JP2008003582A - Photosensitive resin composition and circuit substrate using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali developable photosensitive polyimide resin composition which does not produce by-products resulting from a photobase generator and requires no curing at a high temperature, unlike a conventional photosensitive resin composition, by using a new photobase generator from which no by-product appears and an alkali developable soluble polyimide, and to provide a circuit substrate using the composition. <P>SOLUTION: The photosensitive resin composition contains the photobase generator (A) and the soluble polyimide (B), wherein the photobase generator (A) contains a cyclic compound containing a cleavable moiety which generates a base upon cleavage with light in its cyclic structure. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel photosensitive resin composition using a photobase generator and a circuit board using the same.

  Polyimide resins are applied in various fields based on excellent properties such as high insulation, heat and cold resistance, and high strength. In recent years, polyimides have been used as base materials and coverlays in flexible printed wiring boards (hereinafter abbreviated as FPCs) that are remarkably elongated. FPCs are required to be finer in line with the recent advancement and density of IC mounting technology, and high workability is also required for coverlays using polyimide. In manufacturing the FPC, the polyimide base material is mechanically punched, and the alignment is performed for bonding. Therefore, there is a problem that the alignment accuracy cannot be increased. In order to solve this problem, a photosensitive film based on a solder resist film using an acrylate resin or an epoxy resin has been studied. However, it has not reached polyimide in terms of physical properties such as flexibility (for example, And Patent Documents 1 to 3).

  As the photosensitive polyimide, for example, there is a proposal of a negative photosensitive polyimide using a combination of an olefin compound such as (meth) acrylic acid and a photo radical generator, but when used as an insulating film, an olefin coexisting after exposure and development. The compound needs to be removed by heating and decomposition. In this case, high-temperature heating at 200 ° C. or higher is necessary after development (for example, Patent Document 4). There is also a proposal using a polyamic acid ester having a photosensitive group in the side chain, but also in this case, it is necessary to cure at about 300 ° C. to 450 ° C. after development to decompose and imidize the side chain photosensitive group ( For example, Patent Document 5). When these photosensitive polyimides or photosensitive polyamic acid esters are used as FPC coverlays, there is a concern that curing at high temperatures may damage the circuit board.

As a photosensitive polyimide using a photobase generator, there is a proposal using a photobase generator having a polyamide precursor polyamic acid and an acyloxyimino group (for example, Patent Document 6). However, in the conventionally known acyclic photobase generator, since radical species are divided into two molecules after photocleavage, the radical species diffuse to reduce the probability of recoupling, Since the conversion efficiency to amine is lowered, it is necessary to add about 100 parts by weight with respect to 100 parts by weight of the resin, and there is a concern that the mechanical properties of the film are deteriorated. In addition, by-products of aldehyde compounds and ketone compounds are formed as completely separated molecules together with amines. In the negative photolithography process, the produced by-product is likely to be eluted into the developer and cause a reduction in film thickness. Moreover, when the by-product has high volatility, there is a concern that it may cause odor or contaminate the optical system of photolithography.
JP-A-56-6498 JP-A 61-243869 JP-A-6-332171 International Publication WO2002 / 023276 Japanese Patent Laid-Open No. 2001-194783 JP-A-6-295063

  The present invention has been made in view of the above points, and can reduce the amount of photobase generator added, which has been difficult with conventional photosensitive resin compositions. It aims at providing the photosensitive polyimide resin composition which does not have, and a circuit board using the same.

（式中、Ｘは−（ＣＨ_２）_ｎ−基、脂環式基、アリーレン基、−（ＣＨ_２）_ｎ−基と脂環式基とが結合したもの、−（ＣＨ_２）_ｎ−基とアリーレン基とが結合したもの、から選択され、ｎは２〜７の整数、Ｒ^１は芳香族基又は置換アルキル基である）

（式中、Ｙは−（ＣＨ_２）_ｍ−基、脂環式基、アリーレン基、−（ＣＨ_２）_ｍ−基と脂環式基とが結合したもの、−（ＣＨ_２）_ｍ−基とアリーレン基とが結合したもの、から選択され、ｍは２〜７の整数、Ｒ^２は芳香族基又は置換アルキル基である） The photosensitive resin composition of the present invention is a photosensitive resin composition containing a photobase generator (A) and a soluble polyimide (B), and the photobase generator (A) is represented by the formula (1). It contains the compound containing the acyloxyimino group represented by these, and / or the compound containing the carbamoyl oxyimino group represented by Formula (2), It is characterized by the above-mentioned.

(In the formula, X represents a — (CH ₂ ) _n — group, an alicyclic group, an arylene group, a — (CH ₂ ) _n — group and an alicyclic group, or — (CH ₂ ) _n — group. And an arylene group bonded to each other, n is an integer of 2 to 7, and R ¹ is an aromatic group or a substituted alkyl group)

(In the formula, Y represents a — (CH ₂ ) _m — group, an alicyclic group, an arylene group, a group in which a — (CH ₂ ) _m — group and an alicyclic group are bonded, and a — (CH ₂ ) _m — group. And an arylene group bonded to each other, m is an integer of 2 to 7, and R ² is an aromatic group or a substituted alkyl group)

  The photosensitive resin composition of the present invention can be developed with an aqueous alkali solution by causing a difference in solubility or / and a difference in dissolution rate between an irradiated part and an unirradiated part only by light irradiation or by light irradiation and heating. It is preferable that it is a negative photosensitive resin composition which is.

