WO2013084714A1 - 黒色感光性樹脂組成物及びその利用 - Google Patents
黒色感光性樹脂組成物及びその利用 Download PDFInfo
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- WO2013084714A1 WO2013084714A1 PCT/JP2012/080052 JP2012080052W WO2013084714A1 WO 2013084714 A1 WO2013084714 A1 WO 2013084714A1 JP 2012080052 W JP2012080052 W JP 2012080052W WO 2013084714 A1 WO2013084714 A1 WO 2013084714A1
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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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
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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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
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
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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
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/05—Flexible printed circuits [FPCs]
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/16—Inspection; Monitoring; Aligning
- H05K2203/161—Using chemical substances, e.g. colored or fluorescent, for facilitating optical or visual inspection
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
Definitions
- the present invention relates to a black photosensitive resin composition and use thereof. More specifically, the present invention relates to a black photosensitive resin composition, a resin film obtained from the black photosensitive resin composition, an insulating film, and an insulating film. The present invention relates to a printed wiring board.
- 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 is used as a base material or surface protective material for flexible circuit boards and integrated circuit boards, or when an insulating film or protective coating film is formed on a semiconductor device. Used when forming a film or a protective film.
- a coverlay film obtained by applying an adhesive to a molded body such as a polyimide film is used.
- an opening is provided in advance by a method such as punching in a terminal portion of a circuit or a joint portion with a component, and after alignment, thermocompression bonding is performed by a hot press or the like. The method 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.
- the 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 has excellent electrical insulation reliability as an insulating material, it has poor mechanical properties such as flexibility and has a large cure shrinkage, so it is laminated on a thin and flexible circuit board such as a flexible circuit board. In this case, the warpage of the substrate increases. For this reason, it is difficult to use a photosensitive solder resist for a flexible circuit board.
- cover pattern films and photosensitive solder resists which are surface protection materials for circuit boards, are colored black to conceal them, thereby concealing circuit patterns and protecting confidential information contained in circuit patterns. Attempts have been made.
- Patent Document 1 For example, a black photo solder resist having sufficient blackness and excellent resolution has been proposed (see, for example, Patent Document 1).
- Patent Document 2 a black photo solder resist ink having excellent photocurability has been proposed (see, for example, Patent Document 2).
- Patent Documents 1 and 2 are all excellent in resolution, blackness, heat resistance and gold plating resistance, but have poor folding resistance, large warpage after curing, and flame retardancy. It has a problem of poor nature. Furthermore, in the reflow mounting process for component mounting, there are disadvantages that problems such as a large amount of outgas generation and a reduction in film thickness occur.
- the present inventors have at least (A) a binder polymer, (B) a thermosetting resin, (C) a flame retardant that does not substantially dissolve in an organic solvent, and (D) photopolymerization.
- An initiator (E) a black colorant having a reflective region in the infrared region, and (F) a black photosensitive resin composition containing an organic solvent, or at least (A) a binder polymer, (B) a thermosetting resin (G) spherical organic beads, (D) a photopolymerization initiator, (E) a black colorant having a reflective region in the infrared region, and (F) a black photosensitive resin composition containing an organic solvent is photosensitive.
- the present invention has been achieved. This invention can solve the said subject with the black photosensitive resin composition of the following novel structures.
- the black photosensitive resin composition according to the present invention comprises at least (A) a binder polymer, (B) a thermosetting resin, (C) a flame retardant that does not substantially dissolve in an organic solvent, and (D) a photopolymerization initiator.
- the black photosensitive resin composition according to the present invention comprises at least (A) a binder polymer, (B) a thermosetting resin, (C) a flame retardant that does not substantially dissolve in an organic solvent, (G) spherical organic beads, More preferably, it is a black photosensitive resin composition containing (D) a photopolymerization initiator, (E) a black colorant having a reflective region in the infrared region, and (F) an organic solvent.
- the (E) black colorant having a reflective region in the infrared region is preferably a metal composite oxide or an organic pigment, and the metal composite oxide is a group consisting of iron, chromium, manganese and bismuth.
- the organic pigment is more preferably a perylene compound.
- the flame retardant that does not substantially dissolve in the organic solvent (C) is more preferably at least one selected from the group consisting of the following (c1) to (c3).
- the resin film according to the present invention is obtained by applying the black photosensitive resin composition to the substrate surface 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 obtained by coating the insulating film on a printed wiring board or a flexible printed wiring board.
- the black photosensitive resin composition according to the present invention comprises at least (A) a binder polymer, (B) a thermosetting resin, (C) a flame retardant that does not substantially dissolve in an organic solvent, and (D) light.
- a composition including a polymerization initiator, (E) a black colorant having a reflective region in the infrared region, and (F) an organic solvent, or at least (A) a binder polymer, (B) a thermosetting resin, (G) Spherical organic beads, (D) a photopolymerization initiator, (E) a black colorant having a reflective region in the infrared region, and (F) an organic solvent are included.
- the black photosensitive resin composition concerning this invention has photosensitivity, fine processing is possible. Furthermore, the cured film obtained from the black photosensitive resin composition has excellent flexibility, small warpage of the substrate after curing, excellent flame retardancy and electrical insulation reliability, and generation of outgas during reflow mounting. Therefore, process contamination is reduced and the film thickness is not reduced.
- the black photosensitive resin composition according to the present invention comprises at least (A) a binder polymer, (B) a thermosetting resin, (C) a flame retardant that does not substantially dissolve in an organic solvent, (G) spherical organic beads, More preferably, (D) a photopolymerization initiator, (E) a black colorant having a reflective region in the infrared region, and (F) an organic solvent are included. Therefore, the black photosensitive resin composition according to the present invention has an excellent effect that it can be suitably used as a surface protective material for various circuit boards. Moreover, the resin film obtained from the said black photosensitive resin composition, an insulating film, and the printed wiring board with an insulating film can be provided.
- the black photosensitive resin composition according to the present invention will be described in detail below.
- the black photosensitive resin composition according to the present invention comprises at least (A) a binder polymer, (B) a thermosetting resin, (C) a flame retardant that does not substantially dissolve in an organic solvent, (D) a photopolymerization initiator, E) The black colorant which has a reflective area
- the black photosensitive resin composition according to the present invention includes at least (A) a binder polymer, (B) a thermosetting resin, (G) spherical organic beads, (D) a photopolymerization initiator, and (E) an infrared region.
- region, and the (F) organic solvent should just be included.
- the black photosensitive resin composition according to the present invention comprises at least (A) a binder polymer, (B) a thermosetting resin, (C) a flame retardant that does not substantially dissolve in an organic solvent, (G) spherical organic beads, It preferably contains (D) a photopolymerization initiator, (E) a black colorant having a reflective region in the infrared region, and (F) an organic solvent.
- the present inventors have found that the above black photosensitive resin composition is excellent in various properties, and this is presumed to be due to the following reasons.
- the problem of outgas generation and thinning during the reflow mounting process is a problem that was newly found when the present inventors diligently studied the black photosensitive resin composition.
- This problem is that, since the heating method of the reflow mounting process is an infrared heater, the surface temperature of the photosensitive resin composition layer rises to the decomposition temperature of the photosensitive resin composition due to the infrared absorption of the black colorant. It is presumed that a large amount of outgas is generated by the decomposition of the conductive resin composition, and further, the film thickness is reduced.
- component (G) by using spherical organic beads as component (G), it becomes possible to effectively form irregularities on the surface of the insulating film obtained from the black photosensitive resin composition, which is excellent in tack-free properties,
- the filling effect by the component (G) is obtained, the warpage of the insulating film obtained from the black photosensitive resin composition is reduced, and the flexibility to withstand repeated bending is improved by improving the stress relaxation effect and fracture toughness. I guess.
- the component (G) is polymer particles, it is presumed that there is little influence on the generation of outgas.
- the above property balance can be more easily obtained by using both a flame retardant that is substantially insoluble in the organic solvent as the component (C) and the spherical organic beads as the component (G).
- A a binder polymer
- B a thermosetting resin
- C a flame retardant that does not substantially dissolve in an organic solvent
- D a photopolymerization initiator
- E a black color having a reflective region in the infrared region
- the mixing method of the agent, (F) organic solvent, (G) spherical organic beads, other components, and the black photosensitive resin composition will be described.
- the (A) binder polymer in the present invention is a polymer having a weight average molecular weight of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol, which is soluble in an organic solvent.
- the organic solvent is not particularly limited, and examples thereof include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide, Examples include acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, hexamethylphosphoramide, and ⁇ -butyrolactone. Further, if necessary, these organic solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.
- sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide
- formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide
- organic solvent further include, for example, methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyethyl) ether), methyl triglyme (1,2-bis (2-methoxyethoxy).
