WO2008018364A1 - Préimprégné, stratifié et carte de câblage imprimé - Google Patents

Préimprégné, stratifié et carte de câblage imprimé Download PDF

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Publication number
WO2008018364A1
WO2008018364A1 PCT/JP2007/065186 JP2007065186W WO2008018364A1 WO 2008018364 A1 WO2008018364 A1 WO 2008018364A1 JP 2007065186 W JP2007065186 W JP 2007065186W WO 2008018364 A1 WO2008018364 A1 WO 2008018364A1
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WIPO (PCT)
Prior art keywords
epoxy resin
general formula
printed wiring
curing agent
wiring board
Prior art date
Application number
PCT/JP2007/065186
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English (en)
Japanese (ja)
Inventor
Masashi Kaji
Koichiro Ogami
Tomomi Fukunaga
Original Assignee
Nippon Steel Chemical Co., Ltd.
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Publication date
Application filed by Nippon Steel Chemical Co., Ltd. filed Critical Nippon Steel Chemical Co., Ltd.
Priority to JP2008528796A priority Critical patent/JP5234962B2/ja
Publication of WO2008018364A1 publication Critical patent/WO2008018364A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to an epoxy resin composition excellent in high thermal conductivity, low thermal expansion, high heat resistance and low moisture absorption, a pre-preda to which the epoxy resin composition is applied, and a laminate or printed wiring using the pre-preda. Regarding the board.
  • JP-A-7-90052 discloses a biphenol type epoxy resin. And epoxy resin composition containing polyhydric phenol resin curing agent as essential components, excellent stability and strength at high temperatures, and can be used in a wide range of fields such as adhesion, casting, sealing, molding and lamination Is disclosed.
  • Japanese Patent Application Laid-Open No. 9118673 discloses an epoxy compound having two mesogen structures connected by a bent chain in the molecule.
  • JP-A-11-323162 discloses a resin composition containing an epoxy compound having a mesogenic group.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 7 90052
  • Patent Document 2 JP-A-9 118673
  • Patent Document 3 Japanese Patent Laid-Open No. 11 323162
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004 123847
  • such an epoxy resin having a mesogenic structure has a feature that it is very difficult to dissolve in an organic solvent having a high melting point.
  • High temperatures are required to uniformly mix such epoxy resins with curing agents. At high temperatures, the epoxy resin cures rapidly and the gelation time is shortened, so the mixing process is severely limited and difficult to handle.
  • epoxy resin mixtures that are insoluble in organic solvents have a problem that it is difficult to produce prepregs and laminates that are difficult to impregnate fiber substrates.
  • a soluble third component was added to compensate for this drawback, the melting point of the resin was lowered and the resin was easily dissolved in an organic solvent, but the cured product had a problem that the thermal conductivity was lowered.
  • Patent Document 4 describes a sealing agent using a biphenyl ether type epoxy resin, and only teaches its application to a sealing agent.
  • the present invention is a pre-predder and laminate using an epoxy resin composition excellent in high thermal conductivity, low thermal expansion, high heat resistance and low hygroscopicity in addition to solubility in an organic solvent! / It is to provide a printed wiring board.
  • the present inventors have found that an extremely specific phenomenon of crystallization occurs even in a three-dimensional cross-linked state after the epoxy resin power curing reaction having a diphenyl ether structure.
  • the present invention can be achieved for the first time by applying this phenomenon to a pre-preda. Due to the development of crystallinity in the hardened state, the present invention has high thermal conductivity, low thermal expansion, high heat resistance and low resistance. It is possible to manufacture a laminated board having excellent characteristics with ensured hygroscopicity.
  • the present invention provides a pre-preda that is impregnated into a semi-cured state by impregnating a sheet-like fiber base material with an epoxy resin composition containing an epoxy resin and a curing agent.
  • the present invention is a pre-preda characterized by using an epoxy resin represented by the following general formula (1).
  • n is a number greater than or equal to 0.
  • the epoxy resin represented by the general formula (1) includes an epoxy resin represented by the following general formula (2).
  • n is a number greater than or equal to 0
  • a phenolic resin or an aromatic diamine compound represented by the following general formula (3) can be used as a part or all of the curing agent.
  • a phenolic resin represented by the general formula (3) there is a phenolic resin represented by the following general formula (4).
  • m represents a number from 1 to 3
  • q represents a number of 0 or more.
  • the present invention is a laminated board obtained by heat-pressing a laminated material having the above-mentioned pre-predder as all or a part of the pre-predder layer. Furthermore, this invention is a printed wiring board provided with the insulating layer formed by heat-press-molding the layer of said pre-preder.
