WO2008065905A1 - Composition de résine photosensible et carte de circuit imprimé souple comprenant cette composition - Google Patents

Composition de résine photosensible et carte de circuit imprimé souple comprenant cette composition Download PDF

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Publication number
WO2008065905A1
WO2008065905A1 PCT/JP2007/072222 JP2007072222W WO2008065905A1 WO 2008065905 A1 WO2008065905 A1 WO 2008065905A1 JP 2007072222 W JP2007072222 W JP 2007072222W WO 2008065905 A1 WO2008065905 A1 WO 2008065905A1
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Prior art keywords
formula
group
resin composition
photosensitive resin
compound
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PCT/JP2007/072222
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English (en)
Japanese (ja)
Inventor
Takeki Shimizu
Toshiaki Nagasawa
Hideaki Takahashi
Win Maw Soe
Toshiyuki Goshima
Original Assignee
Asahi Kasei Kabushiki Kaisha
Pi R & D Co., Ltd.
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Application filed by Asahi Kasei Kabushiki Kaisha, Pi R & D Co., Ltd. filed Critical Asahi Kasei Kabushiki Kaisha
Priority to CN200780041451.8A priority Critical patent/CN101535895B/zh
Publication of WO2008065905A1 publication Critical patent/WO2008065905A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • 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.
  • the dry film has photosensitivity. This is because, when a general polyimide material is finely processed, an etching process using a photoresist is performed, so that a large number of steps are required.
  • photosensitive polyimide materials that can form a pattern directly on the insulation layer polyimide itself have been attracting attention. Among them, alkaline aqueous solutions have been considered in consideration of safety during work and impact on the environment. There has been a growing demand for photosensitive resin compositions that can be developed at a low temperature. In general, in the case of the negative type, the exposed portion is swollen by the developer, and it is difficult to perform high resolution fine processing. Therefore, fine processing by a positive type photosensitive system is strongly desired.
  • the dry film is mechanically punched into a predetermined outer shape pattern, aligned with the circuit board, and then placed on the circuit board.
  • the punched dry film was pasted together.
  • the circuit board and dry film can be bonded together, and then the dry film can be patterned into a desired pattern by photolithography, so processes such as mechanical pattern punching and alignment with the circuit board are possible. Is no longer necessary.
  • Kapton registered trademark
  • Kapton film is insoluble in a solvent, so it cannot be formed from polyimide varnish (for example, Non-Patent Document 1). Therefore, when Kapton is used, it is formed into a film in the form of polyamic acid and then imidized by heating to a high temperature.
  • the Kapton film thus obtained is excellent in flexibility and flexibility, but has a glass transition point of 400 ° C or higher (eg, Non-Patent Document 2), so it is used as a dry film with low plasticity. That is, it is difficult to laminate on a circuit board.
  • Patent Document 3 a composition in which a quinonediazide compound is added to polyimide has been proposed (for example, Patent Document 3).
  • This photosensitive resin composition can also be made into a dry film. S, warping occurs when it is made into a dry film, and it is not sufficiently embedded in a wiring pattern board, and it is used as a dry film. It is difficult to
  • a polyimide precursor or a polybenzoxazo A positive-type photosensitive resin composition in which a quinonediazide compound is added to a copper precursor is disclosed (Patent Document 4).
  • Patent Document 4 a positive-type photosensitive resin composition in which a quinonediazide compound is added to a copper precursor is disclosed.
  • the precursor type is excellent in final film physical properties, the precursor is used as a composition, so that some of the precursor types have poor storage stability, which may cause inconvenience in processing.
  • a photosensitive resin composition containing polyimide a photosensitive resin composition containing a polyimide containing a sulfonic acid group and a naphthoquinonediazide compound is disclosed (Patent Document 5). Although the photosensitive resin composition has improved storage stability, it is difficult to press-bond to a substrate or the like because of the high Tg of polyimide.
  • Patent Document 6 a positive photosensitive resin composition made of polyimide having a siloxane skeleton is disclosed!.
  • polyimide introduces a siloxane skeleton, but Tg decreases, but flame retardancy tends to decrease.
  • the composition is not sufficiently plastic, warping occurs when it is formed into a dry film, and it is difficult to use it as a photosensitive film.
  • Non-Patent Document 3 a method of adding a phosphorus compound to the resin composition is known (for example, Non-Patent Document 3).
  • a method of adding a phosphorus compound to the resin composition is known (for example, Non-Patent Document 3).
  • a conventionally known technique If this technique is used in a photosensitive resin composition, the developability deteriorates and the photosensitive performance is lowered. Resulting in.
  • Patent Document 7 for the purpose of improving the heat-resistant deterioration stability of mechanical properties such as breaking strength, a technique of blending a small amount of a specific phosphorus compound with a polyimide resin is also known (for example, Patent Document 7). In this technique, the phosphorus compound does not exhibit flame retardancy, and the occurrence of warpage during dry film formation cannot be suppressed.
  • a positive photosensitive resin in which a quinonediazide compound is added to a conventionally known polyimide.
  • a monomer such as (meth) acrylate which is a conventionally known reactive diluent improves the warpage but impairs the flame retardancy.
  • it is possible to simultaneously suppress warpage during dry film formation, embedding and adhesion to a wiring pattern substrate, photosensitivity and image clarity, and flame retardancy at the same time. It was difficult to do.
  • Non-Patent Document 1 Latest Polyimides -Basics and Applications- (NTT) p. 4
  • Non-patent document 2 Electronics packaging technology 2003. 2 (Vol. 19 No. 2) p. 66
  • Non-patent document 3 Flame retardant technology using non-halogen flame retardant materials (NTS) ⁇ ⁇ 2
  • Patent Document 1 Japanese Patent Publication No. 7-35440
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-140339
  • Patent Document 3 Japanese Patent No. 2906637
  • Patent Document 4 Japanese Patent No. 3078175
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2004-238591
  • Patent Document 6 International Publication No. 2003/060010 Pamphlet
  • Patent Document 7 Japanese Patent No. 2955712
  • An object of the present invention is to have a laminating property and embedding property, which are difficult with a conventional photosensitive resin composition, and can be easily bonded to a substrate that does not warp during dry film formation.
  • the present invention provides a positive photosensitive dry film having good development characteristics and flame retardancy, and a flexible printed wiring board using the positive photosensitive dry film.
  • the inventors of the present invention are photosensitive resin compositions containing the component (A), the component (B), and the component (C).
  • the component (B) is an alkali-soluble resin
  • the component (B) is a compound having the structure represented by the formula (1), a compound having an isocyanuric acid ring, and one or two imide groups other than the component (A). It is at least one compound selected from the group consisting of imide compounds, and the component (C) is a key.
  • the photosensitive resin composition which is a non-diazide compound, suppresses warping during dry film formation, and at the same time provides embedding and adhesion to the wiring pattern substrate, photosensitivity, image clarity, and flame retardancy.
  • the inventors have found that it can be imparted, and have completed the present invention. Therefore, using the photosensitive resin composition of the present invention, it is possible to provide a photosensitive dry film, a photosensitive laminated film, a coverlay using them, and a flexible printed wiring board useful as an FPC board material.
  • P represents a phosphorus atom and the number of covalent bonds is 5.
  • X represents a nitrogen atom or an oxygen atom.
  • the number of covalent bonds is 3, and in the case of an oxygen atom, The number of shared bonds is 2.
  • the phosphorus atom and the nitrogen or oxygen atom are bonded by a double bond! /
  • the present inventor has found that a specific compound has an effect of improving warpage in dry film formation, embedding in a wiring pattern, adhesion, and flame retardancy, and further combining it with a quinonediazide compound. It was found that both photosensitivity and developability were expressed.
  • a photosensitive resin composition obtained by blending these specific compound and quinonediazide compound with a resin composition such as soluble polyimide is curl-free (warping is suppressed), laminating, photosensitive,
  • the inventors have found that a positive photosensitive dry film satisfying all of the flame retardancy has been realized, and have completed the present invention.
  • the component (B) in the photosensitive resin composition of the present invention includes a functional group capable of exhibiting a warp improving effect of a dry film in its structure, and a phosphorus capable of exhibiting flame retardancy. Includes atoms or nitrogen atoms.
  • the component (C) in the photosensitive resin composition of the present invention has a nitrogen atom capable of expressing flame retardancy in its structure, while being a relatively bulky quinone diazide group, specifically Has one or more naphthoquinone diazide groups and benzoquinone diazide groups.
  • the inventor of the present invention combined the component (B) and the component (C), so that the phosphorus atom or nitrogen atom of the component (B) and the nitrogen atom of the component (C) are sufficient. Have found that it can exhibit excellent flame retardancy. Surprisingly, when (B) and (C) are combined, the flame retardant does not impair the warp improvement performance of the dry film of (B). It was found that sex can be imparted. Furthermore, it has been found that by combining the (B) component and the (C) component, even a polyimide resin having a siloxane skeleton, which has been difficult to be flame retardant, can be imparted with flame retardancy.
  • the photosensitive resin composition of the present invention contains the component (A), the component (B), and the component (C), wherein the component (A) is an alkali-soluble resin, and the component (B) Is at least one selected from the group consisting of a compound having a structure represented by the formula (1), a compound having an isocyanuric acid ring, and an imide compound containing one or two imide groups other than the component (A). It is a compound, and the component (C) is a quinonediazide compound.
  • the component (C) is a quinonediazide compound.
  • P represents a phosphorus atom and the number of covalent bonds is 5.
