WO2012081295A1 - 新規な感光性樹脂組成物及びその利用 - Google Patents
新規な感光性樹脂組成物及びその利用 Download PDFInfo
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- WO2012081295A1 WO2012081295A1 PCT/JP2011/072612 JP2011072612W WO2012081295A1 WO 2012081295 A1 WO2012081295 A1 WO 2012081295A1 JP 2011072612 W JP2011072612 W JP 2011072612W WO 2012081295 A1 WO2012081295 A1 WO 2012081295A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0041—Photosensitive materials providing an etching agent upon exposure
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0296—Conductive pattern lay-out details not covered by sub groups H05K1/02 - H05K1/0295
- H05K1/0298—Multilayer circuits
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- 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
Definitions
- This invention is excellent in tack-free property after drying of the coating film and has photosensitivity so that it can be finely processed.
- the resulting cured film is excellent in flexibility, flame retardancy and electrical insulation reliability, and is a substrate after curing.
- the present invention relates to a photosensitive resin composition, a resin film, an insulating film, and a printed wiring board with an insulating film.
- Polyimide resins are widely used in electrical and electronic applications because of their excellent heat resistance, electrical insulation reliability, chemical resistance, and mechanical properties.
- polyimide resin forms insulating films and protective coatings on semiconductor devices, base materials such as flexible circuit boards and integrated circuits, surface protective materials, and further, interlayer insulating films and protective films for fine circuits. Used in cases.
- a coverlay film obtained by applying an adhesive to a molded body such as a polyimide film has been used.
- an opening is provided in advance by a method such as punching in a terminal portion of a circuit or a joint with a component, and the opening and the cover lay film are aligned.
- a method of thermocompression bonding with a hot press or the like is common.
- a solder resist or the like may be used as a surface protective material for a circuit board.
- a solder resist having a photosensitive function is preferably used when fine processing is required.
- a photosensitive solder resist a photosensitive resin composition mainly composed of acid-modified epoxy acrylate, epoxy resin, or the like is used. This photosensitive solder resist is excellent in electrical insulation reliability as an insulating material, but is bent. It is difficult to use for flexible circuit boards because the warpage of the board increases when laminated on a thin and flexible circuit board such as a flexible circuit board due to poor mechanical properties such as properties and large cure shrinkage. .
- this photosensitive solder resist is poor in flame retardancy, and when a flame retardant is added for the purpose of imparting flame retardancy, contact failure and process due to deterioration of physical properties or bleeding out of the cured film from the cured film. Contamination was a problem.
- a photosensitive resin composition has been proposed that is excellent in flexibility and solder heat resistance, has good sensitivity and resolution, and can easily form a fine pattern of a heat-resistant protective film (see, for example, Patent Document 1). ).
- one of the important characteristics when carrying out photosensitive solder resist processing is that the surface of the coating film is less sticky (tack-free) after the coating film is applied and the solvent is dried.
- the good tack-free property prevents the photomask from sticking to the coating film when it is irradiated with UV light by placing the photomask necessary for fine pattern formation on the coating surface. This is an important characteristic for preventing the circuit boards from sticking to each other when the circuit boards with the coating film are stacked.
- Japanese Patent Publication Japanese Patent Laid-Open No. 2000-241969 (published on September 8, 2000)” Japanese Patent Publication “JP 9-137109 A (published May 27, 1997)”
- the photosensitive resin composition described in Patent Document 1 contains a urethane compound having an ethylenically unsaturated bond containing a flexible skeleton and an aromatic phosphate, sensitivity, resolution, folding resistance, Although it is excellent in flame retardancy, it has a large stickiness after drying of the coating film and is inferior in tack-free property. Therefore, there are problems such as contamination of a photomask during ultraviolet irradiation and difficulty in sticking when circuit boards are stacked.
- solder resist ink composition described in Patent Document 2 is excellent in the tack-free property of the coating film due to the dispersion of polymer fine particles having a glass transition temperature of 20 ° C. or lower, and the occurrence of cracks and volume shrinkage.
- the solder resist ink composition described in Patent Document 2 is excellent in the tack-free property of the coating film due to the dispersion of polymer fine particles having a glass transition temperature of 20 ° C. or lower, and the occurrence of cracks and volume shrinkage.
- bending resistance and flame retardancy are poor and warpage is large.
- the present inventors have at least (A) a binder polymer, (B) a crosslinked polymer particle containing a urethane bond in the molecule, (C) a thermosetting resin, and (D) light.
- a photosensitive resin composition characterized by containing a polymerization initiator is superior in tack-free property after drying of the coating film and has photosensitivity so that it can be finely processed, and the resulting cured film is flexible and difficult.
- the present invention comprises at least (A) a binder polymer, (B) a crosslinked polymer particle containing a urethane bond in the molecule, (C) a thermosetting resin, and (D) a photopolymerization initiator.
- the photosensitive resin composition comprises at least (A) a binder polymer, (B) a crosslinked polymer particle containing a urethane bond in the molecule, (C) a thermosetting resin, and (D) a photopolymerization initiator.
- the photosensitive resin composition of the present invention comprises at least (A) a binder polymer, (B) a crosslinked polymer particle containing a urethane bond in the molecule, (C) a thermosetting resin, and (D) photopolymerization. Since it has a structure containing an initiator, the photosensitive resin composition of the present invention is excellent in tack-free property after drying the coating film and has photosensitivity, and thus can be finely processed. Excellent flexibility, flame retardancy, and electrical insulation reliability, and less warped substrate after curing. Therefore, the photosensitive resin composition of the present invention can be used for protective films of various circuit boards and exhibits excellent effects.
- the photosensitive resin composition of the present invention includes at least (A) a binder polymer, (B) crosslinked polymer particles containing a urethane bond in the molecule, (C) a thermosetting resin, ( D) A photosensitive resin composition containing a photopolymerization initiator.
- the photosensitive resin composition of the present invention is excellent in various properties, but this is presumed to be due to the following reasons.
- the crosslinked polymer particles containing a urethane bond in the molecule as the component (B) are excellent in tack-free property after drying the coating film because they serve to provide unevenness on the coating film surface, and are soft because they contain a urethane bond. It does not cause a decrease in flexibility of the cured film obtained by curing the photosensitive resin composition.
- (B) component has a crosslinked structure, it is excellent in heat resistance and chemical resistance.
- the cured film has a lower flexibility necessary to withstand repeated bending, but combining the components (A) and (B).
- the cured film is very soft and has excellent folding resistance. This is presumably because the (A) component constituting the cured film matrix penetrates into the (B) component, so that strong adhesiveness can be obtained at the interface between the (A) component and the (B) component. is doing.
- A binder polymer, (A1) resin containing urethane bond in molecule, (A2) resin containing imide group in molecule, (A3) resin containing (meth) acryloyl group in molecule, ( A4) Resin containing a carboxyl group in the molecule, (B) Crosslinked polymer particles containing a urethane bond in the molecule, (C) Thermosetting resin, (D) Photopolymerization initiator, (E) Phosphorus flame retardant The mixing method of the other components and the photosensitive resin composition will be described.
- the (A) binder polymer of the present invention is a polymer that is soluble in an organic solvent and has a weight average molecular weight of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol.
- the organic solvent is not particularly limited.
- sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide
- formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide
- acetamide solvents such as N, N-diethylacetamide
- pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, hexamethylphosphoramide, and ⁇ -butyrolactone.
- these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.
- the solubility of the organic solvent which is an index of solubility in the organic solvent, can be measured as parts by weight of the base polymer dissolved in 100 parts by weight of the organic solvent, and the base polymer dissolved in 100 parts by weight of the organic solvent. If it is 5 parts by weight or more, it can be made soluble in an organic solvent.
- the organic solvent solubility measurement method is not particularly limited. For example, 5 parts by weight of the base polymer is added to 100 parts by weight of the organic solvent, stirred at 40 ° C. for 1 hour, cooled to room temperature, and left for 24 hours or longer. It can be measured by a method for confirming that the solution is uniform without generation of insoluble matter and precipitates.
- the weight average molecular weight of the component (A) of the present invention can be measured, for example, by the following method.
- the weight average molecular weight is 1,000 or less, flexibility and chemical resistance may decrease, and when the weight average molecular weight is 1,000,000 or more, the viscosity of the photosensitive resin composition may increase. is there.
- the polymer contained in the component (A) of the present invention is not particularly limited.
- polyurethane resin poly (meth) acrylic resin, polyvinyl resin, polystyrene resin, polyethylene resin, polypropylene resin, polyimide Resin, polyamide resin, polyacetal resin, polycarbonate resin, polyester resin, polyphenylene ether resin, polyphenylene sulfide resin, polyether sulfone resin, polyether ether ketone resin, etc.
- two or more types can be used in combination.
- (A1) when a polyurethane-based resin, which is a resin containing a urethane bond in the molecule, is contained, the flexibility and bending resistance of the cured film obtained by curing the photosensitive resin composition are improved, and the cured film This is preferable because the warpage is small.
