JP2009276526A - Photosensitive resin composition and flexible printed wiring board using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having flame retardancy and low warpage properties in forming into the coverlay of an FPC, without deteriorating flexibility and bendability, wherein it is difficult for the conventional photosensitive resin compositions to have advantages. <P>SOLUTION: The photosensitive resin composition includes a component (A), a component (B) and a component (C). The component (A) is a soluble polyimide, the component (B) is a quinonediazide compound, and a specific compound having an isocyanuric acid ring is used as the component (C), so that the photosensitive resin composition, having flame retardancy and low warpage properties in forming into the coverlay of an FPC without deteriorating flexibility and bendability, is provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition suitable for a coverlay of a flexible printed wiring board and a flexible printed wiring board using the same.

  In recent years, flexible printed wiring boards (hereinafter abbreviated as “FPC”), which are remarkably elongated, have been demanded as materials having excellent flexibility and flexibility as base materials and coverlays. FPC coverlays are desired to have excellent photosensitivity for microfabrication. However, when photosensitivity is imparted, characteristics such as flame retardancy and low warpage when used as an FPC coverlay are impaired.

In order to reduce warpage, negative photosensitive coverlays have been proposed that use a polyimide with a siloxane skeleton and use a monomer such as (meth) acrylate which is a reactive diluent to impart plasticity and photosensitivity. (For example, patent document 1). However, when a siloxane skeleton is introduced, the polyimide resin may reduce flame retardancy. Also, the use of a monomer such as (meth) acrylate is concerned about a decrease in flame retardancy, and further, the monomer may be polymerized and crosslinked to impair flexibility and flexibility.
JP 2003-140339 A

  The present invention has been made in view of the above points, and has a flame retardancy when it is used as an FPC coverlay and low without impairing flexibility and flexibility, which has been difficult with conventional photosensitive resin compositions. It aims at providing the photosensitive resin composition which has curvature property.

（式中Ｒ^１はエチレングリコール鎖及び／又はプロピレングリコール鎖を含む有機基である。複数のＲ^１はそれぞれ同一でも異なっていても良い。） The photosensitive resin composition of the present invention is a photosensitive resin composition containing the component (A), the component (B) and the component (C), wherein the component (A) is a soluble polyimide, ) Component is a quinonediazide compound, and the component (C) is a compound having an isocyanuric acid ring represented by the formula (1).

(In the formula, R ¹ is an organic group containing an ethylene glycol chain and / or a propylene glycol chain. The plurality of R ¹ may be the same or different.)

  In the photosensitive resin composition of the present invention, the component (A) is preferably a soluble polyimide having a siloxane skeleton.

  In the photosensitive resin composition of the present invention, the component (A) is preferably a soluble polyimide having a carboxyl group and / or a hydroxyl group.

  In the photosensitive resin composition of this invention, it is preferable that the said (B) component is a naphthoquinone diazide compound.

（式中Ｒ^２は下記式（３）又は式（４）であり、Ｒ^３はＨ、メチル基、エチル基、プロピル基、ブチル基、イソブチル基から選ばれる有機基である。ｎは１〜１０であり、ｍは１又は２であり、Ｌは１〜１０である。）

In the photosensitive resin composition of the present invention, it is preferable that R ^{1 of the} component (C) is an organic group represented by the formula (2).

(In the formula, R ² is the following formula (3) or formula (4), and R ³ is an organic group selected from H, methyl group, ethyl group, propyl group, butyl group, and isobutyl group. 10 and m is 1 or 2, and L is 1 to 10.)

  In the photosensitive resin composition of this invention, it is preferable to contain a phosphorus-type flame retardant as (D) component, and it is more preferable that (D) component contains a cyclic phosphazene compound.

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

  The laminated film of the present invention comprises a carrier film and the film 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 photosensitive ink of the present invention contains the photosensitive resin composition.

  The flexible printed wiring board of the present invention comprises: a base material having wiring; and a coverlay formed on the base material so as to cover the wiring and configured using the photosensitive resin composition. Features.

  In the flexible printed wiring board of this invention, it is preferable that the said coverlay is a coverlay laminated | stacked using the said film or laminated film.

  In the flexible printed wiring board of the present invention, it is preferable that the coverlay is a coverlay formed using the photosensitive ink.

  The photosensitive resin composition of the present invention is a photosensitive resin composition containing the component (A), the component (B) and the component (C), wherein the component (A) is a soluble polyimide, ) Component is a quinonediazide compound, and the component (C) is a compound having an isocyanuric acid ring represented by the above formula (1), it is difficult to obtain an FPC coverlay without impairing flexibility and flexibility. A photosensitive resin composition having both flammability and low warpage can be provided.

  The present inventors have found that a specific compound having an isocyanuric acid skeleton has both flame retardancy and low warpage without impairing flexibility and flexibility, and have completed the present invention.

  Specifically, the component (C) in the photosensitive resin composition of the present invention includes an organic group capable of exhibiting a warp improving effect of a dry film in its structure and a nitrogen-containing ring capable of exhibiting flame retardancy. Including structure. For this reason, when combined with the soluble polyimide of the component (A), the flexibility and flexibility of the polyimide are not impaired. Therefore, when combined with a photosensitizer such as the quinonediazide compound of component (B), a photosensitive resin composition having both flame retardancy and low warpage can be expressed.

Hereinafter, embodiments of the present invention will be described in detail.
The gist of the present invention is a photosensitive resin composition comprising a combination of (A) component: soluble polyimide, (B) component: quinonediazide compound, and (C) component: a specific compound having an isocyanuric acid ring. It is an object of the present invention to provide a flexible printed wiring board which has a positive type photosensitive dry film or photosensitive ink and a cover lay using the composition and which has a low warpage and flame retardancy.

First, the component (A) will be described.
The component (A) used in the photosensitive resin composition of the present invention uses a resin that is soluble in an organic solvent. As such a resin, polyimide having excellent flexibility is preferable.

  The polyimide is preferably a soluble polyimide that is soluble in the component (B) and the component (C) and / or other additives and a solvent that can be prepared in a solution.

  A soluble polyimide means a polyimide soluble in an organic solvent. Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or an organic solvent and toluene. Examples thereof include mixed solvents. In the present invention, the term “soluble” specifically means that it is dissolved in N-methyl-2-pyrrolidone or γ-butyrolactone at least 5 mass%, preferably 10 mass% or more.

