JP2012247560A - Alkali-developing type photosensitive resin composition, and photosensitive film and resist using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali-developing type photosensitive thermosetting resin composition from which such a coating film can be formed, the alkali-developing type photosensitive thermosetting resin composition having high flame retardancy and excellent plasticity, resolution, heat resistance, moisture resistance, adhesiveness, chemical resistance and the like.SOLUTION: The alkali-developing type photosensitive resin composition comprises: (A) a resin component having a (meth)acryloyl group and a carboxyl group in one molecule and soluble with a diluted alkali solution; (B) a base polymer component; (C) a photopolymerizable monomer having at least on ethylenically unsaturated group; (D) a photopolymerization initiator; (E) a heat-resistant aluminum hydroxide; (F) a (meth)acryl group-containing phosphorus compound expressed by general formula (1) (where Rrepresents H or CH); and (G) a phosphazene compound.

Description

  The present invention relates to an alkali developing type photosensitive resin composition, and a photosensitive film and a resist using the same.

  Conventionally, a flexible printed circuit board (FPC) is formed by press punching and laminating an insulating film in which a low-shrinkage thermosetting resin is bonded via an adhesive to a polyimide film called a coverlay. By thermosetting, it was used as a cover layer on the surface of the flexible substrate on which the circuit was formed. Since this cover lay is composed of a low shrinkage thermosetting resin based on a polyimide film, the warpage after lamination and press curing is very small. The warpage during the reflow of the mounting can be extremely reduced, and it is used in a large amount for FPC applications.

  However, since punching is performed with a press, fine processing is difficult, and there is a disadvantage that alignment accuracy is not good when laminating with a circuit board on which a circuit is formed. In contrast, an alkali-developable photosensitive resin composition and a dry film thereof have been proposed as a photosensitive coverlay (see, for example, Patent Document 1).

  On the other hand, since FPC is mounted on an electronic device, there is a demand for flame retardancy. Along with this, solder resist for FPC is also required to be flame retardant. The FPC is usually a polyimide substrate and is a thin film unlike a printed wiring board of a glass epoxy substrate. However, since the solder resist to be applied has the same film thickness for both the printed wiring board and the FPC, in the case of FPC, the burden of flame retarding on the solder resist is relatively increased. On the other hand, a composition of a solder resist for FPC having a compound having an unsaturated double bond polymerizable with a halogenated aromatic ring has been proposed (see, for example, Patent Document 2). From the viewpoint of

  Furthermore, in recent years, organophosphorous flame retardants have been used in place of brominated flame retardants in response to environmental problems. However, this organophosphorus flame retardant is not so excellent in flame retardant properties, and when adding equivalent flame retardancy to the resin composition, the amount added is higher than that of bromine flame retardant. Therefore, there are problems such as deterioration of characteristics and bleeding of the composition.

  In order to improve such characteristics, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- is used as a flame retardant for the photosensitive resin composition based on epoxy acrylate resin and epoxy resin. Addition of oxide or 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof has been studied (for example, Patent Document 3).

  Moreover, 6-H-dibenzo [c, e] [1, which is a thermosetting phosphorus atom-containing epoxy monomer as a flame retardant, for a photosensitive resin composition having a carboxy-modified epoxy (meth) acrylate resin as a base polymer. 2] Attempts have been made to add oxaphospholine-6- [2,5-bis (oxiranylmethoxy) phenyl] -6-oxide (see, for example, Patent Document 4).

  However, even in a photosensitive resin composition containing such a specific organic flame retardant, sufficient flame retardancy cannot be obtained.

From such a viewpoint, studies on inorganic flame retardants are in progress. Among inorganic flame retardants, aluminum hydroxide (Al (OH) ₃ ) is particularly rich in structural water and has excellent flame resistance, as well as excellent acid resistance and alkali resistance, and is advantageous in terms of cost. It is widely used. Regarding the flame retardant properties of this aluminum hydroxide, it is known that dehydration starts gradually from about 200 ° C. and dehydrates all at once from around 230 ° C. to 250 ° C. However, when this is used for a printed circuit board, the environmental temperature when soldering on the electronic board is about 230 ° C., so that the aluminum hydroxide is dehydrated and the yield of the electronic board may be reduced.

Under such circumstances, it is conceivable to use other inorganic flame retardant having a high dehydration temperature. However, for example, boehmite (AlO (OH)) has a dehydration peak at about 500 ° C. and seems to be advantageous, but has a drawback that the amount of dehydration is small due to a small amount of structural water. Magnesium hydroxide (Mg (OH) ₂ ) has a high dehydration temperature peak of about 380 ° C., but has strong alkalinity and easily deteriorates the synthetic resin, and also lacks acid resistance. In addition to being unusable, there is a drawback that it is easily dissolved when etching with an acid in electronic device parts. Also, in high humidity conditions, magnesium hydroxide absorbs carbon dioxide in the air and turns into basic carbonate, causing a whitening phenomenon on the resin surface containing the flame retardant magnesium hydroxide, which in turn affects the product characteristics. Has drawbacks.

JP 2000-131836 A Patent 2007-10794 JP 2001-72835 A JP 2007-147720 A

  An object of the present invention is an alkali development type photosensitive thermosetting type which has a high flame retardancy and can form a film excellent in plasticity, resolution, heat resistance, moisture resistance, adhesion, chemical resistance and the like. It aims at providing a resin composition.