（式中αは４価の有機基、βは少なくとも１以上のカルボキシル基を有する２価の有機基、ｂは２価の有機基である。複数あるαはそれぞれ同じでも異なっていても良い。ｘは１以上の整数を表し、ｙは０以上の整数を表す） In the photosensitive resin composition of this invention, it is preferable that the said soluble polyimide (B) is a soluble polyimide containing the repeating unit represented by Formula (3).

(In the formula, α is a tetravalent organic group, β is a divalent organic group having at least one carboxyl group, and b is a divalent organic group. The plural αs may be the same or different. x represents an integer of 1 or more, and y represents an integer of 0 or more)

  In the photosensitive resin composition of the present invention, the soluble polyimide (B) preferably contains a silicone chain.

（式中のα、β、ｂ、ｘ、ｙは式（３）と同じである） In the photosensitive resin composition of this invention, the said soluble polyimide (B) is represented by Formula (4) which has the terminal structure W which has a functional group which can be bridge | crosslinked only by light irradiation or by light irradiation and a heating. It is preferable.

(Α, β, b, x, and y in the formula are the same as those in the formula (3))

  In the photosensitive resin composition of this invention, it is preferable to contain a photosensitizer (C) further.

  The photosensitive resin composition of the present invention preferably further contains an amidation catalyst (D).

  The film of this invention was comprised with the said photosensitive resin composition, It is characterized by the above-mentioned.

  The laminated film of the present invention preferably comprises a carrier film and the film according to claim 8 provided on the carrier film.

  In the laminated | multilayer film of this invention, it is preferable to comprise the cover film formed on the said film.

  The circuit board according to the present invention includes a cover lay configured using the film or the laminated film.

  The method for producing a circuit board according to the present invention includes a step of forming a resin composition layer on at least a substrate having wiring using the photosensitive resin composition, and a step of performing pattern exposure on the resin composition layer. And a step of developing the resin composition layer after the pattern exposure using an alkaline aqueous solution, and a step of curing the resin composition layer after the development processing.

  The method for producing a circuit board according to the present invention includes a step of laminating at least the film or the laminated film on a substrate having wiring to form a resin composition layer, and pattern exposure to the resin composition layer. And a step of developing the resin composition layer after the pattern exposure using an alkaline aqueous solution.

  Since the photosensitive resin composition of the present invention contains a photobase generator (A) containing a cyclic compound containing a cleavage site by light in a cyclic structure and a soluble polyimide (B), it is produced as a by-product. An alkali-soluble photosensitive polyimide resin composition in which no ketone is liberated is provided, and photolithography by alkali development can be realized. That is, by combining the photobase generator (A) and the soluble polyimide (B), the solubility difference or dissolution rate difference between the light-irradiated part and the unirradiated part of the composition with respect to the alkali developer is increased, and the alkali is satisfactorily improved. A novel photosensitive resin composition that can be developed and a circuit board using the same can be provided. In addition, since the photobase generator (A) has a cyclic structure, the efficiency of radical recoupling after cleavage by light can be made higher than that of known acyclic compounds, and the generation efficiency of bases can be improved. Since it can improve, it becomes possible to reduce the addition amount of a photobase generator.

Embodiments of the present invention will be described in detail.
The photobase generator (A) of the present invention can be decomposed satisfactorily with respect to light having a wavelength of 200 nm to 500 nm to generate a base. In that case, since the photooxygen generator of the present invention contains an acyloxyimino group or a carbamoyloxyimino group in a cyclic structure, the radical species generated in the photocleavage reaction are linked by a covalent bond, No product is produced. Furthermore, since the photobase generator in the present invention has radical species generated after cleavage by light covalently bonded to each other, the efficiency of radical recoupling is higher than that of an acyclic photobase generator, It is possible to improve the generation efficiency of the base.

（式中、Ｘは−（ＣＨ_２）_ｎ−基、脂環式基、アリーレン基、−（ＣＨ_２）_ｎ−基と脂環式基とが結合したもの、−（ＣＨ_２）_ｎ−基とアリーレン基とが結合したもの、から選択され、ｎは２〜７の整数、Ｒ^１は芳香族基又は置換アルキル基である） The photobase generator in the present invention is, for example, a compound represented by the formula (1).

(In the formula, X represents a — (CH ₂ ) _n — group, an alicyclic group, an arylene group, a — (CH ₂ ) _n — group and an alicyclic group, or — (CH ₂ ) _n — group. And an arylene group bonded to each other, n is an integer of 2 to 7, and R ¹ is an aromatic group or a substituted alkyl group)

（式中、Ｙは−（ＣＨ_２）_ｍ−基、脂環式基、アリーレン基、−（ＣＨ_２）_ｍ−基と脂環式基とが結合したもの、−（ＣＨ_２）_ｍ−基とアリーレン基とが結合したもの、から選択され、ｍは２〜７の整数、Ｒ^２は芳香族基又は置換アルキル基である） Moreover, it is a compound represented, for example by Formula (2).