  The structure of the soluble polyimide is not particularly limited, but it is preferable to have a siloxane skeleton in consideration of mechanical properties such as elongation, flexibility and flexibility when formed into a film, and a warp improving effect. The warp improving effect is achieved by blending the component (C), but is considered to be further improved by lowering the elastic modulus and lowering Tg by having a siloxane skeleton.

  Moreover, it is preferable to use alkali-soluble resin from the viewpoint of developability when the photosensitive resin composition is used. For the purpose of imparting alkali solubility to the soluble polyimide, it is preferable to introduce an ester group, a carboxyl group and / or a hydroxyl group into the soluble polyimide. Among them, it is preferable to introduce a carboxyl group and / or a hydroxyl group.

  The soluble polyimide of the present invention can be obtained using, for example, diamine and tetracarboxylic dianhydride as raw materials.

  As the diamine, aromatic diamine and aliphatic diamine can be used. Further, for the purpose of introducing a carboxyl group and / or a hydroxyl group, a diamine having a carboxyl group or a diamine having a hydroxyl group can be used. Moreover, diaminosiloxane can be used for the purpose of introducing a siloxane skeleton.

  As aromatic diamines, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′- Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3, 4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiph Nilketone, 3,4'-diaminodiphenylketone, 4,4'-diaminodiphenylketone, 2,2-bis (3-aminophenyl) propane, 2,2- (3,4'-diaminodiphenyl) propane, 2, 2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4 -Aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-[1,4-phenylenebis (1-methyl) Ethylidene)] bisaniline, 3,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-fluoro Nylenebis (1-methylethylidene)] bisaniline, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfide, Bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,3-bis (4- Aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminopheno) Xyl) heptane.

  Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1, Examples include 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and 1,11-diaminoundecane.

  Examples of the diamine having a carboxyl group include 3,3'-dicarboxy-4,4'-diaminodiphenylmethane and 3,5-diaminobenzoic acid.

  Examples of the diamine having a hydroxyl group include 1,2-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 1,3-diamino-4-hydroxybenzene, 1,4-diamino-6-hydroxybenzene. 1,5-diamino-6-hydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, 1,2-diamino-3,5-dihydroxybenzene, 4- (3,5-diaminophenoxy) phenol, 3- (3,5-diaminophenoxy) phenol, 2- (3,5-diaminophenoxy) phenol, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-diamino-4,4 ′ -Dihydroxybiphenyl, 2,2-bis (4-hydroxy-3-aminophenyl) propane, 2,2-bis (4-hydride) Xyl-3-aminophenyl) hexafluoropropane, bis (4-hydroxy-3-aminophenyl) ketone, 2,2-bis (4-hydroxy-3-aminophenyl) sulfide, 2,2-bis (4-hydroxy) -3-aminophenyl) ether, 2,2-bis (4-hydroxy-3-aminophenyl) sulfone, 2,2-bis (4-hydroxy-3-aminophenyl) methane, 4-[(2,4- Diamino-5-pyrimidinyl) methyl] phenol, p- (3,6-diamino-s-triazin-2-yl) phenol, 2,2-bis (4-hydroxy-3-aminophenyl) difluoromethane, 2,2 -Bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropa Bis (4-amino-3-hydroxyphenyl) ketone, 2,2-bis (4-amino-3-hydroxyphenyl) sulfide, 2,2-bis (4-amino-3-hydroxyphenyl) ether, 2, 2-bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-hydroxyphenyl) methane, 2,2-bis (4-amino-3-hydroxyphenyl) difluoromethane Can be mentioned.

（式（５）において、Ｒ^４は２価の有機基であり、ｋは１〜３０の整数である。Ｒ^４で示される２価の有機基としては、炭化水素基、芳香族基が挙げられる。炭化水素基は、エチレン基、プロピレン基、ブチレン基などである。芳香族基は、フェニレン基などである。） Examples of diaminosiloxane include a compound represented by the formula (5).

(In Formula (5), R ⁴ is a divalent organic group, and k is an integer of 1 to 30. Examples of the divalent organic group represented by R ⁴ include a hydrocarbon group and an aromatic group. (The hydrocarbon group is an ethylene group, a propylene group, a butylene group, etc. The aromatic group is a phenylene group, etc.)

  In the soluble polyimide of component (A), the content of the site derived from diaminosiloxane is preferably 60 mol% or less from the viewpoint of flame retardancy when the site derived from all diamines is 100 mol%.

  These diamine components can be used alone or in combination.

As a preferable diamine component, a diamine component having an ether group or a sulfone group is preferable among aromatic diamines from the viewpoint of solvent solubility. Examples of such diamines include 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, and 4,4′-diaminodiphenylsulfone. In addition, a diamine having a carboxyl group is preferred from the viewpoint of alkali solubility. Such a diamine is, for example, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane. Further, diaminosiloxane is preferred from the viewpoint of low warpage. As such a diaminosiloxane, for example, k in formula (5) is preferably 5 to 25 and R ⁴ is a propylene group.

  Examples of the tetracarboxylic dianhydride include an aromatic tetracarboxylic dianhydride having an ester group, an alicyclic tetracarboxylic dianhydride, and an aliphatic tetracarboxylic dianhydride.

  Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3′4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride. Anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- Dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2 , 3-Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10- Perylene tetraca Boronic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetra Carboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride Thing, 2, 3, 6, 7 Tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride Bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) ) Benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic acid monoester anhydride) ), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) Enoxy) phenyl] hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 4,4-bis (3,4-dicarboxyphenoxy) diphenyl And sulfide dianhydrides.

  Examples of aromatic tetracarboxylic dianhydrides having an ester group include 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitate anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl). ) Benzene bis (trimellitate anhydride), 1,2- (ethylene) bis (trimellitate anhydride), 1,3- (trimethylene) bis (trimellitate anhydride), 1,4- (tetramethylene) bis (trimellitate anhydride) ), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8 -(Octamethylene) bis (trimellitate anhydride), 1,9- (nonamethylene) bis ( Rimerimate anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecamethylene) bis (trimellitic anhydride), 1,16- (hexadecamethylene) bis (trimellitic anhydride), 1,18- (octadecamethylene) bis (trimellitic anhydride), 1,2- (phenylene) bis (trimellitate anhydride), ethylene glycol bis (trimellitic acid monoester acid anhydride). An aromatic tetracarboxylic dianhydride having an ester group can be used when an ester group is introduced into a soluble polyimide.