  • the resin phase is crystallized and preferably has a melting point of 120 ° C. to 280 ° C.
  • the present invention is a pre-precured cured product having a melting point of 120 ° C. to 280 ° C.
  • the laminate according to the present invention is obtained by integrally laminating a laminate material having the above-mentioned pre-predder as all or a part of the pre-predator layer by heating and pressing.
  • the printed wiring board according to the present invention includes an insulating layer formed by heating and pressing the above-described pre-preder layer.
  • the epoxy resin represented by the general formula (1) is represented by the following general formula (5),
  • ⁇ is an integer greater than or equal to 0.
  • the value of S, n varies the molar ratio of epichlorohydrin used in the epoxy resin synthesis reaction to the bisphenol compound. Can be adjusted easily. Further, the average value of n is preferably in the range of 0.;! To 10 ⁇ 0. When larger than this, melting
  • n is 0 in the general formula (1).
  • a method in which an epoxy resin containing a main component as a main component and a bisphenol compound of the above general formula (5) is reacted in advance is employed.
  • m is 1, 2 or 3, preferably 1 or 2.
  • the raw material of the epoxy resin may be a mixture thereof, but is preferably 4,4′-dihydroxydiphenyl ether or a bisphenol compound having a content of 50 wt% or more.
  • an epoxy resin represented by the general formula (2) is preferably exemplified.
  • This epoxy resin is an epoxy resin in which m is 1 in the general formula (1), and n has the same meaning as that in the general formula (1).
  • the epoxy resin used in the prepreader of the present invention contains a part or all of the epoxy resin represented by the general formula (1), preferably 50 wt% or more, more preferably 70 wt% or more. If it is less than this, the crystallinity of the cured product will be reduced, and the effect of improving high thermal conductivity, low thermal expansion, high heat resistance and low hygroscopicity will be small.
  • the epoxy equivalent of the epoxy resin represented by the general formula (1) is usually in the range of 160 force, etc., and in the range of 50,000, from the viewpoint of imparting film properties and flexibility, Preferably it is the range of 400-40,000. It is preferable to satisfy this epoxy equivalent even when two or more epoxy resins are used. In this case, the epoxy equivalent is calculated by the total weight (g) / epoxy group (mono).
  • the purity of the epoxy resin, in particular, the amount of hydrolyzable chlorine, is less and / or better from the viewpoint of improving reliability. Although not particularly limited, it is preferably lOOOppm or less, more preferably 5 OOppm or less.
  • the hydrolyzable chlorine as used in the present invention means a value measured by the following method. That is, after dissolving 0.5 g of the sample in 30 ml of dioxane, add 1 ⁇ - ⁇ and 10 ml, boil and reflux for 30 minutes, cool to room temperature, add 100 ml of 80% acetone water, and add a potential difference with 0.002N-AgNO aqueous solution. This is a value obtained by titration.
  • epoxy resin represented by the general formula (1) examples include bisphenol A, bisphenol F, 3,3 ', 5,5'-tetramethyl-1,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone, 4, 4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenyl ketone, fluorene bisphenol, 4,4'-biphenol, 3,3 ', 5,5'-tetramethyl mono 4,4'-dihydroxybifu Enil, 2,2'-Bihuenore, Noduloquinone, Resonoresin, Force Teconole, t-Butinore Force Teconole, t-Butinorehydroquinone, 1,2-Dihydroxynaphthalene, 1,3-Dihydroxynaphthalene, 1,
  • Divalent phenols or phenol novolaks, bisphenol monoreno A novolaks, 0-crezo monorenovolacs, m-crezo monorenovolacs, p-crezo monorenovolacs, xylenol novolacs, poly-p-hydroxystyrene, tris-one (4-hydroxyphenol), methane, 1,1,2,2-tetrakis (4-hydroxyphenol) ethane, fluorologinole, pyrogallol, t-butyl pyrogallol, arylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxy Darcydyl ethers derived from trivalent or higher phenols such as benzophenone, phenol aralkyl resins, naphthol aralkyl resins, dicyclopentagen resins, or halogenated bisphenols such as tetrabromobis
  • the curing agent used in the present invention it is possible to use what is generally known as an epoxy resin curing agent.
  • examples include dicyandiamide, imidazoles, amine-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, polymercaptan-based curing agents, polyaminoamide-based curing agents, isocyanate-based curing agents, and block isocyanate-based curing.
  • Agents and the like include aliphatic amines, polyether polyamines, alicyclic amines, aromatic amines and the like.
