WO2008065905A1 - Photosensitive resin composition, and flexible print circuit board using the same - Google Patents

Photosensitive resin composition, and flexible print circuit board using the same 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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WO
WIPO (PCT)
Prior art keywords
formula
group
resin composition
photosensitive resin
compound
Prior art date
Application number
PCT/JP2007/072222
Other languages
French (fr)
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.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
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/en
Publication of WO2008065905A1 publication Critical patent/WO2008065905A1/en

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Classifications

    • 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.

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  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

Disclosed is a photosensitive resin composition comprising components (A), (B) and (C), wherein the component (A) is an alkali-soluble resin, the component (B) is at least one compound selected from the group consisting of a compound having a structure represented by the formula (1), a compound having an isocyanurate ring and an imide compound having one or two imide groups which is different from the compound of the component (A), and the component (C) is a quinonediazide compound. P=X (1) wherein P represents a phosphorus atom, wherein the number of covalent bonds is 5; X represents a nitrogen atom or an oxygen atom, wherein the number of covalent bonds is 3 when X represents a nitrogen atom, the number of covalent bonds is 2 when X represents an oxygen atom, and the phosphorus atom and the nitrogen or oxygen atom are bound to each other via a double bond.

Description

明 細 書  Specification
感光性樹脂組成物及びそれを用いたフレキシブルプリント配線板 技術分野  Photosensitive resin composition and flexible printed wiring board using the same
[0001] 本発明は、フレキシブルプリント配線板のカバーレイに好適な感光性樹脂組成物及 びそれを用レ、たフレキシブルプリント配線板に関する。  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.
背景技術  Background art
[0002] 近年、伸長著し!/、フレキシブルプリント配線板（以下、 FPCと省略する）にお!/、ては 、柔軟性、屈曲性に優れる素材が基材、カバーレイとして求められている。 FPCの力 バーレイには、プロセスの優位性からラミネート可能なドライフィルム化が望まれて!/、  [0002] In recent years, there has been a growing demand! /, Flexible printed wiring boards (hereinafter abbreviated as FPC)! /, And materials that are excellent in flexibility and flexibility are required as base materials and coverlays. . The power of FPC For Burley, a dry film that can be laminated is desired because of the superiority of the process! /
[0003] さらに、ドライフィルムには感光性を持つことが望まれている。これは、一般的なポリ イミド材料を微細加工する際には、フォトレジストを使用したエッチング処理が行われ るため、多くの工程数を必要とする。そこで、絶縁層であるポリイミド自体に直接バタ ーンを形成することのできる感光性ポリイミド材料が注目されてきており、なかでも、作 業時の安全性や環境への影響に対する配慮から、アルカリ水溶液での現像処理が 可能な感光性樹脂組成物への要望が強くなつてきている。一般にネガ型の場合は、 その現像液により露光部の膨潤が起こり、高解像度の微細加工を行うことが難しい。 そのため、ポジ型の感光システムによる微細加工が強く望まれている。 [0003] Further, it is desired that 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. In view of this, 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.
[0004] 感光性を持たないドライフィルムを用いて FPCを製造する場合には、ドライフィルム を所定の外形パターンに機械的に打ち抜き、回路基板との間で位置合わせを行った 後、回路基板に打ち抜いたドライフィルムを貼り合わせていた。ドライフィルムの感光 化が実現すると、回路基板とドライフィルムとを貼り合わせた後に、フォトリソグラフィー によって所望パターンにドライフィルムをパターユングできるため、機械的なパターン 打ち抜き、回路基板との位置合わせなどの工程が不要となる。  [0004] When manufacturing an FPC using a dry film having no photosensitivity, 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. When dry film sensitization is realized, 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.
[0005] また、従来のスクリーン印刷では、溶媒除去のプロセスや両面加工の際には 2回の プロセスになるなどの問題があるため、工業プロセスの観点からも、感光性樹脂組成 物をドライフィルム化することが望まれて!/、る。 [0006] 一方、カバーレイの材料としては、柔軟性、屈曲性に優れるポリイミドが用いられて いる。一般に、ポリイミドは 300°C以上の耐熱性と優れた機械特性を有しており、かつ 低誘電率や高絶縁性などの電気特性にも優れている。このため、耐熱性に優れた絶 縁材料、特に半導体工業における固体素子の絶縁層や保護層として、ポリイミドなど の高耐熱性樹脂が注目されてレ、る。 [0005] In addition, conventional screen printing has a problem that the process of solvent removal and double-sided processing requires two processes, and therefore, from the viewpoint of an industrial process, a photosensitive resin composition is used as a dry film. It is hoped that! [0006] On the other hand, polyimide having excellent flexibility and flexibility is used as a material for the coverlay. In general, polyimide has a heat resistance of 300 ° C or higher and excellent mechanical properties, and also has excellent electrical properties such as low dielectric constant and high insulation. For this reason, high heat-resistant resins such as polyimide are attracting attention as insulating materials with excellent heat resistance, especially as insulating layers and protective layers for solid elements in the semiconductor industry.
[0007] このポリイミドとしては、カプトン（登録商標）などが公知である力 カプトンフィルムは 溶媒に不溶であるため、ポリイミドワニスよりフィルムを製膜することができない (例え ば、非特許文献 1)。そのため、カプトンを用いる場合には、ポリアミド酸の状態で製膜 した後、高温に加熱することによりイミド化してフィルム化している。このようにして得ら れたカプトンフィルムは、柔軟性、屈曲性に優れる反面、ガラス転移点が 400°C以上 と高温であるため（例えば、非特許文献 2)、可塑性がなぐドライフィルムとして用いる こと、すなわち回路基板上にラミネートするのは困難である。  [0007] As this polyimide, Kapton (registered trademark) and the like are known. 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.
[0008] 溶媒可溶で柔軟性、屈曲性に優れたポリイミドとして、シロキサン骨格を導入したポ リイミドの提案 (例えば、特許文献 1)がある。また、シロキサン骨格を導入したポリイミ ドを用いて、可塑性及び感光性を付与するため反応性希釈剤である（メタ）アタリレー トなどのモノマーを併用したネガ型の感光性カバーレイも提案 (例えば、特許文献 2) されている。 [0008] As a polyimide that is soluble in a solvent and excellent in flexibility and flexibility, there is a proposal of a polyimide having a siloxane skeleton introduced (for example, Patent Document 1). In addition, using a polyimide with a siloxane skeleton, we also propose a negative photosensitive coverlay that uses a monomer such as (meth) atrelate, which is a reactive diluent, to impart plasticity and photosensitivity (for example, Patent Document 2).
[0009] このようなシロキサン骨格を導入したポリイミドゃ反応性希釈剤の併用によれば、ガ ラス転移点が低下するため、カプトンでは困難であったドライフィルム化が可能である 。しかしながら、シロキサン骨格を導入すると、ポリイミド樹脂は燃えやすくなる恐れが あり、また (メタ）アタリレートなどのモノマーの使用も難燃性を低下させる可能性があ  [0009] According to the combined use of such a polyimide-reactive diluent introduced with a siloxane skeleton, the glass transition point is lowered, so that a dry film that has been difficult with Kapton can be formed. However, if a siloxane skeleton is introduced, the polyimide resin may become flammable, and the use of a monomer such as (meth) acrylate may also reduce the flame retardancy.
[0010] また、ポジ型の感光性樹脂組成物として、ポリイミドにキノンジアジド化合物を添カロ する組成物も提案されている（例えば、特許文献 3)。この感光性樹脂組成物もドライ フィルム化が可能である力 S、ドライフィルム化した時に反りが発生し、また可塑性も充 分ではなぐ配線パターン基板への埋め込み性も不十分で、ドライフィルムとして用い ることが困難である。 [0010] Further, as a positive photosensitive resin composition, 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
[0011] また、ポジ型感光性樹脂組成物として、ポリイミド前駆体又はポリベンゾォキサゾー ル前駆体にキノンジアジド化合物を添加したポジ型感光性樹脂組成物が開示されて いる（特許文献 4)。前記前駆体タイプは、最終的な膜物性に優れているものの、前 駆体の状態で組成物とするため、保存安定性が悪いものもあり、加工上で不都合を 生じる場合があった。 [0011] Further, as the positive photosensitive resin composition, 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). Although 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.
[0012] また、ポリイミドを含有するポジ型感光性樹脂組成物として、スルホン酸基を含有す るポリイミドとナフトキノンジアジド化合物とを含む感光性樹脂組成物が開示されてい る（特許文献 5)。前記感光性樹脂組成物は、保存安定性は改良されたものの、ポリイ ミドの Tgが高いために、基板などへの圧着が困難である。  [0012] Further, as a positive 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.
[0013] また、ポリイミドの Tgを下げたポジ型感光性樹脂組成物として、シロキサン骨格を有 するポリイミドからなるポジ型感光性樹脂組成物が開示されて!/、る (特許文献 6)。こ の文献における技術のように、ポリイミドはシロキサン骨格を導入することにより、 Tgは 低下するものの、難燃性が低下する傾向がある。また、前記組成物は可塑性が充分 でないため、ドライフィルム化時に反りが発生し、感光性フィルムとして用いることが困 難である。  [0013] Further, as a positive photosensitive resin composition having a reduced Tg of polyimide, a positive photosensitive resin composition made of polyimide having a siloxane skeleton is disclosed! (Patent Document 6). Like the technology in this document, polyimide introduces a siloxane skeleton, but Tg decreases, but flame retardancy tends to decrease. Further, since 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.
[0014] 樹脂組成物に難燃性を付与する方法としては、樹脂組成物にリン化合物を添加す る方法が知られている（例えば、非特許文献 3)。しかしながら、従来公知の技術で難 燃性を発現させるためには、リン化合物を大量に添加する必要があり、感光性樹脂 組成物にこの技術を用いると、現像性が悪化し、感光性能が低下してしまう。また、破 断強度など機械的特性の耐熱劣化安定性を向上する目的で、ポリイミド樹脂に特定 のリン化合物を少量配合する技術も知られている（例えば、特許文献 7)。この技術に おいては、リン化合物が難燃性を発現せず、またドライフィルム化時の反りの発生も 抑えることができない。  [0014] As a method for imparting flame retardancy to a resin composition, a method of adding a phosphorus compound to the resin composition is known (for example, Non-Patent Document 3). However, it is necessary to add a large amount of a phosphorus compound in order to develop flame retardancy with 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. In addition, 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.
[0015] これら従来公知の技術の単なる組み合わせ、例えば、シロキサン骨格を導入したポ リイミドにリン化合物を添加した組成物においては、ドライフィルム化時に反りが発生 し、配線パターンへの埋め込み性が不十分となり、また、シロキサン骨格を導入した ポリイミドが燃え易い性質を持っために、リン化合物の難燃性も充分に発現できなか つた。  [0015] In a simple combination of these conventionally known techniques, for example, a composition in which a phosphorus compound is added to a polyimide having a siloxane skeleton introduced, warpage occurs during the formation of a dry film, and the embedding in a wiring pattern is insufficient. In addition, since the polyimide having a siloxane skeleton has the property of easily burning, the flame retardancy of the phosphorus compound could not be sufficiently exhibited.
[0016] また、従来公知のポリイミドにキノンジアジド化合物を添加するポジ型の感光性樹脂 組成物においては、樹脂としてシロキサン骨格を導入したポリイミドを用いてもドライフ イルム化時に反りが発生した。この反りを改善するため、従来公知の反応性希釈剤で ある (メタ）アタリレートなどのモノマーを添加すると、反りは改善するが、難燃性が損な われた。このように、これら従来公知の技術を単に組み合わせただけでは、ドライフィ ルム化時の反りの抑制、配線パターン基板への埋め込み性や密着性、感光性や現 像性、さらに難燃性を同時に付与することは困難であった。 Further, a positive photosensitive resin in which a quinonediazide compound is added to a conventionally known polyimide. In the composition, even when a polyimide having a siloxane skeleton introduced as a resin was used, warping occurred during dry film formation. In order to improve this warpage, the addition of a monomer such as (meth) acrylate which is a conventionally known reactive diluent improves the warpage but impairs the flame retardancy. In this way, by simply combining these conventionally known technologies, 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.
非特許文献 1 :最新ポリイミド〜基礎と応用〜 （ェヌ ·ティー'エス） p. 4  Non-Patent Document 1: Latest Polyimides -Basics and Applications- (NTT) p. 4
非特許文献 2 :エレクトロニクス実装技術 2003. 2 (Vol. 19 No. 2) p. 66 非特許文献 3 :ノンハロゲン系難燃材料による難燃化技術 （ェヌ ·ティー ·エス） ρ· 2 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) ρ · 2
8 8
特許文献 1 :特公平 7— 35440号公報  Patent Document 1: Japanese Patent Publication No. 7-35440
特許文献 2：特開 2003— 140339号公報  Patent Document 2: Japanese Patent Laid-Open No. 2003-140339
特許文献 3：特許第 2906637号公報  Patent Document 3: Japanese Patent No. 2906637
特許文献 4 :特許第 3078175号公報  Patent Document 4: Japanese Patent No. 3078175
特許文献 5：特開 2004— 238591号公報  Patent Document 5: Japanese Patent Application Laid-Open No. 2004-238591
特許文献 6：国際公開第 2003/060010号パンフレット  Patent Document 6: International Publication No. 2003/060010 Pamphlet
特許文献 7：特許第 2955712号公報  Patent Document 7: Japanese Patent No. 2955712
発明の開示  Disclosure of the invention
[0017] 本発明の目的は、従来の感光性樹脂組成物では困難であった、ドライフィルム化時 の反りがなぐ基板などへの圧着が容易であるラミネート性、及び、埋め込み性を有し 、現像特性が良ぐ且つ、難燃性を有するポジ型の感光性ドライフィルム、及びそれ を用いたフレキシブルプリント配線板を提供することである。  [0017] 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.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0018] 本発明者らは上記課題を解決するために鋭意検討した結果、（A)成分、（B)成分 、及び (C)成分を含有する感光性樹脂組成物であって、前記 (A)成分はアルカリ可 溶性樹脂であり、前記 (B)成分は式（1)に示す構造を有する化合物、イソシァヌル酸 環を有する化合物、及び前記 (A)成分以外のイミド基を 1つ若しくは 2つ含有するイミ ド化合物からなる群から選ばれた少なくとも一つの化合物であり、前記（C)成分はキ ノンジアジド化合物であることを特徴とする感光性樹脂組成物により、ドライフィルム 化時の反りが抑制され、配線パターン基板への埋め込み性や密着性、感光性や現 像性、さらに難燃性を同時に付与できることを見出し、本発明を完成するに至った。 したがって、本発明の感光性樹脂組成物を用いて、 FPC基板材料として有用な感光 性ドライフィルム、感光性積層フィルム及びそれらを用いたカバーレイ、フレキシブノレ プリント配線板を提供することができる。 [0018] As a result of intensive studies to solve the above problems, 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 = X 式（1)  P = X formula (1)
(式中 Pはリン原子を表し、その共有結合数は 5である。 Xは窒素原子又は酸素原子 を表し、 Xが窒素原子の場合、その共有結合数は 3であり、酸素原子の場合、その共 有結合数は 2である。リン原子と窒素原子又は酸素原子とは二重結合で結合して!/、 る。 )  (In the formula, P represents a phosphorus atom and the number of covalent bonds is 5. X represents a nitrogen atom or an oxygen atom. When X is a nitrogen 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! /
[0019] 本発明者は、特定の化合物がドライフィルム化の反り改善効果、配線パターンへの 埋め込み性、密着性、及び、難燃性を併せ持つことを見出し、さらにキノンジアジド化 合物と組み合わせることで、感光性と現像性を共に発現することを見出した。また、こ れらの特定の化合物及びキノンジアジド化合物を可溶性ポリイミドなどの樹脂組成物 に配合してなる感光性樹脂組成物がカールフリー（反りが抑制されていること）、ラミ ネート性、感光性、難燃性をすベて満足するポジ型の感光性ドライフィルムを実現す ることを見出し、本発明を完成するに至った。  [0019] 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. In addition, 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.
[0020] 具体的に説明すると、本発明の感光性樹脂組成物における（B)成分は、その構造 中にドライフィルムの反り改善効果を発現し得る官能基と、難燃性を発現し得るリン原 子又は窒素原子とを含む。また、本発明の感光性樹脂組成物における（C)成分は、 その構造中に難燃性を発現し得る窒素原子を有している一方で、比較的かさ高いキ ノンジァジド基、具体的にはナフトキノンジアジド基やべンゾキノンジアジド基を 1っ以 上有している。  [0020] Specifically, 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. In addition, 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.
[0021] 本発明者は、鋭意検討の結果、（B)成分と（C)成分とを組み合わせることにより、 ( B)成分のリン原子又は窒素原子と（C)成分の窒素原子とで、充分な難燃性を発揮 できることを見出した。また、驚くべきことに、（B)成分と（C)成分とを組み合わせた場 合において、（B)成分の有するドライフィルムの反り改善性能を損なうことなぐ難燃 性を付与できることが分った。さらに、（B)成分と（C)成分とを組み合わせることにより 、従来難燃化が困難であったシロキサン骨格を有するポリイミド樹脂にさえも難燃性 を付与できることが分った。このような難燃性とドライフィルムの反り改善との両立は、（ B)成分において、 1分子中に難燃性を付与し得るリン原子又は窒素原子とドライフィ ルムの反り改善効果を発現し得る官能基とを備えていることに起因するものと推定さ れる。さらに驚くべきことに脂肪族有機基を有するリン酸エステルを用いる場合、感光 性 (感度）に優れ、また、現像性 (現像時間の短縮や現像残渣スカムの低減、等)も向 上することが分かった。 [0021] As a result of intensive studies, 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. Coexistence of such flame retardancy and improvement of warpage of dry film can manifest the effect of improving warpage of phosphorus atom or nitrogen atom that can impart flame retardancy in one molecule and dry film in component (B). This is presumably due to the functional group. Surprisingly, when a phosphate ester having an aliphatic organic group is used, the photosensitivity (sensitivity) is excellent, and the developability (development time, development scum, etc.) can be improved. I understood.
[0022] 以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明の感光性樹脂組成物は、（A)成分、（B)成分、及び (C)成分を含有するも のであって、前記 (A)成分はアルカリ可溶性樹脂であり、前記 (B)成分は式（1)に示 す構造を有する化合物、イソシァヌル酸環を有する化合物、及び前記 (A)成分以外 のイミド基を 1つ若しくは 2つ含有するイミド化合物からなる群から選ばれた少なくとも 一つの化合物であり、前記（C)成分はキノンジアジド化合物であることを特徴とする。 これにより、ドライフィルム化時の反りがなぐラミネート性や密着性を有し、感光性や 現像性に優れ、難燃性を有するポジ型の感光性ドライフィルム、さらにそれを用いた カバーレイを備えたフレキシブルプリント配線板を提供することができる。  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. As a result, there is a positive photosensitive dry film that has laminating properties and adhesiveness that prevent warping during dry film formation, excellent photosensitivity and developability, and flame retardancy, and a coverlay using it. A flexible printed wiring board can be provided.
P = X 式（1)  P = X formula (1)
(式中 Pはリン原子を表し、その共有結合数は 5である。 Xは窒素原子、又は、酸素原 子を表し、 Xが窒素原子の場合、その共有結合数は 3であり、酸素原子の場合、その 共有結合数は 2である。リン原子と窒素原子又は酸素原子とは二重結合で結合して いる。 )  (In the formula, 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.)
[0023] まず、（A)成分について説明する。  [0023] First, the component (A) will be described.
本発明に用いられるアルカリ可溶性樹脂は、アルカリ溶液に溶解し得る樹脂であれ ば、限定されない。このような樹脂としては、主鎖及び/又は側鎖にカルボキシル基 、芳香族性水酸基、スルホン酸基などの公知のアルカリに溶解する官能基を有する 樹脂が挙げられる。このような樹脂としては、耐熱性の観点から、アルカリ可溶性ポリ イミド、ポリアミド酸、ポリベンゾォキサゾール前駆体などのアル力リ可溶性ポリアミドが 好ましぐドライフィルム化の観点からアルカリ可溶性ポリイミド及びポリイミド前駆体が より好ましく、アルカリ可溶性ポリイミドが特に好ましい。 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. Examples of such 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. As such resins, from the viewpoint of heat resistance, 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.
[0024] 本発明に用いられるアルカリ可溶性ポリイミドは、例えば、ジァミンとテトラカルボン 酸二無水物を原料にして得ることができる。アルカリ可溶性ポリイミドの構造としては、 アルカリに溶解する官能基を有することが好ましぐカルボキシル基及び/又は水酸 基を有して!/、ることが好まし!/、。  [0024] 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! /.
[0025] ジァミンとしては、芳香族ジァミン、脂肪族ジァミン、脂環式ジァミンを用いることが できる。また、カルボキシル基及び/又は水酸基を導入する目的で、カルボキシル基 を有するジァミンや水酸基を有するジァミンを用いることができる。また、シロキサン骨 格を導入する目的で、ジァミノシロキサンを用いることができる。  [0025] As the diamine, 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.
[0026] 芳香族ジァミンとしては、 o フエ二レンジァミン、 m フエ二レンジァミン、 p フエ二 レンジァミン、 3, 3 'ージアミノジフエニルエーテル、 4, 4 'ージアミノジフエニルエーテ ノレ、 3, 4 '—ジアミノジフエニルエーテル、 3, 3 'ージアミノジフエニルメタン、 3, 4 '— ジアミノジフエニルメタン、 4, 4 'ージアミノジフエニルメタン、 3, 3 'ージアミノジフエ二 ノレジフルォロメタン、 4, 4 'ージアミノジフエニルジフルォロメタン、 3, 3 'ージアミノジ フエニノレスノレホン、 3, 4 '—ジアミノジフエニノレスノレホン、 4, 4 'ージアミノジフエニノレス ノレホン、 3, 3 'ージアミノジフエニルスルフイド、 3, 4 '—ジアミノジフエニルスルフイド、 4, 4 'ージアミノジフエニルスルフイド、 3, 3 'ージアミノジフエ二ルケトン、 3, 4 '—ジァ ミノジフエ二ルケトン、 4, 4 'ージアミノジフエ二ルケトン、 2, 2 ビス（3 ァミノフエ二 ノレ）プロパン、 2, 2 - (3, 4 'ージアミノジフエ二ノレ）プロパン、 2, 2 ビス（4 アミノフ ェニノレ）プロパン、 2, 2 ビス（3 ァミノフエ二ノレ）へキサフルォロプロパン、 2, 2—（ [0026] 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'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone, 3,4'-diaminodi Ethyl ketone, 4,4'-diaminodiphenyl ketone, 2,2 bis (3 aminophenol), propane, 2,2- (3,4'-diaminodiphenol) propane, 2,2 bis (4 aminophenol) propane, 2, 2 bis (3 aminophenenole) hexafluoropropane, 2, 2— (
3, 4 '—ジアミノジフエ二ノレ）へキサフルォロプロパン、 2, 2 ビス（4ーァミノフエニル )へキサフルォロプロパン、 1 , 3—ビス（3—アミノフエノキシ）ベンゼン、 1 , 4—ビス（4 —アミノフエノキシ）ベンゼン、 3, 3， 一 [1 , 4—フエ二レンビス（1—メチルェチリデン） ]ビスァニリン、 3, 4， 一 [1 , 4 フエ二レンビス（1ーメチルェチリデン）]ビスァニリン、3,4'-diaminodiphenenole) hexafluoropropane, 2,2bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4 —Aminophenoxy) benzene, 3, 3, 1 [1,4-phenylphenylenebis (1-methylethylidene)] bisaniline, 3,4,1 [1,4 phenylbis (1-methylethylidene)] bisaniline,
4, 4， 一 [1 , 4 フエ二レンビス（1—メチルェチリデン）]ビスァニリン、 2, 2 ビス [4 — (3 アミノフエノキシ）フエニル]プロパン、 2, 2 ビス [4— (4 アミノフエノキシ）フ ェニノレ]プロパン、 2, 2 ビス [4一（3 アミノフエノキシ）フエニル]へキサフルォロプ 口パン、 2, 2 ビス [4— (4 アミノフエノキシ）フエ二ノレ]へキサフルォロプロパン、ビ ス [4— (3—アミノフエノキシ）フエニル]スルフイド、ビス [4— (4—アミノフエノキシ）フ ェニノレ]スルフイド、ビス [4— (3—アミノフエノキシ）フエ二ノレ]スルホン、ビス [4— (4— アミノフエノキシ）フエ二ノレ]スルホン、 1, n ビス（4—ァミノフエ 4, 4, 1 [1, 4 Phenylenebis (1-methylethylidene)] bisaniline, 2, 2 bis [4 — (3 aminophenoxy) phenyl] propane, 2, 2 bis [4— (4 aminophenoxy) phenole] propane 2, 2 Bis [4 (3-aminophenoxy) phenyl] hexafluoro Mouth bread, 2, 2 bis [4— (4 aminophenoxy) phenyl] hexafluoropropane, bis [4— (3-aminophenoxy) phenyl] sulfide, bis [4— (4-aminophenoxy) phenol ] Sulfide, bis [4- (3-aminophenoxy) phenol] sulfone, bis [4- (4-aminophenoxy) phenol] sulfone, 1, n bis (4-aminophenol)
1, 3—ビス（4 アミノフエノキシ）プロパン、 1, 4 ビス（4 アミノフエノキシ）ブタン、 1, 5—ビス（4 アミノフエノキシ）ヘプタン、が挙げられる。  1,3-bis (4 aminophenoxy) propane, 1,4 bis (4 aminophenoxy) butane, 1,5-bis (4 aminophenoxy) heptane.
[0027] 脂肪族ジァミンとしては、 1, 2—ジアミノエタン、 1, 3 ジァミノプロパン、 1, 4ージ アミノブタン、 1, 5—ジァミノペンタン、 1, 6 ジァミノへキサン、 1, 7 ジァミノへプタ ン、 1, 8—ジアミノ才クタン、 1, 9ージアミノノナン、 1, 10 ジァミノデカン、 1, 11- ジアミノウンデカンが挙げられる。  [0027] 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.
[0028] 脂環式ジァミンとしては、式（19)で示される化合物が挙げられる。  [0028] Examples of the alicyclic diamine include compounds represented by the formula (19).
[化 18]  [Chemical 18]
Figure imgf000009_0001
Figure imgf000009_0001
(1 9) (1 9)
[0029] カルボキシル基を有するジァミンとしては、式（20)で示される化合物が挙げられる
Figure imgf000010_0001
[0029] Examples of the diamine having a carboxyl group include a compound represented by the formula (20).
