process margin. Can be taken widely. Note that the temperature at which lamination is possible is that there is no problem such as remaining bubbles, and the pattern can be sufficiently embedded, and at the same time, the photosensitive layer can be controlled to a viscosity at which the resin does not flow out of the pattern. It means temperature. Moreover, the photosensitive dry film can be suitably laminated by lowering the Tg of the photosensitive layer below the laminating temperature. After lamination of the photosensitive layer, the support film may or may not be peeled off. When not peeling off a support film, it peels after an exposure process.

2. A step of irradiating the photosensitive layer obtained in this step with actinic rays.

The photosensitive layer is exposed through a photomask on which an arbitrary pattern is drawn in order to form fine holes and fine width lines. Although an exposure amount changes with compositions of the photosensitive resin composition, it is 100-3,000 mJ / cm < ² > normally. Examples of actinic rays used at this time include X-rays, electron beams, ultraviolet rays, and visible rays. As the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, or the like can be used. In the present invention, it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. As a method of irradiating with actinic rays, either contact exposure or projection exposure may be used.

3. Development and rinsing process of the portion irradiated with actinic rays.
After the exposure, development can be performed by a known method such as a dipping method or a spray method using a developer, and a line image can be obtained. As the developer, an aqueous alkali solution such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, or an aqueous potassium carbonate solution can be used. After development, washing is performed using a rinse solution. Examples of the rinsing liquid include water and water obtained by adding an organic solvent.

4). Resin pattern formation by baking.
A resin pattern is formed by baking the line image obtained by development. Baking is performed continuously or stepwise at a temperature of 100 ° C. to 200 ° C. for 5 minutes to 5 hours. And the processed product is completed. Moreover, when using the said photosensitive resin composition, an actinic ray is irradiated to the line image obtained at the said process, and it can also bake after that.
Examples of the processed product thus obtained include FPC and multilayer printed wiring boards.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited at all by these examples.
(Synthesis of polyimide precursor)
(Synthesis Method 1) Synthesis of Polyamic Acid (I) 9.7 g of 1,3-bis (3-aminophenoxy) benzene and 93 g of γ-butyrolactone were placed in a three-necked separable flask and stirred at room temperature until a homogeneous solution was obtained. . Next, 15 g of pentanediol-bis-trimellitic anhydride ester was added, and the mixture was stirred for 1 hour while cooling with ice and then for 6 hours at room temperature. Next, the product was subjected to pressure filtration with a 5 μm filter to obtain polyamic acid (I). An IR chart when the polyamic acid of Synthesis Example 1 is cured at 140 ° C. is shown in FIG.

(Synthesis Method 2) Synthesis of Polyamic Acid (II) In a three-necked separable flask, 4.9 g of 1,3-bis (3-aminophenoxy) benzene, 6.4 g of 1,4-bis (4-aminophenoxy) pentane, γ -99 g of butyrolactone was added and stirred at room temperature until a homogeneous solution was obtained. Next, 15 g of pentanediol-bis-trimellitic anhydride ester was added, and the mixture was stirred for 1 hour while cooling with ice and then for 6 hours at room temperature. Next, the product was subjected to pressure filtration with a 5 μm filter to obtain polyamic acid (II).

(Synthesis Method 3) Synthesis of Polyamic Acid (III)
In a three-necked separable flask, 14.3 g of 1,3-bis (3-aminophenoxy) benzene and 110 g of γ-butyrolactone were added and stirred at room temperature until a homogeneous solution was obtained. Next, 15 g of 4,4′-oxydiphthalic dianhydride was added, and the mixture was stirred for 1 hour while cooling with ice and then for 6 hours at room temperature. Next, the product was subjected to pressure filtration with a 5 μm filter to obtain polyamic acid (III).