  As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that a heat-treated aluminum hydroxide and phosphorus compound are contained in the resin composition of the alkali development type photosensitive thermosetting resin composition. The present invention has been completed by finding that the above-mentioned problems can be solved by using together.

（但し、Ｒ^１はＨまたはＣＨ₃ である。）と、
（Ｇ）ホスファゼン化合物とを含むことを特徴とする。 That is, the alkali development type photosensitive thermosetting resin composition of the present invention is:
(A) a resin component having a (meth) acryloyl group and a carboxyl group in one molecule and soluble in a dilute alkali solution;
(B) a base polymer component;
(C) a photopolymerizable monomer having one or more ethylenically unsaturated groups;
(D) a photopolymerization initiator;
(E) heat resistant aluminum hydroxide;
(F) a (meth) acryl group-containing phosphorus compound represented by the general formula (1),

(Where R ¹ is H or CH ₃ );
(G) a phosphazene compound.

  According to the present invention, an alkali development type photosensitivity that can form a film having high flame retardancy and excellent electrical properties such as plasticity, resolution, heat resistance, moisture resistance, adhesion, and electromigration. A thermosetting resin composition can be provided.

Hereinafter, the present invention will be described in detail.
The resin component soluble in the diluted alkaline solution (A) used in the present invention has a (meth) acryloyl group and a carboxyl group in one molecule, and is soluble in the diluted alkaline solution. In this component, the (meth) acryloyl group in the molecule is polymerized by radicals generated from the photopolymerization initiator (E) described later by irradiation with active energy rays such as ultraviolet rays. As a result, the resin composition is It has an insolubilizing function.

  Examples of the resin component soluble in the (A) dilute alkali solution include, for example, epoxy acrylate obtained by esterifying (meth) acrylic acid with an epoxy resin to modify acrylic, and adding an acid anhydride. A compound (for example, an epoxy acrylate oligomer) is mentioned.

  As said epoxy resin, a well-known epoxy resin can be used, and especially a general bisphenol-type epoxy resin etc. can be used preferably. Moreover, as (meth) acrylic acid, acrylic acid, methacrylic acid, and a mixture thereof can be used. Furthermore, acid anhydrides include phthalic anhydride, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, methylendomethylene. Tetrahydrophthalic anhydride or the like can be used, and succinic anhydride or phthalic anhydride is particularly preferable.

  In addition, (A) a resin component soluble in a dilute alkaline solution includes a polyol compound and a polybasic acid anhydride containing a base such as an amino group having two anhydrides in the molecule, and one in the molecule. It is also possible to use a carboxyl group-containing urethane compound (for example, a carboxyl group-containing urethane oligomer) obtained by reacting (meth) acrylic acid having an epoxy group.

  The resin component soluble in the (A) dilute alkaline solution of the present invention preferably has an acid value in the range of 50 to 200 mg KOH / g. (A) If the acid value of the resin component as a component soluble in the dilute alkali solution is less than 50 mgKOH / g, the alkali solubility is lowered and alkali development becomes difficult, and if it exceeds 200 mgKOH / g, the alkali development type When used as a photoresist, film loss during development increases and resolution may be significantly reduced. (A) The acid value of the resin component soluble in the dilute alkali solution is more preferably in the range of 80 to 150 mgKOH / g.

  (A) As a compounding quantity of the resin component soluble in a dilute alkali solution, it is preferable that it is 20-70 mass% with respect to the whole photosensitive thermosetting resin composition of this invention.

  The base polymer which is the component (B) of the present invention, so-called binder polymer, is, for example, acrylic resin, polyurethane, epoxy resin, phenoxy resin, polyester, polyamide, polyimide, polyamideimide, polyesterimide, polycarbonate, melamine resin, polyphenylene sulfide, And known resins such as polyoxybenzoyl and acid-modified resins thereof having a carboxyl group in the molecule. Among them, those obtained by polymerizing a monomer (polymerizable monomer) having an ethylenically unsaturated double bond (such as radical polymerization) are more preferable because they themselves function as a photosensitive prepolymer. .

  Examples of the monomer having an ethylenically unsaturated double bond include acrylamide such as diacetone acrylamide, esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether, alkyl (meth) acrylate, (meth ) Acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2 , 2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, and β -(Meth) such as styryl (meth) acrylic acid Maleic monomers such as crylic acid monomers, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, Examples include itaconic acid, crotonic acid, and propiolic acid. These can be used alone or in combination of two or more.

  Among the above-mentioned resins, the base polymer is preferably an acrylic resin from the viewpoint of high photosensitivity and easy formation of a resist shape after photocuring. The acrylic resin can be obtained by radical polymerization using, for example, (meth) acrylic acid and (meth) acrylic acid alkyl ester as a copolymerization component. In particular, a vinyl copolymer compound obtained by using methacrylic acid, an alkyl (meth) acrylate and a vinyl monomer as a copolymerization component is preferable.

  Examples of (meth) acrylic acid alkyl esters include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester. Examples include esters, (meth) acrylic acid hexyl esters, (meth) acrylic acid heptyl esters, (meth) acrylic acid octyl esters, and (meth) acrylic acid 2-ethylhexyl esters.