  • X represents a nitrogen atom or an oxygen atom, and when X is a nitrogen atom, the number of covalent bonds is 3 and the oxygen atom. In this case, the number of covalent bonds is 2.
  • the phosphorus atom and the nitrogen or oxygen atom are bonded by a double bond.
  • the alkali-soluble resin used in the present invention is not limited as long as it is a resin that can be dissolved in an alkaline solution.
  • a resin include resins having a functional group that dissolves in a known alkali such as a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group in the main chain and / or side chain.
  • alkali-soluble polyamides such as alkali-soluble polyimides, polyamic acids, and polybenzoxazole precursors are used. From the viewpoint of preferable dry film formation, alkali-soluble polyimide and polyimide precursor are more preferable, and alkali-soluble polyimide is particularly preferable.
  • the alkali-soluble polyimide used in the present invention can be obtained using, for example, diamine and tetracarboxylic dianhydride as raw materials.
  • As the structure of the alkali-soluble polyimide it is preferable to have a carboxyl group and / or a hydroxyl group that preferably has a functional group that is soluble in alkali! /.
  • an aromatic diamine, an aliphatic diamine, and an alicyclic 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. In addition, diaminosiloxane can be used for the purpose of introducing a siloxane skeleton.
  • Aromatic diamines include 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'-diaminodiphenylmethane, 4, 4 '-Diaminodiphenyl difluoromethane, 3, 3' -diaminodiphenenoles norephone, 3, 4 '-diaminodiphenenoles norephone, 4, 4' -diaminodiphenenoles norephone, 3, 3 '-diaminodi Phenylsulfide, 3,4'-diamino
  • the aliphatic diamines include 1,2-diaminoethane, 1,3 diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6 diaminohexane, 1,7 diaminoheptane, 1 , 8-diamino talented kutan, 1,9-diaminononane, 1,10 diaminodecane, 1,11-diaminoundecane.
  • Examples of the alicyclic diamine include compounds represented by the formula (19).
  • Examples of the diamine having a carboxyl group include a compound represented by the formula (20).
  • diamine having a hydroxyl group examples 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 1,4,4 ' Dihydroxybiphenyl, 2,2bis (4hydroxy-3-aminophenol) propane, 2,2bis (4hydroxy-1-aminophenol) xafluoropropane, bis (4hydroxy) 1 3 aminophenol) ketone, 2, 2 bis
  • Examples of the diaminosiloxane include a compound represented by the formula (21).
  • R represents a hydrocarbon group having 1 to 20 carbon atoms.
  • A represents an integer of 1 to 10 carbon atoms.
  • b represents an integer from 1 to 20.
  • the hydrocarbon group (R 1) having 1 to 20 carbon atoms is not particularly limited.
  • Preferable examples include a sum hydrocarbon group, an aliphatic unsaturated hydrocarbon group, a functional group containing a cyclic structure, and a group obtained by combining them.
  • the aliphatic saturated hydrocarbon group includes a primary hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a secondary class such as an isobutyl group and an isopentyl group. And tertiary hydrocarbon groups such as hydrocarbon groups and t-butyl groups.
  • Examples of the aliphatic unsaturated hydrocarbon group include a hydrocarbon group containing a double bond such as a bur group and a allyl group, and a hydrocarbon group containing a triple bond such as an ethul group.
  • Examples of the functional group containing a cyclic structure include a monocyclic functional group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group, and a cyclooctyl group; a polycyclic functional group such as a norbornyl group and an adamantyl group; Examples include pyrrole, furan, thiophene, imidazole, oxazole, thiazole, tetrahydrofuran, a heterocyclic functional group having a dioxane structure; an aromatic hydrocarbon group containing a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring structure, and the like.
  • the hydrocarbon group having 1 to 20 carbon atoms (R) is a halogen atom, a hetero atom and
  • Metal atoms can be included.
  • the halogen atom in the present invention include fluorine, chlorine, fluorine, iodine power.
  • examples of the hetero atom in the present invention include oxygen, sulfur, nitrogen, and phosphorus.
  • examples of the metal atom in the present invention include silicon and titanium.
  • the hydrocarbon group having 1 to 20 carbon atoms (R) is a hetero atom and / or a metal atom.
  • R may be bonded directly to the binding hetero atom and / or metal atom
  • the carbon number of R in formula (21) is preferably 1 or more and 20 or less in consideration of flame retardancy.
  • the number of carbon atoms is particularly preferably 1 or more and 10 or less.
  • the most preferred hydrocarbon group (R 1) is a methyl group.
  • a in the formula (21) is 1 or more and 10 or less in consideration of flame retardancy. From the viewpoint of solvent solubility of the polyimide to be produced, a is preferably 2 or more and 8 or less, more preferably 3 or more and 6 or less.
  • b in the formula (21) is 1 or more and 20 or less in consideration of flame retardancy. From the viewpoint of solvent solubility of the polyimide to be formed, b is preferably 1 or more and 15 or less, more preferably 1 or more and 12 or less.
  • tetracarboxylic dianhydrides used in the present invention include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides.
  • the aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3, 3 '4, 4'-biphenyl tetracarboxylic dianhydride, 2, 2', 3, 3, -bifu Enyltetracarboxylic dianhydride, 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 anhydride, 1,1 bis (3,4-dicarboxyphenyl) ethane anhydride, Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone
  • the aromatic tetracarboxylic dianhydride having an ester group imparts flexibility to the alkali-soluble polyimide, and also enhances alkali solubility and imparts an inhibitory effect such as scum during development. It is preferable to be contained in alkali-soluble polyimide.
  • aromatic tetracarboxylic dianhydride having an ester group examples include 1,4 bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitate anhydride), 1,3-bis (2 —Hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), p phenylene bis (trimellitic acid monoester anhydride), 1,2- (ethylene) bis (trimellitic anhydride), 1, 3 — (Trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6 (hexamethylene) bis ( Trimellitate anhydride), 1,7 (heptamethylene) bis (trimellitic anhydride), 1,8- (otatamethylene) bis (trimellitic anhydride) 1,9- (nonamethylene) bis (trimellitic
  • 1,2 (ethylene) bis (trimellitic anhydride) represented by the formula (6) or P-phenylene bis (trimellitic acid monoester acid anhydride) represented by the formula (7) is preferable.
  • Examples of alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides include ethylene tetracarboxylic dianhydride, 1, 2, 3, 4 butanetetracarboxylic dianhydride, 1, 5 cyclohexane.
  • tetracarboxylic dianhydride components can be used alone or in combination.
  • bis (3,4-dicarboxyphenyl) ether dianhydride bis (3,4-dicarboxyphenyl) ether dianhydride, ethylene glycol bis (trimellitic acid monoester acid) from the viewpoint of solubility of polyimide in an organic solvent and pressure bonding to a substrate, etc.
  • Anhydride ⁇ -phenylene bis (trimellitic acid monoester anhydride), 4- (2,5 dioxotetrahydrofuran-3-inole) 1, 2, 3, 4 tetrahydro
  • the alkali-soluble polyimide used in the present invention is obtained by polymerizing and cyclizing silicon diamine, a diamine having an alkali-soluble functional group and / or other diamine, and an acid dianhydride as represented by the formula (5). It is preferable that the polyimide be made.
  • R and R represent a tetravalent organic group, which may be the same or different.
  • R is carbon.
  • R has at least one alkali-soluble functional group
  • a represents an integer of 1 to 10.
  • b represents an integer from 1 to 20.
  • R represents a tetravalent organic group having an ester structure, and R represents a divalent organic group.
  • ⁇ , / 3, and ⁇ are at least 1 and 0 ⁇ 01 ⁇ / 3 / ( ⁇ + / 3 + ⁇ ) ⁇ 0. )
  • the content of other diamine-derived sites is 35 mol0 / 0 from the viewpoint of flame retardancy, assuming that all diamine-derived sites are 100 mol%. Preferably less than 0 ! /.
  • the diamine derived from R in the present invention is a diamine having an alkali-soluble functional group as described above. If it is amin, it is not limited! /.
  • the diamine derived from R is limited as long as it is the above-mentioned diamine.
  • the acid dianhydride derived from R and R used in the present invention includes silicone diamine, alcohol
  • Any dianhydride capable of reacting with diamine having a potassium-soluble functional group and / or other diamine is not limited.
  • R and R in the formula (5) are the above-mentioned tetracarboxylic acid dicarboxylic acids.
  • the end of the polyimide used in the present invention is not particularly limited as long as it does not affect the performance.
  • the terminal may be sealed with an acid dianhydride used when producing polyimide, the terminal derived from diamine, or any other acid anhydride or amine compound.
  • the number average molecular weight of the polyimide used in the present invention is preferably 1000 or more and 1000000 or less from the viewpoints of flame retardancy, viscosity of the polyimide-containing resin composition, and moldability.
  • the number average molecular weight refers to 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 5000 to 500,000, most preferably 10,000 to 300,000.
  • the copolymerization mode of the polyimide used in the present invention may be a block structure or a random structure.
  • ⁇ , ⁇ , and ⁇ constituting the copolymer component in the present invention are at least 1, and 0.01 ⁇ ⁇ / ( ⁇ + ⁇ + y) ⁇ 0.9. If the value of + / 3 + ⁇ ) is 0 ⁇ 01 or more, there are sufficiently many silicone diamine parts necessary for pressure bonding to the substrate and the like, so that pressure bonding to the substrate is manifested.
