WO2006129663A1 - Curable resin composition and cured object obtained therefrom - Google Patents

Curable resin composition and cured object obtained therefrom 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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WO
WIPO (PCT)
Prior art keywords
resin composition
curable resin
inorganic filler
composition according
mass
Prior art date
Application number
PCT/JP2006/310781
Other languages
French (fr)
Japanese (ja)
Inventor
Yoshikazu Daigo
Shoji Minegishi
Gen Itokawa
Original Assignee
Taiyo Ink Mfg. Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2005159607A external-priority patent/JP2006335807A/en
Priority claimed from JP2005159205A external-priority patent/JP4713948B2/en
Application filed by Taiyo Ink Mfg. Co., Ltd. filed Critical Taiyo Ink Mfg. Co., Ltd.
Priority to CN200680019298.4A priority Critical patent/CN101189551B/en
Priority to KR1020077027819A priority patent/KR100928362B1/en
Publication of WO2006129663A1 publication Critical patent/WO2006129663A1/en

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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.

Abstract

A curable resin composition which contains an inorganic filler in a high concentration. It can easily attain a reduced coefficient of thermal expansion, increased coefficient of thermal conductivity, reduced water absorption, etc. The composition can be developed with a dilute aqueous alkali solution. It is reduced in the content of gasifiable components to be released at high temperatures from organic ingredients including the resin. The resin composition is an alkali-developable insulating resin composition comprising (A) a carboxylated copolymer resin, (B) a compound having two or more reactive groups which cure by the action of actinic energy rays, (C) a photopolymerization initiator, and (D) an inorganic filler, the content of the inorganic filler (D) being 65 mass% or higher based on the solid ingredients.

Description

硬化性樹脂組成物及びその硬化物  Curable resin composition and cured product thereof
技術分野  Technical field
[0001] 本発明は、無機充填材を高濃度で充填し、希アルカリ水溶液により現像可能な硬 化性榭脂組成物及びその硬化物に関する。さら〖こ詳しくは、本発明は、無機充填材 を高濃度で充填することにより、低線膨張率化、高熱伝導率化、低吸水率化等を容 易に実現することができ、榭脂などの有機成分から高温時に放出されるガス化成分 が少な！/ヽ、希アルカリ水溶液により現像可能な硬化性榭脂組成物及びその硬化物に 関する。  [0001] 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. In more detail, 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.
背景技術  Background art
[0002] 近年、電子機器の小型化、高性能化に伴!、、半導体の高密度化、高機能化が求 められている。そのため、半導体を実装する回路基板も小型高密度のものが要求さ れている。このような高密度化の要求に対応し、コア基板に榭脂絶縁層を形成し、無 電解銅めつき等で銅箔層を形成し、多層化したビルドアップ基板や、回路形成する 半導体チップを基板に表面実装する BGA (ボール ·グリッド 'アレイ)や CSP (チップ · スケール .パッケージ)等のノ ッケージ基板が登場してきた。  In recent years, with the downsizing and high performance of electronic devices, there is a demand for higher density and higher functionality of semiconductors. For this reason, circuit boards on which semiconductors are mounted are also required to be small and dense. Responding to such demands for higher density, a resin insulation layer is formed on the core substrate, a copper foil layer is formed by electroless copper plating, etc., and a multilayer build-up substrate or a semiconductor chip for circuit formation BGA (Ball Grid Array) and CSP (Chip Scale Package) etc. have been introduced.
[0003] このようなビルドアップ基板やパッケージ基板に用いられて 、る榭脂組成物（例え ば、特許文献 1及び特許文献 2参照。 )は、低分子量のエポキシィ匕合物をベースとし た榭脂組成物であり、低線膨張係数ィ匕に有用な溶融シリカや放熱性を向上させる酸 化アルミニウムなどの無機充填材を高充填することが困難であった。  [0003] 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.
[0004] 一方、放熱性のよい回路基板として、銅やアルミニウムなどの金属板を使用し、この 金属板の片面又は両面に、プリプレダや熱硬化性榭脂組成物などの電気絶縁層を 介して回路パターンを形成する金属ベース基板が挙げられる（例えば、特許文献 3参 照)。し力しながら、力かる金属ベース基板は、電気絶縁層の熱伝導性が悪いために 絶縁層を薄くする必要があり、その結果として、絶縁耐圧の問題が生じる場合がある  [0004] On the other hand, 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. Examples thereof include a metal base substrate on which a circuit pattern is formed (see, for example, Patent Document 3). However, 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.
[0005] 放熱性の問題に対しては、半導体上部にヒートシンクを付帯させるという方法も考え られる力 放出される熱の約 50%はパッケージ基板に蓄積されるため、依然として、 ノ ッケージ基板の放熱性が問題となって ヽる。 [0005] To solve the problem of heat dissipation, a method of attaching a heat sink to the upper part of the semiconductor is also considered. Force Generated About 50% of the released heat is stored on the package substrate, so the heat dissipation of the knock substrate still becomes a problem.
[0006] また、多数の表面実装型発光ダイオードがプッシュボタン表示に用いられている最 近の携帯電話などでは、発光ダイオードから発散される熱の大部分が、基板に蓄積 するという問題がある。具体的には、例えば、端子部が形成された榭脂絶縁層上に 発光ダイオードチップが配置され、その上部にレンズ層を兼ねた封止榭脂でパッケ ージされて 、る表面実装型発光ダイオードにお!/、て、前記榭脂絶縁層の放熱性が 問題となる。  [0006] In addition, in recent mobile phones and the like in which a large number of surface-mounted light emitting diodes are used for push button display, there is a problem that most of the heat dissipated from the light emitting diodes accumulates on the substrate. Specifically, for example, 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.
[0007] また、従来の液状フォトソルダーレジスト組成物（例えば、特許文献 4参照。 )では、 無機充填材の含有率が 50質量％以下であり、硫酸バリウム、シリカ、タルク、クレーな どの無機充填材、特に硫酸バリウムが多用されてきた。この系では、塗膜の吸水率が 1. 2〜1. 5質量％となり、吸水によるポップコーン現象や、塗膜中の水分による電食 性が問題となっていた。さらに、高温時に樹脂から分解放出される多塩基酸無水物 や光重合開始剤がガス化し電子機器の動作不良を起こすことが問題となっている。  [0007] In addition, in the conventional liquid photo solder resist composition (see, for example, Patent Document 4), 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. In this system, 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.
[0008] [特許文献 1]特開平 9 148748号公報 (特許請求の範囲） [Patent Document 1] JP-A-9 148748 (Claims)
[特許文献 2]特開平 11 288091号公報 (特許請求の範囲）  [Patent Document 2] JP-A-11 288091 (Claims)
[特許文献 3]特開平 6— 224561号公報 (特許請求の範囲）  [Patent Document 3] JP-A-6-224561 (Claims)
[特許文献 4]特開昭 61— 243869号公報 (特許請求の範囲）  [Patent Document 4] Japanese Patent Application Laid-Open No. 61-243869 (Claims)
発明の開示  Disclosure of the invention
[0009] [発明が解決しょうとする課題] [0009] [Problems to be solved by the invention]
本発明は、上記問題点に鑑み開発されたものであり、その主たる目的は、無機充填 材を高濃度で充填することにより、低線膨張率化、高熱伝導率化、低吸水率化等を 容易に実現することができ、希アルカリ水溶液により現像可能で、かつ榭脂などの有 機成分から、高温時に放出されるガス化成分が少な!ヽ硬化性榭脂組成物を提供す ることにめる。  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.