  Examples of vinyl monomers include (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, methacrylic acid glycidyl ester, and 2,2,2-trifluoroethyl. (Meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate acrylamide, diacetone acrylamide, styrene, vinyltoluene and the like.

  Moreover, what contains the acrylic acrylate which has an ethylenically unsaturated group as a copolymerization component as a vinyl-type copolymer compound which is an acrylic resin is applicable.

  As the base polymer, an acid-modified polyester resin is also preferable. Examples of the acid-modified polyester resin include a chain structure including an ester bond formed by a polymerization reaction between a diglycidyl ether type epoxy compound and a dibasic acid using a tertiary amine having a pKa of 9.0 or less as a catalyst. And a resin having a carboxyl group formed by adding an acid anhydride to this chain structure.

  Diglycidyl ether type epoxy compounds for forming this acid-modified polyester resin include bisphenol A type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F type epoxy resins such as bisphenol F diglycidyl ether, and bisphenol S diester. Bisphenol S type epoxy resins such as glycidyl ether, biphenol type epoxy resins such as biphenol diglycidyl ether, bixylenol type epoxy resins such as bixylenol diglycidyl ether, hydrogenated bisphenol A type epoxy resins such as hydrogenated bisphenol A glycidyl ether, These dibasic acid-modified diglycidyl ether type epoxy resins and the like can be mentioned. Among these, bisphenol A type epoxy resins are preferable because they are excellent in heat resistance and chemical resistance and do not relatively shrink due to curing. These can be used alone or in combination of two or more.

  From the viewpoint of improving the alkali developability, the acid value of the binder polymer is preferably 50 to 170 mgKOH / g, for example 70 to 150 mgKOH / g in the case of an acrylic or acid-modified polyester binder polymer. More preferably, it is more preferably 90 to 130 mgKOH / g.

  The weight average molecular weight (Mw) of the binder polymer is preferably 20000 to 150,000, more preferably 40000 to 130,000, from the viewpoint of improving the coating properties and alkali developability of the photosensitive resin composition. More preferably, it is 60000-120,000. The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) (in terms of standard polystyrene).

  (B) As a compounding quantity of a binder polymer, when the resin component soluble in a (A) dilute alkali solution is 100 mass parts, it is preferable that it is 20-60 mass parts.

  The photopolymerizable monomer which is the component (C) of the present invention is a compound having one or more ethylenically unsaturated groups in the molecule. Examples of such photopolymerizable monomers include bisphenol A (meth) acrylate compounds, compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, and glycidyl group-containing compounds with α, β- Examples thereof include a compound obtained by reacting an unsaturated carboxylic acid, a urethane monomer such as a (meth) acrylate compound having a urethane bond in the molecule, or a urethane oligomer. Besides these, nonylphenoxy polyoxyethylene acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxy Examples thereof include phthalic acid compounds such as alkyl-o-phthalate, (meth) acrylic acid alkyl esters, and EO-modified nonylphenyl (meth) acrylate. These may be used alone or in combination of two or more.

  The photopolymerizable monomer as the component (C) contributes to adhesion and heat resistance through photocrosslinking.

  Among the above-described components, the component (C) preferably contains a bisphenol A (meth) acrylate compound from the viewpoint of improving alkali developability. Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). ) Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Is mentioned.

  Among those exemplified, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is more preferable. Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl), 2,2- Bis (4-((meth) acryloxydodecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl), 2,2-bis (4-((meth) acrylic) Loxytetradecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl), and 2,2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) Etc. You may use these individually or in combination of 2 or more types.

  Among the above compounds, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.) or BPE-500 (Shin Nakamura Chemical Co., Ltd.). ), Commercially available as trade name), and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) is BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) It is commercially available.

  Examples of 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl ) Propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl), 2,2-bis (4- ( (Meth) acryloxytetradecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl), and 2,2-bis (4-((meth) acryloxyhexadeca) Propoxy) phenyl) and the like. These may be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydibutoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytributoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrabutoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaboxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexabutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptavoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctabutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonabutoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecabutoxy) phenyl), 2,2-bis (4-((meth) acryloxyundecabutoxy) phenyl), 2,2- Bis (4-((meth) acryloxide decabutoxy) phenyl), 2,2-bis (4-((meth) acryloxytridecabutoxy) phenyl), 2,2-bis (4-((meth) acryl Loxytetradecabutoxy) phenyl), 2,2-bis (4-((meth) acryloxypentadebutoxy) phenyl), and 2,2-bis (4-((meth) acryloxyhexadecabutoxy) phenyl) Etc. These may be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, Examples include 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane. . These can be used alone or in combination of two or more.

  In the component (C), examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups. Polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, Methylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO / PO modified trimethylolpropane tri (meth) Acrylate, tetra Examples include methylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.

“EO” refers to “ethylene oxide”, and “PO” refers to “propylene oxide”. Further, “EO modified” means having a block structure of ethylene oxide units (—CH ₂ —CH ₂ —O—), and “PO modified” means propylene oxide units (—CH ₂ —CH ₂ —CH _{2). -O -, - CH 2 (CH} 3) means having a block structure of _CH 2 -O-).