(In the formula, Y represents a — (CH ₂ ) _m — group, an alicyclic group, an arylene group, a group in which a — (CH ₂ ) _m — group and an alicyclic group are bonded, and a — (CH ₂ ) _m — group. And an arylene group bonded to each other, m is an integer of 2 to 7, and R ² is an aromatic group or a substituted alkyl group)

  When the photobase generator is represented by the formula (1), n is preferably 2 to 7 from the viewpoint of radical coupling efficiency after cleavage by light. More preferably, n is 3 to 7.

In formula (1), R ¹ is an aromatic group or a substituted alkyl group. An aromatic group is, for example, a phenyl group or a naphthyl group. These may have a substituent. The substituted alkyl group is, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, phenoxy group, methoxy group, ethoxy group, butoxy group, isobutoxy group, sec-butoxy group. Etc.

  When the photobase generator is represented by the formula (2), m is preferably 2 to 7 from the viewpoint of compatibility with the photosensitive resin composition.

In formula (2), R ² is an aromatic group or a substituted alkyl group. An aromatic group is, for example, a phenyl group or a naphthyl group. These may have a substituent. The substituted alkyl group is, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, phenoxy group, methoxy group, ethoxy group, butoxy group, isobutoxy group, sec-butoxy group. Etc.

The photobase generator of the present invention may be a monofunctional compound or a polyfunctional compound. As a monofunctional thing, what is shown to a formula (5) is mentioned, for example, As a polyfunctional thing, what is shown to a formula (6) is mentioned, for example.

  Although there is no restriction | limiting in particular in the quantity of a photobase generator, In consideration of photosensitivity and the mechanical characteristic of resin after hardening, it is preferable to mix | blend 1 to 50 weight part with respect to 100 weight part of soluble polyimide. More preferably, it is 3 to 30 parts by weight. Most preferably, it is 5 to 20 parts by weight.

  In the photosensitive resin composition of the present invention, the photobase generator and a known photobase generator can be used in combination. For example, acyclic acyloxyimino compound, acyclic carbamoyl oxime compound, carbamoyl hydroxylamine compound, carbamic acid compound, formamide compound, acetamide compound, carbamate compound, benzyl carbamate compound, nitrobenzyl carbamate compound, sulfonamide compound, imidazole derivative compound Amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and the like. Of these, acyloxyimino compounds having relatively high amine generation efficiency are preferred. More preferably, an acyloxyimino compound capable of generating 1 to 4 amino groups from one molecule by light irradiation is preferred. More preferably, it is an acyloxyimino compound capable of generating 2 or more and 3 or less amino groups. The addition amount of these known photobase generators is preferably as small as possible.

Next, soluble polyimide (B) is demonstrated.
The soluble polyimide of the present invention is a polyimide soluble in an organic solvent. Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, and γ-butyrolactone. Soluble in an organic solvent means that it is dissolved in at least 5% by weight, preferably 10% by weight or more in one or more mixed solvents selected from these.

  The photosensitive resin composition of the present invention is a resin composition containing a photobase generator (A) and a soluble polyimide (B), and the solubility of the soluble polyimide in an alkaline developer is such that the light irradiated part and the non-irradiated part. It changes with. The soluble polyimide of the present invention can introduce a hydrophilic functional group that imparts alkali solubility. Examples of the hydrophilic functional group include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfonyl group, an amide group, a carbonyl group, an ester group, and an ether group. Of these, an acidic group is preferable, and a carboxyl group and a phenolic hydroxyl group are preferable.

  In addition, a functional group having reactivity with a base generated from the photobase generator (A) can be introduced into the soluble polyimide of the present invention.

  Examples of such a functional group reactive with a base include an epoxy group, an oxetane group, a vinyl group, a thiol group, and a carboxyl group. A carboxyl group is preferable from the viewpoints of reactivity with a base and alkali solubility.

（式中αは４価の有機基、βは少なくとも１以上のカルボキシル基を有する２価の有機基、ｂは２価の有機基である。複数あるαはそれぞれ同じでも異なっていても良い。ｘは１以上の整数を表し、ｙは０以上の整数を表す） The soluble polyimide having a carboxyl group is, for example, a soluble polyimide represented by the formula (3).

(In the formula, α is a tetravalent organic group, β is a divalent organic group having at least one carboxyl group, and b is a divalent organic group. The plural αs may be the same or different. x represents an integer of 1 or more, and y represents an integer of 0 or more)

In formula (3), α is a tetravalent organic group. Polyimide can be synthesized via polyamic acid using tetracarboxylic dianhydride and diamine as raw materials. α can be introduced into the polyimide by, for example, tetracarboxylic dianhydride represented by the formula (7).

  Examples of such tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3, and the like. 4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynor Bonane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2- Aliphatic or alicyclic tetracarboxylic dianhydrides such as dicarboxylic dianhydrides and bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydrides Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4, 5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′ , 4,4′-Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′- (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic Acid dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene bis (trimellitic acid monoester acid anhydride), ethylene glycol bis (trimellitic acid monoester acid anhydride), m-phenylene bis (Trimellitic acid monoester acid anhydride), bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane acid dianhydride, etc. Aromatic tetracarboxylic dianhydride; 1,3,3a, 4,5,9b-hexahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-Hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) ) -Naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) ) -Naphtho [1,2-c] furan-1,3-dione, and the like.