(Synthesis Example 4: Synthesis of thermal base generator)
Add 40 ml of tetrahydrofuran and 12.00 g of 1,3-bis (4-aminophenoxy) benzene to a three-necked flask and stir at room temperature until a homogeneous solution is obtained. Next, 18.81 g of dibutyl dicarbonate was slowly added with a dropping funnel, and then heated and stirred at 50 ° C. for 8 hours. After naturally cooling to room temperature, it was poured into 200 ml of ethyl acetate and washed three times with 50 ml of distilled water. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed with an evaporator. A white solid was obtained. The yield was 59%. (Measurement of Tg)

1. Tg after baking
Coating: An electrolytic copper foil sheet (F2-ws Furukawa Circuit Foil) is placed on a coating table (Matsuki Kagaku Co., Ltd.) that can be vacuum-adsorbed and heated, with the glossy surface facing up, and vacuum-adsorbed. A copper foil sheet was attached. On the electrolytic copper foil sheet, a photosensitive resin composition was applied using an applicator (manufactured by Matsuki Scientific Co., Ltd.) having a gap of 100 μm.
Pre-baking: Solvent removal was performed with a dryer (SPH-201, manufactured by Espec Corp.) at 60 ° C. for 30 minutes and then at 95 ° C. for 20 minutes.
Baking: Using a dryer (SPH-201 manufactured by Espec Corp.), baking was performed under the conditions of a heating rate of 1 ° C./min, an air atmosphere at 110 ° C. for 60 minutes, and 140 ° C. for 60 minutes.
Etching: The copper foil was etched using a ferric chloride aqueous solution (40 Baume degree, manufactured by Tsurumi Soda Co., Ltd.).
Drying: After etching, the sample was allowed to stand overnight at a temperature of 23 ° C. and a humidity of 50%.
Measurement of Tg: The film obtained in the above process was measured using a heat / stress / strain measuring device (TMA / SS6100, manufactured by Seiko Instruments Nanotechnology Co., Ltd.) under a nitrogen atmosphere (flow rate 250 cc / min). Tg was measured at 30 ° C to 200 ° C.

(Observation of warping)
Coating: A polyimide film (KAPTON EN-100 trade name, manufactured by Toray DuPont) was placed on a coating table (manufactured by Matsuki Kagaku Co., Ltd.) that can be vacuum-adsorbed and heated, and the polyimide film was attached by vacuum-adsorption. On the polyimide film, a photosensitive resin composition was applied using an applicator (manufactured by Matsuki Scientific Co., Ltd.) having a gap of 100 μm.
Solvent removal: Solvent removal was performed with a dryer (SPH-201, manufactured by Espec Corp.) at 60 ° C. for 30 minutes and then at 95 ° C. for 20 minutes. Baking: Using a dryer (SPH-201 manufactured by Espec Corp.), baking was performed under the conditions of a heating rate of 1 ° C./min, an air atmosphere at 110 ° C. for 60 minutes, and 140 ° C. for 60 minutes.
Measurement of warpage: The film obtained after baking was cut into a length of 5 cm and a width of 5 cm, and the warpage was measured using a ruler.

(Flame retardancy test)
Coating 1: A polyimide film (KAPTON EN-100 trade name, manufactured by Toray DuPont) was placed on a coating table (manufactured by Matsuki Kagaku Co., Ltd.) that can be vacuum-adsorbed and heated, and the polyimide film was attached by vacuum-adsorption. On the polyimide film, a photosensitive resin composition was applied using an applicator (manufactured by Matsuki Scientific Co., Ltd.) having a gap of 100 μm.
Solvent removal: Solvent removal was performed with a dryer (SPH-201, manufactured by Espec Corp.) at 60 ° C. for 30 minutes and then at 95 ° C. for 20 minutes to obtain a photosensitive dry film. Coating 2: The photosensitive resin composition was applied to the support film side of the photosensitive dry film obtained in the above step under the same conditions as in Coating 1.
Solvent removal: Photosensitive dry film having a photosensitive layer formed on both sides of the support film by removing the solvent with a dryer (SPH-201, manufactured by Espec Corp.) at 60 ° C. for 30 minutes and then at 95 ° C. for 20 minutes. Got.