  Furthermore, in the component (C), examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2- Bis (4- (meth) acryloxy-2-hydroxy-propyloxy) phenyl and the like can be mentioned. Examples of the α, β-unsaturated carboxylic acid for obtaining the above compound include (meth) acrylic acid.

  In the component (C), as the urethane monomer or urethane oligomer such as a (meth) acrylate compound having a urethane bond in the molecule, for example, a (meth) acryl monomer having an OH group at the β-position, isophorone diisocyanate, Addition reaction products with diisocyanate compounds such as 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, Examples include EO-modified urethane di (meth) acrylate, EO or PO-modified urethane di (meth) acrylate, and the like.

  Furthermore, examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid 2-ethylhexyl ester. Can be mentioned. These (b) components can be used individually by 1 type or in combination of 2 or more types.

  (C) As a compounding quantity of a photopolymerization monomer, it is preferable that it is 20-40 mass parts with respect to 100 mass parts of the resin component soluble in (A) dilute alkali solution.

  Examples of the photopolymerization initiator as the component (D) of the present invention include benzophenone, N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4- Aromatic ketones such as morpholinophenyl) -butanone-1 and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 4,4'-bis (dimethylamino) benzophenone (Michererketone) ), 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-morpholinophenone) -butanone-1,2-ethylanthraquinone, and phenanthrene Aromatic ketones such as quinone, benzoin methyl ether, benzoin ethyl Ethers, benzoin ethers such as benzoin phenyl ether, benzoins such as methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o -Chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, etc. 2,4,5-triarylimidazole dimer, 9-phenylacridine and 1 7- bis (9,9 ' - acridinyl) acridine derivatives such as heptane, N- phenylglycine, N- phenylglycine derivatives, coumarin-based compounds. These can be used singly or in combination of two or more.

  (D) It is preferable that the compounding quantity of a photoinitiator is the range of 1-20 mass parts with respect to 100 mass parts of the resin component soluble in the (A) dilute alkali solution.

  The (E) heat-resistant aluminum hydroxide used in the present invention can be produced as described in WO 2004/080808. Specifically, an aluminum hydroxide and a reaction retarder for delaying boehmite formation can be obtained by pressurizing and heating in hot water or in a steam atmosphere. The reaction under hot water means that the aluminum hydroxide and the reaction retarder are heat-treated in a pressure vessel such as an autoclave in the presence of water. For the reaction by pressurization and heating in a steam atmosphere, pressurize aluminum hydroxide and reaction retarder in a pressure vessel such as an autoclave in the absence of water or in the presence of a very small amount of water. Means.

  The heat-resistant aluminum hydroxide of the present invention includes a mixture in which boehmite is partially advanced and aluminum hydroxide and boehmite are mixed, but preferably the total dehydration amount is 30% or more. More preferably, the boehmite conversion rate is 14% or less and the total dehydration amount is 32% or more. Most preferably, the boehmite conversion rate is 0% and the total dehydration amount is 35%.

  The heat-resistant aluminum hydroxide of the present invention preferably has a 1% by mass dehydration temperature of 255 ° C. or more and a total dehydration amount of 30% or more. In this case, the average particle size of the starting aluminum hydroxide is 2 It is preferable that it is 5 μm or less.

  Here, the 1% by mass dehydration temperature refers to the temperature at which 1% by mass of structural water dehydrates with respect to the total mass of aluminum hydroxide, and the total dehydration amount refers to the dehydration of the structural water contained in aluminum hydroxide. It means the amount of water dehydrated.

  (E) The heat-resistant aluminum hydroxide is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the resin component soluble in the (A) dilute alkali solution.

  The (F) (meth) acryl group-containing phosphorus compound used in the present invention is represented by the general formula (1). This (F) (meth) acryl group-containing phosphorus compound contributes to flame retardancy, heat resistance, moisture resistance and electrical properties.

（但し、Ｒ^１はＨまたはＣＨ₃ である。）で表される。
具体的には、下記［化２］、［化３］が挙げられる。

(However, R ¹ is H or CH ₃ ).
Specifically, the following [Chemical 2] and [Chemical 3] are mentioned.

  Here, the blending amount of the (F) (meth) acrylic group-containing phosphorus compound is preferably in the range of 5 to 50 parts by mass with respect to 100 parts by mass of the resin component soluble in the (A) dilute alkali solution.

  The (F) (meth) acrylic group-containing phosphorus compound is a known compound as described in, for example, JP-A-7-48394.

（但し、式中、Ｒ^２及びＲ^３は、それぞれ水素原子又はハロゲンを含まない１価の有機基であり、ｎは３〜１０の整数である。）を挙げることができ、このとき、Ｒ^２ 及びＲ^３の１価の有機基としてはフェニル基、アルキル基、アミノ基、アリル基等の基が好ましいものとして挙げられる。また、一般式（４）の末端基としては、水素原子、水酸基、アルキル基、アルコキシル基、アリールオキシ基、シアネート基等が挙げられる。 The (G) phosphazene compound used in the present invention contributes to flame retardancy, and a known phosphazene compound can be used. For example, it is represented by the following general formulas (4) and (5). Phosphazene oligomer

(Wherein, R ² and R ³ are each a monovalent organic group not containing a hydrogen atom or halogen, and n is an integer of 3 to 10). Preferred examples of the monovalent organic group of ² and R ³ include a phenyl group, an alkyl group, an amino group, and an allyl group. Moreover, as a terminal group of General formula (4), a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxyl group, an aryloxy group, a cyanate group etc. are mentioned.

