WO2006129663A1 - Composition de resine durcissable et objet durci obtenu a partir de celle-ci - Google Patents

Composition de resine durcissable et objet durci obtenu a partir de celle-ci Download PDF

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Publication number
WO2006129663A1
WO2006129663A1 PCT/JP2006/310781 JP2006310781W WO2006129663A1 WO 2006129663 A1 WO2006129663 A1 WO 2006129663A1 JP 2006310781 W JP2006310781 W JP 2006310781W WO 2006129663 A1 WO2006129663 A1 WO 2006129663A1
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WIPO (PCT)
Prior art keywords
resin composition
curable resin
inorganic filler
composition according
mass
Prior art date
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Ceased
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PCT/JP2006/310781
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English (en)
Japanese (ja)
Inventor
Yoshikazu Daigo
Shoji Minegishi
Gen Itokawa
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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Filing date
Publication date
Priority claimed from JP2005159205A external-priority patent/JP4713948B2/ja
Priority claimed from JP2005159607A external-priority patent/JP2006335807A/ja
Application filed by Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Priority to KR1020077027819A priority Critical patent/KR100928362B1/ko
Priority to CN200680019298.4A priority patent/CN101189551B/zh
Publication of WO2006129663A1 publication Critical patent/WO2006129663A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • 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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present invention relates to a curable resin composition filled with an inorganic filler at a high concentration and developable with a dilute alkaline aqueous solution, and a cured product thereof.
  • the present invention can easily achieve low linear expansion coefficient, high thermal conductivity, low water absorption, etc. by filling the inorganic filler at a high concentration. Less gasification components are released from organic components such as at high temperatures! Relates to a curable resin composition developable with a dilute alkaline aqueous solution and its cured product.
  • a resin composition (see, for example, Patent Document 1 and Patent Document 2) used for such a build-up substrate or a package substrate is based on a low molecular weight epoxy compound. It is a fat composition, and it has been difficult to highly fill inorganic fillers such as fused silica useful for a low linear expansion coefficient and aluminum oxide for improving heat dissipation.
  • a metal plate such as copper or aluminum is used as a circuit board having good heat dissipation, and an electric insulation layer such as a pre-preda or a thermosetting resin composition is provided on one or both surfaces of the metal plate.
  • an electric insulation layer such as a pre-preda or a thermosetting resin composition
  • Examples thereof include a metal base substrate on which a circuit pattern is formed (see, for example, Patent Document 3).
  • a strong metal base substrate requires a thin insulating layer due to the poor thermal conductivity of the electrical insulating layer. As a result, there may be a problem of withstand voltage.
  • a light-emitting diode chip is disposed on a resin insulating layer on which a terminal portion is formed, and is packaged with a sealing resin that also serves as a lens layer on top of the light-emitting diode chip. In the diode, the heat dissipation of the resin insulation layer becomes a problem.
  • the content of the inorganic filler is 50% by mass or less, and inorganic fillers such as barium sulfate, silica, talc, and clay are used. Materials, particularly barium sulfate, have been frequently used.
  • the water absorption rate of the coating film was 1.2 to 1.5% by mass, and popcorn phenomenon due to water absorption and galvanic corrosion due to moisture in the coating film were problematic.
  • Another problem is that polybasic acid anhydrides and photopolymerization initiators that are decomposed and released from the resin at high temperatures gasify and cause malfunction of electronic devices.
  • Patent Document 2 JP-A-11 288091 (Claims)
  • Patent Document 4 Japanese Patent Application Laid-Open No. 61-243869 (Claims)
  • the present invention was developed in view of the above problems, and its main purpose is to reduce the linear expansion coefficient, increase the thermal conductivity, reduce the water absorption rate, etc. by filling the inorganic filler with a high concentration.
  • To provide a curable resin composition that can be easily realized can be developed with a dilute aqueous alkali solution, and emits less gasification components at high temperatures from organic components such as resin. I will.
  • the curable resin composition obtained by irradiation with active energy rays and Z or thermosetting is excellent in low linear expansion coefficient, high thermal conductivity, low water absorption, etc. It is to provide a cured product with a small amount of gasified components released, such as fats and other organic components.
  • the carboxyl group-containing copolymer resin (A) is a compound represented by the following general formula (I) or (A)