[ooio] また、上記硬化性榭脂組成物を活性エネルギー線照射及び Z又は熱硬化して得 られる、低線膨張率化、高熱伝導率化、低吸水率化等に優れ、さらに高温時に榭脂 などの有機成分力 放出されるガス化成分の少ない硬化物を提供することにある。 [0011] [課題を解決するための手段] [ooio] In addition, 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. [0011] [Means for solving the problems]
発明者らは、前記目的の実現に向け鋭意研究した結果、（A)カルボキシル基含有 共重合榭脂、 (B)活性エネルギー線により硬化する反応基を 2個以上有する化合物 、 （C)光重合開始剤力もなる組成物が、バインダー榭脂成分として優れており、 (D) 無機充填材を、固形分中に 65質量％以上充填することが可能となり、無機充填材（ D)の種類により、低線膨張率化、高熱伝導率化、低吸水率化等が容易に実現でき、 希アルカリ水溶液により現像可能で、かつ榭脂などの有機成分から、高温時に放出 されるガス化成分が少な ヽ硬化性榭脂組成物を提供出来ることを見出し、本発明を 完成するに至った。  As a result of intensive research aimed at realizing the above object, the inventors have found that (A) a carboxyl group-containing copolymer resin, (B) a compound having two or more reactive groups that are cured by active energy rays, (C) photopolymerization A composition that also has an initiator power is excellent as a binder resin component. (D) It is possible to fill an inorganic filler with a solid content of 65% by mass or more. Depending on the type of inorganic filler (D), Low linear expansion coefficient, high thermal conductivity, low water absorption, etc. can be easily realized, development is possible with dilute alkaline aqueous solution, and less gasification components are released at high temperatures from organic components such as resin. The present inventors have found that a curable resin composition can be provided and have completed the present invention.
[0012] より好適な態様としては、前記カルボキシル基含有共重合榭脂 (A)が、下記一般 式 (I)又は（Π)で示される化合物  As a more preferred embodiment, the carboxyl group-containing copolymer resin (A) is a compound represented by the following general formula (I) or (A)
[化 1]  [Chemical 1]
Figure imgf000004_0001
Figure imgf000004_0001
Figure imgf000004_0002
Figure imgf000004_0002
[0013] (式中、 R1は水素原子又はメチル基、 R2は炭素数 2〜6の直鎖又は分岐状のアルキ レン基、 R3は炭素数 3〜： LOのアルキレン基、 R4は二塩酸無水物残基を表わす。 ) を構成成分として含むカルボキシル基含有共重合榭脂である。 [Wherein 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.
[0014] また、前記活性エネルギー線により硬化する反応基を 2個以上有する化合物（B)が 、エチレン性不飽和結合を 2個以上有する化合物であり、かつ、前記光重合開始剤（ C)が、光ラジカル重合開始剤であることが、光硬化性の点から好ましい。  [0014] 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.
[0015] また、本発明の硬化性榭脂組成物において所望とする特性の実現を容易ならしめ るために、前記無機充填材 (D)の含有率は、固形分中に 80質量％以上であることが 好ましい。高熱伝導率化の観点からは、該無機充填材 (D)はその熱伝導率が 15W Ζπι·Κ以上であることが好ましぐ特に酸ィ匕アルミニウムであることが好ましい。 [0015] Further, in order to easily realize the desired characteristics in the curable resin composition of the present invention, 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 15πι · Κ or more, and is particularly preferably acid aluminum.
[0016] また、本発明の硬化性榭脂組成物の第二の態様としては、上記組成物に、更に、 ( Ε)熱硬化性成分を含有する光硬化性'熱硬化性組成物が提供される。この好適な 態様においては、前記熱硬化性成分 (Ε)が、分子中の 2個以上のォキシラン環を有 する多官能エポキシ榭脂である。  [0016] Further, as a second aspect of the curable resin composition of the present invention, there is provided a photocurable thermosetting composition containing (i) a thermosetting component in addition to the above composition. Is done. In this preferred embodiment, the thermosetting component (Ε) is a polyfunctional epoxy resin having two or more oxysilane rings in the molecule.
[0017] さらに別の態様としては、本発明の硬化性榭脂組成物は絶縁性であることが好まし い。  [0017] As yet another aspect, the curable resin composition of the present invention is preferably insulating.
[0018] また、他の態様としては、上記硬化性榭脂組成物を、活性エネルギー線照射及び [0018] As another aspect, the curable resin composition is irradiated with active energy rays and
Ζ又は熱硬化して得られる低線膨張率化、高熱伝導率化、低吸水率化に優れ、さら に高温時に榭脂などの有機成分力 放出されるガス化成分の少ない硬化物が提供 される。高熱伝導性の観点からは、該硬化物はその熱伝導率が lWZm'K以上であ ることが好ましい。 Provided is a cured product that is excellent in low coefficient of linear expansion, high thermal conductivity and low water absorption obtained by drought or heat curing, and also has little gasification component released, such as rosin and other organic components at high temperatures. The From the viewpoint of high thermal conductivity, the cured product preferably has a thermal conductivity of lWZm′K or more.
[0019] [発明の効果] [0019] [Effect of the invention]
本発明の硬化性榭脂組成物に用いられカルボキシル基含有共重合榭脂 (A)は、 共重合榭脂であるため、有機溶剤等で希釈しても、高い粘性を維持することができ、 これにより、無機充填材を高充填することが可能となり、硬化物の低線膨張率化、高 熱伝導率化、低吸水率化等が容易に達成することができる。  Since 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.
[0020] このような硬化物の低線膨張率化、高熱伝導率化、低吸水率化等が容易に達成で きる、本発明の硬化性榭脂組成物は、反りの問題が発生しやすい薄板のビルドアツ プ基板や発熱量の多い半導体チップを搭載したパッケージ基板のソルダーレジストと して、好適に用いることができる。 [0020] 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.
[0021] また、可視光反射性の高!、無機充填材ゃ遮光性のある無機充填材を用いることで[0021] Further, by using an inorganic filler having high visible light reflectivity and an inorganic filler having a light-shielding property.
、ソルダーレジストに光反射性や光拡散性または遮光性を付与することができ、光学 機能を要求する LEDデバイス等の光学デバイスに好適に用いることが出来る。 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.
[0022] さらに、榭脂などの有機成分が少ないことから、高温時に放出されるガス化成分が 少なぐ熱信頼性の高い基板が提供できる。 [0022] Furthermore, since there are few organic components such as rosin, it is possible to provide a highly reliable substrate with less gasified components released at high temperatures.
発明を実施するための最良の形態 [0023] 本発明の硬化性榭脂組成物の基本的な態様は、 (A)カルボキシル基含有共重合 榭脂、（B)活性エネルギー線により硬化する反応基を 2個以上有する化合物、（C) 光重合開始剤、及び (D)無機充填材を含有してなり、前記無機充填材 (D)の含有 率力 固形分中に 65質量％以上であることを特徴としている。さらに、耐熱性を向上 させるために、（E)熱硬化性成分を含有してもよい。 BEST MODE FOR CARRYING OUT THE INVENTION [0023] 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.
[0024] 以下、本発明の硬化性榭脂組成物の各構成成分について詳しく説明する。  [0024] Hereinafter, each component of the curable resin composition of the present invention will be described in detail.
[0025] まず、カルボキシル基含有共重合榭脂 (A)は、分子中にカルボキシル基を有する 公知慣用の共重合樹脂が使用できる。さらに、分子中にエチレン性不飽和結合を併 せ持つ共重合樹脂が、光硬化性ゃ耐現像性の面力 より好ましぐ使用できる。  [0025] First, as 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.