  • Aliphatic amines include ethylene diamine, 1,3-diamine propane, 1,4-diamine propane, hexamethylene diamine, 2,5-dimethyl hexamethylene diamine, trimethyl hexamethylene diamine, Diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethynoleethylenediamine, tetra (hydroxyethyl) ethylenediamine Etc.
  • polyether polyamines examples include triethylene glycol diamine, tetraethylene glycol diamine, jetylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like.
  • Cycloaliphatic amines include isophorone diamine, metasendiamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methan, bis (aminomethyl) cyclohexane, 3,9- Bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, norbornene diamine and the like can be mentioned.
  • Aromatic amines include Tetrachrome-P-xylenediamine, m-xylenediamine, P-xylenediamine, m-phenylenediamine, 0-phenylenediamine, p-phenylenediamine, 2,4-diaminoanizone, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4 '-Diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethinole) phenol, triethanolamine, methylbenzylamine, ⁇ - (m-aminophenyl) Ethylamine, ⁇ - ( ⁇ -
  • the acid anhydride-based curing agent include dodecenyl succinic anhydride, polyadipic acid anhydrous, polyazelinic acid anhydride, polysebacic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, Poly (phenylhexadecanedioic anhydride), methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene Dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, anhydrous lid Phosphoric acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene
  • phenolic curing agent examples include bisphenol A, bisphenol F, phenol mononovolak, bisphenolenovol A, novolak, 0-crezo mononovolac, m-crezo mononorenopolac, P-cresol monovolak, Xylenol novolac, poly-p-hydroxystyrene, resorcin, force teconole, t-butylcatechol, t-butylhydroquinone, fluorologinol, pyrogallol, t-butyl pyrogallol, arylated pyrogallol, polyarinorelated pyrogalonore, 1, 2, 4 benzenetriol 2, 3, 4 trihydroxybenzophenone,
  • Dihydroxynaphthalene 2,5 dihydroxynaphthalene, 2,6 dihydroxynaphthalene, 2,7 dihydroxynaphthalene, 2,8 dihydroxynaphthalene, arylated or polyallylated products of the above-mentioned dihydroxynaphthalene, arylated bisphenol A, arylated bis Examples include phenol F, arylated phenol nopolac, and arylated pyrogallol.
  • curing agents may be appropriately selected in consideration of the physical properties of the resulting prepreader or laminated board! /, But preferably from the viewpoint of heat resistance, moisture resistance and electrical insulation, a phenolic curing agent or An aromatic diamine compound, particularly preferably a phenolic resin represented by the above general formula (3).
  • the amount of the curing agent to be added to the epoxy resin is usually determined so that the number of functional groups in the curing agent is in the range of 0.8 mol to 1.2 mol with respect to 1 mol of the epoxy group. .
  • the amount used is preferably 50% by weight or more, more preferably 70% by weight or more in the total curing agent component in the epoxy resin composition. .
  • a cured epoxy resin is obtained.
  • the crystallinity at the time is high, and the effects such as high thermal conductivity, low thermal expansion, high heat resistance and low hygroscopicity are excellent.
  • the hydroxyl group equivalent of the phenolic resin represented by the general formula (3) is usually in the range of 40,000 at 100 forces. However, in applications such as laminates, from the viewpoint of providing film properties and flexibility. The preferred range is 200 to 20,000. This hydroxyl equivalent is preferably satisfied even when two or more types of epoxy resins are used. In this case, the hydroxyl equivalent is calculated by the total weight (g) / hydroxyl (mole).
  • the phenolic resin represented by the general formula (4) is preferable, and examples thereof include a phenolic resin.
  • the phenolic resin represented by the general formula (4) is a phenolic resin in which m is 1 in the general formula (3), and q has the same meaning as that of the general formula (3). Note that n can be calculated from the above hydroxyl group equivalent, and may be calculated as an average value.
  • the phenolic resin is a bisphenol compound represented by the general formula (5).
  • this phenolic resin when q is a number greater than 0, this phenolic resin is produced, for example, by reacting the bisphenol compound of the general formula (5) with epichlorohydrin. That power S.
  • 1 mol or less of epichlorohydrin is used per 1 mol of hydroxyl group in the bisphenol compound, and the reaction is made in the presence of an alkali metal hydroxide.
  • the bisphenol compound used as a raw material for the phenolic resin is preferably a bisphenol compound represented by the general formula (5).
  • m is 1, 2 or 3, preferably 1 or 2.
