Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
  • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0387—Polyamides or polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
  • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
• • 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
  • G03F7/075—Silicon-containing compounds
  • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
• • 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 siloxane polyimide resin composition, a printed wiring board provided with a protective layer formed therefrom, and a method for suppressing bleeding out of cyclic dimethylsiloxane oligomer from the protective layer of the printed wiring board.
• Aromatic polyimide resin formed by imidizing aromatic tetracarboxylic acid and aromatic diamine is widely used as an interlayer insulation film and coverlay material for electronic parts because of its excellent heat resistance and insulation.
• excellent flexibility and adhesiveness are required for such aromatic polyimide resins.
• siloxane polyimide resins in which a part of the aromatic diamine is replaced with siloxane diamine and the siloxane skeleton is introduced into the polyimide skeleton is increasing.
• siloxane diamine which is a raw material of siloxane polyimide resin, contains an oily cyclic dimethylsiloxane oligomer having no amino group as an impurity
• the produced siloxane polyimide resin can be used as an interlayer insulation film, coverlay, etc. for electronic parts.
• the cyclic dimethylsiloxane oligomer generated as outgas on the surface of the interlayer-line insulating film or coverlay is reattached or bleed out, and the There have been problems such as contact failure, reduced conductivity, and reduced adhesive strength.
• bleed out refers to a phenomenon in which a substance contained in a solid layer such as a film moves to the surface of the solid layer and liquefies or solidifies there, or volatilizes and diffuses there. means.
• a diamine compound containing at least diaminosiloxane as a diamine component and a tetracarboxylic dianhydride are subjected to an imidization reaction in toluene or an ether solvent.
• a method has been proposed in which the solvent is discharged out of the system and the solvent is replenished (Patent Document 1).
• Patent Document 1 since the oily cyclic dimethylsiloxane oligomer has a relatively low boiling point compared to the solvent, the siloxane polyimide varnish with the reduced concentration of the cyclic dimethylsiloxane oligomer is discharged together with the volatile solvent. It is supposed to be obtained.
• the siloxane polyimide varnish obtained by the method of Patent Document 1 is mixed with a photosensitizer to impart photosensitivity, and is also widely used as a crosslinker for polyimide, silane coupling agent, epoxyamine, solid epoxy
• a resin or the like is blended, the resulting photosensitive siloxane polyimide resin composition is formed on a printed wiring board, patterned and cured, and the cyclic dimethylsiloxane oligomer, which is an impurity, bleeds out from the thin protective layer. There was a problem that it was still difficult to suppress.
• the object of the present invention is to solve the above-mentioned problems of the conventional technique, and from a protective layer obtained by forming a photosensitive siloxane polyimide resin composition on a printed wiring board, patterning, and curing. In other words, it is possible to sufficiently suppress bleeding out of the cyclic dimethylsiloxane oligomer which is an impurity.
• the present inventors prepare a siloxane polyimide resin by using a siloxane diamine having a diphenylsilylene unit as a diamine component, and further use a photosensitive siloxane polyimide resin composition in which a specific kind and amount of a crosslinking agent are blended. As a result, the inventors have found that the above-described object can be achieved and completed the present invention.
• the present invention relates to 100 parts by mass of a siloxane polyimide resin obtained by imidizing a tetracarboxylic dianhydride, a siloxane diamine having a diphenylsilylene unit and a siloxane-free diamine, a liquid epoxy resin, a benzoxazine, and a resole.