  More preferable phosphazene compounds include phosphazene oligomers such as propoxyphosphazene oligomers, phenoxyphosphazene oligomers, methylphenoxyphosphazene oligomers cyanate phenyl phosphazene oligomers, and cyanophenoxyphosphazene oligomers.

  As these (G) phosphazene compounds, phosphazene compounds having a thermal decomposition temperature of 250 ° C. or higher or a melting point of 80 ° C. or higher can be preferably used from the viewpoint of heat resistance. This (G) phosphazene compound can be used individually or in mixture of 2 or more types.

  And it is preferable that the compounding quantity of this (G) phosphazene compound is 5-50 mass parts with respect to 100 mass parts of (A) resin components soluble in a dilute alkali solution, and it is 5-40 mass parts. Is particularly preferred.

  The photosensitive resin composition of the present invention preferably further contains (H) a block type isocyanate. The block type isocyanate is inactive at room temperature (20 to 30 ° C.), but is a compound that regenerates isocyanate groups by reversibly dissociating the blocking agent when heated. The dissociation temperature of the blocking agent is preferably 120 to 200 ° C.

  Examples of such isocyanate compounds include isocyanurate type, biuret type, and adduct type. Among these, the isocyanurate type is preferable from the viewpoint of improving the adhesion by the photosensitive resin composition. These can be used alone or in combination of two or more.

  In the block type isocyanate compound, examples of the blocking agent bonded to the isocyanate include at least one selected from diketones, oximes, phenols, alkanols and caprolactams. Specific examples include methyl ethyl ketone oxime and ε-caprolactam.

  Examples of such blocked isocyanate compounds include Duranate manufactured by Asahi Kasei Chemicals, Takenate manufactured by Takeshi Mitsui Chemicals, and the like. These can be used alone or in combination of two or more.

  When the insulating property excellent in the photosensitive resin composition is calculated | required, as above-mentioned, as a block type isocyanate, what contains aromatic rings, such as an isocyanuric skeleton and a benzene ring, is preferable in the structure.

  (H) It is preferable that the compounding quantity of block isocyanate is the range of 5-50 mass parts with respect to 100 mass parts of (A) resin components soluble in a dilute alkali solution.

  In addition to the components (A) to (H) described above, the photosensitive resin composition may further include other components according to desired characteristics.

As other components, first, a diluent may be mentioned. By including a diluent, the viscosity of the photosensitive resin composition is adjusted, and application on a predetermined substrate becomes easy. Examples of the diluent include aliphatic alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, n-pentanol and hexanol, hydrocarbons such as benzyl alcohol and cyclohexane, diacetone alcohol, Aliphatic ketones such as 3-methoxy-1-butanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, methyl hexyl ketone, ethyl butyl ketone, dibutyl ketone, ethylene glycol, diethylene glycol, tri Ethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, Ethylene glycol alkyl ethers such as pyrene glycol diacetate, propylene glycol monoethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate And acetate thereof, diethylene glycol monoalkyl ethers and acetate thereof, diethylene glycol dialkyl ethers, triethylene glycol alkyl ethers, propylene glycol alkyl ethers and acetate thereof, and dipropylene glycol alkyl ethers.
Also, petroleum solvents such as toluene, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate Carboxylic acid esters such as ethyl propionate, methyl butyrate, and ethyl butyrate, amines, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone, dimethyl sulfoxide Examples of the diluent include dioxane, tetrahydrofuran, cyclohexanone, γ-butyrolactone, 3-hydroxy-2-butanone, 4-hydroxy-2-pentanone, and 6-hydroxy-2-hexanone. These can be used alone or in combination of two or more.

  Furthermore, if necessary, known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, hydroquinone, hydroquinone monomethyl ether, t-butyl Known and conventional polymerization inhibitors such as catechol, pyrogallol and phenothiazine, known and conventional thickeners such as asbestos, olben, benton and montmorillonite, antifoaming agents such as silicones, fluorines and polymers, leveling agents and imidazoles In addition, known and commonly used additives such as silane coupling agents such as thiazole type and triazole type can be used.

  In addition to the components described above, the photosensitive resin composition of the present invention may further include barium sulfate, barium titanate, silicon oxide powder, for the purpose of improving properties such as adhesion and hardness, Known and commonly used inorganic fillers such as finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, and mica powder can be used.

  The photosensitive film and dry film resist formed by using the photosensitive resin composition of the present invention may be used alone or as a support film (carrier film) on the photosensitive resin composition layer of the present invention. May be used as a photosensitive resin laminate in which a protective film (cover film) is further laminated.

  The support film is not particularly limited as long as it is transparent and flexible and can withstand coating drying. For example, a polyester film such as a polyethylene terephthalate (PET) film, or a stretched polypropylene (OPP) ) A film etc. are mentioned, Preferably it is a PET film.