[0026] 具体的には、下記に列挙するようなカルボキシル基含有共重合樹脂が挙げられる  [0026] Specific examples include carboxyl group-containing copolymer resins as listed below.
[0027] (1) (メタ）アクリル酸などの不飽和カルボン酸と、それ以外の不飽和二重結合を有 する化合物の 1種類以上との共重合することにより得られるカルボキシル基含有共重 合樹脂、 [0027] (1) 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,
(2) (メタ）アクリル酸などの不飽和カルボン酸と、それ以外の不飽和二重結合を有 する化合物の 1種類以上との共重合体に、グリシジル (メタ)アタリレートや 3, 4—ェポ キシシクロへキシルメチル (メタ）アタリレートなどのエポキシ基と不飽和二重結合を有 する化合物や (メタ)アクリル酸クロライドなどによって、エチレン性不飽和基をベンダ ントとして付加させることによって得られる感光性のカルボキシル基含有共重合榭脂  (2) Copolymers of unsaturated carboxylic acids such as (meth) acrylic acid and one or more other compounds having unsaturated double bonds with glycidyl (meth) atarylate or 3, 4— Photosensitivity obtained by adding an ethylenically unsaturated group as a benton with a compound having an epoxy group and an unsaturated double bond such as epoxycyclohexylmethyl (meth) acrylate or (meth) acrylic acid chloride. -Functional carboxyl group-containing copolymer resin
(3)グリシジル (メタ）アタリレートや 3, 4—エポキシシクロへキシルメチル (メタ）アタリ レート等のエポキシ基と不飽和二重結合を有する化合物と、それ以外の不飽和二重 結合を有する化合物との共重合体に、（メタ)アクリル酸などの不飽和カルボン酸を反 応させ、生成した二級の水酸基に多塩基酸無水物を反応させて得られる感光性の力 ルポキシル基含有共重合榭脂、 (3) A compound having an unsaturated double bond with an epoxy group, such as glycidyl (meth) acrylate or 3, 4-epoxycyclohexylmethyl (meth) acrylate, and another compound having an unsaturated double bond This copolymer is reacted with an unsaturated carboxylic acid such as (meth) acrylic acid, and the resulting secondary hydroxyl group is reacted with a polybasic acid anhydride. Fat,
(4)無水マレイン酸などの不飽和二重結合を有する酸無水物と、それ以外の不飽 和二重結合を有する化合物との共重合体に、 2—ヒドロキシェチル (メタ)アタリレート などの水酸基と不飽和二重結合を有する化合物を反応させて得られる感光性のカル ボキシル基含有共重合榭脂、 (4) 2-hydroxyethyl (meth) acrylate, etc. for copolymers of acid anhydrides with unsaturated double bonds such as maleic anhydride and other compounds with unsaturated double bonds A photosensitive polymer obtained by reacting a hydroxyl group with a compound having an unsaturated double bond. Bauxyl group-containing copolymer resin
(5)ポリビニルアルコー誘導体などの水酸基含有共重合ポリマーに、多塩基酸無 水物を反応させて得られるカルボキシル基含有榭脂、  (5) A carboxyl group-containing resin obtained by reacting a hydroxyl group-containing copolymer such as a polyvinyl alcohol derivative with a polybasic acid anhydride,
(6)さらに上記カルボキシル基含有榭脂に、グリシジル (メタ)アタリレートや 3, 4— エポキシシクロへキシルメチル (メタ）アタリレートなどのエポキシ基と不飽和二重結合 を有する化合物を反応させて得られる感光性のカルボキシル基含有共重合榭脂等 が挙げられる。  (6) Further obtained by reacting the carboxyl group-containing resin with a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3, 4-epoxycyclohexylmethyl (meth) acrylate. And photosensitive carboxyl group-containing copolymer resin.
[0028] これら共重合榭脂 (A)の構成成分として、下記一般式 (I)又は (Π)で示される化合 物  [0028] As a constituent of these copolymerized resin (A), a compound represented by the following general formula (I) or (I)
[化 2]  [Chemical 2]
Figure imgf000007_0001
Figure imgf000007_0001
Figure imgf000007_0002
Figure imgf000007_0002
[0029] (式中、 R1は水素原子又はメチル基、 R2は炭素数 2〜6の直鎖又は分岐状のアルキ レン基、 R3は炭素数 3〜： LOのアルキレン基、 R4は二塩酸無水物残基を表わす。 ) を含んで!/ヽるカルボキシル基含有共重合樹脂が、前記無機充填材 (D)を高充填す るときのバインダー榭脂として好まし 、。 [In the formula, 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).
[0030] なお、本明細書において、（メタ)アタリレートとは、アタリレート、メタタリレート及びそ れらの混合物を総称する用語で、他の類似の表現につ！、ても同様である。  [0030] In the present specification, "(meth) atalylate" is a term that collectively refers to talate, metatalate, and a mixture thereof, and other similar expressions! The same is true.
[0031] 上記カルボキシル基含共重合榭脂 (A)の固形分酸価は、 40〜200mgKOHZg の範囲であり、より好ましくは 80〜120mgKOHZgの範囲である。カルボキシル基 含有共重合樹脂の酸価が 40mgKOH/g未満であるとアルカリ現像が困難となり、 一方、 200mgKOHZgを超えると現像液による露光部の溶解が進むために、必要 以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶 解剥離してしまい、正常なレジストパターンの描画が困難となるので好ましくない。 [0031] 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. When 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.
[0032] また、このようなカルボキシル基含有共重合榭脂 (A)の重量平均分子量は、 2, 00 0〜50, 000、好まし <ίま、 5, 000〜20, 000の範囲力 ^望まし!/ヽ。重量平均分子量力 、 2, 000未満の場合、塗膜の指触乾燥性が低下し、硬化物の耐衝撃性が得られ難 くなるので好ましくない。一方、重量平均分子量が、 50, 000を超えた場合、現像性 が低下するので好ましくな 、。  [0032] The weight average molecular weight of the carboxyl group-containing copolymer resin (A) is 2,000 to 50,000, preferably <ί, 5,000 to 20,000. Desire! / ヽ. When 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. On the other hand, when the weight average molecular weight exceeds 50,000, the developability is lowered, which is preferable.
[0033] 次に、前記活性エネルギー線により硬化する反応基を 2個以上有する化合物（Β)と しては、エチレン性不飽和結合を 2個以上有する化合物、ォキシラン環やォキセタン 環などのカチオン重合性の環状エーテルィ匕合物、カルコンゃ桂皮酸エステルなどの 光二量ィ匕する化合物などが挙げられる。これらの中で、光硬化性、保存安定性の面 から、  Next, 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. And photodimeric compounds such as chalcone cinnamate, and other cyclic ether compounds. Among these, from the viewpoint of photocurability and storage stability,
エチレン性不飽和結合を 2個以上有する化合物が好ましい。  A compound having two or more ethylenically unsaturated bonds is preferred.