  • diphenyl ether 1,4'-dihydroxydiphenyl ether, 1,4 bis (4 hydroxyphenoxy) benzene, 1,3 bis (4 hydroxyphenoxy) benzene, 1,3 bis (3 hydroxyphenoxy) Benzene, 4,4 'bis (4-hydroxyphenoxy) diphenyl ether, 3,3'-bis (3-hydroxyphenoxy) Ii)
  • the raw material of the phenolic resin may be a mixture thereof, but is preferably 4,4′-dihydroxydiphenyl ether or a bisphenol compound having a content of 50 wt% or more.
  • the phenolic resin represented by the general formula (3) is an epoxy resin mainly composed of the bisphenol compound of the general formula (5) and n of 0 in the general formula (1). It can also be synthesized by a reaction method. In this case, the usage ratio of the two is such that the epoxy group in the epoxy resin is 1 mol or less, preferably 0.1 to 0.9, more preferably 0.2 to 1 mol of the hydroxyl group in the bisphenol compound. Adjusted to be ⁇ 0.6.
  • the phenolic resin represented by the general formula (3) may be a single bisphenol compound in which q is 0 in the general formula (3), or a mixture thereof.
  • m is 1, 2, or 3 in the general formula (3) or (5), but is preferably 1 or 2.
  • the epoxy resin composition used in the present invention may contain a conventionally known curing accelerator in addition to the epoxy resin and the curing agent.
  • a conventionally known curing accelerator examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8 diazabicyclo (5,4,0) undecene-7, triethylenediamine, Tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methyl imidazole, 2 phenyl imidazole, 2 phenol 4 methyl imi Dazonole, 2 Imidazoles such as 1-heptadecylimidazole, Organic phosphines such as tributylphosphine, methyldiphenylenophosphine, triphenylenophosphine, diphenylenophosphine, phenenolephosphine, tetraphenyl
  • the amount added is usually 0.2 to 10 parts by weight per 100 parts by weight of the epoxy resin.
  • Thermoplastic oligomers can be added to the epoxy resin composition used in the present invention from the viewpoint of improving fluidity during molding and improving adhesion to a lead frame and the like.
  • Thermoplastic oligomers include C5 and C9 petroleum resins, styrene resins, indene resins, inden 'styrene copolymer resins, inden' styrene 'phenol copolymer resins, inden' coumarone copolymer resins, and inden 'benzothiophene copolymers.
  • Examples include polymerized resins. The addition amount is usually in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin.
  • the epoxy resin composition used in the present invention includes flame retardants such as brominated epoxy, mold release agents such as carnauba wax and ester wax, epoxy silane, amino silane, ureido silane, bur silane, alkyl silane, organic titanate, Power coupling agents such as aluminum alcoholate, colorants such as carbon black, flame retardant aids such as antimony trioxide, low stress agents such as silicone oil, lubricants such as higher fatty acids and higher fatty acid metal salts can be used.
  • flame retardants such as brominated epoxy
  • mold release agents such as carnauba wax and ester wax
  • epoxy silane amino silane, ureido silane, bur silane, alkyl silane, organic titanate
  • Power coupling agents such as aluminum alcoholate, colorants such as carbon black, flame retardant aids such as antimony trioxide, low stress agents such as silicone oil, lubricants such as higher fatty acids and higher fatty acid metal salts can be used.
  • an appropriate amount of an inorganic filler can be added to the epoxy resin composition in order to improve the thermal conductivity of the cured epoxy resin.
  • the inorganic filler include metals, metal oxides, metal nitrides, metal carbides, metal hydroxides, and carbon materials.
  • Metals include silver, copper, gold, platinum, and zircon, metal oxides include silica, aluminum oxide, magnesium oxide, titanium oxide, and tungsten trioxide, and metal nitrides include boron nitride and nitride.
  • a crushed shape, a spherical shape, a whisker shape, or a fiber shape can be applied as the shape of the inorganic filler.
  • These inorganic fillers may be blended alone or in combination of two or more. Ordinary coupling agent treatment may be applied to the inorganic filler for the purpose of improving the wettability between the inorganic filler and the epoxy resin, reinforcing the interface of the inorganic filler, and improving the dispersibility.
  • the epoxy resin composition used in the present invention is usually a sheet using a solvent as a varnish. It is preferable that the prepreg is produced by impregnating the fibrous fiber base material and drying it.
  • Solvents in this case include aromatic solvents such as benzene, toluene, xylene and black benzene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, hexane, heptane, and methylcyclohexane.
  • Aliphatic hydrocarbon solvents such as ethanol, alcohol solvents such as ethanol, isopropanol, butanol and ethylene glycol, ether solvents such as jetyl ether, divalent xylene, tetrahydrofuran and diethylene glycol dimethyl ether, N, N-dimethylformamide, N, N —Polar solvents such as dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone can be used.