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a linear or branched alkylene group having 2 to 6 carbon atoms
  • R 3 is an alkylene group having 3 to 3 carbon atoms
  • R 4 Represents a dihydrochloride anhydride residue, which is a carboxyl group-containing copolymer resin containing) as a constituent component.
  • the compound (B) having two or more reactive groups that are cured by active energy rays is a compound having two or more ethylenically unsaturated bonds, and the photopolymerization initiator (C) is From the viewpoint of photocurability, a radical photopolymerization initiator is preferred.
  • the content of the inorganic filler (D) is 80% by mass or more in the solid content. There is preferable. From the viewpoint of increasing the thermal conductivity, the inorganic filler (D) preferably has a thermal conductivity of 15 W 15 ⁇ ⁇ ⁇ or more, and is particularly preferably acid aluminum.
  • thermosetting component ( ⁇ ) is a polyfunctional epoxy resin having two or more oxysilane rings in the molecule.
  • the curable resin composition of the present invention is preferably insulating.
  • the curable resin composition is irradiated with active energy rays and
  • the cured product preferably has a thermal conductivity of lWZm′K or more.
  • the carboxyl group-containing copolymer resin (A) used in the curable resin composition of the present invention is a copolymer resin, it can maintain a high viscosity even when diluted with an organic solvent, As a result, it is possible to highly fill the inorganic filler, and it is possible to easily achieve a low linear expansion coefficient, a high thermal conductivity, a low water absorption, and the like of the cured product.
  • the curable resin composition of the present invention which can easily achieve such low linear expansion coefficient, high thermal conductivity, low water absorption, etc., of the cured product, is likely to cause warpage problems. It can be suitably used as a solder resist for a thin build-up substrate or a package substrate on which a semiconductor chip with a large amount of heat generation is mounted.
  • the solder resist can be imparted with light reflectivity, light diffusibility or light shielding property, and can be suitably used for optical devices such as LED devices that require optical functions.
  • the basic embodiment of the curable resin composition of the present invention includes (A) a carboxyl group-containing copolymer resin, (B) a compound having two or more reactive groups that are cured by active energy rays, (C It is characterized by containing a photopolymerization initiator and (D) an inorganic filler, and the content ratio of the inorganic filler (D) is 65% by mass or more in the solid content. Further, in order to improve heat resistance, (E) a thermosetting component may be contained.
  • the carboxyl group-containing copolymer resin (A) a known and commonly used copolymer resin having a carboxyl group in the molecule can be used. Furthermore, a copolymer resin having an ethylenically unsaturated bond in the molecule can be used more favorably than the surface strength of development resistance.
  • a carboxyl group-containing copolymer obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond. Resin,
  • a carboxyl group-containing resin obtained by reacting a hydroxyl group-containing copolymer such as a polyvinyl alcohol derivative with a polybasic acid anhydride,
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a linear or branched alkylene group having 2 to 6 carbon atoms
  • R 3 is an alkylene group having 3 to 3 carbon atoms
  • R 4 Represents a dihydrochloric acid anhydride residue.
  • a carboxyl group-containing copolymer resin containing) is preferred as a binder resin when highly filling the inorganic filler (D).
  • (meth) atalylate is a term that collectively refers to talate, metatalate, and a mixture thereof, and other similar expressions! The same is true.
  • the solid content acid value of the carboxyl group-containing copolymerized resin (A) is in the range of 40 to 200 mgKOHZg, more preferably in the range of 80 to 120 mgKOHZg.
  • the acid value of the carboxyl group-containing copolymer resin is less than 40 mgKOH / g, alkali development becomes difficult.On the other hand, when it exceeds 200 mgKOHZg, it is necessary to dissolve the exposed area by the developer. This is not preferable because the lines are thinned or, depending on the case, dissolution and peeling with a developer without distinction between exposed and unexposed areas makes it difficult to draw a normal resist pattern.
  • the weight average molecular weight of the carboxyl group-containing copolymer resin (A) is 2,000 to 50,000, preferably ⁇ , 5,000 to 20,000. Desire! / ⁇ .
  • the weight average molecular weight force is less than 2,000, it is not preferable because the dryness to touch of the coating film is lowered and it becomes difficult to obtain the impact resistance of the cured product.
  • the weight average molecular weight exceeds 50,000, the developability is lowered, which is preferable.
  • the compound (2) having two or more reactive groups that are cured by the active energy ray includes a compound having two or more ethylenically unsaturated bonds, and cationic polymerization such as an oxsilane ring or an oxetane ring.
