WO2008018364A1

WO2008018364A1 - Prepreg, laminate and printed wiring board

Info

Publication number: WO2008018364A1
Application number: PCT/JP2007/065186
Authority: WO
Inventors: Masashi Kaji; Koichiro Ogami; Tomomi Fukunaga
Original assignee: Nippon Steel Chemical Co., Ltd.
Priority date: 2006-08-07
Filing date: 2007-08-02
Publication date: 2008-02-14
Also published as: JPWO2008018364A1; JP5234962B2; TW200833745A

Abstract

Disclosed is a printed wiring board having excellent heat-dissipating property because of good heat conductivity of an insulating layer. Also disclosed are a prepreg which enables to obtain such a printed wiring board, and a laminate. Specifically disclosed is a prepreg obtained by impregnating a sheet-like fiber base with an epoxy resin composition containing an epoxy resin and a curing agent, and half-curing the composition. A diphenyl ether epoxy resin obtained by epoxydizing a dihydroxydiphenyl ether is used as a part or all of the epoxy resin. A printed wiring board and a laminate are obtained by arranging materials including the prepreg in layers and subjecting the resulting to heat-press molding. In the prepreg cured product obtained by heat-press molding of the prepreg, a resin layer is crystallized, while having a melting point of 120-280˚C.

Description

Specification

Pre-preda, laminated board and printed wiring board

Technical field

[0001] 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.

Background art

[0002] As an epoxy resin composition excellent in high thermal conductivity, one using an epoxy resin having a mesogen structure is known. For example, 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. Further, 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

[0004] However, 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. Furthermore, 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. When 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. [0005] In addition, a cured product obtained from an epoxy resin having a mesogenic structure has high thermal conductivity, low thermal expansion, high heat resistance, and low moisture absorption, which are manifested by an improvement in crystallinity that does not progress sufficiently. Effects such as sex were not sufficient. Patent Document 4 describes a sealing agent using a biphenyl ether type epoxy resin, and only teaches its application to a sealing agent.

Disclosure of the invention

Problems to be solved by the invention

[0006] 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.

Means for solving the problem

[0007] 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.

[0008] That is, 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. In all, the present invention is a pre-preda characterized by using an epoxy resin represented by the following general formula (1).

(Here, m is a number from 1 to 3, and n is a number greater than or equal to 0.)

[0009] The epoxy resin represented by the general formula (1) includes an epoxy resin represented by the following general formula (2). Ru

(Where n is a number greater than or equal to 0)

As a part or all of the curing agent, a phenolic resin or an aromatic diamine compound represented by the following general formula (3) can be used. As the phenolic resin represented by the general formula (3), there is a phenolic resin represented by the following general formula (4). In the general formulas (3) and (4), m represents a number from 1 to 3, and q represents a number of 0 or more.

Further, 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. Here, in the above laminated board or printed wiring board, the resin phase is crystallized and preferably has a melting point of 120 ° C. to 280 ° C. Further, the present invention is a pre-precured cured product having a melting point of 120 ° C. to 280 ° C. in which a resin phase in a cured product obtained by heating and press-molding the above-mentioned pre-predator is crystallized. [0012] 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.

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] The epoxy resin represented by the general formula (1) is represented by the following general formula (5),

(However, m represents an integer from;! To 3.)

It can be produced by reacting the bisphenol compound represented by the formula with epichlorohydrin. This reaction can be performed in the same manner as a normal epoxidation reaction.

[0014] For example, after dissolving the bisphenol compound of the general formula (5) in an excess of epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, 50 to 150 ° C, preferably 60 to; 100 to 100 ° C for 1 to 10 hours. The amount of alkali metal hydroxide used here is 0.8—1.2 monolayers, preferably 0.9—1.0 monolayers, relative to 1 monohydroxy group of bisphenol compound. Epoxy chlorohydrin is used in an excess amount relative to the hydroxyl group in the bisphenol compound, and is usually 1.2 forces or 15 moles per mole of the hydroxyl group in the bisphenol compound. After completion of the reaction, excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene or methylisobutylketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off. By leaving, the desired epoxy resin can be obtained.

[0015] In the above general formula (1), η 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 | fusing point and a viscosity will become high and a handleability will fall.

In addition, in order to obtain a high molecular weight epoxy resin, 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.

In the above general formula (5), m is 1, 2 or 3, preferably 1 or 2.

Specifically, 4,4'-dihydroxydiphenyl ether, 1,4 bis (4-hydroxyphenoxy) benzene, 1,3 bis (4-hydroxyphenoxy) benzene, 1,3 bis (3 hydroxy) Ciphenoxy) benzene, 4,4 'bis (4-hydroxyphenoxy) diphenyl ether, 3,3'-bis (4-hydroxyphenoxy) diphenyl ether, 3,3'-bis (3-hydroxyphene) Noxy) diphenyl ether. 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.