  Preferably, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester acid Anhydride), ethylene glycol bis (trimellitic acid monoester anhydride) and bicyclo [2,2,2] -oct-7-enetetracarboxylic dianhydride. In particular, p-phenylenebis (trimellitic acid monoester acid anhydride) or ethylene glycol bis (trimellitic acid monoester acid anhydride) is preferable from the viewpoint of improving developability when a photosensitive film is obtained.

  In addition, from the viewpoint of imparting solvent solubility to polyimide, a tetracarboxylic dianhydride or aliphatic tetracarboxylic dianhydride having a hexafluoroisopropylidene group or a tetracarboxylic dianhydride having no symmetry is introduced. It is preferable.

  Examples of such tetracarboxylic dianhydrides include 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 1,5-cyclooctadiene-1,2, and the like. 5,6-tetracarboxylic dianhydride (COEDA), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl 3-cyclohexene-1,2-dicarboxylic anhydride (MCTC, EpiclonB- 4400), 5-carboxymethylbicyclo [2.2.1] heptane-2,3,6, -tricarboxylic acid-2,3: 5,6-dianhydride (NDA), 1-carboxymethyl-2,3 , 5-cyclopentanetricarboxylic acid-2,6: 3,5-dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 4 − ( , 5-oxo-tetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (RIKACID TDA-100), and the like. These tetracarboxylic dianhydrides can be used alone or in combination.

Next, β will be described. β is a divalent organic group having a carboxyl group, and can be introduced by a diamine represented by formula (8) when a polyimide is synthesized.

  Such a diamine is not particularly limited as long as it is a diamine having a carboxyl group. For example, diaminobenzoic acids such as 3,5-diaminobenzoic acid; 3,3′-diamino-4,4′-dicarboxy Biphenyl, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl, 4,4′-diamino-2,2 ′, 5,5 ′ Carboxybiphenyl compounds such as tetracarboxybiphenyl; 3,3′-diamino-4,4′-dicarboxydiphenylmethane, 4,4′-diamino-3,3′-dicarboxydiphenylmethane, 4,4′-diamino- 2,2′-dicarboxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4 Amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenylmethane, etc. Carboxydiphenylalkanes such as carboxydiphenylmethane; 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-dicarboxydiphenyl ether, 4,4′-diamino-2, Carboxydiphenyl ether compounds such as 2′-dicarboxydiphenyl ether, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenyl ether; 3,3′-diamino-4,4′-dicarboxydiphenyl sulfone, 4,4'-diamino-3,3'-dicarboxy Diphenylsulfone compounds such as phenylsulfone, 4,4′-diamino-2,2′-dicarboxydiphenylsulfone, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenylsulfone; 2,2 -Bis [(carboxyphenoxy) phenyl] alkane compounds such as bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane; 4,4′-bis (4-amino-3-carboxyphenoxy) biphenyl and the like And bis [(carboxyphenoxy) phenyl] sulfone compounds such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone.

  Among these, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane and 3,5-diaminobenzoic acid are preferable because of good alkali solubility.

  These diamines having a carboxyl group can be used alone or in combination.

Next, b will be described. b is a divalent organic group, and can be introduced by a diamine represented by the formula (9) when a polyimide is synthesized.

  Examples of such diamines include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3 , 3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 4,4′-diaminobenzanilide, 3,5-diamino-3′-trifluoromethyl Benzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodi Phenyl ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'- Tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4, 4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) -biphenyl, 1,3-bis (4-amino) Phenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-( m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-bis [4- (4-amino-2) -Trifluoromethyl) phenoxy] -aromatic diamine such as octafluorobiphenyl; aromatic diamine having two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and a heteroatom other than the nitrogen atom of the amino group 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, Pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindani Examples include aliphatic diamines and alicyclic diamines such as range methylene diamine and 4,4′-methylene bis (cyclohexylamine).

  Further, a diamine having a hydroxyl group may be used. For example, diaminophenols such as 2,4-diaminophenol; 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino Hydroxybiphenyl compounds such as 2,2′-dihydroxybiphenyl and 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl; 3,3′-diamino-4,4′-dihydroxydiphenylmethane 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2, 2-bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxy) Phenyl) hexafluoropropane, hydroxydiphenylalkanes such as hydroxydiphenylmethane such as 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylmethane; 3,3′-diamino-4,4′-dihydroxy Diphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2′-dihydroxydiphenyl ether, 4,4′-diamino-2,2 ′, 5,5′-tetra Hydroxydiphenyl ether compounds such as hydroxydiphenyl ether; 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, 4,4′-diamino-2,2 '-Dihydroxydiphenylsulfone, 4 Diphenylsulfone compounds such as 4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylsulfone; bis [2, such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane (Hydroxyphenyl) phenyl] alkane compounds; bis (hydroxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl; 2,2-bis [4- (4 And bis [(hydroxyphenoxy) phenyl] sulfone compounds such as -amino-3-hydroxyphenoxy) phenyl] sulfone.

  Preferred are 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino) from the viewpoint of the glass transition point of the polyimide film. Phenoxy) benzene.