• a photosensitive siloxane polyimide resin composition comprising 1 to 20 parts by mass of a crosslinking agent selected from the group consisting of 5 to 30 parts by mass of a photoacid generator is provided.
• the present invention also provides a printed wiring board provided with a protective layer obtained by thermosetting the above-described photosensitive siloxane polyimide resin composition.
• the present invention provides a photosensitive resin containing a siloxane polyimide resin obtained by imidizing a tetracarboxylic dianhydride, a siloxane diamine having a diphenylsilylene unit and a siloxane-free diamine, a crosslinking agent, and a photoacid generator.
• a method for suppressing bleed out of a cyclic dimethylsiloxane oligomer As a crosslinking agent, at least one member selected from the group consisting of a liquid epoxy resin, benzoxazines and resols is used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the siloxane polyimide resin, and a photoacid generator is used as the photosensitive agent. Provided is a method characterized by using 5 to 30 parts by mass per 100 parts by mass.
• a siloxane diamine having a diphenylsilylene unit is used as a diamine component, and a molded product such as a thin film made of a photosensitive siloxane polyimide resin composition has a three-dimensional structure with a specific thermosetting crosslinking agent.
• the cyclic dimethylsiloxane oligomer which is an impurity, is trapped in the three-dimensional structure, and as a result, bleeding out of the cyclic dimethylsiloxane oligomer can be prevented or suppressed, and further excellent plating resistance can be obtained by thermosetting. Is obtained.
• the photoacid generator is contained in a specific amount as a photosensitizer, the siloxane polyimide resin composition becomes positive photosensitivity and can be patterned by exposure and alkali development.
• the photosensitive siloxane polyimide resin composition of the present invention is composed of 100 parts by mass of a siloxane polyimide resin obtained by imidizing a tetracarboxylic dianhydride, a siloxane diamine having a diphenylsilylene unit and a siloxane-free diamine, a liquid epoxy resin, It contains 1 to 20 parts by mass of at least one crosslinking agent selected from the group consisting of benzoxazines and resols, and 5 to 30 parts by mass of a photoacid generator as a photosensitive agent.
• siloxane polyimide resin that is the main component of the photosensitive siloxane polyimide resin composition of the present invention will be described. Since this siloxane polyimide resin uses diaminosiloxane having a diphenylsilylene unit as the diamine component, the amount of cyclic dimethylsiloxane oligomer generated can be reduced.
• siloxane diamine which becomes a structural unit of the siloxane polyimide resin used in the present invention
• a compound having at least a dimethylsilylene skeleton in the molecule, and those conventionally used for siloxane modification of polyimide resins can be used.
• equation (1) can be used preferably from the point of a flame retardance and compatibility ensuring.
• n is an integer of 1 to 30, preferably 1 to 20, and m is an integer of 1 to 20, preferably 1 to 10. Since m is 1 or more, the siloxane diamine of the formula (1) has a diphenylsilylene skeleton, and the flame retardancy of the siloxane polyimide resin is improved. And since m is 1 or more, it becomes possible to suppress the bleeding out of the cyclic dimethylsiloxane oligomer which is an impurity to some extent. Specific examples of such siloxane diamine include X-22-9409 (m> 1) manufactured by Shin-Etsu Chemical Co., Ltd.
• siloxane diamine those having an amino group protected by a carbamate type such as a tert-butoxycarbonyl group, an imide type such as a phthaloyl group, or a sulfonamide type such as a p-toluenesulfonyl group can be used.
• a carbamate type such as a tert-butoxycarbonyl group
• an imide type such as a phthaloyl group
• a sulfonamide type such as a p-toluenesulfonyl group
• siloxane-free diamine which is a constituent unit of the siloxane polyimide resin used in the present invention
• a diamine having no dimethylsilylene skeleton and diphenylsilylene skeleton in the molecule can be used, and specific examples thereof include 3, 3 '-Diamino-4,4'-dihydroxydiphenyl sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,4-diaminophenol, 9,9-bis (3-amino-4-hydroxy Diaminophenol derivatives such as phenyl) fluorene; p-phenylenediamine, 4,4 -Diaminodiphenyl ether, 2,2-bis [4-