  Examples of alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides include ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,5-cyclo Octadiene-1,2,5,6-tetracarboxylic dianhydride, 5-carboxymethylbicyclo [2.2.1] heptane-2,3,6-tricarboxylic acid-2,3: 5,6-di Anhydride, 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, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4 , 5-Tetracarboxylic acid Anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, decahydronaphthalene-1,4,5,8 -Tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1, 2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo- Bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride) sulfone.

  These tetracarboxylic dianhydride components can be used alone or in combination.

  As a preferable tetracarboxylic dianhydride component, a tetracarboxylic dianhydride component having an ether group or an ester group is preferable among aromatic tetracarboxylic dianhydride components from the viewpoint of solvent solubility and low warpage. Examples of such tetracarboxylic dianhydrides include bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, and 1,2- (ethylene). Bis (trimellitic anhydride) and 1,2- (phenylene) bis (trimellitate anhydride).

  The terminal of the soluble polyimide of this invention will not be specifically limited if it is a structure which does not affect performance. A terminal derived from an acid dianhydride or diamine used for producing polyimide may be used, or the terminal may be sealed with another acid anhydride or an amine compound.

The number average molecular weight of the polyimide according to the present invention is preferably from 1,000 to 1,000,000 from the viewpoints of flame retardancy, the viscosity of the polyimide-containing resin composition, and moldability. Here, the number average molecular weight means a molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard. The molecular weight is more preferably from 5,000 to 500,000, and most preferably from 10,000 to 300,000.
The copolymerization mode of the soluble polyimide according to the present invention may be a block structure or a random structure.

  The soluble polyimide according to the present invention is prepared by, for example, mixing the above diamine and tetracarboxylic dianhydride in a suitable solvent to synthesize a polyamic acid which is a polyimide precursor, and then heating the reaction solution to imidize. Can be obtained. In view of low warpage and alkali developability when used as a coverlay, introduction of a siloxane skeleton, carboxyl group and / or hydroxyl group is preferred.

  The soluble polyimide according to the present invention can be obtained by reacting an acid dianhydride and a diamine to synthesize a polyamic acid and then heating (heating imidization). It can also be obtained by reacting an acid dianhydride and a diamine to synthesize a polyamic acid and subsequently imidizing (chemical imidization) after adding a catalyst. Among these, chemical imidation is preferable in that imidization can be completed at a lower temperature.

  Next, a method for synthesizing a polyamic acid by reacting an acid dianhydride and a diamine will be described, followed by an example of a method of imidizing after adding a catalyst, and the production conditions of the soluble polyimide according to the present invention explain.

  The method for producing the polyamic acid is not particularly limited, and a known method can be applied. More specifically, it is obtained by the following method. First, diamine is dissolved and / or dispersed in a polymerization solvent, acid dianhydride powder is gradually added thereto, and the mixture is stirred for 0.5 to 96 hours, preferably 0.5 to 30 hours using a mechanical stirrer. In this case, the monomer concentration is 0.5% by mass or more and 95% by mass or less, preferably 1% by mass or more and 90% by mass or less. By performing polymerization in this monomer concentration range, a polyamic acid solution can be obtained.

  Examples of the reaction solvent used in the production of the polyamic acid include ether compounds having 2 to 6 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether; acetone, methyl ethyl ketone, and the like. Ketone compounds having 2 to 6 carbon atoms; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; benzene, toluene, xylene, mesitylene, tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as: ester compounds having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and γ-butyrolactone; chloroform, methylene chloride, 1, 2 Halogen-containing compounds having 1 to 10 carbon atoms such as dichloroethane; nitrogen-containing compounds having 2 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Compound; Sulfur-containing compounds such as dimethyl sulfoxide are exemplified. These may be one kind or a mixture of two or more kinds as necessary. Particularly preferable solvents include ester compounds having 3 to 6 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  The reaction temperature for producing the polyamic acid is preferably 0 ° C. or higher and 250 ° C. or lower. If it is 0 degreeC or more, reaction will be started, and if it is 250 degrees C or less, there will be no influence of a side reaction. Preferably they are 15 degreeC or more and 220 degrees C or less, More preferably, they are 20 degreeC or more and 200 degrees C or less.

  The time required for the reaction of the polyamic acid varies depending on the purpose or reaction conditions, but is usually within 96 hours, and particularly preferably 30 minutes to 30 hours.

  Next, a method of obtaining a soluble polyimide according to the present invention by adding a catalyst to polyamic acid (chemically) to imidize will be described.

  The imidization catalyst for producing the soluble polyimide according to the present invention is not particularly limited, but an acid anhydride such as acetic anhydride, γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin. , Lactone compounds such as γ-phthalidic acid, pyridine, quinoline, N-methylmorpholine, tertiary amines such as triethylamine, and the like. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. Among these, a mixed system of γ-valerolactone and pyridine is particularly preferable from the viewpoint of high reactivity.

  The amount of the imidization catalyst added is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less when the polyamic acid is 100 parts by mass.

  As the reaction solvent, the same solvent as used for the production of polyamic acid can be used. In that case, the polyamic acid solution can be used as it is. Moreover, you may use the solvent different from what was used for manufacture of a polyamic acid.

  Examples of the reaction solvent include ether compounds having 2 to 6 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether; ketones having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone. Compound: saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, decalin; 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene and tetralin Aromatic hydrocarbon compounds; ester compounds having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and γ-butyrolactone; carbon numbers such as chloroform, methylene chloride, and 1,2-dichloroethane A halogen-containing compound having 10 to 10 carbon atoms; a nitrogen-containing compound having 2 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone; like dimethyl sulfoxide A sulfur-containing compound is mentioned. If necessary, one kind or a mixture of two or more kinds may be used.

  Particularly preferable solvents include ester compounds having 3 to 6 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  In the production of the soluble polyimide according to the present invention, the reaction temperature is preferably 15 ° C. or more and 250 ° C. or less. If it is 15 degreeC or more, reaction will be started, and if it is 250 degrees C or less, there will be no deactivation of a catalyst. Preferably they are 20 degreeC or more and 220 degrees C or less, More preferably, they are 20 degreeC or more and 200 degrees C or less.