  • the polyimide used in the present invention can be obtained by reacting acid dianhydride and diamine to synthesize polyamic acid and then heating (heating imidization). It can also be obtained by reacting acid dianhydride and diamine to synthesize polyamic acid, and then adding a catalyst followed by imidization (chemical imidization). In this, chemical imidation is This is preferable because imidization can be completed at a lower temperature.
  • acid dianhydride and diamine are reacted at an unequal molar ratio to synthesize polyamic acid, followed by addition of a catalyst and imidization (chemical imidization) to prepare a polyimide block,
  • the following acid dianhydride and / or diamine are reacted so as to finally have an approximately equimolar ratio to grow a polyamic acid block, and then imidized (chemical imidization). It is also preferable to synthesize block polyimide.
  • 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, and acid dianhydride powder is gradually added thereto, followed by stirring 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 mass% or more and 95 mass% or less, preferably 1 mass% or more and 90 mass% or less. A polyamic acid solution can be obtained by performing polymerization in this monomer concentration range.
  • reaction solvent used in the production of the polyamic acid examples include ether compounds having 2 to 6 carbon atoms such as dimethyl ether, dimethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether; acetone.
  • Ketone compounds having 2 to 6 carbon atoms such as methyl ethyl ketone; saturated hydrocarbons having 5 to 10 carbon atoms such as normal pentane, cyclopentane, nonolemanolehexane, cyclohexane, methinorecyclohexane, and decalin Compound: Aromatic hydrocarbon compound having 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene and tetralin; Ester compound having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and ⁇ -butyrolatatone Chloroform, methylene chloride Halogen-containing compounds having 1 to 10 carbon atoms such as 1,2-dichloroethane; 2 to 10 carbon atoms such as acetonitrile, ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ -dimethylacetamide, ⁇ -methyl-2-pyrrol
  • Particularly preferred solvents are those having 3 or more carbon atoms. Examples thereof include ester compounds having 6 or less, 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 in the production of the polyamic acid is preferably 0 ° C or higher and 250 ° C or lower. If it is 0 ° C or higher, the reaction starts. If it is 250 ° C or lower, there is no side reaction.
  • the temperature is preferably 15 ° C or higher and 220 ° C or lower, more preferably 20 ° C or higher and 200 ° C or lower. Most preferably, it is 20 ° C or higher and 100 ° C or lower.
  • the time required for the reaction of the polyamic acid varies depending on the purpose or reaction conditions, and is usually 96 hours or less, particularly preferably 30 minutes to 30 hours.
  • the imidization catalyst for producing the alkali-soluble polyimide used in the present invention is not particularly limited, but acid anhydrides such as acetic anhydride, ⁇ -noratolataton, ⁇ -butyrolataton, ⁇ -tetronic acid , Y-phthalide, ⁇ -coumarin, latathone compounds such as ⁇ -phthalide acid, pyridine, quinoline, ⁇ -methylmorpholine, and tertiary amines such as triethylamine.
  • one kind or a mixture of two or more kinds may be used as necessary.
  • a mixed system of ⁇ -valerolatatone and pyridine is particularly preferable from the viewpoint of high reactivity.
  • the amount of the imidization catalyst added is preferably 50% by mass or less, more preferably 30% by mass or less, based on 100% by mass of the polyamic acid. 10% by mass or less is more preferable. 5% by mass or less is most preferable.
  • reaction solvent the same solvent used for the production of polyamic acid can be used.
  • the polyamic acid solution can be used as it is. It is also possible to use a different solvent from that used for the production of polyamic acid.
  • reaction solvent examples include ether compounds having 2 to 6 carbon atoms, such as dimethyl ether, jetyl ether, methyl ethyl ethere, tetrahydrofuran, divalent xylene, ethylene glyconoresimethinole etherol; acetone, methyl ethyl Ketone compounds such as ketones having 2 to 6 carbon atoms; normal pentane, cyclopentane, normal hexane Saturated hydrocarbon compounds having 5 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene and tetralin, and aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as cyclohexane, methylcyclohexane, and decalin
  • An ester compound having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and ⁇ -ptyroratone; a halogen-containing compound having 1 to 10 carbon
  • Particularly preferred 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 is preferably 15 ° C or higher and 250 ° C or lower. If it is 15 ° C or higher, the reaction starts, and if it is 250 ° C or lower, there is no deactivation of the catalyst.
  • the temperature is preferably 20 ° C or higher and 220 ° C or lower, more preferably 20 ° C or higher and 200 ° C or lower.
  • the water produced by the imidization reaction can be removed from the reaction system together with a solvent azeotropic with water, such as toluene and xylene.
  • the obtained reaction solution can be used as it is as a polyimide varnish.
  • the time required for the reaction varies depending on the purpose or reaction conditions, and is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.
  • the polyimide can be recovered by distilling off the solvent in the reaction solution under reduced pressure.
  • Examples of the method for purifying the polyimide used in the present invention include a method of removing insoluble acid dianhydride and diamine in the reaction solution by filtration under reduced pressure, pressure filtration or the like. In addition, a so-called reprecipitation purification method in which the reaction solution is precipitated in a poor solvent can be carried out. In addition, if a particularly high-purity polyimide is required, extraction using a carbon dioxide supercritical method is also possible. [0072] Using the polyimide used in the present invention, a resin composition containing a solvent in which the polyimide can be uniformly dissolved and / or dispersed can be obtained.
  • the solvent constituting the polyimide-containing resin composition used in the present invention is not limited as long as it can uniformly dissolve and / or disperse the polyimide used in the present invention. It is also preferable to use the solvent used for the polymerization.
  • a solvent include ethers having 2 to 6 carbon atoms, such as dimethyl ether, jetyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycolo-resin methinole etherol, and propylene glycolanol monomethylol acetate.
  • Ketone compound having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin Saturated hydrocarbon compounds; aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene, tetralin; 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and ⁇ -ptyroratone Ester compounds; black mouth form, chloride Chlorine-containing compounds having 1 to 10 carbon atoms such as methylene and 1,2-dichloroethane; 2 to 10 carbon atoms such as acetonitrile, ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylformamide, ⁇ , ⁇ ⁇ ⁇ dimethylacetamide, ⁇ methyl
  • one kind or a mixture of two or more kinds may be used as necessary.
  • ⁇ ⁇ ⁇ methyl 2-pyrrolidone, ⁇ -butarate rataton, ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylformamide, and ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylacetamide are preferred.
  • the concentration of the polyimide in the resin composition comprising the polyimide and the solvent used in the present invention is not particularly limited as long as it is a concentration at which a resin molded body can be produced. From the viewpoint of the film thickness of the resin molding to be produced, it is preferable that the polyimide concentration is 1% by mass or more, and the uniformity of the film thickness of the resin molding is 90% by mass or less! From the viewpoint of the film thickness of the resulting resin molding, it is more preferably 2% by mass or more and 80% by mass or less!
  • the structure of the alkali-soluble polyimide or polyimide precursor used in the present invention is not particularly limited, but mechanical properties such as elongation, flexibility and flexibility when formed into a film, and warpage when formed into a dry finale. Considering the improvement effect, it is preferable to have a siloxane skeleton.
  • the warping improvement effect during dry film formation is achieved by blending component ( ⁇ ), but siloxane It is considered that the lower elastic modulus and lower Tg due to having a skeleton further contribute to the improvement of warpage.
  • the alkali-soluble polyimide or polyimide precursor preferably has a siloxane structure of 10% by mass or more and 90% by mass or less from the viewpoint of warpage and flame retardancy during the formation of a dry film. It is more preferable to have the following siloxane structure.
  • the terminal of the polyimide precursor of the present invention is not particularly limited as long as it does not affect the performance! /.
  • the terminal may be sealed with an acid dianhydride, a terminal derived from diamine, or other acid anhydrides or amine compounds used for producing the polyimide precursor.
  • the polyimide precursor in the resin composition of the present invention can be synthesized from the diamine used in the alkali-soluble polyimide described above and tetracarboxylic dianhydride. However, since the polyimide precursor has a carboxyl group in the molecule, it has a diamine having a carboxyl group or a hydroxyl group! It is also soluble in organic solvents.
  • the component (B) is selected from the group consisting of a compound having a structure represented by the formula (1), a compound having an isocyanuric acid ring, and an imide compound containing one or two imide groups other than the component (A). At least one compound.
  • P represents a phosphorus atom and the number of covalent bonds is 5.
  • X represents a nitrogen atom or an oxygen atom, and when X is a nitrogen atom, the number of covalent bonds is 3 and the oxygen atom. In this case, the number of covalent bonds is 2.
  • the phosphorus atom and the nitrogen or oxygen atom are bonded by a double bond.
  • Examples of the phosphoric acid compound include a phosphoric acid ester compound represented by the formula (2) and the formula (3), a phosphine oxide compound represented by the formula (4), a formula (17), and a formula (18). At least one compound selected from the group consisting of the phosphazene compounds represented is used.
  • the addition of these phosphorus compounds can reduce warpage during dry film formation, has excellent laminating properties (embeddability and adhesion) to the wiring pattern substrate, improves development characteristics, and can also impart flame retardancy.
  • 1 is an organic group. Multiple groups may be the same or different.
  • R is a monovalent organic group.
  • the phosphate ester compound represented by the formula (2) used in the present invention is not limited as long as it is a phosphate ester compound having an aliphatic organic group having 1 to 30 carbon atoms.