• the siloxane polyimide resin used in the present invention is produced by imidization reaction of a tetracarboxylic dianhydride, a siloxane diamine having a diphenylsilylene unit and, if necessary, a siloxane-free diamine in a solvent under reflux conditions.
• a production method having the following steps (a) and (b).
• Step (a) First, a tetracarboxylic dianhydride and a siloxane diamine having a diphenylsilylene unit are subjected to an imidization reaction under a reflux condition to obtain a reaction mixture containing an acid anhydride-terminated siloxane imide oligomer.
• the molar amount of the first tetracarboxylic dianhydride may be increased as compared with siloxane diamine.
• the amount of siloxane diamine used is too small relative to 1 mol of all tetracarboxylic dianhydrides, it tends to be difficult to maintain adhesion and flexibility, and if too large, heat resistance tends to decrease. Therefore, the amount is preferably 0.1 to 0.9 mol, more preferably 0.3 to 0.8 mol.
• the reason for carrying out the imidation reaction under reflux conditions is to remove imidized water using a Dean-Stark separation tube or the like. Therefore, as the solvent, a solvent that is refluxed at a temperature at which an imidization reaction between tetracarboxylic dianhydride and siloxane diamine occurs and can separate water by azeotropy is used.
• a solvent include glymes such as diglyme and triglyme, ether solvents such as dioxane and tetrahydrofuran, lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone, and mixtures thereof.
• an aromatic hydrocarbon solvent such as toluene, xylene, benzene and mesitylene
• an amide solvent such as N-methyl-2-pyrrolidone
• step (a) The amount of solvent used in step (a) varies depending on the type of solvent and reaction substrate, but if it is too small, it will cause poor monomer dispersion and decrease in reflux efficiency. If it is too large, the heat of vaporization of the solvent will increase and the temperature in the reaction vessel will increase. Therefore, the total mass of tetracarboxylic dianhydride and siloxane diamine is preferably used in an amount of 5 to 60% by mass.
• the reaction temperature during the imidation reaction varies depending on the type and amount of the solvent and reaction substrate, but if it is too low, the imidization reaction cannot be completed, and if it is too high, side reactions other than the imidization reaction may occur. Therefore, it is preferably 150 to 220 ° C, more preferably 160 to 200 ° C.
• the reaction time is the time required to remove the theoretical amount of imidized water, and is usually 0.5 to 12 hours, preferably 1 to 8 hours.
• a tertiary amine such as triethylamine
• a basic catalyst such as aromatic isoquinoline and pyridine
• an acid catalyst such as benzoic acid and parahydroxybenzoic acid
• Step (b) After completion of the reaction in the step (a), a siloxane-free diamine is added to the solution of the acid anhydride-terminated siloxane imide oligomer obtained in the step (a), and the siloxane-free diamine and the acid anhydride-terminated siloxane imide oligomer are added.
• An imidization reaction is performed to obtain a siloxane polyimide resin.
• step (a) those that can be used in step (a) can be used.
• an ether solvent, a lactone solvent, an aromatic hydrocarbon solvent, or the like which is a relatively low hygroscopic solvent, is used to prevent polyimide precipitation due to moisture absorption during coating. They can be used alone or in combination.
• the amount of the siloxane-free diamine used is preferably such that the number of moles combined with the siloxane diamine is 1 mol of all tetracarboxylic dianhydrides in order to ensure a molecular weight for obtaining a protective layer having sufficient mechanical properties. Is in an amount of 0.1 to 0.9 mol, more preferably 0.3 to 0.8 mol.
• a basic catalyst such as a tertiary amine such as triethylamine, aromatic isoquinoline or pyridine, benzoic acid, An acid catalyst such as parahydroxybenzoic acid may be added.