  The time required for the reaction varies depending on the purpose or reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.

  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 it is for preparing the photosensitive resin composition of the present invention as a polyimide varnish.

  Moreover, when recovering a polyimide after completion | finish of manufacture, it can carry out by depressurizingly distilling the solvent in a reaction solution.

  When purifying polyimide, as a method for purifying polyimide, when insoluble acid dianhydride and diamine remain in the reaction solution, a method of removing them by vacuum filtration, pressure filtration or the like can be mentioned. In addition, a so-called reprecipitation purification method in which the reaction solution is precipitated by adding it to a poor solvent can be carried out. Furthermore, when a particularly high-purity polyimide is required, an extraction method using a carbon dioxide supercritical method is also possible. Even when the recovered or purified polyimide is used, a resin composition containing a solvent in which the soluble polyimide can be uniformly dissolved and / or dispersed can be obtained.

  The solvent which comprises the resin composition containing a polyimide will not be limited if the soluble polyimide which concerns on this invention can be melt | dissolved and / or disperse | distributed uniformly. Examples of such solvents include ether compounds having 2 to 6 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and propylene glycol monomethyl acetate; 2 or more carbon atoms such as acetone and methyl ethyl ketone. 6 or less ketone compounds; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; carbon numbers such as benzene, toluene, xylene, mesitylene and tetralin Aromatic hydrocarbon compound having 6 to 10 carbon atoms; ester compound having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and γ-butyrolactone; chloroform, methylene chloride Chlorine-containing compounds having 1 to 10 carbon atoms such as 1,2-dichloroethane; 2 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone Examples thereof include the following nitrogen-containing compounds; sulfur-containing compounds such as dimethyl sulfoxide. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. From the viewpoint of the solubility of the polyimide, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.

  The density | concentration of the soluble polyimide in the resin composition which consists of a soluble polyimide and a solvent will not be restrict | limited especially if the resin molding is a density | concentration manufactured. It is preferable that the concentration of polyimide is 1% by mass or more from the viewpoint of the film thickness of the resin molded body to be produced, and the concentration of soluble polyimide is 90% by mass or less from the uniformity of the film thickness of the resin molded body. From the viewpoint of the film thickness of the obtained resin molded body, it is more preferably 2% by mass or more and 80% by mass or less.

Next, the component (B) will be described.
Examples of the photosensitive agent used in the present invention include those whose structure changes due to light irradiation and whose solubility in a solvent changes. Examples of such a compound include compounds containing a quinonediazide structure.

  Examples of the quinone diazide compound include 1,2-benzoquinone diazide sulfonic acid esters, 1,2-benzoquinone diazide sulfonic acid amides, 1,2-naphthoquinone diazide sulfonic acid esters, 1,2-naphthoquinone diazide sulfonic acid amides. Is mentioned. Among these, 1,2-naphthoquinone diazide sulfonic acid esters are preferable from the viewpoint of dissolution inhibiting ability.

  As 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester at the 4-position of the sulfonic acid group and 1,2-naphthoquinone diazide-5-sulfonic acid ester at the 5-position Any of these may be used, but 1,2-naphthoquinonediazide-5-sulfonic acid ester is preferred from the viewpoint of low warpage.

  1,2-naphthoquinonediazide sulfonic acid ester can be obtained by esterifying with sulfonic acid using a compound having a phenolic hydroxyl group as a raw material. For example, 1,2-naphthoquinonediazide-4-sulfonic acid or its acid chloride or its sulfonate, or 1,2-naphthoquinonediazide-5-sulfonic acid at the 5-position or 1 mol of the functional group of the phenolic hydroxyl group The acid chloride or its sulfonate can be obtained by mixing in a suitable solvent such as acetone. At this time, a basic catalyst such as triethylamine may be used. The esterification rate with sulfonic acid is preferably 0.60 or more and 0.98 or less from the viewpoint of dissolution inhibiting ability and alkali solubility after exposure.

  Examples of 1,2-naphthoquinonediazide sulfonic acid esters include monofunctional phenols, bifunctional phenols, trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, and (polyhydroxyphenyl) alkanes. 1,2-naphthoquinone diazide sulfonic acid esters.

  Monofunctional phenols such as 1,2-naphthoquinone diazide sulfonic acid esters include phenyl-1,2-naphthoquinone diazide-4-sulfonic acid ester, phenyl-1,2-naphthoquinone diazide-5-sulfonic acid ester, o- Methylphenyl-1,2-naphthoquinonediazide-4-sulfonic acid ester, o-methylphenyl-1,2-naphthoquinonediazide-5-sulfonic acid ester, m-methylphenyl-1,2-naphthoquinonediazide-4-sulfonic acid Ester, m-methylphenyl-1,2-naphthoquinonediazide-5-sulfonic acid ester, p-methylphenyl-1,2-naphthoquinonediazide-4-sulfonic acid ester, p-methylphenyl-1,2-naphthoquinonediazide- 5-sulfonic acid ester, etc.

  As 1,2-naphthoquinone diazide sulfonic acid esters of bifunctional phenols, 4,4′-dihydroxydiphenyl sulfone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 4,4′-dihydroxydiphenyl sulfone-1 , 2-Naphthoquinonediazide-5-sulfonic acid ester, 4,4′-dihydroxydiphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4′-dihydroxydiphenylmethane-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2,2 '-(4-hydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2'-(4-hydroxyphenyl) propane-1,2-naphthoquinonediazide- 5-sulfonic acid ester etc. are mentioned.

  Examples of 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenones include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2 -Naphthoquinonediazide-5-sulfonic acid ester etc. are mentioned.

  Examples of 1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenones include 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2 ′, 4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2 , 2 ′, 4,3′-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid Ester, 2,3,4,4'-tetrahydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2′-tetra Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3 4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and the like.

  Examples of 1,2-naphthoquinone diazide sulfonic acid esters of pentahydroxybenzophenones include 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3 , 4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and the like.

  Examples of 1,2-naphthoquinone diazide sulfonic acid esters of hexahydroxybenzophenones include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone -1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, and the like.

  Examples of 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (2,4 -Dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane- 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p -Hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-s Phosphonate, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,2′-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2′-bis (2,3 , 4-Trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2 -Naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3- Phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1, 2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide— 5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxy) Phenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-4- Sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide— 5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 Examples include ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester.