  • a carbon number of 1 or more is preferable because warpage and embedding properties tend to be improved when forming a dry film.
  • a carbon number of 30 or less is preferred because it tends to exhibit flame retardancy.
  • the R force in formula (2) or formula (3) S methyl group, ethyl group, butyl group, isobutyl group, 2-ethylhexyl group, butoxetyl group, phenyl It is preferably an organic group selected from a nyl group, a cresyl group, a xylenyl group, and an aminophenyl group.
  • R in the formula (4) is hydrogen, dihydroxyphenyl group, dibutylhydroxybenzyl group, (meth) acrylate.
  • R is preferably hydrogen.
  • Examples of such compounds include phosphoric acid having an aliphatic hydrocarbon group as a substituent such as trimethylenophosphate, triethylenophosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, and the like.
  • Examples thereof include phosphoric acid esters having an aliphatic organic group containing an oxygen atom as a substituent, such as esters and tris (butoxychetyl) phosphate.
  • tributyl phosphate triisobutyl phosphate, tris (2-ethylhexyl) phosphate, and tris (butoxetyl) phosphate are used. preferable.
  • the phosphate ester compound used in the present invention may be used alone or in combination of two or more. Among them, it is preferable to use a combination of two or more types because both flame retardancy and warp during dry film formation tend to be compatible.
  • the two types of combinations include tributyl phosphate, tris (butoxychetyl) phosphate, tris (2-ethylhexyl) phosphate, tris (butoxychetyl) phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, Triisobutyl phosphate, a combination of tris (butoxychetyl) phosphate, and the like.
  • the aliphatic organic group when the aliphatic organic group has an ether structure, there is an effect of shortening development time and reducing development residue (scum) during development.
  • the aliphatic organic group preferably contains a phosphate ester having an ether structure.
  • a preferred compound is tris (butoxetyl) phosphate.
  • the phosphoric acid ester compound used in the present invention is preferably used in a combination of two or more kinds, and among them, at least the aliphatic organic group contains a phosphoric acid ester having an ether structure. Is more preferable. Preferred combinations include tributyl phosphate, a combination of tris (butoxetyl) phosphate, a triisobutyl phosphate, a combination of tris (butoxychetyl) phosphate, and the like.
  • the addition amount of the phosphoric acid ester compound is 50% by mass from the viewpoint of photosensitivity and the like when the amount of (A) the alkali-soluble resin is 100% by mass.
  • the following is preferred. From the viewpoint of heat resistance of the cured body, it is preferably 45% by mass or less, more preferably 40% by mass or less.
  • the compound having an isocyanuric acid ring the compound represented by the formula (8) can be suitably used. Addition of a compound having an isocyanuric acid ring is also preferable from the viewpoint of flame retardancy and improvement of warpage when formed into a dry film, like the phosphoric ester compound.
  • R is a monovalent organic group.
  • a plurality of R may be the same or different from each other.
  • R is a monovalent organic group.
  • a monovalent organic group is, for example, an organic group having a carboxyl group.
  • organic group having a functional group or an ester group It is an organic group having a functional group or an ester group.
  • a monovalent organic group is, for example, an organic group represented by the formula (22).
  • an organic group having an ester group is preferable from the viewpoint of compatibility with a solvent used for a resin or varnish.
  • R takes into account the adhesion with copper, formula (12) or
  • R is an organic group selected from the formulas (12) and (13)).
  • R is an organic group selected from hydrogen and a methyl group.
  • an imide compound containing one or two imide groups other than the component (A) used in the present invention a compound represented by the formula (9) can be preferably used. Addition of an imide compound containing one or two imide groups is also preferable from the viewpoint of flame retardancy and improvement of warpage when formed into a dry film, as in the case of the phosphoric ester compounds.
  • R is a monovalent or divalent organic group.
  • M is 1 or 2.
  • Y is a formula (10).
  • R is a divalent organic group.
  • the imide compound is diamine and
  • the divalent organic group of amine will be introduced.
  • the diamine can use an aromatic diamine, an aliphatic diamine or an alicyclic diamine used in the synthesis of the aforementioned soluble polyimide.
  • aliphatic amines are preferable from the viewpoint of improving warpage. More preferably, 1,2-diaminoethane, 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,3-bis having an aliphatic carbon number of 2 to 6 is used.
  • a pyrene group, a butylene group, a pentene group, a hexene group, and a group represented by the formula (23) are preferable.
  • R is a monovalent organic group.
  • monovalent organic groups include alkyl groups,
  • alkyloxide group etc. are mentioned.
  • the alkyl group include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.
  • the alkyl oxide group include an ethylene oxide group, a polyethylene oxide group, a propylene oxide group, a polypropylene oxide group, a butylene oxide group, and a polybutylene oxide group.
  • m 1, when these monovalent organic groups are It is possible to have an acrylic or methacrylic group at the end.
  • R is a monovalent organic group represented by the formula (13) where R in the formula (11). For example, the expression (2
  • Component (B) can be used alone or in combination.
  • a combination of a phosphate ester compound and a compound having an isocyanuric acid ring, or one or two imide groups other than the phosphate ester compound and the component (A) A combination with the contained imide compound is preferred.
  • the compounding ratio is 50 for the compound having an isocyanuric acid ring or 100 parts by mass of the phosphoric acid ester compound or the imide compound containing one or two imide groups other than the component (A). 200 to 200 parts by mass is preferred!
  • the component (B) is a group consisting of compounds represented by formula (25), formula (26), formula (27), formula (28), and formula (29). At least one compound selected from is particularly preferred.
  • R is an organic group selected from hydrogen or a methyl group.
  • the component (B) is preferably 50 parts by mass or less with respect to 100 parts by mass of the component (A). More preferably, it is 30 parts by mass or less. More preferably, it is 20 parts by mass or less. This addition range is preferable because the film has good elongation and flexibility and good alkali solubility.
  • R R R R is not limited as long as it is an organic group having 3 to 20 carbon atoms. Carbon number 3
  • a carbon number of 30 or less is preferred because it tends to be compatible with the alkali-soluble resin.
  • functional groups derived from aromatic compounds having 6 to 18 carbon atoms are particularly preferred from the viewpoint of flame retardancy.
  • examples of such functional groups include phenyl groups, 2-hydroxyphenyl groups, 3-hydroxyphenyl groups, 4-hydroxyphenyl groups, and other functional groups having a phenyl group, 1-naphthyl group, 2-naphthyl group, and other naphthyl groups.
  • functional groups derived from nitrogen-containing heterocyclic compounds such as pyridine, imidazole, triazole, and tetrazole. These compounds may be used alone or in combination of two or more as required. Of these, compounds having a phenyl group and a 4-hydroxyphenyl group are preferred because of their availability.
  • p in the phosphazene compound represented by the formula (17) used in the present invention is not limited as long as it is 3 or more and 25 or less. If it is 3 or more, it exhibits flame retardancy, and if it is 25 or less, it is highly soluble in organic solvents. Among these, m is preferably 3 or more and 10 or less in view of availability.
  • q is not limited as long as it is 3 or more and 10 000 or less. If it is 3 or more, it exhibits flame retardancy, and if it is 10000 or less, it is highly soluble in organic solvents. Among these, 3 or more and 100 or less are preferable because of availability.
  • a and B in the phosphazene compound represented by the formula (18) used in the present invention are not limited as long as they are organic groups having 3 to 30 carbon atoms.
  • B is P (OC H) P (OC H) (OC H OH) P (OC H) (OC H OH) P (OC H) (OC H OH) P (
  • the amount of the phosphazene compound added is preferably 50% by mass or less from the viewpoint of photosensitivity when the amount of (A) alkali-soluble resin is 100% by mass. . From the viewpoint of the heat resistance of the cured product, it is preferably 45% by mass or less, more preferably 40% by mass or less.
  • the compound represented by formula (1) and / or the compound having an isocyanuric acid ring and / or the imide compound (B) containing one or two imide groups other than the component (A) are the photosensitive compound of the present invention. When combined with the component (C), it exhibits high flame retardancy.
  • photosensitivity is expressed by the (C) component quinonediazide compound. Furthermore, when the component (C) is used in combination with the component (B), the photosensitive resin composition of the present invention can exhibit high heat resistance and flame retardancy.
  • Examples of the quinonediazide compound include 1,2-benzoquinonediazidesulfonic acid esters, 1,2-benzoquinonediazidesulfonic acid amides, 1,2-naphthoquinonediazidesulfonic acid esters, 1,2- Naphthoquinone diazide sulfonic acid amides may be mentioned. Of these, 1,2-naphthoquinonediazide sulfonic acid esters are preferred from the viewpoint of dissolution inhibiting ability.
  • the 1, 2 naphthoquinone diazide sulfonic acid ester includes 1, 2 naphthoquinone diazide 4 sulfonic acid esters in which the sulfonic acid group is substituted at the 4-position as shown in the formulas (14) and (15) 1 and 2 naphthoquinone diazide 5 sulfonic acid esters may be used, and any of them may be used, but 1, 2 naphthoquinone diazide 4 sulfonic acid ester is preferable from the viewpoint of flame retardancy.
  • 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.
  • the acid chloride or the sulfonate can be obtained by mixing in a suitable solvent such as acetone.
  • 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.
  • 1,2-Naphthoquinonediazide sulfonic acid esters include trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, (polyhydroxyphenones) Enyl) alkanes such as 1,2-naphthoquinone diazide sulfonic acid esters.