  Moreover, the polyimide which has a silicone chain can be obtained by using the diamine which has a silicone chain as diamine. A polyimide having a silicone chain is preferred from the viewpoints of glass transition point, film elongation, and film flexibility.

（Ｒ^３は２価の炭化水素基、ｋは１〜１０の整数である） As the diamine having a silicone chain, for example, diaminosiloxane can be used. Specifically, the diaminosiloxane is diaminosiloxane represented by the formula (10).

(R ³ is a divalent hydrocarbon group, k is an integer of 1 to 10)

  These diamine components can be used alone or in combination.

  The soluble polyimide according to the present invention synthesizes polyamic acid, which is a polyimide precursor, by mixing one or more tetracarboxylic dianhydrides and two or more diamines as monomers and mixing them in a suitable solvent. Thereafter, the reaction solution can be heated to imidize and synthesized. At this time, it is essential that the diamine contains one or more diamines selected from diamines having a carboxyl group. The molar ratio of (total tetracarboxylic dianhydride) / (total diamine) is preferably 0.95 or more and 1.05 or less from the viewpoint of mechanical properties when the film is prepared as the monomer charge amount.

  Examples of the solvent used for the synthesis include polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexanemethylphosphoric triamide, and γ-butyrolactone. It is done.

  In addition to these solvents, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons can be mentioned.

  Ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Esters include methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, dimethyl carbonate, diethyl malonate, and the like. Examples of ethers include diethyl ether, isopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran. Halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, chloroform, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, and the like. Hydrocarbons include hexane, heptane, octane, benzene, toluene, xylene and the like. These can be used alone or in combination of two or more.

  Imidization may be performed only by heating, or may be performed by adding a catalyst. As the catalyst, for example, acid anhydrides, lactones, and bases can be used. Examples of acid anhydrides include acetic anhydride. The lactone is preferably γ-valerolactone, and the base is preferably pyridine and / or methylmorpholine.

  When imidation is performed by heating or by adding a catalyst and heating, the heating temperature is preferably 150 to 200 ° C, more preferably 160 to 180 ° C.

  The water produced by the imidation reaction can be removed from the reaction system together with a solvent azeotropic with water, such as toluene and xylene.

  The obtained reaction liquid can be used as a polyimide varnish as it is.

  The soluble polyimide includes units having a carboxyl group and units having no carboxyl group, and the composition is indicated by x and y. Specifically, x is an integer of 1 or more, and y is an integer of 0 or more. Introduction of a unit having a carboxyl group is preferred from the viewpoint of alkali developability.

  From the viewpoint of alkali developability, the ratio of (number of units containing carboxyl groups) / (total units x + y) is preferably in the range of 0.01 to 1, more preferably 0.2 to 0. .9 or less, more preferably 0.3 or more and 0.8 or less.

（式中のα、β、ｂ、ｘ、ｙは式（３）と同じである。） Moreover, the soluble polyimide of this invention may have a photosensitive functional group at the terminal. The terminal photosensitive functional group is represented by W in the formula (4), for example.

(Α, β, b, x, and y in the formula are the same as those in the formula (3).)

  W represents a functional group terminal structure that can be crosslinked only by light irradiation or by light irradiation and heating. W may be a terminal structure having a functional group that can be crosslinked only by light irradiation in the presence of a base derived from the photobase generator (A), or by light irradiation and heating.

  Examples of the functional group that can be crosslinked only by light irradiation or by light irradiation and heating include functional groups having cinnamic acid, maleimide groups, and the like. Examples of functional groups having cinnamic acid include a cinnamoyl group, a cinnamylideneacetyl group, a chalcone group, and a styrylpyridine group. Maleimide groups include a maleimide group, an α-phenylmaleimide group, and the like.

  The terminal structure W that can be crosslinked only by light irradiation or by light irradiation and heating can be specifically introduced by the following method, for example. For example, cinnamic acid can be introduced into the terminal structure W by reacting cinnamic acid chloride with the amine terminal of polyimide. For example, maleimide group can be introduced into the terminal structure W by reacting maleic anhydride with the amine terminal of polyimide.

  A functional group that can be crosslinked only by light irradiation in the presence of a base derived from the photobase generator (A) or by light irradiation and heating is one that can form a crosslinked structure with an amine and the functional group, or an amine. Becomes a catalyst and can form a crosslink between the functional groups. Specific examples include a carboxyl group, an ethylenically unsaturated double bond, and an acetylenically unsaturated bond.

（式中Ｒ^６はｂ若しくはβで表される２価の有機基である。）

（式中Ｒ^７はエチレン性不飽和二重結合又はアセチレン性不飽和結合を含有する２価の有機基である。） Specific examples of the terminal structure W that can be crosslinked only by light irradiation in the presence of a base derived from the photobase generator (A) or by light irradiation and heating include, for example, formula (11) or formula (12). Or Formula (13) etc. are mentioned.

(In the formula, R ⁶ is a divalent organic group represented by b or β.)

(In the formula, R ⁷ is a divalent organic group containing an ethylenically unsaturated double bond or an acetylenic unsaturated bond.)

