JP2003292570A - Epoxy resin composition for laminated plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition imparting a printed circuit board material excellent in dielectric properties, molding properties, heat resistance, etc., and to provide a laminated plate and printed-circuit board comprising the same. <P>SOLUTION: The thermosetting resin composition comprises an epoxide of a polyphenylene ether oligomer having 700-3,000 of number average molecular weight and epoxy groups on both terminals, and a hardener and the laminated plate and the printed-circuit board using the same. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a composition using a novel epoxy resin and a copper clad laminate using the composition. The obtained composition has a low dielectric property, is excellent in moldability, and is a thermosetting resin composition useful for a printed wiring board that requires high reliability such as solder heat resistance after moisture absorption.

[0002]

2. Description of the Related Art In recent years, with the progress of communication, computers and the like, higher frequencies have been developed, and it is required for printed wiring boards to have low dielectric characteristics for the purpose of improving signal transmission speed. In order to meet this requirement, a thermoplastic resin such as a fluororesin having excellent dielectric properties or polyphenylene ale is usually used, but there are problems in workability, moldability, heat resistance and the like. This is because the solvent used for forming the varnish is limited, the melt viscosity is high, a multilayer structure cannot be obtained, and high temperature and high pressure are required during molding.

On the other hand, examples of the thermosetting resin include polyphenylene ether-modified epoxy resin and thermosetting polyphenylene ether. However, the same problems as those of the above-mentioned thermoplastic resins still remain. Cyanate ester resin is known as a thermosetting resin having good dielectric properties and moldability. However, when the cyanate ester resin alone is used, the cured product is too hard and brittle, and there is a problem in adhesiveness and solder resistance. Therefore, these drawbacks can be covered by using the epoxy resin together, but it has been difficult to meet the demand for lower dielectric properties of the laminated plate which has become more severe with the past use together with the epoxy resin.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermosetting resin which is excellent in dielectric properties as well as in moldability and heat resistance in printed wiring board materials, in the increasingly demanding performance requirements. It is intended to provide a composition, and a laminated board and a printed wiring board using the composition.

[0005]

The present invention aims to provide a thermosetting resin composition having excellent dielectric properties, moldability, and heat resistance, and as a result of diligent studies on an epoxy resin, a structural formula having epoxy groups at both ends is shown. By using the epoxy compound of the polyphenylene ether oligomer represented by (1) as a constituent material of the epoxy resin composition for laminates, it was found that the above object was satisfied, and the present invention was completed.

That is, the epoxy resin composition for laminates according to claim 1 of the present invention has a number average molecular weight as a constituent material.
It is characterized by containing a polyphenylene ether oligomer epoxy body represented by the structural formula (1) having an epoxy group at both ends of 700 to 3,000, and a curing agent.

[Chemical 3]

(In the formula (1),-(OXO)-is represented by the structural formula (2), and R ¹ , R ² , R ⁷ and R ⁸ may be the same or different,
Indicates a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ³ , R ⁴ , R ⁵ , and R ^{6, which} may be the same or different, represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. A has 20 carbon atoms
The following are linear or branched hydrocarbons, phenyl groups, and organic groups having cyclic hydrocarbons. -(YO)-is one type of structure defined by structural formula (3),
Alternatively, two or more kinds of structures defined by the structural formula (3) are randomly arranged. R ⁹ and R ^{10, which} may be the same or different, represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ¹¹ and R ¹² may be the same or different and each is a hydrogen atom, a halogen atom or a carbon number.
Indicates an alkyl group or phenyl group having 6 or less. Z is an organic group having 1 or more carbon atoms and may include an oxygen atom.
At least one of a and b is an integer of 0 to 20 in which at least one is not 0. At least one of c and d is not 0
Indicates an integer of 20. i independently represents an integer of 0 or 1. j represents an integer of 0 to 5. )

The epoxy resin composition for laminates according to claim 2 of the present invention has a number average molecular weight of 700 as a constituent material.
~ 3,000 epoxy compounds of polyphenylene ether oligomer represented by the structural formula (1) having epoxy groups at both ends,
And a cyanate ester resin.