  • Naphthoquinonediazide sulfonic acid esters of trihydroxybenzophenones include 2,3,4-trihydroxybenzophenone 1,2-naphthoquinonediazide 4-ose norephonic acid ester, 2 , 3, 4 Trihydroxybenzophenone 1, 2 Naphthoquinone diazide 5-Sulphonate, 2, 4, 6-Trihydroxybenzophenone 1, 2-Naphtho
  • 1,2-Naphthoquinone diazide sulfonate esters of tetrahydroxybenzophenones include 2, 2 ', 4, 4' tetrahydroxybenzophenone 1, 2 naphthoquinone diazide 4 sulfonate esters, 2 , 2 ', 4, 4' tetrahydroxybenzophenone 1,2-naphthoquinone diazide 5 sulfonic acid ester, 2, 2 ', 4, 3'-tetrahydroxybenzazophenone 1, 2, naphthoquinone diazide 1 sulfonic acid Ester, 2, 2 ', 4, 3'-tetrahydroxybenzophenone 1,2 naphthoquinonediazide 5 sulfonate ester, 2, 3, 4, 4'-tetrahydroxybenzophenone 1,2 naphthoquinonediazide 4 sulfone Acid ester, 2, 3, 4, 4'-tetrahydroxybenzophenone 1,2 naphthoquinon
  • 1,2-Naphthoquinonediazide sulfonic acid esters of pentahydroxybenzophenones include 2, 3, 4, 2 ', 6' pentahydroxybenzophenone and 1,2 naphthoquinone diazide 4 sulfonic acid esters. 2, 3, 4, 2 ', 6, monopentahydroxybenzophenone-1, 2 naphthoquinonediazido 5 sulfonate, and the like.
  • 1,2-Naphthoquinonediazide sulfonic acid esters of hexahydroxybenzophenones include 2, 4, 6, 3 ', 4', 5 'hexahydroxybenzophenone and 1,2 naphthoquinone diazide.
  • 1,2-Naphthoquinonediazide sulfonic acid esters of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid esters.
  • 1,2-Naphthoquinone diazide sulfonic acid esters are preferred from the viewpoint of dissolution inhibiting ability, 1,2-naphthoquinone diazide 4-sulfonic acid esters, 1,2-naphthoquinone diazide 5-sulfonic acid esters Is more preferable from the viewpoint of photosensitive contrast.
  • the compound represented by the formula (16) is preferable in consideration of flame retardancy.
  • each Q is independently hydrogen or a monovalent organic group selected from the formula (14) or the formula (15). However, at least one of a plurality of Q is the formula (14) or the formula (15). It is an organic base that can be selected from the power.)
  • the compound represented by the formula (16) is more flame retardant than other 1,2-naphthoquinonediazide compounds. Excellent effect.
  • a compound having a 1,2-naphthoquinonediazido 4-sulfonic acid ester having a 4-position substitution position represented by the Q force formula (14) is particularly excellent in flame retardancy and is preferable.
  • the component (C) is preferably 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 40% by mass or less with respect to 100% by mass of the component (A). More preferably, it is 15% by mass or more and 30% by mass or less. Within this range, flame retardancy and photosensitivity are favorable.
  • the preferred blending amount of component (B) and component (C) is that the total of component (B) and component (C) is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of component (A). I like it! / More preferably, it is 10 to 50 parts by mass. More preferably, it is 20 parts by mass or more and 40 parts by mass or less.
  • the direct ratio of component (B) / component (C) is 0.4 or more and 4 or less. More preferably, it is 0.5 or more and 3 or less. More preferably, it is 0.75 or more and 2 or less. Within this range, flame retardancy and photosensitivity are good, warpage during dry film formation is suppressed, and embedding into a substrate is also good.
  • a component (D): a polyether compound to the photosensitive resin composition of the present invention in order to further improve the warp during dry film formation!
  • polyether compounds include linear polyethers and cyclic crown ethers.
  • the linear polyether is, for example, a compound having an ethylene oxide chain, a propylene oxide chain, or a butylene oxide chain.
  • a compound having an ethylene oxide chain is particularly effective and preferable for improving the warp during dry film formation.
  • Examples of the crown ether include 12 crown-4 ether, 15 crown-5 ether, 18 crown-6 ethere and the like.
  • the polyether compound is preferably a compound having an OH group at the terminal in order to improve the adhesion of the wiring of the wiring pattern substrate to the copper surface.
  • Examples of the polyether compound having an ethylene oxide chain and having an OH group at the terminal include polyethylene glycols such as ethylene glycolol, diethylene glycolol, triethylene glycolol, and tetraethylene glycol.
  • Examples of the compound having a propylene oxide chain and having an OH group at the terminal include propylene dariconol, dipropylene glycol, tripropylene glycol and tetrapropylene glycol.
  • Examples of the compound having a butylene oxide chain and having an OH group at the terminal include polybutylene glycols such as butylene glycol mononole, dibutylene glycol, tributylene glycol and tetrabutylene glycol.
  • polyethylene glycol is preferred in consideration of the warp of the dry film.
  • Polyethylene glycol is preferably a compound having a molecular weight of 300 to 1000, which is highly compatible with a resin varnish, which has a high effect of improving warpage. Further, the molecular weight is more preferably 400 force 800 from the viewpoint of achieving both the effect of improving warpage and the effect of suppressing the scattering of components remaining in the film after heating. Specifically, polyethylene glycol having a molecular weight of about 600 is preferable.
  • Plasticizer component in the photosensitive resin composition containing phosphazene used in the present invention is not particularly limited as long as it imparts plasticity to the resin composition and can lower the Tg of the composition.
  • plasticizers include phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-butoxetyl) phosphate; Ether compounds such as polyethylene glycol, polypropylene glycol and crown ether; Methacrylic group-containing compounds such as tetraethylene glycol dimetatalylate and polyethylene glycol dimetatalylate; Acrylic groups such as tetraethylene glycol ditalylate and polyethylene gallium ditalarate Containing compounds; phthalic acid esters such as dimethyl phthalate and jetyl phthalate; trimellitic
  • phosphate ester, methacryl group-containing compound, isocyanuric acid Preference is given to ethylene glycol-modified triatalylate, 8—force prolataton-modified tris (Atari mouth kichetil) isocyanurate!
  • the amount of the plasticizer: (E) component is set in consideration of sufficient plasticity.
  • the amount of the alkali-soluble resin is 100% by mass. In this case, 30% by mass or less is preferable. Further, from the viewpoint of flame retardancy of the cured body, 20 mass% or less is more preferable.
  • additives that are already known can be added as needed 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, and antifoaming agents.
  • the photosensitive resin composition of the present invention is obtained by mixing the component (A), the component (B), and the component (C) in an arbitrary solvent.
  • the solvent it is possible to use the solvent used in the polyimide resin composition described above. Moreover, you may add (D) component and (E) component as needed.
  • the solution obtained by mixing can be used as a coating solution.
  • a liquid mixture is apply
  • a circuit board can be produced using the photosensitive resin composition of the present invention.
  • a photosensitive resin composition layer is laminated on at least a substrate having wiring, pattern exposure is performed on the photosensitive resin composition layer, and the resin composition after the pattern exposure is performed.
  • the layer is developed using an aqueous alkaline solution.
  • the substrate having wiring includes, for example, a substrate having wiring on an arbitrary substrate such as a hard substrate such as a glass epoxy substrate or a glass maleimide substrate, or a flexible substrate such as a polyimide film.
  • the photosensitive resin composition of the present invention can be suitably used as a coverlay for a flexible printed wiring board having wiring on a flexible substrate such as a polyimide film.
  • a cover lay for a flexible printed wiring board for example, it is applied in a dry film state on a substrate having wiring. To do.
  • a dry film composed of the photosensitive resin composition of the present invention When a dry film composed of the photosensitive resin composition of the present invention is used, a solution of the photosensitive resin composition is applied on an arbitrary carrier film such as a polyethylene terephthalate film or a metal phenolic film by an arbitrary method. After that, it is dried and formed into a dry film to obtain a laminated film having a carrier film and a dry film.
  • a laminated film may be formed by providing at least one arbitrary antifouling film such as a low density polyethylene film or a protective film on the dry film.
  • This dry film is laminated on a substrate having wiring by any method such as a thermal laminating method, a hot pressing method, a thermal vacuum laminating method, or a thermal vacuum pressing method.
  • the substrate is coated with the photosensitive resin composition of the present invention.
  • the substrate is not limited as long as it is a substrate that is not damaged during the formation of the photosensitive dry film.
  • examples of such a substrate include silicon wello, glass, ceramic, heat resistant resin, and carrier film.
  • Examples of the carrier film in the present invention include a polyethylene terephthalate film and a metal film. From the viewpoint of ease of handling, a polyethylene terephthalate film is particularly preferred from the viewpoint of peelability after pressure bonding to the substrate, which is preferable for heat-resistant resins and carrier films.
  • Examples of the coating method include bar coating, roller coating, die coating, blade coating, date coating, doctor knife, spray coating, flow coating, spin coating, slit coating, brush coating, and the like. After coating, if necessary, a heat treatment called pre-baking may be performed with a hot plate or the like.
  • a solution of the photosensitive resin composition is applied on an arbitrary substrate by an arbitrary method and then dried.
  • Dry film for example, a laminated film having a carrier film and a photosensitive film
  • At least one layer of an optional antifouling or protective cover film may be provided on the photosensitive film to form a laminated film.
  • the force Examples of the bar film include a photosensitive film made of low-density polyethylene.