（式中Ｑはそれぞれ独立に水素又は式（７）又は式（８）から選ばれる１価の有機基である。ただし、複数のＱのうち少なくとも一つは式（７）又は式（８）から選ばれる有機基である。）

As the component (B), a compound represented by the formula (6) is preferable in consideration of low warpage and developability.

(In the formula, each Q is independently hydrogen or a monovalent organic group selected from the formula (7) or the formula (8). However, at least one of the plural Qs is the formula (7) or the formula (8). An organic group selected from

  The component (B) is preferably 15 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the component (A). In this range, flame retardancy and photosensitivity are good.

（式中Ｒ^１はエチレングリコール鎖及び／又はプロピレングリコール鎖を含む有機基である。複数のＲ^１はそれぞれ同一でも異なっていても良い。）

（式中Ｒ^２は下記式（３）又は式（４）に示される有機基であり、Ｒ^３はＨ、メチル基、エチル基、プロピル基、ブチル基、イソブチル基から選ばれる有機基である。ｎは１から１０であり、ｍは１又は２であり、Ｌは１から１０である。） Next, the component (C) will be described.
Component (C) is a compound represented by formula (1) having an organic group containing an ethylene glycol chain and / or a propylene glycol chain and an isocyanuric acid ring. Even such a compound is preferably a compound having a specific R ¹ represented by the formula (2) from the viewpoint of flame retardancy and low warpage.

(In the formula, R ¹ is an organic group containing an ethylene glycol chain and / or a propylene glycol chain. The plurality of R ¹ may be the same or different.)

(Wherein R ² is an organic group represented by the following formula (3) or formula (4), and R ³ is an organic group selected from H, methyl group, ethyl group, propyl group, butyl group, and isobutyl group) N is 1 to 10, m is 1 or 2, and L is 1 to 10.)

  n is a number from 1 to 10. If there is a distribution, it represents the average value. As n is larger, the plasticizing effect is higher and low warpage is more likely to occur. L is a number from 1 to 10. If there is a distribution, it represents the average value. The larger L is, the higher the solubility in an alkaline developer is, and the smaller L is, the higher the ability to inhibit dissolution in an alkaline developer. m is a number from 1 to 2. If there is a distribution, it represents the average value. When m is close to 1, the low warping effect is high.

R ² is an organic group represented by Formula (3) or Formula (4), and Formula (3) is preferable from the viewpoint of flexibility. When R ³ is H, the alkali solubility is high, and when it becomes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or an isobutyl group, an alkali dissolution inhibiting effect is exhibited.

Considering these, n is preferably 2 to 8, L is preferably 2 to 8, m is preferably 1 to 1.5, R ² is preferably formula (3), and R ³ is preferably a methyl group.

A plurality of R ^{1 s in the} compound represented by formula (1) may be the same or different. For example, n, m, L, R ² and R ^{3 in} formula (2) may have different R ^{1 s} in the same molecule. A plurality of compounds represented by formula (1) may be used in combination.

（式中ｎ’は２から８であり、Ｌ’は２から８である。） Preferred examples of the component (C) include compounds having a structure represented by the formula (9) for R ¹ .

(Where n ′ is from 2 to 8, and L ′ is from 2 to 8.)

  (C) It is preferable that a component is 2 to 20 mass parts with respect to 100 mass parts of (A) component. More preferably, they are 3 to 10 mass parts. In this range, flame retardancy and low warpage are good.

Next, the component (D) will be described.
The photosensitive resin composition of the present invention can be further improved in flame retardancy by adding component (D). The component (D) is preferably a phosphorus-based flame retardant, and among them, a phosphate ester compound and / or a phosphazene compound are preferable from the viewpoint of flexibility and flexibility of the composition. Among the phosphate ester compounds or phosphazene compounds, cyclic phosphazene compounds are more preferable from the viewpoint of heat stability.

  As the phosphate ester compound, an aromatic phosphate ester, an alkyl phosphate ester or an alkoxy phosphate ester is preferable.

  Examples of the aromatic phosphate include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, triisopropylphenyl phosphate, resorcinol bis (diphenyl phosphate) (hereinafter also referred to as “RDP”), and the like.

  Examples of the alkyl phosphate ester include triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate (hereinafter also referred to as “TIBP”), and the like.

  Examples of the alkoxyphosphate include tris (butoxyethyl) phosphate, tris (butoxybutyl) phosphate (hereinafter also referred to as “TBXP”), tris (2-ethylhexyl) phosphate, and the like.

（式中、ｘはそれぞれ３から５の数である。）
これらの（Ｄ）成分は単独又は組み合わせて用いることができる。 As the phosphazene compound, a cyclic compound is preferable from the viewpoint of heat stability. For example, a compound selected from the compounds represented by formula (10) is preferable.

(Wherein x is a number from 3 to 5, respectively)
These components (D) can be used alone or in combination.

  In the photosensitive resin composition of the present invention, additives that are already known can be added as necessary within a quantitative and qualitative range that does not depart from the effects of the present invention. Specific additives include adhesion improvers, surfactants, antioxidants, UV inhibitors, light stabilizers, plasticizers, waxes, fillers, pigments, dyes, foaming agents, antifoaming agents, dehydration Agents, antistatic agents, antibacterial agents, antifungal agents, leveling agents, dispersants, ethylenically unsaturated compounds and the like.

  Examples of the adhesion improver include imidazole compounds, triazole compounds, tetrazole compounds, and sulfide compounds, preferably 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-ethyl-4-methylimidazole. 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1 Examples include silicon-containing imidazoles such as -cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, and imidazolesilane. As the imidazole silane, for example, IM-1000 manufactured by Nikko Metal Co., Ltd. is preferable.

  The photosensitive resin composition of the present invention can be suitably used for a photosensitive film or a photosensitive ink. From the viewpoint of producing a photosensitive film or photosensitive ink, the concentration of soluble polyimide in the photosensitive resin composition is preferably 1% by mass or more and 90% by mass or less. The concentration of the soluble polyimide is preferably 1% by mass or more from the viewpoint of the coverlay film thickness when used as a coverlay, and preferably 90% by mass or less from the viewpoint of the viscosity and film thickness uniformity of the photosensitive resin composition. From the viewpoint of the coverlay film thickness to be obtained, 2% by mass or more and 80% by mass or less is more preferable.