Figure imgf000010_0001
( 2 0 )  (2 0)
式 20の中でも、 3, 3'ージカルボキシ 4, 4'ージアミノジフエニルメタン、 3, 5 ジ ァミノ安息香酸などが好ましレ、。  Among formula 20, 3,3′-dicarboxy 4,4′-diaminodiphenylmethane, 3,5 diaminobenzoic acid, etc. are preferred.
水酸基を有するジァミンとしては、 1 , 2 ジアミノー 4ーヒドロキシベンゼン、 1 , 3— ジァミノー 5—ヒドロキシベンゼン、 1 , 3—ジアミノー 4ーヒドロキシベンゼン、 1 , 4ージ アミノー 6—ヒドロキシベンゼン、 1 , 5—ジアミノー 6—ヒドロキシベンゼン、 1 , 3—ジァ ミノー 4, 6—ジヒドロキシベンゼン、 1 , 2—ジアミノー 3, 5—ジヒドロキシベンゼン、 4 — (3, 5—ジァミノフエノキシ）フエノール、 3— (3, 5—ジァミノフエノキシ）フエノール、 2—（3, 5 ジアミノフエノキシ）フエノール、 3, 3'—ジヒドロキシ 4, 4'ージアミノビ フエニル、 3, 3'—ジァミノ一 4, 4' ジヒドロキシビフエニル、 2, 2 ビス（4 ヒドロキ シ一 3 ァミノフエ二ノレ）プロパン、 2, 2 ビス（4 ヒドロキシ一 3 ァミノフエ二ノレ）へ キサフルォロプロパン、ビス（4 ヒドロキシ一 3 ァミノフエ二ノレ）ケトン、 2, 2 ビス（4 —ヒドロキシ一 3 ァミノフエ二ノレ）スルフイド、 2, 2 ビス（4 ヒドロキシ一 3 アミノフ ェニノレ）エーテル、 2, 2 ビス（4 ヒドロキシ一 3 ァミノフエ二ノレ）スルホン、 2, 2- ビス（4—ヒドロキシ一 3 -ァミノフエニル）メタン、 4— [ (2, 4 ジァミノ一 5 -ピリミジニ ル）メチル]フエノール、 p— (3, 6 ジァミノ一 s トリアジン一 2 ィル）フエノール、 2 , 2 ビス（4 ヒドロキシ一 3 ァミノフエ二ノレ）ジフルォロメタン、 2, 2 ビス（4 アミ ノー 3 ヒドロキシフエ二ノレ）プロパン、 2, 2 ビス（4 アミノー 3 ヒドロキシフエ二ノレ )へキサフルォロプロパン、ビス（4 アミノー 3 ヒドロキシフエ二ノレ）ケトン、 2, 2 ビ ス（4 ァミノ一 3 ヒドロキシフエ二ノレ）スルフイド、 2, 2 ビス（4 ァミノ一 3 ヒドロ キシフエ二ノレ）エーテル、 2, 2 ビス（4 ァミノ一 3 ヒドロキシフエ二ノレ）スルホン、 2 , 2 ビス（4 アミノー 3 ヒドロキシフエ二ノレ）メタン、 2, 2 ビス（4 アミノー 3 ヒド ロキシフエニル）ジフルォロメタンが挙げられる。 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 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 (4 —hydroxy 1 3 amino phenol) sulfide, 2, 2 bis (4 hydroxy 1 3 amino phenol) ether, 2, 2 bis (4 hydroxy 1 3 amino phenol) Nole) sulfone, 2,2-bis (4-hydroxy-1-3-aminophenyl) methane, 4-[(2,4-diamino-1-5-pyrimidinyl) methyl] phenol, p- (3,6 diamino-1-striazine 1 2 Yl) phenol, 2,2 bis (4 hydroxy-l-3aminophenol) difluoromethane, 2,2 bis (4 amino 3-hydroxyphenol) propane, 2,2 bis (4 amino-3 hydroxyphenol) Xafluoropropane, bis (4 amino-3 hydroxyphenol) ketone, 2, 2 bis (4 amino-3-hydroxyphenol) sulfide, 2, 2 bis (4 amino-3-hydroxy) B Kishifue two Honoré) ether, 2, 2-bis (4 Amino one 3-hydroxy-phenylene Honoré) sulfone, 2, 2-bis (4-amino-3-hydroxy-phenylene Honoré) methane, 2, 2-bis (4-amino-3 hydrate Roxyphenyl) difluoromethane.
[0031] ジァミノシロキサンとしては、式（21)で示される化合物が挙げられる。 [0031] Examples of the diaminosiloxane include a compound represented by the formula (21).
[化 20]
Figure imgf000011_0001
[Chemical 20]
Figure imgf000011_0001
(Rは炭素数 1以上 20以下の炭化水素基を表す。 aは 1以上 10以下の整数を表す。  (R represents a hydrocarbon group having 1 to 20 carbon atoms. A represents an integer of 1 to 10 carbon atoms.
6  6
bは 1以上 20以下の整数を表す。 )  b represents an integer from 1 to 20. )
[0032] 炭素数 1以上 20以下の炭化水素基 (R )としては、特に限定されないが、脂肪族飽 [0032] The hydrocarbon group (R 1) having 1 to 20 carbon atoms is not particularly limited.
6  6
和炭化水素基、脂肪族不飽和炭化水素基、環状構造を含む官能基、及びそれらを 組み合わせた基などが好ましく挙げられる。  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.
[0033] 上記脂肪族飽和炭化水素基としては、メチル基、ェチル基、プロピル基、ブチル基 、ペンチル基、へキシル基などの第一級炭化水素基、イソブチル基、イソペンチル基 などの第二級炭化水素基、 t ブチル基などの第三級炭化水素基などが挙げられる [0033] 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.
[0034] 上記脂肪族不飽和炭化水素基としては、ビュル基、ァリル基などの二重結合を含 む炭化水素基、ェチュル基などの三重結合を含む炭化水素基などが挙げられる。 [0034] 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.
[0035] 上記環状構造を含む官能基としては、シクロブチル基、シクロペンチル基、シクロへ キシル基、シクロデシル基、シクロオタチル基などの単環式官能基；ノルボルニル基、 ァダマンチル基などの多環式官能基；ピロール、フラン、チォフェン、イミダゾール、ォ キサゾール、チアゾール、テトラヒドロフラン、ジォキサン構造を有する複素環式官能 基;ベンゼン環、ナフタレン環、アントラセン環、フエナントレン環構造を含む芳香族 炭化水素基などが挙げられる。  [0035] 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.
[0036] 前記炭素数 1以上 20以下の炭化水素基 (R )は、ハロゲン原子、ヘテロ原子及び  [0036] The hydrocarbon group having 1 to 20 carbon atoms (R) is a halogen atom, a hetero atom and
6  6
金属原子を含むことができる。本発明におけるハロゲン原子には、フッ素、塩素、臭 素、ヨウ素力 s挙げられる。また、本発明におけるヘテロ原子には、酸素、硫黄、窒素、 リンが挙げられる。また、本発明における金属原子には、ケィ素及びチタンが挙げら れる。 [0037] また、炭素数 1以上 20以下の炭化水素基 (R )がへテロ原子及び/又は金属原子 Metal atoms can be included. Examples of the halogen atom in the present invention include fluorine, chlorine, fluorine, iodine power. In addition, examples of the hetero atom in the present invention include oxygen, sulfur, nitrogen, and phosphorus. In addition, examples of the metal atom in the present invention include silicon and titanium. [0037] Further, the hydrocarbon group having 1 to 20 carbon atoms (R) is a hetero atom and / or a metal atom.
6  6
を含む場合、 Rは結合するへテロ原子及び/又は金属原子に直接結合していても、  R may be bonded directly to the binding hetero atom and / or metal atom,
6  6
ヘテロ原子及び/又は金属原子を介して結合して!/、ても良レ、。  Bonded via heteroatoms and / or metal atoms! /
[0038] 式（21)の Rの炭素数は、難燃性を考慮して、 1以上 20以下が好ましい。生成する [0038] The carbon number of R in formula (21) is preferably 1 or more and 20 or less in consideration of flame retardancy. Generate
6  6
ポリイミドの溶媒可溶性の観点から、炭素数は 1以上 10以下が特に好ましい。  From the viewpoint of solvent solubility of polyimide, the number of carbon atoms is particularly preferably 1 or more and 10 or less.
最も好ましい炭化水素基 (R )はメチル基である。  The most preferred hydrocarbon group (R 1) is a methyl group.
6  6
[0039] 式（21)の aは、難燃性を考慮すると、 1以上 10以下である。生成するポリイミドの溶 媒可溶性の観点から、 aは 2以上 8以下であることが好ましぐ 3以上 6以下がより好ま しい。  [0039] 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.
[0040] 式（21)の bは、難燃性を考慮すると、 1以上 20以下である。生成するポリイミドの溶 媒可溶性の観点から、 bは 1以上 15以下であることが好ましぐ 1以上 12以下がより好 ましい。  [0040] 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.
[0041] なお、これらのジァミン成分は、単独又は組み合わせて用いることができる。  [0041] These diamine components can be used alone or in combination.
[0042] 本発明に用いられるテトラカルボン酸二無水物としては、芳香族テトラカルボン酸二 無水物、脂環式テトラカルボン酸二無水物、脂肪族テトラカルボン酸二無水物が挙 げられる。  [0042] Examples of tetracarboxylic dianhydrides used in the present invention include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides.
[0043] 芳香族テトラカルボン酸二無水物としては、ピロメリット酸二無水物、 3, 3' 4, 4'— ビフエニルテトラカルボン酸二無水物、 2, 2' , 3, 3，ービフエニルテトラカルボン酸二 無水物、 2, 3, 3' , 4'—ビフエニルテトラカルボン酸二無水物、 2, 2 ビス（3, 4— ジカルボキシフエニル）プロパン二無水物、 2, 2 ビス（2, 3 ジカルボキシフエニル )プロパン二無水物、 1 , 1 ビス（2, 3—ジカルボキシフエニル）エタンニ無水物、 1 , 1 ビス（3, 4—ジカルボキシフエニル）エタンニ無水物、ビス（2, 3—ジカルボキシフ ヱニル）メタン二無水物、ビス（3, 4—ジカルボキシフヱニル）メタン二無水物、ビス（3 , 4ージカルボキシフエ二ノレ）スルホン二無水物、 3, 4, 9, 10 ペリレンテトラカルボ ン酸ニ無水物、ビス（3, 4—ジカルボキシフエニル）エーテル二無水物、ベンゼン 1 , 2, 3, 4 テトラカルボン酸二無水物、 3, 4, 3' , 4'—べンゾフエノンテトラカルボン 酸二無水物、 2, 3, 2' , 3，一べンゾフエノンテトラカルボン酸二無水物、 2, 3, 3，， 4 ，一べンゾフエノンテトラカルボン酸二無水物、 1 , 2, 5, 6 ナフタレンテトラカルボン 酸二無水物、 2, 3, 6, 7 ナフタレンテトラカルボン酸二無水物、 1 , 2, 4, 5 ナフ タレンテトラカルボン酸二無水物、 1 , 4, 5, 8—ナフタレンテトラカルボン酸二無水物 、 2, 6 ジクロルナフタレン 1 , 4, 5, 8 テトラカルボン酸二無水物、 2, 7 ジクロ ノレナフタレン 1 , 4, 5, 8 テトラ力ノレボン酸二無水物、 2, 3, 6, 7 テトラクロノレナ フタレン一 1 , 4, 5, 8—テトラカルボン酸二無水物、フエナントレン一 1 , 8, 9, 10- テトラカルボン酸二無水物、ビス（3, 4—ジカルボキシフエニル）ジメチルシラン二無 水物、ビス（3, 4—ジカルボキシフエニル）メチルフエニルシラン二無水物、ビス（3, 4 ージカルボキシフエニル）ジフエニルシラン二無水物、 1 , 4 ビス（3, 4—ジカルボキ シフエ二ルジメチルシリル）ベンゼン二無水物、 1 , 3—ビス（3, 4—ジカルボキシフエ ニル）ー1 , 1 , 3, 3 テトラメチルジシクロへキサン二無水物、 2, 2 ビス（3, 4 ジ カルボキシフエニル）へキサフルォロプロパン二無水物、 2, 2 ビス [4一（3, 4 ジ カルボキシフエノキシ）フエニル]へキサフルォロプロパン二無水物、 2, 2 ビス [4 (3, 4—ジカルボキシフエノキシ）フエ二ノレ]プロパン二無水物、 4, 4 ビス（3, 4—ジ カルボキシフエノキシ）ジフエニルスルフイド二無水物が挙げられる。 [0043] 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 dianhydride, 3, 4, 9, 10 Perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether , Benzene 1, 2, 3, 4 tetracarboxylic dianhydride, 3, 4, 3 ', 4'-benzophenone tetracarboxylic dianhydride, 2, 3, 2', 3, monoben Zophenone tetracarboxylic dianhydride, 2, 3, 3 ,, 4, monobenzophenone tetracarboxylic dianhydride, 1, 2, 5, 6 naphthalenetetracarboxylic Acid dianhydride, 2, 3, 6, 7 Naphthalene tetracarboxylic dianhydride, 1, 2, 4, 5 Naphthalene tetracarboxylic dianhydride, 1, 4, 5, 8-Naphthalene tetracarboxylic dianhydride 2,6 Dichloronaphthalene 1, 4, 5, 8 Tetracarboxylic dianhydride, 2, 7 Dichloronaphthalene 1, 4, 5, 8 Tetra-force nolevonic dianhydride, 2, 3, 6, 7 1,4,5,8-tetracarboxylic dianhydride, phenanthrene 1,8,9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane Dihydrate, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4 bis (3,4-dicarboxy) Schiffenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxy) Phenyl) -1, 1, 3, 3, 3 tetramethyldicyclohexane dianhydride, 2, 2 bis (3,4 carboxyphenyl) hexafluoropropane dianhydride, 2, 2 bis [4 Mono (3,4 dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 2,2 bis [4 (3,4-dicarboxyphenoxy) phenenoyl] propane dianhydride, 4 , 4 bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride.
[0044] また、エステル基を有する芳香族テトラカルボン酸二無水物は、アルカリ可溶性ポリ イミドに柔軟性を与え、また、アルカリ可溶性を高めて現像時のスカム等の抑制効果 を付与するために、アルカリ可溶性ポリイミドに含まれることが好ましい。  [0044] In addition, 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.
[0045] 該エステル基を有する芳香族テトラカルボン酸二無水物としては、 1 , 4 ビス（2— ヒドロキシへキサフルォロイソプロピル）ベンゼンビス（トリメリテート無水物）、 1 , 3—ビ ス（2—ヒドロキシへキサフルォロイソプロピル）ベンゼンビス（トリメリテート無水物）、 p フエ二レンビス（トリメリット酸モノエステル酸無水物）、 1 , 2—（エチレン）ビス（トリメリ テート無水物）、 1 , 3— (トリメチレン）ビス（トリメリテート無水物）、 1 , 4— (テトラメチレ ン）ビス（トリメリテート無水物）、 1 , 5—（ペンタメチレン）ビス（トリメリテート無水物）、 1 , 6 （へキサメチレン）ビス（トリメリテート無水物）、 1 , 7 （ヘプタメチレン）ビス（トリメ リテート無水物）、 1 , 8—(オタタメチレン）ビス（トリメリテート無水物）、 1 , 9—(ノナメ チレン）ビス（トリメリテート無水物）、 1 , 10— (デカメチレン）ビス（トリメリテート無水物） 、 1 , 12 （ドデカメチレン）ビス（トリメリテート無水物）、 1 , 16 （へキサデカメチレン )ビス（トリメリテート無水物）、 1 , 18— (ォクタデカメチレン)ビス（トリメリテート無水物） が挙げられる。エステル基を有する芳香族テトラカルボン酸二無水物は、可溶性ポリ イミド中にエステル基を導入する際に用いることができる。 [0045] Examples of the aromatic tetracarboxylic dianhydride having an ester group 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 anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12 (dodecamethylene) bis (trimellitic anhydride), 1,16 (hexa) Decamethylene) bis (trimellitate anhydride), 1, 18- (octadecamethylene) bis (trimellitate anhydride) Is mentioned. An aromatic tetracarboxylic dianhydride having an ester group can be used when an ester group is introduced into a soluble polyimide.
中でも式（6)で表される 1 , 2 （エチレン）ビス（トリメリテート無水物）、又は、式（7) で表される P—フエ二レンビス（トリメリット酸モノエステル酸無水物）が好ましい。  Of these, 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.
[化 21] [Chemical 21]
Figure imgf000014_0001
Figure imgf000014_0001
[化 22] [Chemical 22]
Figure imgf000014_0002
Figure imgf000014_0002
脂環式テトラカルボン酸二無水物、脂肪族テトラカルボン酸二無水物としては、ェ チレンテトラカルボン酸二無水物、 1 , 2, 3, 4 ブタンテトラカルボン酸二無水物、 1 , 5 シクロォクタジェン 1 , 2, 5, 6 テトラカルボン酸二無水物、 5 カルボキシメ チルビシクロ [2· 2. 1]ヘプタン 2, 3, 6—トリカルボン酸 2, 3 : 5, 6—二無水物 、 1—カルボキシメチル一 2, 3, 5 シクロペンタントリカルボン酸一 2, 6 : 3, 5 二無 水物、ビシクロ [2· 2. 2]オタトー 7 ェンー 2, 3, 5, 6 テトラカルボン酸二無水物、 5 - (2, 5 ジォキソテトラヒドロ一 3 フラニル） 3 メチル 3 シクロへキセン一 1 , 2 ジカルボン酸無水物、テトラヒドロフラン 2, 3, 4, 5 テトラカルボン酸二無 水物、 4一（2, 5 ジォキソテトラヒドロフラン 3 ィノレ） 1 , 2, 3, 4 テトラヒドロナ  Examples of alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides include ethylene tetracarboxylic dianhydride, 1, 2, 3, 4 butanetetracarboxylic dianhydride, 1, 5 cyclohexane. Tatagene 1, 2, 5, 6 Tetracarboxylic dianhydride, 5 Carboxymethylbicyclo [2.2.1] heptane 2, 3, 6-tricarboxylic acid 2, 3: 5, 6-dianhydride, 1— Carboxymethyl 1,2,3,5 cyclopentanetricarboxylic acid 1,2,6: 3,5 dihydrate, bicyclo [2.2.2] otato 7-en 2,3,5,6 tetracarboxylic dianhydride, 5-(2,5 dioxotetrahydro-3-furanyl) 3 methyl 3 cyclohexene mono 1,2 dicarboxylic anhydride, tetrahydrofuran 2, 3, 4, 5 tetracarboxylic dihydrate, 4 one (2, 5 Dioxotetrahydrofuran 3 Inole) 1, 2, 3, 4 Tetrahydrona
2 ジカルボン酸無水物、デカヒドロナフタレン 1 , 4, 5, 8 テトラ力 ルボン酸二無水物、 4, 8 ジメチノレー 1 , 2, 3, 5, 6, 7 へキサヒドロナフタレンー1 , 2, 5, 6 テトラ力ノレボン酸二無水物、シクロペンタン 1 , 2, 3, 4 テトラ力ノレボン 酸二無水物、ピロリジン 2, 3, 4, 5 テトラカルボン酸二無水物、 1 , 2, 3, 4 シク ロプタンテトラカルボン酸二無水物、ビス（ェキソービシクロ [2· 2. 1]ヘプタン 2, 3 ージカルボン酸無水物）スルホンが挙げられる。 2 Dicarboxylic acid anhydride, decahydronaphthalene 1, 4, 5, 8 Tetra force Rubonic acid dianhydride, 4, 8 Dimethylolene 1, 2, 3, 5, 6, 7 Hexahydronaphthalene 1, 2, 5, 6 Tetra-force norevon dianhydride, cyclopentane 1, 2, 3, 4 Tetra-force norevon dianhydride, pyrrolidine 2, 3, 4, 5 Tetracarboxylic dianhydride, 1, 2, 3, 4 And loptantetracarboxylic dianhydride and bis (exocyclocyclo [2.2.1] heptane 2,3-dicarboxylic anhydride) sulfone.
[0047] これらのテトラカルボン酸二無水物成分は、単独又は組み合わせて用いることがで きる。  [0047] These tetracarboxylic dianhydride components can be used alone or in combination.
これらの中で、ポリイミドの有機溶剤への溶解性、基板などへの圧着性の観点から、 ビス（3, 4—ジカルボキシフエニル）エーテル二無水物、エチレングリコールビス（トリ メリット酸モノエステル酸無水物）、 ρ フエ二レンビス（トリメリット酸モノエステル酸無 水物）、 4ー（2, 5 ジォキソテトラヒドロフランー3 ィノレ） 1 , 2, 3, 4 テトラヒドロ  Among these, 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), ρ-phenylene bis (trimellitic acid monoester anhydride), 4- (2,5 dioxotetrahydrofuran-3-inole) 1, 2, 3, 4 tetrahydro
2 ジカルボン酸無水物、 5—（2, 5- - 3 ーメチルー 3 シクロへキセン一 1 , 2 ジカルボン酸無水物が好ましい。  2 Dicarboxylic anhydride, 5- (2,5--3-methyl-3-cyclohexene mono 1,2 dicarboxylic anhydride, is preferred.
[0048] 本発明に用いられるアルカリ可溶性ポリイミドは、式（5)で表されるよう シリコー ンジァミン、アルカリ可溶性官能基を有するジァミン及び/又はその他ジ ミンと、酸 二無水物とを重合、環化させてなるポリイミドであることが好ましレ、。  [0048] 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.
[化 23]  [Chemical 23]
Figure imgf000015_0001
Figure imgf000015_0001
(式中、 R、 Rは 4価の有機基を表し、同じであっても異なっていても良い。 Rは炭素 (In the formula, R and R represent a tetravalent organic group, which may be the same or different. R is carbon.
3 5 6 数 1以上 20以下の炭化水素基を表す。 Rはアルカリ可溶性官能基を少なくとも一つ  3 5 6 A hydrocarbon group having a number of 1 or more and 20 or less. R has at least one alkali-soluble functional group
4  Four
以上有する 2価の有機基を表す。 aは 1以上 10以下の整数を表す。 bは 1以上 20以 下の整数を表す。 Rはエステル構造を有する 4価の有機基を表し、 Rは 2価の有機  It represents a divalent organic group having the above. 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.
7 8  7 8
基を表す。 α、 /3、 γは少なくとも 1以上であり、 0· 01≤/3 / ( α + /3 + γ )≤0. ある。 )  Represents a group. α, / 3, and γ are at least 1 and 0 · 01≤ / 3 / (α + / 3 + γ) ≤0. )
[0049] また、本発明に用いられるポリイミドにおいて、その他ジァミンに由来する部位の含 有量は、すべてのジァミンに由来する部位を 100モル％とした時、難燃性の観点から 35モル0 /0以下であることが好まし!/、。 [0049] In addition, in the polyimide used in the present invention, 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 ! /.
[0050] 本発明における Rに由来するジァミンは、前述のアルカリ可溶性官能基を有するジ ァミンであれば限定されな!/、。 [0050] 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! /.
[0051] また、本発明において Rに由来するジァミンは、前述のジァミンであれば限定され [0051] In the present invention, the diamine derived from R is limited as long as it is the above-mentioned diamine.
8  8
ない。  Absent.
[0052] 本発明に用いられる R及び Rに由来する酸二無水物は、シリコーンジァミン、アル  [0052] The acid dianhydride derived from R and R used in the present invention includes silicone diamine, alcohol
3 5  3 5
カリ可溶性官能基を有するジァミン及び/又はその他ジァミンと反応し得る酸二無水 物であれば、限定されない。式（5)における R、 Rは、前述のテトラカルボン酸二無  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.
3 5  3 5
水物に由来する 4価の有機基であり、同じであっても異なって!/、ても良!/、。  It is a tetravalent organic group derived from aquatic products.
[0053] 本発明に用いられるポリイミドの末端は、性能に影響を与えない構造であれば、特 に限定されない。ポリイミドを製造する際に用いる酸二無水物、ジァミンに由来する末 端でも良ぐその他の酸無水物、ァミン化合物などにより末端を封止しても良い。  [0053] 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.
[0054] 本発明に用いられるポリイミドの数平均分子量は、難燃性、ポリイミド含有樹脂組成 物の粘度、成型性の観点から、 1000以上 1000000以下であること力 S好ましい。ここ で、数平均分子量とは、既知の数平均分子量のポリスチレンを標準として、ゲルパー ミエーシヨンクロマトグラフィーによって測定される分子量をいう。前記分子量は 5000 以上 500000以下カより好ましく、 10000以上 300000以下カもっとも好ましい。  [0054] 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. Here, 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.
[0055] 本発明に用いられるポリイミドの共重合様式は、ブロック構造でもランダム構造でも 良い。本発明における共重合成分を構成する α、 β、 γは少なくとも 1であり、 0. 01 ≤ β / ( α + β + y )≤0. 9である。 + /3 + γ )の値が 0· 01以上であれば 、基材などへの圧着に必要なシリコーンジァミン部分が充分に多いため、基材への 圧着性が発現する。また、 + /3 + γ )の値が 0· 9以下であれば、アルカリ可 溶性に必要なアルカリ可溶性官能基を有するジァミンに由来する部分の割合が充分 に多いため、アルカリ可溶性が発現する。アルカリ可溶性と基材への圧着性のバラン スの観点、力、ら、 + /3 + γ )のィ直は 0. 02以上 0. 8以下カ好ましく、 0. 03以上 0. 67以下がより好ましい。  [0055] The copolymerization mode of the polyimide used in the present invention may be a block structure or a random structure. Α, β, and γ constituting the copolymer component in the present invention are at least 1, and 0.01 ≦ ≤β / (α + β + y) ≤0.9. If the value of + / 3 + γ) 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. On the other hand, if the value of + / 3 + γ) is 0.9 or less, the ratio of the portion derived from diamine having an alkali-soluble functional group necessary for alkali-solubility is sufficiently high, so that alkali-solubility is manifested. From the standpoint of balance between alkali solubility and press-fitness to the substrate, force, et al., + / 3 + γ) is preferably 0.02 or more and 0.8 or less, more preferably 0.03 or more and 0.67 or less. preferable.
[0056] 本発明に用いられるポリイミドは、酸二無水物とジァミンを反応させ、ポリアミド酸を 合成した後に、加熱 (加熱イミド化）することによって得ることができる。また酸二無水 物とジァミンを反応させ、ポリアミド酸を合成し、続いて触媒を添加した後にイミド化（ 化学的イミド化）させることによつても、得ること力 Sできる。この中で、化学的イミド化が、 より低温でイミド化を完結できる点で好ましい。さらに、酸二無水物とジァミンを非等モ ル比で反応させ、ポリアミド酸を合成し、続いて触媒を添加した後にイミド化（化学的 イミド化）させてポリイミドブロックを調製し、続いて、次の酸二無水物、及び/又は、 ジァミンを、最終的にほぼ等モル比になるように反応させて、ポリアミド酸ブロックを成 長させた後、イミド化（化学的イミド化）させて、ブロックポリイミドを合成することも好ま しい。 [0056] 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. Furthermore, 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.