- (A2) a polyimide resin, which is a resin containing an imide group in the molecule, is contained, the heat resistance, flame retardancy, and electrical insulation reliability of a cured film obtained by curing the photosensitive resin composition Is preferable.
- the resin containing a urethane bond in the molecule of the present invention contains a repeating unit containing at least one urethane bond in the molecule, and the weight average molecular weight is 1,000 or more in terms of polyethylene glycol, 1, 000,000 or less polymer.
- the cross-linked polymer particles as component (B) contain a urethane bond in the molecule and are oil-absorbing, thereby forming a urethane bond in the molecule constituting the coating film matrix.
- the resin having a good affinity with the resin and a resin containing a urethane bond in the molecule from the surface of the crosslinked polymer particles soaks into the interior, and thus a strong matrix adhesion can be obtained.
- the resin (A1) containing a urethane bond in the molecule of the present invention can be obtained by any reaction.
- the following general formula (1) the following general formula (1)
- R 1 and X 1 each independently represent a divalent organic group, and n represents an integer of 1 or more
- the diol compound of the present invention is not particularly limited as long as it has the above structure.
- Polyoxyls such as diols, alkylene diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and random copolymers of tetramethylene glycol and neopentyl glycol Ring-
- the diisocyanate compound of the present invention is not particularly limited as long as it has the above structure.
- the photosensitive resin composition is excellent in photosensitivity.
- the resin containing a urethane bond in the molecule of the present invention can be synthesized using a plurality of types of diol compounds and a plurality of types of diisocyanate compounds. In this case, of course, one may be one type of compound and the other may be a plurality of types of compounds.
- the reaction with the diisocyanate compound may be performed after mixing two or more types of diol compounds, or each diol compound and diisocyanate compound may be reacted separately. Moreover, after making a diol compound and a diisocyanate compound react, you may make the obtained terminal isocyanate compound react with another diol compound, and also make this react with a diisocyanate compound. The same applies when two or more types of diisocyanate compounds are used. In this way, a resin containing a urethane bond in the desired (A1) molecule can be produced.
- the reaction temperature between the diol compound and the diisocyanate compound is preferably 40 to 160 ° C., more preferably 60 to 150 ° C. If it is less than 40 ° C., the reaction time becomes too long. If it exceeds 160 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur.
- the reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed. If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.
- the above reaction can be carried out in the absence of a solvent, but in order to control the reaction, it is desirable to carry out the reaction in an organic solvent system.
- organic solvent used here is not specifically limited, For example, what was illustrated above can be used.
- the amount of the organic solvent used in the reaction is desirably such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5% by weight or more and 90% by weight or less.
- the solute weight concentration in the reaction solution is more preferably 10 wt% or more and 80 wt% or less. When the solution concentration is lower than 5% by weight, the polymerization reaction is unlikely to occur and the reaction rate is lowered, and a desired structural substance may not be obtained.
- the resin containing a urethane bond in the molecule (A1) of the present invention is at least one organic group selected from the group consisting of (a1) (meth) acryloyl group, (a2) carboxyl group, and (a3) imide group. It is preferable to contain.
- the (meth) acryloyl group is an acryloyl group and / or a methacryloyl group.
- the photosensitivity of the photosensitive resin composition is improved.
- the photosensitive resin composition can be cured by short-time ultraviolet irradiation.
- (a1) (meth) acryloyl group-containing (A1) resin containing a urethane bond in the molecule can be obtained by any reaction.
- a diol compound and a diisocyanate compound in addition to a diol compound and a diisocyanate compound, The following general formula (4)
- R 2 represents an m + 1 valent organic group
- R 3 represents hydrogen or an alkyl group
- m represents an integer of 1 to 3
- the compound containing a hydroxyl group and at least one (meth) acryloyl group of the present invention is not particularly limited as long as it has the above structure.
- the compound containing an isocyanate group and at least one (meth) acryloyl group of the present invention is not particularly limited as long as it has the above structure.
- a carboxyl group-containing (A1) resin containing a urethane bond in the molecule can be obtained by any reaction.
- a diol compound and a diisocyanate compound the following general formula (6)
- R 4 represents a trivalent organic group
- the compound containing two hydroxyl groups and one carboxyl group of the present invention is not particularly limited as long as it has the above structure.
- an imide group-containing (A1) resin containing a urethane bond in the molecule can be obtained by any reaction.
- a diol compound and a diisocyanate compound the following general formula (7)
- the tetracarboxylic dianhydride of the present invention is not particularly limited as long as it has the above structure.
- the resin containing an imide group in the molecule (A2) of the present invention contains a repeating unit containing at least one imide group in the molecule, and the weight average molecular weight is 1,000 or more in terms of polyethylene glycol. 1,000,000 or less polymer.
- the resin containing an imide group in the molecule (A2) of the present invention can be obtained by any reaction.
- (A3) containing the imide group (A1) containing a urethane bond in the molecule It is obtained by the same method as that for obtaining the resin to be obtained.
- the diamino compound of the present invention is not particularly limited as long as it has the above structure.
- Hydroxybiphenyl compounds 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane
- Dihydroxydiphenylmethanes such as 2,2-bis [3-amino-4-hydroxyphenyl] pro Bis [hydroxyphenyl] propanes such as 2,2-bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2 -Bis [hyhydroxyphenyl] hexafluoropropanes such as bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-
- the above reaction between the tetracarboxylic anhydride and the diamino compound can be carried out by any method, for example, by the following method.
- Method 1 A polyamic acid solution is prepared by adding and reacting a diamino compound in a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent. At this time, the total amount of diamino compound added is 0.50 to 1.50 moles per mole of tetracarboxylic dianhydride. After the reaction between the tetracarboxylic dianhydride and the diamino compound is completed, the resulting polyamic acid solution is heated to 100 ° C. or higher and 300 ° C. or lower, more preferably 150 ° C. or higher and 250 ° C. or lower to perform imidization.
- Method 2 A polyamic acid solution is prepared in the same manner as in Method 1 above. Add an imidization catalyst (preferably tertiary amines such as pyridine, picoline, isoquinoline, trimethylamine, triethylamine, tributylamine, etc.) and a dehydrating agent (acetic anhydride, etc.) to this polyamic acid solution at 60 ° C. or higher. The imidization is carried out by heating to 180 ° C. or lower.
- an imidization catalyst preferably tertiary amines such as pyridine, picoline, isoquinoline, trimethylamine, triethylamine, tributylamine, etc.
- acetic anhydride acetic anhydride, etc.
- Method 3 A polyamic acid solution is prepared in the same manner as in Method 1 above.
- the polyamic acid solution is placed in a vacuum oven heated to 100 ° C. or more and 250 ° C. or less, and imidation is performed by drawing a vacuum while heating and drying.
- the resin (A3) containing a (meth) acryloyl group in the molecule of the present invention means that the resin has at least one (meth) acryloyl group in the molecule and has a weight average molecular weight of 1,000 in terms of polyethylene glycol. As mentioned above, it is a polymer of 1,000,000 or less.
- the (A3) resin containing a (meth) acryloyl group in the molecule of the present invention can be obtained by any reaction.
- the (A1) molecule containing the (a1) (meth) acryloyl group It can be obtained by a method similar to the method for obtaining a resin containing a urethane bond therein.
- the epoxy resin of the present invention is not particularly limited.
- the bisphenol A type epoxy resin trade names jER828, jER1001, jER1002 manufactured by Japan Epoxy Resin Co., Ltd., trade names Adeka Resin EP-4100E manufactured by ADEKA Co., Ltd., Adeka Resin EP-4300E, trade names RE-310S, RE-410S manufactured by Nippon Kayaku Co., Ltd., trade names Epicron 840S, Epicron 850S, Epicron 1050, Epicron 7050, trade names Epototo YD manufactured by Toto Kasei Co., Ltd.
- Epototo YD-127 Epototo YD-128, Bisphenol F type epoxy resins are trade names of Japan Epoxy Resin Co., Ltd., jER806, jER807, and ADEKA Corporation.
- Decalesin EP-4901E Adekaresin EP-4930, Adekaresin EP-4950, trade names RE-303S, RE-304S, RE-403S, RE-404S manufactured by Nippon Kayaku Co., Ltd., trade names Epicron 830 manufactured by DIC Corporation, Epicron 835, trade names Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001, and bisphenol S-type epoxy resins manufactured by Toto Kasei Co., Ltd.
- biphenyl type epoxy resins include trade names jERYX4000, jERYL6121H, jERYL6640, jERYL6677, Nippon Kayaku Trade names NC-3000, NC-3000H, manufactured by Co., Ltd., trade names jER1256, jER4250, jER4275, manufactured by Japan Epoxy Resin Co., Ltd., and trade names, manufactured by DIC Corporation, as naphthalene-type epoxy resins.