• step (b) when an acid dianhydride or diamine component having a polar group is used, the viscosity of the siloxane polyimide resin produced by the Weiselberg effect increases and winds around the stirring rod. A phenomenon may occur.
• water be present in the reaction system. In this case, if the amount of water is too small, the risk of thickening increases, and if it is too large, the molecular weight of the polyimide may decrease. Therefore, water is added at a ratio of 0.01 to 1.1% by mass in the reaction mixture. Preferably it is present.
• the reaction temperature at the time of imidation in the step (b) varies depending on the type and amount of the solvent and reaction substrate, but if it is too low, the imidization reaction is not completed, and if it is too high, side reactions other than the imidization reaction occur. Since there is a possibility, it is preferably 150 to 220 ° C., more preferably 160 to 200 ° C.
• the reaction time is usually 0.5 to 12 hours, preferably 1 to 8 hours. Thereby, the siloxane polyimide resin with little content of cyclic dimethylsiloxane oligomer is obtained in a varnish state.
• the crosslinking agent used in the photosensitive siloxane polyimide resin composition of the present invention will be described.
• the crosslinking agent itself is polymerized and cured by heating to form a three-dimensional crosslinked structure.
• the cyclic dimethylsiloxane oligomer as an impurity can be confined in the three-dimensional structure, and the bleedout can be suppressed or prevented.
• Such a crosslinking agent examples include at least one selected from the group consisting of liquid epoxy resins, benzoxazines, and resoles, which are compatible with siloxane polyimide resins.
• a liquid epoxy resin and a benzoxazine may be used at the same time, or a liquid epoxy resin, a benzoxazine and a resole may be used at the same time.
• the polymerization of the liquid epoxy resin proceeds with the amino group remaining in the siloxane polyimide resin as an anionic polymerization starting point by heating.
• Polymerization of benzoxazines proceeds by heating to open the oxazine ring to produce a methylenium cation and a phenolic oxonium anion, and the methylenium cation proceeds by nucleophilic substitution polymerization on the benzene ring.
• the phenolic hydroxyl group proceeds by dehydration condensation polymerization of the benzene ring by heating.
• Such liquid epoxy resins and resols are preferably 1 to 100,000 mPa ⁇ s, more preferably 1 to 50,000 mPa ⁇ s so as to have good compatibility with the siloxane polyimide resin.
• the viscosity is a value measured with a B-type viscometer at 25 ° C.
• benzoxazines are usually solid at room temperature, but if the softening point is too high, the compatibility with the siloxane polyimide resin is lowered, so that those having a temperature of about 100 ° C. or less are preferable.
• liquid epoxy resin used as a crosslinking agent examples include bisphenol F type epoxy resin (for example, jER807, Japan Epoxy Resin Co., Ltd.), bisphenol A type epoxy resin (for example, jER828, Japan Epoxy Resin Co., Ltd.), glycidyl.
• examples thereof include amine type epoxy resins (for example, jER604, Japan Epoxy Resin Co., Ltd .; GAN, Nippon Kayaku Co., Ltd.), and alicyclic epoxy resins (for example, Celoxide 2021, Daicel Chemical Industries, Ltd.).
• bisphenol F type epoxy resin and bisphenol A type epoxy resin can be preferably used from the viewpoint of availability.
• benzoxazines used as a crosslinking agent include bisphenol S-type benzoxazine of the following formula (1), bisphenol F-type benzoxazine of formula (2), bisphenol A-type benzoxazine of formula (3) ( All of them are manufactured by Konishi Chemical Industry Co., Ltd.).
• bisphenol F-type benzoxazine can be preferably used from the viewpoint of availability.
• resoles used as a crosslinking agent include alkali resole resins obtained using alkali metal or alkaline earth metal hydroxides as catalysts, ammonia resole resins obtained using ammonia as a catalyst, Examples thereof include a high ortho resole resin obtained by using a divalent metal salt as a catalyst.
• alkali resole resins can be preferably used from the viewpoint of availability.