Of the epoxy resins represented by the general formula (1), 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).

[0019] 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. In addition, 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

[0020] 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 1Ν-ΚΟΗ 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. [0021] In addition to the epoxy resin represented by the general formula (1), other epoxy resins having two or more epoxy groups in the molecule may be used in combination with the epoxy resin used in the present invention. 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, 1,4-Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxy are polyallylated, arylated bisphenol A, arylated bisphenol F, arylated phenol novolak, etc. 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 tetrabromobisphenol A. There are chemicals. These epoxy resins can be used alone or in combination of two or more.

[0022] As 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. [0023] Specific examples of the amine curing agent 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. Examples of the polyether polyamines 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, α- (m-aminophenyl) Ethylamine, α- (ρ-Aminophenyl) ethylamine, Diaminojetyldimethyldiphenylmethane, α, α'-bis (4-amino) Enyl)-p-Jie isopropyl benzene.

[0024] Specific examples of 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 glycol bis trimellitate, anhydrous het acid, nadic anhydride, methyl nadic anhydride, 5- (2, 5 Dioxotetrahydro-1,3 furanyl) 1-3 methinole-1, cyclohexan 1,2-dicarboxylic anhydride, 3,4-dicarboxy 1,2,3,4-tetrahydro-1 naphthalene succinic dianhydride, 1- Examples include methyl-dicarboxy-1,2,3,4 tetrahydrahydrate 1 naphthalene succinic dianhydride.

[0025] Specific examples of the phenolic curing agent 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.

[0026] These 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).

[0027] 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. . When the phenolic resin represented by the general formula (3) is used, 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. . By using more than the above amount of this phenolic resin, 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.

[0028] 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).

[0029] Among the phenolic resins represented by the general formula (3), 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. In the general formula (3), when q is 0, the phenolic resin is a bisphenol compound represented by the general formula (5).

[0030] In the general formula (3), 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. In this case, 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.

[0031] The bisphenol compound used as a raw material for the phenolic resin is preferably a bisphenol compound represented by the general formula (5). In the general formula (5), m is 1, 2 or 3, preferably 1 or 2. Specifically, 4,4'-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 (4-hydroxyphenoxy) diphenyl ether, 3,3'-bis (3-hydroxyphenoxy) Ii) Speaking of diphenyl ether. 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. [0032] In addition, 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.

[0033] Furthermore, 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. In the general formula (3) or (5), m is 1, 2, or 3 in the general formula (3) or (5), but is preferably 1 or 2. Specifically, 4,4'-dihydroxydiphenyl ether, 1,4 bis (4 hydroxyphenoxy) benzene, 1,3 bis (4 hydroxyphenoxy) benzene, 1,3 bis (3 hydroxyphenoxy) B) Benzene, 4,4'bis (4-hydroxyphenoxy) diphenyl ether, 3,3'-bis (4-hydroxyphenoxy) diphenyl ether, 3,3'-bis (3-hydroxyphene) Enoxy) Diphenyl ether.

[0034] 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. 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, tetraphenylphosphonium 'tetraphenylporate Tetraphenyl phosphonium. Rate, tetrabutyl phosphonyl © beam. Tetrasubstituted Hosuhoniumu 'tetrasubstituted borate, 2 Echiru 4-methyl Imidazonore' such Tetorapuchi Ruporeto Tetorafue two Ruporeto, and the like N-methylmorpholine 'Tetorafue two Ruporeto of any Tetorafue two Ruporon salt. The amount added is usually 0.2 to 10 parts by weight per 100 parts by weight of the epoxy resin. [0035] 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.

[0036] 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.

[0037] Furthermore, 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. Examples of 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. Aluminum, silicon nitride, etc., metal carbide, carbide, etc., metal hydroxide, aluminum hydroxide, magnesium hydroxide, etc., carbon material, carbon fiber, graphitized carbon fiber, natural graphite, artificial graphite, Examples thereof include spherical graphite particles, mesocarbon microphone mouth beads, whisker-like carbon, microcoiled carbon, nanocoiled carbon, carbon nanotube, and carbon nanohorn. As the shape of the inorganic filler, a crushed shape, a spherical shape, a whisker shape, or a fiber shape can be applied. 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.

[0038] 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.

[0039] 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.

[0040] 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. When the pre-preder layer is composed of a plurality of layers, it has at least one pre-preda of the present invention. Advantageously, it should be 50% or more, preferably 70% or more of the total pre-preda layer thickness in the laminate.

[0041] Another kind of base material can be laminated on one side or both sides or in the middle of the pre-preder layer. 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. And polymer base materials such as polyethylene naphthalate, liquid crystal polymer, polyamide, polyimide, and Teflon (registered trademark).

[0042] 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.