- Cyclopentadiene type epoxy resin The product name is XD-1000 manufactured by Nippon Kayaku Co., Ltd., the product name Epicron HP-7200 manufactured by DIC Corporation, and the amine type epoxy resin includes the product names jER604 and jER630 manufactured by Japan Epoxy Resin Co., Ltd. Kasei Co., Ltd. trade names Epototo YH-434, Epototo YH-434L, Mitsubishi Gas Chemical Co., Ltd. trade names TETRAD-X, TERRAD-C, and flexible epoxy resins are trade names of Japan Epoxy Resin Co., Ltd.
- urethane-modified epoxy resins include trade names Adeka Resin EPU-6, Adeka Resin EPU-73, Adeka Resin EPU-78 manufactured by ADEKA Corporation. 11.
- Adeka Resin EP-49-20, and heterocyclic ring-containing epoxy resins include trade name TEPIC manufactured by Nissan Chemical Co., Ltd. These can be used alone or in combination of two or more.
- the above-mentioned reaction between the epoxy resin and (meth) acrylic acid can be carried out by any method.
- (meth) acrylic acid is used in the solution in which the epoxy resin is dispersed or dissolved in an organic solvent.
- a catalyst for esterification preferably trimethylamine, which is a tertiary amine, triethylamine, triphenylphosphine which is a phosphorus compound, 2-ethyl-4-methylimidazole which is an imidazole compound, etc.
- An epoxy (meth) acrylate resin solution is prepared by heating to 120 ° C. or lower and reacting. At this time, the total amount of (meth) acrylic acid added is 0.1 to 1.0 mol with respect to 1 mol of the epoxy group of the epoxy resin.
- the resin containing a carboxyl group in the molecule (A4) of the present invention contains at least one carboxyl group in the molecule, and the weight average molecular weight is 1,000 or more, 1,000,000 in terms of polyethylene glycol. 000 or less polymer.
- the resin containing a carboxyl group in the molecule (A4) of the present invention can be obtained by any reaction.
- (A2) containing a carboxyl group (A1) containing a urethane bond in the molecule It is obtained by the same method as that for obtaining the resin to be obtained.
- the reaction between the (meth) acrylic acid and the (meth) acrylic acid ester of the present invention can be performed by any method.
- (meth) acrylic acid and / or (meth) acrylic acid ester derivatives It can be obtained by reacting in a solvent in the presence of a radical polymerization initiator.
- the (meth) acrylic acid ester derivative of the present invention is not particularly limited.
- (meth) acrylic acid ester derivatives it is particularly preferable to use methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate to improve the flexibility and resistance of the cured film of the photosensitive resin composition. It is preferable from the viewpoint of chemical properties.
- radical polymerization initiator examples include azo compounds such as azobisisobutyronitrile, azobis (2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile, t- Organic peroxides such as butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, Acid value hydrogen etc. are mentioned, These can be used individually or in combination of 2 or more types.
- azo compounds such as azobisisobutyronitrile, azobis (2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile
- t- Organic peroxides such as butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-
- the amount of the radical polymerization initiator used is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer used. When the amount is less than 0.001 part by weight, the reaction hardly proceeds, and when the amount is more than 5 parts by weight, the molecular weight may be lowered.
- the amount of the solvent used in the reaction is preferably such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5 wt% or more and 90 wt% or less, and is 20 wt% or more and 70 wt% or less. More preferably.
- the solution concentration is less than 5%, the polymerization reaction hardly occurs and the reaction rate is lowered, and a desired structural substance may not be obtained.
- the solution concentration is more than 90% by weight, the reaction solution is not obtained. The viscosity may become high and the reaction may become non-uniform.
- the reaction temperature is preferably 20 to 120 ° C, more preferably 50 to 100 ° C.
- the reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed.
- the (B) crosslinked polymer particle containing a urethane bond in the molecule of the present invention is a spherical polymer having at least one urethane bond and a crosslinked structure in the molecule and having an average particle diameter of 1 to 100 ⁇ m.
- the spherical shape may be a true spherical shape or an elliptical shape.
- the average particle size is smaller than 1 ⁇ m, the viscosity and thixotropy of the photosensitive resin composition are increased, and appearance defects may occur due to foaming of the coating film during coating or insufficient leveling. If it is larger than 100 ⁇ m, the particles may be exposed at the opening when the fine pattern is formed, resulting in poor resolution.
- the average particle size of the component (B) of the present invention is preferably 1 to 50 ⁇ m, more preferably 1 to 20 ⁇ m, so that the resolution of the fine pattern, the flexibility of the resulting cured film, and the chemical resistance are excellent. Therefore, it is preferable.
- the average particle diameter of the component (B) of the present invention can be measured, for example, as a volume-based median diameter (particle diameter with respect to an integrated distribution value of 50%) by the following method.
- Equipment used LA-950V2 equivalent product manufactured by Horiba, Ltd.
- Measuring method Laser diffraction / scattering method.
- the oil absorption amount of the component (B) of the present invention can be measured, for example, as the number of ml of oil per 100 g of particles by the boiled oil method specified in JIS K 5101-13-2.
- the oil absorption amount of the component (B) is preferably 50 ml / 100 g or more because a strong adhesion to the matrix can be obtained.
- the oil absorption is smaller than 50 ml / 100 g, the penetration of the matrix component into the particles becomes insufficient and the interfacial adhesion is poor, and the flexibility of the resulting cured film may be reduced.
- the upper limit of the oil absorption amount is not particularly limited, but when the oil absorption amount is larger than 500 ml / 100 g, the viscosity of the photosensitive resin composition becomes high, and the appearance due to insufficient foaming or leveling of the coating film during coating. Defects may occur. Therefore, the oil absorption amount of the component (B) is particularly preferably 50 ml / 100 g or more and 500 ml / 100 g or less.
- the content of the component (B) of the present invention is preferably 30 to 100 parts by weight, more preferably 40 to 80 parts by weight with respect to 100 parts by weight of the component (A). It is possible to form irregularities on the surface and is excellent in tack-free properties, and since the filling effect by the component (B) is obtained, the warp of the cured film is reduced, and the flexibility that can withstand repeated bending by improving the stress relaxation effect and fracture toughness Improves. When the amount of the component (B) is less than 30 parts by weight, the tack-free property and the flexibility to withstand repeated bending may be inferior. When the amount is more than 100 parts by weight, the flame retardant or photosensitive resin composition solution is applied. The coatability at the time of processing deteriorates, and the appearance defect may occur due to foaming of the coating film at the time of coating or insufficient leveling.
- thermosetting resin of the present invention is a compound containing at least one thermosetting organic group in the molecule.
- (C) component of this invention will not be specifically limited if it is the said structure,
- the component (C) of the present invention can use a polyfunctional epoxy resin, in particular, can impart heat resistance to a cured film obtained by curing the photosensitive resin composition, This is preferable because adhesion to a conductor such as a metal foil or a circuit board can be imparted.
- the polyfunctional epoxy resin is a compound containing at least two epoxy groups in the molecule, and is not particularly limited. For example, those listed as the epoxy resin can be used.
- the photosensitive resin composition of the present invention is not particularly limited as a curing agent for the above thermosetting resin, for example, phenol novolac resin, cresol novolac resin, phenol resin such as naphthalene type phenol resin, amino resin, urea resin, Melamine, dicyandiamide and the like can be contained alone or in combination of two or more.
- the photosensitive resin composition of the present invention is not particularly limited as a curing accelerator, but examples thereof include phosphine compounds such as triphenylphosphine; tertiary amines, trimethanolamine, triethanolamine, tetraethanolamine and the like.
- phosphine compounds such as triphenylphosphine; tertiary amines, trimethanolamine, triethanolamine, tetraethanolamine and the like.
- Amine compounds such as 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole Imidazoles such as 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, etc.
- Imidazoles such as 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, etc.
- 2-Methylimidazoli Imidazolines such as 2-ethylimidazoline, 2-isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; 2,4-diamino-6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4 It is possible to contain azine-based imidazoles such as -diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine alone or in combination of two or more. It is.
- the (D) photopolymerization initiator of the present invention is a compound that is activated by energy such as UV and initiates / promotes a reaction of a radical polymerizable group.
- the component (D) of the present invention is not particularly limited as long as it has the above structure.
- the (E) phosphorus flame retardant of the present invention is a compound that contains at least one phosphorus element in the molecule and has an effect of suppressing the combustion of organic matter.
- the component (E) of the present invention is not particularly limited as long as it has the above structure.
- red phosphorus, condensed phosphate ester compounds, cyclic organic phosphorus compounds, phosphazene compounds, phosphorus-containing (meth) acrylate compounds , Phosphorus-containing epoxy compounds, phosphorus-containing polyol compounds, phosphorus-containing amine compounds, ammonium polyphosphate, melamine phosphate, phosphinate, and the like can be used alone or in combination of two or more. .