[0057] さらに詳しく説明するために、次に、まず、酸二無水物とジァミンを反応させてポリア ミド酸を合成する方法について説明し、続いて触媒を添加した後にイミド化させる方 法を例にあげて、本発明に用いられるポリイミドの製造条件について説明する。  [0057] To explain in more detail, first, a method of synthesizing polyamic acid by reacting acid dianhydride and diamine will be described, followed by an example of imidization after adding a catalyst. The manufacturing conditions for the polyimide used in the present invention will be described.
[0058] ポリアミド酸を製造する方法は特に限定されず、公知の方法を適用することができる 。より具体的には、以下の方法により得られる。まずジァミンを重合溶媒に溶解及び /又は分散し、これに酸二無水物粉末を徐々に添加し、メカニカルスターラーを用い 、 0. 5〜96時間好ましくは 0. 5〜30時間攪拌する。この際モノマー濃度は、 0. 5質 量％以上 95質量％以下、好ましくは 1質量％以上 90質量％以下である。このモノマ 一濃度範囲で重合を行うことにより、ポリアミド酸溶液を得ることができる。  [0058] 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.
[0059] 前記ポリアミド酸の製造の際に使用される反応溶媒としては、ジメチルエーテル、ジ ェチルエーテル、メチルェチルエーテル、テトラヒドロフラン、ジォキサン、エチレング リコールジメチルエーテルのような炭素数 2以上 6以下のエーテル化合物；アセトン、 メチルェチルケトンのような炭素数 2以上 6以下のケトン化合物；ノルマルペンタン、シ クロペンタン、ノノレマノレへキサン、シクロへキサン、メチノレシクロへキサン、デカリンの ような炭素数 5以上 10以下の飽和炭化水素化合物；ベンゼン、トルエン、キシレン、メ シチレン、テトラリンのような炭素数 6以上 10以下の芳香族炭化水素化合物；酢酸メ チル、酢酸ェチル、 γ—ブチロラタトンのような炭素数 3以上 6以下のエステル化合物 ；クロロホルム、塩化メチレン、 1 , 2—ジクロロェタンのような炭素数 1以上 10以下の 含ハロゲン化合物；ァセトニトリル、 Ν, Ν—ジメチルホルムアミド、 Ν, Ν—ジメチルァ セトアミド、 Ν—メチルー 2—ピロリドンのような炭素数 2以上 10以下の含窒素化合物； ジメチルスルホキシドのような含硫黄化合物が挙げられる。これらは必要に応じて 1種 、あるいは 2種以上の混合物であっても良い。特に好ましい溶媒としては、炭素数 3以 上 6以下のエステル化合物、炭素数 6以上 10以下の芳香族炭化水素化合物、炭素 数 2以上 10以下の含窒素化合物が挙げられる。これらは工業的な生産性、次反応 への影響などを考慮して任意に選択可能である。 [0059] 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, 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 γ -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, ァ, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Ν-methyl-2-pyrrolidone And a sulfur-containing compound such as dimethyl sulfoxide. These may be one kind or a mixture of two or more kinds as necessary. 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.
[0060] ポリアミド酸製造の際の反応温度は、 0°C以上 250°C以下が好ましい。 0°C以上あ れば反応が開始され、また 250°C以下であれば副反応などの影響が無い。好ましく は 15°C以上 220°C以下、さらに好ましくは 20°C以上 200°C以下である。最も好ましく は 20°C以上、 100°C以下である。 [0060] 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.
[0061] ポリアミド酸の反応に要する時間は、 目的あるいは反応条件によって異なる力 通 常は 96時間以内であり、特に好適には 30分から 30時間の範囲で実施される。 [0061] 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.
[0062] 次に、ポリアミド酸に触媒を添加し (化学的)イミド化し、本発明に用いられるアルカリ 可溶性ポリイミドを得る方法について説明する。 [0062] Next, a method for obtaining an alkali-soluble polyimide used in the present invention by adding a catalyst to polyamic acid to (chemical) imidization will be described.
[0063] 本発明に用いられるアルカリ可溶性ポリイミドを製造する際のイミド化触媒は特に制 限されないが、無水酢酸のような酸無水物、 γ —ノ レ口ラタトン、 γ —ブチロラタトン、 γ—テトロン酸、 y—フタリド、 γ—クマリン、 γ—フタリド酸のようなラタトン化合物、ピ リジン、キノリン、 Ν—メチルモルホリン、トリェチルァミンのような三級ァミンのなどが挙 げられる。また、必要に応じて 1種、あるいは 2種以上の混合物であっても良い。この 中でも特に、反応性の高さの観点から γ —バレロラタトンとピリジンの混合系が特に 好ましい。 [0063] 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, γ-noratolataton, γ-butyrolataton, γ-tetronic acid , Y-phthalide, γ-coumarin, latathone compounds such as γ-phthalide acid, pyridine, quinoline, Ν-methylmorpholine, and tertiary amines such as triethylamine. In addition, one kind or a mixture of two or more kinds may be used as necessary. Among these, a mixed system of γ-valerolatatone and pyridine is particularly preferable from the viewpoint of high reactivity.
[0064] イミド化触媒の添加量は、ポリアミド酸を 100質量％とすると、 50質量％以下が好ま しぐ 30質量％以下がより好ましい。 10質量％以下がさらに好ましぐ 5質量％以下 が最も好ましい。  [0064] 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.
[0065] 反応溶媒としては、ポリアミド酸の製造に使用したものと同じものを用いることができ る。その場合、ポリアミド酸溶液をそのまま用いることができる。また、ポリアミド酸の製 造に用いたものと異なる溶媒を用いても良レ、。  [0065] As the reaction solvent, the same solvent used for the production of polyamic acid can be used. In that case, 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.
[0066] 反応溶媒としては、例えば、ジメチルエーテル、ジェチルエーテル、メチルェチル エーテノレ、テトラヒドロフラン、ジ才キサン、エチレングリコーノレジメチノレエーテノレのよう な炭素数 2以上 6以下のエーテル化合物；アセトン、メチルェチルケトンのような炭素 数 2以上 6以下のケトン化合物；ノルマルペンタン、シクロペンタン、ノルマルへキサン 、シクロへキサン、メチルシクロへキサン、デカリンのような炭素数 5以上 10以下の飽 和炭化水素化合物；ベンゼン、トルエン、キシレン、メシチレン、テトラリンのような炭素 数 6以上 10以下の芳香族炭化水素化合物；酢酸メチル、酢酸ェチル、 γ—プチロラ タトンのような炭素数 3以上 6以下のエステル化合物；クロ口ホルム、塩化メチレン、 1 , 2—ジクロロェタンのような炭素数 1以上 10以下の含ハロゲン化合物；ァセトニトリル、 Ν, Ν ジメチルホルムアミド、 Ν, Ν ジメチルァセトアミド、 Ν メチル 2—ピロリド ンのような炭素数 2以上 10以下の含窒素化合物；ジメチルスルホキシドのような含硫 黄化合物が挙げられる。必要に応じて 1種、あるいは 2種以上の混合物であっても良 い。特に好ましい溶媒としては炭素数 3以上 6以下のエステル化合物、炭素数 6以上 10以下の芳香族炭化水素化合物、炭素数 2以上 10以下の含窒素化合物が挙げら れる。これらは工業的な生産性、次反応への影響などを考慮して任意に選択可能で ある。 [0066] Examples of the reaction solvent 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 γ -ptyroratone; a halogen-containing compound having 1 to 10 carbon atoms such as black mouth form, methylene chloride, and 1,2-dichloroethane; Examples include nitrogen-containing compounds having 2 to 10 carbon atoms such as acetonitrile, Ν, ジ メ チ ル dimethylformamide, Ν, ジ メ チ ル dimethylacetamide, メ チ ル methyl 2-pyrrolidone; and sulfur-containing yellow compounds such as dimethyl sulfoxide. If necessary, one or a mixture of two or more may be used. 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.
[0067] 本発明に用いられるポリイミドの製造においては、反応温度は 15°C以上 250°C以 下で実施することが好ましい。 15°C以上あれば反応が開始され、また 250°C以下で あれば触媒の失活が無い。好ましくは 20°C以上 220°C以下、さらに好ましくは 20°C 以上 200°C以下である。  [0067] In the production of the polyimide used in the present invention, 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.
[0068] イミド化反応に伴い生成する水は、水と共沸する溶剤、例えばトルエンゃキシレンと 共に反応系外に取り除くことができる。得られた反応液はそのままポリイミドワニスとし て用いることができる。  [0068] 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.
[0069] 反応に要する時間は、 目的あるいは反応条件によって異なる力 S、通常は 96時間以 内であり、特に好適には 30分から 30時間の範囲で実施される。  [0069] 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.
[0070] 製造終了後における、ポリイミドの回収は、反応溶液中の溶媒を減圧留去すること に fiうことができる。  [0070] After the production is completed, the polyimide can be recovered by distilling off the solvent in the reaction solution under reduced pressure.
[0071] 本発明に用いられるポリイミドの精製方法としては、反応溶液中の不溶解な酸二無 水物及びジァミンを減圧濾過、加圧濾過などで除去する方法が挙げられる。また、反 応溶液を貧溶媒に加え析出させる、いわゆる再沈精製法を実施することができる。更 に特別に高純度なポリイミドが必要な場合は、二酸化炭素超臨界法による抽出法も 可能である。 [0072] 本発明に用いられるポリイミドを用いて、前記ポリイミドが均一に溶解及び/又は分 散し得る溶媒を含む樹脂組成物を得ることができる。 [0071] 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.
[0073] 本発明に用いられるポリイミドを含有する樹脂組成物を構成する溶媒は、本発明に 用いられるポリイミドを均一に溶解及び/又は分散させ得るものであれば限定されな い。重合に使用した溶媒を用いることも好ましい。このような溶媒として、ジメチルエー テノレ、ジェチルエーテル、メチルェチルエーテル、テトラヒドロフラン、ジォキサン、ェ チレングリコーノレジメチノレエーテノレ、プロピレングリコーノレモノメチノレアセテートのよう な炭素数 2以上 6以下のエーテル化合物；アセトン、メチルェチルケトンのような炭素 数 2以上 6以下のケトン化合物；ノルマルペンタン、シクロペンタン、ノルマルへキサン 、シクロへキサン、メチルシクロへキサン、デカリンのような炭素数 5以上 10以下の飽 和炭化水素化合物；ベンゼン、トルエン、キシレン、メシチレン、テトラリンのような炭素 数 6以上 10以下の芳香族炭化水素化合物；酢酸メチル、酢酸ェチル、 γ—プチロラ タトンのような炭素数 3以上 6以下のエステル化合物；クロ口ホルム、塩化メチレン、 1 , 2—ジクロロェタンのような炭素数 1以上 10以下の含塩素化合物；ァセトニトリル、 Ν, Ν ジメチルホルムアミド、 Ν, Ν ジメチルァセトアミド、 Ν メチル 2—ピロリドンの ような炭素数 2以上 10以下の含窒素化合物;ジメチルスルホキシドのような含硫黄化 合物などが挙げられる。また、必要に応じて、 1種、あるいは 2種以上の混合物であつ ても良い。ポリイミドの溶解性の観点から、 Ν メチル 2—ピロリドン、 γ—ブチ口ラタ トン、 Ν, Ν ジメチルホルムアミド、 Ν, Ν ジメチルァセトアミドが好ましい。 [0073] 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. Examples of such 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. Compound: 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 γ -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, Ν, ジ メ チ ル dimethylformamide, Ν, ジ メ チ ル dimethylacetamide, Ν methyl 2-pyrrolidone Examples include the following nitrogen-containing compounds; sulfur-containing compounds such as dimethyl sulfoxide. In addition, one kind or a mixture of two or more kinds may be used as necessary. From the viewpoint of the solubility of the polyimide, メ チ ル methyl 2-pyrrolidone, γ-butarate rataton, Ν, ジ メ チ ル dimethylformamide, and Ν, ジ メ チ ル dimethylacetamide are preferred.
[0074] 本発明に用いられるポリイミドと溶媒とからなる樹脂組成物におけるポリイミドの濃度 は、樹脂成型体が製造される濃度であれば、特に制限されない。作製する樹脂成型 体の膜厚の観点からポリイミドの濃度が 1質量％以上、樹脂成型体の膜厚の均一性 力もポリイミドの濃度が 90質量％以下であることが好まし!/、。得られる樹脂成型体の 膜厚の観点から、 2質量％以上 80質量％以下がより好まし!/、。  [0074] 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!
[0075] 本発明に用いられるアルカリ可溶性ポリイミド又はポリイミド前駆体の構造に特に制 限はないが、フィルムにした際の伸度、柔軟性、屈曲性などの機械物性、ドライフィノレ ム化した際の反り改善効果を考慮すると、シロキサン骨格を有することが好ましい。ド ライフイルム化時の反り改善効果は、（Β)成分の配合により達成されるが、シロキサン 骨格を有することによる低弾性率化と低 Tg化が反り改善にさらに寄与するものと考え られる。 [0075] 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 (Β), 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.
[0076] アルカリ可溶性ポリイミド又はポリイミド前駆体は、ドライフィルム化時の反り及び難 燃性の観点から、 10質量％以上 90質量％以下のシロキサン構造を有することが好 ましぐ 20質量％以上質量％以下のシロキサン構造を有することがより好ましい。  [0076] 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.
[0077] 本発明のポリイミド前駆体の末端は、性能に影響を与えな!/、構造であれば、特に限 定されない。ポリイミド前駆体を製造する際に用いる酸二無水物、ジァミンに由来する 末端でも良ぐその他の酸無水物、ァミン化合物などにより末端を封止しても良い。  [0077] 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.
[0078] なお、本発明の樹脂組成物におけるポリイミド前駆体は、前述したアルカリ可溶性 ポリイミドに用いているジァミンと、テトラカルボン酸二無水物とより合成することができ る。ただし、ポリイミド前駆体は、分子内にカルボキシル基を有しているため、カルボ キシル基を有するジァミンや水酸基を有して!/、るジァミンを原料として用いなくても、 アル力リ可溶性であり、また有機溶剤に可溶である。  [0078] 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.
[0079] 次に (B)成分について説明する。  [0079] Next, the component (B) will be described.
(B)成分は、式（1)に示す構造を有する化合物、イソシァヌル酸環を有する化合物 、及び前記 (A)成分以外のイミド基を 1つ若しくは 2つ含有するイミド化合物からなる 群から選ばれた少なくとも一つの化合物である。  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 = X 式（1)  P = X formula (1)
(式中 Pはリン原子を表し、その共有結合数は 5である。 Xは窒素原子、又は、酸素原 子を表し、 Xが窒素原子の場合、その共有結合数は 3であり、酸素原子の場合、その 共有結合数は 2である。リン原子と窒素原子又は酸素原子とは二重結合で結合して いる。 )  (In the formula, 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.)
[0080] リン酸化合物としては、式（2)、式（3)に示すリン酸エステル化合物、又は式 (4)に 示すホスフィンォキシド化合物、さらには、式（17)、式（18)に表されるホスファゼン 化合物からなる群より選ばれた少なくとも一つの化合物を用いる。これらのリン化合物 の添加は、ドライフィルム化時の反りを低減し、配線パターン基板へのラミネート性（ 埋め込み性、密着性）に優れ、現像特性も向上し、さらに難燃性も付与できる。  [0080] 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.
[化 24] Ri [Chemical 24] Ri
9  9
R「 O- 0_  R 'O- 0_
O ( 2 )  O (2)
(式中 は 1 の有機基である。複数の はそれぞれ同一でも異なっていても良い。(In the formula, 1 is an organic group. Multiple groups may be the same or different.
) )
[化 25]  [Chemical 25]
Figure imgf000022_0001
Figure imgf000022_0001
(式中の Rは式（1)と同じである。複数の Rはそれぞれ同一でも異なっていても良い o ) (R in the formula is the same as in formula (1). Multiple Rs may be the same or different from each other o)
[化 26]  [Chemical 26]
Figure imgf000022_0002
Figure imgf000022_0002
(式中 Rは 1価の有機基である。 ) (In the formula, R is a monovalent organic group.)
2  2
[化 27]  [Chemical 27]
Figure imgf000022_0003
Figure imgf000022_0003
[化 28]
Figure imgf000023_0001
これらの化合物は、熱安定性が良好であり、（A)成分の樹脂と共に 200°C以上の 高温で加熱しても分解せず、また (A)成分の分解も引き起こさない。また、（C)成分と 組み合わせたときの難燃性を考慮すると、特に式（3)で示される化合物が難燃性の 効果が高くより好ましい。 [Chemical 28]
Figure imgf000023_0001
These compounds have good thermal stability and do not decompose when heated at a high temperature of 200 ° C or higher together with the resin of component (A) and do not cause decomposition of component (A). In view of the flame retardancy when combined with the component (C), the compound represented by the formula (3) is particularly preferable because of its high flame retardancy effect.
[0081] 本発明に用いられる式（2)で表されるリン酸エステル化合物としては、炭素数 1以上 30以下の脂肪族有機基を有するリン酸エステル化合物であれば限定されない。炭 素数 1以上であれば、ドライフィルム化時の反りや埋め込み性が改善される傾向にあ るため好ましい。炭素数 30以下であれば、難燃性が発現する傾向にあるため好まし い。 [0081] 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.
[0082] ドライフィルムの反り改善効果を考慮すると、式（2)又は式（3)中の R力 Sメチル基、 ェチル基、ブチル基、イソブチル基、 2—ェチルへキシル基、ブトキシェチル基、フエ ニル基、クレジル基、キシレニル基、ァミノフエニル基から選ばれる有機基であること が好ましい。  [0082] In consideration of the effect of improving the warp of the dry film, 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.
[0083] また、同様に熱安定性と、ドライフィルムの反り改善効果を考慮すると、式 (4)中の R が水素、ジヒドロキシフエニル基、ジブチルヒドロキシベンジル基、（メタ）アタリレート [0083] Similarly, when considering the thermal stability and the effect of improving the warp of the dry film, R in the formula (4) is hydrogen, dihydroxyphenyl group, dibutylhydroxybenzyl group, (meth) acrylate.
2 2
含有有機基から選ばれる有機基であることが好ましい。さらに、樹脂ワニスとの相溶 性やドライフィルム化した際の反り改善効果を考慮すると、 Rは水素が好ましい。  An organic group selected from the containing organic groups is preferred. Furthermore, in consideration of the compatibility with the resin varnish and the effect of improving warpage when formed into a dry film, R is preferably hydrogen.
2  2
[0084] このような化合物としては、トリメチノレホスフェート、 トリェチノレホスフェート、 トリブチル ホスフェート、トリイソブチルホスフェート、トリス（2—ェチルへキシル）ホスフェートなど の脂肪族炭化水素基を置換基とするリン酸エステル、トリス（ブトキシェチル)ホスフエ ートなどの酸素原子を含む脂肪族有機基を置換基とするリン酸エステル、などが挙げ られる。焼成時の不揮発の観点から、トリブチルホスフェート、トリイソブチルホスフエ ート、トリス（2—ェチルへキシル）ホスフェート、トリス（ブトキシェチル）ホスフェートが 好ましい。 [0084] 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. From the viewpoint of non-volatility during firing, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, and tris (butoxetyl) phosphate are used. preferable.
[0085] 本発明に用いられるリン酸エステル化合物は、 1種類でも 2種類以上の組み合わせ で用いても良い。その中で、 2種類以上の組み合わせで用いると、難燃性とドライフィ ルム化時の反りが両立する傾向にあるため、好ましい。 2種類の組み合わせとしては 、トリブチルホスフェート、トリス（ブトキシェチル）ホスフェートの組み合わせ、トリス（2 ーェチルへキシル）ホスフェート、トリス（ブトキシェチル）ホスフェートの組み合わせ、 トリブチルホスフェート、トリス（2—ェチルへキシル）ホスフェートの組み合わせ、トリイ ソブチルホスフェート、トリス（ブトキシェチル）ホスフェートの組み合わせ、などが挙げ られる。  [0085] 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.
[0086] 脂肪族有機基を有するリン酸エステルにおいて、脂肪族有機基がエーテル構造を 有する場合、現像時にお!/、て現像時間の短縮及び現像残渣 (スカム）の低減効果が あり、このため、脂肪族有機基がエーテル構造を有するリン酸エステルを含むことが 好ましい。好ましい化合物として、トリス（ブトキシェチル)ホスフェートが挙げられる。  [0086] In the phosphate ester having an 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.
[0087] 本発明に用いられるリン酸エステル化合物は、 2種類以上の組み合わせで用いるこ とが好ましいが、その内、少なくとも、脂肪族有機基がエーテル構造を有するリン酸ェ ステルを含んでいることがより好ましい。好ましい組み合わせとして、トリブチルホスフ エート、トリス（ブトキシェチル）ホスフェートの組み合わせ、トリイソブチルホスフェート 、トリス（ブトキシェチル)ホスフェートの組み合わせ、などが挙げられる。  [0087] 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.
[0088] 本発明の感光性樹脂組成物において、前記リン酸エステル化合物の添加量は、 ( A)アルカリ可溶性樹脂の量を 100質量％とした場合、感光性などの観点から、 50質 量％以下が好ましい。硬化体の耐熱性の観点から、 45質量％以下が好ましぐ 40質 量％以下がより好ましい。  [0088] In the photosensitive resin composition of the present invention, 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.
[0089] イソシァヌル酸環有する化合物としては、式（8)で示される化合物を好適に用いる こと力 Sできる。イソシァヌル酸環を有する化合物の添加も前記リン酸エステル化合物と 同様に、難燃性とドライフィルム化した時の反り改善の観点から好ましい。  [0089] As 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.
[化 29]
Figure imgf000025_0001
[Chemical 29]
Figure imgf000025_0001
(式中 Rは 1価の有機基である。複数の Rはそれぞれ同一でも異なっていても良い。  (In the formula, R is a monovalent organic group. A plurality of R may be the same or different from each other.)
9 9  9 9
)  )
Rは 1価の有機基である。 1価の有機基とは、例えば、カルボキシル基を有する有 R is a monovalent organic group. A monovalent organic group is, for example, an organic group having a carboxyl group.
9 9
機基やエステル基を有する有機基である。このような 1価の有機基とは、例えば、式（ 22)で表される有機基である。また、樹脂やワニスに用いる溶媒との相溶性の観点よ り、エステル基を有する有機基が好ましい。 It is an organic group having a functional group or an ester group. Such a monovalent organic group is, for example, an organic group represented by the formula (22). In addition, an organic group having an ester group is preferable from the viewpoint of compatibility with a solvent used for a resin or varnish.
[化 30] [Chemical 30]
0 0
— CH2CH20- C- C2H4- 0- C2H4— 0_C2H5 ( 2 2 ) ドライフィルムの反り改善効果を考慮すると、式（8)中の Rは式（11)で示される有 - CH 2 CH 2 0- C- C 2 H 4 - 0- C 2 H 4 - 0_C 2 H 5 (2 2) In view of the warping effect of improving dry film, the R in the formula (8) (11 )
9  9
機基から選ばれることが好ましい。また、 R は銅との密着性を考慮すると、式（12)又 It is preferably selected from functional groups. In addition, R takes into account the adhesion with copper, formula (12) or
11  11
は式（13)で示される構造が好ましぐ式（13)で示される構造がより好ましい。なお、 式（13)中の R は水素であることが好ましい。また、式（13)中の cは反り改善効果を The structure represented by the formula (13) is more preferable, and the structure represented by the formula (13) is more preferable. Note that R in the formula (13) is preferably hydrogen. Also, c in Equation (13)
12  12
考慮すると 4から 5が好ましい。 Considering 4 to 5 is preferable.
[化 31] [Chemical 31]
0 I I  0 I I
Hつ-リ—し— R" ( 1 1 )  H-Lease — R "(1 1)
(式中 R は式（12)、式（13)力 選ばれる有機基である。 ) (Wherein R is an organic group selected from the formulas (12) and (13)).
11  11
[化 32]  [Chemical 32]
^12 ^ 12
— C=Cn2 ( 1 2 ) — C = Cn 2 (1 2)
(式中 R は水素、メチル基から選ばれる有機基である。 ) (Wherein R is an organic group selected from hydrogen and a methyl group.)
12  12
[化 33] — (CH2)c-0-C-C=CH2 ( 1 3 ) [Chemical 33] — (CH 2 ) c -0-CC = CH 2 (1 3)
(式中 cは 2から 5の整数である。式中 R は式（12)と同じ有機基である。 ) (In the formula, c is an integer of 2 to 5. In the formula, R is the same organic group as in formula (12).)
12  12
本発明に用いられる (A)成分以外のイミド基を 1つ若しくは 2つ含有するイミド化合 物としては、式（9)で示される化合物を好適に用いることができる。イミド基を 1つ若し くは 2つ含有するイミド化合物の添加も前記リン酸エステル化合物同様に、難燃性と ドライフィルム化した時の反り改善の観点から好ましい。  As the 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.
[化 34] [Chemical 34]
Figure imgf000026_0001
( 9 )
Figure imgf000026_0001
(9)
(式中 R は 1価もしくは 2価の有機基である。 mは 1もしくは 2である。 Yは式（10)で  (In the formula, R is a monovalent or divalent organic group. M is 1 or 2. Y is a formula (10).
10  Ten
示される有機基を表す。 ) Represents the organic group shown. )
[化 35]
Figure imgf000026_0002
[Chemical 35]
Figure imgf000026_0002
mが 2である場合、 R は 2価の有機基である。この場合、イミド化合物は、ジァミンと  When m is 2, R is a divalent organic group. In this case, the imide compound is diamine and
10  Ten
ジカルボン酸無水物の縮合反応により得ることができる。このとき、 R は該当するジ It can be obtained by condensation reaction of dicarboxylic acid anhydride. At this time, R is the corresponding
10  Ten
ァミンの 2価の有機基が導入されることとなる。ジァミンは、例えば前述した可溶性ポリ イミドを合成する際に用いられる芳香族ジァミン、脂肪族ジァミン、脂環式ジァミンを 用いること力 Sできる。中でも反り改善の観点より、脂肪族を有するジァミンが好ましい。 さらに好ましくは、脂肪族の炭素数が 2から 6の 1 , 2 ジアミノエタン、 1 , 3 ジァミノ プロパン、 1 , 4ージアミノブタン、 1 , 5—ジァミノペンタン、 1 , 6—ジァミノへキサン、 1 , 3—ビス（4 アミノフエノキシ）プロパン、 1 , 4 ビス（4 アミノフエノキシ）ブタン、 1 , 5—ビス（4 アミノフエノキシ）ヘプタンである。すなわち、 R は、エチレン基、プロ The divalent organic group of amine will be introduced. For example, the diamine can use an aromatic diamine, an aliphatic diamine or an alicyclic diamine used in the synthesis of the aforementioned soluble polyimide. Among these, 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. (4 aminophenoxy) propane, 1,4 bis (4 aminophenoxy) butane, 1,5-bis (4 aminophenoxy) heptane. That is, R is an ethylene group,
10  Ten
ピレン基、ブチレン基、ペンテン基、へキセン基、式（23)で示される基が好ましい。 A pyrene group, a butylene group, a pentene group, a hexene group, and a group represented by the formula (23) are preferable.