  • the film thickness of the coverlay formed by these methods is not particularly limited, but it is preferably 4 ⁇ m to 50 ⁇ m from the viewpoint of circuit characteristics, etc. 6 ⁇ m to 40 ⁇ m It is particularly preferred that the power is 8, 1 m-30, 1 m! / ⁇ .
  • the photosensitive film composed of the resin composition of the present invention is applied to a printed wiring board obtained by pressure-bonding to a substrate having wiring so as to cover the wiring, performing alkali development, and firing. Can be used.
  • Examples of the substrate having wiring in the printed wiring board used in the present invention include a hard substrate such as a glass epoxy substrate and a glass maleimide substrate, or a flexible substrate such as a polyimide film. Of these, flexible substrates are preferred from the standpoint of bendability!
  • the method for producing the printed wiring board is not limited as long as the photosensitive film is formed on the substrate so as to cover the wiring.
  • Examples of such a production method include a method of performing hot pressing, thermal laminating, thermal vacuum pressing, thermal vacuum laminating, etc. in a state where the wiring side of the substrate having the wiring is in contact with the photosensitive film of the present invention. Can be mentioned. Among these, from the viewpoint of embedding the photosensitive film between the wirings, a thermal vacuum press or a thermal vacuum lamination is preferable.
  • the heating temperature for laminating the photosensitive film on the substrate having the wiring is not limited as long as the photosensitive film can adhere to the substrate. From the viewpoint of adhesion to the substrate, decomposition of the photosensitive film, and side reactions, 30 ° C or more and 400 ° C or less are preferable. More preferably, it is 50 ° C or higher and 150 ° C or lower.
  • the photosensitive resin composition of the present invention can dissolve the light irradiation site by alkali development after the light irradiation, it can be used as a patterning material by positive photolithography.
  • the light source used for light irradiation is not particularly limited, but high pressure mercury lamp, ultra high pressure mercury lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, fluorescent lamp, tungsten lamp, argon laser, helium cadmium laser, etc. Can be mentioned. Among them, high-pressure mercury lamp, ultra-high A pressure mercury lamp is preferred.
  • the aqueous alkali solution used for development is not limited as long as it is a solution capable of dissolving the light irradiation site.
  • a solution capable of dissolving the light irradiation site examples include a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and a tetramethyl ammonium hydroxide aqueous solution.
  • 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 film or positive pattern obtained on the substrate by these methods can be subjected to a heat treatment, if necessary.
  • the heating temperature is preferably 100 ° C or more and 300 ° C or less. More preferably, it is 150 ° C or higher and 250 ° C or lower. Particularly preferably, it is 160 ° C or higher and 200 ° C or lower.
  • Heating may be performed in an air atmosphere or a nitrogen atmosphere.
  • the heating method is not particularly limited, but can be performed using an oven, a firing furnace, a hot plate, or the like.
  • Firing when the photosensitive film of the present invention is pressure-bonded and fired may be 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. Preferred. More preferably, it is 100 ° C or higher and 300 ° C or lower.
  • the reaction atmosphere in the firing can be carried out in an air atmosphere or an inert gas atmosphere.
  • the time required for the firing varies depending on the reaction conditions, usually within 24 hours, and particularly preferably in the range of 1 to 8 hours.
  • the photosensitive resin composition of the present invention is sufficiently suppressed in warpage as a photosensitive film, has good developability, and exhibits chemical resistance when used as a cured product.
  • ODPA oxydiphthalic dianhydride (bis (3,4-dicarboxyphenyl) etherole dianhydride)
  • TAHQ p-phenylene bis (trimellitic acid monoester anhydride)
  • TMEG Ethylene glycol bis (trimellitic acid monoester anhydride)
  • APB 1,3-bis (3-aminophenoxybenzene)
  • TBP Tributyl phosphate
  • TBXP Tris (Butki Shechinor) phosphate
  • TIBP Triisobutyl phosphate
  • RDP resorcinol bis (diphenyl phosphate)
  • CR741 Bisphenol A bis (diphenyl phosphate)
  • CDP Cresino Resifeninorephosphate
  • Compound C 2 Refers to an average of 2.34 of the three Qs in the general formula (16) that have the structure represented by the general formula (15)! /. [0152] ⁇ Reagent>
  • the reagents used are silicone diamine (KF-8010) (manufactured by Shin-Etsu Chemical Co., Ltd.), MBAA (manufactured by Wakayama Seika Co., Ltd.), ODPA (manufactured by Wako Pure Chemical Industries, Ltd.), A PB (Mitsui Chemicals Co., Ltd.), TMEG (New Nippon Rika Co., Ltd.), Compound B-1, Compound B-2, TB P (Daihachi Chemical Co., Ltd.), TOP (Daihachi Chemical Co., Ltd.), TBXP (Daihachi Chemical Co., Ltd.) TIBP (manufactured by Ajinomoto Fine Techno Co., Ltd.), resorcinol bis (diphenyl phosphate) (manufactured by Ajinomoto Fine Tetano Co., Ltd., hereinafter abbreviated as RDP), acetiltyl buty
  • a 1-liter separable three-necked flask equipped with a stirrer was fitted with a ball condenser equipped with a moisture meter. Under nitrogen flow, ⁇ -petit-mouth rataton 268.52 g (Wako Pure Chemical Industries, Ltd.), oxydiphthalic dianhydride 31.02 g (100 mmol) (Manac Co., Ltd.), 1,3-bis (3 —Aminopropyl) Polysiloxane 68 ⁇ 55g (75mm monole) (Molecular weight 914 / Shin-Etsu Chemical Co., Ltd.), 3,5 Diaminobenzoic acid 7.61g (50mmol) (Aldrich) was charged and stirred at room temperature for 2 hours. did.
  • Polyimide varnish is applied to a 25 111 thick easily peelable PET (T100—H25 / Mitsubishi Chemical Polyester Film Co., Ltd.) with a blade coater, dried in an oven at 95 ° C for 30 minutes, and then peeled off.
  • the elongation of the obtained film measured by a tensile tester was 50% or more (test piece 24 ⁇ thickness, 15 mm ⁇ 100 mm).
  • the compound (a) represented by the following formula (30) or the compound (b) represented by the following formula (31) was used as the (C) component quinonediazide compound.
  • Compound (a) consists of a, a, ⁇ , monotris (4-hydroxyphenyl) 1 ethyl 4 isopropyl benzene (1 monole) and 3-diazo-1,4 dihydro-4 oxonaphthalene 1-sulfone It is an ester with acid (2 ⁇ 3 monole).
  • Compound (b) consists of a, a, ⁇ , -tris (4-hydroxyphenyl) — 1-ethyl-4-isopropylbenzene (1 monole) and 4 diazo-4,5-dihydro-5-oxonaphthalene 1-sulfone. It is an ester with acid (2 ⁇ 34 monole).
  • component (B) bisphenol A bis (diphenyl phosphate) (CR741 / manufactured by Daihachi Chemical Co., Ltd.), (ii) 9, 10 dihydro-9-oxa 10 phosphaphenanthrene — 10-oxide ( made HCA / SANKO Co.), (iii) .epsilon. force Purorataton modified tris (Atari port Kishechiru) Isoshianureto (Aronikkusu .mu.
  • GPC Gel permeation chromatography
  • RI 2031P1US (RI: differential refractometer, manufactured by JASCO)
  • UV— 2075Plus UV-VIS: UV-Visible Absorber, JASCO
  • the calibration curve for calculating the molecular weight was prepared using standard polystyrene (manufactured by Tosohichi Co., Ltd.).
  • the film thickness of the cured product was measured using a film thickness meter (ID-C112B, manufactured by Mitutoyo).
  • the coating of the photosensitive resin composition in the present invention was performed by a doctor blade method using FILMCOATER (manufactured by Tester SA NGYO, PI1210). That is, the photosensitive resin composition was dropped onto an easy-peeling PET film (Mitsubishi Chemical Polyester Film Co., Ltd., DIAFOIL, T100H25) and coated with a clearance of 200 m. The coated film was dried at 95 ° C. for 30 minutes using a dryer (ESPEC, SPHH-101) to obtain a photosensitive dry film.
  • FILMCOATER manufactured by Tester SA NGYO, PI1210
  • a 111-thick PET film (T100-H25 / Mitsubishi Chemical Polyester Film Co., Ltd.) was coated with a blade coater and then dried in an oven at 95 ° C for 30 minutes to obtain a photosensitive dry film.
  • the coated part was cut into a size of 20 cm ⁇ 20 cm to give a test film, and the warpage was visually evaluated.
  • the case where no warpage occurred was marked as ⁇
  • the case where slight warpage occurred was marked as ⁇
  • the case where warpage occurred and the film was rolled up was marked as X.
  • the flame retardancy test was performed according to the following procedure. Coat the photosensitive resin composition on one side of Kapton (registered trademark) (EN-100 / Toray DuPont) film by the above-mentioned coating method, dry at 95 ° C for 30 minutes, and then on the other side After coating the photosensitive resin composition on the both sides of the Kapton (registered trademark) film by drying at 95 ° C for 30 minutes, a baking furnace (manufactured by Koyo Lindberg) was used to cure the photosensitive resin composition by baking at 120 ° C. for 60 minutes and then at 200 ° C. for 60 minutes to obtain a cured product. This cured product was cut into 20 cm ⁇ 5 cm and evaluated for flame retardancy by UL94 VTM test.