- the solubility of the organic solvent which is an index for judging whether or not the binder polymer is soluble in the organic solvent, can be determined by measuring the weight part of the binder polymer dissolved in 100 parts by weight of the organic solvent. . If the weight part of the binder polymer dissolved with respect to 100 parts by weight of the organic solvent is 5 parts by weight or more, it can be determined that the binder polymer is soluble in the organic solvent.
- the method for measuring the solubility of the organic solvent is not particularly limited. For example, 5 parts by weight of the binder polymer is added to 100 parts by weight of the organic solvent, stirred at 40 ° C. for 1 hour, and then cooled to room temperature (23 ° C.). And leaving it for 24 hours or longer. And it is judged that a binder polymer is soluble with respect to an organic solvent by confirming that there is no generation
- the weight average molecular weight of the component (A) can be measured, for example, under the following measurement conditions.
- the cured film obtained has excellent flexibility and chemical resistance by controlling the weight average molecular weight of the component (A) within the range of 1,000 to 1,000,000 in terms of polyethylene glycol. preferable.
- the weight average molecular weight is less than 1,000, flexibility and chemical resistance may be lowered.
- the weight average molecular weight is larger than 1,000,000, the viscosity of the black photosensitive resin composition is high. There is a risk.
- a polyurethane-type resin for example, a polyurethane-type resin, a poly (meth) acrylic-type resin, a polyvinyl-type resin, a polystyrene-type resin, a polyethylene-type resin, a polypropylene-type resin, a polyimide-type resin, polyamide Resin, polyacetal resin, polycarbonate resin, polyester resin, polyphenylene ether resin, polyphenylene sulfide resin, polyethersulfone resin, or polyetheretherketone resin. More than one type can be used in combination.
- component (A) in the present invention when a polyurethane resin or a poly (meth) acrylic resin, which is a resin containing a urethane bond in the molecule, is used, it is obtained by curing the black photosensitive resin composition. It is preferable because the flexibility and crease resistance of the cured film are improved and the warp of the cured film is reduced.
- the resin containing a urethane bond in the molecule is soluble in an organic solvent, contains a repeating unit containing at least one urethane bond in the molecule, and has a weight average molecular weight in terms of polyethylene glycol. It is a polymer of 1,000 or more and 1,000,000 or less.
- the resin containing a urethane bond in the molecule 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 in the present invention is not particularly limited as long as it is a structure represented by the above general formula (1).
- the black photosensitive resin composition it is preferable because the elastic modulus of the cured film obtained by curing the product is lowered, the flexibility and the bending resistance are improved, and the warp of the cured film is reduced.
- the diisocyanate compound in the present invention is not particularly limited as long as it is a structure represented by the above general formula (2).
- the black photosensitive resin composition has excellent photosensitivity.
- the blending amount of the diol compound and the diisocyanate compound is such that the ratio of the number of hydroxyl groups to the number of isocyanate groups (isocyanate group / hydroxyl group) is 0.5 or more. , 2.0 or less, and the reaction is carried out without solvent or in an organic solvent.
- the reaction with the diisocyanate compound may be performed after mixing two or more kinds of diol compounds with each other. Each diol compound and diisocyanate compound may be reacted separately.
- the isocyanate group at the terminal of the obtained resin may be reacted with another diol compound, and the product after the reaction may be further reacted with the diisocyanate compound. Good. The same applies when two or more types of diisocyanate compounds are used. Using the method described above, a desired resin containing a urethane bond in the molecule can be produced.
- the reaction temperature between the diol compound and the diisocyanate compound is preferably 40 ° C. or higher and 160 ° C. or lower, and more preferably 60 ° C. or higher and 150 ° C. or lower. 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 between the diol compound and the diisocyanate compound can be appropriately selected depending on the scale of the batch or the reaction conditions employed.
- 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, or cobalt, or a metalloid compound.
- a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, or cobalt, or a metalloid compound.
- the reaction between the diol compound and the diisocyanate compound 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.
- an organic solvent used here For example, the organic solvent illustrated above can be used.
- the amount of the organic solvent used for the reaction between the diol compound and the diisocyanate compound is desirably an amount 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. More preferably, the solute weight concentration in the reaction solution is 10 wt% or more and 80 wt% or less.
- the solution concentration is less than 5% by weight, the polymerization reaction is difficult to occur, the reaction rate is lowered, and a desired structural substance may not be obtained.
- the solution concentration is higher than 90% by weight, the reaction solution may have a high viscosity and the reaction may become non-uniform.
- the resin containing a urethane bond in the molecule of the present invention further contains 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.
- the (a1) (meth) acryloyl group is an acryloyl group and / or a methacryloyl group.
- the photosensitivity of the black photosensitive resin composition is improved, so that the time is short. It is possible to cure by irradiation with ultraviolet rays.
- the resin containing the (a1) (meth) acryloyl group and containing a urethane bond in the molecule can be obtained by any reaction.
- the diol compound and the diisocyanate compound 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
- X 2 represents a (l + 1) -valent organic group
- X 3 represents hydrogen or an alkyl group
- l represents an integer of 1 to 3
- a compound containing at least one (meth) acryloyl group
- the compound containing a hydroxyl group and at least one (meth) acryloyl group in the present invention is not particularly limited as long as it is a structure represented by the general formula (4).
- 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, o-phenylphenol Glycidyl ether (meth) acrylate, polyethylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, 1,4-cyclohexanedimethano Rummono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2- (4-hydroxyphenyl) ethyl (meth)
- the compound containing an isocyanate group and at least one (meth) acryloyl group in the present invention is not particularly limited as long as it is a structure represented by the general formula (5).
- 2- (meth) acryloyloxyethyl examples thereof include isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, and 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, and these can be used alone or in combination of two or more.
- the resin containing the (a2) carboxyl group and containing a urethane bond in the molecule can be obtained by any reaction.
- the following general formula ( 6) in addition to the diol compound and the diisocyanate compound, the following general formula ( 6)
- R 4 represents a trivalent organic group
- the compound containing two hydroxyl groups and one carboxyl group in the present invention is not particularly limited as long as it is a structure represented by the general formula (6).
- 2,2-bis (hydroxymethyl) propionic acid 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, 2,3-dihydroxy-2-methylpropionic acid, 2,2-bis (hydroxymethyl) Butanoic acid, 2,2-bis (2-hydroxyethyl) butanoic acid, 2,2-bis (3-hydroxypropyl) butanoic acid, 2,3-dihydroxybutanoic acid, 2,4-dihydroxy-3,3-dimethyl Butanoic acid, 2,3-dihydroxyhexadecanoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydro Shi benzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid or 3,5-dihydroxybenzoic
- the black photosensitive resin composition It is preferable because of excellent photosensitivity.
- the resin containing the (a3) imide group and containing a urethane bond in the molecule can be obtained by any reaction.
- the following general formula ( 7) in addition to the diol compound and the diisocyanate compound, the following general formula ( 7)
- the tetracarboxylic dianhydride in the present invention is not particularly limited as long as it is a structure represented by the general formula (7).
- 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Pyromellitic dianhydride, 3,3 ′, 4,4′-oxydiphthalic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2, 2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3 , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, or 5- (2,5-dioxotetrahydr
- the poly (meth) acrylic resin in the present invention is a polymer that is soluble in an organic solvent, and contains a repeating unit obtained by copolymerizing (meth) acrylic acid and / or (meth) acrylic acid ester derivatives.
- the polymer has a weight average molecular weight of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol.
- (meth) acryl is methacryl and / or acrylic.
- the poly (meth) acrylic resin in the present invention can be obtained by an arbitrary reaction.
- a (meth) acrylic acid and / or a (meth) acrylic ester derivative is used as a radical polymerization initiator in a solvent. It is obtained by reacting in the presence.
- (meth) acrylic acid ester derivative for example, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid propyl, (meth) acrylic acid butyl, Isobutyl acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylic acid
- Examples include decyl, dodecyl (meth) acrylate, stearyl (meth) acrylate, and benzyl (meth) acrylate, and these can be used alone or in combination of two or more.
- (meth) acrylic acid ester derivatives in particular, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic, from the viewpoint of flexibility and chemical resistance of the cured film of the black photosensitive resin composition It is preferable to use butyl acid.
- radical polymerization initiator examples include azo compounds such as azobisisobutyronitrile, azobis (2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile, and t-butyl.
- Organic peroxides such as hydroperoxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, or di-t-butyl peroxide, persulfates such as potassium persulfate, sodium persulfate, or ammonium persulfate, Or hydrogen peroxide etc. are mentioned, These can be used individually or in combination of 2 or more types.
- the amount of the radical polymerization initiator used is preferably 0.001 part by weight or more and 5 parts by weight or less, and 0.01 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the monomer used. It is more preferable.
- the amount of the radical polymerization initiator used is less than 0.001 part by weight, the reaction hardly proceeds, and when it is more than 5 parts by weight, the molecular weight may decrease.
- the amount of solvent used in the reaction for synthesizing the poly (meth) acrylic resin is preferably an amount 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. 20% by weight or more and 70% by weight or less is more preferable.