  • a pre-preda according to the present invention is obtained by impregnating the above-mentioned epoxy resin composition into a sheet-like fiber base material (woven fabric or non-woven fabric) made of glass fiber or organic fiber, followed by drying by heating. Semi-cured state. Further, the epoxy resin composition obtained by heating and partially curing the above epoxy resin composition solution may be impregnated into a sheet-like fiber base material and dried by heating.
  • the laminated plate of the present invention is obtained by heat-pressing a laminated material having all or part of the pre-preder layer.
  • the laminated material may be composed only of the pre-predder layer or may have a layer other than the pre-predder layer.
  • the pre-preder layer is composed of a plurality of layers, it has at least one pre-preda of the present invention.
  • it should be 50% or more, preferably 70% or more of the total pre-preda layer thickness in the laminate.
  • the base material to be laminated includes sheet-like and film-like materials such as copper foil, aluminum foil, stainless steel foil, etc., polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, polyethylene terephthalate, polybutylene terephthalate.
  • polymer base materials such as polyethylene naphthalate, liquid crystal polymer, polyamide, polyimide, and Teflon (registered trademark).
  • a printed wiring board of the present invention is provided with an insulating layer formed by heat-pressing the above-mentioned pre-preder layer.
  • a single-sided printed wiring board, a double-sided printed wiring board, and further an inner layer with printed wiring Is a multilayer printed wiring board.
  • the pre-preder of the present invention When the pre-preder of the present invention is heated and pressure-molded, a pre-preda cured product is obtained.
  • This pre-preda As for hardened
  • the resin phase In the laminated board or printed wiring board of the present invention, the resin phase is preferably crystallized. Since the crystal phase grows in a turbid state and eventually becomes opaque, the force that can be confirmed by visual observation The degree of crystal phase growth can be estimated from the endothermic amount by differential thermal analysis.
  • the preferred endothermic amount is 10 J / g or more per unit weight of the resin component (corresponding to the total of the epoxy resin, the curing agent and the curing accelerator) excluding the filler, the sheet-like fiber base material, the metal foil and the like. More preferably, it is 30 J / g or more, and particularly preferably 60 J / g or more. If it is smaller than this, the effect of improving the thermal conductivity, low thermal expansion, high heat resistance and low hygroscopicity as a cured epoxy resin is small. Furthermore, those with a large endotherm, that is, those with a high degree of crystallinity, can maintain strength at high temperatures by maintaining crystallinity even if the glass transition point is low, and are practically heat resistant.
  • the heat distortion temperature can be kept high.
  • the melting point of the crystallized resin phase is in the range of 120 ° C to 280 ° C, preferably in the range of 150 ° C to 250 ° C.
  • the endothermic amount refers to the endothermic amount obtained by measuring with a differential thermal analyzer using a sample that weighed approximately 10 mg under a nitrogen stream at a temperature rising rate of 5 ° C / min.
  • the melting point is the endothermic peak temperature of differential thermal analysis.
  • the degree of crystallization of the resin can be adjusted by controlling the curing conditions of the pre-preda.
  • the optimum curing conditions largely depend on the compounding conditions of the epoxy resin composition, but usually the molding temperature is 80 ° C to 250 ° C, and the molding time is 1 minute to 20 hours.
  • the forming pressure is preferably in the range of 0.2 MPa to 20 MPa, but may be a vacuum press.
  • Preferred curing temperatures range from 120 ° C to 200 ° C, more preferably 140 ° C force, and 180 ° C.
  • the preferable curing time is 10 minutes to 6 hours, more preferably 30 minutes to 3 hours.
  • post-cure can increase the crystallinity.
  • the post cure temperature is 130 ° C to 250 ° C and the time ranges from 1 hour to 24 hours, but preferably 5 ° C to 50 ° C lower than the endothermic peak temperature in differential thermal analysis It is desirable to post-cure for 1 to 24 hours at temperature.
  • epichlorohydrin was distilled off under reduced pressure, dissolved in 3660 g of methylisoptyl ketone, and the salt formed by filtration was removed, and then 119.4 g of 20% aqueous sodium hydroxide solution was added, and 80 The reaction was allowed to proceed for 2 hours at ° C. After the reaction, filtration and washing with water were carried out, and then the solvent methylolisobutyl ketone was distilled off under reduced pressure to obtain 144 Og of light yellow crystalline epoxy resin (epoxy resin A).
  • the epoxy equivalent of the obtained epoxy resin is 163 g / eq.
  • Decomposable chlorine was 280 ppm, melting point was 78 force 84, C, 150.