The epoxy resin composition for laminate according to claim 3 of the present invention is the epoxy resin composition for laminate according to claim 1, which has epoxy groups at both ends represented by the structural formula (1). Polyphenylene ether oligomer-
(OXO) -at least R ¹ , R ^{2 of} structural formula (2) represented by,
R ⁷ and R ⁸ are methyl groups, and-(YO)-has structural formula (4), structural formula (5), or a structure in which structural formulas (4) and (5) are randomly arranged. It is characterized by

[Chemical 4]

The epoxy resin composition for laminated boards of the present invention comprises
It contains an epoxy compound of a polyphenylene ether oligomer represented by the structural formula (1) having epoxy groups at both ends, and a curing agent.

The above epoxy resin composition contains the epoxy compound of the polyphenylene ether oligomer represented by the structural formula (1) having epoxy groups at both ends, and has a low dielectric constant and excellent flexibility, and a resin. The melt viscosity of the composition can be reduced. When the melt viscosity of the resin composition is small, the resin can be easily embedded in the laminate during molding, and voids do not occur, resulting in good moldability.

The epoxy compound of the polyphenylene ether oligomer represented by the structural formula (1) having epoxy groups at both ends, which is characteristic of the present invention (hereinafter referred to as bifunctional OPE-2Ep), will be described.

The above-mentioned bifunctional OPE-2Ep is a structural formula obtained by oxidatively copolymerizing divalent phenol and monovalent phenol.
The polyphenylene ether oligomer represented by (6) (hereinafter referred to as bifunctional OPE) can be obtained by dehydrohalogenation reaction with halogenated glycidyl such as epichlorohydrin in the presence of a base.

[Chemical 5]

The bifunctional OPE represented by the structural formula (6) is-(OX
-O)-is represented by structural formula (2), and-(YO)-is one type of structure defined by structural formula (3) or two or more types of structure defined by structural formula (3). It is arranged randomly. In the formula,
R ¹ , R ² , R ⁷ , R ⁸ , R ⁹ , and R ^{10, which} may be the same or different, are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , and R ^{12, which} may be the same or different, are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. A
Is a linear or branched hydrocarbon having 20 or less carbon atoms, a phenyl group, or an organic group having a cyclic hydrocarbon. a and b show the integer of 0-20 whose at least one is not 0. Preferably,-(OXO)-is R ¹ ,
R ² , R ⁷ and R ⁸ are methyl groups, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, and-(YO)-is structural formula (4) or structural formula
It is desirable to have a structure in which (5) or the structural formulas (4) and (5) are randomly arranged.

The bifunctional OPE represented by the above structural formula (6) is
Efficiently by oxidative polymerization of a divalent phenol represented by the structural formula (7) and a monovalent phenol defined by the structural formula (8) alone or in a mixture in a toluene-alcohol or ketone solvent. It can be manufactured.

[Chemical 6]