The photosensitive resin composition of this invention can be used suitably for a photosensitive film.
First, the photosensitive resin composition according to the present invention is coated on a substrate to prepare a photosensitive dry film. The substrate is not limited as long as it is a substrate that is not damaged during the formation of the photosensitive dry film. Such a substrate is used as a carrier film. Examples of the carrier film include a heat resistant resin, a polyethylene terephthalate film, and a metal film. From the viewpoint of easy handling, a polyethylene terephthalate film is particularly preferable from the viewpoint of heat resistance resin and releasability after pressure bonding to the substrate.

  Examples of the coating method include bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, flow coating, spin coating, slit coating, and brush coating. After coating, if necessary, heat treatment is performed with an oven, a hot plate, etc., and the solvent is dried to form a laminated film having a carrier film and a photosensitive film.

  Moreover, it is good also as a laminated | multilayer film by providing at least one layer of arbitrary antifouling and protective cover films on a photosensitive film. In the laminated film according to the present invention, examples of the cover film include low density polyethylene.

  Next, the photosensitive dry film of the present invention can be pressure-bonded to a substrate having wiring so as to cover the wiring, thereby forming a coverlay on an arbitrary substrate.

  The photosensitive resin composition of this invention can be used suitably for photosensitive ink. When used as a photosensitive ink, a coverlay can be formed on an arbitrary base material by applying it by screen printing on an arbitrary base material and then drying it. The screen printing method is a known printing method in which ink is passed through a screen on which a pattern is formed using a squeegee or the like.

  The cover lay formed on the arbitrary base material formed by the above method is subjected to a treatment such as baking through at least exposure and alkali development steps.

  Examples of an arbitrary base material having wiring in the printed wiring board according to the present invention include a hard base material such as a glass epoxy substrate and a glass maleimide substrate, or a flexible substrate such as a polyimide film. Among these, a flexible substrate is preferable from the viewpoint of bendability.

  As a method for forming the coverlay, when a photosensitive film is used, with the wiring side of the substrate having the wiring and the photosensitive film of the present invention in contact with each other, heat pressing, heat laminating, heat vacuum pressing, heat The method of performing vacuum lamination etc. is mentioned. Among these, from the viewpoint of embedding the photosensitive film between the wirings, a heat vacuum press or a heat vacuum laminate is preferable. The heating temperature when laminating the photosensitive film on the substrate having the wiring is not limited as long as the photosensitive film can be in close contact with the substrate. From the viewpoint of adhesion to the substrate, from the viewpoint of decomposition of the photosensitive film and side reactions, 30 ° C. or more and 400 ° C. or less are preferable. More preferably, it is 50 degreeC or more and 150 degrees C or less.

  In addition, when using photosensitive ink, the screen printing method mentioned above is used suitably.

  The cover lay according to the present invention can be subjected to positive photolithography by dissolving the light irradiated portion by alkali development after the light irradiation. In this case, examples of the light source used for light irradiation 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 are preferable.

  The aqueous alkali solution used for development is not limited as long as it is a solution capable of dissolving the light irradiation site. Examples of such a solution include a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and a tetramethylammonium hydroxide aqueous solution. From the viewpoint of developability, an aqueous sodium carbonate solution and an aqueous sodium hydroxide solution are preferred. Examples of the development method include spray development, immersion development, and paddle development.

  The cover lay according to the present invention can be subjected to light irradiation (hereinafter referred to as “post-exposure”) again if necessary after performing positive photolithography by alkali development after light irradiation. As the light source used for the post-exposure, the same light source as that used in the previous light irradiation can be used. The coverlay according to the present invention is further improved in substrate warpage and plating resistance by post-exposure.

  Next, the printed wiring board on which the cover lay of the present invention is formed is fired as necessary to form a printed wiring board having the cover lay. Firing is preferably performed at a temperature of 30 ° C. or higher and 400 ° C. or lower from the viewpoint of solvent removal, side reaction, decomposition, or the like. More preferably, it is 100 degreeC or more and 300 degrees C or less.

  The reaction atmosphere in the firing can be carried out in an air atmosphere or an inert gas atmosphere. In the production of the printed wiring board, the time required for the firing varies depending on the reaction conditions, but is usually within 24 hours, particularly preferably in the range of 1 to 8 hours.

  The photosensitive resin composition according to the present invention sufficiently suppresses warpage as a coverlay, has good developability, and exhibits chemical resistance when used as a cured product. Protective layer formation for printed wiring boards and circuit boards used for operation panels, etc., insulating layer formation for laminated substrates, silicon wafers used for semiconductor devices, semiconductor chips, semiconductor device peripheral members, semiconductor mounting substrates, heat sinks It is used for film formation on electronic parts for use in protection, insulation and adhesion of lead pins and semiconductors themselves.

Next, examples performed for clarifying the effects of the present invention will be described.
<Reagents for synthesis examples>
In the synthesis examples, silicone diamine (KF-8010) (manufactured by Shin-Etsu Chemical Co., Ltd.), 3,3′-dicarboxy-4,4′-diaminodiphenylmethane (hereinafter also referred to as “MBAA”), which is the reagent used. Wakayama Seika Co., Ltd.), oxydiphthalic dianhydride (hereinafter also referred to as “ODPA”) (manufactured by Wako Pure Chemical Industries), 1,3-bis (3-aminophenoxy) benzene (hereinafter referred to as “APB”) (Mitsui Chemicals Co., Ltd.), ethylene glycol bis (trimellitic acid monoester anhydride) (hereinafter also referred to as “TMEG”) (manufactured by Shin Nippon Chemical Co., Ltd.), 1,5-bis (4-amino) Phenoxy) alkane (Wakayama Seika Co., Ltd.) (hereinafter also referred to as “DA5MG”), toluene (Wako Pure Chemical Industries, for organic synthesis), γ-butyrolactone (Wako Pure Chemical Industries, special grade), pyri Down (manufactured by Wako Pure Chemical Industries, Ltd., for organic synthesis), .gamma.-valerolactone (manufactured by Wako Pure Chemical Industries, Ltd., first grade), was used for the reaction without carrying out any special purification.

（式中、Ｑの約９７％が式（８）でありそれ以外が水素である。） <Reagents for formulation examples>
As the component (B), a compound represented by the formula (11) was used. This is B-1.

(In the formula, about 97% of Q is the formula (8) and the others are hydrogen.)