[0043] 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 | cured material, it is desirable for the resin phase to crystallize. 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. Here, 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. In order to increase the crystallinity of the cured epoxy resin, it is desirable to cure it at a low temperature for a long time. 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. Further, after forming, post-cure can increase the crystallinity. Usually 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.

Example [0045] Hereinafter, examples according to the present invention will be shown, and the present invention will be described in detail.

[0046] Synthesis Example 1

Dissolve 1010 g of 4,4, -dihydroxydiphenyl ether in 6475 g of epichlorohydrin and reduce the pressure (approx. 120 mmHg, 60. 48% sodium hydroxide aqueous solution at C at 808 g for 4 days. During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After that, 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. , 1Ν-ΚΟΗ, 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.

Three

It is. The melting point is a value obtained at a rate of temperature rise of 2 ° C / min by the one-way method.

[0047] Synthesis Example 2

Into a 1L, 4-separable flask equipped with a stirrer, thermometer, cooling tube, and nitrogen introduction tube, charge 489g of the epoxy resin synthesized in Synthesis Example 1 and 75.8g of 4,4'-dihydroxydiphenyl ether. After melt-mixing at 150 ° C with stirring under an air stream, 0.226 g of triphenylphosphine was added, and the reaction was carried out for 2 hours. After the reaction, the obtained epoxy resin (epoxy resin B) was allowed to cool to room temperature and showed crystallinity and solidified. 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. In addition, each component it in the general formula (1) obtained by GPC measurement of the obtained resin is n = 0 force 45.8%, 1 = 2 28.0%, n = 4 force 2. 3%, n≥6 force 3.9%. Here, the viscosity was measured with Rheomatt 115 manufactured by Contrabass. In addition, 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.

[0048] Example 1

In a 1L, 4 separable flask equipped with a stirrer, thermometer, cooling pipe, and nitrogen introduction pipe, epoxy resin A185.2g obtained in Synthesis Example 1 as an epoxy resin component, and a curing agent component, 4 , 4'-dihydroxydiphenyl ether (curing agent A) 141.8 g and 2-ethyl 4-methylimidazole 0.18 g as a curing accelerator were dissolved in 246 g of cyclohexanone and 0.5 at 120 ° C. It was made to react for time and the epoxy resin composition varnish was prepared. The viscosity at 25 ° C. in an E-type viscometer was 0.42 Pa ′s. Regarding the GPC measurement power, 25.7% of the epoxy resin obtained in Reference Example 1 remained, and 24.2% of 4,4′-dihydroxydiphenyl ether remained.

[0049] 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.

[0050] Example 2

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. Thus, an epoxy resin composition varnish was prepared. The viscosity at 25 ° C was 0.56 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.

[0051] Example 3

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.

[0052] 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.

[0053] Example 5

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.

[0054] Comparative Example 1

As an 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. Og, as a curing agent component 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.

[0055] Comparative Example 2

As an 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.

Yes

[0056] Comparative Example 3

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.

[0057] The measurement results are summarized in Table 1. In Table 1, Tg is the glass transition point, CTE is the coefficient of thermal expansion, HDT is the heat distortion temperature, and m.p. is the melting point. In the appearance, X is transparent, Δ is slightly turbid, and ◯ is completely opaque.

[0058] [Table 1]

Industrial applicability

[0059] According to the present invention, 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. In the printed wiring board of the present invention, 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.

Claims

The scope of the claims

An epoxy resin represented by the following general formula (1) is used as a part or all of the epoxy resin in 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. A pre-preda characterized by using

Here, m is a number from 1 to 3, and n is a number greater than or equal to 0.

[2] The pre-preda according to claim 1, wherein the epoxy resin represented by the general formula (1) is an epoxy resin represented by the following general formula (2).

Here, n represents a number of 0 or more.

[3] The pre-preda according to claim 1, wherein a phenolic resin represented by the following general formula (3) is used as a part or all of the curing agent.

Here, m is a number from 1 to 3, and q is a number greater than or equal to 0.

[4] Phenolic resin strength represented by general formula (3) Phenolic resin represented by the following general formula (4) 4. The resin according to claim 3, which is a functional resin

Here, q represents a number of 0 or more.

[5] The pre-preda according to [1], wherein an aromatic diamine compound is used as part or all of the curing agent.

[6] A laminated board obtained by heat-pressing a laminated material having the pre-preder according to any one of claims 1 to 5 as a whole layer or a part of a pre-preder layer.

[7] The resin phase in the cured product obtained by heat-press molding the prepreader according to any one of claims 1 to 5 is crystallized and has a melting point of 120 ° C to 280 ° C. Pre-precured cured product characterized by

[8] A printed wiring board comprising an insulating layer obtained by heating and pressing the layer of the pre-preder according to any one of [1] to [5].

[9] The printed wiring board according to claim 8, wherein the resin phase in the insulating layer is crystallized and has a melting point of 120 ° C to 280 ° C.