Here, R ¹ , R ² , R ⁷ , and R ⁸ may be the same or different from the divalent phenol of the structural formula (7), and a halogen atom, an alkyl group having 6 or less carbon atoms, or phenyl. It is a base. R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and A is a linear group having 20 or less carbon atoms. Alternatively, it is a branched hydrocarbon, a phenyl group, or an organic group having a cyclic hydrocarbon.
R ¹ , R ² , R ⁷ and R ⁸ are divalent phenols which are essential not to be hydrogen atoms, and are 4,4′-methylenebis (2,6-dimethylphenol) and 4,4 ′-(1-methyl Ethylidene) bis (2,6-dimethylphenol), 4,4'-methylenebis (2,3,6-trimethylphenol), 4,4'-cyclohexylidenebis (2,6-dimethylphenol), 4,4 '-(Phenylmethylene) bis (2,3,6
-Trimethylphenol), 4,4 '-[1,4-phenylenebis (1
-Methylethylidene)] bis (2,6-dimethylphenol),
4,4'-methylenebis [2,6-bis (1,1-dimethylethyl) phenol], 4,4'-cyclopentylidenebis (2,6-dimethylphenol), 4,4 '-(2-furyl Methylene) bis (2,6-dimethylphenol), 4,4 '-(1,4-phenylenebismethylene)
Bis (2,6-dimethylphenol), 4,4 '-(3,3,5-trimethylcyclohexidene) bis (2,6-dimethylphenol),
4,4 '-[4- (1-Methylethyl) cyclohexylidene] bis (2,
6-dimethylphenol), 4,4 '-(4-methylphenylethylene) bis (2,3,6-trimethylphenol), 4,4'-(1,4-
(Phenylene bismethylene) bis (2,3,6-trimethylphenol), 4- [1- [4- (4-hydroxy-3,5-dimethylphenyl)
-4-Methylcyclohexyl] -1-methylethyl] -2,6-dimethylphenol, 4,4 '-(4-methoxyphenylmethylene)
Bis (2,3,6-trimethylphenol), 4,4 '-[4- (1-methylethyl) phenylmethylene] bis (2,3,6-trimethylphenol), 4,4'-(9H-fluorene -9-Ylidene) Bis (2,6
-Dimethylphenol), 4,4 '-[1,3-phenylenebis (1-
Methylethylidene)] bis (2,3,6-trimethylphenol), 4,4 '-(1,2-ethanediyl) bis [2,6-di- (1,1-dimethylethyl) phenol], 5,5 '-(1-methylethylidene)
Examples thereof include, but are not limited to, bis [3- (1,1-dimethylethyl) -1,1-biphenyl-2-ol].

Next, the monovalent phenol of the structural formula (8) is
R ⁹ and R ¹⁰ may be the same or different and each is a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ¹¹ and R ¹² may be the same or different, and a hydrogen atom,
It is a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. In particular, it is preferable to use one having a substituent at the 2,6 position alone or a combination thereof with one having a substituent at the 3 position or the 3,5 position. More preferably, 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable alone, and 2,6-dimethylphenol and 2,3,3,2 are used in combination.
6-trimethylphenol is good.

As a method of oxidation, there is a method of directly using oxygen gas or air. There is also a method of electrode oxidation. Either method may be used and is not particularly limited. Air oxidation is preferable because of safety and inexpensive capital investment.

As a catalyst for oxidative polymerization using oxygen gas or air, CuCl, CuBr, Cu ₂ SO ₄ , CuCl
₂ , CuBr ₂ , CuSO ₄ , one or more of copper salts such as CuI are used, and in addition to the above catalyst, mono- and dimethylamine, mono- and diethylamine, mono- and dipropylamine, mono- and di- n-Butylamine, mono- and di-sec-dipropylamine, mono and dibenzylamine, mono and dicyclohexylamine, mono and diethanolamine, ethylmethylamine, methylpropylamine, butyldimethylamine, allylethylamine, methylcyclohexylamine, morpholine , Methyl-n-butylamine, ethylisopropylamine, benzylmethylamine, octylbenzylamine, octylchlorobenzylamine, methyl (phenylethyl) amine, benzylethylamine, Nn-butyldimethylamine, N, N'-di-tert
-Butylethylenediamine, di (chlorophenylethyl) amine, 1-methylamino-4-pentene, pyridine,
One or more amines such as methylpyridine, 4-dimethylaminopyridine, piperidine and the like are used in combination. If it is a copper salt and an amine, it will not be limited to these.

As the reaction solvent, toluene, benzene,
In addition to an aromatic hydrocarbon solvent such as xylene, a halogenated hydrocarbon solvent such as methylene chloride, chloroform and carbon tetrachloride, etc., it can be used in combination with an alcohol solvent or a ketone solvent. Examples of the alcohol solvent include methanol, ethanol, butanol, propanol, methyl propylene diglycol, diethylene glycol ethyl ether, butyl propylene glycol and propyl propylene glycol, and examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone and methyl butyl. Ketone, methyl isobutyl ketone and the like, and others, tetrahydrofuran,
Examples include, but are not limited to, dioxane and the like.