- the solution concentration is less than 5% by weight, the polymerization reaction is difficult to occur, the reaction rate decreases, and a desired structural substance may not be obtained.
- the solution concentration is more than 90% by weight There is a possibility that the reaction solution becomes highly viscous and the reaction becomes non-uniform.
- the reaction temperature for the synthesis of the poly (meth) acrylic resin is preferably 20 ° C. or higher and 120 ° C., more preferably 50 ° C. or higher and 100 ° C. or lower.
- the reaction time for synthesizing the poly (meth) acrylic resin can be appropriately selected depending on the scale of the batch or the reaction conditions employed.
- thermosetting resin in the present invention is a compound having a structure containing at least one thermosetting organic group in the molecule.
- (B) component in this invention will not be specifically limited if it is the said structure,
- thermosetting resins as the component (B) in the present invention, in particular, a polyfunctional epoxy resin can be used to impart heat resistance to a cured film obtained by curing the black 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.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, Biphenyl type epoxy resin, phenoxy type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, dicyclopentadiene type epoxy resin, amine type epoxy resin, flexible epoxy
- Examples thereof include resins, urethane-modified epoxy resins, rubber-modified epoxy resins, chelate-modified epoxy resins, and heterocyclic-containing epoxy resins.
- Examples of the bisphenol F type epoxy resin include Japan Epoxy Resin Co., Ltd. trade name: jER806 or jER807, ADEKA Corporation trade name: Adeka Resin EP-4901E, Adeka Resin EP-4930, Adeka Resin EP-4950, Nippon Kayaku Trade name: RE-303S, RE-304S, RE-403S, or RE-404S manufactured by Yakuhin Co., Ltd.
- Product name Epicron 830 or Epicron 835 manufactured by DIC Corporation, Trade name: Epototo manufactured by Toto Kasei Co., Ltd. YDF-170, Epototo YDF-175S, or Epototo YDF-2001.
- Examples of the bisphenol S-type epoxy resin include trade name: Epicron EXA-1514 manufactured by DIC Corporation.
- As the hydrogenated bisphenol A type epoxy resin trade names of Japan Epoxy Resin Co., Ltd .: jERYX8000, jERYX8034, or jERYL7170, trade names of ADEKA Corporation: Adeka Resin EP-4080E, trade names of DIC Corporation: Epicron EXA-7015, trade name: Epototo YD-3000 or Epototo YD-4000D manufactured by Toto Kasei Co., Ltd.
- Examples of the biphenyl type epoxy resin include trade names manufactured by Japan Epoxy Resins Co., Ltd .: jERYX4000, jERYL6121H, jERYL6640, or jERYL6677, and trade names of Nippon Kayaku Co., Ltd .: NC-3000 or NC-3000H.
- phenoxy type epoxy resin the brand name: jER1256, jER4250, or jER4275 by Japan Epoxy Resin Co., Ltd. is mentioned.
- Examples of the naphthalene type epoxy resin include DIC Corporation trade names: Epicron HP-4032, Epicron HP-4700, or Epicron HP-4200, and Nippon Kayaku Co., Ltd. trade names: NC-7000L.
- Examples of the phenol novolac type epoxy resin include Japan Epoxy Resin Co., Ltd. trade name: jER152 or jER154, Nippon Kayaku Co., Ltd. trade name: EPPN-201-L, DIC Corporation trade name: Epicron N -740, or Epicron N-770, trade name: Epototo YDPN-638 manufactured by Tohto Kasei Co., Ltd.
- Examples of the cresol novolac type epoxy resin include Nippon Kayaku Co., Ltd. trade names: EOCN-1020, EOCN-102S, EOCN-103S, or EOCN-104S, DIC Corporation trade names: Epicron N-660, Epicron N-670, Epicron N-680, or Epicron N-695.
- Examples of the trisphenolmethane type epoxy resin include Nippon Kayaku Co., Ltd. trade names: EPPN-501H, EPPN-501HY, or EPPN-502H.
- Examples of the dicyclopentadiene type epoxy resin include Nippon Kayaku Co., Ltd. trade name: XD-1000, and DIC Corporation trade name: Epicron HP-7200.
- Examples of the amine type epoxy resin include Japan Epoxy Resin Co., Ltd. trade name: jER604 or jER630, Toto Kasei Co., Ltd. trade name: Epototo YH-434 or Epototo YH-434L, Mitsubishi Gas Chemical Co., Ltd. Name: TETRAD-X or TERRAD-C.
- Examples of the flexible epoxy resin include trade names of Japan Epoxy Resin Co., Ltd .: jER871, jER872, jERYL7175, or jERYL7217, trade names of DIC Corporation: Epicron EXA-4850.
- Examples of the urethane-modified epoxy resin include Adeka Resin EPU-6, Adeka Resin EPU-73, and Adeka Resin EPU-78-11 manufactured by ADEKA Corporation.
- Examples of the rubber-modified epoxy resin include Adeka Resin EPR-4023, Adeka Resin EPR-4026, and Adeka Resin EPR-1309 manufactured by ADEKA Corporation.
- Examples of the chelate-modified epoxy resin include trade name: Adeka Resin EP-49-10 or Adeka Resin EP-49-20 manufactured by ADEKA Corporation.
- Examples of the heterocyclic ring-containing epoxy resin include trade name: TEPIC (triglycidyl isocyanurate) manufactured by Nissan Chemical Co., Ltd.
- thermosetting resin contained in the black photosensitive resin composition in this invention
- phenol resins such as a phenol novolak resin, a cresol novolak resin, or a naphthalene type phenol resin
- phosphine type compounds such as a triphenylphosphine
- Tertiary amine type Trimethanol Amine compounds such as amine, triethanolamine or tetraethanolamine
- borate compounds such as 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate
- imidazole, 2-ethyl Imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, or 2-Phenyl-4-methyl Imidazoles such as dazole; 2-methylimidazoline, 2-ethylimidazoline, 2-is
- the content of the component (B) in the present invention is preferably 1 part by weight or more and 100 parts by weight or less, more preferably 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the component (A). Good. Thereby, the cured film obtained by hardening a black photosensitive resin composition is excellent in electrical insulation reliability, heat resistance, and bending resistance. When the component (B) is less than 1 part by weight, the electrical insulation reliability and heat resistance may be inferior, and when it is more than 100 parts by weight, the folding resistance may be inferior.
- the flame retardant that does not substantially dissolve in the organic solvent (C) in the present invention is a compound that does not dissolve in the organic solvent, exists as a solid at room temperature (23 ° C.), and has an effect of suppressing the combustion of organic matter.
- the organic solvent here means the organic solvent which is the component (F) in the present invention. Therefore, the flame retardant that does not substantially dissolve in the organic solvent (C) in the present invention refers to a flame retardant that does not substantially dissolve in the component (F) constituting the black photosensitive resin composition in the present invention.
- being substantially insoluble in an organic solvent means not dissolving in an organic solvent at all, or may be dissolved in a range that does not impair the effects of the present invention.
- the range not impairing the expression of the effect of the present invention means that the weight of the component (C) dissolved in 100 parts by weight of the organic solvent at room temperature (23 ° C.) is less than 0.1 parts by weight. Therefore, the flame retardant that does not substantially dissolve in the organic solvent (C) refers to a flame retardant having a dissolution amount of less than 0.1 parts by weight with respect to 100 parts by weight of the organic solvent at room temperature.
- the organic solvent is not particularly limited, and for example, the organic solvents exemplified above can be used.
- the method for measuring the weight part of the component (C) dissolved in 100 parts by weight of the organic solvent at room temperature is not particularly limited.
- 1 part by weight of the component (C) is added to 100 parts by weight of the organic solvent.
- the mixture was stirred at 40 ° C. for 1 hour, cooled to room temperature (23 ° C.), allowed to stand for 24 hours or longer, and then filtered under reduced pressure using a PTFE membrane filter having a pore size of 0.45 ⁇ m.
- the filter is washed three times, and the filter is dried at 60 ° C. under reduced pressure for 8 hours, and then the weight change of the filter is measured.
- the component (C) in the present invention is at least one selected from the group consisting of (c1) phosphorus compounds, (c2) melamine compounds, and (c3) metal hydroxides, a black photosensitive resin
- the cured film obtained by curing the composition is preferable because the flame retardancy of the cured film is improved, the generation of outgas is reduced, the electrical insulation reliability is excellent, and the warp of the cured film is reduced.
- the (c1) phosphorus compound is not particularly limited as long as it is a compound that does not substantially dissolve in an organic solvent and contains a phosphorus element.
- the (c2) melamine compound is not particularly limited as long as it is a compound that does not substantially dissolve in an organic solvent and contains a melamine structure.
- melamine polyphosphate, melamine cyanurate, nitrilotrismethylene phosphate examples include acid melamine adducts or melamine oligomer condensates, and these can be used alone or in combination of two or more.
