JP2003268227A - Thermosetting resin composition for laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which is excellent in dielectric properties and in moldability, flexibility, heat resistance, etc., and is used as a printed circuit board material; and a laminate and a printed circuit board prepared by using the same. <P>SOLUTION: This thermosetting resin composition contains a polyphenylene ether oligomer cyanate having a number-average mol.wt. of 700-3,000 and cyanate groups at both the molecular ends. The laminate and the printed circuit board are prepared by using the composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for laminates using a novel cyanate resin, and a copper clad laminate using the same. The resulting composition has low dielectric properties,
It is a thermosetting resin composition which is excellent in moldability and flexibility and is useful for a printed wiring board which 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, but the same problems as those of the above-mentioned thermoplastic resins remain. Further, a cyanate ester resin is known as a thermosetting resin having a good dielectric property and good moldability, but the cyanate ester resin alone has a problem that the cured product is too hard and brittle, and there is a problem in adhesiveness and solder resistance. is there. Therefore,
These defects can be covered to some extent by using together with an epoxy resin, but the combination of conventional cyanate ester resin and epoxy resin meets both the ever-stricter requirements for low dielectric properties and flexibility. Was difficult.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to meet the ever-stricter demand for low dielectric properties in printed wiring board materials without lowering the properties such as excellent moldability and heat resistance that have been achieved so far. Correspondingly, it is intended to provide a thermosetting resin composition having flexibility and a laminated board and a printed wiring board using the same.

[0005]

[Means for Solving the Problems] The present invention has excellent moldability and heat resistance, and as a result of diligent studies aimed at achieving both low dielectric characteristics and flexibility, both ends of the structural formula (1) are represented. By using a cyanate body of a polyphenylene ether oligomer having a cyanate group as a constituent material of a resin composition for laminates, it has been found that the above object is satisfied, and the present invention has been completed.

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

[Chemical 3] (In the formula, -X- is represented by the structural formula (2), and R ¹ , R ² , R ⁷ and R ⁸ are
May be the same or different, halogen atom or carbon number
An alkyl group of 6 or less or a phenyl group. R ³ , R ⁴ , R
⁵ , 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. A is a linear or branched hydrocarbon having 20 or less carbon atoms, a phenyl group, or an organic group having a cyclic hydrocarbon. -(O-Y)-is one type of structure defined by structural formula (3) or defined by structural formula (3)
Two or more structures are randomly arranged.
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 ¹¹ and R ¹² 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. 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 30, at least one of which is not 0. i independently represents an integer of 0 or 1. )

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

The resin composition for laminates according to claim 3 of the present invention is the resin composition for laminates according to claim 1,
-X- of a cyanate form of a polyphenylene ether oligomer having cyanate groups at both ends represented by the structural formula (1)
At least R ¹ , R ² , R ³ , R ⁷ , and R ^{8 of the} structural formula (2) represented by
Is a methyl group, or in addition among R ⁴ , R ⁵ and R ⁶
One or more is a methyl group, and-(O-Y)-has a structural formula (4), a structural formula (5), or a structure in which the structural formulas (4) and (5) are randomly arranged. It is characterized by

[Chemical 4]

The resin composition for laminates of the present invention contains a cyanate body of a polyphenylene ether oligomer having cyanate groups at both ends.

The above-mentioned resin composition for laminates contains a cyanate body of a polyphenylene ether oligomer having cyanate groups at both ends, so that the resin composition has low dielectric properties and excellent flexibility. The melt viscosity 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 cyanate form of the polyphenylene ether oligomer represented by the structural formula (1) having cyanate groups at both ends, which is characteristic of the present invention (hereinafter referred to as bifunctional OPE-
2CN) will be described.

The above-mentioned bifunctional OPE-2CN 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) is obtained by dehydrohalogenation reaction with a cyanogen halide such as chlorocyan or bromocyan in the presence of a base.

[Chemical 5]

The bifunctional OPE represented by the structural formula (6) is --X--
Is represented by structural formula (2), and one type of structure defined by structural formula (3) is-(O-Y)-, or two or more types of structure defined by structural formula (3) are randomly generated. It is arranged. Where R ¹ ,
R ² , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may be the same or different,
It is a halogen atom or 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. at least one of a and b is not 0, 0
Indicates an integer of ~ 20. Preferably, -X- is R ¹ , R ² , R ³ ,
R ⁶ , R ⁷ , and R ⁸ are methyl groups, R ⁴ and R ⁵ are hydrogen atoms, and — (O—Y) — is structural formula (4), structural formula (5), or structural formula It is desirable to have a structure in which (4) and structural formula (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 may be used.
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-2CN is represented by structural formula (1). That is, -X- is represented by Structural Formula (2), and R ¹ , R ² , R
⁷ , 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, 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. -(O-Y)-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. R ⁹ , R ^1
0 may be the same or different and 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. Z is an organic group having 1 or more carbon atoms and may include an oxygen atom. a and b show the integer of 0-300 in which at least one is not 0. i independently represents an integer of 0 or 1.