[0034] 上記エチレン性不飽和結合を 2個以上有する化合物は、光硬化して、上記カルボ キシル基含有共重合榭脂 (Α)を希アルカリ水溶液に対して不溶ィ匕するために使用 するものである。その代表的なものとしては、例えば、 2—ヒドロキシェチル (メタ）ァク リレート、 1, 4 ブタンジオールジ（メタ）アタリレート、 1, 6 へキサンジオールジ (メ タ）アタリレート、ネオペンチルグリコールジ (メタ）アタリレート、ポリエチレングリコール ジ（メタ）アタリレート、ネオペンチルグリコールアジペートジ (メタ）アタリレート、ヒドロキ シピバリン酸ネオペンチルグリコールジ (メタ）アタリレート、ジシクロペンタ -ルジ (メタ )アタリレート、力プロラタトン変性ジシクロペンタ-ルジ (メタ）アタリレート、 ΕΟ変性リ ン酸ジ (メタ）アタリレート、ァリル化シクロへキシルジ (メタ）アタリレート、イソシァヌレー トジ (メタ）アタリレート、トリメチロールプロパントリ（メタ）アタリレート、ジペンタエリスリト ールトリ（メタ）アタリレート、プロピオン酸変性ジペンタエリスリトールトリ（メタ）アタリレ ート、ペンタエリスリトールトリ（メタ）アタリレート、 ΡΟ変性トリメチロールプロパントリ（メ タ）アタリレート、トリス（アタリロイルォキシェチル)イソシァヌレート、プロピオン酸変性 ジペンタエリスリトールペンタ（メタ）アタリレート、ジペンタエリスリトールへキサ（メタ）ァ タリレート、力プロラタトン変性ジペンタエリスリトールへキサ (メタ）アタリレート等が挙 げられる。 [0034] The compound having two or more ethylenically unsaturated bonds is used for photocuring and insolubilizing the carboxyl group-containing copolymer resin (榭) 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, ΕΟ-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, ΡΟ modified trimethylol propane tri (meth) acrylate, tris (ataryl oxychase) Til) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hex (meth) acrylate, force prolatataton modified dipentaerythritol hex (meth) acrylate, etc. I can get lost.
[0035] これらの中で、特に耐現像性の面から、二官能以上、好ましくは三官能以上の (メタ )アタリレートが好ましい。  Of these, from the standpoint of development resistance, bifunctional or higher, preferably trifunctional or higher (meth) acrylate is preferable.
[0036] これらのエチレン性不飽和結合を 2個以上有する化合物等の活性エネルギー線に より硬化する反応基を 2個以上有する化合物（B)の配合量としては、前記カルボキシ ル基含有共重合榭脂 (A) 100質量部に対して、 5〜100質量部が好ましぐ特に好 ましくは 10〜50質量部である。前記 (B)成分が 5質量部未満の場合、十分な硬化性 が得られず、設計通りのパターン形状が得られなくなる。一方、 100質量部を超えた 場合、指触乾燥性が悪くなり、好ましくない。  [0036] 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. When the component (B) is less than 5 parts by mass, sufficient curability cannot be obtained and a pattern shape as designed cannot be obtained. On the other hand, when the amount exceeds 100 parts by mass, the dryness to the touch is deteriorated, which is not preferable.
[0037] 本発明に用いられる前記光重合開始剤 (C)としては、活性エネルギー線照射によ り、活性基を発生する化合物、例えば光ラジカル重合開始剤、光力チオン重合開始 剤、光ァ-オン重合開始剤などが挙げられる。これらの中で、光ラジカル重合開始剤 力 光硬化性、保存安定性、硬化物の電気特性等から好ましい。  [0037] 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.
[0038] 上記光ラジカル重合開始剤としては、公知慣用のもの、例えば、ベンゾイン、ベンゾ インメチルエーテル、ベンゾインェチルエーテル、ベンゾインイソプロピルエーテル等 のべンゾインとベンゾインアルキルエーテル類；ァセトフエノン、 2, 2—ジメトキシ一 2 —フエ-ルァセトフエノン、 2, 2—ジエトキシ一 2—フエ-ルァセトフエノン、 2, 2—ジ エトキシ一 2—フエ-ルァセトフエノン、 1, 1—ジクロロアセトフエノン等のァセトフエノ ン類； 2 メチル 1 [4 （メチルチオ）フエ-ル] 2 モルフォリノプロパン 1 オン、 2—ベンジル一 2—ジメチルァミノ一 1— (4—モルフォリノフエ-ル）一ブタノン —1等のアミノアセトフエノン類； 2—メチルアントラキノン、 2—ェチルアントラキノン、 2 ターシャリーブチルアントラキノン、 1 クロ口アントラキノン等のアントラキノン類； 2 , 4 ジメチルチオキサントン、 2, 4 ジェチルチオキサントン、 2 クロ口チォキサン トン、 2, 4 ジイソプロピルチオキサントン等のチォキサントン類；ァセトフエノンジメチ ルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフエノン等のベンゾフ エノン類；又はキサントン類；（2, 6 ジメトキシベンゾィル）—2, 4, 4 ペンチルホス フィンオキサイド、ビス（2, 4, 6 トリメチルベンゾィル） フエ-ルフォスフィンォキサ イド、 2, 4, 6 トリメチルベンゾィルジフエ-ルフォスフィンオキサイド、ェチルー 2, 4 , 6 -トリメチルベンゾィルフエ-ルフォスフイネイト等のフォスフィンオキサイド類など が挙げられ、これら公知慣用の光ラジカル重合開始剤は、単独で又は 2種以上を組 み合わせて用いることができる。 [0038] Examples of the radical photopolymerization initiator 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 anthraquinone, 1 black mouth Anthraquinones such as laquinone; thioxanthones such as 2,4 dimethylthioxanthone, 2,4 jetylthioxanthone, 2 chlorothioxanthone, 2,4 diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone Benzophenones such as: xanthones; (2, 6 dimethoxybenzoyl) -2,4,4 pentylphosphine oxide, bis (2,4,6 trimethylbenzoyl) phenolphosphine oxide, 2 , 4, 6 Trimethylbenzoyldiphosphine oxide, ethyl 2, 4 Phosphine oxides such as 1,6-trimethylbenzoylphosphinate and the like, and these known and commonly used radical photopolymerization initiators can be used alone or in combination of two or more.
[0039] これら光ラジカル重合開始剤等の光重合開始剤 (C)の配合量は、前記カルボキシ ル基含有共重合榭脂 (Α) 100質量部に対して、 0. 1〜30質量部、好ましくは、 2〜2 0質量部の割合で含まれることが好ましい。この（C)成分の配合量力 カルボキシル 基含有共重合榭脂 (Α) 100質量部に対して、 0. 1質量部未満の場合、光硬化性や 作業性が低下するので好ましくない。一方、 30質量部を超えた場合、塗膜特性が低 下するので、好ましくない。  [0039] 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 (榭). 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 (榭) 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.
[0040] 本発明の硬化性榭脂組成物に用いられる無機充填材 (D)としては、適宜選択する ことができる。例えば、絶縁性硬化性榭脂組成物に用いられ得る公知慣用の無機充 填材としては、結晶性シリカ、溶融シリカ、硫酸バリウム、タルク、クレー、水酸化アルミ ユウム、酸ィ匕アルミニウム、窒化ホウ素、窒化アルミニウム、酸化マグネシウム、炭酸マ グネシゥム、酸化亜鉛、炭酸カルシウム、チタン酸バリウムなどが挙げられる。これら は用途、 目的により使い分けられる。また、導電性硬化性榭脂組成物に用いられ得る 公知慣用の無機充填材としては、銅粉、銀粉などの導電性を有する金属粉が挙げら れ、これらも用途、 目的により使い分けられる。  [0040] The inorganic filler (D) used in the curable resin composition of the present invention can be appropriately selected. For example, 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. In addition, 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.