  • a 111-thick PET film (T100-H25 / Mitsubishi Chemical Polyester Film Co., Ltd.) was coated with a blade coater and dried in an oven at 95 ° C / 30 minutes to obtain a photosensitive dry film with a thickness of 24 m.
  • the following evaluation was performed using a copper foil laminated with a photosensitive film obtained by laminating evaluation. In addition, since it was difficult to evaluate the sample from which the PET film and the photosensitive film were peeled off, the following evaluation was performed with the photosensitive dry film being not laminated on the copper foil.
  • a 1-liter separable three-necked flask equipped with a stirrer was fitted with a ball condenser equipped with a moisture meter.
  • ⁇ -petit-mouth rataton 341.64 g (Wako Pure Chemical Industries, Ltd.), oxydiphthalic dianhydride 31.02 g (100 mmol) (Manac Co., Ltd.), 1,3-bis (3 —Aminopropyl) polysiloxane 68 ⁇ 55g (75mm monolayer) (molecular weight 914 / Shin-Etsu Chemical Co., Ltd.), 3,3'-dicarboxy-4,4'-diaminodiphenylmethane 14 ⁇ 31g (50mmol) (Wakayama Seika Co., Ltd.) ) And stirred at room temperature for 2 hours.
  • ⁇ -nozzle rattan 1 ⁇ 5 g (15 mm monole), pyridine 2.4 g (30 mm monole), and ⁇ nolene 50 g were charged into the above flask, heated to 180 ° C, and combined with toluene-water. The mixture was stirred at 80 rpm for 2 hours while removing boiling components.
  • Example 12 the (A) component-containing varnish of Example 5 was used as the (A) component described in Polyimide Synthesis Example 2. The evaluation was carried out in the same manner as in Example 5 except that the varnish was replaced with the component-containing varnish. As a result, it was warped, flame retardant, laminating, and photosensitive.
  • Example 13 the (A) component-containing varnish of Example 11 was replaced with the (A) component-containing varnish described in Polyimide Synthesis Example 2, and evaluation was performed in the same manner as in Example 11 except that. As a result, it was warped ⁇ , flame retardant ⁇ , laminate property ⁇ , and photosensitivity ⁇ .
  • the photosensitive films (Examples 1 to 13) obtained using the photosensitive resin composition of the present invention were warped, flame retardant, laminate and photosensitive. All of the properties were good.
  • the photosensitive films of Comparative Examples 1 to 4 Comparative Example 6, Comparative Example 7 and Comparative Example 9, the flame resistance is poor, and the photosensitive films of Comparative Examples 5 and 8 are warped. And the laminating property was bad.
  • Lamination in the present invention was performed using a vacuum press (manufactured by Meiki Seisakusho).
  • the press was performed at a press temperature of 110 ° C, a press pressure of 1.23 MPa, and a press time of 5 minutes.
  • the photosensitive resin composition thus obtained was coated on an easily peeled PET film by the above-described coating method and dried at 95 ° C. for 30 minutes to obtain a photosensitive dry film. The warpage was a dry finale and was ⁇ .
  • the above photosensitive dry film was laminated on a copper circuit (50 am copper line width, line spacing was 50 m, copper wiring thickness 12 m) under the above laminating conditions. When the obtained laminate was cut and the cross section was observed with an electron microscope, it was embedded without voids and the surface of the coverlay layer was flat.
  • the positive photosensitive resin composition was coated on Kapton (registered trademark) by the above-described coating method, dried at 95 ° C for 30 minutes, and then coated on the opposite side to be 95 ° Kapton (registered trademark) coated with a positive photosensitive resin composition obtained by drying at C for 30 minutes was heated in an air atmosphere in a baking furnace at 120 ° C for 60 minutes, and then at 200 ° C for 60 minutes. A cured product was obtained by baking for a minute. The cured product was evaluated for flame retardancy by UL94 VTM test. The results are shown in Table 5 below.
  • the above-mentioned photosensitive film was laminated on a copper-clad laminate under the above-mentioned laminating conditions.
  • the resulting laminate is exposed using a positive mask at an irradiation dose of 1. Oj / cm 2 , followed by alkaline development with a 3% aqueous sodium hydroxide solution and rinsing with water.
  • the pattern was observed with an optical microscope. In each dry film, a copper surface appeared in the exposed area, and the thickness of the coverlay layer in the unexposed area was 15 111 or more (20 mm).
  • Compound C-2 (20% by mass), 100% relative to 100% by mass of the polyimide (1) produced in Example 14? (15% by mass) and Ding 8? (15% by mass) was mixed to prepare a photosensitive resin composition.
  • the photosensitive resin composition was warped in the same manner as in Example 14 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 5 below.
  • Compound 100-2 (20% by mass), Ding 18? (15% by mass) and Ding 8 against 100% by mass of the polyimide (1) produced in Example 14? (15% by mass) was mixed to prepare a photosensitive resin composition.
  • the photosensitive resin composition was warped in the same manner as in Example 14 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 5 below.
  • Compound C-2 (20% by mass) was mixed with 100% by mass of the polyimide (1) produced in Example 14 to prepare a photosensitive resin composition.
  • the photosensitive resin composition was warped in the same manner as in Example 14 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 5 below.
  • the photosensitive resin composition was warped in the same manner as in Example 14 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 5 below.
  • Compound C-2 (20% by mass) and general plasticizer ATC (30% by mass) were mixed with 100% by mass of polyimide (1) produced in Example 14, and a photosensitive resin composition was prepared. It was adjusted. The photosensitive resin composition was warped in the same manner as in Example 14 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 5 below.
  • Compound C-1 (20% by mass) was mixed with 100% by mass of the polyimide (2) produced in Example 17 to prepare a photosensitive resin composition.
  • the same photosensitive resin composition as in Example 14 was used.
  • the warpage, flame retardancy, embedding property, and alkali developability were evaluated by the same methods. The results are shown in Table 5 below.
  • a fat composition was prepared.
  • the photosensitive resin composition was warped in the same manner as in Example 14 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 5 below.
  • TMEG 31.8 mmol
  • 120 ° The mixture was stirred for 2 hours at C.
  • Toluene (10mU was added, and the mixture was stirred for 2 hours at 180 ° C. Cooled to 140 ° C, so that the polymer solids concentration was 30% by mass.
  • ⁇ -petit-mouthed rataton was added to and cooled to room temperature to obtain a ⁇ -petit-mouthed rataton solution of polyimide (3).
  • the number average molecular weight of the polyimide (3) was 37000, and the value of / 3 / ( ⁇ + / 3 + ⁇ ) in the general formula (5) was 0.33.
  • the photosensitive resin composition thus obtained was coated on an easily peeled PET film by the above-described coating method and dried at 95 ° C. for 30 minutes to obtain a photosensitive dry film. The warpage was a dry finale and was ⁇ .
  • the above photosensitive dry film was laminated on a copper circuit (copper line width of 50 am, line spacing was 50 m, copper wiring thickness 12 m) under the above laminating conditions.
  • a copper circuit copper line width of 50 am, line spacing was 50 m, copper wiring thickness 12 m
  • the positive photosensitive resin composition was coated on Kapton (registered trademark) by the above-mentioned coating method, dried at 95 ° C for 30 minutes, and then coated on the opposite side to be 95 ° Kapton (registered trademark) coated with a positive photosensitive resin composition obtained by drying at C for 30 minutes was heated in an air atmosphere in a baking furnace at 120 ° C for 60 minutes, and then at 200 ° C for 60 minutes. A cured product was obtained by baking for a minute. The cured product was evaluated for flame retardancy by UL94 VTM test. The results are shown in Table 2 below. Table 6 below shows the blending amounts of polyimide, photosensitizer, and phosphate ester. The amounts of the following examples and comparative examples are also shown in Table 6 below.
  • the above photosensitive film was laminated on a copper-clad laminate under the above-mentioned laminating conditions.
  • the resulting laminate is exposed using a positive mask at an irradiation dose of 1. Oj / cm 2 , followed by alkaline development with a 3% aqueous sodium hydroxide solution and rinsing with water.
  • the pattern was observed with an optical microscope. In each dry film, a copper surface appeared in the exposed area, and the thickness of the coverlay layer in the unexposed area was 15 111 or more (20 mm).
  • Compound 100-2 (20% by mass) relative to 100% by mass of the polyimide (3) produced in Example 18 Ding ⁇ ? (15% by mass) and Ding 8? (15% by mass) was mixed to prepare a photosensitive resin composition.
  • the photosensitive resin composition was warped in the same manner as in Example 1 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 7 below.
  • ODPA ODPA
  • silicone diamine KF-8010, 15. Ommol
  • ⁇ -butyrorataton 40 mU
  • pyridine 11.4 mmol
  • ⁇ -valerolataton 7.5 mmol
  • APB 3. Ommol
  • MBAA 10. Ommol
  • Polyimide (4) was mixed with 100% by mass of compound C 1 (20% by mass), Ding 18? (35% by mass) and cocoon (15% by mass) to prepare a photosensitive resin composition. .
  • the photosensitive resin composition was warped in the same manner as in Example 18 and evaluated for flame retardancy and embedding property.
  • alkali developability developability was evaluated in the same manner as in Example 18 except that 1% aqueous sodium hydroxide solution was used as the developer. The results are shown in Table 7 below.
  • Compound C-2 (20% by mass) was mixed with 100% by mass of the polyimide (3) produced in Example 18 to prepare a photosensitive resin composition.