- the (c3) metal hydroxide is not particularly limited as long as it is a metal compound that does not substantially dissolve in an organic solvent and contains crystal water.
- metal hydroxide aluminum hydroxide, magnesium hydroxide, zirconium hydroxide , Zinc hexahydroxide, zinc borate 3.5 hydrate, calcium aluminate hydrate, and the like. These can be used alone or in combination of two or more.
- the content of the component (C) in the present invention is preferably 5 parts by weight or more and 100 parts by weight or less, more preferably 10 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the component (A). Good. Thereby, the cured film obtained by hardening
- the amount of the component (C) is less than 5 parts by weight, the flame retardancy may be inferior.
- the amount is more than 100 parts by weight, the folding resistance is inferior or the black photosensitive resin composition solution is applied.
- the coating property is deteriorated, the appearance of the coating film may be deteriorated due to foaming or insufficient leveling during coating.
- the (D) photopolymerization initiator in 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) in the present invention is not particularly limited as long as it is a compound having the above-mentioned function.
- the component (D) in the present invention is an oxime ester photopolymerization initiator, particularly among the photopolymerization initiators.
- the content of the component (D) in the present invention is preferably 0.1 parts by weight or more and 10 parts by weight or less, more preferably 0.5 parts by weight or more and 10 parts by weight with respect to 100 parts by weight of the component (A). What is necessary is as follows. Thereby, the obtained black photosensitive resin composition is excellent in photosensitivity, and the amount of outgas is reduced. When the component (D) is less than 0.1 parts by weight, the photosensitivity may be inferior, and when it is more than 10 parts by weight, the amount of outgas may increase.
- the black colorant having a reflective region in the infrared region in the present invention is a material having an effect of coloring other materials black, such as a black dye or a black pigment, and is the infrared region of the present invention. It means a black colorant having a reflectance of 5% or more in a wavelength region of 800 nm to 2000 nm.
- the method for measuring the reflectance in the present invention is not particularly limited, and examples thereof include a method in which a measurement specimen is introduced into a cell and measured using a Japanese spectrophotometer U-4100.
- the black pigment having a reflective region in the infrared region is not particularly limited.
- trade name: AB820 black or AG235 black manufactured by Kawamura Chemical Co., Ltd. trade names: Black 6350, Black 6301, Black 6302, Black 6303 manufactured by Asahi Chemical Industry Co., Ltd.
- the black colorant include aniline compounds, anthraquinone compounds, and perylene compounds that are organic pigments.
- the metal composite oxide is more preferably a metal composite oxide containing iron, chromium, manganese, or bismuth from the viewpoint of insulation.
- a perylene type compound is more preferable from an insulating viewpoint.
- the content of the component (E) in the present invention is preferably 0.1 parts by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the component (A). do it.
- the cured film obtained by hardening a black photosensitive resin composition is excellent in blackness and concealment property.
- the component (E) is less than 0.1 parts by weight, the blackness and the hiding property may be inferior.
- the component is more than 30 parts by weight, the transmittance of the black photosensitive resin composition is decreased. Photosensitivity may be reduced.
- the organic solvent (F) in the present invention is not particularly limited as long as it is an organic polar solvent.
- a sulfoxide solvent such as dimethyl sulfoxide or diethyl sulfoxide, N, N-dimethylformamide, or N, N-diethylformamide Formamide solvents such as N, N-dimethylacetamide, or acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone, or N-vinyl-2-pyrrolidone, or hexa Examples thereof include methyl phosphoramide and ⁇ -butyrolactone.
- the organic polar solvent and an aromatic hydrocarbon such as xylene or toluene can be used in combination.
- examples of the organic solvent (F) in the present invention include methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyethyl) ether), methyl triglyme (1,2-bis).
- the content of the component (F) in the present invention is preferably 10 parts by weight or more and 500 parts by weight or less, more preferably 50 parts by weight or more and 300 parts by weight or less with respect to 100 parts by weight of the component (A). Good. Thereby, the black photosensitive resin composition obtained is excellent in printability.
- the amount of the component (F) is less than 10 parts by weight, foaming after printing, leveling property failure and film thickness non-uniformity may occur.
- the component is more than 500 parts by weight, film thickness shortage may occur. There is.
- the (G) spherical organic beads in the present invention are spherical polymers containing carbon, and also include elliptical polymers.
- the average particle diameter of the component (G) in the present invention can be measured as, for example, a volume-based median diameter (particle diameter with respect to an integrated distribution value of 50%) using the following measurement conditions.
- the average particle diameter of the component (G) in the present invention is not particularly limited, but in the case of 3 ⁇ m or more and 15 ⁇ m or less, black photosensitive
- the insulating film obtained from the conductive resin composition is preferable because of its excellent flexibility and chemical resistance.
- the average particle size of the component (G) in the present invention is smaller than 3 ⁇ m, unevenness is not effectively formed on the surface of the insulating film obtained from the black photosensitive resin composition, and the tack-free property may be inferior.
- the particle diameter is larger than 15 ⁇ m, the particles may be exposed in the opening when the fine pattern of the black photosensitive resin composition is formed, resulting in poor resolution.
- any method can be used.
- a flexible printed circuit board (FPC) including an insulating film obtained from the conductive resin composition is embedded with a thermosetting resin, and a cross section in the thickness direction is polished with an ion beam to obtain a cross section of the insulating film.
- FPC flexible printed circuit board
- the difference in the average atomic number of the observation region is strongly reflected in the contrast, so the region where the heavy element exists is bright (white) and the region where the light element exists is dark ( Observed black). Therefore, an organic substance composed of relatively light elements such as carbon, hydrogen, oxygen, and nitrogen, and the spherical (G) component is observed as a dark (black) circular region.
- the component (G) in the present invention is not particularly limited.
- examples of the polymethyl methacrylate-based spherical organic beads include Gantz Pearl GM-0600 or GM-0600W manufactured by Gantz Kasei Co., Ltd.
- trade names of Gantz Kasei Co., Ltd . Gantz Pearl GM-0401S, GM-0801S, GM-0807S, GM-1001-S, GM-1007S, GM-1505S- S, GMX-0610, GMX-0810, GMP-0800, GMDM-050M, GMDM-080M, GMDM-100M, or GMDM-150M, or trade names manufactured by Sekisui Plastics Co., Ltd .: Techpolymer MBX-5, MBX -8 or MBX-12.
- cross-linked polybutyl methacrylate-based spherical organic beads trade names of Gantz Kasei Co., Ltd .: Gantz Pearl GB-05S, GB-08S, GB-10S, or GB-15S, or Sekisui Chemicals Co., Ltd. Trade name: Techpolymer BM30X-5 or BM30X-8.
- the crosslinked acrylic spherical organic beads include Gantz Pearl GMP-0820 manufactured by Gantz Kasei Co., Ltd.
- acrylic copolymer-based spherical organic beads include Gantz Pearl GBM-55COS manufactured by Gantz Kasei Co., Ltd.
- Examples of the crosslinked styrene-based spherical organic beads include Gantz Kasei Co., Ltd. trade name: Ganz Pearl GS-0605 or GS-1105, or Sekisui Kasei Kogyo Co., Ltd. trade name: Techpolymer SBX-6, or SBX. -8.
- Examples of the cross-linked polyacrylic ester organic beads include trade names manufactured by Sekisui Plastics Co., Ltd .: Techpolymer ABX-8, AF10X-8, AFX-15, or ARX-15.
- Examples of the nylon spherical organic beads include Gantz Pearl GPA-550 manufactured by Ganz Kasei Co., Ltd.
- silicone-based spherical organic beads examples include Gantz Pearl SI-020, SI-030, or SI-045 manufactured by Ganz Kasei Co., Ltd.
- crosslinked silicone-based spherical organic beads examples include Gantz Pearl SIG-070 manufactured by Gantz Kasei Co., Ltd.
- Component (G) in the present invention is a reduction in warpage of the insulating film obtained from the black photosensitive resin composition, in particular, by using crosslinked spherical organic beads containing a urethane bond in the molecule among the spherical organic beads. It is preferable for improving flexibility to withstand repeated bending and improving adhesion with the component (A).
- the blending amount of the component (G) in the present invention is preferably 30 parts by weight or more and 100 parts by weight or less, more preferably 40 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the component (A). Good. Thereby, it becomes possible to effectively form irregularities on the surface of the insulating film obtained from the black photosensitive resin composition, and the tack-free property is excellent. Moreover, since the filling effect by (G) component is acquired, the curvature of the insulating film obtained from a black photosensitive resin composition falls, and the softness
- the amount of the component (G) is less than 30 parts by weight, there is a possibility that the flexibility to withstand repeated bending may be inferior, and when it is more than 100 parts by weight, the flame retardancy of the insulating film or the resin composition is applied.
- the coating property is deteriorated, the appearance of the coating film may be deteriorated due to foaming or insufficient leveling during coating.