  The protective film has a role to prevent transfer of the photosensitive resin composition layer having adhesiveness to the support film when the photosensitive resin laminate is rolled, for example, a polyethylene (PE) film, A polyolefin film such as a polypropylene (PP) film, a PET film, a fluororesin (PTFE) film, a polyvinyl alcohol film, a nylon film, or the like is used, and a polyolefin film, particularly a PE film is preferably used. Since the composition layer formed using the photosensitive resin composition of this invention is excellent in vacuum laminating property, the surface roughness of the protective film for ensuring the surface roughness of the composition layer is not particularly limited. In particular, the surface roughness of the protective film can provide more reliable and excellent vacuum laminating properties by using a protective film having an average roughness (Ra) of 1 or more. In addition, the said surface average roughness (Ra) is an average height which remove | divided the area of the roughness curve by the measurement length, as shown by JISB06011994.

  For example, the photosensitive resin laminate may be formed by uniformly coating the photosensitive resin composition of the present invention on one surface of the support film and then drying to form a photosensitive resin composition layer, and then forming a protective film. It can be manufactured by stacking.

  In the photosensitive resin laminate of the present invention, the thickness of the photosensitive resin composition layer varies depending on the thickness of the copper wiring, but is usually preferably 100 μm or less, more preferably 80 μm or less, and particularly preferably 20 to 60 μm. If the thickness of the photosensitive resin composition layer is too thick, curing due to pattern exposure tends to be insufficient at the bottom of the resist, so that there is a tendency for poor adhesion or difficulty in obtaining sufficient resolution.

  The thickness of the support film is preferably 10 to 25 μm. If the thickness of the film is too thin, the resistance of the photosensitive resin laminate itself is inferior, and the support film tends to be broken when peeled off, and if it is too thick, the support film becomes hard, due to its hardness. There is a tendency that the followability of the photosensitive resin composition layer to the conductor circuit is inferior. Moreover, the thickness of a protective film is 10-50 micrometers normally, Preferably it is 15-35 micrometers.

  Next, the manufacturing method of the flexible printed wiring board at the time of using the photosensitive resin laminated body of the said this invention as a soldering resist dry film is demonstrated below.

〔laminate〕
The protective film of the photosensitive resin laminate is peeled off, and the surface of the photosensitive resin composition layer is bonded to a wiring surface of a substrate on which a conductor circuit such as FPC is formed using a laminator. A vacuum laminator is preferably used from the viewpoint of followability to a conductor circuit, and the photosensitive resin composition layer of the laminate of the present invention can be neatly laminated without involving air or the like.

〔exposure〕
Next, the pattern mask is directly contacted (adhered) on the support film on the opposite side of the photosensitive resin composition layer and exposed. In the case of proximity exposure and projection exposure, the pattern mask is exposed in a non-contact state. Furthermore, direct imaging (direct exposure) using a laser may be performed without using a pattern mask. The exposure is usually performed by ultraviolet (UV) irradiation, and as a light source at that time, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, an argon laser, or the like is used.

〔developing〕
After the exposure, the support film on the photosensitive resin composition layer is peeled off, and then the unexposed portion (uncured portion) is dissolved and dispersed by development. When the photosensitive resin composition is a dilute alkali development type, a dilute aqueous solution having an alkali concentration of about 0.3 to 5% by mass such as sodium carbonate or potassium carbonate is used as the developer. In the development, a method of spraying at a uniform pressure is preferable from the viewpoint of resolution and adhesion stability. The alkaline aqueous solution may contain a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like. And after development, it is sufficiently washed with water and dried. By developing, the unexposed resist portion is dissolved to expose the lower copper pattern portion that requires plating or soldering.

[Heat cure]
In order to further enhance characteristics such as surface curability, solder heat resistance, and chemical resistance, a further crosslinking reaction step is performed. The cross-linking reaction step which becomes the thermal cure is usually performed at 100 to 180 ° C. for about 15 to 90 minutes.

In addition, in order to improve characteristics such as surface curability, solder heat resistance, and chemical resistance before heat curing, UV curing (post-exposure) may be performed after sufficiently drying after development. UV cure is usually used at 0.5 to ¹⁰ J / cm ² .

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

(Examples 1-4, Comparative Examples 1-4)

[Preparation of photosensitive film]
First, the solution of the photosensitive resin composition was obtained by mixing the component (1) to the component (7) shown in Table 1 and other components in the solid content (parts by mass) shown in the table. . In the table, ZAR-2000 in component (1) has a (meth) acryloyl group and a carboxyl group in one molecule, and is a resin component soluble in dilute alkali solution (manufactured by Nippon Kayaku Co., Ltd.) , Weight average molecular weight: 11000), which corresponds to the component (A) in the above-described embodiment.

  The resin in component (2) is an acrylic resin, and is a copolymer of methacrylic acid, methyl methacrylate, butyl acrylate, and styrene (methacrylic acid: methyl methacrylate: butyl acrylate: styrene = 25 wt%: 45 wt. %: 15% by weight: 15% by weight) and a weight average molecular weight of 110,000 and an acid value of 125 mgKOH / g. Component (1) corresponds to component (B) in the above-described embodiment.

  BPE-500 in component (3) is bisphenol A polyoxyethylene dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). These correspond to the component (C) in the above-described embodiment.

Furthermore, IRGACURE 819 in component (4) is acylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) and corresponds to component (D) in the above-described embodiment.
Furthermore, ALH in the component (5) is heat-resistant aluminum hydroxide (manufactured by Kawai Lime Industry Co., Ltd., dehydration temperature 260 ° C., total dehydration amount 35% by mass), and corresponds to the component (E) in the above-described embodiment. .