[化 36]
Figure imgf000027_0001
[Chemical 36]
Figure imgf000027_0001
(式中 dは 3から 5の整数を表す。） (Where d represents an integer of 3 to 5)
[0092] mが 1である場合、 R は 1価の有機基である。 1価の有機基としては、アルキル基、 [0092] When m is 1, R is a monovalent organic group. Examples of monovalent organic groups include alkyl groups,
10  Ten
アルキルォキシド基などが挙げられる。アルキル基としては、例えばェチル基、プロピ ル基、ブチル基、ペンチル基、へキシル基、ヘプチル基が挙げられる。アルキルォキ シド基としてはエチレンォキシド基、ポリエチレンォキシド基、プロピレンォキシド基、 ポリプロピレンォキシド基、ブチレンォキシド基、ポリブチレンォキシド基が挙げられる mが 1である場合、これら 1価の有機基の末端にアクリル基若しくはメタクリル基を有 してレ、ても良レ、。末端にアクリル基若しくはメタクリル基を有する 1価の有機基である 場合、 R は式（11)中の R が式（13)で示される 1価の有機基である。例えば、式（2 An alkyloxide group etc. are mentioned. Examples of the alkyl group include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Examples of 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. When m is 1, when these monovalent organic groups are It is possible to have an acrylic or methacrylic group at the end. In the case where it is a monovalent organic group having an acryl group or a methacryl group at the terminal, R is a monovalent organic group represented by the formula (13) where R in the formula (11). For example, the expression (2
10 11 10 11
4)に示される化合物が挙げられる。  The compound shown by 4) is mentioned.
[化 37]  [Chemical 37]
Figure imgf000027_0002
Figure imgf000027_0002
[0094] このような化合物は、難燃性に優れるために好ましい。 （B)成分は、単独又は組み 合わせて用いることができる。  [0094] Such a compound is preferable because of its excellent flame retardancy. Component (B) can be used alone or in combination.
[0095] 難燃性とドライフィルムの反りの観点から、リン酸エステル化合物とイソシァヌル酸環 有する化合物との組み合わせ、若しくはリン酸エステル化合物と (A)成分以外のイミ ド基を 1つ若しくは 2つ含有するイミド化合物との組み合わせが好ましい。この場合、 その配合比は、リン酸エステル化合物 100質量部に対してイソシァヌル酸環有する 化合物若しくは (A)成分以外のイミド基を 1つ若しくは 2つ含有するイミド化合物が 50 質量部から 200質量部が好まし!/、。 [0095] From the viewpoint of flame retardancy and warping of the dry film, 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. In this case, 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!
難燃性とドライフィルムの反りを考慮すると、（B)成分は、式（25)、式（26)、式（27 )、式（28)、及び式（29)で示される化合物からなる群から選ばれる少なくとも 1つの 化合物が特に好ましい。  In consideration of the flame retardancy and the warp of the dry film, 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.
[化 38] [Chemical 38]
Figure imgf000028_0001
Figure imgf000028_0001
(式中 R は水素若しくはメチル基から選ばれる有機基である。複数の R は同じでも (In the formula, R is an organic group selected from hydrogen or a methyl group.
17 17 異なっていても良い。 ) 17 17 May be different. )
[化 39] [Chemical 39]
Figure imgf000028_0002
Figure imgf000028_0002
[化 40]  [Chemical 40]
Figure imgf000028_0003
Figure imgf000028_0003
[化 41]
Figure imgf000028_0004
[Chemical 41]
Figure imgf000028_0004
(式中 R は式（25)と同じ意味である。複数の R は同じでも異なっていても良い。） (Wherein R has the same meaning as in formula (25). Multiple Rs may be the same or different.)
17 17 [0097] (B)成分は、（A)成分 100質量部に対して 50質量部以下であることが好ましい。さ らに好ましくは 30質量部以下である。さらに好ましくは 20質量部以下である。この添 加範囲であると、フィルムの伸度、屈曲性が良好であり、またアルカリ可溶性も良好で あり好ましい。 17 17 [0097] 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.
[0098] 本発明に用いられる式（ 17)及び式（18)で表されるホスファゼン化合物における R [0098] R in the phosphazene compound represented by formula (17) or formula (18) used in the present invention
R R R は、炭素数 3以上 20以下の有機基であれば限定されない。炭素数 3 R R R is not limited as long as it is an organic group having 3 to 20 carbon atoms. Carbon number 3
3 14 15 16 3 14 15 16
以上であれば、難燃性が発現する傾向にあるため好ましい。炭素数 30以下であれ ば、アルカリ可溶性樹脂と相溶する傾向にあるため好ましい。この中で、難燃性発現 の観点から、炭素数 6以上 18以下の芳香族性化合物に由来する官能基が特に好ま しい。このような官能基として、フエニル基、 2 ヒドロキシフエニル基、 3 ヒドロキシフ ェニル基、 4ーヒドロキシフエニル基などのフエ二ル基を有する官能基、 1 ナフチル 基、 2—ナフチル基などのナフチル基を有する官能基、ピリジン、イミダゾール、トリア ゾール、テトラゾールなどの含窒素複素環化合物に由来する官能基、などが挙げら れる。これらの化合物は、必要に応じて 1種類でも 2種類以上の組み合わせで用いて も良い。この中で、入手の容易さ力、らフエ二ル基、 4ーヒドロキシフエ二ル基を有する 化合物が好ましい。  The above is preferable because the flame retardancy tends to be exhibited. A carbon number of 30 or less is preferred because it tends to be compatible with the alkali-soluble resin. Of these, 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. And 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.
[0099] 本発明に用いられる式（17)で表されるホスファゼン化合物における pは、 3以上 25 以下であれば限定されない。 3以上であれば、難燃性を発現し、 25以下であれば、 有機溶剤に対する溶解性が高い。この中で特に、入手の容易さから mが 3以上 10以 下であることが好ましい。  [0099] 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.
[0100] 本発明に用いられる式（18)で表されるホスファゼン化合物における qは、 3以上 10 000以下であれば限定されない。 3以上であれば、難燃性を発現し、 10000以下で あれば、有機溶剤に対する溶解性が高い。この中で特に、入手の容易さから 3以上 1 00以下が好ましい。  [0100] In the phosphazene compound represented by the formula (18) used in the present invention, 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.
[0101] 本発明に用いられる式（18)で表されるホスファゼン化合物における A及び Bは、炭 素数 3以上 30以下の有機基であれば限定されない。この中で、 Aは N = P (OC H  [0101] 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. In this, A is N = P (OC H
6 N = P (OC H ) (OC H OH) N = P (OC H ) (OC H OH) N = 6 N = P (OC H) (OC H OH) N = P (OC H) (OC H OH) N =
5 3 6 5 2 6 4 3 6 5 6 4 25 3 6 5 2 6 4 3 6 5 6 4 2
P (OC H OH) -N = P (0) OC H N = P (0) (OC H OH)が好ましい。 Bは P (OC H ) P (OC H ) (OC H OH) P (OC H ) (OC H OH) P ( P (OCHOH) -N = P (0) OCHN = P (0) (OCHOH) is preferred. B is P (OC H) P (OC H) (OC H OH) P (OC H) (OC H OH) P (
6 5 4 6 5 3 6 4 6 5 2 6 4 2  6 5 4 6 5 3 6 4 6 5 2 6 4 2
OC H ) (OC H OH) P (OC H OH) P (O) (OC H ) P (O) (OC H  OC H) (OC H OH) P (OC H OH) P (O) (OC H) P (O) (OC H
6 5 6 4 3 6 4 4 6 5 2 6 6 5 6 4 3 6 4 4 6 5 2 6
OH) P (O) (OC H ) (OC H OH)などが好ましい。 OH) P (O) (OC H) (OC H OH) and the like are preferable.
4 2 6 5 6 4  4 2 6 5 6 4
[0102] 本発明の感光性樹脂組成物において前記ホスファゼン化合物の添加量は、（A)ァ ルカリ可溶性樹脂の量を 100質量％とした場合、感光性などの観点から、 50質量％ 以下が好ましい。硬化体の耐熱性の観点から、 45質量％以下が好ましぐ 40質量％ 以下がより好ましい。  [0102] In the photosensitive resin composition of the present invention, 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.
[0103] 式（1)に示す化合物、及び/又はイソシァヌル酸環有する化合物、及び/又は (A )成分以外のイミド基を 1つ若しくは 2つ含有するイミド化合物（B)は、本発明の感光 性樹脂組成物にぉレ、て (C)成分と組み合わせることで高!/、難燃性を発現する。  [0103] 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.
[0104] 次に（C)成分について説明する。  Next, the component (C) will be described.
本発明の樹脂組成物においては、（C)成分のキノンジアジド化合物により感光性を 発現する。さらに、（C)成分は、前記 (B)成分と併用することで、本発明の感光性樹 脂組成物は高!/、難燃性を発現できる。  In the resin composition of the present invention, 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.
[0105] キノンジアジド化合物としては、例えば、 1 , 2—ベンゾキノンジアジドスルホン酸エス テル類、 1 , 2—べンゾキノンジアジドスルホン酸アミド類、 1 , 2—ナフトキノンジアジド スルホン酸エステル類、 1 , 2—ナフトキノンジアジドスルホン酸アミド類が挙げられる。 この中で、溶解抑止能の観点から、 1 , 2—ナフトキノンジアジドスルホン酸エステル 類が好ましい。  [0105] 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.
[0106] 1 , 2 ナフトキノンジアジドスルホン酸エステルとしては、式（14)、式（15)に示すよ うにスルホン酸基の置換位置が 4位の 1 , 2 ナフトキノンジアジド 4 スルホン酸ェ ステルと 5位の 1 , 2 ナフトキノンジアジドー 5 スルホン酸エステルがあり、いずれを 用いても良いが、難燃性の観点から 1 , 2 ナフトキノンジアジドー 4 スルホン酸エス テルが好ましい。  [0106] 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.
[化 42]
Figure imgf000031_0001
( 1 4 ) [Chemical 42]
Figure imgf000031_0001
( 14 )
[化 43] [Chemical 43]
Figure imgf000031_0002
Figure imgf000031_0002
[0107] 1 , 2 ナフトキノンジアジドスルホン酸エステルは、フエノール性水酸基を有する化 合物を原料として用い、スルホン酸でエステル化して得ることができる。例えば、フエノ ール性水酸基の官能基数 1モルに対して 1 , 2 ナフトキノンジアジドー 4ースルホン 酸もしくはその酸塩化物もしくはそのスルホン酸塩、又は 5位の 1 , 2 ナフトキノンジ アジドー 5—スルホン酸もしくはその酸塩化物もしくはそのスルホン酸塩を、アセトンな ど適当な溶剤中で混合することによって得ることができる。このとき、トリェチルァミン など塩基性の触媒を用いても良い。スルホン酸によるエステル化率としては、 0. 60 以上 0. 98以下が溶解抑止能と露光後のアルカリ可溶性の観点から好ましい。  [0107] 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 naphthoquinone diazide 4-sulfonic acid or its acid chloride or its sulfonate, or 1,2-naphthoquinone diazido 5-sulfonic acid at the 5-position or 1 mol of the functional group of the phenolic hydroxyl group The acid chloride or the 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.
[0108] 1 , 2—ナフトキノンジアジドスルホン酸エステル類としては、トリヒドロキシベンゾフエ ノン類、テトラヒドロキシベンゾフエノン類、ペンタヒドロキシベンゾフエノン類、へキサヒ ドロキシベンゾフエノン類、（ポリヒドロキシフエニル）アルカン類の 1 , 2—ナフトキノン ジアジドスルホン酸エステル類が挙げられる。 [0108] 1,2-Naphthoquinonediazide sulfonic acid esters include trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, (polyhydroxyphenones) Enyl) alkanes such as 1,2-naphthoquinone diazide sulfonic acid esters.
[0109] トリヒドロキシベンゾフエノン類の 1 , 2 ナフトキノンジアジドスルホン酸エステル類と しては、 2, 3, 4—トリヒドロキシベンゾフエノン 1 , 2—ナフトキノンジアジドー 4ース ノレホン酸エステノレ、 2, 3, 4 トリヒドロキシベンゾフエノン 1 , 2 ナフトキノンジアジ ド一 5—スルホン酸エステル、 2, 4, 6—トリヒドロキシベンゾフエノン一 1 , 2—ナフトキ [0109] 1,2, 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
-4 スルホン酸エステル、 2, 4, 6 トリヒドロキシベンゾフエノン一 1 , 2  -4 Sulfonic acid ester, 2, 4, 6 Trihydroxybenzophenone 1, 2
- 5—スルホン酸エステルなどが挙げられる。 [0110] テトラヒドロキシベンゾフエノン類の 1, 2—ナフトキノンジアジドスルホン酸エステル 類としては、 2, 2', 4, 4' テトラヒドロキシベンゾフエノン 1, 2 ナフトキノンジアジ ドー 4 スルホン酸エステル、 2, 2', 4, 4' テトラヒドロキシベンゾフエノン一 1, 2- ナフトキノンジアジドー 5 スルホン酸エステル、 2, 2', 4, 3'—テトラヒドロキシベン ゾフエノン一 1, 2 ナフトキノンジアジド一 4 スルホン酸エステル、 2, 2', 4, 3' - テトラヒドロキシベンゾフエノン 1, 2 ナフトキノンジアジド 5 スルホン酸エステ ノレ、 2, 3, 4, 4'—テトラヒドロキシベンゾフエノン 1, 2 ナフトキノンジアジドー 4 スルホン酸エステル、 2, 3, 4, 4'—テトラヒドロキシベンゾフエノン 1, 2—ナフトキノ ンジアジドー 5 スルホン酸エステル、 2, 3, 4, 2，ーテトラヒドロキシベンゾフエノン 1, 2 ナフトキノンジアジドー 4ースルホン酸エステル、 2, 3, 4, 2'—テトラヒドロキシ ベンゾフエノン一 1, 2 ナフトキノンジアジド一 5 スルホン酸エステル、 2, 3, 4, 4' ーテトラヒドロキシー 3'—メトキシベンゾフエノン 1, 2 ナフトキノンジアジドー 4ース ノレホン酸エステノレ、 2, 3, 4, 4'—テトラヒドロキシー 3'—メトキシベンゾフエノン 1, 2 ナフトキノンジアジド 5 スルホン酸エステルなどが挙げられる。 -5-Sulphonic acid esters. [0110] 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-naphthoquinone diazide 5 sulfonate ester, 2, 3, 4, 2, -tetrahydroxybenzophene Enone 1, 2 Naphthoquinonediazido 4-sulfonic acid ester, 2, 3, 4, 2'-tetrahydroxy benzophenone 1,2 Naphthoquinone diazide-5 sulfonic acid ester, 2, 3, 4, 4'-tetrahydroxy 3'- Examples thereof include methoxybenzophenone 1,2 naphthoquinonediazide 4-ose norephonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone 1,2 naphthoquinonediazide 5 sulfonate, and the like.
[0111] ペンタヒドロキシベンゾフエノン類の 1, 2—ナフトキノンジアジドスルホン酸エステル 類としては、 2, 3, 4, 2', 6' ペンタヒドロキシベンゾフエノン一 1, 2 ナフトキノンジ アジドー 4 スルホン酸エステル、 2, 3, 4, 2', 6，一ペンタヒドロキシベンゾフエノン -1, 2 ナフトキノンジアジドー 5 スルホン酸エステルなどが挙げられる。  [0111] 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.
[0112] へキサヒドロキシベンゾフエノン類の 1, 2—ナフトキノンジアジドスルホン酸エステル 類としては、 2, 4, 6, 3', 4', 5' へキサヒドロキシベンゾフエノン一 1, 2 ナフトキ ノンジアジドー 4 スルホン酸エステル、 2, 4, 6, 3，， 4，， 5' へキサヒドロキシベン ゾフエノン一 1, 2 ナフトキノンジアジド一 4 スルホン酸エステル、 3, 4, 5, 3', 4' , 5，一へキサヒドロキシベンゾフエノン 1, 2—ナフトキノンジアジドー 4ースルホン酸 エステノレ、 3, 4, 5, 3，， 4，， 5，一へキサヒドロキシベンゾフエノン一 1, 2 ナフトキノ ンジアジドー 5—スルホン酸エステルなどが挙げられる。  [0112] 1,2-Naphthoquinonediazide sulfonic acid esters of hexahydroxybenzophenones include 2, 4, 6, 3 ', 4', 5 'hexahydroxybenzophenone and 1,2 naphthoquinone diazide. 4 Sulfonic acid ester, 2, 4, 6, 3, 4, 4, 5 'Hexahydroxybenzazophenone 1, 2 Naphthoquinone diazide 1 4 Sulfonic acid ester, 3, 4, 5, 3', 4 ', 5, Monohexahydroxybenzophenone 1,2-Naphthoquinonediazido 4-sulfonic acid Estenole 3, 4, 5, 3, 4, 4, 5, Monohexahydroxybenzophenone 1,2 Naphthoquinone diazide 5-sulfonic acid Examples include esters.
[0113] (ポリヒドロキシフエニル）アルカン類の 1, 2—ナフトキノンジアジドスルホン酸エステ ル類としては、ビス（2, 4—ジヒドロキシフエニル）メタン一 1, 2—ナフトキノンジアジド —4—スルホン酸エステル、ビス（2, 4—ジヒドロキシフエ二ノレ）メタン一 1, 2—ナフトキ ノンジアジドー 5 スルホン酸エステル、ビス（p ヒドロキシフエ二ノレ）メタン一 1, 2- ナフトキノンジアジドー 4—スルホン酸エステル、ビス（p ヒドロキシフエ二ノレ）メタン一 1, 2—ナフトキノンジアジドー 5—スルホン酸エステル、 1, 1, 1—トリ（p ヒドロキシフ ェニル）ェタン一 1, 2—ナフトキノンジアジドー 4—スルホン酸エステル、 1, 1, 1—トリ (p ヒドロキシフエ二ノレ）ェタン一 1, 2 ナフトキノンジアジドー 5 スルホン酸エステ ノレ、 ビス（2, 3, 4 トリヒドロキシフエ二ノレ）メタン 1, 2 ナフトキノンジアジドー 4 スルホン酸エステル、ビス（2, 3, 4 トリヒドロキシフエ二ノレ）メタン一 1, 2 ナフトキノ ンジアジドー 5 スルホン酸エステル、 2, 2，一ビス（2, 3, 4 トリヒドロキシフエニル） プロパン 1, 2 ナフトキノンジアジドー 4ースルホン酸エステル、 2, 2，一ビス（2, 3 , 4 トリヒドロキシフエ二ノレ）プロパン 1, 2 ナフトキノンジアジドー 5 スルホン酸 エステル、 1, 1, 3—トリス（2, 5—ジメチルー 4—ヒドロキシフエ二ル）一 3—フエニル プロパン 1, 2 ナフトキノンジアジドー 4ースルホン酸エステル、 1, 1, 3 トリス（2 , 5 ジメチル一 4 ヒドロキシフエ二ル）一 3 フエニルプロパン一 1, 2 ナフトキノン ジアジドー 5—スルホン酸エステル、 4, 4， [1 [4 [1 [4ーヒドロキシフエニル] 1ーメチルェチノレ]フエ二ノレ]ェチリデン]ビスフエノールー 1, 2—ナフトキノンジァ ジドー 4ースルホン酸エステル、 4, 4，一 [1 [4— [1 [4ーヒドロキシフエニル ] 1 ーメチルェチノレ]フエ二ノレ]ェチリデン]ビスフエノールー 1, 2—ナフトキノンジアジド —5 スルホン酸エステル、ビス（2, 5 ジメチルー 4 ヒドロキシフエ二ル）一 2 ヒド ロキシフエニルメタン 1, 2 ナフトキノンジアジドー 4ースルホン酸エステル、ビス（2 , 5—ジメチル一 4—ヒドロキシフエ二ル）一 2—ヒドロキシフエニルメタン一 1, 2—ナフ トキノンジアジドー 5—スルホン酸エステル、 3, 3, 3', 3'—テトラメチルー 1, 1'ース ピロビインデンー 5, 6, 7, 5', 6', 7'—へキサノーノレー 1, 2 ナフトキノンジアジド —4—スルホン酸エステル、 3, 3, 3', 3'—テトラメチル一 1, 1'—スピロビインデン —5, 6, 7, 5', 6', 7'—へキサノール一 1, 2 ナフトキノンジアジドー 5 スルホン 酸エステノレ、 2, 2, 4 トリメチノレー 7, 2，， 4，一トリヒドロキシフラバン一 1, 2 ナフト キノンジアジド一 4 スルホン酸エステル、 2, 2, 4 トリメチノレー 7, 2', 4，一トリヒドロ キシフラバン 1, 2 ナフトキノンジアジドー 5 スルホン酸エステルなどが挙げられ れる化合物が挙げられる。 [0113] 1,2-Naphthoquinonediazide sulfonic acid esters of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid esters. Bis (2,4-dihydroxyphenol) methane 1,2-naphtho Non-diazido 5-sulfonic acid ester, bis (p-hydroxyphenenole) methane-1,2-naphthoquinonediazido 4-sulfonic acid ester, bis- (p-hydroxyphenolinole) methane 1,2-naphthoquinone diazide 5-sulfonic acid 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazido 4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinone Diazido 5 sulfonic acid ester Nole, bis (2, 3, 4 trihydroxyphenol) methane 1, 2 Naphthoquinone diazido 4 sulfonic acid ester, bis (2, 3, 4 trihydroxyphenol) methane 1, 2 Naphthoquinone diazide 5 Sulfonic acid ester, 2, 2, monobis (2, 3, 4 trihydroxyphenyl) Propane 1, 2 Naphthoquinone diazide 4- Sulfonic acid ester, 2, 2, 1 bis (2, 3, 4 trihydroxyphenol) propane 1, 2 Naphthoquinonediazido 5 Sulfonic acid ester, 1, 1, 3-tris (2, 5-dimethyl-4-hydroxy 1) 3-phenyl propane 1, 2 naphthoquinone diazide 4-sulfonic acid ester, 1, 1, 3 tris (2,5 dimethyl 1-4-hydroxyphenyl) 1 3 phenyl propane 1, 1 naphthoquinone diazide 5 —Sulfonate ester, 4, 4, [1 [4 [1 [4-Hydroxyphenyl] 1-methylethinole] pheninole] ethylidene] bisphenol- 1,2-naphthoquinone didido 4-sulfonate ester, 4, 4, 1 [1 [4 -— [1 [4-Hydroxyphenyl] 1-methylethinole] pheninole] ethylidene] bisphenol- 1,2-naphthoquinonediazide —5 sulfonic acid ester, bis (2,5 dimethyl ester 1-Hydroxyphenylmethane 1,2-Naphthoquinonediazido 4-sulfonic acid ester, bis (2,5-dimethyl-1-4-hydroxyphenyl) 1-2-hydroxyphenylmethane 1, 2-Naphthoquinonediazido 5-sulfonic acid ester 3, 3, 3 ', 3'-tetramethyl-1, 1'-pyrobiindene 5, 6, 7, 5', 6 ', 7'-hexanolol 1, 2 Naphthoquinonediazide —4-sulfonic acid ester, 3, 3, 3 ′, 3′—tetramethyl 1,1,1′—spirobiindene —5, 6, 7, 5 ′, 6 ′, 7′—hexanol 1 , 2 Naphthoquinone diazide 5 Sulfonic acid ester, 2, 2, 4 Trimethylolene 7, 2, 4, 1, 1 Trihydroxyflavan 1, 2 Naphthoquinone diazide 1 4 Sulfonic acid ester, 2, 2, 4 Trimethinole 7, 2 ', 4, monotrihydroxyflavan 1, 2 naphthoquinone Ajido 5 sulfonic acid ester can be mentioned Compounds.
[化 44][Chemical 44]
Figure imgf000034_0001
Figure imgf000034_0001
(式中 Qは式（14)、式（15)と同じである。 ) (In the formula, Q is the same as formula (14) and formula (15).)
溶解抑止能の観点から、 1 , 2—ナフトキノンジアジドスルホン酸エステル類が好まし く、 1 , 2—ナフトキノンジアジドー 4—スルホン酸エステル類、 1 , 2—ナフトキノンジァ ジドー 5—スルホン酸エステル類が感光性コントラストの観点からより好ましい。なかで も、難燃性を考慮すると、式（16)で示される化合物が好ましい。  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. Of these, the compound represented by the formula (16) is preferable in consideration of flame retardancy.
[化 45][Chemical 45]
Figure imgf000034_0002
Figure imgf000034_0002
(式中 Qはそれぞれ独立に水素又は式（14)又は式（15)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（14)又は式（15)力、ら選ばれる有 機基である。 )  (In the formula, 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.)
式（16)で示される化合物は、他の 1 , 2—ナフトキノンジアジド化合物よりも難燃化 効果に優れている。中でも特に、 Q力 式（14)で表される置換位置が 4位の 1 , 2— ナフトキノンジアジドー 4ースルホン酸エステルを有する化合物が特に難燃性に優れ ており好ましい。 The compound represented by the formula (16) is more flame retardant than other 1,2-naphthoquinonediazide compounds. Excellent effect. In particular, 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.
[0117] (C)成分は、（A)成分 100質量％に対して 1質量％以上 50質量％以下が好ましく 、より好ましくは 5質量％以上 40質量％以下である。さらに好ましくは、 15質量％以 上 30質量％以下であることが好ましい。この範囲において、難燃性及び感光性が良 好である。 （B)成分と（C)成分の好ましい配合量としては、（A)成分 100質量部に対 して (B)成分と（C)成分との合計が 5質量部以上 60質量部以下であることが好まし!/、 。より好ましくは 10質量部以上 50質量部以下である。さらに好ましくは 20質量部以 上 40質量部以下である。 （B)成分と（C)成分との比率としては、（B)成分/ (C)成分 のィ直が 0. 4以上 4以下である。より好ましくは 0. 5以上 3以下である。さらに好ましくは 0. 75以上 2以下である。この範囲においては難燃性及び感光性が良好であり、ドラ ィフィルム化時の反りが抑制され、基板への埋め込み性も良好である。  [0117] 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. As for the ratio of component (B) to component (C), 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.