- the black photosensitive resin composition according to the present invention may further contain a radical polymerizable compound, a filler, an adhesion aid, an antifoaming agent, a leveling agent, a polymerization inhibitor, or (C) an organic solvent, if necessary.
- a flame retardant other than a flame retardant that does not dissolve can be added.
- the above radical polymerizable compound is a compound containing in the molecule a radical polymerizable group that undergoes a polymerization reaction by a radical polymerization initiator.
- a resin having at least one unsaturated double bond as a radical polymerizable group in the molecule is more preferable.
- the unsaturated double bond is preferably a (meth) acryloyl group or a vinyl group.
- the radical polymerizable compound is preferably used when the component (A) does not contain a (meth) acryloyl group. However, it may be used when the component (A) contains a (meth) acryloyl group.
- the radical polymerizable compound is a compound containing 2 to 50 mol of EO (ethylene oxide) repeating unit in one molecule of diacrylate or dimethacrylate
- an aqueous solution represented by an alkaline aqueous solution is used. This is preferable because the solubility of the black photosensitive resin composition in the developer is improved and the development time is shortened.
- filler examples include fine (particulate) inorganic fillers such as silica, mica, talc, barium sulfate, wollastonite, or calcium carbonate.
- adhesion assistant also referred to as an adhesion-imparting agent
- examples of the adhesion assistant include silane coupling agents, triazole compounds, tetrazole compounds, and triazine compounds.
- antifoaming agent examples include acrylic compounds, vinyl compounds, and butadiene compounds.
- leveling agent examples include acrylic compounds and vinyl compounds.
- polymerization inhibitor examples include hydroquinone or hydroquinone monomethyl ether.
- Examples of flame retardants other than the flame retardant that does not substantially dissolve in the organic solvent (C) include, for example, phosphate ester compounds, halogen-containing compounds, metal hydroxides, organic phosphorus A system compound, a silicone system compound, or the like can be used.
- additional flame retardant for example, it can be used as an additive type flame retardant or a reactive type flame retardant.
- the additional flame retardant it is more preferable to use a non-halogen compound from the viewpoint of environmental pollution, and a phosphorus flame retardant is particularly preferable.
- the black photosensitive resin composition according to the present invention can be obtained by pulverizing, dispersing, and mixing the above components (A) to (G) and other components.
- 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.
- the particle diameter of the particles contained in the black photosensitive resin composition can be measured by a method using a gauge specified in JIS K 5600-2-5. Moreover, if a particle size distribution measuring apparatus is used, the average particle diameter of the particle
- a cured film or a relief pattern can be formed as follows. First, the black photosensitive resin composition or the black photosensitive resin composition solution is applied to a substrate and dried to remove the organic solvent. Application to the substrate can be performed by screen printing, curtain roll, reverse roll, spray coating, or spin coating using a spinner. Drying of the coating film (preferably thickness: 5 ⁇ m or more and 100 ⁇ m or less, particularly 10 ⁇ m or more and 100 ⁇ m or less) is performed at 120 ° C. or less, preferably 40 ° C. or more and 100 ° C. or less.
- a negative photomask is placed on the dried coating film and irradiated with actinic rays such as ultraviolet rays, visible rays, or electron beams.
- actinic rays such as ultraviolet rays, visible rays, or electron beams.
- the relief pattern can be obtained by washing the unexposed portion with a developer using various methods such as spraying, showering, paddle, dipping or ultrasonic waves. Since the time until the pattern is exposed varies depending on the spraying pressure and flow velocity of the developing device, the temperature of the etching solution, and the like, it is desirable to appropriately find the optimum apparatus conditions.
- 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 or hydrogencarbonates, amine compounds, and the like of alkali metals, alkaline earth metals, or ammonium ions.
- alkaline compound examples include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide. Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, or triisopropylamine Of course, other compounds can be used as long as the aqueous solution exhibits basicity.
- the concentration of the alkaline compound in the aqueous alkaline solution that can be suitably used in the development step of the black photosensitive resin composition is 0.01% by weight or more and 20% by weight or less, particularly 0.02% by weight or more and 10% by weight.
- the temperature of the developer may be appropriately set according to the composition of the black photosensitive resin composition or the composition of the developer, and is generally 0 ° C. or higher, 80 ° C. or lower, more generally 10 ° C. or higher, It is preferable to make it 60 degrees C or less.
- the relief pattern formed by the above development process is washed to remove unnecessary residues.
- the cleaning liquid include water or an acidic aqueous solution.
- a cured film rich in heat resistance can be obtained by performing a heat treatment and reacting the reactive groups remaining in the molecular structure of the black photosensitive resin composition.
- the thickness of the cured film is determined in consideration of the thickness of the wiring and the like, but is preferably about 2 ⁇ m or more and 50 ⁇ m or less.
- As the final curing temperature of the above heat treatment a temperature that can be cured by heating at a lower temperature is desired for the purpose of preventing the oxidation of the wiring and the like and not reducing the adhesion between the wiring and the substrate. .
- the curing temperature in the heat treatment 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.
- the curing temperature is higher than 250 ° C., it is not desirable because the oxidation deterioration of the wiring proceeds.
- the cured film formed from the black photosensitive resin composition according to the present invention has excellent concealability, excellent flexibility, and small warpage of the substrate after curing.
- the insulating film obtained from the black photosensitive resin composition preferably has a thickness of about 2 ⁇ m to 50 ⁇ m, and has a resolution of at least 10 ⁇ m after photocuring, particularly about 10 ⁇ m to 1000 ⁇ m. It has the resolving power of For this reason, the insulating film obtained from a black photosensitive resin composition is especially suitable as an insulating material of a flexible circuit board. Further, 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 provides the same insulating material even if it uses the resin film obtained by apply
- 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.
- polycarbonate diol 50.00 g (0.025 mol) manufactured by Asahi Kasei Corporation, trade name: PCDL T5652, weight average molecular weight: 2,000
- 2-hydroxyethyl methacrylate 6.51 g (0.050 mol) A solution of 30.00 g of methyltriglyme was dropped from the dropping funnel over 1 hour. After completion of the dropwise addition, this solution was reacted by heating and stirring at 80 ° C. for 5 hours. By performing the above reaction, a resin solution containing a urethane bond and a methacryloyl group in the molecule was obtained. The resulting resin solution had a solid content concentration of 53% and a weight average molecular weight of 5,200. The solid content concentration and the weight average molecular weight were measured in the same manner as in Synthesis Example 1.
- the obtained resin solution had a solid content concentration of 52%, a weight average molecular weight of 5,600, and a solid content acid value of 22 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 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.
- This solution was cooled to 80 ° C., and 3.60 g (0.200 mol) of pure water was added. After the addition, 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.
- (F) 1,2-bis (2-methoxyethoxy) ethane which is an organic solvent, is the total amount of solvent including the solvent contained in the synthesized resin solution.
- the black photosensitive resin composition was first mixed with a stirrer equipped with a general stirring blade, and then passed twice through a three-roll mill to obtain a uniform solution.
- the particle diameter of the black photosensitive resin composition in the mixed solution was measured with a grindometer, all were 10 ⁇ m or less. After the foam in the mixed solution was completely defoamed with a defoaming apparatus, the following evaluation was performed.
- ⁇ 1> to ⁇ 13> in Table 1 are as follows.
- Product name of phosphinic acid salt manufactured by Clariant Japan Co., Ltd. 100 weight of 1,2-bis (2-methoxyethoxy) ethane Solubility in parts: less than 0.01 parts by weight
- Black colorant (metal composite oxide) Product name ⁇ 7> Product name of black colorant (metal composite oxide) manufactured by Asahi Kasei Kogyo Co., Ltd.
- Product name of black colorant (organic pigment) ⁇ 10>
- Trade name of EO-modified bisphenol A dimethacrylate manufactured by Hitachi Chemical Co., Ltd. ⁇ 13> Trade name of butadiene type antifoaming agent manufactured by Kyoeisha Chemical Co., Ltd.
- the black photosensitive resin composition according to Examples 1 to 10 was subjected to a final dry thickness on the surface of a 25 ⁇ m-thick polyimide film (trade name: 25NPI manufactured by Kaneka Corporation) as a base material using a Baker type applicator.
- the film was cast and applied to an area of 100 mm ⁇ 100 mm so as to be 20 ⁇ m, dried at 80 ° C. for 20 minutes to obtain a resin film, and then exposed by irradiating with an ultraviolet ray having an accumulated exposure amount of 300 mJ / cm 2 .
- the evaluation method of the bending resistance of the cured film laminated film is that the cured film laminated film is cut into a 50 mm ⁇ 10 mm strip and bent at 180 ° at a 25 mm (center) with the cured film on the outside, After applying a 5 kg load for 3 seconds, the load was removed, and the top of the bent portion was observed with a microscope. And after observing with a microscope, the bending part was opened at 180 degrees, and after applying 5 kg of load again for 3 seconds, the load was removed and the cured film laminated film was completely opened. The above operation was repeated, and the number of occurrences of cracks in the bent portion was defined as the number of bending times.