  • the photosensitive resin composition was the same as in Example 18.
  • the warpage, flame retardancy, embedding property, and alkali developability were evaluated by the same methods. The results are shown in Table 7 below.
  • a fat composition was prepared.
  • the photosensitive resin composition was warped in the same manner as in Example 18 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 7 below.
  • Compound C-2 (20% by mass) and general plasticizer ATC (30% by mass) were mixed with 100% by mass of the polyimide (3) produced in Example 18, and a photosensitive resin composition was prepared. It was adjusted. The photosensitive resin composition was warped in the same manner as in Example 18 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 7 below.
  • Compound C-1 (20% by mass) was mixed with 100% by mass of the polyimide (3) produced in Example 18 to prepare a photosensitive resin composition.
  • the photosensitive resin composition was warped in the same manner as in Example 18 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 7 below.
  • a fat composition was prepared.
  • the photosensitive resin composition was warped in the same manner as in Example 18 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 7 below.
  • Compound C-1 (20% by mass) was mixed with 100% by mass of the polyimide (4) produced in Example 21 to prepare a photosensitive resin composition.
  • the photosensitive resin composition was warped in the same manner as in Example 18 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 7 below.
  • Compound 100-1 (20% by mass) and RDP (50% by mass) which is a phosphate ester having an aromatic group were mixed with 100% by mass of the polyimide (4) produced in Example 21, and the photosensitive resin was mixed.
  • a fat composition was prepared.
  • the photosensitive resin composition was warped in the same manner as in Example 18 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 7 below.
  • Compound 100-1 (20% by mass) and general plasticizer ATC (50% by mass) are mixed with 100% by mass of the polyimide (4) produced in Example 4, and a photosensitive resin composition is prepared. Adjusted. The photosensitive resin composition was warped in the same manner as in Example 18 and evaluated for flame retardancy, embedding property, and alkali developability. The results are shown in Table 7 below.
  • the photosensitive films (Comparative Example 18, Comparative Example 21, and Comparative Example 24) composed of a photosensitive resin composition to which a general plasticizer is added, although warpage and embedding are improved, flame retardancy is improved. It can be seen that the properties are reduced. From the above, the photosensitive film made of the photosensitive resin composition to which the phosphoric acid compound of the present invention is added has improved warpage and embedding property when formed into a dry film while maintaining flame retardancy. Moreover, the developability was also good.
  • Evaluation of developability was conducted by laminating a copper-clad laminate with a photosensitive dry film (thickness of photosensitive layer: approx. 15 m) under the above laminating conditions, and then using a positive mask to irradiate 1.
  • OjZcm Perform exposure at 2 followed by 1% or 3% aqueous sodium hydroxide solution. Potash development and rinsing with water were performed, and the pattern was evaluated with an optical microscope after drying.
  • the mask used a circular pattern with a diameter of 10011 m (interval of 100 Hm pitch).
  • the film thickness of the unexposed area of the photosensitive layer is 13 inches or more, ⁇ , and a case where it is 10 111 or more and less than 13 111, ⁇ , otherwise the resolution is inferior X or the case where the film thickness is less than 10 m.
  • Polyimide (5) is mixed with 100% by mass of Compound J-1 (20% by mass), 3-8-100 (20% by mass), and ⁇ -325 (30% by mass).
  • a resin composition was prepared. The composition is shown in Table 9 below.
  • the photosensitive resin composition thus obtained was coated on an easily peelable PET film by the aforementioned coating method and dried at 95 ° C. for 30 minutes to obtain a photosensitive dry film. The warp was ⁇ by Dreifu Inrem.
  • the above photosensitive dry film was laminated on a copper circuit (copper line width of 50 m, line spacing was 50 m, copper wiring thickness 12 m) under the above laminating conditions.
  • a copper circuit copper line width of 50 m, line spacing was 50 m, copper wiring thickness 12 m
  • the positive photosensitive resin composition was coated on Kapton (registered trademark) by the above-mentioned coating method, dried at 95 ° C for 30 minutes, and then coated on the opposite side to be 95 ° Kapton (registered trademark) coated with a positive photosensitive resin composition obtained by drying at C for 30 minutes, A cured product was obtained by firing at 120 ° C. for 60 minutes in a firing furnace and then at 200 ° C. for 60 minutes. The cured product was evaluated for flame retardancy by UL94 VTM test. The results are shown in Table 10 below.
  • the above photosensitive film was laminated on a copper-clad laminate under the above-mentioned laminating conditions.
  • the resulting laminate is exposed using a positive mask at an irradiation dose of 1. Oj / cm 2 , followed by alkaline development with a 3% aqueous sodium hydroxide solution and rinsing with water.
  • the pattern was observed with an optical microscope. In each dry film, a copper surface appeared in the exposed area, and the film thickness of the coverlay layer in the unexposed area was 13 m or more.
  • silicone diamine KF-8010, 45. Ommol
  • ⁇ -butyrolatone 120 mL
  • ODPA 60. Ommol
  • toluene 60 mU, pyridine (34. 13 mmol)
  • ⁇ -bare ratatotone 22. 47 mmol
  • APB 9.
  • Compound J-2 (20% by mass) and 3-8-100 (20% by mass) were mixed with 100% by mass of polyimide (6) to prepare a photosensitive resin composition.
  • the composition is shown in Table 9 below.
  • the photosensitive resin composition was warped in the same manner as in Example 22 to evaluate flame retardancy and press-bonding property to a substrate.
  • the alkali developability was evaluated using a 1% aqueous sodium hydroxide solution. The results are shown in Table 10 below.
  • Compound C-2 (20% by mass), SPB-100 (20% by mass), and cocoon (10% by mass) were mixed with 100% by mass of the polyimide (6) produced in Example 23 to obtain a photosensitive resin composition. Adjust things did.
  • the composition is shown in Table 9 below.
  • the photosensitive resin composition was warped in the same manner as in Example 22 and evaluated for flame retardancy, pressure-bondability to a substrate, and alkali developability. The results are shown in Table 10 below.
  • Compound C-2 (20% by mass), SPH-100 (20% by mass), TBXP (10% by mass) are mixed with 100% by mass of the polyimide (6) produced in Example 23 to obtain a photosensitive resin composition. I adjusted things. The composition is shown in Table 9 below. The photosensitive resin composition was warped in the same manner as in Example 22 and evaluated for flame retardancy, pressure-bondability to a substrate, and alkali developability. The results are shown in Table 10 below.
  • Compound C-2 (20% by mass) was mixed with 100% by mass of the polyimide (6) produced in Example 23 to prepare a photosensitive resin composition.
  • the composition is shown in Table 9 below.
  • the photosensitive resin composition was warped in the same manner as in Example 22 and evaluated for flame retardancy, pressure-bondability to a substrate, and alkali developability. The results are shown in Table 10 below.
  • composition of positive photosensitive resin composition is composition of positive photosensitive resin composition
  • Warpage Film thickness ( ⁇ ) One flame resistance Bondability to substrate Developability Example 22 ⁇ 16 VTM-0 ⁇ ⁇
  • the photosensitive resin composition of the present invention sufficiently suppresses warpage as a photosensitive film, is excellent in embedding and adhesion to a substrate, has good developability, and is flame retardant after curing. Therefore, it can be applied to photosensitive dry films and coverlays. In the field of etatronicitas, it can be used to form a protective layer for flexible printed circuit boards and circuit boards, as well as for laminated boards. Insulating layer formation, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripherals, semiconductor mounting substrates, heat sinks, lead pins, semiconductors themselves, etc. Used for film formation.

Abstract

L'invention concerne une composition de résine photosensible comprenant les constituants (A), (B) et (C), le constituant (A) étant une résine alcalino-soluble, le constituant (B) étant au moins un composé choisi dans le groupe constitué par un composé présentant une structure représentée par la formule (1), un composé possédant un noyau isocyanurate et un composé imide possédant au moins un groupe imide différent du composé du constituant (A), et le constituant (C) étant un composé quinonediazide. Dans la formule (1), P représente un atome de phosphore, le nombre de liaisons covalentes étant 5, X représente un atome d'azote ou un atome d'oxygène, le nombre de liaisons covalentes étant 3 lorsque X représente un atome d'azote, et 2 lorsque X représente un atome d'oxygène, et l'atome de phosphore et l'atome d'azote ou d'oxygène sont liés l'un à l'autre par l'intermédiaire d'une double liaison.
PCT/JP2007/072222 2006-11-15 2007-11-15 Composition de résine photosensible et carte de circuit imprimé souple comprenant cette composition WO2008065905A1 (fr)

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JP2009053646A (ja) * 2007-07-31 2009-03-12 Asahi Kasei Corp 感光性樹脂組成物及びそれを用いた感光性フィルム
WO2010016256A1 (fr) * 2008-08-07 2010-02-11 太陽インキ製造株式会社 Composition de résine photodurcissable ignifuge, film sec et produit durci obtenus à partir de celle-ci, et carte de câblage imprimé utilisant la composition, le film sec ou le produit durci
WO2010016258A1 (fr) * 2008-08-07 2010-02-11 太陽インキ製造株式会社 Composition de résine photodurcissable ignifuge, film sec et produit durci obtenus à partir de celle-ci, et carte de câblage imprimé utilisant la composition, le film sec ou le produit durci
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JP2013095894A (ja) * 2011-11-04 2013-05-20 Asahi Kasei E-Materials Corp ポリイミド前駆体又はポリイミド及び感光性樹脂組成物
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