Baking: Using a dryer (SPH-201 manufactured by Espec Corp.), baking was performed under the conditions of a heating rate of 1 ° C./min, an air atmosphere at 110 ° C. for 60 minutes, and 140 ° C. for 60 minutes.
Flame retardancy test: The film obtained after baking was cut into a length of 5 cm and a width of 1 cm to produce a strip. The lower end of the strip was ignited with a lighter, and the state of combustion was confirmed visually. Immediately after ignition, the flame extinguisher was marked with ◯, and the completely fired flame was marked with x.

(Calculation of imidization rate)
Infrared absorption was measured by the ATR method using a Fourier transform infrared spectrophotometer (FT-IR-460 plus manufactured by JASCO Corporation). After the measurement, the imidization ratio was calculated using the following formula (1). Here, the imidization ratio refers to the ratio of ring closure in the ring closure reaction from polyamic acid to polyimide. The higher the ratio of polyimide, the better the inherent heat resistance and bending resistance of polyimide. Therefore, it is necessary to increase the imidization rate by baking.

[Equation 1]
(Imidization rate (%)) = [A / B (baking temperature) −A / B (60 ° C.)] / [A / B (250 ° C.) − A / B (60 ° C.)]
A: Imidation-derived peak (about 1375 cm ⁻¹ )
B: Reference peak (about 1480 cm ⁻¹ )
A / B (baking temperature): Represents each A / B ratio at 140 ° C.
A / B (60 ° C.): A / B ratio at 60 ° C.
A / B (250 ° C.): A / B ratio at 250 ° C.

[Example 1]
5 g of the polyamic acid obtained in Synthesis Example 1, 12.5 parts by weight of 3′-hydroxyphenylacetanilide 0.13 g (0.86 mmol) with respect to the polyamic acid as a dissolution inhibitor, and 20 with respect to the polyamic acid as a plasticizer. 0.21 g (0.72 mmol) of tris (4-hydroxyphenyl) methane (PHBA) by weight, 0.21 g of quinonediazide compound (Formula 9) (TS (4)) with respect to polyamic acid as a photosensitizer Was put into a 20 cc glass bottle and stirred with a mix rotor (MR-5, manufactured by ASONE Co.) until uniform to obtain a photosensitive polyamic acid composition (I). Using the obtained photosensitive polyamic acid composition (I), Tg measurement after baking, warpage, flame retardancy evaluation, and imidation rate were calculated. The results are shown in Table 1. FIG. 2 shows an IR chart when the composition of Example 1 is cured at 140 ° C.

[Example 2]
5 g of the polyamic acid obtained in Synthesis Example 2, 0.13 g (0.86 mmol) of 3′-hydroxyphenylacetanilide as the dissolution inhibitor and 12.5 parts by weight of the polyamic acid, and 20 as the plasticizer for the polyamic acid. 20 cc glass bottle containing 0.21 g (0.72 mmol) of tris (4-hydroxyphenyl) methane by weight and 0.21 g of quinonediazide compound (formula 9) (TS (4)) with respect to polyamic acid as a photosensitizer. The mixture was stirred with a mix rotor (MR-5 ASONE) until it became uniform to obtain a photosensitive polyamic acid composition (III). Using the obtained photosensitive polyamic acid composition (III), Tg measurement after baking, warpage, evaluation of flame retardancy, and calculation of imidation ratio were performed. The results are shown in Table 1. An IR chart when the composition of Example 2 is cured at 140 ° C. is shown in FIG.

[Example 3]
5 g of the polyamic acid obtained in Synthesis Example 1, 12.5 parts by weight of 3′-hydroxyphenylacetanilide 0.13 g (0.86 mmol) with respect to the polyamic acid as a dissolution inhibitor, and 35 with respect to the polyamic acid as a plasticizer. 1,4-bis (3-amino) in which 0.37 g (1.27 mmol) of tris (4-hydroxyphenyl) methane in parts by weight and the terminal amine was blocked with dibutyl dicarbonate in Synthesis Example 4 as a thermal base generator Phenoxy) benzene 0.05 g (0.1 mmol) and 20 parts by weight of quinonediazide compound (Formula 10) (TS (5)) 0.21 g based on polyamic acid as a photosensitizer were placed in a 20 cc glass bottle and mixed rotor (MR- No. 5 manufactured by ASONE Co., Ltd.) until stirring to obtain a photosensitive polyamic acid composition (IV). Using the obtained photosensitive polyamic acid composition (IV), Tg measurement after baking, warpage, flame retardancy evaluation, and imidation rate were calculated. The results are shown in Table 1.