  Moreover, FRM-1000 in the component (6) is a phosphorus-containing monomer (manufactured by Nippon Kayaku Co., Ltd.) and corresponds to the component (F) in the above-described embodiment.

  Furthermore, FP-300 in the component (7) is cyanophenoxyphosphazene (manufactured by Fushimi Pharmaceutical Co., Ltd.) and corresponds to the component (G) in the above-described embodiment.

  Moreover, TPA-B80E in the component (8) is block type isocyanate (manufactured by Asahi Kasei Chemicals Corporation) and corresponds to the component (H) in the above-described embodiment.

  In addition, methyl ethyl ketone was added to these photosensitive resin compositions as a diluent. Next, these photosensitive resin composition solutions were uniformly applied onto a 16 μm polyethylene terephthalate film (product name: G2-16, manufactured by Teijin Limited) as a support, and a hot air convection dryer was used. The photosensitive resin composition layer was formed on the support by using and drying at 100 ° C. for 10 minutes. The film thickness after drying of the photosensitive resin composition layer was 30 μm.

  Subsequently, on the surface of the photosensitive resin composition layer opposite to the side in contact with the support layer, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name NF-15) is bonded as a protective film, and the photosensitive film Got.

[Characteristic evaluation]
Using the photosensitive films prepared in Examples 1 to 4 and Comparative Examples 1 to 4, each of the following tests was performed, and the plating resistance, solder heat resistance, crack resistance when each photosensitive film was used, HAST resistance, laminating properties and resolution were evaluated. The results are summarized in Table 2.

  First, an evaluation substrate was produced as follows using each photosensitive film. That is, first, the copper surface of a copper-clad polyimide film substrate for FPC (copper thickness 18 μm / polyimide film thickness 25 μm)] was polished with an abrasive brush, washed with water, and then dried. Using this printed wiring board substrate and a 12.5μm thick polyimide film (Kapton (registered trademark) 50V, manufactured by Toray DuPont Co., Ltd.) using a vacuum laminator (Nichigo Morton, product name V-130), press heat Under the conditions of a plate temperature of 70 ° C., a vacuum drawing time of 20 seconds, a laminating press time of 30 seconds, an atmospheric pressure of 4 kPa or less, and a pressure bonding pressure of 0.4 MPa, the photosensitive film is peeled and laminated to obtain a laminate for evaluation. It was.

The laminate for evaluation after lamination was irradiated on the entire surface with an exposure amount equivalent to 8 steps of a 21-step tablet made by Stouffer with the 2 kW ultra-high pressure mercury short arc lamp (parallel light), and 1% Na at 30 ° C. Spray development (spray pressure 0.15 MPa) was performed twice with a ₂ CO ₃ aqueous solution for the minimum development time, followed by washing with water and drying. Subsequently, UV irradiation is performed with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd., and further heat treatment is performed at 1700C for 60 minutes, so that the printed circuit board substrate is exposed. An evaluation substrate on which a solder resist was formed was obtained.

<Electroless gold plating resistance>
The evaluation substrate is plated using commercially available electroless nickel plating bath and electroless gold plating bath under the conditions of nickel 0.5 μm and gold 0.03 μm. After evaluating the presence or absence of penetration, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
○: Infiltration and peeling are not seen.
X: There is peeling after soaking and plating.

<Solder heat resistance>
Using the evaluation substrate, solder heat resistance was evaluated as follows. That is, after applying a rosin flux (product name: MH-820V, manufactured by Tamura Kaken Co., Ltd.) to the substrate for evaluation, a soldering treatment was performed in which the substrate was immersed in a 260 ° C. solder bath for 30 seconds.

  The state of occurrence of cracks in the solder resist on the evaluation substrate subjected to solder plating in this way, and the degree to which the solder resist floated from the substrate and peeling were observed with a 100-fold metal microscope. The results were evaluated according to the following criteria. In other words, “O” indicates that no cracking of the solder resist was observed and no solder resist was lifted or peeled off, and “X” indicates that any of them was recognized.

<Lamination>
Using a continuous press type vacuum laminator (product name: MV-130, manufactured by Nichigo Morton Co., Ltd.) on the wiring pattern of the evaluation substrate, the press hot plate temperature is 70 ° C., the evacuation time is 20 seconds, the lamination press time is 30 seconds, and the atmospheric pressure. The polyethylene film of the photosensitive film was peeled off and laminated under conditions of 4 kPa or less and a pressure bonding pressure of 0.4 MPa.

  After the lamination, bubbles between the substrate of the laminate and the photosensitive resin composition layer and between the wiring patterns were visually observed and evaluated according to the following criteria. That is, “O” indicates that no bubbles were observed between the substrate and the photosensitive resin composition layer and between the wiring patterns, and “X” indicates that bubbles were observed.

<Resolution>
A pattern mask (silver salt-PET film) of line / space = 20 μm / 20 μm to 120 μm / 120 μm is brought into intimate contact with the PET film of the evaluation laminate, and the 2 kW ultra-high pressure mercury short arc lamp (parallel light) is used for Stouffer Development was performed by irradiating with an exposure amount equivalent to 8 steps of a 21-step tablet manufactured by the company. At this time, the value of the minimum line width indicating the resolution (the value of the minimum width (μm) between the cured lines formed by development) was defined as the resolution.