  • Viscosity was 0.0026 Pa's, where hydrolysable chlorine was 0.5 g of sample dissolved in 30 ml of dioxane. , 1 ⁇ - ⁇ , 10ml was added, boiled and refluxed for 30 minutes, cooled to room temperature, and further added with 100ml of 80% acetone water, measured by potentiometric titration with 0.002N-AgNO aqueous solution.
  • the melting point is a value obtained at a rate of temperature rise of 2 ° C / min by the one-way method.
  • the epoxy resin thus obtained had an epoxy equivalent of 261 g / eq., A melting point of 100 power, a viscosity at 122 ° C and 150 ° C of 0.037 Pa's.
  • the viscosity was measured with Rheomatt 115 manufactured by Contrabass.
  • GPC measurement is performed using the following equipment: HLC-82A (manufactured by Tosohichi Co., Ltd.), column; TSK-GEL2000 X 3 and TSK-GEL4000 X 1 Solvent; tetrahydrofuran, flow rate; 1 ml / min, temperature; 38 ° C, detector; RI conditions were followed.
  • the epoxy resin composition was impregnated into a glass fiber woven fabric having a thickness of 0.07 mm and dried by heating at 150 ° C for 8 minutes to obtain a pre-preda.
  • the four pre-predas were stacked and devolatilized at a temperature of 130 ° C for 15 minutes using a vacuum press machine, and then heated and pressurized for 90 minutes under the conditions of a temperature of 175 ° C and a pressure of 2 MPa, and the thickness was 0.
  • a 4 mm laminate was obtained.
  • a plate-like sample of 50 mm ⁇ 120 mm was cut out from the laminated plate and subjected to various physical property measurements.
  • the epoxy resin component was the same as in Example 1 except that the epoxy resin B216.3g obtained in Synthesis Example 2 and the curing agent component were 4,4'-dihydroxydiphenyl ether (curing agent A) 83.7g.
  • an epoxy resin composition varnish was prepared.
  • the viscosity at 25 ° C was 0.56 Pa's.
  • a laminate was obtained in the same manner as in Example 1, and subjected to various physical property measurements.
  • Epoxy resin component epoxy resin A189.5g obtained in Synthesis Example 1, curing agent component 4,4'-dihydroxydiphenyl ether (curing agent A) 99.4 g and 4,4'-diaminodiphenyl sulfone (Curing agent B)
  • An epoxy resin composition varnish was prepared in the same manner as in Example 1 except that 11.0 g was used. The viscosity at 25 ° C. was 0.61 Pa ′s. Using this epoxy resin composition, a laminate was obtained in the same manner as in Example 1 and subjected to various physical property measurements.
  • Example 4 The epoxy resin component was the same as Example 1 except that the epoxy resin B242.3g obtained in Synthesis Example 2 and the curing agent component were 4,4'-diaminodiphenylsulfone (curing agent B) 57.6g Thus, an epoxy resin composition varnish was prepared. The viscosity at 25 ° C. was 0.78 Pa ′s. Using this epoxy resin composition, a laminate was obtained in the same manner as in Example 1, and subjected to various physical property measurements.
  • Epoxy resin component the epoxy resin A183.8g obtained in Synthesis Example 1, the curing agent component? 3 ⁇ — 4261 (curing agent: Gunei Chemical Co., phenol nopolak resin; OH equivalent 103 g / eq., Softening point 80 ° C) 116.
  • Epoxy resin composition in the same manner as in Example 1 except that lg was used. A varnish was prepared. The viscosity at 25 ° C. was 0.47 Pa ′s. Using this epoxy resin composition, a laminate was obtained in the same manner as in Example 1, and subjected to various physical property measurements.
  • epoxy resin component YD-128 (epoxy resin C: manufactured by Tohto Kasei Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 186 g / eq.) 193.
  • PSM— 4261 curing agent C: Gunei Chemical
  • the reaction was carried out in the same manner as in Example 1 using 106.9 g of phenol nopolac resin (OH equivalent 103 g / eq., Softening point 80 ° C.) to prepare an epoxy resin composition varnish.
  • the viscosity at 25 ° C. was 0.43 Pa ′s.
  • Using this epoxy resin composition a laminate was obtained in the same manner as in Example 1, and subjected to various physical property measurements.
  • epoxy resin component YD-128 (epoxy resin C: manufactured by Tohto Kasei, bisphenol A type epoxy resin, epoxy equivalent 186 g / eq.) 225. Og, 4, 4'- diaminodiphenyl as a curing agent component Using sulfone (curing agent B) 75. Og, the reaction was carried out in the same manner as in Example 1 to prepare an epoxy resin composition varnish. The viscosity at 25 ° C. was 0.61 Pa ′s. Using this epoxy resin composition, a laminate was obtained in the same manner as in Example 1 and subjected to various physical property measurements.