- the component (E) of the present invention can impart excellent flame retardancy to a cured film obtained by curing a photosensitive resin composition, particularly using a phosphinate.
- a photosensitive resin composition particularly using a phosphinate.
- contact failure and process contamination can be suppressed, which is preferable.
- the phosphinic acid salt of the present invention is a compound represented by the following general formula (9).
- R 5 and R 6 each independently represent a linear or branched alkyl group or aryl group having 1 to 6 carbon atoms, and M represents Mg, Ca, Al, Sb, Sn, Ge, Ti , Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and K represents a metal selected from at least one selected from the group consisting of 1 to 4).
- the phosphinic acid salt of the present invention is not particularly limited as long as it has the above structure.
- aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, bismethylethylphosphine examples thereof include zinc oxide, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanyl bismethylethylphosphinate, titanyl bisdiphenylphosphinate, and the like. These can be used alone or in combination of two or more. Of these, aluminum trisdiethylphosphinate and aluminum trismethylethylphosphinate are particularly preferable because high flame retardancy can be obtained.
- the content of the component (E) of the present invention is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the component (A). And electrical insulation reliability can be improved.
- the amount of the component (E) is less than 5 parts by weight, the flame retardancy may be inferior.
- the amount is more than 100 parts by weight, the crease resistance may be inferior or when the photosensitive resin composition solution is applied. The coatability deteriorates, and appearance defects may occur due to foaming of the coating film during coating or insufficient leveling.
- the above radical polymerizable compound is a compound containing in its molecule a radical polymerizable group that undergoes a polymerization reaction by a radical polymerization initiator.
- a resin having at least one unsaturated double bond in the molecule is preferable.
- the unsaturated double bond is preferably a (meth) acryloyl group or a vinyl group.
- the radical polymerizable compound is preferably used when the (A) binder polymer does not contain a (meth) acryloyl group.
- a radical polymerizable compound may be used.
- an aqueous development represented by an alkaline aqueous solution of the photosensitive resin composition is used. This is preferable because the solubility in the solution is improved and the development time is shortened.
- filler examples include fine inorganic fillers such as silica, mica, talc, barium sulfate, wollastonite, and calcium carbonate.
- antifoaming agent examples include acrylic compounds, vinyl compounds, and butadiene compounds.
- leveling agent examples include acrylic compounds and vinyl compounds.
- Examples of the colorant include phthalocyanine compounds, azo compounds, and carbon black.
- adhesion assistant also referred to as adhesion-imparting agent
- adhesion-imparting agent examples include silane coupling agents, triazole compounds, tetrazole compounds, and triazine compounds.
- polymerization inhibitor examples include hydroquinone and hydroquinone monomethyl ether.
- a flame retardant may be added to the photosensitive resin composition of the present invention in order to obtain a higher flame retardant effect.
- the flame retardant for example, a halogen-containing compound, a metal hydroxide, a melamine compound, or the like can be added.
- the above various additives can be used alone or in combination of two or more.
- the photosensitive resin composition of the present invention can be obtained by pulverizing and dispersing the above components (A) to (E) and other components and mixing them.
- the pulverizing / dispersing method is not particularly limited, and for example, it is performed using a general kneading apparatus such as a bead mill, a ball mill, or a three roll.
- a general kneading apparatus such as a bead mill, a ball mill, or a three roll.
- the particle size distribution of the component (B) present as fine particles is preferably uniform.
- the above components (A) to (E) and other components, and if necessary, a solvent are mixed, mixed with beads, and agitated with a predetermined device to cut off.
- fine particles can be pulverized and dispersed to be mixed.
- beads zirconia, zircon, glass, titania, etc. are used, and beads suitable for the target particle size and application may be used.
- the bead particle size is not particularly limited as long as it is suitable for the target particle size.
- the stirring speed (peripheral speed) varies depending on the apparatus, but stirring may be performed within a range of 100 to 3000 rpm. If the speed is increased, the temperature rises.
- the temperature rise is suppressed. Just do it.
- beads can be separated by filtration to obtain the photosensitive resin composition of the present invention.
- the particle diameter of the fine particles can be measured by a method using a gauge defined in JIS K 5600-2-5. Moreover, if a particle size distribution measuring apparatus is used, an average particle diameter, a particle diameter, and a particle size distribution can be measured.
- a cured film or a relief pattern is formed as follows. can do.
- the photosensitive resin composition or the photosensitive resin composition solution is applied to a substrate and dried to remove the organic solvent.
- the substrate can be applied by screen printing, curtain roll, river roll, spray coating, spin coating using a spinner, or the like.
- the coating film (preferably having a thickness of 5 to 100 ⁇ m, particularly 10 to 100 ⁇ m) is dried at 120 ° C. or less, preferably 40 to 100 ° C.
- a negative photomask is placed on the dried coating film and irradiated with actinic rays such as ultraviolet rays, visible rays, and electron beams.
- actinic rays such as ultraviolet rays, visible rays, and electron beams.
- the relief pattern can be obtained by washing out the unexposed portion with a developer using various methods such as shower, paddle, dipping or ultrasonic waves. Since the time until the pattern is exposed varies depending on the spraying pressure and flow rate of the developing device and the temperature of the etching solution, it is desirable to find the optimum device conditions as appropriate.
- This developer may contain a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, or N-methyl-2-pyrrolidone.
- alkaline compound that gives the alkaline aqueous solution include hydroxides, carbonates, hydrogen carbonates, amine compounds, and the like of alkali metals, alkaline earth metals, or ammonium ions, and specifically sodium hydroxide.
- Ropiruamin aqueous solution with compounds of other long as it exhibits basicity can also be naturally used.
- the concentration of the alkaline compound that can be suitably used in the development step of the photosensitive resin composition of the present invention is preferably 0.01 to 20% by weight, particularly preferably 0.02 to 10% by weight.
- the temperature of the developer depends on the composition of the photosensitive resin composition and the composition of the alkali developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 10 ° C. or higher and 60 ° C. or lower. It is preferable to use it.
- the relief pattern formed by the above development process is rinsed to remove unnecessary residues.
- the rinsing liquid include water and acidic aqueous solutions.
- the relief pattern obtained above is heat-treated.
- a cured film having high heat resistance can be obtained.
- the thickness of the cured film is determined in consideration of the wiring thickness and the like, but is preferably about 2 to 50 ⁇ m.
- the final curing temperature at this time is desired to be able to be cured by heating at a low temperature for the purpose of preventing oxidation of the wiring and the like and not reducing the adhesion between the wiring and the substrate.
- the curing temperature at this time is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, and particularly preferably 130 ° C. or higher and 180 ° C. or lower. If the final heating temperature is high, the wiring is oxidatively deteriorated, which is not desirable.
- the cured film formed from the photosensitive resin composition of the present invention is excellent in flexibility, flame retardancy, and electrical insulation reliability, and the warpage of the substrate after curing is small.
- the insulating film obtained from the photosensitive resin composition preferably has a thickness of about 2 to 50 ⁇ m and a resolution of at least 10 ⁇ m after photocuring, particularly a resolution of about 10 to 1000 ⁇ m.
- the insulating film obtained from the photosensitive resin composition is particularly suitable as an insulating material for a flexible substrate.
- it is used for various photo-curing wiring coating protective agents, photosensitive heat-resistant adhesives, electric wire / cable insulation coatings, and the like.
- this invention can provide the same insulating material even if it uses the resin film obtained by apply
- the present invention can also be configured as follows.
- the (A) binder polymer preferably contains (A1) a resin containing a urethane bond in the molecule.
- the resin (A1) containing a urethane bond in the molecule further comprises (a1) (meth) acryloyl group, (a2) carboxyl group, and (a3) imide group. It is preferable to contain at least one organic group selected from the group consisting of
- the (A) binder polymer preferably contains (A2) a resin containing an imide group in the molecule.
- the (A) binder polymer preferably contains (A3) a resin containing a (meth) acryloyl group in the molecule.
- the (A) binder polymer preferably contains (A4) a resin containing a carboxyl group in the molecule.
- the average particle size of the crosslinked polymer particles (B) containing a urethane bond in the molecule is preferably 1 to 20 ⁇ m.
- the oil absorption of the crosslinked polymer particles (B) containing a urethane bond in the molecule is preferably 50 ml / 100 g or more.
- the blending amount of the crosslinked polymer particles (B) containing a urethane bond in the molecule is 30 to 100 parts by weight with respect to 100 parts by weight of the (A) binder polymer. Preferably there is.
- the photosensitive resin composition according to the present invention preferably further contains (E) a phosphorus-based flame retardant.
- the (E) phosphorus flame retardant is a phosphinate.
- the amount of the (E) phosphorus flame retardant is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the (A) binder polymer.
- the (C) thermosetting resin is preferably a polyfunctional epoxy resin.
- the resin film according to the present invention is obtained by applying the above photosensitive resin composition to the surface of a substrate and then drying it.