• the content of the crosslinking agent in the photosensitive siloxane polyimide resin composition of the present invention is 1 to 20 parts by mass, preferably 1 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the siloxane polyimide resin. Part by mass. If the content of the crosslinking agent is below this range, the effect of suppressing the volatilization / diffusion of the cyclic siloxane becomes insufficient, and if it exceeds, the flexibility tends to be poor and the film tends to be hard, which is not preferable.
• the benzoxazine is preferably used at a ratio of 0.5 to 10 parts by mass with respect to 1 part by mass of the liquid epoxy resin. This is because if the amount of benzoxazine is too small, the effect of suppressing the volatilization / diffusion of the cyclic siloxane is insufficient, and if it is too large, the flexibility tends to be poor and the film tends to be hard.
• the benzoxazines are preferably 0.5 to 10 parts by weight and the resols are preferably 0.5 to 1 part by weight of the liquid epoxy resin.
• the photoacid generator gives the composition the property that when the thin film of the siloxane polyimide resin composition containing it is exposed to ultraviolet rays or the like, it decomposes in the thin film to generate an acid, and the thin film can be developed with an alkali. It is used as a photosensitizer.
• Such photoacid generators include diazonium salts, diazoquinone sulfonic acid amides, diazoquinone sulfonic acid esters, diazoquinone sulfonates, nitrobenzyl esters, onium salts, halides, halogenated isocyanates, halogenated triazines, bis.
• Arylsulfonyldiazomethane, disulfone, o-quinonediazide compound and the like can be mentioned.
• o-quinonediazide compounds having an effect of suppressing water solubility in unexposed areas can be preferably used.
• o-quinonediazide compounds include 1,2-benzoquinone-2-azido-4-sulfonic acid ester or sulfonic acid amide, 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or sulfonic acid amide, Examples thereof include 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester or sulfonic acid amide.
• 1,2-benzoquinone-2-azido-4-sulfonyl chloride 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, etc.
• o-quinonediazide sulfonyl chlorides and polyhydroxy compounds or polyamine compounds can be obtained by condensation reaction in the presence of a dehydrochlorination catalyst.
• the content of the photoacid generator in the photosensitive siloxane polyimide resin composition of the present invention is 5 to 30 parts by mass, preferably 5 to 20 parts by mass with respect to 100 parts by mass of the siloxane polyimide resin. If the content of the photoacid generator is below this range, sufficient sensitivity cannot be obtained, and if it exceeds, the heat resistance of the resin composition tends to decrease, such being undesirable.
• the photosensitive siloxane polyimide resin composition of the present invention known additives such as a metal deactivator, an antifoaming agent, a rust preventive agent and an organic solvent can be blended as necessary.
• an antifoaming agent examples include a fluorine-modified siloxane antifoaming agent.
• the photosensitive siloxane polyimide resin composition of the present invention can be produced by uniformly mixing a siloxane polyimide resin, a crosslinking agent, a photosensitive agent, other additives and a solvent by a conventional method.
• thermosetting product of the photosensitive siloxane polyimide resin composition of the present invention is one in which bleeding out of the cyclic dimethylsiloxane oligomer is greatly suppressed. Therefore, it is useful as an insulating material for various electronic parts, for example, a protective layer or an interlayer insulating film of a printed wiring board.
• Such a printed wiring board is formed by applying the photosensitive siloxane polyimide resin composition of the present invention to a printed circuit board by a conventional method, drying it, and forming an active energy ray such as ultraviolet rays through the exposure mask. Irradiate and expose, remove exposed portion by alkali development using aqueous sodium hydroxide solution, pattern, then heat cure by post-bake to form protective layer, and further electroless plating such as electroless nickel plating It can be manufactured by applying electroplating as necessary.