[0118] 次に (D)成分について説明する。  [0118] Next, the component (D) will be described.
本発明の感光性樹脂組成物に、ドライフィルム化時の反りをさらに改善するために（ D)成分：ポリエーテル化合物を添加することも好まし!/、。  It is also preferable to add 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!
[0119] ポリエーテル化合物としては、直鎖状のポリエーテルや環状のクラウンエーテルな どが挙げられる。  [0119] Examples of polyether compounds include linear polyethers and cyclic crown ethers.
[0120] 直鎖状のポリエーテルとは、例えばエチレンォキシド鎖、プロピレンォキシド鎖、ブ チレンォキシド鎖を有する化合物である。中でも、エチレンォキシド鎖を有する化合 物は、ドライフィルム化時の反りの改善に特に有効であり好ましい。  [0120] The linear polyether is, for example, a compound having an ethylene oxide chain, a propylene oxide chain, or a butylene oxide chain. Among them, a compound having an ethylene oxide chain is particularly effective and preferable for improving the warp during dry film formation.
[0121] クラウンエーテルとは、例えば 12 クラウンー4 エーテル、 15 クラウンー5 ェ 一テル、 18 クラウン 6 エーテノレなどである。  [0121] Examples of the crown ether include 12 crown-4 ether, 15 crown-5 ether, 18 crown-6 ethere and the like.
[0122] ポリエーテル化合物としては、配線パターン基板の配線の銅表面との密着性を向 上させるため、末端に OH基を有する化合物が好ましい。  [0122] 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.
[0123] エチレンォキシド鎖を有し、末端に OH基を有するポリエーテル化合物としては、ェ チレングリコーノレ、ジエチレングリコーノレ、トリエチレングリコーノレ、テトラエチレングリコ ールなどのポリエチレングリコールが挙げられる。 [0124] プロピレンォキシド鎖を有し、末端に OH基を有する化合物としては、プロピレンダリ コーノレ、ジプロピレングリコーノレ、トリプロピレングリコーノレ、テトラプロピレングリコーノレ
Figure imgf000036_0001
[0123] 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. [0124] 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.
Figure imgf000036_0001
[0125] ブチレンォキシド鎖を有し、末端に OH基を有する化合物としては、ブチレングリコ 一ノレ、ジブチレングリコール、トリブチレンダリコール、テトラブチレングリコールなどの ポリブチレンダリコールが挙げられる。  [0125] 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.
[0126] これらの中でドライフィルムの反りを考慮すると、ポリエチレングリコールが好ましい。  Of these, polyethylene glycol is preferred in consideration of the warp of the dry film.
ポリエチレングリコールは、分子量が 300から 1000の化合物が反り改善の効果が高 ぐ樹脂ワニスとの相溶性も良く好ましい。さらに反り改善効果と加熱後もフィルム中 に残存する成分の飛散を抑える効果とを両立させる観点から、分子量は 400力 80 0がより好ましい。具体的には、分子量 600程度のポリエチレングリコールが好ましい  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.
[0127] また、ホスファゼンを含む本発明の感光性樹脂組成物に、ドライフィルム化時の反り や現像性をさらに改善するために（E)成分：可塑剤を添加することも好まし!/、。 [0127] It is also preferable to add a component (E): a plasticizer to the photosensitive resin composition of the present invention containing phosphazene in order to further improve the warp and developability when formed into a dry film! /, .
[0128] 本発明に用いられるホスファゼンを含む感光性樹脂組成物における可塑剤：（E)成 分とは、樹脂組成物に可塑性を与え、組成物の Tgを下げ得るものであれば特に限 定されない。このような可塑剤として、トリクレジルホスフェート、トリキシレニルホスフエ ート、トリブチルホスフェート、トリイソブチルホスフェート、トリス（2—ェチルへキシル） ホスフェート、トリス（2—ブトキシェチル）ホスフェートなどのリン酸エステル；ポリェチ レングリコール、ポリプロピレングリコール、クラウンエーテルなどのエーテル化合物； テトラエチレングリコールジメタタリレート、ポリエチレングリコールジメタタリレートなど のメタクリル基含有化合物；テトラエチレングリコールジアタリレート、ポリエチレンダリ コールジアタリレートなどのアクリル基含有化合物；ジメチルフタレート、ジェチルフタ レートなどのフタル酸エステル；トリス（2—ェチルへキシル）トリメリテートなどのトリメリ ット酸エステル;ジメチルアジペート、ジブチルアジペートなどの脂肪族二塩基酸エス テル；イソシァヌル酸エチレングリコール変性トリアタリレート、 ε —力プロラタトン変性 トリス（アタリ口キシェチル)イソシァヌレートなどが挙げられる。この中で、ドライフィル ム化後の反りの観点から、リン酸エステル、メタクリル基含有化合物、イソシァヌル酸 エチレングリコール変性トリアタリレート、 8 —力プロラタトン変性トリス（アタリ口キシェ チル)イソシァヌレートが好まし!/、。 [0128] Plasticizer: (E) 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. Not. Examples of such 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 acid esters such as tris (2-ethylhexyl) trimellitate Le; dimethyl adipate, aliphatic dibasic acid ester ether such as dibutyl adipate; Isoshianuru acid ethylene glycol-modified tri Atari rate, epsilon - force Purorataton modified tris (Atari port Kishechiru) Isoshianureto the like. Among these, from the viewpoint of warping after dry film formation, 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!
[0129] 本発明に用いられるホスファゼンを含む感光性樹脂組成物における可塑剤：（E)成 分の添加量は、充分な可塑性を考慮すると (A)アルカリ可溶性樹脂の量を 100質量 %とした場合、 30質量％以下が好ましい。また、硬化体の難燃性の観点から、 20質 量％以下がより好ましい。  [0129] In the photosensitive resin composition containing phosphazene used in the present invention, the amount of the plasticizer: (E) component is set in consideration of sufficient plasticity. (A) 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.
[0130] 本発明の感光性樹脂組成物には、本発明の効果を逸脱しない量的、質的範囲内 で、既に公知である添加剤を必要に応じて添加することができる。具体的に添加剤と しては、密着性向上剤、界面活性剤、酸化防止剤、紫外線防止剤、光安定剤、可塑 剤、ワックス類、充填剤、顔料、染料、発泡剤、消泡剤、脱水剤、帯電防止剤、抗菌 剤、防カビ剤、レべリング剤、分散剤、エチレン性不飽和化合物などが挙げられる。  [0130] To the photosensitive resin composition of the present invention, 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. , Dehydrating agents, antistatic agents, antibacterial agents, antifungal agents, leveling agents, dispersants, and ethylenically unsaturated compounds.
[0131] 本発明の感光性樹脂組成物は、（A)成分と (B)成分と（C)成分とを任意の溶剤中 にて混合して得られる。溶媒としては、前述のポリイミド樹脂組成物に用いる溶媒を使 用すること力 Sできる。また、必要に応じて (D)成分や (E)成分を加えても良い。混合に より得られた溶液は、塗工液として用いること力 Sできる。また、本発明の感光性樹脂組 成物を溶剤中にて混合した後、混合液を所定の基材に塗布し、任意の方法で溶剤 を乾燥させることによりドライフィルムを得ることができる。  [0131] 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. As 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. Moreover, after mixing the photosensitive resin composition of this invention in a solvent, a liquid mixture is apply | coated to a predetermined base material, A dry film can be obtained by drying a solvent by arbitrary methods.
[0132] 本発明の感光性樹脂組成物を用いて、回路基板を製造することが可能である。回 路基板を製造する場合においては、少なくとも配線を有する基材上に感光性樹脂組 成物層を積層し、前記感光性樹脂組成物層にパターン露光を行い、前記パターン 露光後の樹脂組成物層に対してアルカリ水溶液を用いて現像処理を行う。配線を有 する基材とは、例えば、ガラスエポキシ基板、ガラスマレイミド基板などの硬質な基材 、あるいはポリイミドフィルムなどの可撓性のある基材などの任意の基材上に配線を 有するものをいう。  [0132] A circuit board can be produced using the photosensitive resin composition of the present invention. In the case of producing a circuit board, 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. Say.
[0133] 中でも特に、本発明の感光性樹脂組成物は、ポリイミドフィルムなどのフレキシブル な基材上に配線を有するフレキシブルプリント配線板のカバーレイとして好適に用い ること力 Sできる。本発明の感光性樹脂組成物をフレキシブルプリント配線板のカバー レイとする場合は、例えば、ドライフィルムの状態にして、配線を有する基材上に貼付 する。 [0133] In particular, 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. When the photosensitive resin composition of the present invention is used as 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.
[0134] 本発明の感光性樹脂組成物で構成されたドライフィルムを用いる場合は、感光性 樹脂組成物の溶液を任意の方法でポリエチレンテレフタレートフィルムや金属フィノレ ムなどの任意のキャリアフィルム上に塗布した後に乾燥し、ドライフィルム化して、キヤ リアフィルムとドライフィルムとを有する積層フィルムとする。また、ドライフィルム上に、 低密度ポリエチレンフィルムなど任意の防汚用のフィルムや保護用のフィルムを少な くとも一層設けて積層フィルムとしても良い。このドライフィルムを、熱ラミネート法、熱 プレス法、熱真空ラミネート法、熱真空プレス法など任意の方法で配線を有する基材 上にラミネートする。このようにして、配線を有する基材と、この配線を覆うように前記 基材上に形成され、本発明の感光性樹脂組成物を露光 ·現像してなる物質で構成さ れたカバーレイと、を具備するフレキシブルプリント配線板を作製することができる。  [0134] 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. In addition, 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. Thus, a base material having wiring, and a cover lay formed on the base material so as to cover the wiring and formed by exposing and developing the photosensitive resin composition of the present invention, , A flexible printed wiring board can be produced.
[0135] まず、本発明の感光性樹脂組成物を基材にコートする。前記基材としては、感光性 ドライフィルム形成の際に損傷しない基材であれば、限定されない。このような基材と しては、シリコンウエノ、、ガラス、セラミック、耐熱性樹脂、キャリアフィルムなどが挙げ られる。本発明におけるキャリアフィルムとしては、ポリエチレンテレフタレートフィルム や金属フィルムが挙げられる。取扱いの良さから、耐熱性樹脂及びキャリアフィルム が好ましぐ基板圧着後の剥離性の観点から、ポリエチレンテレフタレートフィルムが 特に好ましい。 [0135] First, 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.
[0136] コート方法としては、バーコート、ローラーコート、ダイコート、ブレードコート、デイツ プコート、ドクターナイフ、スプレーコート、フローコート、スピンコート、スリットコート、 はけ塗り、などが例示できる。コート後、必要に応じてホットプレートなどによりプリべ ークと呼ばれる加熱処理を行っても良い。  [0136] 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.
[0137] このように、本発明の感光性樹脂組成物で構成された感光性フィルムを用いる場合 は、感光性樹脂組成物の溶液を任意の方法で任意の基材上に塗布後乾燥し、ドライ フィルム化し、例えばキャリアフィルムと感光性フィルムとを有する積層フィルムとする  [0137] Thus, when using a photosensitive film composed of the photosensitive resin composition of the present invention, 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
[0138] また、感光性フィルム上に、任意の防汚用や保護用のカバーフィルムを少なくとも 一層設けて積層フィルムとしても良い。本発明に用いられる積層フィルムおいて、力 バーフィルムとしては、低密度ポリエチレンなどで構成された感光性フィルムなどが挙 げられる。 [0138] Further, at least one layer of an optional antifouling or protective cover film may be provided on the photosensitive film to form a laminated film. In the laminated film used in the present invention, the force Examples of the bar film include a photosensitive film made of low-density polyethylene.
[0139] これらの方法によって形成されたカバーレイの膜厚には特に制限はないが、回路 特性などの点から、 4 μ m〜50 μ mであることが好ましぐ 6 μ m〜40 μ mであること 力はり好ましぐ 8 ,1 m〜30 ,1 mであることが特に好まし!/ヽ。  [0139] The film thickness of the coverlay formed by these methods is not particularly limited, but it is preferably 4 μm to 50 μm from the viewpoint of circuit characteristics, etc. 6 μm to 40 μm It is particularly preferred that the power is 8, 1 m-30, 1 m! / ヽ.
[0140] 本発明の樹脂組成物で構成された感光性フィルムは、配線を有する基材に前記配 線を覆うように圧着し、アルカリ現像を行い、焼成を行うことにより得られるプリント配線 板に用いることができる。  [0140] 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.
[0141] 本発明に用いられるプリント配線板における配線を有する基材としては、ガラスェポ キシ基板、ガラスマレイミド基板などのような硬質基材、あるいはポリイミドフィルムなど のフレキシブルな基板などが挙げられる。この中で、折り曲げ可能の観点からフレキ シブルな基板が好まし!/、。  [0141] 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!
[0142] 前記プリント配線板の作製方法は、前記感光性フィルムが配線を覆うように基材に 形成されれば、限定されない。このような作製方法としては、前記配線を有する基材 の配線側と本発明の感光性フィルムを接触させた状態で、熱プレス、熱ラミネート、熱 真空プレス、熱真空ラミネートなどを行う方法などが挙げられる。この中で、配線間へ の感光性フィルムの埋め込みの観点から、熱真空プレス、熱真空ラミネートが好まし い。  [0142] 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.
[0143] 前記配線を有する基材上に感光性フィルムを積層する際の加熱温度は、感光性フ イルムが基材に密着し得る温度であれば限定されなレ、。基材への密着の観点や感光 性フィルムの分解や副反応の観点から、 30°C以上 400°C以下が好ましい。より好まし くは、 50°C以上 150°C以下である。  [0143] 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.
[0144] 本発明の感光性樹脂組成物は、光照射後、光照射部位をアルカリ現像にて溶解 することができるので、ポジ型のフォトリソグラフィ一によるパターユング材料に用いる こと力 Sでさる。  [0144] Since 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.
[0145] 光照射に用いる光源は、特に制限はないが、高圧水銀灯、超高圧水銀灯、低圧水 銀灯、メタルハライドランプ、キセノンランプ、蛍光灯、タングステンランプ、アルゴンレ 一ザ一、ヘリウムカドミウムレーザーなどが挙げられる。この中で、高圧水銀灯、超高 圧水銀灯が好ましい。 [0145] 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.
[0146] 現像に用いるアルカリ水溶液としては、光照射部位を溶解し得る溶液であれば限定 されない。このような溶液として、炭酸ナトリウム水溶液、炭酸カリウム水溶液、水酸化 ナトリウム水溶液、水酸化カリウム水溶液、テトラメチルアンモニゥムヒドロキシド水溶 液などが挙げられる。現像性の観点から、炭酸ナトリウム水溶液及び水酸化ナトリウム 水溶液が好ましい。現像方法としては、スプレー現像、浸漬現像、パドル現像などが 挙げられる。  [0146] 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 tetramethyl ammonium 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.
[0147] これらの方法により基材上に得られたフィルムあるいはポジ型のパターンには、必 要に応じて加熱処理を施すことができる。加熱温度は 100°C以上 300°C以下が好ま しい。さらに好ましくは 150°C以上 250°C以下である。特に好ましくは 160°C以上 20 0°C以下である。この範囲の加熱処理により、本発明の感光性樹脂組成物は高い難 燃性を発現することができる。加熱は空気雰囲気下、窒素雰囲気下のいずれで行つ ても良い。また、加熱方法としては特に制限はないが、オーブン、焼成炉、ホットプレ ートなどを用いて行うことができる。  [0147] 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. By the heat treatment within this range, the photosensitive resin composition of the present invention can exhibit high flame retardancy. 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.
[0148] 本発明の感光性フィルムを圧着して焼成する際の焼成は、溶媒の除去の観点や副 反応や分解などの観点から、 30°C以上 400°C以下の温度で実施することが好ましい 。より好ましくは、 100°C以上 300°C以下である。  [0148] 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.
[0149] 前記焼成における反応雰囲気は、空気雰囲気下でも不活性ガス雰囲気下でも実 施可能である。前記プリント配線板の製造において、前記焼成に要する時間は、反 応条件によって異なる力 通常は 24時間以内であり、特に好適には 1時間から 8時間 の範囲で実施される。  [0149] 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, usually within 24 hours, and particularly preferably in the range of 1 to 8 hours.
[0150] 本発明の感光性樹脂組成物は、感光性フィルムとして反りが充分に抑制され、かつ 現像性も良好であり、硬化体とした際に耐薬品性を示すことから、エレクトロニクス分 野で各種電子機器の操作パネルなどに使用されるプリント配線板や回路基板の保護 層形成、積層基板の絶縁層形成、半導体装置に使用されるシリコンウェハ、半導体 チップ、半導体装置周辺の部材、半導体搭載用基板、放熱板、リードピン、半導体自 身などの保護や絶縁及び接着に使用するための電子部品への膜形成用途に利用さ れる。 次に、本発明の効果を明確にするために行った実施例について説明する。 [0150] 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. Protective layer formation of printed wiring boards and circuit boards used for operation panels of various electronic devices, insulating layer formation of laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripherals, and semiconductor mounting Used for film formation on electronic parts for protection, insulation and adhesion of substrates, heat sinks, lead pins, semiconductors, etc. Next, examples performed for clarifying the effects of the present invention will be described.
<略記〉 <Abbreviation>
本発明で用レ、た試薬の略記名称を記載する。  Abbreviated names of the reagents and reagents used in the present invention are described.
•酸二無水物 • Acid dianhydride
ODPA：ォキシジフタル酸二無水物（ビス（3 , 4—ジカルボキシフエニル）エーテノレ 二無水物）  ODPA: oxydiphthalic dianhydride (bis (3,4-dicarboxyphenyl) etherole dianhydride)
TAHQ： p—フエ二レンビス（トリメリット酸モノエステル酸無水物）  TAHQ: p-phenylene bis (trimellitic acid monoester anhydride)
TMEG：エチレングリコールビス（トリメリット酸モノエステル酸無水物）  TMEG: Ethylene glycol bis (trimellitic acid monoester anhydride)
'ジァミン 'Jamin
ΜΒΑΑ: 3, 3'—ジカルボキシ 4, 4'ージアミノジフエニルメタン  ΜΒΑΑ: 3, 3'-Dicarboxy 4, 4'-diaminodiphenylmethane
APB： 1 , 3—ビス（3—ァミノフエノキシベンゼン）  APB: 1,3-bis (3-aminophenoxybenzene)
•(B)成分 • (B) component
TBP：トリブチルホスフェート  TBP: Tributyl phosphate
TOP：トリス（2—ェチルへキシル）ホスフェート  TOP: Tris (2-ethylhexyl) phosphate
TBXP：トリス（ブトキシェチノレ）ホスフェート  TBXP: Tris (Butki Shechinor) phosphate
TIBP：トリイソブチルホスフェート  TIBP: Triisobutyl phosphate
RDP：レゾルシノールビス（ジフエニルホスフェート）  RDP: resorcinol bis (diphenyl phosphate)
CR741：ビスフエノール Aビス（ジフエニルホスフェート） CR741: Bisphenol A bis (diphenyl phosphate)
HCA: 9, 10 ジヒドロ一 9 ォキサ 10 ホスファフェナントレン一 10 ォキシド M— 325 : ε 一力プロラタトン変性トリス（アタリ口キシェチル）イソシァヌレート  HCA: 9, 10 Dihydro-9 oxa 10 Phosphaphenanthrene 10 Oxide M— 325: ε One strength prolatatone modified tris (Atari mouth kichetil) isocyanurate
Μ— 140： Ν アタリロイルォキシェチルへキサヒドロフタルイミド  Μ— 140: Ν Ataliloyloxetylhexahydrophthalimide
CDP：クレジノレジフエ二ノレホスフェート  CDP: Cresino Resifeninorephosphate
•(C)成分 • (C) component
化合物 C 1 :一般式（16)における 3個の Qのうち、平均 2. 3個が一般式（14)で 表される構造になって!/、るもの  Compound C 1: Of the three Qs in the general formula (16), an average of 2.3 of them has a structure represented by the general formula (14)! /
化合物 C 2 :—般式（16)における 3個の Qのうち、平均 2. 34個が一般式（15)で 表される構造になって!/、るものを指す。 [0152] <試薬〉 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>
実施例及び比較例において、用いた試薬であるシリコーンジァミン (KF— 8010) ( 信越化学工業社製）、 MBAA (和歌山精化社製）、 ODPA (和光純薬工業社製）、 A PB (三井化学社製）、 TMEG (新日本理化社製）、化合物 B— 1、化合物 B— 2、 TB P (大八化学社製）、 TOP (大八化学社製）、 TBXP (大八化学社製）、 TIBP (味の素 ファインテクノ社製）、レゾルシノールビス（ジフエニルホスフェート）（味の素ファインテ タノ社製、以下 RDPと略称する）、ァセチルトリブチルシトレート（フアイザ一ケミカル社 製、以下、 ATCと略称する）、 ε—力プロラタトン変性トリス（アタリ口キシェチル)イソ シァヌレート（ァロニックス Μ— 325、東亞合成社製、以下 Μ— 325と略称する）、ホス ファゼン化合物（SPB— 100、 SPH— 100、大塚化学社製）、トルエン（和光純薬ェ 業社製、有機合成用）、 7—プチ口ラ外ン (和光純薬工業社製、特級）、ピリジン (和 光純薬工業社製、有機合成用）、 γ バレロラタトン (和光純薬工業社製、一級）、は 特別な精製を実施せずに、反応に用いた。  In the examples and comparative examples, 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 butyl citrate (manufactured by Huisa Isa Chemical Co., Ltd., hereinafter referred to as ATC) Abbreviation), ε-force prolataton-modified tris (Atariguchi Kichetil) iso cyanurate (Alonics Μ-325, manufactured by Toagosei Co., Ltd., hereinafter abbreviated as Μ-325), phosphazene compounds (SPB-100, SPH-100, Otsuka) Chemical), toluene (Japanese) Junyaku Co., Ltd., for organic synthesis), 7-Puchiguchi Rajin (Wako Pure Chemical Industries, special grade), Pyridine (Wako Pure Chemical Industries, for organic synthesis), γ Valero Rataton (Wako Pure Chemicals) Kogyo Co., Ltd., first grade) was used for the reaction without any special purification.
[0153] [可溶性ポリイミド合成例 1]  [0153] [Soluble polyimide synthesis example 1]
攪拌器を取り付けた 1リットルのセパラブル 3つ口フラスコに、水分定量計を備えた 玉付冷却管を取り付けた。窒素気流下にて、 γ—プチ口ラタトン 268. 52g (和光純 薬株式会社製）、ォキシジフタル酸二無水物 31. 02g (100ミリモル）（マナック株式会 社製）、 1 , 3—ビス（3—ァミノプロピル）ポリシロキサン 68· 55g (75ミリモノレ）（分子量 914/信越化学工業株式会社製）、 3, 5 ジァミノ安息香酸 7. 61g (50ミリモル）（A ldrich社製)を仕込み室温で 2時間攪拌した。  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, γ-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.
[0154] γ ノ レ口ラタ卜ン 1 · 5g (15ミリモノレ）及びピリジン 2· 4g (30ミリモノレ）、卜ノレェン 50 gを上記フラスコに仕込み、 180°Cに昇温し、トルエン—水の共沸分を除去しながら 1 80rpmで 2時間攪拌した。室温放冷後、 1 , 2— (エチレン）ビス（トリメリテート無水物） 20. 62g (50ミリモル）（新日本理化株式会社製）、 1 , 3 ビス（4 アミノフエノキシ） ベンゼン 7. 31g (25ミリモル）（和歌山精化株式会社製）、 γ ブチロラタトン 166. 2 lgを仕込み、室温で 2時間攪拌した。その後 180°Cに昇温し、トルエン—水の共沸 分を除去しながら 180rpmで 2時間攪拌後、放冷した。得られたポリイミド溶液のポリ マー濃度は 25質量％であった。得られたポリイミドワニスは (A)成分含有ワニスとして 用いた。 [0154] 1-5 g (15 millimonoles) of γ-nozzle neck and 15 g of pyridine and 50 g of styrene are placed in the flask, heated to 180 ° C, and heated with toluene-water. The mixture was stirred at 80 rpm for 2 hours while removing boiling components. After cooling to room temperature, 1,2- (ethylene) bis (trimellitic anhydride) 20.62 g (50 mmol) (manufactured by Shin Nippon Chemical Co., Ltd.), 1,3 bis (4 aminophenoxy) benzene 7.31 g (25 mmol) (Manufactured by Wakayama Seika Co., Ltd.) and γ-butyroratone 166.2 lg were charged and stirred at room temperature for 2 hours. Thereafter, the temperature was raised to 180 ° C., and the mixture was stirred at 180 rpm for 2 hours while removing the toluene-water azeotrope, and then allowed to cool. The polymer concentration of the obtained polyimide solution was 25% by mass. The resulting polyimide varnish is (A) component-containing varnish Using.
[0155] ポリイミドワニスを 25 111厚の易剥離 PET (T100— H25/三菱化学ポリエステル フィルム株式会社製）にブレードコーターで塗工後、 95°C/30分間オーブンで乾燥 した後、剥離して得られたフィルムを引っ張り試験機（AUTOGRAPH AGS— H/ 島津製作所株式会社製）にて測定した伸度は 50%以上 (試験片 24 ίη厚、 15mm X 100mm)であった。  [0155] 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 (AUTOGRAPH AGS-H / manufactured by Shimadzu Corporation) was 50% or more (test piece 24 ίη thickness, 15 mm × 100 mm).
[0156] [配合例]  [0156] [Composition example]
表 1に示す組成の成分を表 1に示す割合で配合した。  Components of the composition shown in Table 1 were blended in the proportions shown in Table 1.
なお、（C)成分のキノンジアジド化合物としては、下記式（30)に示す化合物（a)、 若しくは下記式（31 )に示す化合物 (b)を用いた。化合物（a)は、 a , a , α ， 一トリス (4ーヒドロキシフエニル） 1 ェチル 4 イソプロピル ベンゼン（ 1モノレ）と 3—ジ ァゾ一 3, 4 ジヒドロ一 4 ォキソナフタレン一 1—スルホン酸（2· 3モノレ）とのエステ ルである。化合物（b)は、 a , a , α，—トリス（4—ヒドロキシフエ二ル）— 1—ェチル— 4イソプロピル ベンゼン（ 1モノレ）と 4 ジァゾ 4 , 5—ジヒドロー 5—ォキソナフタレ ン一 1—スルホン酸（2· 34モノレ）とのエステルである。  As the (C) component quinonediazide compound, the compound (a) represented by the following formula (30) or the compound (b) represented by the following formula (31) was used. Compound (a) consists of a, a, α, 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, α, -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).