- the insulating film according to the present invention is obtained by curing the resin film.
- the printed wiring board with an insulating film according to the present invention is formed by coating the insulating film on the printed wiring board.
- the resulting resin solution had a solid content concentration of 50%, a weight average molecular weight of 48,000, and a solid content acid value of 78 mgKOH / g.
- the solid content concentration, weight average molecular weight, and acid value were measured by the following methods.
- the obtained resin solution had a solid content concentration of 52%, a weight average molecular weight of 8,600, and a solid content acid value of 18 mgKOH / g.
- the solid content concentration, weight average molecular weight, and acid value were measured in the same manner as in Synthesis Example 1.
- the temperature was raised to 110 ° C. and heated to reflux for 5 hours.
- a resin solution containing a urethane bond, a carboxyl group and an imide group in the molecule was obtained.
- the obtained resin solution had a solid content concentration of 53%, a weight average molecular weight of 9,200, and a solid content acid value of 86 mgKOH / g.
- the solid content concentration, weight average molecular weight, and acid value were measured in the same manner as in Synthesis Example 1.
- the photosensitive resin composition was first mixed with a general stirring device with a stirring blade, and then passed twice with a three-roll mill to obtain a uniform solution.
- a general stirring device with a stirring blade
- a three-roll mill to obtain a uniform solution.
- the particle size was measured with a grindometer, all were 10 ⁇ m or less.
- the following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device.
- the photosensitive resin composition is an area of 100 mm ⁇ 100 mm so that the final dry thickness becomes 20 ⁇ m on a 25 ⁇ m polyimide film (manufactured by Kaneka Corporation: trade name 25 NPI).
- the coated film was dried at 80 ° C. for 20 minutes to produce a solvent-dried coating film.
- the method for evaluating the tack-free property of the coating film is to cut out the film with the coating film after drying the solvent into 50 mm x 30 mm strips, and the coating film surfaces overlap each other with the coating film on the inside. After applying a load of 300 g for 3 seconds, the load was removed and the state when the coating film surface was peeled off was observed.
- ⁇ There is no sticking between the coating films, and no sticking marks remain on the coating film.
- X The coating films adhered completely and cannot be peeled off.
- the bent portion was opened, and a 5 kg load was again applied for 3 seconds, and then the load was removed to completely open the cured film laminated film.
- the above operation was repeated, and the number of occurrences of cracks in the bent portion was defined as the number of bending times.
- a 100 V direct current was applied to both terminals of the test piece in an environmental test machine at 85 ° C. and 85% RH, and changes in the insulation resistance value and occurrence of migration were observed.
- ⁇ A resistance value of 10 8 or more in 1000 hours after the start of the test, and no occurrence of migration or dendrite.
- X Migration, dendrite, etc. occurred in 1000 hours after the start of the test.
- (V) Solder heat resistance By a method similar to the above item ⁇ Preparation of coating film on polyimide film>, a photosensitive resin composition having a thickness of 20 ⁇ m is formed on the surface of a polyimide film having a thickness of 75 ⁇ m (Apical 75NPI manufactured by Kaneka Corporation). A cured film laminated film was produced. The obtained cured film laminated film was floated so that the surface coated with the cured film of the photosensitive resin composition was in contact with the solder bath completely dissolved at 260 ° C., and then pulled up 10 seconds later. The operation was performed three times, and the state of the film surface was observed. ⁇ : There is no abnormality in the coating film. X: Abnormality such as swelling or peeling occurs in the coating film.
- a laminated film was produced. The obtained cured film laminated film was cut into an area of 50 mm ⁇ 50 mm and placed on a smooth table so that the coating film was on the upper surface, and the warp height of the film edge was measured.
- a schematic diagram of the measurement site is shown in FIG. The smaller the amount of warpage on the polyimide film surface, the smaller the stress on the surface of the printed wiring board and the lower the amount of warping of the printed wiring board.
- the warp amount is preferably 5 mm or less. In addition, when rounding cylindrically, it was set as x.