• the manufacturing method of the printed wiring board mentioned above has the meaning of suppressing the bleed-out of cyclic dimethylsiloxane oligomer from the said protective layer of the printed wiring board which provided the protective layer which consists of siloxane polyimide resin if a viewpoint is changed. . That is, a photosensitive siloxane polyimide resin composition containing a siloxane polyimide resin obtained by imidizing tetracarboxylic dianhydride, siloxane diamine and siloxane-free diamine, a crosslinking agent, and a photoacid generator is formed into a film.
• a method of suppressing the bleed-out of cyclic dimethylsiloxane oligomer from the protective layer of a printed wiring board provided with a protective layer obtained by patterning by exposure, development and thermal curing, and a liquid epoxy as a crosslinking agent At least one member selected from the group consisting of resins, benzoxazines, and resoles is used in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the siloxane polyimide resin.
• the method is characterized by using ⁇ 30 parts by mass.
• the components of the invention of this method are as described in the photosensitive siloxane polyimide resin composition of the present invention.
• Example 1 Manufacture of siloxane polyimide resin
• a reaction vessel of a polyimide resin synthesizer equipped with a Dean-Stark trap 862.65 g (0.639 mol) of diaminosiloxane (diaminodiphenyl / dimethylsiloxane (amine equivalent 675 g / mol), product Name: X-22-9409, manufactured by Shin-Etsu Chemical Co., Ltd.) and 363.6 g (1.01 mol) of 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride (Ricacid DSDA, Shin Nippon Rika Co., Ltd .; purity 99.6%), 547 g of triglyme and 200 g of toluene were added, and the mixture was sufficiently stirred for 2 hours. Thereafter, the temperature was raised to 185 ° C., the temperature was maintained for 2 hours, and the reaction solution was stirred under reflux while collecting water with
• the obtained reaction mixture was applied onto a silicon wafer from which the oxide film was removed, dried at 100 ° C. for 10 minutes, and terminal functional groups were identified by the FT-IR transmission method. Absorption of imide carbonyl appeared in the vicinity of 1780 cm ⁇ 1 , and absorption of cyclic acid anhydride carbonyl stretching vibration was confirmed in the vicinity of 1860 cm ⁇ 1 , confirming the formation of an acid anhydride-terminated siloxane oligomer.
• the reaction mixture was allowed to cool to 80 ° C., and 101.44 g (0.361 mol) of 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone (BSDA, manufactured by Konishi Chemical Industries, Ltd .; purity 99.7%) And stirred at room temperature for 12 hours. After stirring, the temperature was raised to 185 ° C., and the mixture was heated and stirred at that temperature for 2 hours. Then, it cooled to room temperature and obtained the varnish of the diphenylsilylene unit containing siloxane polyimide resin.
• BSDA 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone
• Comparative Example 3 Implemented except that 5 phr of epoxy silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) and 0.5 phr of antifoaming agent (FA-600, Shin-Etsu Chemical Co., Ltd.) are used as cross-linking agents.
• a siloxane polyimide resin was obtained, and a photosensitive siloxane polyimide resin composition was further obtained.
• Comparative Example 4 As Example 1, except that 5 phr of amino epoxy resin (YH-434, Toto Kasei Co., Ltd.) and 0.5 phr of antifoaming agent (FA-600, Shin-Etsu Chemical Co., Ltd.) are used as the cross-linking agent. In addition, a siloxane polyimide resin was obtained, and a photosensitive siloxane polyimide resin composition was obtained.
• amino epoxy resin YH-434, Toto Kasei Co., Ltd.
• antifoaming agent F-600, Shin-Etsu Chemical Co., Ltd.
• Comparative Example 5 As Example 1, except that 5 phr of solid epoxy resin (jER1007FS, Japan Epoxy Resin Co., Ltd.) and 0.5 phr of antifoaming agent (FA-600, Shin-Etsu Chemical Co., Ltd.) are used as the crosslinking agent. In addition, a siloxane polyimide resin was obtained, and a photosensitive siloxane polyimide resin composition was obtained.
• solid epoxy resin jER1007FS, Japan Epoxy Resin Co., Ltd.
• antifoaming agent FA-600, Shin-Etsu Chemical Co., Ltd.