  • photodimeric compounds such as chalcone cinnamate, and other cyclic ether compounds.
  • a compound having two or more ethylenically unsaturated bonds is preferred.
  • the compound having two or more ethylenically unsaturated bonds is used for photocuring and insolubilizing the carboxyl group-containing copolymer resin ( ⁇ ) in a dilute alkaline aqueous solution. It is. Typical examples include 2-hydroxyethyl (meth) acrylate, 1,4 butanediol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, neopentyl.
  • Glycol di (meth) acrylate polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopenta-ldi (meth) acrylate Forced prolataton-modified dicyclopenta-di-di (meth) acrylate, ⁇ -modified di- (meth) acrylate, arylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) Atalylate, dipentaerythritol Li (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ⁇ modified trimethylol propane tri (meth) acryl
  • bifunctional or higher preferably trifunctional or higher (meth) acrylate is preferable.
  • the amount of the compound (B) having two or more reactive groups that are cured by active energy rays, such as a compound having two or more ethylenically unsaturated bonds, is the above-mentioned carboxyl group-containing copolymer IV.
  • Fat (A) With respect to 100 parts by mass, 5 to 100 parts by mass is particularly preferable, and 10 to 50 parts by mass is particularly preferable.
  • the component (B) is less than 5 parts by mass, sufficient curability cannot be obtained and a pattern shape as designed cannot be obtained.
  • the amount exceeds 100 parts by mass the dryness to the touch is deteriorated, which is not preferable.
  • Examples of the photopolymerization initiator (C) used in the present invention include compounds that generate active groups upon irradiation with active energy rays, such as photoradical polymerization initiators, photopower thione polymerization initiators, and photopolymers. -On polymerization initiators and the like. Among these, photo radical polymerization initiators are preferred from the viewpoint of photocurability, storage stability, electrical properties of cured products, and the like.
  • radical photopolymerization initiator examples include those known and commonly used, for example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2, 2- 1-Phenylacetophenone, 2,2-Diethoxy-1-2-Ph-Luacetophenone, 2,2-Diethoxy-1-2-Pha-Luacetophenone, 1,1-Dichloroacetophenone, etc .; 2-Methyl 1 [4 (Methylthio) phenol] 2 Morpholinopropane 1-one, 2-Benzyl-1-2-dimethylamino-1- 1- (4-Morpholinol) monobutanone — 1-aminoacetophenones; 2-methyl Anthraquinone, 2-ethyl anthraquinone, 2 tertiary butyl anthraquinon
  • the blending amount of the photopolymerization initiator (C) such as the photoradical polymerization initiator is 0.1 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing copolymer resin ( ⁇ ). Preferably, it is contained in a proportion of 2 to 20 parts by mass.
  • the compounding power of this component (C) Carboxyl group-containing copolymer resin ( ⁇ ) With respect to 100 parts by mass, if less than 0.1 part by mass, the photocurability and workability deteriorate, which is not preferable. On the other hand, if it exceeds 30 parts by mass, the coating film properties deteriorate, which is not preferable.
  • the inorganic filler (D) used in the curable resin composition of the present invention can be appropriately selected.
  • known and commonly used inorganic fillers that can be used in insulating curable resin compositions include crystalline silica, fused silica, barium sulfate, talc, clay, aluminum hydroxide, aluminum oxide, boron nitride. , Aluminum nitride, magnesium oxide, magnesium carbonate, zinc oxide, calcium carbonate, barium titanate and the like. These are properly used according to the purpose and purpose.
  • examples of known and commonly used inorganic fillers that can be used in the conductive curable resin composition include conductive metal powders such as copper powder and silver powder, and these can be properly used depending on the application and purpose.
  • the inorganic filler (D) having a thermal conductivity of 15 WZm'K or more aluminum oxide having a purity of 92% or more (40 WZm ⁇ K) having a thermal conductivity of about 15 WZm ⁇ K.
  • Boron nitride (40WZm'K or more) aluminum nitride (260WZm'K), magnesium oxide (60WZm'K), zinc oxide (45WZm'K) and other insulating compounds
  • conductive metal powders such as silver powder (420WZm'K).
  • fused silica is preferable from the viewpoint of low linear expansion coefficient
  • acid aluminum is preferable from the viewpoint of high thermal conductivity and chemical resistance.
  • the particle size of these inorganic fillers (D) is 30 ⁇ m or less, preferably 20 ⁇ m or less, and spherical ones are preferred for high filling. In addition, it is preferable to mix those with two or more particle sizes that have a particle size distribution that results in closest packing. Inorganic filler (D) When the particle size of the particles exceeds 30 m, the inorganic filler (D) is dropped from the surface of the coating film, or the blending ratio of the inorganic filler (D) is decreased.
  • the amount of the inorganic filler (D) to be blended is 65% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more in the solid (cured product).