- Example 1 Comparative Example 1
- polymethyl methacrylate-based crosslinked polymer particles manufactured by Ganz Kasei Co., Ltd., trade name GANTZPARL GM-0801S
- the physical properties were evaluated in the same manner as in Example 1 using an oil absorption of 45 ml / 100 g). The results are listed in Table 3.
- a mixed resin solution of ethyl carbitol acetate containing 58.6% of a photocurable resin having an acid value of 90 mgKOH / g. 90 g of the obtained resin solution (5.8 g of polymer fine particles as solid content, 52.7 g of photocurable resin), 15.0 g of pentaerythritol tetraacrylate as a polyfunctional monomer, 20.0 g of ethyl carbitol acetate as a diluent, light 8.0 g of Irgacure 907 (product name manufactured by BASF Japan Ltd.) as the polymerization initiator, 20.0 g of phenol novolac type epoxy resin as the thermosetting resin, 2.0 g of dicyandiamide as the epoxy curing agent, and barium sulfate 30 as the filler 1.0 g, 1.2 g of product name Floren AC300 manufactured by Kyoeisha Chemical Co., Ltd.
- the present invention can be used for protective films of various circuit boards.
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Abstract
Description
本願発明の感光性樹脂組成物とは、少なくとも(A)バインダーポリマー、(B)分子内にウレタン結合を含有する架橋ポリマー粒子、(C)熱硬化性樹脂、(D)光重合開始剤を含有する感光性樹脂組成物である。
本願発明の(A)バインダーポリマーとは、有機溶媒に対して可溶性であり、重量平均分子量が、ポリエチレングリコール換算で1,000以上、1,000,000以下のポリマーである。
使用装置 :東ソーHLC-8220GPC相当品
カラム :東ソー TSK gel Super AWM-H(6.0mmI.D.×15cm)×2本
ガードカラム:東ソー TSK guard column Super AW-H
溶離液 :30mM LiBr+20mM H3PO4 in DMF
流速 :0.6mL/min
カラム温度 :40℃
検出条件 :RI:ポラリティ(+)、レスポンス(0.5sec)
試料濃度 :約5mg/mL
標準品 :PEG(ポリエチレングリコール)。
本願発明の分子内にウレタン結合を含有する樹脂とは、分子内に少なくとも1つのウレタン結合を含有する繰り返し単位を含有している、重量平均分子量が、ポリエチレングリコール換算で1,000以上、1,000,000以下のポリマーである。
で示されるジオール化合物と、下記一般式(2)
で示されるジイソシアネート化合物と、を反応させることにより、下記一般式(3)
で示されるウレタン結合を含有する繰り返し単位を含有する構造として得られる。
で示される、水酸基及び少なくとも1つの(メタ)アクリロイル基を含有する化合物、及び/又は、下記一般式(5)
で示される、イソシアネート基及び少なくとも1つの(メタ)アクリロイル基を含有する化合物を反応させることにより得られる。
で示される、2つの水酸基及び1つのカルボキシル基を含有する化合物を反応させることにより得られる。
で示されるテトラカルボン酸二無水物を反応させることにより得られる。
本願発明の(A2)分子内にイミド基を含有する樹脂とは、分子内に少なくとも1つのイミド基を含有する繰り返し単位を含有している、重量平均分子量が、ポリエチレングリコール換算で1,000以上、1,000,000以下のポリマーである。
で示されるジアミノ化合物を反応させることにより得られる。
本願発明の(A3)分子内に(メタ)アクリロイル基を含有する樹脂とは、分子内に少なくとも1つの(メタ)アクリロイル基を含有している、重量平均分子量が、ポリエチレングリコール換算で1,000以上、1,000,000以下のポリマーである。
本願発明の(A4)分子内にカルボキシル基を含有する樹脂とは、分子内に少なくとも1つのカルボキシル基を含有している、重量平均分子量が、ポリエチレングリコール換算で1,000以上、1,000,000以下のポリマーである。
本願発明の(B)分子内にウレタン結合を含有する架橋ポリマー粒子とは、分子内に少なくとも1つのウレタン結合及び架橋構造を有している、平均粒子径が1~100μmの球状ポリマーである。ここで、球状とは、真球状であってもよいし、楕円状であってもよい。平均粒子径が1μmよりも小さい場合は、感光性樹脂組成物の粘度やチクソ性が高くなり、塗工時の塗膜の発泡やレベリング不足による外観不良が発生する場合があり、平均粒子径が100μmよりも大きい場合は微細パターン形成時の開口部に粒子が露出し、解像性不良になる場合がある。
使用装置:株式会社堀場製作所製LA-950V2相当品
測定方式:レーザー回折/散乱式。
本願発明の(C)熱硬化性樹脂とは、分子内に少なくとも1つの熱硬化性の有機基を含有する化合物である。
本願発明の(D)光重合開始剤とは、UVなどのエネルギーによって活性化し、ラジカル重合性基の反応を開始・促進させる化合物である。
本願発明の(E)リン系難燃剤とは、分子内に少なくとも1つのリン元素を含有し、有機物の燃焼を抑制する効果を有する化合物である。
本願発明の感光性樹脂組成物には、さらに必要に応じてラジカル重合性化合物、充填剤、接着助剤、消泡剤、レベリング剤、着色剤、重合禁止剤等の各種添加剤を加えることができる。
本願発明の感光性樹脂組成物は、上記(A)~(E)成分及びその他成分を粉砕・分散させて混合し、得られることができる。粉砕・分散方法としては、特に限定されるものではないが、例えばビーズミル、ボールミル、3本ロール等の一般的な混練装置を用いて行われる。この中でも、特にビーズミルを用いて粉砕・分散させて混同した場合、微粒子として存在する(B)成分の粒度分布が均一になるため好ましい。
本願発明の感光性樹脂組成物を直接に用いて、又は、感光性樹脂組成物溶液を調製した後に、以下のようにして硬化膜又はレリーフパターンを形成することができる。先ず、上記感光性樹脂組成物、又は、感光性樹脂組成物溶液を基板に塗布し、乾燥して有機溶媒を除去する。基板への塗布はスクリ-ン印刷、カ-テンロ-ル、リバ-スロ-ル、スプレーコーティング、スピンナーを利用した回転塗布等により行うことができる。塗布膜(好ましくは厚み:5~100μm、特に10~100μm)の乾燥は120℃以下、好ましくは40~100℃で行う。
<(A)バインダーポリマー1>
攪拌機、温度計、滴下漏斗、及び窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2-ビス(2-メトキシエトキシ)エタン)100.0gを仕込み、窒素気流下で攪拌しながら80℃まで昇温した。これに、室温で予め混合しておいた、メタクリル酸12.0g(0.14モル)、メタクリル酸ベンジル28.0g(0.16モル)、メタクリル酸ブチル60.0g(0.42モル)、ラジカル重合開始剤としてアゾビスイソブチロニトリ0.5gを80℃に保温した状態で3時間かけて滴下漏斗から滴下した。滴下終了後、反応溶液を攪拌しながら90℃まで昇温し、反応溶液の温度を90℃に保ちながら更に2時間攪拌を行い反応させた。上記反応を行うことで分子内にカルボキシル基を含有する樹脂溶液を得た。得られた樹脂溶液の固形分濃度は50%、重量平均分子量は48,000、固形分の酸価は78mgKOH/gであった。尚、固形分濃度、重量平均分子量、酸価は下記の方法で測定した。
JIS K 5601-1-2に従って測定を行った。尚、乾燥条件は170℃×1時間の条件を選択した。
下記条件で測定を行った。
使用装置 :東ソーHLC-8220GPC相当品
カラム :東ソー TSK gel Super AWM-H(6.0mmI.D.×15cm)×2本
ガードカラム:東ソー TSK guard column Super AW-H
溶離液 :30mM LiBr+20mM H3PO4 in DMF
流速 :0.6mL/min
カラム温度 :40℃
検出条件 :RI:ポラリティ(+)、レスポンス(0.5sec)
試料濃度 :約5mg/mL
標準品 :PEG(ポリエチレングリコール)。
JIS K 5601-2-1に従って測定を行った。
<(A)バインダーポリマー2>
攪拌機、温度計、及び窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2-ビス(2-メトキシエトキシ)エタン)25.00gを仕込み、これに、ノルボルネンジイソシアネート5.16g(0.024モル)を仕込み、窒素気流下で攪拌しながら80℃に加温して溶解させた。この溶液に、ポリカーボネートジオール50.00g(0.025モル)(旭化成株式会社製、製品名PCDL T5652、重量平均分子量2000)をメチルトリグライム25.00gに溶解した溶液を1時間かけて添加した。この溶液を5時間80℃で加熱攪拌を行い反応させた。上記反応を行うことで分子内にウレタン結合を含有する樹脂溶液を得た。得られた樹脂溶液の固形分濃度は53%、重量平均分子量は5,600であった。尚、固形分濃度、重量平均分子量は合成例1と同様の方法で測定した。
<(A)バインダーポリマー3>