[化 46]  [Chem 46]
Figure imgf000043_0001
Figure imgf000043_0001
(式 3 0中の Qは、 それぞれ独立に水素又は式 （1 4 ) から選ばれる 1価の有機基である) [化 47] (Q in Formula 30 is each independently hydrogen or a monovalent organic group selected from Formula (1 4)).
Figure imgf000044_0001
Figure imgf000044_0001
(式 3 1中の Qは、 それぞれ独立に水素又は式 1 5から選ばれる 1価の有機基である）  (Q in Formula 31 is each independently hydrogen or a monovalent organic group selected from Formula 15)
[0157] (B)成分としては、（i)ビスフエノーノレ Aビス（ジフエニルホスフェート）（CR741/大 八化学株式会社製）、（ii) 9, 10 ジヒドロー 9ーォキサ 10 ホスファフェナントレン — 10—ォキシド（HCA/三光株式会社製）、 (iii) ε—力プロラタトン変性トリス（アタリ 口キシェチル)イソシァヌレート（ァロニックス Μ— 325/東亞合成株式会社製）、（iv) N アタリロイルォキシェチルへキサヒドロフタルイミド（ァロニックス M— 140/東亞 合成株式会社製）、（V)トリス（ブトシキエチル)ホスフェート (TBXP/大八化学株式 会社製）、（viリ）クレジルジフヱニルホスフェート（CDP/大八化学株式会社)を用い た。また (A)成分、（B)成分、（C)成分以外の添加成分としては、（vii)ポリエチレング リコールジアタリレート（n = 4) (NKエステル 4G/新中村化学製）、（viii)レゾルシノ ールビス（ジキシリルホスフェート）（PX200/大八化学株式会社製）（ix)ポリエチレ ングリコール分子量 600 (和光純薬株式会社製）を用いた。 [0157] As the component (B), (i) 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. 3 2 5 / Toagosei Co., Ltd.), to (iv) N Atari Roy Ruo key shell chill hexa Hydrophthalimide (Alonics M—140 / manufactured by Toagosei Co., Ltd.), (V) Tris (butoxyethyl) phosphate (TBXP / Daihachi Chemical Co., Ltd.), (vi) Cresyl diphenyl phosphate (CDP / Daihachi Chemical) Co., Ltd.) was used. Additives other than (A), (B), and (C) include (vii) polyethylene glycol diatalate (n = 4) (NK ester 4G / manufactured by Shin-Nakamura Chemical), (viii) Resorcinol bis (dixylyl phosphate) (PX200 / manufactured by Daihachi Chemical Co., Ltd.) (ix) polyethylene glycol molecular weight 600 (manufactured by Wako Pure Chemical Industries, Ltd.) was used.
[表 1]  [table 1]
Figure imgf000044_0002
Figure imgf000044_0002
[0158] 評価は以下の方法により行った。  [0158] Evaluation was performed by the following method.
<数平均分子量測定〉 数平均分子量の測定法であるゲルパーミエーシヨンクロマトグラフィー（GPC)は、 下記の条件により測定を行った。溶媒として N, N—ジメチルホルムアミド（和光純薬 工業社製、高速液体クロマトグラフ用）を用い、測定前に 24. 8mmol/Lの臭化リチ ゥム一水和物（和光純薬工業社製、純度 99. 5%)及び 63. 2mmol/Lのリン酸（和 光純薬工業社製、高速液体クロマトグラフ用）を加えたものを使用した。 <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. N, N-dimethylformamide (Wako Pure Chemical Industries, high-performance liquid chromatograph) was used as the solvent, and 24.8 mmol / L lithium bromide monohydrate (Wako Pure Chemical Industries, Ltd.) was used before the measurement. , Purity 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) were used.
カラム： Shodex KD— 806M (昭和電工社製）  Column: Shodex KD—806M (made by Showa Denko)
流速： 1. OmL/分  Flow rate: 1. OmL / min
カラム温度： 40°C  Column temperature: 40 ° C
ポンプ： PU— 2080Plus (JASCO社製）  Pump: PU— 2080Plus (manufactured by JASCO)
検出器: RI— 2031P1US (RI :示差屈折計、 JASCO社製）  Detector: RI— 2031P1US (RI: differential refractometer, manufactured by JASCO)
UV— 2075Plus (UV-VIS：紫外可視吸光計、 JASCO社製）  UV— 2075Plus (UV-VIS: UV-Visible Absorber, JASCO)
[0159] また、前記分子量を算出するための検量線は、スタンダードポリスチレン (東ソ一社 製）を用いて作成した。 [0159] The calibration curve for calculating the molecular weight was prepared using standard polystyrene (manufactured by Tosohichi Co., Ltd.).
[0160] <膜厚測定〉 [0160] <Film thickness measurement>
硬化体の膜厚測定は、膜厚計（Mitutoyo社製、 ID— C112B)を用いて行った。  The film thickness of the cured product was measured using a film thickness meter (ID-C112B, manufactured by Mitutoyo).
[0161] <ドライフィルム製造方法〉 [0161] <Dry film manufacturing method>
本発明における感光性樹脂組成物のコートは、 FILMCOATER (TESTER SA NGYO社製、 PI1210)を用いるドクターブレード法により行った。すなわち、易剥離 PETフィルム（三菱化学ポリエステルフィルム社製、 DIAFOIL、 T100H25)に前記 感光性樹脂組成物を滴下し、クリアランス 200 mでコートを行った。コートした前記 フィルムを、乾燥器 (ESPEC社製、 SPHH— 101)を用いて 95°Cで 30分間乾燥する ことにより、感光性ドライフィルムを得た。  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.
[0162] <反り〉 [0162] <Warpage>
25 111厚の PETフィルム（T100— H25/三菱化学ポリエステルフィルム株式会社 製）にブレードコーターで塗工後、 95°C/30分間オーブンで乾燥し感光性ドライフィ ルムを得た。塗工部分を 20cm X 20cmの大きさに切り出し試験フィルムとし、反りを 目視評価した。反り発生なしの場合を◎とし、軽度の反り発生の場合を〇とし、反り発 生しフィルムがロール状に丸まる場合を Xとした。 [0163] <難燃性試験〉 25 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 ◯, and the case where warpage occurred and the film was rolled up was marked as X. [0163] <Flame retardancy test>
難燃性試験は以下の手順で行った。前述のコート方法によって、カプトン (登録商 標）（EN— 100/東レ ·デュポン株式会社製)フィルムの片面に感光性樹脂組成物を コートし、 95°Cで 30分間乾燥し、次いで反対の面に感光性樹脂組成物をコートし、 9 5°Cで 30分間乾燥させることにより、カプトン (登録商標）フィルムの両面に感光性樹 脂組成物をコートした後、焼成炉（光洋リンドバーグ社製）を用いて、 120°Cで 60分 間、続いて 200°Cで 60分間焼成することにより感光性樹脂組成物を硬化させて硬化 体を得た。この硬化体を 20cm X 5cmに切り取り、 UL94 VTM試験により難燃性の 評価を行った。各試料の残炎時間が 10秒以下で、かつ 12. 5cmの標線まで燃焼し なかったサンプルを VTM— 0 (又は〇）とし、各試料の残炎時間が 10秒以上ある!/、 は 12. 5cmの標線まで燃焼したサンプルを難燃性 Xとした。  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. Samples that did not burn to the 12.5cm mark after each sample had an afterflame time of 10 seconds or less were designated as VTM-0 (or ◯), and each sample had an afterflame time of 10 seconds or more! 12. Flame retardant X was defined as the sample burned to the 5cm mark.
[0164] <ラミネート性〉  [0164] <Lamination>
25 111厚の PETフィルム（T100— H25/三菱化学ポリエステルフィルム株式会社 製）にブレードコーターで塗工後、 95°C/30分間オーブンで乾燥し膜厚 24 mの 感光性ドライフィルムを得た。  25 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.
[0165] 18 μ m厚の銅箔（F3— WS/光沢面）にバフロール整面（ # 200)及びジェットスク ラブ整面を行!/、、得られた感光性ドライフィルムを AL— 700 (旭化成株式会社製）を 用い、基板余熱 60°C、ラミネート温度、 140°Cにて 0. 34MPa、 0. 5m/minの条件 でラミネートをし、 PETフィルムを剥離した。 PETフィルムのみ剥離の場合を〇とし、 P ETフィルムと感光性フィルムが剥離の場合を Xとした。  [0165] 18 μm-thick copper foil (F3— WS / Glossy surface) with buffalo surface (# 200) and jet scrub surface! /, And the resulting photosensitive dry film is AL- 700 ( Asahi Kasei Co., Ltd.) was used to laminate at a substrate residual heat of 60 ° C, lamination temperature of 140 ° C under conditions of 0.34 MPa and 0.5 m / min, and the PET film was peeled off. The case where only the PET film was peeled was marked as ◯, and the case where the PET film and the photosensitive film were peeled was marked as X.
[0166] <感光性〉  [0166] <Photosensitivity>
ラミネート性評価で得た、感光性フィルムがラミネートされた銅箔を用い以下の評価 をおこなった。尚、 PETフィルムと感光性フィルムが剥離したサンプルについては評 価が困難な為、銅箔にラミネートせずに感光性ドライフィルムのまま以下の評価を行 つた。  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.
[0167] ポジ型のマスクを用い超高圧水銀灯（HMW— 201KB/オーク株式会社製）でコ ンタクト露光を行った。露光量は 1 , 300mj/cm2であった。また、現像は、 3%の水 酸化ナトリウム水溶液で現像温度 40°C、スプレー圧 0. 2MPa、現像時間 40秒にて スプレー現像を行った。蒸留水で室温にてスプレー水洗を行!/、得られたパターンを 光学顕微鏡で観察した。 100 mの円孔パターン形成の場合を〇とし、 100 mの 円孔パターン形成不可の場合を Xとした。 [0167] Contact exposure was performed with an ultra-high pressure mercury lamp (HMW-201KB / Oak Co., Ltd.) using a positive mask. The exposure dose was 1,300 mj / cm 2 . Also, development was performed with a 3% aqueous sodium hydroxide solution at a development temperature of 40 ° C, a spray pressure of 0.2 MPa, and a development time of 40 seconds. Spray development was performed. Spray water washing was performed at room temperature with distilled water! The resulting pattern was observed with an optical microscope. The case where a 100 m hole pattern was formed was marked as ◯, and the case where a 100 m hole pattern was not formed was marked as X.
[表 2]  [Table 2]
Figure imgf000047_0001
Figure imgf000047_0001
[0168] [ポリイミド合成例 2] [Polyimide synthesis example 2]
攪拌器を取り付けた 1リットルのセパラブル 3つ口フラスコに、水分定量計を備えた 玉付冷却管を取り付けた。窒素気流下にて、 γ—プチ口ラタトン 341. 64g (和光純 薬株式会社製）、ォキシジフタル酸二無水物 31. 02g (100ミリモル）（マナック株式会 社製）、 1 , 3—ビス（3—ァミノプロピル）ポリシロキサン 68· 55g (75ミリモノレ）（分子量 914/信越化学工業株式会社製）、 3, 3'ージカルボキシー 4, 4'ージアミノジフエ二 ルメタン 14· 31g (50ミリモル）（和歌山精化株式会社製）を仕込み室温で 2時間攪拌 した。  A 1-liter separable three-necked flask equipped with a stirrer was fitted with a ball condenser equipped with a moisture meter. In a nitrogen stream, γ-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.
[0169] γ ノ レ口ラタ卜ン 1 · 5g (15ミリモノレ）及びピリジン 2· 4g (30ミリモノレ）、卜ノレェン 50 gを上記フラスコに仕込み、 180°Cに昇温し、トルエン—水の共沸分を除去しながら 1 80rpmで 2時間攪拌した。室温放冷後、 1 , 2— (エチレン）ビス（トリメリテート無水物） 20. 62g (50ミリモル）（新日本理化株式会社製）、 1 , 3 ビス（3 アミノフエノキシ） ベンゼン 7. 31g (25ミリモル）（和歌山精化株式会社製）、 γ—ブチロラタトン 67. 59 gを仕込み、室温で 2時間攪拌した。その後 180°Cに昇温し、トルエン—水の共沸分 を除去しながら 180rpmで 2時間攪拌後、放冷した。得られたポリイミド溶液のポリマ 一濃度は約 25質量％であった。得られたポリイミドワニスは (A)成分含有ワニスとして 実施例 12、実施例 13の評価に用いた。  [0169] γ-nozzle rattan 1 · 5 g (15 mm monole), pyridine 2.4 g (30 mm monole), and 卜 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. After standing to cool to room temperature, 1,2- (ethylene) bis (trimellitic anhydride) 20.62 g (50 mmol) (manufactured by Shin Nippon Chemical Co., Ltd.), 1,3 bis (3 aminophenoxy) benzene 7.31 g (25 mmol) (Wakayama Seika Co., Ltd.) and γ-butyroratatone 67.59 g were charged and stirred at room temperature for 2 hours. Thereafter, the temperature was raised to 180 ° C., and the mixture was stirred at 180 rpm for 2 hours while removing the toluene-water azeotrope and allowed to cool. The resulting polyimide solution had a polymer concentration of about 25% by mass. The obtained polyimide varnish was used for the evaluation of Example 12 and Example 13 as the component (A) -containing varnish.
[0170] 実施例 12は、実施例 5の (A)成分含有ワニスをポリイミド合成例 2に記載の (A)成 分含有ワニスに替え、それ以外は実施例 5と同様に評価を行った。その結果、反り◎ 、難燃性〇、ラミネート性〇、感光性〇であった。 [0170] In 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.
[0171] 実施例 13は、実施例 11の (A)成分含有ワニスをポリイミド合成例 2に記載の (A)成 分含有ワニスに替え、それ以外は実施例 11と同様に評価を行った。その結果、反り ◎、難燃性〇、ラミネート性〇、感光性〇であった。  [0171] In 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 ◯.
[0172] 上記から明らかなように、本発明の感光性樹脂組成物を用いて得られた感光性フィ ルム（実施例 1〜実施例 13)については、反り、難燃性、ラミネート性及び感光性のす ベてについて良好であった。一方、比較例 1〜比較例 4、比較例 6、比較例 7及び比 較例 9の感光性フィルムについては、難燃性が悪ぐ比較例 5及び比較例 8の感光性 フィルムについては、反りやラミネート性が悪かった。  [0172] As is apparent from the above, 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. On the other hand, for 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.
[0173] 以下の実施例 14〜21、比較例 10〜24では、以下の評価条件で評価を行った。  [0173] In Examples 14 to 21 and Comparative Examples 10 to 24 below, the evaluation was performed under the following evaluation conditions.
[0174] <ラミネート条件〉  [0174] <Lamination conditions>
本発明におけるラミネートは、真空プレス機 (名機製作所製）を用いて行った。プレ スは、プレス温度 110°C、プレス圧 1. 23MPa、プレス時間 5分間にて行った。  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.
[0175] <反り評価〉  [0175] <Evaluation of warpage>
反りの評価は、 A4サイズの感光性ドライフィルムを製造した際に、エッジ部分にお いて 5mmを上回って持ち上がる部分が無い場合を〇とし、上回る部分が発生した場 合を Xとした。  In the evaluation of warpage, when an A4 size photosensitive dry film was manufactured, ◯ was given when there was no part that lifted more than 5 mm at the edge part, and X was given when a part exceeding it was generated.
[0176] <現像性評価〉  [0176] <Developability evaluation>
現像性評価は、銅張積層板上に、感光性ドライフィルム (感光層の厚さ約 20 m) を用いて、上記のラミネート条件でラミネートした後に、ポジ型マスクを用いて照射量 1. Oj/cm2にて露光を行い、続いて 3%水酸化ナトリウム水溶液によるアルカリ現像 処理と水によるリンスを行い、乾燥後にパターンを光学顕微鏡にて評価することにより 行った。マスクには 100 m径の円形パターン（間隔 100 mピッチ）を用いた。現像 により、露光部で銅面が現れており、かつ未露光部の感光層の膜厚が 18 ^ 111以上 の場合を◎とし、 15 m以上 18 m未満の場合を〇とし、それ以外の解像度が劣る 場合や膜厚が 15 ,i m未満の場合を Xとした。 Evaluation of developability was carried out by laminating a copper-clad laminate with a photosensitive dry film (thickness of photosensitive layer: approx. 20 m) under the above laminating conditions, and then using a positive mask. Exposure was performed at / cm 2 , followed by alkali development with a 3% aqueous sodium hydroxide solution and rinsing with water, and after drying, the pattern was evaluated with an optical microscope. The mask used was a circular pattern with 100 m diameter (100 m pitch). As a result of development, the copper surface appears in the exposed area and the photosensitive layer thickness in the unexposed area is 18 ^ 111 or more. When X is inferior or when the film thickness is less than 15, im.
[0177] <真空埋め込み性評価〉 銅製回路（50 πιの銅ライン幅、ライン間隔は δθ ΐι 銅配線の厚み 12 πι)上 に感光性ドライフィルムを用いて、前述のラミネート条件によりラミネートした後に、得 られた積層体をカットして断面を電子顕微鏡にて観察した。埋め込みに不十分なとこ ろが無ぐカバーレイ層の表面の平坦性が良いものを〇とした。埋め込みが不十分で 空隙が観測された場合を Xとした。 [0177] <Vacuum embedding evaluation> After laminating using a photosensitive dry film on a copper circuit (copper line width of 50 πι, line spacing is δθ ΐι copper wiring thickness 12 πι) under the aforementioned laminating conditions, the resulting laminate is cut. The cross section was observed with an electron microscope. The case where the surface of the cover lay layer had good flatness and was not insufficient for embedding was marked as ◯. X when the gap was observed due to insufficient embedding.
[0178] [実施例 14] [Example 14]
窒素雰囲気下、セパラブルフラスコに、 ΜΒΑΑ(30· Ommol)、シリコーンジァミン（ KF— 8010、 30. Ommol)、 APB (15. Ommol)、 γ—ブチ口ラタトン（lOOmUを入 れ、続いて ODPA(60. Ommol)を加え、室温で 2時間撹拌した。続いて、トルエン（ 30mL)、ピリジン（34. 13mmol)、 γ—ノ レロラタトン（22. 47mmol)をカロえ、ディ 一ンシュタルク装置及び還流器をつけ、 180°Cで 2時間加熱撹拌した。 120°Cまで冷 却した後に、 APB (15. Ommol)を加え、 10分間撹拌した後に、 ODPA(30. Omm ol)を加え、 120°Cで 2時間加熱撹拌した。続いて、トルエン（lOmL)を加え、 180°C で 2時間加熱撹拌した。 140°Cまで冷却し、ポリマー固形分濃度 30質量％となるよう に γ—プチ口ラタトンを加え、室温まで冷却することにより、ポリイミド（1)の γ プチ 口ラ外ン溶液を得た。数平均分子量及びシロキサン構造に由来する部位の質量 (含 有率）（％)を下記表 3に示す。また、ポリイミド、感光剤、及びリン酸エステルの配合 量について下記表 4に示す。また、以下の実施例及び比較例の配合量も下記表 4に 併記する。 In a nitrogen atmosphere, put separable flasks with ΜΒΑΑ (30 · Ommol), silicone diamine (KF-8010, 30. Ommol), APB (15. Ommol), γ-butyral rataton (lOOmU), followed by ODPA (60. Ommol) was added and stirred for 2 hours at room temperature, followed by toluene (30mL), pyridine (34.13mmol), γ-norolalataton (22.47mmol), and a starch and reflux apparatus. The flask was heated and stirred for 2 hours at 180 ° C. After cooling to 120 ° C., APB (15. Ommol) was added, and after stirring for 10 minutes, ODPA (30. Ommol) was added, and 120 ° heating for 2 hours and stirred at C followed by addition of toluene (lOmL), 2 hours under heating and stirred at 180 ° C 140 ° C until cool, so that 30 wt% polymer solids concentration gamma -.. Petit port By adding rataton and cooling to room temperature, a solution of polyimide (1) was obtained. The mass (content) (%) of the site derived from the sun structure is shown in the following Table 3. The blending amounts of polyimide, photosensitizer and phosphate ester are shown in the following Table 4. Also, the following examples The amounts of the comparative examples are also shown in Table 4 below.
[0179] ポリイミド（1) 100質量％に対して、化合物 C 2 (20質量％)、丁8? (15質量％)及 び丁8 ？（15質量％)を混合し、感光性樹脂組成物を調整した。このようにして得ら れた感光性樹脂組成物を、前述のコート方法にて易剥離 PETフィルムにコートし、 9 5°Cで 30分間乾燥させることにより、感光性ドライフィルムを得た。反りはドライフィノレ ムで、〇であった。  [0179] Polyimide (1) 100% by mass of compound C 2 (20% by mass), Ding 8? (15% by mass) and Ding 8? (15% by mass) was mixed to prepare a photosensitive resin composition. 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 ◯.
[0180] 上記の感光性ドライフィルムを、銅製回路（50 a mの銅ライン幅、ライン間隔は 50 m、銅配線の厚み 12 m)上に前述のラミネート条件によりラミネートを行った。得 られた積層体をカットし、断面を電子顕微鏡にて観察したところ、空隙なく埋め込み ができており、カバーレイ層の表面も平坦であった。 [0181] 前記ポジ型感光性樹脂組成物を、前述のコート方法にてカプトン (登録商標）にコ ートし、 95°Cで 30分間乾燥させ、続いて反対の面にコートし、 95°Cで 30分間乾燥さ せることによって得たポジ型感光性樹脂組成物をコートしたカプトン (登録商標）を、 焼成炉にて空気雰囲気下、 120°Cで 60分間、続いて 200°Cで 60分間焼成すること により、硬化体を得た。前記硬化体に対し、 UL94 VTM試験による難燃性の評価 を行った。その結果を下記表 5に示す。 [0180] 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. [0181] 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.
[0182] 上記の感光性フィルムを、銅張積層板上に前述のラミネート条件によりラミネートを 行った。得られた積層体を、ポジ型マスクを用いて照射量 1. Oj/cm2にて露光を行 い、続いて 3%水酸化ナトリウム水溶液によるアルカリ現像処理と水によるリンスを行 い、乾燥後にパターンを光学顕微鏡にて観察した。それぞれのドライフィルムにおい て露光部で銅面が現れており、かつ未露光部のカバーレイ層の膜厚が 15 111以上（ 20〃m)であった。 [0182] 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).
[0183] [実施例 15]  [0183] [Example 15]
実施例 14で製造したポリイミド（1) 100質量％に対して、化合物 C— 2 (20質量％) 、丁〇？（15質量％)及び丁8 ？（15質量％)を混合し、感光性樹脂組成物を調整し た。前記感光性樹脂組成物を実施例 14と同様の方法にて反り、難燃性、埋め込み 性、アルカリ現像性の評価を行った。その結果を下記表 5に示す。  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.
[0184] [実施例 16]  [0184] [Example 16]
実施例 14で製造したポリイミド（1) 100質量％に対して、化合物 C— 2 (20質量％) 、丁18? (15質量％)及び丁8 ？（15質量％)を混合し、感光性樹脂組成物を調整し た。前記感光性樹脂組成物を実施例 14と同様の方法にて反り、難燃性、埋め込み 性、アルカリ現像性の評価を行った。その結果を下記表 5に示す。  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.
[0185] [実施例 17]  [Example 17]
窒素雰囲気下、セパラブルフラスコに、 ΜΒΑΑ(30· Ommol)、シリコーンジァミン（ KF— 8010、 45. Ommol) , γ ブチロラタトン（lOOmUを入れ、続いて ODPA(6 0. Ommol)を加え、室温で 2時間撹拌した。続いて、トルエン（30mL)、ピリジン（34 . 13mmol)、 γ バレロラタトン（22· 47mmol)を加え、ディーンシュタルク装置及 び還流器をつけ、 180°Cで 2時間加熱撹拌した。 120°Cまで冷却した後に、 APB (1 5. Ommol)をカロ免、 10分間 ft禅した後に、 ODPA (30. Ommol)をカロ免、 120。Cで 2時間加熱撹拌した。続いて、トルエン（lOmL)を加え、 180°Cで 2時間加熱撹拌し た。 140°Cまで冷却し、ポリマー固形分濃度 30質量％となるように γ—プチ口ラタトン を加え、室温まで冷却することにより、ポリイミド（2)の γ—プチ口ラタトン溶液を得た。 数平均分子量及びシロキサン構造に由来する部位の質量 (含有率）（％)を下記表 3 に示す。 Under a nitrogen atmosphere, put 入 れ (30 · Ommol), silicone diamine (KF-8010, 45. Ommol), γ-butyroratatone (lOOmU), and then add ODPA (60.Ommol) at room temperature. Then, toluene (30 mL), pyridine (34.13 mmol), and γ-valerolataton (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, APB (1 5. Ommol) Calo-free, after 10 minutes ft Zen, ODPA (30. Ommol) Calo-free, 120. The mixture was heated and stirred at C for 2 hours. Subsequently, toluene (10 mL) was added, and the mixture was stirred with heating at 180 ° C for 2 hours. The mixture was cooled to 140 ° C., γ-petit-mouth rataton was added so that the polymer solid content concentration was 30% by mass, and the mixture was cooled to room temperature to obtain a γ-petit-mouthed rataton solution of polyimide (2). Table 3 below shows the number average molecular weight and the mass (content) (%) of the part derived from the siloxane structure.
[0186] ポリイミド（2) 100質量％に対して、化合物 C 1 (20質量％)及び ΤΒΧΡ (15質量 %)を混合し、感光性樹脂組成物を調整した。前記感光性樹脂組成物を実施例 1と 同様の方法にて反り、難燃性、埋め込み性、アルカリ現像性の評価を行った。その結 果を下記表 5に示す。  [0186] Compound C 1 (20% by mass) and cocoon (15% by mass) were mixed with 100% by mass of polyimide (2) 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 5 below.
[0187] [比較例 10]  [0187] [Comparative Example 10]
実施例 14で製造したポリイミド（1) 100質量％に対して、化合物 C— 2 (20質量％) を混合し、感光性樹脂組成物を調整した。前記感光性樹脂組成物を実施例 14と同 様の方法にて反り、難燃性、埋め込み性、アルカリ現像性の評価を行った。その結果 を下記表 5に示す。  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.
[0188] [比較例 11]  [Comparative Example 11]
実施例 14で製造したポリイミド（1) 100質量％に対して、化合物 C— 2 (20質量％) 及び芳香族基を有するリン酸エステルである RDP (30質量％)を混合し、感光性樹 脂組成物を調整した。前記感光性樹脂組成物を実施例 14と同様の方法にて反り、 難燃性、埋め込み性、アルカリ現像性の評価を行った。その結果を下記表 5に示す。  Compound 100-2 (20% by mass) and RDP (30% by mass), which is a phosphate ester having an aromatic group, were mixed with 100% by mass of the polyimide (1) produced in Example 14. 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.