<Electrical characteristics>
Using an IPC B-25 comb-type electrode B coupon instead of a copper foil substrate, an evaluation board was prepared under the above conditions, and a bias voltage of DC 100 V was applied to the comb-type electrode, and 85 ° C., 85% R.D. H. The presence or absence of migration after 1,000 hours was confirmed in a constant temperature and humidity chamber. The judgment criteria are as follows.
○: No change at all ×: Migration has occurred

<Flame retardance>
The test was conducted according to the UL94 flame retardant test.

<Bleed resistance>
The substrate for evaluation was exposed to a super accelerated high temperature high humidity life test (HAST) bath for 100 hours under the condition of 121 ° C./85% Rh. After the test, the occurrence of bleeding of the resin component (flame retardant) on each evaluation substrate was observed with a 100 × microscope and evaluated according to the following criteria. That is, “O” indicates that no bleeding occurred in the solder resist (permanent resist film), and “X” indicates that bleeding did not occur.

<Warpage property>
The polyimide film after thermosetting was cut into 5 cm × 5 cm, placed with the printed surface facing up, and the height of the warp of the film was measured.

<Evaluation of flexibility (fold resistance)>
A sample prepared in the same manner as the sample for flame retardancy evaluation is repeatedly bent 180 ° by goblet folding several times, and the occurrence of cracks in the coverlay at that time is observed visually and with a 200 × optical microscope. The number of times it did not occur was evaluated.
The results of each evaluation test are summarized in Table 2.

  As is clear from Table 2, the photosensitive films of Examples 1 to 4 obtained according to the present invention have electroless gold plating resistance (adhesion), solder heat resistance (heat resistance), laminating properties, resolution, difficulty. It can be seen that good characteristics are exhibited in all of flammability, bleed resistance (moisture resistance), warpage and bending resistance. It was also found that the electromigration was excellent in electrical characteristics.

  On the other hand, in the comparative example 1 which does not contain the (G) phosphazene compound of the present invention, the electroless gold plating resistance (adhesion) is inferior and the comparative example which does not contain the (F) (meth) acrylic group-containing phosphorus compound of the present invention. No. 2 was found to be inferior in heat resistance, moisture resistance and electrical properties. Moreover, it turned out that it is inferior to a flame retardance in the comparative example 3 which does not contain the (F) (meth) acryl group containing phosphorus compound and (G) phosphazene compound of this invention. Furthermore, it can be seen that (C) Comparative Example 4 which does not contain a photopolymerizable monomer having an ethylenically unsaturated group is inferior in electroless gold plating resistance (adhesion) and solder heat resistance (heat resistance).

  The present invention has been described in detail based on the above specific examples. However, the present invention is not limited to the above specific examples, and various modifications and changes can be made without departing from the scope of the present invention.

Claims (8)

(A) a resin component having a (meth) acryloyl group and a carboxyl group in one molecule and soluble in a dilute alkali solution;
(B) a base polymer component;
(C) a photopolymerizable monomer having one or more ethylenically unsaturated groups;
(D) a photopolymerization initiator;
(E) heat resistant aluminum hydroxide;
(F) a (meth) acryl group-containing phosphorus compound represented by the general formula (1),

(Where R ¹ is H or CH ₃ );
(G) An alkali-developable photosensitive resin composition comprising a phosphazene compound. The (F) phosphazene compound is a phosphazene oligomer represented by the general formula (2) or (3)

(Wherein R ² and R ³ are each a monovalent organic group not containing a hydrogen atom or halogen, and n is an integer of 3 to 10). 2. The alkali developing type photosensitive resin composition according to 1.   The alkali according to claim 1 or 2, wherein the (B) binder polymer is a vinyl copolymer compound obtained by using (meth) acrylic acid and a (meth) acrylic acid alkyl ester as a copolymerization component. Development type photosensitive resin composition.   The (E) heat-resistant aluminum hydroxide is produced by hydrothermal treatment or pressurizing and heating in a steam atmosphere using a mixture of aluminum oxide and a reaction retarder that delays boehmite formation as a raw material. The alkali development type photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is an alkali development type photosensitive resin composition.   (B) 20 to 60 parts by mass of (B) binder polymer and (C) a photopolymerizable monomer having an ethylenically unsaturated group 20 to 100 parts by mass of the resin component soluble in the (A) dilute alkali solution. 40 parts by mass, 1-20 parts by mass of the (D) photopolymerization initiator, 1-50 parts by mass of the (E) heat-resistant aluminum hydroxide, 5-50 parts by mass of the (F) phosphorus-containing monomer, and the (G 5) The alkali-developable photosensitive resin composition according to any one of claims 1 to 4, which comprises 5 to 50 parts by mass of phosphazene. (H) Block-type isocyanate is contained, The alkali developing type photosensitive resin composition as described in any one of Claims 1-5 characterized by the above-mentioned.   A photosensitive film comprising a support and a layer made of the photosensitive resin composition according to any one of claims 1 to 6 formed on the support.   A resist comprising a photocured product of the photosensitive resin composition according to any one of claims 1 to 6, which is applied onto a substrate for a printed wiring board.