攪拌機、温度計、及び窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2-ビス(2-メトキシエトキシ)エタン)30.00gを仕込み、これに、ノルボルネンジイソシアネート10.31g(0.050モル)を仕込み、窒素気流下で攪拌しながら80℃に加温して溶解させた。この溶液に、ポリカーボネートジオール50.00g(0.025モル)(旭化成株式会社製、製品名PCDL T5652、重量平均分子量2000)及び2-ヒドロキシエチルメタクリレート6.51g(0.050モル)をメチルトリグライム30.00gに溶解した溶液を1時間かけて添加した。この溶液を5時間80℃で加熱攪拌を行い反応させた。上記反応を行うことで分子内にウレタン結合及びメタクリロイル基を含有する樹脂溶液を得た。得られた樹脂溶液の固形分濃度は53%、重量平均分子量は5,200であった。尚、固形分濃度、重量平均分子量は合成例1と同様の方法で測定した。
<(A)バインダーポリマー4>
攪拌機、温度計、及び窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2-ビス(2-メトキシエトキシ)エタン)30.00gを仕込み、これに、ノルボルネンジイソシアネート10.31g(0.050モル)を仕込み、窒素気流下で攪拌しながら80℃に加温して溶解させた。この溶液に、ポリカーボネートジオール50.00g(0.025モル)(旭化成株式会社製、製品名PCDL T5652、重量平均分子量2000)及び2,2-ビス(ヒドロキシメチル)ブタン酸3.70g(0.025モル)をメチルトリグライム30.00gに溶解した溶液を1時間かけて添加した。この溶液を5時間80℃で加熱攪拌を行い反応させた。上記反応を行うことで分子内にウレタン結合及びカルボキシル基を含有する樹脂溶液を得た。得られた樹脂溶液の固形分濃度は52%、重量平均分子量は5,600、固形分の酸価は22mgKOH/gであった。尚、固形分濃度、重量平均分子量、酸価は合成例1と同様の方法で測定した。
<(A)バインダーポリマー5>
攪拌機、温度計、及び窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2-ビス(2-メトキシエトキシ)エタン)40.00gを仕込み、これに、ノルボルネンジイソシアネート20.62g(0.100モル)を仕込み、窒素気流下で攪拌しながら80℃に加温して溶解させた。この溶液に、ポリカーボネートジオール50.00g(0.025モル)(旭化成株式会社製、製品名PCDL T5652、重量平均分子量2000)、2,2-ビス(ヒドロキシメチル)ブタン酸3.70g(0.025モル)及び2-ヒドロキシエチルメタクリレート13.02g(0.100モル)をメチルトリグライム40.00gに溶解した溶液を1時間かけて添加した。この溶液を5時間80℃で加熱攪拌を行い反応させた。上記反応を行うことで分子内にウレタン結合、カルボキシル基及び(メタ)アクリロイル基を含有する樹脂溶液を得た。得られた樹脂溶液の固形分濃度は52%、重量平均分子量は8,600、固形分の酸価は18mgKOH/gであった。尚、固形分濃度、重量平均分子量、酸価は合成例1と同様の方法で測定した。
<(A)バインダーポリマー6>
攪拌機、温度計、及び窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2-ビス(2-メトキシエトキシ)エタン)35.00gを仕込み、これに、ノルボルネンジイソシアネート10.31g(0.050モル)を仕込み、窒素気流下で攪拌しながら80℃に加温して溶解させた。この溶液に、ポリカーボネートジオール50.00g(0.025モル)(旭化成株式会社製、製品名PCDL T5652、重量平均分子量2000)をメチルトリグライム35.00gに溶解した溶液を1時間かけて添加した。この溶液を2時間80℃で加熱攪拌を行った。反応終了後、3,3’,4,4’-オキシジフタル酸二無水物(以下、ODPA)15.51g(0.050モル)を前述の反応溶液に添加した。添加後に190℃に加温して1時間反応させた。この溶液を80℃まで冷却し純水3.60g(0.200モル)を添加した。添加後に110℃まで昇温し5時間加熱還流した。上記反応を行うことで分子内にウレタン結合、カルボキシル基及びイミド基を含有する樹脂溶液を得た。得られた樹脂溶液の固形分濃度は53%、重量平均分子量は9,200、固形分の酸価は86mgKOH/gであった。尚、固形分濃度、重量平均分子量、酸価は合成例1と同様の方法で測定した。
<感光性樹脂組成物の調製>
合成例で得られた(A)バインダーポリマー、(B)分子内にウレタン結合を含有する架橋ポリマー粒子、(C)熱硬化性樹脂、(D)光重合開始剤、(E)リン系難燃剤、その他成分、及び有機溶媒を添加して感光性樹脂組成物を作製した。それぞれの構成原料の樹脂固形分での配合量及び原料の種類を表1、2に記載する。なお、表中の溶媒である1,2-ビス(2-メトキシエトキシ)エタンは上記合成した樹脂溶液に含まれる溶剤も含めた全溶剤量である。感光性樹脂組成物ははじめに一般的な攪拌翼のついた攪拌装置で混合し、その後3本ロールミルで2回パスし均一な溶液とした。グラインドメーターにて粒子径を測定したところ、いずれも10μm以下であった。混合溶液を脱泡装置で溶液中の泡を完全に脱泡して下記評価を実施した。
<2>大日精化工業株式会社製 分子内にウレタン結合を含有する架橋ポリマー粒子の製品名、吸油量55ml/100g、平均粒子径15μm
<3>日産化学株式会社製 多官能エポキシ樹脂(トリグリシジルイソシアヌレート)の製品名
<4>BASFジャパン株式会社製 光重合開始剤の製品名
<5>クラリアントジャパン株式会社製 ホスフィン酸塩の製品名
<6>日立化成工業株式会社製 EO変性ビスフェノールAジメタクリレートの製品名
<7>共栄社化学株式会社製 ブタジエン系消泡剤の製品名。
<8>根上工業株式会社製 分子内にウレタン結合を含有する架橋ポリマー粒子の製品名、吸油量120ml/100g、平均粒子径2μm
<ポリイミドフィルム上への塗膜の作製>
上記感光性樹脂組成物を、ベーカー式アプリケーターを用いて、25μmのポリイミドフィルム(株式会社カネカ製:商品名25NPI)に最終乾燥厚みが20μmになるように100mm×100mmの面積に流延・塗布し、80℃で20分乾燥した後、300mJ/cm2の積算露光量の紫外線を照射して露光した。次いで、1.0重量%の炭酸ナトリウム水溶液を30℃に加熱した溶液を用いて、1.0kgf/mm2の吐出圧で90秒スプレー現像を行った。現像後、純水で十分洗浄した後、150℃のオーブン中で30分加熱硬化させてポリイミドフィルム上に感光性樹脂組成物の硬化膜を作製した。
得られた硬化膜について、以下の項目につき評価を行った。評価結果を表3、4に記載する。
上記<ポリイミドフィルム上への塗膜の作成>の項目と同様の方法で得られた硬化膜の表面観察を行い判定した。ただし、露光は、ライン幅/スペース幅=100μm/100μmのネガ型フォトマスクを置いて露光した。
〇:ポリイミドフィルム表面に顕著な線太りや現像残渣無くライン幅/スペース幅=100/100μmの感光パターンが描けているもの。
×:ポリイミドフィルム表面にライン幅/スペース幅=100/100μmの感光パターンが描けていないもの。
上記感光性樹脂組成物を、ベーカー式アプリケーターを用いて、25μmのポリイミドフィルム(株式会社カネカ製:商品名25NPI)に最終乾燥厚みが20μmになるように100mm×100mmの面積に流延・塗布し、80℃で20分乾燥して溶媒乾燥後の塗膜を作製した。塗膜のタックフリー性の評価方法は、作製した溶媒乾燥後の塗膜付きフィルムを50mm×30mmの短冊に切り出して、塗膜を内側にして塗膜面同士を重ね合わせ、重ね合わせた部分に300gの荷重を3秒間のせた後、荷重を取り除き、塗膜面を引き剥がした時の状態を観察した。
○:塗膜同士の貼り付きがなく、塗膜に貼り付き跡も残っていない。
△:塗膜同士が少し貼り付き、塗膜に貼り付き跡が残っている。
×:塗膜同士が完全に貼り付いて引き剥がせない。
上記<ポリイミドフィルム上への塗膜の作製>の項目と同様の方法で、25μm厚みのポリイミドフィルム(株式会社カネカ製アピカル25NPI)表面に20μm厚みの感光性樹脂組成物の硬化膜積層フィルムを作製した。硬化膜積層フィルムの耐折れ性の評価方法は、硬化膜積層フィルムを50mm×10mmの短冊に切り出して、硬化膜を外側にして25mmのところで180°に折り曲げ、折り曲げ部に5kgの荷重を3秒間のせた後、荷重を取り除き、折り曲げ部の頂点を顕微鏡で観察した。顕微鏡観察後、折り曲げ部を開いて、再度5kgの荷重を3秒間乗せた後、荷重を取り除き完全に硬化膜積層フィルムを開いた。上記操作を繰り返し、折り曲げ部にクラックが発生する回数を折り曲げ回数とした。
○:折り曲げ回数5回で硬化膜にクラックが無いもの。
△:折り曲げ回数3回で硬化膜にクラックが無いもの。
×:折り曲げ1回目に硬化膜にクラックが発生するもの。
フレキシブル銅貼り積層版(電解銅箔の厚み12μm、ポリイミドフィルムは株式会社カネカ製アピカル25NPI、ポリイミド系接着剤で銅箔を接着している)上にライン幅/スペース幅=100μm/100μmの櫛形パターンを作製し、10容量%の硫酸水溶液中に1分間浸漬した後、純水で洗浄し銅箔の表面処理を行った。その後、上記<ポリイミドフィルム上への塗膜の作製>の項目と同様の方法で櫛形パターン上に20μm厚みの感光性樹脂組成物の硬化膜を作製し試験片の作成を行った。85℃、85%RHの環境試験機中で試験片の両端子部分に100Vの直流電流を印加し、絶縁抵抗値の変化やマイグレーションの発生などを観察した。
○:試験開始後、1000時間で10の8乗以上の抵抗値を示し、マイグレーション、デンドライトなどの発生が無いもの。
×:試験開始後、1000時間でマイグレーション、デンドライトなどの発生があるもの。
上記<ポリイミドフィルム上への塗膜の作製>の項目と同様の方法で、75μm厚みのポリイミドフィルム(株式会社カネカ製アピカル75NPI)表面に20μm厚みの感光性樹脂組成物の硬化膜積層フィルムを作製した。
得られた硬化膜積層フィルムを260℃で完全に溶解してある半田浴に感光性樹脂組成物の硬化膜が塗工してある面が接する様に浮かべて10秒後に引き上げた。その操作を3回行い、フィルム表面の状態を観察した。
○:塗膜に異常がない。
×:塗膜に膨れや剥がれなどの異常が発生する。
上記<ポリイミドフィルム上への塗膜の作製>の項目と同様の方法で、25μm厚みのポリイミドフィルム(株式会社カネカ製アピカル25NPI)表面に20μm厚みの感光性樹脂組成物の硬化膜積層フィルムを作製した。
得られた硬化膜積層フィルムを50mm×50mmの面積に切り出して平滑な台の上に塗布膜が上面になるように置き、フィルム端部の反り高さを測定した。測定部位の模式図を図1に示す。ポリイミドフィルム表面での反り量が少ない程、プリント配線板表面での応力が小さくなり、プリント配線板の反り量も低下することになる。反り量は5mm以下であることが好ましい。尚、筒状に丸まる場合は×とした。