(C) As a component, the compound shown by Formula (12) and Formula (13) was used. Let C-1 and C-2 respectively.

  As component (D), TBXP (manufactured by Daihachi Chemical Co., Ltd.), TIBP (manufactured by Ajinomoto Fine Techno Co., Ltd.), RDP (manufactured by Ajinomoto Fine Techno Co., Ltd.), Ravitor FP-100 (manufactured by Fushimi Pharmaceutical Co., Ltd.), Ravitor FP-300 (Fushimi Pharmaceutical Co., Ltd.) Used).

  As additives, IM-1000 (manufactured by Nikko Metal Co., Ltd.), cresol novolac type epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo EA7420 / PGMAC number average molecular weight about 3200 / solid content 70%, propylene glycol monomethyl ether acetate 30%, containing a polymerization inhibitor) (hereinafter referred to as NK oligo), polyethylene glycol 600 (manufactured by Wako Pure Chemical Industries, Ltd.) (hereinafter referred to as PEG) were used.

<Number average molecular weight measurement>
Gel permeation chromatography (GPC), which is a method for measuring the number average molecular weight, was measured under the following conditions. Using N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) as a solvent, 24.8 mmol / L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity before measurement) 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) were used.
Column: Shodex KD-806M (manufactured by Showa Denko KK)
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Pump: PU-2080 Plus (manufactured by JASCO)
Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO)
UV-2075 Plus (UV-VIS: UV-Visible Absorber, manufactured by JASCO)

  Moreover, the calibration curve for calculating the molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

<Dry film manufacturing method>
The coating method of the photosensitive resin composition in the present invention was performed by a doctor blade method using FILMCOATER (manufactured by TESTER SANGYO, PI1210). The photosensitive resin composition was dropped onto an easily peelable PET film (Mitsubishi Chemical Polyester Film Co., Ltd., DIAFOIL, T100H25) to adjust the clearance and coat. The coated film was dried at 95 ° C. for 30 minutes using a dryer (SPHH-10L, manufactured by ESPEC) to obtain a photosensitive dry film.

<Film lamination conditions>
Film lamination in the present invention was performed using a vacuum press machine (manufactured by Meiki Seisakusho). The press temperature was 120 ° C., the press pressure was 1.1 MPa, and the press time was 1 minute.

<Film thickness measurement>
The film thickness was measured using a film thickness meter (ID-C112B, manufactured by Mitutoyo).
The film thickness of the dry film used for each evaluation was 12 μm to 15 μm.

<Photolithographic evaluation>
Photolithographic evaluation is performed by laminating a copper-clad laminate with a photosensitive dry film (photosensitive layer thickness of about 15 μm) under the above-mentioned lamination conditions, and using a positive mask to apply a dose of 1.3 J / L. Exposure was performed at cm ² , followed by development by spraying with a 1% aqueous sodium hydroxide solution and then water. After development, acid rinsing and water washing were performed, and the pattern was evaluated with an optical microscope after drying with air blow. The case where a circular pattern having a diameter of 100 μm could be formed was indicated by “◯”, and the case where the circular pattern could not be formed was indicated by “X”.

If necessary, post-exposure was performed on the developed sample. Post-exposure was performed with a dose of 2.0 J / cm ² without using a mask.

<Flame retardance test>
The flame retardancy test was performed according to the following procedure. The photosensitive resin composition is coated on one side of a Kapton (registered trademark) film by the above-mentioned coating method, dried at 95 ° C. for 30 minutes, and then coated on the opposite side with the photosensitive resin composition, and 30% at 95 ° C. After coating the photosensitive resin composition on both sides of the Kapton film by drying for a minute, assuming an alkali development step, the sample is pseudo-exposed to an alkali developer and subjected to post-exposure and baking under the conditions shown in Table 2. It was created. This sample film was cut into 20 cm × 5 cm, and the flame retardancy was evaluated by UL94 VTM test. Samples whose afterflame time of each sample was 10 seconds or less and did not burn to the 12.5 cm mark were evaluated as ◯, and the afterflame time of each sample was burned to the mark of 10 seconds or more or 12.5 cm The sample was evaluated as x.

<Evaluation of warpage>
The evaluation of the warp was carried out by laminating a photosensitive dry film on Kapton under the above laminating conditions, assuming an alkali development step, pseudo exposure to an alkali developer, and performing post-exposure and baking under the conditions shown in Table 2. Was cut out to a size of 50 mm × 50 mm and allowed to stand on a horizontal surface, the case where the hem portion floated was 10 mm or less was marked as ◯, and the case where it was larger than 10 mm was marked as x.

<Flexibility evaluation>
Using a photosensitive dry film (thickness of photosensitive layer: about 15 μm) on a copper clad laminate, assuming an alkali development step after laminating under the above lamination conditions, it is exposed to an alkaline developer in a pseudo manner. Samples prepared by post-exposure and baking under the conditions shown in Fig. 6 are folded and the samples that can be folded 10 times or more without cracking or peeling off are marked with ◯, and those with 9 times or less X.

<Plating resistance evaluation>
The photosensitive dry film produced by the above method is laminated on a copper-clad laminate under the above lamination conditions, and then exposed and developed in the same manner as photolithography evaluation through a positive mask having a 400 μm diameter circular pattern, and then 400 μm. A circular pattern of diameter was formed. Samples were prepared by post-exposure and firing under the conditions shown in Table 2, and tin plating resistance was evaluated under the following conditions.
Degreasing: The sample was immersed in an acidic degreasing solution (FR cleaner) at 30 ° C. for 5 minutes.
Water washing: The sample was immersed in purified water for 1 minute at room temperature.
Soft etch: A sample was immersed in a 10% by mass aqueous sodium persulfate solution at room temperature for 30 seconds.
Water washing: The sample was immersed in purified water for 1 minute at room temperature.
Acid treatment: The sample was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 30 seconds.
Water washing: The sample was immersed in purified water for 1 minute at room temperature.
Tin plating: The sample was immersed in a tin plating solution (Rohm and Haas Electronic Materials, LT-34) at 80 ° C. for 5 minutes.
Water washing: The sample was immersed in purified water at 50 ° C. for 1 minute.

  After the test, the plating solution from the circular hole does not soak, swell, or peel off, ◎, the soak of the chemical solution from the pattern wrinkle is about 0 to 10 μm, and the case where the soaking of 10 μm to 30 μm is seen and In addition, a case where penetration, swelling, peeling, or the like of a plating solution of 30 μm or more was observed was evaluated as x.