The reaction temperature is not particularly limited, but is preferably 25 to 50 ° C. Because oxidative polymerization is an exothermic reaction,
Above 50 ° C, temperature control is difficult and molecular weight control becomes difficult. At 25 ° C or lower, the reaction rate becomes extremely slow, and efficient production cannot be performed.

The above-mentioned bifunctional OPE-2Ep is represented by the structural formula (1). That is,-(OXO)-is represented by structural formula (2), R ¹ ,
R ² , R ⁷ and R ⁸ may be the same or different and each is a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different,
A hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. — (YO) — is represented by Structural Formula (3), and R ⁹ and R ¹⁰ may be the same or different and each is a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ¹¹ and R ^{12, which} may be the same or different, are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. A is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms. -(Y-
O)-is one kind of structure defined by the structural formula (3) or two or more kinds of structures defined by the structural formula (3) are randomly arranged. Z is an organic group having 1 or more carbon atoms and may include an oxygen atom. a and b each represent an integer of 0 to 20, at least one of which is not 0. c and d each represent an integer of 0 to 20, at least one of which is not 0. i independently represents an integer of 0 or 1. j represents an integer of 0 to 5.

An organic group having 1 or more carbon atoms and optionally containing an oxygen atom can be placed in the Z portion. For example,-(-CH ₂
-)-,-(CH ₂ -CH ₂ -)-,-(-CH ₂ -Ar-O-)-, and the like, but are not limited thereto. How to add is structural formula
There is a method of directly adding to the bifunctional OPE represented by (6) and a method of using a halide having a long carbon chain during the synthesis of the derivative, but the method is not limited to these.

For the sake of convenience, the bifunctional OPE derivative represented by the structural formula (6), which is the simplest structure, will be described below. In order to produce the bifunctional OPE-2Ep, the bifunctional OPE represented by the above structural formula (6) is used, but it can be used either in the form of powder separated from the reaction solution or in the form of being dissolved in the reaction solution.

A method for producing the bifunctional OPE-2Ep of the present invention will be illustrated. A compound having a phenolic hydroxyl group at both terminals represented by the above structural formula (6) can be synthesized by dehydrohalogenation reaction with a halogenated glycidyl such as epichlorohydrin in the presence of a base. .

Representative examples of the base include sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and the like, but are not limited thereto. Not a thing.

The reaction temperature is preferably between -10 ° C and 110 ° C.

The number average molecular weight of the bifunctional OPE-2Ep obtained as described above is limited to the range of 700 to 3,000. When the number average molecular weight exceeds 3,000, the melt viscosity of the resin composition increases, and when the number average molecular weight is less than 700, mechanical strength and heat resistance decrease. The above-mentioned bifunctional OPE-2Ep has a low melt viscosity, a good fluidity, an excellent compatibility with other resins, and an epoxy group at both ends, so that the resin composition has a good adhesive property. As a result, it is possible to prevent the occurrence of blisters when exposed to a high temperature such as solder after absorbing moisture. Furthermore, since the polyphenylene ether resin is a material having a low dielectric property, a laminated board having a low dielectric property can be provided.

As the curing agent which is a constituent material of the epoxy resin composition for lamination of the present invention, amines such as primary and secondary amines usually used, phenols such as bisphenol A and phenol novolac, and acids are used. An anhydride type, a cyanate ester type, etc. can be mentioned. These can be used alone or in combination.

The bifunctional OPE-2Ep composition of the present invention can be used in combination with various resins depending on the purpose and application. Specifically, various epoxy resins; modified epoxy resins; oxetane resins; (meth) acrylic acid esters; polyallyl compounds such as diallylbenzene and diallyl terephthalate; N-vinyl-2
-Vinyl compounds such as pyrrolidone and divinylbenzene; Polymerizable double bond-containing monomers such as unsaturated polyester; Polyfunctional maleimides; Polyimides; Rubbers such as polybutadiene; Thermally sparse resins such as polyethylene and polystyrene ABS resins, engineering plastics such as polycarbonate, cyanate ester resins and the like,
It is not limited to these.