  • a low linear expansion coefficient, a high thermal conductivity, and a low water absorption rate can be achieved by highly filling the inorganic filler that is the object of the present invention. This is not preferable because it is difficult to make it.
  • the curable resin composition of the present invention may contain a thermosetting component (E) in order to improve the heat resistance of the cured product.
  • a thermosetting component include a polyfunctional epoxy resin having two or more oxirane rings in the molecule, a polyfunctional oxetane compound having two or more oxetane rings in the molecule, and a thermosetting polyimide resin. , Melamine rosin and the like.
  • thermosetting component (E) is 0.1 to 50 parts by mass, preferably 2 to 30 parts by mass, with respect to 100 parts by mass of the carboxyl group-containing copolymer resin (A). Part.
  • polyfunctional epoxy resins are preferably used from the viewpoints of curability, storage stability, and cured coating film characteristics.
  • polyfunctional epoxy resins examples include known and commonly used epoxy compounds such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and brominated bisphenols.
  • glycidyl (meth) acrylate copolymer coagulants can be used.
  • These polyfunctional epoxy compounds can be used alone or in combination of two or more.
  • the blending amount is in the range of 0.6 to 2.0 equivalents, preferably 0.8 to 1.5 equivalents, with respect to 1 equivalent of carboxyl groups of the carboxyl group-containing copolymer resin (A). . If the amount of the polyfunctional epoxy compound is less than the above range, the carboxyl group remains, which is not preferable because the heat resistance, alkali resistance, electrical insulation and the like are lowered. On the other hand, when the above range is exceeded, the low molecular weight polyfunctional epoxy resin remains, which is not preferable because the strength of the coating film is lowered.
  • the curable resin composition of the present invention is preferably added with (F) a wetting and dispersing agent in order to facilitate higher filling.
  • a wet 'dispersant (F) include compounds and polymer compounds having a polar group having an affinity for an inorganic filler (D) such as a carboxyl group, a hydroxyl group, and an acid ester, such as phosphoric acid.
  • Acid-containing compounds such as esters, copolymers containing acid groups, hydroxyl group-containing polycarboxylic acid esters, polysiloxanes, salts of long-chain polyaminoamides and acid esters, and the like can be used.
  • Disperbyk (registered trademark) 1 101, 1 103, -110, -111, -160, -171, -174, which are commercially available and can be particularly suitably used as the wetting and dispersing agent (F).
  • F wetting and dispersing agent
  • BYK-P105, — P104, — P104S, — 240 all manufactured by Bic 'Chemi Co.
  • EFKA Polymer 150
  • EFKA—44 —63, —64, -65, -66, -71, -764, -766, N (V, deviation is also made by F Power Co.).
  • the blending amount of such a wet dispersant (F) is suitably from 0.01 to 5 parts by mass per 100 parts by mass of the inorganic filler (D). If the blending amount of the wetting / dispersing agent (F) is less than the above range, the effect of adding the wetting / dispersing agent cannot be obtained, and it becomes difficult to achieve a high filling of the composition. On the other hand, if it is added in excess of the above range, the proportion of the component that is not photocured increases, which is not preferable because the strength of the coating film is reduced and the thixotropic property of the composition is increased.
  • an organic solvent may be added to the curable resin composition of the present invention for viscosity adjustment.
  • the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; closed sorb, methyl closed sorb, butinoreserosonoreb, Carbitol, methinorecanorebitonore, butinorecarbitol, propylene glycolenomonomethinole ether, dipropyleneglycol Glycol ethers such as dimethyl ether, dipropylene glycol jetyl ether, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl acetate solvate, carbitol acetate, butinole Esters such as carbitoleole acetate, butinole Est
  • the blending amount of these organic solvents is not particularly limited and may be appropriately adjusted according to the coating method, but is generally 50% by mass or less, preferably 30% by mass in the composition. It is as follows. If the content of the organic solvent is large, the sedimentation speed of the inorganic filler (D) increases and the storage stability decreases, which is not preferable.
  • the curable resin composition of the present invention may further include phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and the like, if necessary.
  • known and conventional thickening agents such as quinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol and phenothiazine, and known and conventional thickening agents such as finely divided silica, organic bentonite and montmorillonite
  • additives such as antifoaming agents such as adhesives, silicones, fluorines, and polymers, and silane coupling agents such as Z or leveling agents, imidazole, thiazole, and triazoles can do.
  • the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, the organic solvent, and is applied on a substrate by a dip coating method, a flow coating method, a roll coating method, or a bar coater method. It is applied by a method such as screen printing or curtain coating, and it is about 60-:
  • the organic solvent contained in the composition is evaporated and dried (temporary drying) at a temperature of LOO ° C. Can be formed.
  • a resin insulation layer can be formed by applying the composition on a plastic film, drying it, and laminating it on a substrate.
  • the contact-type (or non-contact-type) is selectively exposed to actinic rays through a photomask having a pattern formed thereon, and the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0. A resist pattern is formed by development with a 3 to 3% sodium carbonate aqueous solution.
  • a dilute alkaline aqueous solution for example 0.
  • a resist pattern is formed by development with a 3 to 3% sodium carbonate aqueous solution.
  • the carboxyl group of the carboxyl group-containing copolymer resin (A) has two or more oxsilane rings in the molecule.
  • the epoxy group of the polyfunctional epoxy resin can react to form a cured coating film excellent in various properties such as heat resistance.
  • a low-pressure mercury lamp a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metalno, or a ride lamp is suitable.
  • a laser beam or the like can also be used as an exposure active light source for direct drawing.
  • alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, ammonia, amines and the like can be used.
  • Sodium carbonate is preferred.
  • a three-dimensional insulating structure can also be formed by repeating coating and volatilization drying twice or more and laminating the coating film. Further, the coated film after development may be heated to a temperature of Tg or more, and the non-turn side wall may be thermally deformed into a smooth taper. Here, exposure and development may be performed every time coating or volatile drying or may be performed at once.
  • reaction product was cooled to 80 to 90 ° C., and 76. lg of tetrahydrophthalic anhydride was added. By infrared absorption analysis, the absorption peak of acid anhydride (1780 cm _1 ) disappeared until about 6 Reacted for hours.
  • reaction solution was added 96.4 g of aromatic solvent ibuzole # 150 manufactured by Idemitsu Petrochemical Co., Inc., diluted, and taken out.
  • the carboxyl group-containing photosensitive polymer solution thus obtained had a nonvolatile content of 65% by mass and a solid acid value of 78 mgKOHZg.
  • this reaction solution is referred to as R-1 varnish.
  • compositions of the above Examples and Comparative Examples were applied on the entire surface of the test substrate by screen printing so that the dry coating film was about 40 m, and dried at 80 ° C. for 20 minutes. After cooling to room temperature Under reduced pressure using an exposure apparatus (metal nose lamp 7KW2 lamp) manufactured by Oak Manufacturing Co., Ltd., with a Kodak Step Tablet No. 2 exposing the entire surface with an exposure amount of about 6 steps, then 1% NaCO at 30 ° C The aqueous solution was developed for 60 seconds at a spray pressure of 0.2 MPa.
  • compositions of the above Examples and Comparative Examples were applied to the entire surface of a glass epoxy substrate by screen printing, dried at 80 ° C. for 20 minutes, allowed to cool to room temperature, and then Kodak Step Tablet No. 2 (21 steps). ) used as a photomask, under reduced pressure at Oak Seisakusho exposure apparatus (Metaruno ⁇ halide lamp 7KW2 lamp), exposure (200MjZcm 2 in integrating actinometer 365nm UV, and 600MjZcm 2) and, 30. 1% Na CO aqueous solution of C sprayed at 0.2 MPa for 1 minute
  • the entire surface was coated on a circuit-formed glass epoxy substrate by screen printing, the substrate was prepared under the above conditions, and the substrate was placed in a 10 vol% sulfuric acid aqueous solution at room temperature for a predetermined time ( After immersion for 10 minutes and 30 minutes, and after washing with water, a peel test using a cellophane adhesive tape was performed to evaluate the resist peeling and discoloration.
  • the coating film has peeling.
  • compositions of the above Examples and Comparative Examples were applied to the entire surface of the glass plate whose mass was measured in advance by screen printing, and an evaluation sample was obtained under the above conditions. After cooling this to room temperature, the mass of the evaluation sample was measured. Next, this evaluation service After immersing the sample in pure water at room temperature for 24 hours, the moisture adhering to the surface was wiped off, the mass of the evaluation sample was measured, and the water absorption rate of the cured product was determined by the following formula.
  • W1 is the mass of the evaluation sample
  • W2 is the mass of the evaluation sample after water absorption
  • Wg is the mass of the glass plate.
  • the cured product alone is used as an evaluation sample, and a
  • the resulting force shown in Table 2 is also clear, it is possible to fill with a high amount of inorganic filler, resulting in low linear expansion coefficient, high thermal conductivity, It has become possible to provide a resin composition that can be easily reduced in water absorption and can be developed with a dilute aqueous alkali solution.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Materials For Photolithography (AREA)