• the photosensitive siloxane polyimide resin composition of Example 1 or Comparative Examples 1 and 2 was applied on a copper foil using a bar coater so as to have a thickness of 10 ⁇ m after drying, and dried at 80 ° C. for 10 minutes.
• the obtained laminate was immersed in a 3% by weight aqueous solution of sodium hydroxide at 40 ° C. for 60 seconds, then washed with 30 ° C. water for 60 seconds, washed with a 10% by weight aqueous solution of dilute sulfuric acid at room temperature for 10 seconds, and And washed with distilled water at room temperature for 120 seconds.
• a sample with a width of 4 mm and a length of 50 mm is cut out from the obtained printed wiring board, and volatile components are purged from the sample by heating at 260 ° C. for 15 minutes under a flow of helium gas at a flow rate of 50 ml / min.
• the volatile components were trapped in a Tenax-TA collection tube at -20 ° C.
• the trapped components were vaporized in a helium gas stream under predetermined conditions, and the helium gas was introduced into a GC-MS apparatus (JAS100, JAI), and the bleedout amount of the cyclic dimethylsiloxane oligomer was quantified.
• Table 1 The obtained results are shown in Table 1.
• Examples 2 to 9 and Comparative Example 6 Examples 2 to 9 and Comparative Example 6 (an example in which no crosslinking agent was used) were performed in order to examine the influence of the amount of the crosslinking agent added.
• siloxane polyimide resin was produced in the same manner as in Example 1.
• the photosensitive siloxane polyimide resin composition of Example 1 using a siloxane polyimide resin having a diphenylsilylene unit as a siloxane polyimide resin and having a protective layer having a three-dimensional cross-linking structure with a cross-linking agent. It can be seen that the bleed-out of the cyclic dimethylsiloxane oligomer is suppressed in the evaluation substrate using.
• the siloxane polyimide resin which has a diphenylsilylene unit was used as a siloxane polyimide resin
• the evaluation board using the photosensitive siloxane polyimide resin composition of the comparative example 1 provided with the protective layer which does not have a three-dimensional crosslinked structure The amount of the cyclic dimethylsiloxane oligomer that bleeds out is greatly increased as compared with the case of Example 1.
• substrate for evaluation using the photosensitive siloxane polyimide resin composition of the comparative example 2 provided with the protective layer using the siloxane polyimide resin which does not have a diphenylsilylene unit as a siloxane polyimide resin has a crosslinked structure.
• the bleedout amount of the cyclic dimethylsiloxane oligomer is greatly increased as compared with the case of Example 1.
• Comparative Example 6 containing an antifoaming agent and Examples 2 to 9 are compared, it can be seen from Table 1 that Comparative Example 2 using a cross-linking agent compared to Comparative Example 6 using no cross-linking agent. It can be seen that in the cases of ⁇ 9, the bleedout amount of the cyclic dimethylsiloxane oligomer is suppressed. In Example 9 where the amount of the crosslinking agent is the largest, it can be seen that the amount of bleed-out of the total siloxane is the smallest.
• the photosensitive siloxane polyimide resin composition of the present invention is sufficient to cause the cyclic dimethylsiloxane oligomer as an impurity to bleed out from a thin protective layer obtained by forming a film on a printed wiring board, patterning, and curing. Can be suppressed. Therefore, it is useful as a protective layer for a printed wiring board.

Landscapes

• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Materials For Photolithography (AREA)
• Epoxy Resins (AREA)
• Non-Metallic Protective Coatings For Printed Circuits (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=42073320

Family Applications (1)

Country Status (4)

Cited By (4)

Families Citing this family (16)

Citations (8)

Family Cites Families (3)

• 2008
  • 2008-09-30 JP JP2008252953A patent/JP5343494B2/ja active Active
• 2009
  • 2009-08-05 CN CN2009801377695A patent/CN102165370B/zh active Active
  • 2009-08-05 WO PCT/JP2009/063885 patent/WO2010038543A1/ja not_active Ceased
  • 2009-08-17 TW TW98127563A patent/TWI394777B/zh active

Patent Citations (8)

Also Published As

Similar Documents

Legal Events