Further, the resin composition includes known inorganic or organic fillers, dyes, pigments, thickeners, lubricants, defoamers, coupling agents, photosensitizers, ultraviolet absorbers, flame retardants, etc. If desired, various additives can be added.

As the epoxy resin used in the present invention,
For example, bisphenol A type epoxy, bisphenol
F type epoxy, bisphenol Z type epoxy, biphenol epoxy, tetramethylbiphenol epoxy, hexamethylbiphenol epoxy, xylene novolac epoxy, biphenyl novolac epoxy,
Examples thereof include dicyclopentadiene novolac epoxy, phenol novolac epoxy, cresol novolac epoxy, and brominated flame-retardant epoxy resins, and the like, or a composition obtained by mixing two or more of them appropriately, or Examples include reaction products.

Examples of the cyanate ester compound used in the present invention include 1,3- or 1,4-dicyanate benzene, 1,3,5-tricyanate benzene, 1,3-, 1,4-, 1 ,
6-, 1,8-, 2,6- or 2,7-dicyanate naphthalene, 1,
3,6-tricyanate naphthalene, 4,4'-dicyanate biphenyl, bis (4-cyanatephenyl) methane, 2,2-
Bis (4-cyanatephenyl) propane, 2,2-bis (3,
5-dibromo-4-cyanatephenyl) propane, bis (4
-Cyanatephenyl) ether, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) sulfone, tris (4-cyanatephenyl) phosphite, tris (4-cyanatephenyl) phosphate, 4,4'-dicyanato- 3,3 ', 5,5'-tetramethylbiphenyl or 4,4'-dicyanato-2,
Cyanates obtained by reacting 2 ', 3,3', 5,5'-hexamethylbiphenyl and novolac with cyanogen halide.

The composition of the present invention can be cured by heating itself, but a thermosetting catalyst may be added for the purpose of increasing the curing rate to improve workability and economy. You can As the thermosetting catalyst, those generally known as thermosetting catalysts for resins to be combined can be used.

The copper-clad laminate using the bifunctional OPE-2Ep composition of the present invention is particularly suitable for printed wiring boards that require low dielectric properties. The copper clad laminate of the present invention can be manufactured by a general manufacturing method. That is, a base material is impregnated with a resin varnish, which is a solution of a thermosetting resin composition in an organic solvent, and heat treated to form a prepreg, and then a prepreg and a copper foil are laminated and heat-molded to form a copper clad laminate. However, the method is not limited to this.

As the organic solvent used, acetone,
Methyl ethyl ketone, ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, toluene, xylene, tetrahydrofuran, N,
N-dimethylformamide and the like can be mentioned, and a wide range of organic solvents can be used without particularly limiting the solvent.
These may be used alone or in admixture of two or more kinds. As the base material to be impregnated with the resin varnish, inorganic base materials such as glass cloth and glass non-woven fabric; organic base materials such as polyamide non-woven fabric and liquid crystal polyester non-woven fabric, etc. can be used for the thermosetting resin laminated plate. . In order to utilize the low dielectric properties of the present invention, it is more effective when used in combination with a substrate having excellent dielectric properties such as D glass cloth and NE glass cloth.

The heat treatment of the prepreg is appropriately selected according to the solvent used, the resin composition, the added catalyst, and the type and amount of other additives used, but it is usually at a temperature of 100 to 250 ° C. for 3 to 30 minutes. Done in. The method of laminating and heating the prepreg and the copper foil varies depending on the type of the prepreg and the form of the copper foil, but generally the temperature is 170 to 23.
Vacuum hot press molding is preferably carried out at 0 ° C. and a pressure of 10 to 30 kg / cm ² for a time of 40 to 120 minutes.

[0038]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” and “%” represent parts by weight unless otherwise specified.