R ⁴ in the formula (11) is a trivalent aromatic or aliphatic organic group, and can be introduced by end-capping the amine terminal with a tricarboxylic acid anhydride. The tricarboxylic acid anhydride is, for example, trimellitic anhydride or hexahydro trimellitic anhydride.

R ⁵ in the formula (12) is a divalent aromatic or aliphatic organic group, and is introduced by end-capping the acid anhydride terminal with a compound having a carboxyl group and an amino group in the same molecule. can do. Examples of such compounds include amino acids and aminobenzoic acids. An amino acid is, for example, glycine, alanine, parin, leucine, isoleucine, phenylalanine, proline whose substituent on the alpha carbon is a hydrogen or alkyl group; serine, threonine, tyrosine where the substituent on the alpha carbon contains a hydroxyl group; alpha Substituents on carbon are cysteine and methionine containing an S atom; aspartic acid and glutamic acid having two carboxyl groups. Aminobenzoic acids include o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and the like.

R ⁷ in the formula (13) is a divalent organic group containing an ethylenically unsaturated double bond or an acetylenic unsaturated bond. The ethylenically unsaturated double bond or acetylenically unsaturated bond can be introduced by end-capping the polyimide with an acid anhydride containing an ethylenically unsaturated double bond or acetylenic unsaturated bond. Acid anhydrides containing ethylenically unsaturated double bonds or acetylenically unsaturated bonds are maleic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, cyclohexene dicarboxylic acid anhydride, bicyclo [2,2 , 2] Oct-7-ene-2,3-dicarboxylic anhydride, 4-phenylethylphthalic anhydride and the like.

  When there is no terminal structure W, the polyimide terminal may be sealed with dicarboxylic acid anhydride. Examples of the dicarboxylic anhydride used in this case include phthalic anhydride, phenylethylphthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, methylnorbornane dicarboxylic anhydride, and the like.

  The photosensitive resin composition of the present invention may further contain a photosensitizer (C). When a photosensitizer is included, the decomposition of the photobase generator can be promoted, and the amount of exposure can be reduced. There is no restriction | limiting in particular as a photosensitizer (C), A well-known photosensitizer can be used. For example, aromatic azides such as azidoanthraquinone and azidobenzalacetophenone; coumarin compounds such as coumarin, ketocoumarin, and 3,3′-carbonylbis (diethylaminocoumarin); aromatic ketones such as benzanthrone and phenontolenquinone. , Benzyl, benzophenone, p, p′-tetramethyldiaminobenzophenone, etc .; as aromatic amines, N-phenyldiethanolamine, N-phenylglycine, p-nitroaniline, 2,4-dinitroaniline, 2-chloro-4- Nitroaniline, 2,6-dinitro-4-nitroaniline, mihira-ketone and the like; thioxanthone compounds as thioxanthone, diethylthioxanthone, isopropylthioxanthone; aromatic hydrocarbons as anthracene, Futaren, diphenyl, p- nitro diphenyl; as quinones, anthraquinone, naphthoquinone, benzoquinone, and the like.

  In addition, for example, a coumarin compound having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335; 3-ketocoumarin compound described in JP-A 63-221110; Xanthene dyes described in JP-A Nos. 221958 and 4-219756; pyromethene dyes described in JP-A No. 6-19240; JP-A Nos. 47-2528 and 54-155292 (P-dialkylaminobenzylidene) ketone and styryl dye described in JP-A-56-166154 and JP-A-59-56403; having a julolidyl group described in JP-A-6-295061 Sensitizing dyes; and diaminobenzene compounds described in JP-A-11-326624. . Of these, compounds having absorption in the vicinity of 300 to 450 nm are preferable, and specifically, benzophenones, coumarin compounds, thioxanthone compounds, aromatic ketones, and Michler-ketones are preferable. The amount of the photosensitizer used is not particularly limited, but it is preferable to mix 1 part by weight to 50 parts by weight with respect to 100 parts by weight of the soluble polyimide in consideration of photosensitivity and mechanical properties of the resin after curing. . More preferably, it is 3 to 30 parts by weight.

  The photosensitive resin composition of the present invention may further contain an amidation catalyst (D). When an amidation catalyst is included, the reaction between the generated amine and the carboxyl group in the soluble polyimide is promoted, so that the heating temperature after exposure and development can be lowered.

  As the amidation catalyst (D), for example, a compound that forms an active ester with a carboxyl group in soluble polyimide, or a compound that can increase the electrophilicity of the carboxyl group can be used. Examples of such compounds include boroxine compounds, N-hydroxy compounds, tertiary amines, phosphate esters, amine salts, urea compounds, organic acids, Lewis acids, and the like. Examples of boroxine compounds include 2,4,6-tris- (3,4,5-trifluorophenyl) boroxine, 2,4,6-tris- (3-nitrophenyl) boroxine, 2,4,6-tris- (3,5-ditrifluoromethylphenyl) boroxine, 2,4,6-tris- (4-trifluoromethylphenyl) boroxine and the like.