[0041] これら無機充填材のうち、熱伝導率が 15WZm'K以上の無機充填材 (D)としては 、熱伝導率が約 15WZm · Kとなる純度 92%以上の酸化アルミニウム（40WZm · K )、窒化ホウ素（40WZm'K以上）、窒化アルミニウム（260WZm'K)、酸化マグネ シゥム（60WZm'K)、酸化亜鉛 (45WZm'K)などの絶縁性を有する化合物や、 銅粉（380WZm'K)、銀粉 (420WZm'K)などの導電性を有する金属粉が挙げら れる。  [0041] Among these inorganic fillers, as 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, copper powder (380WZm'K) And conductive metal powders such as silver powder (420WZm'K).
[0042] これらの中でも溶融シリカは低線膨張率ィ匕の観点力 好ましぐまた酸ィ匕アルミ-ゥ ムは高熱伝導率化、耐薬品性の観点から好まし 、。  [0042] Among these, fused silica is preferable from the viewpoint of low linear expansion coefficient, and acid aluminum is preferable from the viewpoint of high thermal conductivity and chemical resistance.
[0043] これら無機充填材（D)の粒径としては、 30 μ m以下、好ましくは 20 μ m以下であり 、球状のものが、高充填化には好ましい。さらに、これらは、最密充填となるような粒 度分布を持つ 2種類以上の粒径のものを配合することが好ま ヽ。無機充填材 (D) の粒径が 30 mを超えた場合、塗膜表面から、無機充填材 (D)が脱落したり、無機 充填材 (D)の配合割合が低下するので、好ましくな!/、。 [0043] The particle size of these inorganic fillers (D) is 30 μm or less, preferably 20 μm 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.
[0044] このような無機充填材 (D)の配合量としては、固形物 (硬化物）中に、 65質量％以 上、好ましくは 80質量％以上、より好ましくは 90質量％以上である。上記無機充填材 (D)の配合量が、 65質量％未満の場合、本願発明の目的である無機充填材を高充 填することによりできる低線膨張率化、高熱伝導率化、低吸水率化等が困難になる ので、好ましくない。 [0044] 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). When the blending amount of the inorganic filler (D) is less than 65% by mass, 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.
[0045] 本発明の硬化性榭脂組成物は、硬化物の耐熱性を向上させるために、熱硬化性 成分 (E)を配合しても良い。上記熱硬化性成分としては、分子中の 2個以上のォキシ ラン環を有する多官能エポキシ榭脂、分子中の 2個以上のォキセタン環を有する多 官能ォキセタンィ匕合物、熱硬化性ポリイミド榭脂、メラミン榭脂などが挙げられる。  [0045] 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. Examples of the 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.
[0046] このような熱硬化性成分 (E)の配合量は、前記カルボキシル基含有共重合榭脂 (A ) 100質量部に対して、 0. 1〜50質量部、好ましくは 2〜30質量部である。  [0046] The blending amount of such a 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.
[0047] これらの中で、多官能エポキシ榭脂が、硬化性、保存安定性、硬化塗膜特性の面 から、好ましく用いられる。  Of these, polyfunctional epoxy resins are preferably used from the viewpoints of curability, storage stability, and cured coating film characteristics.
[0048] 上記多官能エポキシ榭脂としては、公知慣用のエポキシィ匕合物、例えばビスフエノ ール A型エポキシ榭脂、ビスフエノール F型エポキシ榭脂、ビスフエノール S型ェポキ シ榭脂、臭素化ビスフエノール A型エポキシ榭脂、水添ビスフエノール A型エポキシ 榭脂、ビフエノール型エポキシ榭脂、ビキシレノール型エポキシ榭脂、フエノールノボ ラック型エポキシ榭脂、クレゾ一ルノボラック型エポキシ榭脂、臭素化フエノールノボラ ック型エポキシ榭脂、ビスフエノール Aのノボラック型エポキシ榭脂などのグリシジル エーテル化合物；テレフタル酸ジグリシジルエステル、へキサヒドロフタル酸ジグリシジ ルエステル、ダイマー酸ジグリシジルエステルなどのグリシジルエステル化合物；トリグ リシジノレイソシァヌレート、 N, N, Ν' , Ν，ーテトラグリシジルメタキシレンジァミン、 Ν, Ν, Ν' , Ν'—テトラグリシジルビスアミノメチルシクロへキサン、 Ν, Ν—ジグリシジル ァ-リンなどのグリシジルァミンィ匕合物；ポリブタジエンなどの不飽和結合を持つ榭脂 を酸ィ匕して得られるエポキシィ匕ポリブタジエンなどが挙げられる。さらに、グリシシル（ メタ)アタリレートの共重合榭脂などが使用できる。 [0049] これらの多官能エポキシィ匕合物は、単独又は 2種類以上を組み合わせて用いること ができる。その配合量は、前記カルボキシル基含有共重合榭脂 (A)のカルボキシル 基 1当量に対して、 0. 6〜2. 0当量、好ましくは、 0. 8〜1. 5当量となる範囲である。 多官能エポキシィ匕合物の配合量力 上記範囲より少ない場合、カルボキシル基が残 り、耐熱性、耐アルカリ性、電気絶縁性などが低下するので、好ましくない。一方、上 記範囲を超えた場合、低分子量の多官能エポキシ榭脂が残存することにより、塗膜 の強度などが低下するので、好ましくない。 [0048] Examples of the polyfunctional epoxy resins 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. Phenolic type A epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated phenol Glycidyl ether compounds such as borac-type epoxy resin and bisphenol A novolak-type epoxy resin; glycidyl ester compounds such as terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester and dimer acid diglycidyl ester; Ginoleisocyanurate, N, N, Ν ' , Ν, -tetraglycidyl metaxylene diamine, Ν, Ν, Ν ', Ν'-tetraglycidyl bisaminomethylcyclohexane, Ν, Ν-diglycidyl diamine, and other glycidylamine compounds; polybutadiene Examples thereof include epoxy polybutadiene obtained by acidifying a resin having an unsaturated bond. Furthermore, glycidyl (meth) acrylate copolymer coagulants can be used. [0049] 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.
[0050] 本発明の硬化性榭脂組成物は、さらに高充填化を容易にするために、（F)湿潤- 分散剤を添加することが好ましい。このような湿潤'分散剤 (F)としては、カルボキシ ル基、水酸基、酸エステルなどの無機充填材 (D)と親和性のある極性基を有するィ匕 合物や高分子化合物、例えばリン酸エステル類などの酸含有化合物や、酸基を含む 共重合物、水酸基含有ポリカルボン酸エステル、ポリシロキサン、長鎖ポリアミノアマ イドと酸エステルの塩などを用いることができる。市販されて 、る湿潤 ·分散剤 (F)で 特に好適に用いることができるものとしては、 Disperbyk (登録商標）一 101、一103 、—110、—111、—160、—171、—174、—190、—300、 Bykumen (登録商標） 、 BYK-P105,— P104、— P104S、— 240 (いずれもビック'ケミ一社製）、 EFKA —ポリマー 150、 EFKA— 44、—63、—64、—65、—66、—71、—764、—766、 N (V、ずれもエフ力社製）が挙げられる。  [0050] The curable resin composition of the present invention is preferably added with (F) a wetting and dispersing agent in order to facilitate higher filling. Examples of such 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). —190, —300, Bykumen (registered trademark), 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.).