Preparation of bifunctional OPE-2Ep (preparation of bifunctional OPE) 1.3 g of CuCl (0.013 mo) in a 2 L vertical reactor equipped with a stirrer, a thermometer, an air inlet tube, and a baffle plate.
l), di-n-butylamine 79.5 g (0.62 mol) and methyl ethyl ketone 600 g were charged and stirred at a reaction temperature of 40 ° C.,
4,4 'previously dissolved in 600 g of methyl ethyl ketone
-(1-Methylethylidene) bis (2,6-dimethylphenol) 4
2.6 g (0.15 mol) and 2,6-dimethylphenol 56.7 g (0.46 mo
l) and 2,3,6-trimethylphenol 21.1 g (0.16 mol) mixed solution (molar ratio of divalent phenol to monovalent phenol 1:
4) was added dropwise while bubbling air at 2 L / min over 120 minutes, and stirring was continued for 30 minutes after the completion of dropping while continuing bubbling air at 2 L / min. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, the plate was washed with a 1N hydrochloric acid aqueous solution three times and then with ion-exchanged water. The obtained solution was concentrated with an evaporator and further dried under reduced pressure to obtain bifunctional O.
112.3 g PE was obtained. As a result of measuring the obtained bifunctional OPE by a gel permeation chromatography (GPC) method, the number average molecular weight was 1,080. The hydroxyl equivalent is 5
It was 50.

(Production method of bifunctional OPE-2Ep) Stirrer, thermometer,
A reactor equipped with a dropping funnel was heated to 100 ° C., and 40.0 g of the bifunctional OPE obtained above (hydroxyl group: 0.073 mol) and 201.9 g of epichlorohydrin were charged. Then, a solution prepared by dissolving 5.9 g (0.087 mol) of sodium ethoxide in 20.8 g of ethanol was added dropwise from a dropping funnel over 60 minutes, and stirring was continued for 5 hours after the addition was completed. Then, the product salt and impurities were removed by washing three times with a 0.1 N hydrochloric acid aqueous solution, washing with ion-exchanged water, and further filtering. Excessive epichlorohydrin was distilled off from the obtained solution, and further dried under reduced pressure to obtain 42.4 g of bifunctional OPE-2Ep (number average molecular weight:
1,230). The obtained bifunctional OPE-2Ep showed 100% functional group conversion from the disappearance of the absorption peak (3600 cm-1) of the phenolic hydroxyl group by IR analysis and the appearance of the peak derived from glycidyl ether by NMR analysis. confirmed.

Example 1 70 parts of the above-mentioned bifunctional OPE-2Ep, tetrabromobisphenol A epoxy (manufactured by Dainippon Ink and Chemicals, Inc., trade name: EP
ICLON-153) 20 parts, 4,4'-diaminodiphenylmethane 1
0 part and 0.07 part of 2-methylimidazole were dissolved in methyl ethyl ketone to prepare a varnish having a resin content of 60%.
This varnish is a glass cloth (NE glass product: product name WEX9
83 Nitto Boseki) and treated with a hot air dryer to produce B-
I got the stage prepreg. Eight prepregs and copper foil (18
μm thickness, manufactured by Mitsui Kinzoku Co., Ltd., trade name: 3EC-3) were overlapped and vacuum hot pressed at 200 ° C. for 2 hours to obtain a 0.8 mm thick copper clad laminate. Table 2 shows the physical properties of the obtained copper-clad laminate.
It was shown to.

Example 2 and Comparative Examples 1 to 3 A copper clad laminate was obtained in the same manner as in Example 1 except that the thermosetting resins were mixed in the compounding ratios shown in Table 1. However, since only Comparative Example 2 did not dissolve in methyl ethyl ketone, toluene was used as a solvent.

[0043]

[Table 1] General-purpose PPE polymer: Mitsubishi Gas Chemical Co., Inc., number average molecular weight: 2
4,000 bisphenol A-type cyanate-topolemer: 2,2-bis (4-cyanatophenyl) -pro- phenyleperomer tetrafluoromo-phenol A-epoxy: EPICLON-153 Dainippon Ink & Chemicals Co., Ltd. bisphenol-a-epoxy : DER-331L Dow Chemical Japan Co., Ltd. Phenolic novolak type epoxy: EPPN-201 Nippon Kayaku Co., Ltd.