  Examples of the N-hydroxy compound include N-hydroxybenzotriazole, N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxypiperidine and the like. Examples of the tertiary amine include triethylamine, pyridine, 4,4-dimethylaminopyridine, 1,5-diazabicyclo [4,3,0] -5-nonene. Examples of the phosphate ester include (2,3-dihydro-2-thioxo-3-benzoxazolyl) -phosphonic diphenyl ester. Examples of amine salts include 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholium chloride, p-toluenesulfonate of diazabicycloundecene, phenol Salts, octylates, formates, phthalates and the like. Examples of the urea compound include N, N-dimethylurea derivatives and urea compounds containing a urethane group in the same molecule. Examples of the organic acid include benzenesulfonic acid, acetic acid, trifluoroacetic acid, phenol, and the like. Examples of the Lewis acid include boron trifluoride diethyl ether complex. Of these, boroxine compounds are preferred.

  The amount of the amidation catalyst to be used is not particularly limited, but it is preferable to mix 1 part by weight to 20 parts by weight with respect to 100 parts by weight of the soluble polyimide in consideration of photosensitivity and mechanical properties of the cured resin. More preferably, it is 2 to 10 parts by weight.

  A well-known additive can be added to the photosensitive resin composition of this invention as needed. Specifically, adhesion improvers, surfactants, antioxidants, UV inhibitors, light stabilizers, plasticizers, waxes, fillers, pigments, dyes, foaming agents, antifoaming agents, dehydrating agents, charging Inhibitors, antibacterial agents, antifungal agents, flame retardants, leveling agents, dispersants, radical polymerization initiators, ethylenically unsaturated compounds, and the like.

  Although the photosensitive resin composition of this invention may be used in the state of a solution, it is preferable to form a film. When forming a film, a photobase generator (A), a polyimide (B), a photosensitizer (C) if necessary, and an amidation catalyst (D) if necessary are mixed in an arbitrary solvent. Then, it can obtain by drying by arbitrary methods.

  The film comprised with the resin composition of this invention can be processed into the laminated film which comprises a carrier film. The laminated film may include a cover film.

  As a carrier film, arbitrary carrier films, such as a polyethylene terephthalate film and a metal film, can be used, for example.

  As the cover film, for example, any antifouling film such as a low-density polyethylene film or a protective film can be used.

  A circuit board can be produced using the photosensitive resin composition of the present invention. The step of manufacturing a circuit board includes a step of laminating a resin composition layer on a substrate having at least wiring, a step of pattern exposure on the resin composition layer, and a resin composition layer after the pattern exposure. A development process using an alkaline aqueous solution, and a curing process after development. The base material having wiring has, for example, wiring on an arbitrary base material such as a hard base material such as a glass epoxy substrate or a glass maleimide substrate, or a flexible base material such as a polyimide film.

  Especially, the photosensitive resin composition of this invention can be used suitably as a coverlay of the flexible printed wiring board which has wiring on a flexible base material.

  As a substrate of the flexible printed wiring board, a flexible base material such as a polyimide film can be used. When using the photosensitive resin composition of the present invention as a cover lay of a flexible printed wiring board, for example, a coating solution obtained by dissolving the photosensitive resin composition of the present invention in a solvent is applied to a substrate having wiring. It can be applied to the substrate or processed into a so-called film or laminated film formed by drying the coating solution, and then applied onto the substrate.

  When preparing a coating liquid, it can prepare using a solvent, for example. As the solvent, for example, general organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, and γ-butyrolactone can be used. Moreover, the synthesized polyimide solution can be used as it is for the coating solution.

  Examples of the method for applying the coating liquid containing the photosensitive resin composition of the present invention onto the substrate having wiring include methods such as dipping, casting, spraying, screen printing, and spin coating. It is done. By such a method, a coating liquid is applied on a substrate having wiring, and a coverlay is formed on the substrate having wiring by heating and drying most of the solvent. Thus, a flexible printed wiring board comprising: a base material having wiring; and a coverlay formed on the base material so as to cover the wiring and made of the photosensitive resin composition of the present invention. Can be produced.

  In the case of producing a film or a laminated film, the coating solution is applied on an arbitrary carrier film such as a polyethylene terephthalate film or a metal film by an arbitrary method, and then dried to form a dry film. Thus, it can be set as the laminated | multilayer film containing a carrier film and a dry film. Moreover, it is good also as a laminated film by providing at least 1 layer of cover films, such as arbitrary antifouling films, such as a low density polyethylene film, and a protective film, on a dry film. Further, the carrier film and / or the cover film may be peeled off from the laminated film to form a film.

  The dry film composed of the photosensitive resin composition of the present invention is laminated on a substrate having wiring by an arbitrary method such as a thermal laminating method, a hot pressing method, or a thermal vacuum laminating method. Thus, a flexible printed wiring board comprising: a base material having wiring; and a coverlay formed on the base material so as to cover the wiring and made of the photosensitive resin composition of the present invention. Can be produced.

  Although there is no restriction | limiting in particular in the film thickness of the coverlay formed by these methods, From points, such as a circuit characteristic, it is preferable that it is 4-50 micrometers, It is more preferable that it is 6-40 micrometers, 10-30 micrometers It is particularly preferred.

  When using a photosensitive film as the coverlay, at least a step of forming a resin composition layer on a substrate having wiring, a step of pattern exposure on the resin composition layer, and a resin composition after the pattern exposure And a step of developing the physical layer using an alkaline aqueous solution.