  • epoxy resin component As an epoxy resin component, YX-4000H (epoxy resin C: made by Japan Epoxy Resin, biphenyl type epoxy resin; epoxy equivalent 195 g / eq.) 196.3 g, hardener component and PSM-4261 (curing agent C: manufactured by Gunei Chemical Co., phenol nopolak resin; OH equivalent 103 g Zeq., Softening point 80 ° C) 103.7 g was used for the reaction in the same manner as in Example 1 to produce an epoxy. A resin composition varnish was prepared. The viscosity at 25 ° C in the E type viscometer was 0.45 Pa's. Using this epoxy resin composition, a laminate was obtained in the same manner as in Example 1, and subjected to various physical property measurements.
  • Tg is the glass transition point
  • CTE is the coefficient of thermal expansion
  • HDT is the heat distortion temperature
  • m.p. is the melting point.
  • X is transparent
  • ⁇ is slightly turbid
  • ⁇ is completely opaque.
  • an epoxy resin having a diphenyl ether structure is used as an epoxy resin component, and the diphenyl ether structure has a conventionally known epoxy resin having a mesogenic group which is a rigid main chain. Unlike the above, it has excellent solvent solubility characteristics, and is a pre-preder having excellent heat conductivity.
  • the thermal conductivity of the insulating layer is Since it has good heat dissipation, it is suitably used for printed wiring boards for automobile equipment, power supply unit boards for home appliances, PCs, servers, and other high-density mounting printed wiring boards.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une carte de câblage imprimé ayant d'excellentes propriétés de dissipation de la chaleur du fait d'une bonne conductivité thermique d'une couche isolante. L'invention concerne également un préimprégné qui permet d'obtenir une telle carte de câblage imprimé et un stratifié. L'invention concerne précisément un préimprégné obtenu en imprégnant une base de fibres semblable à une feuille d'une composition de résine époxyde contenant une résine époxyde et un durcisseur et en durcissant à moitié la composition. On utilise pour une partie ou la totalité de la résine époxyde une résine d'éther d'époxydiphényle obtenue en époxydant un éther de dihydroxydiphényle. On obtient une carte de câblage imprimé et un stratifié en disposant des matières comprenant le préimprégné en couches et en soumettant le stratifié résultant à un moulage par compression à chaud. Dans le produit durci du préimprégné obtenu par moulage par compression à chaud du préimprégné, une couche de résine est cristallisée, tout en ayant un point de fusion de 120-280°C.
PCT/JP2007/065186 2006-08-07 2007-08-02 Préimprégné, stratifié et carte de câblage imprimé WO2008018364A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009060897A1 (fr) * 2007-11-08 2009-05-14 Nippon Steel Chemical Co., Ltd. Résine époxy et son procédé de fabrication, composition de résine époxy et produit durci
WO2009113392A1 (fr) * 2008-03-13 2009-09-17 新日本製鐵株式会社 Plaque d'acier électromagnétique contenant un film de revêtement isolant qui présente une excellente conductivité thermique, et son procédé de fabrication
WO2009123058A1 (fr) * 2008-03-31 2009-10-08 新日鐵化学株式会社 Composition de résine époxy et objet moulé
JP2012233206A (ja) * 2012-09-03 2012-11-29 Nippon Steel & Sumikin Chemical Co Ltd エポキシ樹脂組成物および成形物
JP2013007047A (ja) * 2012-09-03 2013-01-10 Nippon Steel & Sumikin Chemical Co Ltd エポキシ樹脂組成物および成形物
KR20140077557A (ko) * 2012-12-14 2014-06-24 엘지이노텍 주식회사 에폭시 수지 조성물 및 이를 이용한 인쇄 회로 기판