- the number of times of folding means that the operation from the bending of the cured film laminated film to the complete opening was performed once.
- the determination result is indicated by the following “ ⁇ ”, “ ⁇ ”, or “ ⁇ ”.
- ⁇ No cracks in the cured film when the number of bendings is five.
- ⁇ No cracks in the cured film when the number of foldings is three.
- ⁇ Cracks occur in the cured film when the number of folding times is one.
- the obtained cured film laminated film (polyimide film obtained by laminating a cured film of a black photosensitive resin composition) 1 is cut into a square shape with an area of 50 mm ⁇ 50 mm and is placed on a smooth table 3.
- the cured film side was placed on the upper surface, and the warp height 2 at the end of the film was measured.
- the warp height 2 is preferably 5 mm or less.
- multilayer film 1 rounded cylindrically, it determined with "x".
- a test piece (printed wiring board with insulating film, flexible printed circuit board with insulating film) was prepared. Then, in an environmental tester at 85 ° C. and 85% RH, a DC current of 100 V was applied to both terminal portions of the test piece, and changes in the insulation resistance value and occurrence of migration were observed. The observation results are indicated by the following “ ⁇ ” or “ ⁇ ”.
- ⁇ A resistance value of 10 8 or more is exhibited after 1,000 hours have elapsed from the start of the test, and there is no occurrence of migration, dendrite, etc.
- ⁇ occurrence of migration, dendrite, etc. after 1,000 hours have elapsed from the start of the test is there.
- (V) Concealment property The test piece (cured film laminated film) obtained in the item “(iii) Warpage” is placed on a graph paper having a 1 mm square grid, and the grid is formed from above the test piece. The concealability was evaluated by a method of visual confirmation. The evaluation results are indicated by the following “ ⁇ ” or “ ⁇ ”. ⁇ : The cell is invisible. ⁇ : The cell is visible.
- the black photosensitive resin composition according to the present invention can be used as protective films for various circuit boards.
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Abstract
Description
(c1)リン系化合物
(c2)メラミン系化合物
(c3)金属水酸化物。
本発明における(A)バインダーポリマーは、有機溶媒に対して可溶性であり、その重量平均分子量が、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)。
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。
本発明における(B)熱硬化性樹脂は、分子内に少なくとも1つの熱硬化性の有機基を含有している構造の化合物である。
本発明における(C)有機溶媒に実質的に溶解しない難燃剤は、有機溶媒中に溶解せず、室温(23℃)で固体として存在し、有機物の燃焼を抑制する効果を有する化合物である。ここでの有機溶媒とは、本発明における(F)成分である有機溶媒を意味している。従って、本発明における(C)有機溶媒に実質的に溶解しない難燃剤とは、本発明における黒色感光性樹脂組成物を構成する(F)成分に実質的に溶解しない難燃剤を指す。
本発明における(D)光重合開始剤は、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。
本発明における(E)赤外線領域において反射領域を有する黒色着色剤は、黒色染料または黒色顔料等の、他の物質を黒色に着色する効果を有する物質であり、かつ本発明の赤外領域である波長領域800nm~2000nmにおける反射率が5%以上である黒色着色剤を意味する。本発明において反射率を測定する方法としては、特に限定はされないが、例えば、セルに測定検体を導入し、日本分光光度計U-4100を用いて測定する方法が挙げられる。
本発明における(F)有機溶媒としては、有機極性溶媒であれば特に限定されないが、例えば、ジメチルスルホキシド、またはジエチルスルホキシドなどのスルホキシド系溶媒、N,N-ジメチルホルムアミド、またはN,N-ジエチルホルムアミドなどのホルムアミド系溶媒、N,N-ジメチルアセトアミド、またはN,N-ジエチルアセトアミドなどのアセトアミド系溶媒、N-メチル-2-ピロリドン、またはN-ビニル-2-ピロリドンなどのピロリドン系溶媒、あるいはヘキサメチルホスホルアミド、あるいはγ-ブチロラクトン等が挙げられる。さらに必要に応じて、上記有機極性溶媒とキシレンまたはトルエン等の芳香族炭化水素とを組み合わせて用いることもできる。
本発明における(G)球状有機ビーズは、炭素を含む球状ポリマーであり、楕円状のポリマーも含まれる。
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
本発明における(G)成分の平均粒子径は、特に限定されないが、3μm以上、15μm以下の場合には、黒色感光性樹脂組成物から得られる絶縁膜の柔軟性及び耐薬品性が優れるため好ましい。本発明における(G)成分の平均粒子径が3μmよりも小さい場合は、黒色感光性樹脂組成物から得られる絶縁膜の表面に効果的に凹凸が形成されず、タックフリー性に劣るおそれがあり、粒子径が15μmよりも大きい場合は、黒色感光性樹脂組成物の微細パターン形成時の開口部に粒子が露出し、解像性不良になるおそれがある。
FPCにおいて、5mm×3mmの範囲をカッターナイフで切り出し、エポキシ系包埋樹脂及びカバーガラスを使用して、切り出したFPCの両面に保護膜層及びカバーガラス層を形成した後、絶縁膜の厚さ方向の断面をイオンビームによるクロスセクションポリッシャ加工を行う。
使用装置:日本電子株式会社製 SM-09020CP相当品
加工条件:加速電圧 6kV。
上記得られた絶縁膜の厚さ方向の断面を、走査型電子顕微鏡によって観察する。
使用装置:株式会社日立ハイテクノロジーズ製 S-3000N相当品
観察条件:加速電圧 15kV
検出器:反射電子検出(組成モード)
倍率:1000倍。
本発明にかかる黒色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、重合禁止剤、または(C)有機溶媒に実質的に溶解しない難燃剤以外の難燃剤等の、各種添加剤を加えることができる。
本発明にかかる黒色感光性樹脂組成物は、上記(A)~(G)成分及びその他の成分を粉砕・分散して混合することにより、得ることができる。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、または3本ロール等の一般的な混練装置を用いて行われる。黒色感光性樹脂組成物に含まれる粒子の粒子径は、JIS K 5600-2-5で規定されるゲージを用いる方法で測定することができる。また、粒度分布測定装置を使用すれば、黒色感光性樹脂組成物に含まれる粒子の平均粒子径、粒子径、及び粒度分布を測定することができる。
本発明にかかる黒色感光性樹脂組成物を直接的に用いて、又は、黒色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、上記黒色感光性樹脂組成物、又は、黒色感光性樹脂組成物溶液を基板に塗布し、乾燥させて有機溶媒を除去する。基板への塗布は、スクリーン印刷、カーテンロール、リバースロール、スプレーコーティング、または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(好ましくは厚さ:5μm以上、100μm以下、特に10μm以上、100μm以下)の乾燥は、120℃以下、好ましくは40℃以上、100℃以下で行う。
<(A)バインダーポリマー1>