<(A) Component synthesis example>
[Synthesis Example 1]
Under a nitrogen atmosphere, MBAA (22.50 mmol), ODPA (59.96 mmol), and γ-butyrolactone (120 mL) were placed in a separable flask and stirred at room temperature for 2 hours. Subsequently, toluene (30 mL), pyridine (34.13 mmol), and γ-valerolactone (22.47 mmol) were added, and a Dean-Stark apparatus and a reflux were attached, followed by heating and stirring at 180 ° C. for 2 hours. After cooling to 120 ° C., silicone diamine (KF-8010, 52.50 mmol) and DA5MG (14.98 mmol) were added and stirred for 10 minutes, then ODPA (29.98 mmol) was added, and the mixture was heated and stirred at 120 ° C. for 2 hours. did. Subsequently, toluene (10 mL) was added, and the mixture was heated and stirred at 180 ° C. for 2 hours. The mixture was cooled to 140 ° C., γ-butyrolactone was added so that the polymer solid concentration was 30% by mass, and the mixture was cooled to room temperature to obtain a γ-butyrolactone solution of polyimide. The mass (%) of the site derived from the siloxane structure in the polyimide was about 53% by mass. This is polymer 1.

[Synthesis Example 2]
Under a nitrogen atmosphere, silicone diamine (KF-8010, 15.0 mmol) and γ-butyrolactone (100 mL) were added to a separable flask, followed by ODPA (20.0 mmol), and the mixture was stirred at 23 ° C. for 2 hours. Subsequently, toluene (15 mL), pyridine (11.38 mmol), and γ-valerolactone (7.49 mmol) were added, and a Dean Stark apparatus and a reflux were attached, and the mixture was heated and stirred at 180 ° C. for 2 hours. After cooling to 120 ° C., MBAA (10.0 mmol) and 1,3-bis (3-aminophenoxy) benzene (3.0 mmol) were added, and after stirring for 10 minutes, ethylene bis (trimellitate) dianhydride (8.6 mmol) was added, and the mixture was stirred with heating at 120 ° C. for 2 hours. Subsequently, toluene (5 mL) was added, and the mixture was stirred with heating at 180 ° C. for 2 hours. It cooled to 140 degreeC, (gamma) -butyrolactone was added so that it might become polymer solid content concentration 25 mass%, and the γ-butyrolactone solution of polyimide was obtained by cooling to room temperature. The mass (%) of the part derived from the siloxane structure in the polyimide was about 50% by mass. This is polymer 2.

[Synthesis Example 3]
Under a nitrogen atmosphere, a separable flask was charged with silicone diamine (15.0 mmol) and γ-butyrolactone (100 mL), followed by addition of ethylene bis (trimellitate) dianhydride (20.0 mmol). Stir for hours. Subsequently, toluene (15 mL), pyridine (11.38 mmol), and γ-valerolactone (7.49 mmol) were added, and a Dean Stark apparatus and a reflux were attached, and the mixture was heated and stirred at 180 ° C. for 2 hours. After cooling to 120 ° C., MBAA (10.0 mmol) and 1,3-bis (3-aminophenoxy) benzene (3.0 mmol) were added, and after stirring for 10 minutes, ODPA (8.6 mmol) was added. The mixture was stirred with heating at ° C for 2 hours. Subsequently, toluene (5 mL) was added, and the mixture was stirred with heating at 180 ° C. for 2 hours. The solution was cooled to 140 ° C., γ-butyrolactone was added so that the polymer solid content concentration was 25% by mass, and the mixture was cooled to room temperature to obtain a γ-butyrolactone solution of polyimide. The mass (%) of the site derived from the siloxane structure in the polyimide was about 48% by mass. This is polymer 3.

[Composition example]
Formulation was performed according to Table 1. The polymer was blended in the state of a polymer varnish so that the mass of the polymer component was the number of parts in Table 1.

[Sample adjustment example]
Various samples were prepared by post-exposure and baking under the conditions shown in Table 2.

[Evaluation example]
Under the conditions described above, photolithography, flame retardancy, warpage, flexibility, and plating resistance were evaluated. The results are shown in Table 3.

  As is apparent from Table 3, the photosensitive resin composition of the present invention is a photosensitive resin composition having both flame retardancy and low warpage when used as an FPC coverlay without impairing flexibility and flexibility. Can be provided.

Claims (14)

A photosensitive resin composition containing a component (A), a component (B) and a component (C), wherein the component (A) is a soluble polyimide, the component (B) is a quinonediazide compound, C) A photosensitive resin composition, wherein the component is a compound having an isocyanuric acid ring represented by formula (1).

(In the formula, R ¹ is an organic group containing an ethylene glycol chain and / or a propylene glycol chain. The plurality of R ¹ may be the same or different.)   The photosensitive resin composition according to claim 1, wherein the component (A) is a soluble polyimide having a siloxane skeleton.   The photosensitive resin composition according to claim 1, wherein the component (A) is a soluble polyimide having a carboxyl group and / or a hydroxyl group.   The said (B) component is a naphthoquinone diazide compound, The photosensitive resin composition in any one of Claims 1-3 characterized by the above-mentioned. The photosensitive resin composition according to any one of claims 1 to 4, wherein R ^{1 of the} component (C) is an organic group represented by the formula (2).

(In the formula, R ² is the following formula (3) or formula (4), and R ³ is an organic group selected from H, methyl group, ethyl group, propyl group, butyl group, and isobutyl group. 10 and m is 1 or 2, and L is 1 to 10.)

  The photosensitive resin composition according to claim 1, comprising a phosphorus-based flame retardant as component (D).   The photosensitive resin composition according to claim 6, wherein the component (D) contains a cyclic phosphazene compound.   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 photosensitive ink comprising the photosensitive resin composition according to claim 1.   A substrate having wiring and a cover lay formed on the substrate so as to cover the wiring and configured using the photosensitive resin composition according to any one of claims 1 to 7. A flexible printed wiring board characterized by:   A flexible printed wiring board, wherein the coverlay is a coverlay laminated using the film or laminated film according to any one of claims 8 to 10.   A flexible printed wiring board, wherein the cover lay is a cover lay formed using the photosensitive ink according to claim 11.