Abstract

L’invention concerne une composition de résine durcissable qui contient une charge inorganique en concentration élevée. Elle peut facilement atteindre un coefficient de dilatation thermique réduit, un coefficient de conductivité thermique accru, une absorption d'eau réduite, etc. La composition peut être développée avec une solution aqueuse alcaline diluée. Elle est réduite en termes de teneur en composants gazéifiables devant être libérés à des températures élevées à partir d’ingrédients organiques compris dans la résine. La composition de résine est une composition isolante développable avec une solution alcaline comprenant (A) une résine de copolymère carboxylé, (B) un composé ayant deux groupes réactifs ou plus qui durcit par l'action des rayons d'énergie actinique, (C) un initiateur de photopolymérisation, et (D) une charge inorganique, la teneur de la charge inorganique (D) étant de 65 % en masse ou plus sur la base des ingrédients solides.
PCT/JP2006/310781 2005-05-31 2006-05-30 Composition de resine durcissable et objet durci obtenu a partir de celle-ci Ceased WO2006129663A1 (fr)

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KR1020077027819A KR100928362B1 (ko) 2005-05-31 2006-05-30 경화성 수지 조성물 및 그의 경화물
CN200680019298.4A CN101189551B (zh) 2005-05-31 2006-05-30 固化性树脂组合物及其固化物

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JP2005159205A JP4713948B2 (ja) 2005-05-31 2005-05-31 硬化性樹脂組成物及びその硬化物
JP2005159607A JP2006335807A (ja) 2005-05-31 2005-05-31 絶縁性硬化性樹脂組成物及びその硬化物
JP2005-159205 2005-05-31
JP2005-159607 2005-05-31

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WO2006129663A1 true WO2006129663A1 (fr) 2006-12-07

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KR (1) KR100928362B1 (fr)
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Cited By (6)