[Example 4]
5 g of the polyamic acid obtained in Synthesis Example 1, 12.5 parts by weight of 3′-hydroxyphenylacetanilide 0.13 g (0.86 mmol) with respect to the polyamic acid as a dissolution inhibitor, and 35 with respect to the polyamic acid as a plasticizer. 1,4-bis (3-amino) in which 0.37 g (1.27 mmol) of tris (4-hydroxyphenyl) methane in parts by weight and the terminal amine was blocked with dibutyl dicarbonate in Synthesis Example 4 as a thermal base generator Phenoxy) benzene 0.05 g (0.1 mmol), 20 parts by weight of quinonediazide compound (Formula 11) (HC5) 0.21 g as a photosensitizer with respect to polyamic acid was placed in a 20 cc glass bottle and mixed rotor (MR-5 ASONE Co., Ltd.). The mixture was stirred until it became uniform to obtain a photosensitive polyamic acid composition (IV). Using the obtained photosensitive polyamic acid composition (IV), Tg measurement after baking, warpage, flame retardancy evaluation, and imidation rate were calculated. The results are shown in Table 1.

[Example 5]
5 g of the polyamic acid obtained in Synthesis Example 1, 12.5 parts by weight of 3′-hydroxyphenylacetanilide 0.13 g (0.86 mmol) with respect to the polyamic acid as a dissolution inhibitor, and 20 with respect to the polyamic acid as a plasticizer. 0.21 g (0.72 mmol) of tris (4-hydroxyphenyl) methane by weight, 0.21 g of the compound represented by the general formula 12, and terminal amine using dibutyl dicarbonate in Synthesis Example 4 as a thermal base generator 0.05 g (0.1 mmol) of 1,4-bis (3-aminophenoxy) benzene sealed, 20 parts by weight of a quinonediazide compound (Formula 10) (TS (5)) 0. 21 g was put into a 20 cc glass bottle and stirred until it became uniform with a mix rotor (MR-5 manufactured by ASONE). The (IV) was obtained. Using the obtained photosensitive polyamic acid composition (IV), Tg measurement after baking, warpage, flame retardancy evaluation, and imidation rate were calculated. The results are shown in Table 1.

[Comparative Example 1]
5 g of the polyamic acid obtained in Synthesis Example 1, 12.5 parts by weight of 3′-hydroxyphenylacetanilide 0.13 g (0.82 mmol) with respect to the polyamic acid as a dissolution inhibitor, and 20 with respect to the polyamic acid as a photosensitizer. 0.21 g of a quinonediazide compound (formula 9) (TS (4)) by weight is placed in a 20 cc glass bottle and stirred with a mix rotor (MR-5, manufactured by ASONE) until uniform, photosensitive polyamic acid composition (I) Got. Using the obtained photosensitive polyamic acid composition (I), Tg measurement after baking, warpage, flame retardancy evaluation, and imidation rate were calculated. The results are shown in Table 1.

[Comparative Example 2]
5 g of the polyamic acid obtained in Synthesis Example 1, 12.5 parts by weight of 3′-hydroxyphenylacetanilide 0.13 g (0.82 mmol) with respect to the polyamic acid as a dissolution inhibitor, and 20 with respect to the polyamic acid as a plasticizer. 20 cc glass bottle containing 0.15 g of compound (PL-44) represented by general formula 13 in parts by weight and 0.21 g of quinonediazide compound (formula 9) (TS (4)) with respect to polyamic acid as a photosensitizer. And stirred with a mix rotor (MR-5, manufactured by ASONE Co.) until uniform to obtain a photosensitive polyamic acid composition (V). Using the obtained photosensitive polyamic acid composition (V), Tg measurement after baking, warpage, evaluation of flame retardancy, and calculation of imidation rate were performed. The results are shown in Table 1.