  The photosensitive resin composition of the present invention can be developed with an alkaline aqueous solution by causing a difference in solubility or / and a difference in dissolution rate between an irradiated part and an unirradiated part only by light irradiation or by light irradiation and heating. Since it is a certain negative photosensitive resin composition, the cover lay composed of this photosensitive resin composition is irradiated with light through a negative mask on which a desired pattern is drawn, and then heated as necessary.

  Next, the unexposed portion is dissolved and removed with a suitable alkaline developer, and then post-cured to produce a desired pattern. Thereby, the coverlay of the flexible printed wiring board conventionally punched mechanically can be processed with light.

  The light source used for light irradiation is not particularly limited, and examples thereof include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser. Among these, a high-pressure mercury lamp and an ultrahigh-pressure mercury lamp that can efficiently irradiate light having a wavelength of 200 nm to 500 nm are preferable.

  The temperature for heating after light irradiation and before development is preferably 160 ° C. or less from the viewpoint of developability. Heating may be performed in either an air atmosphere or a nitrogen atmosphere. Moreover, there is no restriction | limiting in particular as a heating method, However, It can carry out using oven, a baking furnace, a hotplate, etc.

  The aqueous alkali solution used for development is not particularly limited, and examples thereof include an aqueous sodium carbonate solution, an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, and an aqueous tetramethylammonium hydroxide solution. The development method is not particularly limited, and examples thereof include immersion development, paddle development, and spray development.

  The post-cure temperature is preferably from 100 ° C. to 200 ° C. from the viewpoint of not damaging the wiring on the substrate. More preferably, it is 120 degreeC or more and 180 degrees C or less. Post-cure may be performed in either an air atmosphere or a nitrogen atmosphere. Moreover, there is no restriction | limiting in particular as a post-cure method, However, It can carry out using oven, a baking furnace, a hotplate, etc.

  The present invention is not limited to the embodiment described above, and can be implemented with various modifications. It is not limited to this about the numerical value and component in the said embodiment, It is possible to change suitably and to implement. In addition, various modifications can be made without departing from the scope of the present invention.

  The present invention can be applied to a patterning process using photolithography capable of alkali development.

Claims (13)

A photosensitive resin composition containing a photobase generator (A) and a soluble polyimide (B), wherein the photobase generator (A) contains an acyloxyimino group represented by formula (1). A photosensitive resin composition comprising a compound and / or a compound containing a carbamoyloxyimino group represented by formula (2).

(In the formula, X represents a — (CH ₂ ) _n — group, an alicyclic group, an arylene group, a — (CH ₂ ) _n — group and an alicyclic group, or — (CH ₂ ) _n — group. And an arylene group bonded to each other, n is an integer of 2 to 7, and R ¹ is an aromatic group or a substituted alkyl group)

(In the formula, Y represents a — (CH ₂ ) _m — group, an alicyclic group, an arylene group, a group in which a — (CH ₂ ) _m — group and an alicyclic group are bonded, and a — (CH ₂ ) _m — group. And an arylene group bonded to each other, m is an integer of 2 to 7, and R ² is an aromatic group or a substituted alkyl group)   The photosensitive resin composition is a negative that can be developed with an alkaline aqueous solution by causing a difference in solubility or / and a difference in dissolution rate between an irradiated part and an unirradiated part only by light irradiation or by light irradiation and heating. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a type photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the soluble polyimide (B) is a soluble polyimide containing a repeating unit represented by the formula (3).

(In the formula, α is a tetravalent organic group, β is a divalent organic group having at least one carboxyl group, and b is a divalent organic group. The plural αs may be the same or different. x represents an integer of 1 or more, and y represents an integer of 0 or more)   The photosensitive resin composition according to claim 1, wherein the soluble polyimide (B) contains a silicone chain. The photosensitive resin composition is represented by the formula (4), wherein the soluble polyimide (B) has a terminal structure W having a functional group that can be crosslinked only by light irradiation or by light irradiation and heating. The photosensitive resin composition according to claim 3, wherein the photosensitive resin composition is characterized by the following.

(Α, β, b, x, and y in the formula are the same as those in the formula (3))   The photosensitive resin composition according to any one of claims 1 to 5, wherein the photosensitive resin composition further contains a photosensitizer (C).   The photosensitive resin composition according to any one of claims 1 to 6, wherein the photosensitive resin composition further contains an amidation catalyst (D).   A film comprising the photosensitive resin composition according to claim 1.   A laminated film comprising: a carrier film; and the film according to claim 8 provided on the carrier film.   The laminated film according to claim 9, further comprising a cover film formed on the film.   A circuit board comprising a coverlay formed using the film according to claim 8 or the laminated film according to claim 9 or 10.   Using the photosensitive resin composition according to any one of claims 1 to 7, at least a step of forming a resin composition layer on a substrate having wiring, and pattern exposure on the resin composition layer And a step of developing the resin composition layer after the pattern exposure using an alkaline aqueous solution, and a step of curing the resin composition layer after the development treatment. A method of manufacturing a circuit board.   A step of laminating at least the film according to claim 8 or the laminated film according to claim 9 or 10 on a substrate having wiring to form a resin composition layer; and A method for producing a circuit board, comprising: a step of performing pattern exposure; and a step of performing development processing using an alkaline aqueous solution on the resin composition layer after the pattern exposure.