攪拌機、温度計、滴下漏斗、冷却管、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)、及びラジカル重合開始剤としてのアゾビスイソブチロニトリル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、加熱攪拌を行い反応させた。上記反応を行うことで、分子内にカルボキシル基を含有するアクリル系樹脂溶液を得た。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、滴下漏斗、冷却管、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)を添加して、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、商品名:PCDL T5652、重量平均分子量:2,000)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時間かけて滴下漏斗から滴下した。滴下終了後、この溶液を5時間にわたって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、上記合成例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、滴下漏斗、冷却管、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)を添加して、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、商品名:PCDL T5652、重量平均分子量:2,000)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時間かけて滴下漏斗から滴下した。滴下終了後、この溶液を5時間にわたって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、上記合成例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、滴下漏斗、冷却管、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)を添加して、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、商品名:PCDL T5652、重量平均分子量:2,000)、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時間かけて滴下漏斗から滴下した。滴下終了後、この溶液を5時間にわたって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、上記合成例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、滴下漏斗、冷却管、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)を添加して、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、商品名:PCDL T5652、重量平均分子量:2,000)をメチルトリグライム35.00gに溶解した溶液を、1時間かけて滴下漏斗から滴下した。滴下終了後、この溶液を2時間にわたって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と記す)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時間にわたって反応させた。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℃まで昇温して5時間にわたって加熱還流した。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、上記合成例1と同様の方法で測定した。
<黒色感光性樹脂組成物の調製>
合成例1~5で得られた(A)バインダーポリマー1~5に、(B)熱硬化性樹脂、(C)有機溶媒に実質的に溶解しない難燃剤、(D)光重合開始剤、(E)黒色着色剤、(F)有機溶媒、(G)球状有機ビーズ、及びその他の成分を添加して、実施例1~10にかかる黒色感光性樹脂組成物を調製した。それぞれの黒色感光性樹脂組成物における構成原料の、樹脂固形分での配合量及び原料の種類を表1に記載する。尚、表1中の(F)有機溶媒である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。黒色感光性樹脂組成物は、先ず、一般的な攪拌翼を備えた攪拌装置にて混合し、その後、3本ロールミルに2回通して、均一な溶液とした。グラインドメーターにて混合溶液中の黒色感光性樹脂組成物の粒子径を測定したところ、いずれも10μm以下であった。混合溶液中の泡を脱泡装置にて完全に脱泡した後、下記評価を実施した。
<1>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)の商品名
<2>クラリアントジャパン株式会社製 ホスフィン酸塩の商品名、1,2-ビス(2-メトキシエトキシ)エタン100重量部に対する溶解性:0.01重量部未満
<3>BASFジャパン株式会社製 メラミンシアヌレートの商品名、1,2-ビス(2-メトキシエトキシ)エタン100重量部に対する溶解性:0.01重量部未満
<4>ナバルテック社製 ベーマイト型水酸化アルミニウムの商品名、1,2-ビス(2-メトキシエトキシ)エタン100重量部に対する溶解性:0.01重量部未満
<5>BASFジャパン株式会社製 オキシムエステル系光重合開始剤の商品名
<6>アサヒ化成工業株式会社製 黒色着色剤(金属複合酸化物)の商品名
<7>アサヒ化成工業株式会社製 黒色着色剤(金属複合酸化物)の商品名
<8>アサヒ化成工業株式会社製 黒色着色剤(金属複合酸化物)の商品名
<9>BASFジャパン株式会社製 黒色着色剤(有機顔料)の商品名
<10>ガンツ化成株式会社製 架橋ポリメタクリル酸メチル系球状有機ビーズの商品名、平均粒子径4μm
<11>大日精化工業株式会社製 架橋ウレタン系球状有機ビーズの商品名、平均粒子径7μm
<12>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商品名
<13>共栄社化学株式会社製 ブタジエン系消泡剤の商品名。
実施例1~10にかかる黒色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、基材としての厚さ25μmのポリイミドフィルム(株式会社カネカ製 商品名:25NPI)の表面に、最終乾燥厚さが20μmになるように100mm×100mmの面積に流延・塗布し、80℃で20分間乾燥して樹脂フィルムを得た後、300mJ/cm2の積算露光量の紫外線を照射して露光した。次いで、30℃に加熱した1.0重量%炭酸ナトリウム水溶液を用いて、1.0kgf/mm2の吐出圧で90秒間、スプレー現像を行った。現像後、純水で十分洗浄し、150℃のオーブン中で30分間、加熱硬化させた。これにより、ポリイミドフィルム上に黒色感光性樹脂組成物の硬化膜(絶縁膜)を形成して、硬化膜積層フィルムを作製した。
以下の項目について硬化膜積層フィルムの評価を行った。評価結果を表2に記載する。
上記<ポリイミドフィルム上への塗膜の作製>の項目に記載の方法と同様の方法で得られた黒色感光性樹脂組成物の硬化膜の表面観察を行い、感光性を判定した。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行った。判定結果を下記「○」又は「×」で示す。
〇:ポリイミドフィルム表面に顕著な線太りまたは現像残渣が無く、ライン幅/スペース幅=100μm/100μmの感光パターンが描けている
×:ポリイミドフィルム表面にライン幅/スペース幅=100μm/100μmの感光パターンが描けていない。
上記<ポリイミドフィルム上への塗膜の作製>の項目に記載の方法と同様の方法で、基材としての厚さ25μm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)の表面に、最終乾燥厚さが20μmの黒色感光性樹脂組成物の硬化膜を形成して、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、当該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(中央部)で180°に折り曲げ、折り曲げ部に5kgの荷重を3秒間乗せた後、荷重を取り除き、折り曲げ部の頂点を顕微鏡で観察することにより行った。そして、顕微鏡で観察した後、折り曲げ部を180°に開いて、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。折り曲げ回数が1回であるとは、硬化膜積層フィルムを折り曲げる操作から完全に開くまでの操作を一度行ったことを指す。判定結果を下記「○」、「△」又は「×」で示す。
○:折り曲げ回数5回で硬化膜にクラックが無い
△:折り曲げ回数3回で硬化膜にクラックが無い
×:折り曲げ回数1回で硬化膜にクラックが発生する。
上記<ポリイミドフィルム上への塗膜の作製>の項目に記載の方法と同様の方法で、基材としての厚さ25μm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)表面に、最終乾燥厚さが20μmの黒色感光性樹脂組成物の硬化膜を形成して、硬化膜積層フィルムを作製した。フィルムの反り高さの測定方法を説明するための模式図を図1に示す。図1に示すように、得られた硬化膜積層フィルム(黒色感光性樹脂組成物の硬化膜を積層したポリイミドフィルム)1を面積50mm×50mmの正方形状に切り出して、平滑な台3の上に硬化膜側が上面になるように置き、フィルム端部の反り高さ2を測定した。硬化膜積層フィルム1の反り高さ2が小さい程、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も低下することになる。反り高さ2は5mm以下であることが好ましい。尚、硬化膜積層フィルム1が筒状に丸まる場合は「×」と判定した。
フレキシブル銅貼り積層板(電解銅箔の厚さ12μm、ポリイミドフィルムは株式会社カネカ製 商品名: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、純水で洗浄して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>の項目に記載の方法と同様の方法で櫛形パターン上に、最終乾燥厚さが20μmの黒色感光性樹脂組成物の硬化膜を形成して、試験片(絶縁膜付きプリント配線板、絶縁膜付きフレキシブルプリント基板)の作成を行った。そして、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。観察結果を下記「○」又は「×」で示す。
○:試験開始から1,000時間経過後に、10の8乗以上の抵抗値を示し、マイグレーション及びデンドライトなどの発生が無い
×:試験開始から1,000時間経過後に、マイグレーション、デンドライトなどの発生がある。
1mm角のマス目を有する方眼紙の上に、上記「(iii)反り」の項目で得られた試験片(硬化膜積層フィルム)を置き、試験片の上からマス目を目視にて確認する方法で隠蔽性の評価を行った。評価結果を下記「○」又は「×」で示す。
○:マス目が見えない
×:マス目が見える。
上記「(iii)反り」の項目で得られた試験片(硬化膜積層フィルム)を、260℃:ピークトップ260℃×20secのリフロー条件でリフロー処理する方法により、アウトガス及び薄膜化の評価を行った。評価結果を下記「○」又は「×」で示す。
○:目視にてアウトガスが発生していないことを確認することができ、かつ試験前後で硬化膜の膜厚変化が無い
×:目視にてアウトガスが発生していることを確認することができ、かつ試験前後で硬化膜の膜厚変化がある。
プラスチック材料の燃焼性試験規格 UL94VTM に従い、以下のようにして燃焼性試験を行った。すなわち、上記<ポリイミドフィルム上への塗膜の作製>の項目に記載の方法と同様の方法で、基材としての厚さ25μm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)の両表面に、最終乾燥厚さが20μmの黒色感光性樹脂組成物の硬化膜を形成して、硬化膜積層フィルムを作製した。作製した上記硬化膜積層フィルムを幅50mm×長さ200mm×厚さ75μm(ポリイミドフィルムの厚さを含む)の寸法に20枚切り出し、それぞれフィルム端部から125mmの部分に標線を入れ、標線を外側にして直径約13mm×長さ200mmの筒状に丸めた。その後、標線よりも上の重ね合わせ部分(長さ(200-125=)75mmの部分)及びその上部(フィルム端部)に隙間が無いようにしてPI(ポリイミド)テープを貼って固定した。これにより、燃焼性試験用のサンプル(筒)を20本用意した。そのうちの10本は、(1)23℃/50%相対湿度で48時間処理し、残りの10本は、(2)70℃で168時間の処理後に、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。これらサンプルの上部(PIテープを貼った側)をクランプで止めて垂直に(吊り下げるようにして)固定し、サンプルの下部(PIテープを貼っていない側)にバーナーの炎を3秒間近づけて着火した。3秒間経過したらバーナーの炎を遠ざけて、着火したサンプルの炎や燃焼が何秒後に消えるかを測定した。測定結果を下記「○」又は「×」で示す。