[0051] このような湿潤 '分散剤 (F)の配合量は、前記無機充填材 (D) 100質量部当り 0. 0 1〜5質量部が適当である。湿潤 ·分散剤 (F)の配合量が上記範囲よりも少な過ぎる と湿潤'分散剤添加の効果が得られず、組成物の高充填化することが困難となる。一 方、上記範囲よりも過剰に配合すれば、光硬化しない成分の割合が増加することから 、塗膜の強度が低下したり、組成物の揺変性増大の要因となるので好ましくない。  [0051] 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.
[0052] 本発明の硬化性榭脂組成物には、必要に応じて、粘度調整のために有機溶剤を 添加してもよい。前記有機溶剤としては、例えばメチルェチルケトン、シクロへキサノ ン等のケトン類；トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;セ 口ソルブ、メチルセ口ソルブ、ブチノレセロソノレブ、カルビトール、メチノレカノレビトーノレ、 ブチノレカルビトール、プロピレングリコーノレモノメチノレエーテル、ジプロピレングリコー ルモノメチルエーテル、ジプロピレングリコールジェチルエーテル、トリプロピレングリ コールモノメチルエーテル等のグリコールエーテル類；酢酸ェチル、酢酸ブチル、乳 酸ブチル、セロソルブアセテート、ブチルセ口ソルブアセテート、カルビトールァセテ ート、ブチノレカルビトーノレアセテート、プロピレングリコーノレモノメチノレエーテノレァセテ ート、ジプロピレングリコールモノメチルエーテルアセテート、炭酸プロピレン等のエス テル類;オクタン、デカン等の脂肪族炭化水素類;石油エーテル、石油ナフサ、ソル ベントナフサ等の石油系溶剤などの有機溶剤が使用できる。これらの有機溶剤は、 単独で又は 2種類以上を組み合わせて用いることができる。 [0052] If necessary, an organic solvent may be added to the curable resin composition of the present invention for viscosity adjustment. Examples of 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, propylene glycolenomonomethinoleatenoacetate, dipropylene glycol monomethyl ether acetate and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, Organic solvents such as petroleum-based solvents such as solvent naphtha can be used. These organic solvents can be used alone or in combination of two or more.
[0053] これら有機溶剤の配合量は、特に限定されるものでは無ぐ塗布方法に応じて、適 宜調整すれば良いが、一般的に組成物中に 50質量％以下、好ましくは 30質量％以 下である。有機溶剤の含有量が多いと、無機充填材 (D)の沈降スピードが上がり、保 存安定性が低下するので、好ましくない。  [0053] 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.
[0054] 本発明の硬化性榭脂組成物は、さらに必要に応じて、フタロシアニン'ブルー、フタ ロシア-ン.グリーン、アイォジン.グリーン、ジスァゾイェロー、クリスタルバイオレット、 酸化チタン、カーボンブラック、ナフタレンブラックなどの公知慣用の着色剤、ノ、イド口 キノン、ハイドロキノンモノメチルエーテル、 tーブチルカテコール、ピロガロール、フエ ノチアジンなどの公知慣用の熱重合禁止剤、微粉シリカ、有機ベントナイト、モンモリ ロナイトなどの公知慣用の増粘剤、シリコーン系、フッ素系、高分子系などの消泡剤 及び Z又はレべリング剤、イミダゾール系、チアゾール系、トリァゾール系等のシラン カップリング剤などのような公知慣用の添加剤類を配合することができる。  [0054] 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 colorants, 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 Addition of known and commonly used 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.
[0055] 本発明の硬化性榭脂組成物は、例えば前記有機溶剤で塗布方法に適した粘度に 調整し、基材上に、ディップコート法、フローコート法、ロールコート法、バーコ一ター 法、スクリーン印刷法、カーテンコート法等の方法により塗布し、約 60〜： LOO°Cの温 度で組成物中に含まれる有機溶剤を揮発乾燥 (仮乾燥)させることにより、タツタフリ 一の塗膜を形成できる。また、上記組成物をプラスチックフィルム上に塗布し、乾燥さ せてフィルムとして巻き取ったものを基材上に張り合わせることにより、榭脂絶縁層を 形成できる。その後、接触式 (又は非接触方式）により、ノ ターンを形成したフォトマス クを通して選択的に活性光線により露光し、未露光部を希アルカリ水溶液 (例えば 0. 3〜3%炭酸ソーダ水溶液）により現像してレジストパターンが形成される。さらに、例 えば約 140〜 180°Cの温度に加熱して熱硬化させることにより、前記カルボキシル基 含有共重合榭脂 (A)のカルボキシル基と、分子中に 2個以上のォキシラン環を有す る多官能エポキシ榭脂のエポキシ基が反応し、耐熱性などの諸特性に優れた硬化 塗膜を形成することができる。 [0055] 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. In addition, a resin insulation layer can be formed by applying the composition on a plastic film, drying it, and laminating it on a substrate. After that, 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. Furthermore, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, 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.
[0056] ここで、塗膜を光硬化させるための照射光源としては、低圧水銀灯、中圧水銀灯、 高圧水銀灯、超高圧水銀灯、キセノンランプ又はメタルノ、ライドランプが適当である。 その他、レーザー光線なども露光用活性光源として利用し、直接描画することができ る。 Here, as an irradiation light source for photocuring the coating film, 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. In addition, a laser beam or the like can also be used as an exposure active light source for direct drawing.
[0057] また、上記現像に用いられる希アルカリ水溶液としては、水酸ィ匕カリウム、水酸化ナ トリウム、炭酸ナトリウム、炭酸カリウム、ケィ酸ナトリウム、アンモニア、アミン類などの アルカリ水溶液が使用でき、特に、炭酸ナトリウムが好ましい。  [0057] Further, as the dilute alkaline aqueous solution used for the development, 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.
[0058] また、塗布'揮発乾燥を 2回以上繰り返し、塗膜を積層することで立体的な絶縁構 造も形成できる。さらに現像後の塗膜に Tg以上の熱をかけ、ノターン側壁をなめらか なテーパー状に熱変形させてもよい。ここで露光および現像は塗布 ·揮発乾燥の都 度行ってもよぐ一括で行ってもよい。  [0058] 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.
実施例  Example
[0059] 次に本発明の実施例及び比較例を示して本発明につ 、て具体的に説明するが、 本発明が以下の実施例に限定されるものでないことは言うまでもない。なお、以下に おいて「部」及び「％」とあるのは、特に断りのない限り全て「質量部」及び「質量％」を 表わす。  Next, the present invention will be described in detail with reference to examples and comparative examples of the present invention, but it goes without saying that the present invention is not limited to the following examples. In the following, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.
[0060] <合成例 1 > (カルボキシル基含有共重合榭脂 Aの合成）  <Synthesis Example 1> (Synthesis of carboxyl group-containing copolymer resin A)
攪拌機、温度計、還流冷却管、滴下ロートおよび窒素導入管を備えた 2リットルセパ ラブルフラスコに、ジエチレングリコールジメチルエーテル 900g、および tーブチルバ 一ォキシ 2—ェチルへキサノエート [日本油脂 (株)製パーブチル 0] 21. 4gを仕込み 、 90°Cに昇温後、メタクリル酸 309. 9g、メタクリル酸メチル 116. 4g、及び一般式 (I) で示されるラタトン変性 2—ヒドロキシェチルメタタリレート [ダイセルィ匕学工業 (株)製 プラクセル FM1] 109. 8gをビス（4— t—ブチルシクロへキシル）パーォキシジカーボ ネート [日本油脂 (株)製パーロィル TCP] 21. 4gと共にジエチレングリコールジメチ ルエーテル中に 3時間かけて滴下し、さらに 6時間熟成することによってカルボキシル 基含有共重合榭脂 (A)溶液を得た。反応は、窒素雰囲気下で行った。 In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, diethylene glycol dimethyl ether 900 g and tert-butyl 2-ethyl hexanoate [Nippon Yushi Co., Ltd. Perbutyl 0] 21 4g was charged and the temperature was raised to 90 ° C. 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and latathone modified 2-hydroxyethyl methacrylate represented by the general formula (I) [Daicel PLACCEL FM1] 109. 8g of bis (4-tert-butylcyclohexyl) peroxy dicarbo Nate [Nippon Yushi Co., Ltd. Paryl TCP] 21.4 g was added dropwise to diethylene glycol dimethyl ether over 3 hours and aged for 6 hours to obtain a carboxyl group-containing copolymerized resin (A) solution. The reaction was performed under a nitrogen atmosphere.