[0044]

[Table 2]

The measured values in the examples and comparative examples are measured using the following devices and methods. -Glass transition temperature (Tg): Calculated from the loss tangent (tan δ) peak of dynamic viscoelasticity measurement. -Relative permittivity and loss tangent: Measured by the cavity resonator method. -Copper foil peeling strength: Based on JIS C6481, the peeling strength of a copper foil having a width of 10 mm in the 90 ° direction was measured.・ Solder heat resistance after moisture absorption: A sample from which the copper foil has been completely removed is subjected to moisture absorption treatment under PCT conditions of 121 ° C and 0.2MPa for 1 to 3 hours, and then immersed in a solder bath at 260 ° C for 30 seconds for delamination (swelling). )
Was visually observed. Moldability: Judgment was made based on whether or not the inner layer pattern of 70 μm thick copper foil could be embedded without voids.

[0046]

As described above, the resin composition containing the epoxy compound of the polyphenylene ether oligomer of the present invention has excellent electrical characteristics such as high heat resistance, low relative dielectric constant and low dielectric loss tangent, and further excellent moldability. It is a well-balanced resin composition. This performance is further improved by combining it with a cyanate ester resin. A laminated board or a multilayer printed board using this resin is excellent in multi-layer molding, has high reliability, and enables high-speed processing of high-frequency signals and low-loss circuit design.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Seisei Hiramatsu             6-1, 1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi tile             The Chemical Research Institute Tokyo Research Center (72) Inventor Makoto Miyamoto             6-1, 1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi tile             The Chemical Research Institute Tokyo Research Center F term (reference) 4F072 AA07 AB09 AD28 AE02 AE08                       AE10 AF15 AF27 AF28 AG16                       AG19 AH02 AH31 AK14 AL12                       AL13                 4J036 AA01 CD12 DA01 DB06 DB15                       DC02 DC27 JA08

Claims (4)

[Claims] 1. A number average molecular weight of 700 to 3,0 as a constituent material.
An epoxy resin composition for laminates, comprising an epoxy compound of polyphenylene ether oligomer represented by structural formula (1) having an epoxy group at both ends of 00 and a curing agent. [Chemical 1] (In formula (1),-(OXO)-is represented by structural formula (2), R ¹ ,
R ² , R ⁷ and R ⁸ may be the same or different and each represents a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different,
It represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. A is a linear or branched hydrocarbon having 20 or less carbon atoms, a phenyl group, or an organic group having a cyclic hydrocarbon. -(YO)-
Is one type of structure defined by structural formula (3), or structural formula
Two or more types of structures defined in (3) are randomly arranged. R ⁹ and R ¹⁰ may be the same or different,
Indicates a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ¹¹ and R ^{12, which} may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Z is an organic group having 1 or more carbon atoms and may include an oxygen atom. At least one of a and b is an integer of 0 to 20 in which at least one is not 0. c, d
Represents an integer of 0 to 20, at least one of which is not 0. i independently represents an integer of 0 or 1. j is
Indicates an integer from 0 to 5. ) 2. A number average molecular weight of 700 to 3,0 as a constituent material.
An epoxy resin composition for laminates, comprising an epoxy compound of polyphenylene ether oligomer represented by the structural formula (1) having an epoxy group at both ends of 00, and a cyanate ester resin. 3. In the polyphenylene ether oligomer body having epoxy groups at both ends represented by the structural formula (1) of the constituent material, at least R ¹ of the structural formula (2) represented by — (OXO) —, R ² , R ⁷ , and R ⁸ are methyl groups, and-(YO)-is structural formula (4), structural formula (5), or structural formula (4) and structural formula (5) were randomly arranged. 2. The epoxy resin composition for laminated board according to claim 1, which has a structure. [Chemical 2] 4. An epoxy for laminates, which comprises the epoxy compound of the polyphenylene ether oligomer represented by the structural formula (1) having epoxy groups at both ends according to any one of claims 1, 2 and 3. A prepreg, a laminated board, and a printed wiring board using a resin composition.