プラスチック材料の燃焼性試験規格UL94VTMに従い、以下のように燃焼性試験を行った。上記<ポリイミドフィルム上への塗膜の作製>の項目と同様の方法で、25μm厚みのポリイミドフィルム(株式会社カネカ製:商品名アピカル25NPI)両面に20μm厚みの感光性樹脂組成物硬化膜積層フィルムを作製した。上記作製したサンプルを寸法:50mm幅×200mm長さ×75μm厚み(ポリイミドフィルムの厚みを含む)に切り出し、125mmの部分に標線を入れ、直径約13mmの筒状に丸め、標線よりも上の重ね合わせ部分(75mmの箇所)、及び、上部に隙間がないようにPIテープを貼り、燃焼性試験用の筒を20本用意した。そのうち10本は(1)23℃/50%相対湿度/48時間で処理し、残りの10本は(2)70℃で168時間処理後無水塩化カルシウム入りデシケーターで4時間以上冷却した。これらのサンプルの上部をクランプで止めて垂直に固定し、サンプル下部にバーナーの炎を3秒間近づけて着火する。3秒間経過したらバーナーの炎を遠ざけて、サンプルの炎や燃焼が何秒後に消えるか測定する。
○:各条件((1)、(2))につき、サンプルからバーナーの炎を遠ざけてから平均(10本の平均)で10秒以内、最高で10秒以内に炎や燃焼が停止し自己消火し、かつ、評線まで燃焼が達していないもの。
×:1本でも10秒以内に消火しないサンプルがあったり、炎が評線以上のところまで上昇して燃焼するもの。
上記電気絶縁信頼性試験後の試験片を観察し、試験片表面の微小な膨れ、銅配線上の膨れ、油状物質の染み出しなどを観察した。
○:試験開始後、1000時間で試験片表面及び銅配線上に膨れ、染み出しなどの異常が見られないもの。
×:試験開始後、1000時間で試験片表面及び銅配線上に膨れ、染み出しなどの異常が見られるもの。
実施例1で用いた分子内にウレタン結合を含有する架橋ポリマー粒子(吸油量70ml/100g)に代えて、ポリメタクリル酸メチル系架橋ポリマー粒子(ガンツ化成株式会社製、商品名ガンツパールGM-0801S、吸油量45ml/100g)を用いて実施例1と同様の方法で物性評価を行った。その結果を表3に記載する。
攪拌機、温度計、冷却管及び空気導入管付き反応容器に空気を導入させた後、ポリカーボネートジオール(ダイセル化学工業株式会社製、製品名プラクセルCD205PL、数平均分子量:500)196.80g(0.39mol)、2,2-ビス(ヒドロキシメチル)ブタン酸58.30(0.39mol)g、ジエチレングリコール37.60g(0.35mol)、1,4-シクロヘキサンジメタノールモノアクリレート148.10g(0.75mol)g、p-メトキシフェノール0.55g、ジブチル錫ジラウレート0.55g、メチルエチルケトン110.20gを仕込み、空気気流下で65℃まで均一撹拌しながら昇温した。滴下容器にトリメチルヘキサメチレンジイソシアネート305.90g(1.46mol)を仕込み、65℃で均一攪拌しながら3時間かけて反応容器に滴下した。滴下終了後、滴下容器をメチルエチルケトン76.50gを用いて洗浄し、洗浄後の溶液は反応容器にそのまま投入した。さらに均一撹拌しながら2時間保温した後、75℃に昇温し、5時間均一攪拌を行った。次いで、反応容器内にメタノール9.30gを添加し、60℃で30分均一攪拌を行った。その後メチルエチルケトンを56.40g添加し、透明な樹脂溶液を得た。上記反応を行うことで分子内にウレタン結合及びメタクリロイル基を含有する樹脂溶液を得た。得られた樹脂溶液の固形分濃度は75%、重量平均分子量は14,800であった。尚、固形分濃度、重量平均分子量は合成例1と同様の方法で測定した。得られた樹脂溶液を66.7g(固形分として50g)、ラジカル重合性化合物として2,2’-ビス(4-メタクリロキシペンタエトキシフェニル)プロパン30g、バインダー樹脂としてメタクリル酸、メタクリル酸メチル及びアクリル酸ブチルを重量比22:71:7の割合で共重合させた樹脂溶液(重量平均分子量80,000、固形分の酸価143mgKOH/g、メチルセルソルブ/トルエン=6/4(重量比)に固形分濃度40%になるように溶解させた溶液)を162.5g(固形分として65g)、光重合開始剤としてベンゾフェノン3.5g及びN,N’-テトラエチル-4,4’-ジアミノベンゾフェノン0.1g、熱硬化性樹脂としてイソシアヌレート型ヘキサメチレンジイソシアネート系イソシアネート化合物とブロック剤としてメチルエチルケトンオキシムを反応させて得られるブロック化イソシアネート化合物の75%メチルエチルケトン溶液20g(固形分として15g)、リン系難燃剤としてCR-747(大八化学工業株式会社製の製品名)40g、希釈剤としてアセトン85gを配合・攪拌して3本ロールミルにて分散させて感光性樹脂組成物とした。この感光性樹脂組成物を実施例1と同様の方法で物性評価を行った。その結果を表3に記載する。尚、上記感光性樹脂組成物には、(B)成分が含まれない。
クレゾールノボラック型エポキシ樹脂YDCN-703(東都化成株式会社製、エポキシ当量200)100.00gに、カルビトールアセテート80.00gを加え、撹拌下120℃で加熱溶解させた。60℃まで冷却した後、(メタ)アクリル酸エステル系ポリマー微粒子のエマルション(ガラス転移温度-8℃、固形分46.0%)43.48g(固形分として20.00g)を加え、撹拌下で130℃まで昇温し、水を完全に除去した。次いで、アクリル酸36.90g、塩化第二クロム六水和物0.14gおよびメチルハイドロキノン0.11gを加え、110℃で3時間反応させた。反応物の酸価が3.0mgKOH/gになり、アクリロイル基の導入が確認された。次に、テトラヒドロ無水フタル酸45.60g、エチルカルビトールアセテート29.00gおよび無水塩化リチウム0.14gを加え、100℃で3時間反応させて、(メタ)アクリル酸エステル系ポリマー微粒子を6.4%と、酸価90mgKOH/gの光硬化性樹脂を58.6%含むエチルカルビトールアセテートとの混合樹脂溶液を得た。得られた樹脂溶液を90g (固形分としてポリマー微粒子5.8g、光硬化性樹脂52.7g)、多官能モノマーとしてペンタエリスリトールテトラアクリレート15.0g、希釈剤としてエチルカルビトールアセテート20.0g、光重合開始剤としてイルガキュア907(BASFジャパン株式会社製の製品名)を8.0g、熱硬化性樹脂としてフェノールノボラック型エポキシ樹脂20.0g、エポキシ硬化剤としてジシアンジアミド2.0g、充填剤として硫酸バリウム30.0g、消泡剤として共栄社化学株式会社製の製品名フローレンAC300を1.2g、顔料としてフタロシアニングリーン0.6gを配合・攪拌して3本ロールにて分散させて感光性樹脂組成物とした。この感光性樹脂組成物を実施例1と同様の方法で物性評価を行った。その結果を表3に記載する。尚、上記感光性樹脂組成物には、(B)成分が含まれない。
2 反り量
3 平滑な台
Claims (16)
- 少なくとも
(A)バインダーポリマー
(B)分子内にウレタン結合を含有する架橋ポリマー粒子
(C)熱硬化性樹脂
(D)光重合開始剤
を含有することを特徴とする感光性樹脂組成物。 - 前記(A)バインダーポリマーが、(A1)分子内にウレタン結合を含有する樹脂を含有することを特徴とする請求項1に記載の感光性樹脂組成物。
- 前記(A1)分子内にウレタン結合を含有する樹脂が、更に下記(a1)~(a3)からなる群から選ばれる少なくとも1種の有機基を含有することを特徴とする請求項2に記載の感光性樹脂組成物。
(a1)(メタ)アクリロイル基
(a2)カルボキシル基
(a3)イミド基 - 前記(A)バインダーポリマーが、(A2)分子内にイミド基を含有する樹脂を含有することを特徴とする請求項1に記載の感光性樹脂組成物。
- 前記(A)バインダーポリマーが、(A3)分子内に(メタ)アクリロイル基を含有する樹脂を含有することを特徴とする請求項1に記載の感光性樹脂組成物。
- 前記(A)バインダーポリマーが、(A4)分子内にカルボキシル基を含有する樹脂を含有することを特徴とする請求項1に記載の感光性樹脂組成物。
- 前記(B)分子内にウレタン結合を含有する架橋ポリマー粒子の平均粒子径が、1~20μmであることを特徴とする請求項1~6の何れか1項に記載の感光性樹脂組成物。
- 前記(B)分子内にウレタン結合を含有する架橋ポリマー粒子の吸油量が、50ml/100g以上であることを特徴とする請求項1~7の何れか1項に記載の感光性樹脂組成物。
- 前記(B)分子内にウレタン結合を含有する架橋ポリマー粒子の配合量が、(A)バインダーポリマー100重量部に対して30~100重量部であることを特徴とする請求項1~8の何れか1項に記載の感光性樹脂組成物。
- 更に(E)リン系難燃剤を含有することを特徴とする請求項1~9のいずれか1項に記載の感光性樹脂組成物。
- 前記(E)リン系難燃剤が、ホスフィン酸塩であることを特徴とする請求項10に記載の感光性樹脂組成物。
- 前記(E)リン系難燃剤の配合量が、(A)バインダーポリマー100重量部に対して5~100重量部であることを特徴とする請求項10または11に記載の感光性樹脂組成物。
- 前記(C)熱硬化性樹脂が、多官能エポキシ樹脂であることを特徴とする請求項1~12のいずれか1項に記載の感光性樹脂組成物。
- 請求項1~13のいずれか1項に記載の感光性樹脂組成物を基材表面に塗布した後、乾燥して得られた樹脂フィルム。
- 請求項14に記載の樹脂フィルムを硬化させて得られる絶縁膜。
- 請求項15に記載の絶縁膜がプリント配線板に被覆された絶縁膜付きプリント配線板。
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JP2016128922A (ja) | 2016-07-14 |
JPWO2012081295A1 (ja) | 2014-05-22 |
JP5883394B2 (ja) | 2016-03-15 |
TWI507479B (zh) | 2015-11-11 |
CN103282830A (zh) | 2013-09-04 |
TW201224055A (en) | 2012-06-16 |
JP6134403B2 (ja) | 2017-05-24 |
US20130264099A1 (en) | 2013-10-10 |
KR20140005910A (ko) | 2014-01-15 |
KR101842054B1 (ko) | 2018-03-27 |
US9835942B2 (en) | 2017-12-05 |
CN103282830B (zh) | 2016-06-22 |
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