[0061] 次に上記カルボキシル基含有共重合榭脂 (A)溶液に、 3, 4—エポキシシクロへキ シルメチルアタリレート [ダイセル化学 (株）製サイクロマー A200] 363. 9g、ジメチル ベンジルァミン 3. 6g、ハイドロキノンモノメチルエーテル 1. 80gを加え、 100°Cに昇 温し、撹拌することによってエポキシの開環付加反応を行った。 16時間後、固形分 酸価 = 108. 9mgKOHZg、重量平均分子量 =25, 000 (スチレン換算）の感光性 のカルボキシル基含有共重合榭脂 (A)を、 53. 8質量％ (不揮発分)含む溶液を得 た。以下、この反応溶液を A—1ワニスと称す。  [0061] Next, the carboxyl group-containing copolymer resin (A) solution was charged with 3,4-epoxycyclohexylmethyl acrylate [Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd.] 363.9 g, dimethyl benzylamine 3. 6 g and 1.80 g of hydroquinone monomethyl ether were added, and the mixture was heated to 100 ° C and stirred to carry out an epoxy ring-opening addition reaction. 16 hours later, containing 53.8% by mass (non-volatile content) of photosensitive carboxyl group-containing copolymer resin (A) with a solid content of acid value = 108.9 mgKOHZg and weight average molecular weight = 25,000 (in terms of styrene) A solution was obtained. Hereinafter, this reaction solution is referred to as A-1 varnish.
[0062] <比較合成例 1 > (カルボキシル基含有樹脂の合成）  [0062] <Comparative Synthesis Example 1> (Synthesis of carboxyl group-containing resin)
温度計、撹拌器、滴下ロート、及び還流冷却器を備えたフラスコに、クレゾ一ルノボ ラック型エポキシ榭脂（ェピクロン N— 680、大日本インキ化学工業社製、エポキシ当 量 =210) 210gとカノレビトーノレアセテート 96. 4gを量り取り、カロ熱溶解した。次に、重 合禁止剤としてノ、イドロキノン 0. lgと、反応触媒としてトリフエ-ルホスフィン 2. Ogを カロえた。この混合物を 95〜105°Cに加熱し、アクリル酸 72gを徐々に滴下し、酸価が 3. OmgKOHZg以下になるまで、約 16時間反応させた。この反応生成物を、 80〜 90°Cまで冷却し、テトラヒドロフタル酸無水物 76. lgをカ卩え、赤外吸光分析により、 酸無水物の吸収ピーク（1780cm_1)が無くなるまで、約 6時間反応させた。この反応 液に、出光石油化学社製の芳香族系溶剤ィブゾール # 150 96. 4gを加え、希釈し た後、取り出した。このようにして得られたカルボキシル基含有の感光性ポリマー溶液 は、不揮発分 =65質量％、固形物の酸価 78mgKOHZgであった。以下、この反応 溶液を R—1ワニスと称す。 In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, cresol-type novolac epoxy resin (Epiclon N-680, manufactured by Dainippon Ink & Chemicals, epoxy equivalent = 210) 96.4 g of Levitonole acetate was weighed and melted with hot heat. Next, 0.1 g of idroquinone as a polymerization inhibitor and 2. Og of triphenylphosphine as a reaction catalyst were obtained. This mixture was heated to 95 to 105 ° C., 72 g of acrylic acid was gradually added dropwise, and the mixture was allowed to react for about 16 hours until the acid value became 3. OmgKOHZg or less. The 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. To this 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. Hereinafter, this reaction solution is referred to as R-1 varnish.
[0063] 実施例 1〜4及び比較例 1  [0063] Examples 1 to 4 and Comparative Example 1
前記合成例で得られた A— 1ワニス及び R— 1ワニスを用いた表 1に示す配合成分 を、 3本ロールミルで混練し、硬化性榭脂組成物を得た。各硬化性組成物の特性評 価結果を、表 2に示す。  The compounding ingredients shown in Table 1 using the A-1 varnish and R-1 varnish obtained in the above synthesis example were kneaded with a three-roll mill to obtain a curable resin composition. Table 2 shows the results of characteristic evaluation of each curable composition.
[表 1] 表 1 [table 1] table 1
Figure imgf000016_0001
Figure imgf000016_0001
[表 2]  [Table 2]
表 2  Table 2
Figure imgf000016_0002
Figure imgf000016_0002
[0064] *：高充填でのインキ化が出来な力つた。  [0064] *: It was strong enough to make ink with high filling.
なお、上記表 2中の性能試験の方法は以下の通りである。  The performance test methods in Table 2 above are as follows.
[0065] 性能評価： [0065] Performance evaluation:
(1)熱伝導率  (1) Thermal conductivity
上記各実施例及び比較例の組成物を、試験基板上にスクリーン印刷で乾燥塗膜 が約 40 mとなるように全面塗布し、 80°Cで 20分乾燥した。室温まで冷却した後、 オーク製作所製の露光装置 (メタルノヽライドランプ 7KW2灯）にて減圧下、コダック製 ステップタブレット No. 2で約 6段となる露光量で全面露光した後、 30°Cの 1質量％N a CO水溶液をスプレー圧 0. 2MPaの条件で 60秒間現像を行った。 The 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.
2 3  twenty three
[0066] このようにして得られた硬化塗膜の 25〜125°Cでの熱伝導率を、レーザーフラッシ ュ法により測定した。  [0066] The thermal conductivity of the cured coating film thus obtained at 25 to 125 ° C was measured by a laser flash method.
[0067] (2)感度 [0067] (2) Sensitivity
上記各実施例及び比較例の組成物を、ガラスエポキシ基板上にスクリーン印刷で 全面塗布し、 80°Cで 20分乾燥し、室温まで放冷した後、コダック製ステップタブレット No. 2 (21段）をフォトマスクとして用い、オーク製作所製の露光装置 (メタルノヽライド ランプ 7KW2灯）にて減圧下、露光（365nmの紫外線の積算光量計で 200mjZcm 2、及び 600mjZcm2)し、 30。Cの l%Na CO水溶液をスプレー圧 0. 2MPaで 1分 The 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ヽ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
2 3  twenty three
間現像し、残った硬化塗膜の段数を目視で確認した。  Development was performed for a while, and the number of steps of the remaining cured coating film was visually confirmed.
[0068] (3)電気絶縁性  [0068] (3) Electrical insulation
前記の熱伝導率測定と同様に、 IPC B— 25テストパターンのクシ型電極 Bクーポ ンを用い、上記の条件で基板を作製し、このクシ型電極に DC500Vのバイアスを印 加し、絶縁抵抗値を測定した。  Similar to the thermal conductivity measurement described above, using a comb-type electrode B coupon with an IPC B-25 test pattern, a substrate was fabricated under the above conditions, and a bias of 500 V DC was applied to this comb-type electrode, and the insulation resistance The value was measured.