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JP2011164304A (ja) * 2010-02-08 2011-08-25 Taiyo Holdings Co Ltd 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
WO2012090532A1 (fr) * 2010-12-28 2012-07-05 太陽インキ製造株式会社 Composition de résine photodurcissable, film sec et objet durci obtenus à partir de celle-ci et carte de circuits imprimés obtenue à l'aide de ceux-ci
JP2013001807A (ja) * 2011-06-16 2013-01-07 Panasonic Corp 電子回路基板材料用樹脂組成物、プリプレグ及び積層板
JP2014078045A (ja) * 2014-01-24 2014-05-01 Taiyo Holdings Co Ltd 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2016053182A (ja) * 2015-11-25 2016-04-14 パナソニックＩｐマネジメント株式会社 電子回路基板材料用樹脂組成物、プリプレグ、積層板及び金属張積層板
JP2016065250A (ja) * 2015-11-25 2016-04-28 パナソニックＩｐマネジメント株式会社 プリプレグ、積層板及び金属張積層板

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JP5520509B2 (ja) * 2009-03-31 2014-06-11 太陽ホールディングス株式会社 硬化性樹脂組成物
JP5575436B2 (ja) * 2009-09-01 2014-08-20 太陽ホールディングス株式会社 アルカリ現像性の光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP6658648B2 (ja) * 2017-03-28 2020-03-04 味の素株式会社 感光性樹脂組成物
JP6720910B2 (ja) * 2017-03-28 2020-07-08 味の素株式会社 感光性樹脂組成物
JP6677203B2 (ja) * 2017-03-28 2020-04-08 味の素株式会社 感光性樹脂組成物、感光性フィルム、支持体付き感光性フィルム、プリント配線板及び半導体装置
KR102386491B1 (ko) * 2018-04-20 2022-04-14 후지필름 가부시키가이샤 도열층, 감광층, 감광성 조성물, 도열층의 제조 방법, 및 적층체와 반도체 디바이스
JP6431999B1 (ja) * 2018-05-22 2018-11-28 デクセリアルズ株式会社 漏油補修材、漏油補修方法、及び、配管

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JPH03153750A (ja) * 1989-11-10 1991-07-01 Daicel Chem Ind Ltd 光重合性組成物
WO2001004705A1 (fr) * 1999-07-12 2001-01-18 Taiyo Ink Manufacturing Co., Ltd. Composition photodurcissable a developpement alcalin et motif de matiere cuite en etant fait
JP2002148786A (ja) * 2000-08-30 2002-05-22 Toray Ind Inc 感光性セラミックス組成物
JP2002122985A (ja) * 2000-10-18 2002-04-26 Toray Ind Inc 感光性ペーストの製造方法ならびにそれから得られるプラズマディスプレイ用部材およびプラズマディスプレイ
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011164304A (ja) * 2010-02-08 2011-08-25 Taiyo Holdings Co Ltd 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
WO2012090532A1 (fr) * 2010-12-28 2012-07-05 太陽インキ製造株式会社 Composition de résine photodurcissable, film sec et objet durci obtenus à partir de celle-ci et carte de circuits imprimés obtenue à l'aide de ceux-ci
JPWO2012090532A1 (ja) * 2010-12-28 2014-06-05 太陽インキ製造株式会社 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2013001807A (ja) * 2011-06-16 2013-01-07 Panasonic Corp 電子回路基板材料用樹脂組成物、プリプレグ及び積層板
JP2014078045A (ja) * 2014-01-24 2014-05-01 Taiyo Holdings Co Ltd 光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2016053182A (ja) * 2015-11-25 2016-04-14 パナソニックＩｐマネジメント株式会社 電子回路基板材料用樹脂組成物、プリプレグ、積層板及び金属張積層板
JP2016065250A (ja) * 2015-11-25 2016-04-28 パナソニックＩｐマネジメント株式会社 プリプレグ、積層板及び金属張積層板

Also Published As

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CN101189551B (zh) 2011-11-16
TW200710571A (en) 2007-03-16
CN101189551A (zh) 2008-05-28
TWI326393B (fr) 2010-06-21
KR20080008387A (ko) 2008-01-23
KR100928362B1 (ko) 2009-11-23

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