  Mw = 2200

[Comparative Example 3]
5 g of polyamic acid obtained in Synthesis Example 3, 0.13 g (0.82 mmol) of 3′-hydroxyphenylacetanilide as a dissolution inhibitor and 12.5 parts by weight of polyamic acid as a dissolution inhibitor, and 20 as a photosensitizer for polyamic acid. 0.21 g of a quinonediazide compound (Formula 9) (TS (4)) by weight is placed in a 20 cc glass bottle and stirred until it becomes uniform with a mix rotor (MR-5, manufactured by ASONE). Photosensitive polyamic acid composition (VI) Got. Using the resulting photosensitive polyamic acid composition (VI), Tg measurement after baking, warpage, flame retardancy evaluation, and imidation rate were calculated. The results are shown in Table 1.

  The photosensitive resin composition of the present invention to which a specific plasticizer is added, the photosensitive dry film, and the coverlay using them can be suitably used for FPC material applications.

IR chart when PAA of Synthesis Example 1 is cured at 140 ° C. IR chart when the composition of Example 1 is cured at 140 ° C. IR chart when the composition of Example 2 is cured at 140 ° C.

Claims (13)

A photosensitive resin composition comprising (A) a polyimide precursor, (B) a plasticizer represented by the following general formula (1), and (C) a photosensitive agent.

(N is an integer from 0 to 3. R ₇ and R ₈ are a single bond, an oxygen atom, and a divalent or higher organic group. X1 to X14 represent a hydrogen atom, a hydroxyl group, and a monovalent organic group, which are the same or different. Is also good.)   The photosensitive resin composition according to claim 1, wherein the (B) plasticizer is tris (4-hydroxyphenyl) methane. The said (A) polyimide precursor is shown by General formula (2), The photosensitive resin composition of Claim 1 or 2 characterized by the above-mentioned.

(R ₁ is a tetravalent organic group. R ₂ and R ₃ are hydrogen or an organic group having 1 to 20 carbon atoms, and may be the same or different. R ₄ is a divalent to tetravalent organic group. R ₅ and R ₆ are each hydrogen or an organic group having 1 to 20 carbon atoms, and may be the same or different, provided that when R ₂ and R ₃ are not hydrogen, m + n> 0 and n> 0. R ₅ is hydrogen or an organic group having 1 to 20 carbon atoms, R ₆ is hydrogen, m + n ≧ 0 when at least one of R ₂ and R ₃ is hydrogen, and R ₅ and R ₆ are hydrogen. Or an organic group having 1 to 20 carbon atoms, which may be the same or different.   The photosensitive resin composition according to claim 1, wherein the (C) photosensitive agent is a quinonediazide compound.   The photosensitive resin composition according to claim 1, further comprising (D) a dissolution inhibitor.   6. The photosensitive resin composition according to claim 5, wherein the (D) dissolution inhibitor is an amide compound and / or a urea compound containing a phenolic hydroxyl group.   The photosensitivity according to claim 5 or 6, wherein the dissolution inhibitor (D) is at least one selected from 3'-hydroxyphenylacetanilide, 4'-hydroxyphenylacetanilide, and 4-hydroxyphenylbenzamide. Resin composition. The photosensitive resin composition according to any one of claims 1 to 7, further comprising a compound represented by the general formula (3) as the plasticizer (B).

(R ₉ to R ₁₁ are organic groups containing an ethylene glycol chain and / or a propylene glycol chain, and may be the same or different.)   The photosensitive resin composition according to claim 1, further comprising (E) an organic solvent.
The photosensitive resin composition according to claim 9, wherein the (E) organic solvent is γ-butyrolactone.   A photosensitive dry film comprising a layer of the photosensitive resin composition according to claim 1 and a support film layer.   The photosensitive dry film of Claim 11 and the cover film are laminated | stacked, The photosensitive laminated film characterized by the above-mentioned. The coverlay comprising the photosensitive resin composition according to any one of claims 1 to 10, wherein the polyimide precursor (A) is polyimideized.

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