[0069] (4)耐酸性 [0069] (4) Acid resistance
前記の熱伝導率測定と同様に、回路形成されたガラスエポキシ基板上にスクリーン 印刷で全面塗布し、上記と条件で基板を作製し基板を、常温の 10vol%の硫酸水溶 液に、所定時間（10分間、 30分間）浸漬し、水洗後、セロハン粘着テープによるピー ルテストを行い、レジストの剥がれ'変色について評価した。  Similar to the above-described thermal conductivity measurement, 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.
[0070] 〇 ； 全く変化が認められないもの [0070] 〇; No change at all
△ ； ほんの僅か変化したもの  △; Slightly changed
X ； 塗膜に、剥がれがあるもの。  X: The coating film has peeling.
[0071] (5)吸水率 [0071] (5) Water absorption
前記の熱伝導率測定と同様に、予め質量を測定したガラス板に、上記各実施例及 び比較例の組成物をスクリーン印刷で全面塗布し、上記の条件で評価サンプルを得 た。これを室温まで冷却した後、評価サンプルの質量を測定した。次に、この評価サ ンプルを常温の純水に 24時間浸漬した後、表面に付着した水分を拭き取り、評価サ ンプルの質量を測定し、下記算出式により硬化物の吸水率を求めた。 Similar to the thermal conductivity measurement, the 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.
[0072] 吸水率 = (W2-W1) / (Wl -Wg) [0072] Water absorption rate = (W2-W1) / (Wl -Wg)
ここで、 W1は評価サンプルの質量、 W2は吸水後の評価サンプルの質量、 Wgは ガラス板の質量である。  Here, W1 is the mass of the evaluation sample, W2 is the mass of the evaluation sample after water absorption, and Wg is the mass of the glass plate.
[0073] (6)線膨張係数 [0073] (6) Linear expansion coefficient
前記の熱伝導率測定と同様に、硬化物単体を評価サンプルとし、 TMA法により a Similar to the thermal conductivity measurement described above, the cured product alone is used as an evaluation sample, and a
1 (Tg以下の線膨張係数)を測定した。 1 (linear expansion coefficient below Tg) was measured.
[0074] 表 2に示す結果力も明らかな如ぐ本発明の硬化性榭脂組成物によれば、無機充 填材を高充填することが可能となり、低線膨張率化、高熱伝導率化、低吸水率化等 が容易にでき、希アルカリ水溶液により現像可能な榭脂組成物を提供することが可 能となった。 [0074] According to the curable resin composition of the present invention, 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.
[0075] なお、高温時に放出されるガス化成分は、少な 、ことが確認できた。  [0075] It was confirmed that the gasification component released at high temperature was small.

Claims

請求の範囲 The scope of the claims
[1] (A)カルボキシル基含有共重合榭脂、（B)活性エネルギー線により硬化する反応 基を 2個以上有する化合物、（C)光重合開始剤、及び (D)無機充填材を含有してな り、前記無機充填材 (D)の含有率が、固形分中に 65質量％以上であることを特徴と するアルカリ現像可能な硬化性榭脂組成物。  [1] (A) a carboxyl group-containing copolymer resin, (B) a compound having two or more reactive groups that are cured by active energy rays, (C) a photopolymerization initiator, and (D) an inorganic filler. In other words, the alkali-developable curable resin composition is characterized in that the content of the inorganic filler (D) is 65% by mass or more in the solid content.
[2] 前記カルボキシル基含有共重合榭脂 (A)が、下記一般式 (I)又は (Π)で示される 化合物。  [2] A compound in which the carboxyl group-containing copolymer resin (A) is represented by the following general formula (I) or (I).
[化 1]
Figure imgf000019_0001
[Chemical 1]
Figure imgf000019_0001
hC—— R3— 0-HC—— IT—_ C— 0— H ( I I ) hC—— R 3 — 0-HC—— IT—_ C— 0— H (II)
(式中、 R1は水素原子又はメチル基、 R2は炭素数 2〜6の直鎖又は分岐状のアルキ レン基、 R3は炭素数 3〜： LOのアルキレン基、 R4は二塩酸無水物残基を表わす。 ) を構成成分として含むカルボキシル基含有共重合榭脂であることを特徴とする請求 項 1記載の硬化性榭脂組成物。 (Wherein 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: LO, and R 4 is dihydrochloric acid. The curable resin composition according to claim 1, which is a carboxyl group-containing copolymer resin containing an anhydride residue as a constituent component.
前記活性エネルギー線により硬化する反応基を 2個以上有する化合物（B)が、ェ チレン性不飽和結合を 2個以上有する化合物であり、かつ前記光重合開始剤 (C)が 、光ラジカル重合開始剤であることを特徴とする請求項 1又は 2に記載の硬化性榭脂 組成物。  The compound (B) having two or more reactive groups that are cured by the active energy ray is a compound having two or more ethylenically unsaturated bonds, and the photopolymerization initiator (C) is a radical photopolymerization initiator. The curable resin composition according to claim 1 or 2, wherein the composition is an agent.
前記無機充填材 (D)の含有率が、固形分中に 80質量％以上であることを特徴とす る請求項 1乃至 3のいずれか一項に記載の硬化性榭脂組成物。  4. The curable resin composition according to claim 1, wherein the content of the inorganic filler (D) is 80% by mass or more in the solid content. 5.
前記無機充填材 (D)の熱伝導率が、 15WZm'K以上であることを特徴とする請求 項 1乃至 4のいずれか一項に記載の硬化性榭脂組成物。 [6] 前記無機充填材 (D)力 酸ィ匕アルミニウムであることを特徴とする請求項 1乃至 5のThe curable resin composition according to any one of claims 1 to 4, wherein the inorganic filler (D) has a thermal conductivity of 15 WZm'K or more. [6] The inorganic filler (D) force is oxyaluminum.
V、ずれか一項に記載の硬化性榭脂組成物。 V, curable resin composition according to item 1
[7] 更に、（E)熱硬化性成分を含有することを特徴とする請求項 1乃至 6のいずれか一 項に記載の硬化性榭脂組成物。 [7] The curable resin composition according to any one of claims 1 to 6, further comprising (E) a thermosetting component.
[8] 前記熱硬化性成分 (E)が、分子中の 2個以上のォキシラン環を有する多官能ェポ キシ榭脂であることを特徴とする請求項 7に記載の硬化性榭脂組成物。 [8] The curable resin composition according to [7], wherein the thermosetting component (E) is a polyfunctional epoxy resin having two or more oxysilane rings in the molecule. .
[9] 絶縁性であることを特徴とする請求項 1乃至 8の 、ずれか一項に記載の硬化性榭 脂組成物。 [9] The curable resin composition according to any one of claims 1 to 8, wherein the curable resin composition is insulating.
[10] 請求項 1乃至 9のいずれか一項に記載の硬化性榭脂組成物を、活性エネルギー線 照射及び Z又は熱硬化して得られる硬化物。  [10] A cured product obtained by subjecting the curable resin composition according to any one of claims 1 to 9 to irradiation with active energy rays and Z or thermal curing.
[11] 熱伝導率が lWZm'K以上である請求項 10に記載の硬化物。 11. The cured product according to claim 10, wherein the thermal conductivity is lWZm'K or more.
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