[0189] [比較例 12]  [0189] [Comparative Example 12]
実施例 14で製造したポリイミド（1) 100質量％に対して、化合物 C— 2 (20質量％) 及び一般的な可塑剤である ATC (30質量％)を混合し、感光性樹脂組成物を調整 した。前記感光性樹脂組成物を実施例 14と同様の方法にて反り、難燃性、埋め込み 性、アルカリ現像性の評価を行った。その結果を下記表 5に示す。  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.
[0190] [比較例 13]  [0190] [Comparative Example 13]
実施例 17で製造したポリイミド（2) 100質量％に対して、化合物 C— 1 (20質量％) を混合し、感光性樹脂組成物を調整した。前記感光性樹脂組成物を実施例 14と同 様の方法にて反り、難燃性、埋め込み性、アルカリ現像性の評価を行った。その結果 を下記表 5に示す。 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.
[0191] [比較例 14]  [Comparative Example 14]
実施例 17で製造したポリイミド（2) 100質量％に対して、化合物 C— 1 (20質量％) 及び芳香族基を有するリン酸エステルである RDP (30質量％)を混合し、感光性樹 脂組成物を調整した。前記感光性樹脂組成物を実施例 14と同様の方法にて反り、 難燃性、埋め込み性、アルカリ現像性の評価を行った。その結果を下記表 5に示す。  Compound 100-1 (20% by mass) and RDP (30% by mass), which is a phosphate ester having an aromatic group, were mixed with 100% by mass of the polyimide (2) produced in Example 17, and the photosensitive resin was mixed. 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.
[0192] [比較例 15]  [0192] [Comparative Example 15]
実施例 17で製造したポリイミド（2) 100質量％に対して、化合物 C— 1 (20質量％) 及び一般的な可塑剤である ATC (30質量％)を混合し、感光性樹脂組成物を調整 した。前記感光性樹脂組成物を実施例 14と同様の方法にて反り、難燃性、埋め込み 性、アルカリ現像性の評価を行った。その結果を下記表 5に示す。  Compound C-1 (20% by mass) and general plasticizer ATC (30% by mass) were mixed with 100% by mass of the polyimide (2) produced in Example 17, 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.
[0193] 表 5から分かるように、本発明に用いられるリン酸エステル化合物を添加した感光性 樹脂組成物で構成された感光性フィルム（実施例 14〜実施例 17)では、添加しない 感光性樹脂組成物で構成された感光性フィルム（比較例 10、比較例 13)及び芳香 族リン酸エステル化合物を添加した感光性樹脂組成物で構成された感光性フィルム (比較例 11、比較例 14)と比較して、難燃性を維持したまま反り及び埋め込み性が改 善されている。また、一般的な可塑剤を添加した感光性樹脂組成物で構成された感 光性フィルム（比較例 12、比較例 15)では、反り及び埋め込み性は改善されるものの 、難燃性が低下する。以上のことから、本発明に用いられるリン酸化合物を添加した 感光性樹脂組成物で構成された感光性フィルムは、難燃性を維持したまま、ドライフ イルム化時の反り及び埋め込み性が改善されており、し力、も現像性についても良好で あった。  [0193] As can be seen from Table 5, in the photosensitive films (Examples 14 to 17) composed of the photosensitive resin composition to which the phosphate ester compound used in the present invention was added, the photosensitive resin not added. A photosensitive film composed of a composition (Comparative Example 10, Comparative Example 13) and a photosensitive film composed of a photosensitive resin composition added with an aromatic phosphate compound (Comparative Example 11, Comparative Example 14); In comparison, warpage and embedding are improved while maintaining flame retardancy. Further, in the photosensitive films composed of a photosensitive resin composition to which a general plasticizer is added (Comparative Example 12 and Comparative Example 15), although the warpage and embedding are improved, the flame retardancy is lowered. . From the above, the photosensitive film composed of the photosensitive resin composition to which the phosphoric acid compound used in the present invention is added is improved in warp and embedding property during dry film formation while maintaining flame retardancy. The strength and developability were also good.
[表 3]  [Table 3]
ポリイミドの数平均分子量、組成及びシロキサン構造含有率
Figure imgf000052_0001
Number average molecular weight of polyimide, composition and siloxane structure content
Figure imgf000052_0001
[表 4] ポジ型感光性樹脂組成物の組成 [Table 4] Composition of positive photosensitive resin composition
Figure imgf000053_0001
Figure imgf000053_0001
[表 5] ポジ型感光性樹脂組成物から作製した感光性フィルムの物性 [Table 5] Physical properties of photosensitive film prepared from positive photosensitive resin composition
Figure imgf000053_0002
Figure imgf000053_0002
[実施例 18] [Example 18]
窒素雰囲気下、セパラブルフラスコに、 ΜΒΑΑ(30· Ommol)、シリコーンジァミン（ KF— 8010、 30. Ommol)、 APB ( 15. Ommol)、 γ—ブチ口ラタトン（lOOmUを入 れ、続いて ODPA(60. Ommol)を加え、室温で 2時間撹拌した。続いて、トルエン（ 30mL)、ピリジン（34. 13mmol)、 γ—ノ レロラタトン（22. 47mmol)をカロえ、ディ 一ンシュタルク装置及び還流器をつけ、 180°Cで 2時間加熱撹拌した。 120°Cまで冷 却した後に、 APB (15. Ommol)を加え、 10分間撹拌した後に、 TMEG (31. 8mm ol)を加え、 120°Cで 2時間加熱撹拌した。続いて、トルエン（10mUを加え、 180°C で 2時間加熱撹拌した。 140°Cまで冷却し、ポリマー固形分濃度 30質量％となるよう に γ—プチ口ラタトンを加え、室温まで冷却することにより、ポリイミド（3)の γ プチ 口ラタトン溶液を得た。ポリイミド（3)の数平均分子量は 37000、及び一般式（5)にお ける /3 / ( α + /3 + γ )の値は、 0· 33であった。 In a nitrogen atmosphere, put ΜΒΑΑ (30 · Ommol), silicone diamine (KF-8010, 30. Ommol), APB (15 Ommol), γ-buta-mouth rataton (lOOmU), and then into a separable flask. ODPA (60. Ommol) was added and stirred for 2 hours at room temperature, followed by toluene (30mL), pyridine (34.13mmol), γ-norolalataton (22.47mmol), and a starch and reflux apparatus. The vessel was heated and stirred for 2 hours at 180 ° C. After cooling to 120 ° C., APB (15. Ommol) was added, and after stirring for 10 minutes, TMEG (31.8 mmol) was added, and 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. Γ -petit-mouthed rataton was added to and cooled to room temperature to obtain a γ-petit-mouthed rataton solution of polyimide (3). The number average molecular weight of the polyimide (3) was 37000, and the value of / 3 / (α + / 3 + γ) in the general formula (5) was 0.33.
[0195] ポリイミド（3) 100質量％に対して、化合物 C 2 (20質量％)、丁8? (15質量％)及 び丁8 ？（15質量％)を混合し、感光性樹脂組成物を調整した。このようにして得ら れた感光性樹脂組成物を、前述のコート方法にて易剥離 PETフィルムにコートし、 9 5°Cで 30分間乾燥させることにより、感光性ドライフィルムを得た。反りはドライフィノレ ムで、〇であった。 [0195] Polyimide (3) 100% by mass of compound C 2 (20% by mass), Ding 8? (15% by mass) and Ding 8? (15% by mass) was mixed to prepare a photosensitive resin composition. 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 ◯.
[0196] 上記の感光性ドライフィルムを、銅製回路（50 a mの銅ライン幅、ライン間隔は 50 m、銅配線の厚み 12 m)上に前述のラミネート条件によりラミネートを行った。得 られた積層体をカットし、断面を電子顕微鏡にて観察したところ、空隙なく埋め込み ができており、カバーレイ層の表面も平坦であった。  [0196] 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. 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.
[0197] 前記ポジ型感光性樹脂組成物を、前述のコート方法にてカプトン (登録商標）にコ ートし、 95°Cで 30分間乾燥させ、続いて反対の面にコートし、 95°Cで 30分間乾燥さ せることによって得たポジ型感光性樹脂組成物をコートしたカプトン (登録商標）を、 焼成炉にて空気雰囲気下、 120°Cで 60分間、続いて 200°Cで 60分間焼成すること により、硬化体を得た。前記硬化体に対し、 UL94 VTM試験による難燃性の評価 を行った。その結果を下記表 2に示す。また、ポリイミド、感光剤、及びリン酸エステル の配合量について下記表 6に示す。また、以下の実施例及び比較例の配合量も下 記表 6に併記する。  [0197] 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.
[0198] 上記の感光性フィルムを、銅張積層板上に前述のラミネート条件によりラミネートを 行った。得られた積層体を、ポジ型マスクを用いて照射量 1. Oj/cm2にて露光を行 い、続いて 3%水酸化ナトリウム水溶液によるアルカリ現像処理と水によるリンスを行 い、乾燥後にパターンを光学顕微鏡にて観察した。それぞれのドライフィルムにおい て露光部で銅面が現れており、かつ未露光部のカバーレイ層の膜厚が 15 111以上（ 20〃m)であった。 [0198] 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).
[0199] [実施例 19]  [0199] [Example 19]
実施例 18で製造したポリイミド（3) 100質量％に対して、化合物 C— 2 (20質量％) 、丁〇？（15質量％)及び丁8 ？（15質量％)を混合し、感光性樹脂組成物を調整し た。前記感光性樹脂組成物を実施例 1と同様の方法にて反り、難燃性、埋め込み性 、アルカリ現像性の評価を行った。その結果を下記表 7に示す。 Compound 100-2 (20% by mass) relative to 100% by mass of the polyimide (3) produced in Example 18 Ding 〇? (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.
[0200] [実施例 20]  [0200] [Example 20]
実施例 18で製造したポリイミド（1) 100質量％に対して、化合物 C— 1 (20質量％) 及び丁8 ？（30質量％)を混合し、感光性樹脂組成物を調整した。前記感光性樹脂 組成物を実施例 18と同様の方法にて反り、難燃性、埋め込み性、アルカリ現像性の 評価を行った。その結果を下記表 7に示す。  Compound 100-1 (20% by mass) and Ding 8 against 100% by mass of the polyimide (1) produced in Example 18? (30% by mass) was mixed 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.
[0201] [実施例 21]  [0201] [Example 21]
窒素雰囲気下、セパラブルフラスコに、 ODPA (20. Ommol)、シリコーンジァミン（ KF— 8010、 15. Ommol)、 γ ブチロラタトン（40mUを入れ、 80°Cで 2時間撹拌 した。続いて、トルエン（15mL)、ピリジン（11. 4mmol)、 γ—バレロラタトン（7. 5m mol)を加え、ディーンシュタルク装置及び還流器をつけ、 180°Cで 2時間加熱撹拌 した。 80°Cまで冷却した後に、 APB (3. Ommol) , MBAA(10. Ommol)を加え、続 いて TMEG (8. 6mmol)を加え、 80°Cで 1時間加熱撹拌した。続いて、トルエン（5 mL)を加え、 180°Cで 2時間加熱撹拌した。 140°Cまで冷却し、ポリマー固形分濃度 30質量％となるように γ ブチロラタトンを加え、室温まで冷却することにより、ポリイ ミド（4)の γ ブチロラタトン溶液を得た。数平均分子量は 25000、及び /3 / ( α + β + y )の値は、 0· 54であった。 Under a nitrogen atmosphere, ODPA (20. Ommol), silicone diamine (KF-8010, 15. Ommol), and γ-butyrorataton (40 mU) were placed in a separable flask and stirred at 80 ° C for 2 hours. (15 mL), pyridine (11.4 mmol), and γ-valerolataton (7.5 mmol) were added, and a Dean-Stark apparatus and a reflux were attached, and the mixture was heated and stirred for 2 hours at 180 ° C. After cooling to 80 ° C. APB (3. Ommol) and MBAA (10. Ommol) were added, followed by TMEG (8.6 mmol), followed by heating and stirring at 80 ° C. for 1 hour, followed by addition of toluene (5 mL) and 180 ° The mixture was heated and stirred for 2 hours at C. The solution was cooled to 140 ° C., γ-butyrolatatone was added so that the polymer solid concentration was 30% by mass, and the solution was cooled to room temperature to obtain a solution of polyimide (4) in γ- butyrolatatone. The number average molecular weight was 25000, and the value of / 3 / (α + β + y) was 0 · 54.
[0202] ポリイミド（4) 100質量％に対して、化合物 C 1 (20質量％)、丁18? (35質量％) 及び ΤΒΧΡ (15質量％)を混合し、感光性樹脂組成物を調整した。  [0202] 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. .
前記感光性樹脂組成物を実施例 18と同様の方法にて反り、難燃性、埋め込み性 の評価を行った。また、アルカリ現像性については、現像液として 1 %水酸化ナトリウ ム水溶液を用いる以外は、実施例 18と同様の方法で現像性の評価を行った。その 結果を下記表 7に示す。  The photosensitive resin composition was warped in the same manner as in Example 18 and evaluated for flame retardancy and embedding property. Regarding 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.
[0203] [比較例 16]  [0203] [Comparative Example 16]
実施例 18で製造したポリイミド（3) 100質量％に対して、化合物 C— 2 (20質量％) を混合し、感光性樹脂組成物を調整した。前記感光性樹脂組成物を実施例 18と同 様の方法にて反り、難燃性、埋め込み性、アルカリ現像性の評価を行った。その結果 を下記表 7に示す。 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.
[0204] [比較例 17]  [0204] [Comparative Example 17]
実施例 18で製造したポリイミド（3) 100質量％に対して、化合物 C— 2 (20質量％) 及び芳香族基を有するリン酸エステルである RDP (30質量％)を混合し、感光性樹 脂組成物を調整した。前記感光性樹脂組成物を実施例 18と同様の方法にて反り、 難燃性、埋め込み性、アルカリ現像性の評価を行った。その結果を下記表 7に示す。  Compound 100-2 (20% by mass) and RDP (30% by mass), which is a phosphate ester having an aromatic group, were mixed with 100% by mass of the polyimide (3) produced in Example 18, 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.
[0205] [比較例 18]  [Comparative Example 18]
実施例 18で製造したポリイミド（3) 100質量％に対して、化合物 C— 2 (20質量％) 及び一般的な可塑剤である ATC (30質量％)を混合し、感光性樹脂組成物を調整 した。前記感光性樹脂組成物を実施例 18と同様の方法にて反り、難燃性、埋め込み 性、アルカリ現像性の評価を行った。その結果を下記表 7に示す。  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.
[0206] [比較例 19]  [Comparative Example 19]
実施例 18で製造したポリイミド（3) 100質量％に対して、化合物 C— 1 (20質量％) を混合し、感光性樹脂組成物を調整した。前記感光性樹脂組成物を実施例 18と同 様の方法にて反り、難燃性、埋め込み性、アルカリ現像性の評価を行った。その結果 を下記表 7に示す。  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.
[0207] [比較例 20]  [Comparative Example 20]
実施例 18で製造したポリイミド（3) 100質量％に対して、化合物 C— 1 (20質量％) 及び芳香族基を有するリン酸エステルである RDP (30質量％)を混合し、感光性樹 脂組成物を調整した。前記感光性樹脂組成物を実施例 18と同様の方法にて反り、 難燃性、埋め込み性、アルカリ現像性の評価を行った。その結果を下記表 7に示す。  Compound 100-1 (20% by mass) and RDP (30% by mass), which is a phosphate ester having an aromatic group, were mixed with 100% by mass of the polyimide (3) produced in Example 18, 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.
[0208] [比較例 21]  [0208] [Comparative Example 21]
実施例 18で製造したポリイミド（3) 100質量％に対して、化合物 C— 1 (20質量％) 及び一般的な可塑剤である ATC (30質量％)を混合し、感光性樹脂組成物を調整 した。前記感光性樹脂組成物を実施例 18と同様の方法にて反り、難燃性、埋め込み 性、アルカリ現像性の評価を行った。その結果を下記表 7に示す。  Compound C-1 (20% by mass) and general plasticizer ATC (30% by mass) were mixed with 100% by mass of the polyimide (3) produced in Example 18 to obtain a photosensitive resin composition. 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.
[0209] [比較例 22] 実施例 21で製造したポリイミド (4) 100質量％に対して、化合物 C— 1 (20質量％) を混合し、感光性樹脂組成物を調整した。前記感光性樹脂組成物を実施例 18と同 様の方法にて反り、難燃性、埋め込み性、アルカリ現像性の評価を行った。その結果 を下記表 7に示す。 [0209] [Comparative Example 22] 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.
[0210] [比較例 23]  [0210] [Comparative Example 23]
実施例 21で製造したポリイミド (4) 100質量％に対して、化合物 C— 1 (20質量％) 及び芳香族基を有するリン酸エステルである RDP (50質量％)を混合し、感光性樹 脂組成物を調整した。前記感光性樹脂組成物を実施例 18と同様の方法にて反り、 難燃性、埋め込み性、アルカリ現像性の評価を行った。その結果を下記表 7に示す。  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.
[0211] [比較例 24]  [0211] [Comparative Example 24]
実施例 4で製造したポリイミド (4) 100質量％に対して、化合物 C— 1 (20質量％)及 び一般的な可塑剤である ATC (50質量％)を混合し、感光性樹脂組成物を調整した 。前記感光性樹脂組成物を実施例 18と同様の方法にて反り、難燃性、埋め込み性、 アルカリ現像性の評価を行った。その結果を下記表 7に示す。  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.
[0212] 表 7から分るように、本発明のリン酸エステル化合物を添加した感光性樹脂組成物 で構成された感光性フィルム（実施例 18から実施例 21)では、添加しな!/、感光性樹 脂組成物で構成された感光性フィルム（比較例 16、比較例 19、比較例 22)及び芳 香族リン酸エステル化合物を添加した感光性樹脂組成物で構成された感光性フィノレ ム（比較例 17、比較例 20、比較例 23)と比較して、難燃性を維持したまま反り及び埋 め込み性が改善されている。また、一般的な可塑剤を添加した感光性樹脂組成物で 構成された感光性フィルム（比較例 18、比較例 21、比較例 24)では、反り及び埋め 込み性は改善されるものの、難燃性が低下することがわかる。以上のことから、本発 明のリン酸化合物を添加した感光性樹脂組成物からなる感光性フィルムは、難燃性 を維持したまま、ドライフィルム化時の反り及び埋め込み性が改善されており、しかも 現像性についても、良好であった。  [0212] As can be seen from Table 7, in the photosensitive film composed of the photosensitive resin composition to which the phosphate ester compound of the present invention was added (Example 18 to Example 21), it was not added! /, Photosensitive film composed of a photosensitive film composed of a photosensitive resin composition (Comparative Example 16, Comparative Example 19, Comparative Example 22) and a photosensitive resin composition added with an aromatic phosphate compound. Compared with (Comparative Example 17, Comparative Example 20, Comparative Example 23), warpage and embedding were improved while maintaining flame retardancy. In addition, in 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.
[表 6] ポジ型感光性樹脂組成物の組成 [Table 6] Composition of positive photosensitive resin composition
Figure imgf000058_0001
Figure imgf000058_0001
[表 7] ポジ型感光性樹脂組成物から作製した感光性フィルムの物性  [Table 7] Physical properties of photosensitive film prepared from positive photosensitive resin composition
Figure imgf000058_0002
Figure imgf000058_0002
[0213] 以下の実施例 22〜25、比較例 25においては、現像性評価は膜厚約 15 mにて 以下のように実施した。 [0213] In Examples 22 to 25 and Comparative Example 25 below, evaluation of developability was performed at a film thickness of about 15 m as follows.
[0214] ぐ現像性評価〉  [0214] Gudevelopability Evaluation>
現像性評価は、銅張積層板上に、感光性ドライフィルム (感光層の厚さ約 15 m) を用いて、上記のラミネート条件でラミネートした後に、ポジ型マスクを用いて照射量 1. OjZcm2にて露光を行レ、、続いて 1 %又は 3%水酸化ナトリウム水溶液によるアル カリ現像処理と水によるリンスを行い、乾燥後にパターンを光学顕微鏡にて評価する ことにより行った。マスクには 10011 m径の円形パターン（間隔 100 H mピッチ）を用 いた。現像により、露光部で銅面が現れており、かつ未露光部の感光層の膜厚が 13 in以上の場合を◎、 10 111以上13 111未満の場合を〇とし、それ以外の解像度 が劣る場合や膜厚が 10 m未満の場合を Xとした。 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). Due to development, a copper surface appears in the exposed area and 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.
[0215] [実施例 22]  [0215] [Example 22]
窒素雰囲気下、セパラブルフラスコに、 ΜΒΑΑ(30· Ommol)、シリコーンジァミン（ KF— 8010、 45. Ommol)、 γ ブチロラタトン（120mUを入れ、続いて ODPA(6 0. Ommol)を加え、室温で 2時間撹拌した。続いて、トルエン（60mL)、ピリジン（34 . 13mmol)、 γ バレロラタトン（22· 47mmol)を加え、ディーンシュタルク装置及 び還流器をつけ、 180°Cで 2時間加熱撹拌した。 120°Cまで冷却した後に、 APB (1 5. Ommol)をカロ免、 10分間 ft持した後に、丁 MEG (30· Ommol)をカロ免、 120。Cで 2時間加熱撹拌した。続いて、トルエン（15mL)を加え、 180°Cで 2時間加熱撹拌し た。 140°Cまで冷却し、ポリマー固形分濃度 30質量％となるように γ—プチ口ラタトン を加え、室温まで冷却することにより、ポリイミド（5)の γ—プチ口ラタトン溶液を得た。 数平均分子量及びシロキサン構造に由来する部位の質量（％)を下記表 8に示す。  In a nitrogen atmosphere, put ΜΒΑΑ (30 · Ommol), silicone diamine (KF-8010, 45. Ommol), γ-butyroratatone (120mU), and then add ODPA (60.Ommol) at room temperature. Then, toluene (60 mL), pyridine (34.13 mmol), and γ-valerolataton (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, APB (1 5. Ommol) was calorie-free and held for 10 minutes ft, then Ding MEG (30 · Ommol) was calorie-free and stirred at 120 ° C for 2 hours. Toluene (15 mL) was added and stirred for 2 hours at 180 ° C. Cool to 140 ° C. Add γ-petit-mouth rataton to a polymer solid content of 30% by mass, and cool to room temperature. As a result, a γ-petit-mouth ratatone solution of polyimide (5) was obtained. Mass (%) of the site derived from shown in Table 8 below.
[0216] ポリイミド（5) 100質量％に対して、化合物じー1 (20質量％)、3?8— 100 (20質 量％)及び Μ— 325 (30質量％)を混合し、感光性樹脂組成物を調整した。その組 成を下記表 9に示す。このようにして得られた感光性樹脂組成物を、前述のコート方 法にて易剥離 PETフィルムにコートし、 95°Cで 30分間乾燥させることにより、感光性 ドライフィルムを得た。反りはドライフイノレムで、〇であった。  [0216] Polyimide (5) is mixed with 100% by mass of Compound J-1 (20% by mass), 3-8-100 (20% by mass), and Μ-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.
[0217] 上記の感光性ドライフィルムを、銅製回路（50 mの銅ライン幅、ライン間隔は 50 m、銅配線の厚み 12 m)上に前述のラミネート条件によりラミネートを行った。得 られた積層体をカットし、断面を電子顕微鏡にて観察したところ、空隙なく埋め込み ができており、カバーレイ層の表面も平坦であった。  [0217] 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. 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.
[0218] 前記ポジ型感光性樹脂組成物を、前述のコート方法にてカプトン (登録商標）にコ ートし、 95°Cで 30分間乾燥させ、続いて反対の面にコートし、 95°Cで 30分間乾燥さ せることによって得たポジ型感光性樹脂組成物をコートしたカプトン (登録商標）を、 焼成炉にて空気雰囲気下、 120°Cで 60分間、続いて 200°Cで 60分間焼成すること により、硬化体を得た。前記硬化体に対し、 UL94 VTM試験による難燃性の評価 を行った。その結果を下記表 10に示した。 [0218] 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.
[0219] 上記の感光性フィルムを、銅張積層板上に前述のラミネート条件によりラミネートを 行った。得られた積層体を、ポジ型マスクを用いて照射量 1. Oj/cm2にて露光を行 い、続いて 3%水酸化ナトリウム水溶液によるアルカリ現像処理と水によるリンスを行 い、乾燥後にパターンを光学顕微鏡にて観察した。それぞれのドライフィルムにおい て露光部で銅面が現れており、かつ未露光部のカバーレイ層の膜厚が 13 m以上 であった。 [0219] 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.
[0220] [実施例 23]  [0220] [Example 23]
窒素雰囲気下、セパラブルフラスコに、シリコーンジァミン（KF— 8010、 45. Omm ol)、 γ ブチロラタトン（120mL)を入れ、続いて ODPA (60. Ommol)を加え、室 温で 2時間撹拌した。続いて、トルエン（60mU、ピリジン（34. 13mmol)、 γ バレ 口ラタトン（22. 47mmol)を加え、ディーンシュタルク装置及び還流器をつけ、 180°C で 2時間加熱撹拌した。 120°Cまで冷却した後に、 APB (9. Ommol)、 MBAA (30 mmol)を加え、 10分間撹拌した後に、 TMEG (25. 8mmol)を加え、 120°Cで 2時 間加熱撹拌した。続いて、トルエン（15mL)を加え、 180°Cで 2時間加熱撹拌した。 1 40°Cまで冷却し、ポリマー固形分濃度 30質量％となるように γ—プチ口ラタトンを加 え、室温まで冷却することにより、ポリイミド（6)の γ—プチ口ラタトン溶液を得た。数平 均分子量及びシロキサン構造に由来する部位の質量（％)を下記表 8に示す。  In a nitrogen atmosphere, silicone diamine (KF-8010, 45. Ommol) and γ-butyrolatone (120 mL) were added to a separable flask, followed by ODPA (60. Ommol), and stirred at room temperature for 2 hours. . Subsequently, toluene (60 mU, pyridine (34. 13 mmol) and γ-bare ratatotone (22. 47 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 that, APB (9. Ommol) and MBAA (30 mmol) were added and stirred for 10 minutes, then TMEG (25.8 mmol) was added, and the mixture was heated and stirred at 120 ° C for 2 hours, followed by toluene (15 mL). ) And heated and stirred for 2 hours at 180 ° C. 1 Cool to 40 ° C. Add γ-petit-mouth rataton to a polymer solids concentration of 30% by mass, and cool to room temperature. Table 8 below shows the number average molecular weight and the mass (%) of the site derived from the siloxane structure.