○:各条件((1),(2))につき、サンプルからバーナーの炎を遠ざけた後、10本とも最長で10秒以内に炎や燃焼が消えて自己消火し、かつ評線まで燃焼が達していない
×:各条件((1),(2))のうち、サンプルからバーナーの炎を遠ざけた後、1本でも10秒以内に自己消火しない、または炎が評線以上の部分まで達して燃焼する。
攪拌機、温度計、滴下漏斗、冷却管及び空気導入管を備えた反応容器に、空気を導入した後、クレゾールノボラック型エポキシ樹脂(DIC株式会社製 商品名:エピクロンN-680、エポキシ当量:210)210.0g、カルビトールアセテート96.4gを仕込み、加熱溶解した。次いで、重合禁止剤としてのハイドロキノン0.46g、及び反応触媒としてのトリフェニルホスフィン1.38gを添加して、空気気流下で95℃まで均一に撹拌しながら昇温した。次いで、滴下漏斗にアクリル酸72.0gを仕込み、95℃~105℃に加熱しながら反応容器にアクリル酸を滴下した。滴下終了後、酸価が3.0KOHmg/g以下になるまで、約16時間にわたって反応させた。次いで、反応溶液を80℃~90℃に冷却し、テトラヒドロフタル酸無水物76.0gを添加して、8時間にわたって反応させた。これにより、光硬化性樹脂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65%、酸価は78KOHmg/gであった。尚、固形分濃度、酸価は、上記合成例1と同様の方法で測定した。
バインダーポリマーとして、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17:62:21の割合で共重合させた樹脂溶液(重量平均分子量:110,000、固形分の酸価:110mgKOH/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)を調製した。この樹脂溶液150g(固形分として60g)に、ウレタン結合を含有する樹脂としてウレタン変性エポキシアクリレート樹脂(日本化薬株式会社製 商品名:KAYARAD UXE-3024、固形分濃度:65%、重量平均分子量:10,000、固形分の酸価:60mgKOH/g)15.4g(固形分として10g)及びウレタン・不飽和オリゴマー(末端にヒドロキシル基を有するポリカーボネート化合物3モルと、イソホロンジイソシアネート4モルと、2-ヒドロキシエチルアクリレート2モルとを反応させて得られた光重合化合物)を固形分として45g、黒色顔料としてのカーボンブラック1.5g、ラジカル重合性化合物としてのビスフェノールA骨格エチレンオキサイド変性ジメタクリレート30g、光重合開始剤としての2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1(BASFジャパン株式会社製 商品名:イルガキュア369)2.5g、熱硬化性樹脂としてメラミン誘導体17g、その他の成分としてメチルエチルケトン45g、トルエン20gを配合・攪拌して、3本ロールミルにて分散させることにより、黒色感光性樹脂組成物とした。この黒色感光性樹脂組成物の各物性評価を、実施例1の方法と同様の方法で行った。その結果を上記表2に記載する。尚、上記黒色感光性樹脂組成物には、(C)成分、(E)成分、及び(G)成分が含まれていない。
2 反り高さ
3 平滑な台
Claims (11)
- 少なくとも(A)バインダーポリマー、(B)熱硬化性樹脂、(C)有機溶媒に実質的に溶解しない難燃剤、(D)光重合開始剤、(E)赤外線領域において反射領域を有する黒色着色剤、及び(F)有機溶媒を含んでいる黒色感光性樹脂組成物。
- 少なくとも(A)バインダーポリマー、(B)熱硬化性樹脂、(G)球状有機ビーズ、(D)光重合開始剤、(E)赤外線領域において反射領域を有する黒色着色剤、及び(F)有機溶媒を含んでいる黒色感光性樹脂組成物。
- 少なくとも(A)バインダーポリマー、(B)熱硬化性樹脂、(C)有機溶媒に実質的に溶解しない難燃剤、(G)球状有機ビーズ、(D)光重合開始剤、(E)赤外線領域において反射領域を有する黒色着色剤、及び(F)有機溶媒を含んでいる黒色感光性樹脂組成物。
- 上記(E)赤外線領域において反射領域を有する黒色着色剤が、金属複合酸化物または有機顔料であることを特徴とする請求項1~3のいずれか1項に記載の黒色感光性樹脂組成物。
- 上記金属複合酸化物が、鉄、クロム、マンガン及びビスマスからなる群から選ばれる少なくとも1種を含んでいることを特徴とする請求項4に記載の黒色感光性樹脂組成物。
- 上記有機顔料が、ペリレン系化合物であることを特徴とする請求項4に記載の黒色感光性樹脂組成物。
- 上記(C)有機溶媒に実質的に溶解しない難燃剤が、下記(c1)~(c3)からなる群から選ばれる少なくとも1種であることを特徴とする請求項1または3に記載の黒色感光性樹脂組成物。
(c1)リン系化合物
(c2)メラミン系化合物
(c3)金属水酸化物 - 請求項1~7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、乾燥させて得られる樹脂フィルム。
- 請求項8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9に記載の絶縁膜をプリント配線板に被覆してなる絶縁膜付きプリント配線板。
- 請求項9に記載の絶縁膜をフレキシブルプリント基板に被覆してなる絶縁膜付きフレキシブルプリント基板。
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CN201280059964.2A CN103975274B (zh) | 2011-12-06 | 2012-11-20 | 黑色感光性树脂组合物及其利用 |
JP2013548171A JP5639284B2 (ja) | 2011-12-06 | 2012-11-20 | 黒色感光性樹脂組成物及びその利用 |
US14/363,058 US10030133B2 (en) | 2011-12-06 | 2012-11-20 | Black photosensitive resin composition and use of same |
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WO2018180592A1 (ja) * | 2017-03-28 | 2018-10-04 | 東レ株式会社 | 感光性樹脂組成物、硬化膜、硬化膜を具備する素子、硬化膜を具備する有機el表示装置、硬化膜の製造方法、および有機el表示装置の製造方法 |
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- 2012-11-20 WO PCT/JP2012/080052 patent/WO2013084714A1/ja active Application Filing
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JP2014063091A (ja) * | 2012-09-24 | 2014-04-10 | Tamura Seisakusho Co Ltd | 黒色硬化性樹脂組成物 |
JP2015090954A (ja) * | 2013-11-07 | 2015-05-11 | ナミックス株式会社 | フレキシブルプリント配線板、およびその製造方法 |
JP2015232630A (ja) * | 2014-06-10 | 2015-12-24 | 平岡織染株式会社 | 透過投映スクリーン |
JP2015232629A (ja) * | 2014-06-10 | 2015-12-24 | 平岡織染株式会社 | 透過投映スクリーン |
JP2019045865A (ja) * | 2015-09-30 | 2019-03-22 | 東レ株式会社 | ネガ型感光性樹脂組成物、硬化膜、硬化膜を具備する素子及び表示装置、並びにその製造方法 |
JP6127190B1 (ja) * | 2016-09-30 | 2017-05-10 | 太陽インキ製造株式会社 | 感光性樹脂組成物、硬化物および硬化物を有するプリント配線板、並びにプリント配線板を備えた光学センサーモジュール |
JP2018055074A (ja) * | 2016-09-30 | 2018-04-05 | 太陽インキ製造株式会社 | 感光性樹脂組成物、硬化物および硬化物を有するプリント配線板、並びにプリント配線板を備えた光学センサーモジュール |
WO2018180592A1 (ja) * | 2017-03-28 | 2018-10-04 | 東レ株式会社 | 感光性樹脂組成物、硬化膜、硬化膜を具備する素子、硬化膜を具備する有機el表示装置、硬化膜の製造方法、および有機el表示装置の製造方法 |
KR20190125983A (ko) * | 2017-03-28 | 2019-11-07 | 도레이 카부시키가이샤 | 감광성 수지 조성물, 경화막, 경화막을 구비하는 소자, 경화막을 구비하는 유기 el 표시 장치, 경화막의 제조 방법, 및 유기 el 표시 장치의 제조 방법 |
JPWO2018180592A1 (ja) * | 2017-03-28 | 2020-02-06 | 東レ株式会社 | 感光性樹脂組成物、硬化膜、硬化膜を具備する素子、硬化膜を具備する有機el表示装置、硬化膜の製造方法、および有機el表示装置の製造方法 |
KR102254366B1 (ko) | 2017-03-28 | 2021-05-24 | 도레이 카부시키가이샤 | 감광성 수지 조성물, 경화막, 경화막을 구비하는 소자, 경화막을 구비하는 유기 el 표시 장치, 경화막의 제조 방법, 및 유기 el 표시 장치의 제조 방법 |
WO2019083006A1 (ja) * | 2017-10-27 | 2019-05-02 | 積水化学工業株式会社 | 硬化性樹脂組成物、硬化物、接着剤、及び、接着フィルム |
TWI791804B (zh) * | 2018-03-29 | 2023-02-11 | 日商鐘化股份有限公司 | 感光性樹脂組合物、乾式膜、硬化膜、印刷佈線板及其製造方法 |
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CN103975274B (zh) | 2016-10-26 |
TW201329632A (zh) | 2013-07-16 |
US10030133B2 (en) | 2018-07-24 |
JPWO2013084714A1 (ja) | 2015-04-27 |
US20150044451A1 (en) | 2015-02-12 |
TWI488005B (zh) | 2015-06-11 |
CN103975274A (zh) | 2014-08-06 |
JP5639284B2 (ja) | 2014-12-10 |
KR20140100552A (ko) | 2014-08-14 |
KR101596897B1 (ko) | 2016-02-24 |
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