JP2018065892A (ja) * 2016-10-17 2018-04-26 株式会社ダイセル シート状プリプレグ
WO2020100513A1 (fr) 2018-11-12 2020-05-22 東レ株式会社 Composition de résine époxy pour des matériaux composites renforcés par des fibres, produit durci en résine époxy, préforme et matériau composite renforcé par des fibres
WO2022209715A1 (fr) * 2021-03-30 2022-10-06 日鉄ケミカル＆マテリアル株式会社 Composition de résine époxy, préimprégné, et plastique renforcé par fibres obtenu à l'aide de ceux-ci

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5115645B2 (ja) * 2010-11-18 2013-01-09 住友ベークライト株式会社 絶縁性基板、金属張積層板、プリント配線板、及び半導体装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05140269A (ja) * 1991-11-26 1993-06-08 Matsushita Electric Works Ltd エポキシ樹脂組成物
JPH06239966A (ja) * 1993-02-16 1994-08-30 Nippon Kayaku Co Ltd エポキシ樹脂、エポキシ樹脂組成物およびその硬化物
JPH06313025A (ja) * 1993-04-28 1994-11-08 Nippon Steel Chem Co Ltd 新規エポキシ樹脂及びその製造方法並びにそれを用いたエポキシ樹脂組成物
JP2001329046A (ja) * 2000-05-24 2001-11-27 Japan Epoxy Resin Kk 半導体封止用エポキシ樹脂組成物、樹脂封止型半導体装置および半導体装置の実装方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4493748B2 (ja) * 1999-07-13 2010-06-30 新日鐵化学株式会社 エポキシ樹脂、その製造方法、エポキシ樹脂組成物およびその硬化物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05140269A (ja) * 1991-11-26 1993-06-08 Matsushita Electric Works Ltd エポキシ樹脂組成物
JPH06239966A (ja) * 1993-02-16 1994-08-30 Nippon Kayaku Co Ltd エポキシ樹脂、エポキシ樹脂組成物およびその硬化物
JPH06313025A (ja) * 1993-04-28 1994-11-08 Nippon Steel Chem Co Ltd 新規エポキシ樹脂及びその製造方法並びにそれを用いたエポキシ樹脂組成物
JP2001329046A (ja) * 2000-05-24 2001-11-27 Japan Epoxy Resin Kk 半導体封止用エポキシ樹脂組成物、樹脂封止型半導体装置および半導体装置の実装方法

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009060897A1 (fr) * 2007-11-08 2009-05-14 Nippon Steel Chemical Co., Ltd. Résine époxy et son procédé de fabrication, composition de résine époxy et produit durci
WO2009113392A1 (fr) * 2008-03-13 2009-09-17 新日本製鐵株式会社 Plaque d'acier électromagnétique contenant un film de revêtement isolant qui présente une excellente conductivité thermique, et son procédé de fabrication
JP4608600B2 (ja) * 2008-03-13 2011-01-12 新日本製鐵株式会社 熱伝導性に優れた絶縁被膜を持つ電磁鋼板及びその製造方法
JPWO2009113392A1 (ja) * 2008-03-13 2011-07-21 新日本製鐵株式会社 熱伝導性に優れた絶縁被膜を持つ電磁鋼板及びその製造方法
TWI494341B (zh) * 2008-03-31 2015-08-01 Nippon Steel & Sumikin Chem Co Epoxy resin compositions and shaped articles
WO2009123058A1 (fr) * 2008-03-31 2009-10-08 新日鐵化学株式会社 Composition de résine époxy et objet moulé
CN101970526B (zh) * 2008-03-31 2012-05-30 新日铁化学株式会社 环氧树脂组合物及成型物
JP2012233206A (ja) * 2012-09-03 2012-11-29 Nippon Steel & Sumikin Chemical Co Ltd エポキシ樹脂組成物および成形物
JP2013007047A (ja) * 2012-09-03 2013-01-10 Nippon Steel & Sumikin Chemical Co Ltd エポキシ樹脂組成物および成形物
KR20140077557A (ko) * 2012-12-14 2014-06-24 엘지이노텍 주식회사 에폭시 수지 조성물 및 이를 이용한 인쇄 회로 기판
KR101952356B1 (ko) * 2012-12-14 2019-02-26 엘지이노텍 주식회사 에폭시 수지 조성물 및 이를 이용한 인쇄 회로 기판
JP2018065892A (ja) * 2016-10-17 2018-04-26 株式会社ダイセル シート状プリプレグ
WO2018074221A1 (fr) * 2016-10-17 2018-04-26 株式会社ダイセル Préimprégné en forme de feuille
KR20190069408A (ko) * 2016-10-17 2019-06-19 주식회사 다이셀 시트상 프리프레그
KR102402277B1 (ko) 2016-10-17 2022-05-26 주식회사 다이셀 시트상 프리프레그
US11479637B2 (en) 2016-10-17 2022-10-25 Daicel Corporation Sheet-shaped prepreg
WO2020100513A1 (fr) 2018-11-12 2020-05-22 東レ株式会社 Composition de résine époxy pour des matériaux composites renforcés par des fibres, produit durci en résine époxy, préforme et matériau composite renforcé par des fibres
WO2022209715A1 (fr) * 2021-03-30 2022-10-06 日鉄ケミカル＆マテリアル株式会社 Composition de résine époxy, préimprégné, et plastique renforcé par fibres obtenu à l'aide de ceux-ci

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