[0221] ポリイミド（6) 100質量％に対して、化合物じー2 (20質量％)、3?8— 100 (20質 量％)を混合し、感光性樹脂組成物を調整した。その組成を下記表 9に示す。前記感 光性樹脂組成物を実施例 22と同様の方法にて反り、難燃性、基板への圧着性の評 価を行った。アルカリ現像性については、 1 %水酸化ナトリウム水溶液を用いて評価 を行った。その結果を下記表 10に示す。  [0221] 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.
[0222] [実施例 24]  [Example 22]
実施例 23で製造したポリイミド（6) 100質量％に対して、化合物 C— 2 (20質量％) 、 SPB- 100 (20質量％)、 ΤΒΧΡ (10質量％)を混合し、感光性樹脂組成物を調整 した。その組成を下記表 9に示す。前記感光性樹脂組成物を実施例 22と同様の方 法にて反り、難燃性、基板への圧着性、アルカリ現像性の評価を行った。その結果を 下記表 10に示す。 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.
[0223] [実施例 25]  [Example 25]
実施例 23で製造したポリイミド（6) 100質量％に対して、化合物 C— 2 (20質量％) 、 SPH- 100 (20質量％)、 TBXP (10質量％)を混合し、感光性樹脂組成物を調整 した。その組成を下記表 9に示す。前記感光性樹脂組成物を実施例 22と同様の方 法にて反り、難燃性、基板への圧着性、アルカリ現像性の評価を行った。その結果を 下記表 10に示す。  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.
[0224] [比較例 25]  [0224] [Comparative Example 25]
実施例 23で製造したポリイミド（6) 100質量％に対して、化合物 C— 2 (20質量％) を混合し、感光性樹脂組成物を調整した。その組成を下記表 9に示す。前記感光性 樹脂組成物を実施例 22と同様の方法にて反り、難燃性、基板への圧着性、アルカリ 現像性の評価を行った。その結果を下記表 10に示す。  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.
[表 8コ  [Table 8
ポリイミドの数平均分子量、組成及ひ'シロキサン構造含有率
Figure imgf000061_0001
Number average molecular weight of polyimide, composition and content of siloxane structure
Figure imgf000061_0001
[表 9コ  [Table 9
ポジ型感光性樹脂組成物の組成  Composition of positive photosensitive resin composition
Figure imgf000061_0002
Figure imgf000061_0002
[表 10] ポジ型感光 1生樹脂組成物から作製した感光性フィルムの物性 [Table 10] Positive type photosensitivity 1 Physical properties of photosensitive film prepared from raw resin composition
反り 膜厚（ πι)一難燃性 基板への圧着性 現像性 実施例 22 〇 16 VTM-0 〇 ©  Warpage Film thickness (πι) One flame resistance Bondability to substrate Developability Example 22 〇 16 VTM-0 〇 ©
実施例 23 0 17 VTM-0 0 ◎  Example 23 0 17 VTM-0 0 ◎
実施例 24 〇 17 VTM-0 〇 ©  Example 24 ○ 17 VTM-0 ○ ©
実施例 25 〇 16 VTM-0 〇 ◎  Example 25 ○ 16 VTM-0 ○ ◎
比較例 25 O 17 X X ο  Comparative Example 25 O 17 X X ο
[0225] 表 10の結果から、本発明のホスファゼン化合物を添加した実施例 22から実施例 2 5では、添加しない比較例 25と比較して難燃性が向上していることがわかる。また、 現像性についても向上していることがわかる。以上のことから、本発明のホスファゼン 化合物を添加した感光性樹脂組成物からなる感光性フィルムは、難燃性及び現像性 が改善されていることがわかる。また、基板への圧着性についても、良好なことがわか [0225] From the results in Table 10, it can be seen that in Examples 22 to 25 to which the phosphazene compound of the present invention was added, flame retardancy was improved as compared with Comparative Example 25 in which no phosphazene compound was added. It can also be seen that the developability is also improved. From the above, it can be seen that the photosensitive film comprising the photosensitive resin composition to which the phosphazene compound of the present invention is added has improved flame retardancy and developability. In addition, it can be seen that the crimping property to the substrate is good.
産業上の利用可能性 Industrial applicability
[0226] 本発明における感光性樹脂組成物は、感光性フィルムとして反りが充分に抑制さ れ、基板への埋め込み性や密着性に優れ、且つ、現像性も良好であり、硬化後に難 燃性を有することから、感光性ドライフィルムやカバーレイに適用することができ、エレ タトロ二タス分野で各種電子機器の操作パネルなどに使用されるフレキシブル配線 板や回路基板の保護層形成、積層基板の絶縁層形成、半導体装置に使用されるシ リコンウェハ、半導体チップ、半導体装置周辺の部材、半導体搭載用基板、放熱板、 リードピン、半導体自身などの保護や絶縁及び接着に使用するための電子部品への 膜形成用途に利用される。  [0226] 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.

Claims

請求の範囲 The scope of the claims
[1] (A)成分、（B)成分、及び (C)成分を含有する感光性樹脂組成物であって、前記 ( A)成分はアルカリ可溶性樹脂であり、前記 (B)成分は式（1)に示す構造を有する化 合物、イソシァヌル酸環を有する化合物、及び前記 (A)成分以外のイミド基を 1つ若 しくは 2つ含有するイミド化合物からなる群から選ばれた少なくとも一つの化合物であ り、前記 (C)成分はキノンジアジド化合物であることを特徴とする感光性樹脂組成物  [1] A photosensitive resin composition comprising a component (A), a component (B), and a component (C), wherein the component (A) is an alkali-soluble resin, and the component (B) is represented by the formula ( 1) at least one selected from the group consisting of a compound having the structure shown in FIG. 1, a compound having an isocyanuric acid ring, and an imide compound containing one or two imide groups other than the component (A). A photosensitive resin composition, wherein the component (C) is a quinonediazide compound
P = X 式（1) P = X formula (1)
(式中 Pはリン原子を表し、その共有結合数は 5である。 Xは窒素原子又は酸素原子 を表し、 Xが窒素原子の場合、その共有結合数は 3であり、酸素原子の場合、その共 有結合数は 2である。リン原子と窒素原子又は酸素原子とは二重結合で結合して!/、 る。 )  (In the formula, P represents a phosphorus atom and the number of covalent bonds is 5. X represents a nitrogen atom or an oxygen atom. When X is a nitrogen 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! /
[2] 前記式（1)に示す (B)成分が、式（2)若しくは式（3)に示すリン酸エステル化合物、 又は式 (4)に示すホスフィンォキシド化合物であることを特徴とする請求項 1記載の 感光性樹脂組成物。  [2] The component (B) represented by the formula (1) is a phosphate compound represented by the formula (2) or the formula (3), or a phosphine oxide compound represented by the formula (4) The photosensitive resin composition according to claim 1.
[化 1コ 0 [Chemical 1 Co 0
— 0 0- — 0 0-
0 ( 2 ) 0 (2)
(式中 Rは 1価の有機基である。複数の Rはそれぞれ同一でも異なっていても良い。 ) (In the formula, R is a monovalent organic group. A plurality of R may be the same or different.)
[化 2]  [Chemical 2]
Figure imgf000063_0001
Figure imgf000063_0001
(式中の Rは前記一般式（2)と同じである。複数の Rはそれぞれ同一でも異なって いても良い。 ) [化 3] (R in the formula is the same as in the general formula (2). Plural R may be the same or different.) [Chemical 3]
Figure imgf000064_0001
Figure imgf000064_0001
(式中 Rは 1価の有機基である。 )  (In the formula, R is a monovalent organic group.)
2  2
[3] 前記 (A)成分がアルカリ可溶性ポリイミド又はポリイミド前駆体であって、シロキサン 骨格を有することを特徴とする請求項 1又は請求項 2記載の感光性樹脂組成物。  [3] The photosensitive resin composition according to claim 1 or 2, wherein the component (A) is an alkali-soluble polyimide or a polyimide precursor and has a siloxane skeleton.
[4] 前記シロキサン骨格を、ァリカリ可溶性ポリイミド又はポリイミド前駆体の質量に対し て、 10質量％以上含有することを特徴とする請求項 3記載の感光性樹脂組成物。 [4] The photosensitive resin composition according to claim 3, wherein the siloxane skeleton is contained in an amount of 10% by mass or more based on the mass of the alkali-soluble polyimide or the polyimide precursor.
[5] 前記 (A)成分がアルカリ可溶性ポリイミドであって、カルボキシル基及び/又は水 酸基を有するポリイミド樹脂であることを特徴とする請求項 1から請求項 4のいずれか に記載の感光性樹脂組成物。 [5] The photosensitive property according to any one of claims 1 to 4, wherein the component (A) is an alkali-soluble polyimide and is a polyimide resin having a carboxyl group and / or a hydroxyl group. Resin composition.
[6] 前記 (A)成分が下記式（5)で表されるアルカリ可溶性ポリイミドであることを特徴と する請求項 1から請求項 5のいずれかに記載の感光性樹脂組成物。 [6] The photosensitive resin composition according to any one of claims 1 to 5, wherein the component (A) is an alkali-soluble polyimide represented by the following formula (5).
[化 4]  [Chemical 4]
Figure imgf000064_0002
Figure imgf000064_0002
(式中、 R、 Rは 4価の有機基を表し、同じであっても異なっていても良い。 Rは炭素  (In the formula, R and R represent a tetravalent organic group, which may be the same or different. R is carbon.
3 5 6 数 1以上 20以下の炭化水素基を表す。 Rはアルカリ溶解性官能基を少なくとも一つ  3 5 6 A hydrocarbon group having a number of 1 or more and 20 or less. R has at least one alkali-soluble functional group
4  Four
以上有する 2価の有機基を表す。 aは 1以上 10以下の整数を表す。 bは 1以上 20以 下の整数を表す。 Rはエステル構造を有する 4価の有機基を表し、 Rは 2価の有機  It represents a divalent organic group having the above. 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.
7 8  7 8
基を表す。 α、 /3、 γは少なくとも 1以上であり、 0· 01≤/3 / ( α + /3 + γ )≤0. ある。 )  Represents a group. α, / 3, and γ are at least 1 and 0 · 01≤ / 3 / (α + / 3 + γ) ≤0. )
前記 (Α)成分が前記式（5)で表されるアルカリ可溶性ポリイミドであって、式（5)に おいて、 0· 03≤/3 / ( α + /3 + γ )≤0· 67を満足することを特徴とする請求項 6記 載の感光性樹脂組成物。 The component (ii) is an alkali-soluble polyimide represented by the formula (5), and in the formula (5), 0 · 03≤ / 3 / (α + / 3 + γ) ≤0 · 67 Claim 6 characterized by being satisfied The photosensitive resin composition of mounting.
[8] 前記 が下記式（6)又は式（7)で表される酸二無水物に由来する官能基であるこ とを特徴とする請求項 6又は請求項 7記載の感光性樹脂組成物。 [8] The photosensitive resin composition according to claim 6 or 7, wherein the above is a functional group derived from an acid dianhydride represented by the following formula (6) or formula (7).
[化 5]  [Chemical 5]
Figure imgf000065_0001
Figure imgf000065_0001
Figure imgf000065_0002
Figure imgf000065_0002
[9] 前記 (B)成分が前記式（2)又は式（3)に示すリン酸エステル化合物を含み、前記 式（2)又は前記式（3)中の R力 Sメチル基、ェチル基、ブチル基、イソブチル基、 2— ェチルへキシル基、ブトキシェチル基、フエニル基、クレジル基、キシレニル基及びァ ミノフエニル基からなる群より選ばれた有機基であることを特徴とする請求項 2から請 求項 8の!/、ずれかに記載の感光性樹脂組成物。  [9] The component (B) includes a phosphate ester compound represented by the formula (2) or the formula (3), and an R force S methyl group, an ethyl group in the formula (2) or the formula (3), The organic group selected from the group consisting of a butyl group, an isobutyl group, a 2-ethylhexyl group, a butoxystil group, a phenyl group, a cresyl group, a xylenyl group and an aminophenyl group. Item 8. The photosensitive resin composition according to Item 8!
[10] 前記 (B)成分が前記式（2)に示すリン酸エステル化合物を含み、前記式（2)にお ける R力 炭素数 1以上 30以下の脂肪族有機基であり、同じであっても異なっていて  [10] The component (B) is an aliphatic organic group containing a phosphate ester compound represented by the formula (2) and having an R force of 1 to 30 carbon atoms in the formula (2). It ’s different.
1  1
も良いことを特徴とする請求項 2から請求項 8のいずれかに記載の感光性樹脂組成 物。  9. The photosensitive resin composition according to claim 2, wherein the photosensitive resin composition is good.
[11] 前記 (B)成分が前記式（2)に示すリン酸エステル化合物を含み、前記式（2)にお ける R力 メチル基、ェチル基、ブチル基、イソブチル基、 2—ェチルへキシル基、及  [11] The component (B) includes a phosphate ester compound represented by the formula (2), and the R force in the formula (2): methyl group, ethyl group, butyl group, isobutyl group, 2-ethylhexyl Group
1  1
びブトキシェチル基からなる群より選ばれたいずれか一つであることを特徴とする請 求項 2から請求項 10のいずれかに記載の感光性樹脂組成物。  11. The photosensitive resin composition according to any one of claims 2 to 10, wherein the photosensitive resin composition is any one selected from the group consisting of a butoxychetyl group.
[12] 前記 (B)成分が前記式（2)に示すリン酸エステル化合物を含み、前記式（2)にお ける R 1S 炭素数 2以上 30以下の脂肪族有機基であり、同じであっても異なっていて[12] The component (B) contains a phosphate ester compound represented by the formula (2), and the formula (2) R 1S is an aliphatic organic group having 2 to 30 carbon atoms.
1 1
も良ぐ且つ、脂肪族有機基がエーテル構造を有することを特徴とする請求項 2から 請求項 11の!/、ずれかに記載の感光性樹脂組成物。  The photosensitive resin composition according to any one of claims 2 to 11, wherein the aliphatic organic group has an ether structure.
[13] 前記 (B)成分が前記式（2)又は式（3)に示すリン酸エステル化合物を含み、該リン 酸エステル化合物を 2種類以上含むことを特徴とする請求項 2から請求項 12のいず れかに記載の感光性樹脂組成物。  [13] The component (B) contains the phosphate ester compound represented by the formula (2) or (3), and contains two or more types of the phosphate ester compounds. The photosensitive resin composition as described in any of the above.
[14] 前記 (B)成分が前記式（2)に示すリン酸エステル化合物を含み、前記式（2)にお ける Rがブトキシェチル基であることを特徴とする請求項 9から請求項 13のいずれか  [14] The component of (9) to [13], wherein the component (B) contains a phosphate ester compound represented by the formula (2), and R in the formula (2) is a butoxychetyl group. either
1  1
に記載の感光性樹脂組成物。  The photosensitive resin composition as described in 2.
[15] 前記 (A)成分 100質量部に対して、前記 (B)リン酸エステル化合物が 50質量部以 下で含有されることを特徴とする請求項 1から請求項 14のいずれかに記載の感光性 樹脂組成物。  [15] The composition according to any one of claims 1 to 14, wherein the phosphoric acid ester compound (B) is contained in an amount of 50 parts by mass or less with respect to 100 parts by mass of the component (A). Photosensitive resin composition.
[16] 前記 (B)成分がイソシァヌル酸環を有する化合物を含み、前記イソシァヌル酸環を 有する化合物が式 (8)に示す有機基を含有することを特徴とする請求項 1から請求 項 15のいずれかに記載の感光性樹脂組成物。  [16] The component (B) includes a compound having an isocyanuric acid ring, and the compound having an isocyanuric acid ring contains an organic group represented by the formula (8). The photosensitive resin composition in any one.
[化 7]  [Chemical 7]
Figure imgf000066_0001
Figure imgf000066_0001
(式中 Rは 1価の有機基である。複数の Rはそれぞれ同一でも異なっていても良い。  (In the formula, R is a monovalent organic group. A plurality of R may be the same or different from each other.)
9 9  9 9
)  )
[17] 前記 (B)成分がイミド化合物を含み、前記イミド化合物が式 (9)に示す有機基を含 有することを特徴とする請求項 1から請求項 16のいずれかに記載の感光性樹脂組成 物。  [17] The photosensitive resin according to any one of [1] to [16], wherein the component (B) includes an imide compound, and the imide compound includes an organic group represented by the formula (9): Composition.
[化 8]
Figure imgf000067_0001
( 9 ) [Chemical 8]
Figure imgf000067_0001
(9)
(式中 R は 1価、又は 2価の有機基である。 mは 1、又は 2である。 Yは式（10)で示さ  (In the formula, R is a monovalent or divalent organic group. M is 1 or 2. Y is represented by the formula (10).
10  Ten
れる有機基を表す。 )  Represents an organic group. )
[化 9]
Figure imgf000067_0002
[Chemical 9]
Figure imgf000067_0002
[18] 前記 (B)成分がホスフィンォキシド化合物を含み、前記式 (4)中の Rが水素、ジヒド [18] The component (B) contains a phosphine oxide compound, and R in the formula (4) is hydrogen, dihydride
2  2
ロキシフエニル基、ジブチルヒドロキシベンジル基、及び（メタ）アタリレート基を含む有 機基からなる群より選ばれた有機基であることを特徴とする請求項 1から請求項 17の V、ずれかに記載の感光性樹脂組成物。  18. The organic group selected from the group consisting of an organic group including a roxyphenyl group, a dibutylhydroxybenzyl group, and a (meth) atarylate group. Photosensitive resin composition.
[19] 前記イソシァヌル酸環を有する化合物において、前記式（8)中の Rが式（11)で示 [19] In the compound having an isocyanuric acid ring, R in the formula (8) is represented by the formula (11).
9  9
された有機基であることを特徴とする請求項 1から請求項 18記載の感光性樹脂組成 物。  19. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is an organic group formed.
[化 10]  [Chemical 10]
0  0
— CH2CH20- C- ( -, D — CH 2 CH 2 0- C- (-, D
(式中 R は式（12)又は式（13)力 選ばれた有機基である。 ) (Wherein R is an organic group selected from the formula (12) or formula (13)).
11  11
[化 11]  [Chemical 11]
-C=CH2 ( -C = CH 2 (
(式中 R は水素又はメチル基である。 ) (Wherein R is hydrogen or a methyl group.)
12  12
[化 12]  [Chemical 12]
0 R12 0 R 12
-(CH2)c-0-C-C=CH2 ( ) (式中 Cは 2から 5の整数である。 R は前記式（12)と同じである。 ) -(CH 2 ) c -0-CC = CH 2 () (In the formula, C is an integer of 2 to 5. R is the same as the formula (12).)
12  12
[20] 前記イミド化合物において、前記式（9)中の mが 1であり、 R が前記式（11)で示さ  [20] In the imide compound, m in the formula (9) is 1, and R is represented by the formula (11).
10  Ten
れた有機基から選ばれることを特徴とする請求項 1から請求項 19のいずれかに記載 の感光性樹脂組成物。  20. The photosensitive resin composition according to any one of claims 1 to 19, wherein the photosensitive resin composition is selected from organic groups selected.
[21] 前記（C)成分が式（14)又は式（15)で示される有機基を有する化合物であることを 特徴とする請求項 1から請求項 20のいずれかに記載の感光性樹脂組成物。  [21] The photosensitive resin composition according to any one of [1] to [20], wherein the component (C) is a compound having an organic group represented by formula (14) or formula (15) object.
[化 13]  [Chemical 13]
Figure imgf000068_0001
Figure imgf000068_0001
[化 14]  [Chemical 14]
Figure imgf000068_0002
Figure imgf000068_0002
[22] 前記式（14)又は式（15)で示されたいずれかの有機基を有する化合物力 フエノ ール性水酸基を有する化合物をスルホン酸でエステル化して得られる化合物であり、 前記フエノール性水酸基を有する化合物 1モル当たりの前記式（14)又は式（15)で 示されたいずれかの有機基によるエステル化率が 0. 60以上 0. 98以下であることを 特徴とする請求項 21記載の感光性樹脂組成物。  [22] A compound having an organic group represented by the formula (14) or the formula (15) is a compound obtained by esterifying a compound having a phenolic hydroxyl group with a sulfonic acid, and the phenolic 22. The esterification rate by one of the organic groups represented by the formula (14) or the formula (15) per mole of the compound having a hydroxyl group is 0.60 or more and 0.998 or less. The photosensitive resin composition as described.
[23] 前記（C)成分が式（16)で表されるキノンジアジド化合物を含有することを特徴とす る請求項 1から請求項 22のいずれかに記載の感光性樹脂組成物。  23. The photosensitive resin composition according to any one of claims 1 to 22, wherein the component (C) contains a quinonediazide compound represented by the formula (16).
[化 15]
Figure imgf000069_0001
[Chemical 15]
Figure imgf000069_0001
(式中 Qはそれぞれ独立に水素又は前記式（14)又は式（15)から選ばれた 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前記式（14)又は式（15)から選 ばれた有機基である。 )  (In the formula, each Q is independently hydrogen or a monovalent organic group selected from the above formula (14) or formula (15), provided that at least one of a plurality of Q is represented by the above formula (14) or Organic group selected from formula (15).)
[24] (D)成分としてポリエーテル化合物を含有することを特徴とする請求項 1から請求 項 23の!/、ずれかに記載の感光性樹脂組成物。 24. The photosensitive resin composition according to any one of claims 1 to 23, wherein a polyether compound is contained as the component (D).
[25] 前記ポリエーテル化合物がエチレンォキシド鎖を有することを特徴とする請求項 24 記載の感光性樹脂組成物。 25. The photosensitive resin composition according to claim 24, wherein the polyether compound has an ethylene oxide chain.
[26] 前記ポリエーテル化合物が末端に水酸基を有することを特徴とする請求項 24又は 請求項 25記載の感光性樹脂組成物。 26. The photosensitive resin composition according to claim 24 or 25, wherein the polyether compound has a hydroxyl group at a terminal.
[27] 前記式（1)に示す（B)成分が、下記式（17)又は式（18)で表されるホスファゼン化 合物の少なくとも 1つであることを特徴とする請求項 1から請求項 26のいずれかに記 載の感光性樹脂組成物。 [27] The component (B) represented by the formula (1) is at least one phosphazene compound represented by the following formula (17) or the formula (18): Item 26. The photosensitive resin composition according to any one of Items 26.
[化 16] [Chemical 16]
Figure imgf000069_0002
Figure imgf000069_0002
[化 17]
Figure imgf000070_0001
[Chemical 17]
Figure imgf000070_0001
(式中、 R 、R 、R 、R は炭素数 3以上 20以下の有機基であり、同じであっても  (In the formula, R 1, R 2, R 3 and R 4 are organic groups having 3 to 20 carbon atoms.
13 14 15 16  13 14 15 16
異なっていても良い。 pは 3以上 25以下の整数であり、 qは 3以上 10000以下の整数 であり、 A及び Bは、炭素数 3以上 30以下の有機基である。 )  It may be different. p is an integer from 3 to 25, q is an integer from 3 to 10000, and A and B are organic groups having 3 to 30 carbon atoms. )
[28] 前記ホスファゼン化合物における R 、R 、R 、R が芳香環を有することを特徴と [28] In the phosphazene compound, R 1, R 2, R 3 and R 4 have an aromatic ring,
13 14 15 16  13 14 15 16
する請求項 27記載の感光性樹脂組成物。  The photosensitive resin composition according to claim 27.
[29] (E)可塑剤を含有することを特徴とする請求項 27又は請求項 28記載の感光性樹 脂組成物。 [29] The photosensitive resin composition according to claim 27 or 28, further comprising (E) a plasticizer.
[30] 前記可塑剤が、リン酸エステル、エーテル化合物、メタクリル基含有化合物、アタリ ル基含有化合物、フタル酸エステル、脂肪族二塩基酸エステル、芳香族縮合リン酸 エステル、イソシァヌル酸エチレングリコール変性トリアタリレート、及び ε —力プロラタ トン変性トリス（アタリ口キシェチル)イソシァヌレートからなる群より選ばれたいずれか を含むことを特徴とする請求項 29記載の感光性樹脂組成物。  [30] The plasticizer is a phosphate ester, an ether compound, a methacryl group-containing compound, an allyl group-containing compound, a phthalate ester, an aliphatic dibasic acid ester, an aromatic condensed phosphate ester, an isocyanuric acid ethylene glycol-modified tri 30. The photosensitive resin composition according to claim 29, comprising any one selected from the group consisting of attalylate and ε-force prolatatatone-modified tris (atari mouth kichetil) isocyanurate.
[31] 請求項 1から請求項 30のいずれかに記載の感光性樹脂組成物を含むことを特徴と する感光性フィルム。  [31] A photosensitive film comprising the photosensitive resin composition according to any one of claims 1 to 30.
[32] 請求項 6から請求項 8のいずれかに記載のアルカリ可溶性ポリイミドを含むことを特 徴とする請求項 31記載の感光性フィルム。  [32] The photosensitive film according to claim 31, comprising the alkali-soluble polyimide according to any one of claims 6 to 8.
[33] キャリアフィルムと、前記キャリアフィルム上に設けられた請求項 31又は請求項 32 記載の感光性フィルムと、を具備することを特徴とする積層フィルム。 [33] A laminated film comprising a carrier film and the photosensitive film according to claim 31 or 32 provided on the carrier film.
[34] 前記感光性フィルム上に形成されたカバーフィルムを具備することを特徴とする請 求項 33記載の積層フィルム。 [34] The laminated film according to claim 33, further comprising a cover film formed on the photosensitive film.
[35] 請求項 31から請求項 34のいずれかに記載の感光性フィルム又は積層フィルムを 用いて得られることを特徴とするカバーレイ。 [35] A cover lay obtained by using the photosensitive film or laminated film according to any one of claims 31 to 34.
[36] 配線を有する基材と、前記配線を覆うように前記基材上に形成され、請求項 31から 請求項 34のいずれかに記載の感光性フィルム又は積層フィルムを用いて得られる力 バーレイと、を具備することを特徴とするプリント配線板。 [36] The base material having wiring, and formed on the base material so as to cover the wiring, 35. A printed wiring board comprising: a force burley obtained by using the photosensitive film or laminated film according to claim 34.
請求項 1から請求項 30の!/、ずれかに記載の感光性樹脂組成物を用いて配線を有 する基材に塗布することにより得られるカバーレイを具備することを特徴とするプリント 配線板。  A printed wiring board comprising a coverlay obtained by applying the photosensitive resin composition according to any one of claims 1 to 30 to a substrate having wiring. .
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