An organic group having 1 or more carbon atoms and optionally containing an oxygen atom can be placed in the Z portion. For example,-(-CH2
-)-,-(CH2-CH2-)-,-(-CH2-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 intermediate represented by (7), 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 following explanation will be given for the derivative from the intermediate represented by the structural formula (6), which is the simplest structure.
explain. Intermediates for the production of bifunctional OPE-2CN include
Although the bifunctional PPE oligomer represented by the above structural formula (6) is used, 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-2CN of the present invention will be illustrated. Synthesized by a dehydrohalogenation reaction of a compound having a phenolic hydroxyl group at the end with a bifunctional type represented by the above structural formula (6) as an intermediate, with a halogenated cyanide such as chlorocyan or bromocyan in the presence of a base. can do.

As the base, trimethylamine, triethylamine, tripropylamine, dimethylaniline,
Tertiary amines such as pyridine and sodium hydroxide,
Typical examples are potassium hydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and the like.
It is not limited to these.

As the reaction solvent, toluene, xylene,
Chloroform, methylene chloride, carbon tetrachloride, chlorobenzene, nitrobenzene, nitromethane, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane and the like are representative and are not limited to these.

The reaction temperature is, when chlorocyan is used,
It is preferably carried out between -30 ° C and + 13 ° C (boiling point). Also,
When bromocyan is used, it is preferably carried out between -30 ° C and + 65 ° C.

The number average molecular weight of the bifunctional OPE-2CN 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-2CN has a low melt viscosity, good flowability, excellent compatibility with other resins, and also has good adhesiveness of the resin composition because it has cyanate groups at both ends. . 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.

In the resin composition for laminated boards of the present invention,
The content of the bifunctional OPE-2CN is preferably in the range of 1 to 60% by weight with respect to the total amount of the bifunctional OPE-2CN, the epoxy resin and the other cyanate resin. More preferably, 5 to 50% by weight
Is. If the content is less than 1% by weight, sufficient flexibility cannot be obtained, and if the content exceeds 60% by weight, the melt viscosity becomes high, and voids are generated during multilayer molding, resulting in poor moldability.

Examples of the cyanate resin which is a constituent material of the resin composition for laminated plates of 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,
Cyanates obtained by reacting 4′-dicyanato-2,2 ′, 3,3 ′, 5,5′-hexamethylbiphenyl and novolac with cyanogen halide.

Examples of the epoxy resin which is a constituent material of the resin composition for laminated plate of the present invention include bisphenol A.
-Type epoxy, bisphenol F-type epoxy, bisphenol Z-type epoxy, biphenol epoxy, tetramethylbiphenol epoxy, hexamethylbiphenol epoxy, xylene novolac epoxy, biphenyl novolac epoxy, dicyclopentadiene novolac epoxy, phenol novolac epoxy , Cresol novolac epoxy, brominated flame-retardant epoxy resin, and the like, and a composition or a reaction product obtained by mixing two or more kinds of these alone or as appropriate. Further, an epoxy compound of a bifunctional polyphenylene ether oligomer shown in Japanese Patent Application No. 2001-353194 can also be used in combination.

The resin composition for laminates of the present invention can be used in combination with various resins depending on the purpose and application. Specific examples include oxetane resins; (meth) acrylic acid esters; polyallyl compounds such as diallylbenzene and diallyl terephthalate; vinyl compounds such as N-vinyl-2-pyrrolidone and divinylbenzene; unsaturated polyesters and the like. Polymerizable double bond-containing monomers; polyfunctional maleimides; polyimides; rubbers such as polybutadiene; thermoplastic resins such as polyethylene, polystyrene and PPE; engineering plastics such as ABS resin and polycarbonate. 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.

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 resin composition for laminates of the present invention is particularly suitable for printed wiring boards required to have 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 and all those used for thermosetting resin laminates are used. be able to. 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.

[0039]

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-2CN (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 79.5g (0.62 mol), toluene
400 g was charged and stirred at a reaction temperature of 40 ° C., and divalent phenol 4,4′-methylenebis [2,3,6-trimethylphenol] 42.6 g (0.15) was previously dissolved in 400 g of methyl ethyl ketone and 400 g of tetrahydrofuran. mol)
And 2,6-dimethylphenol 73.3 g (0.60 mol) mixed solution (molar ratio of divalent phenol represented by structural formula (7) to monovalent phenol represented by structural formula (8) 1: 4) The mixture was added dropwise over 120 minutes while bubbling air at 2 L / min, and stirring was continued for 60 minutes after completion of the dropping while bubbling air at 2 L / min. An aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogen was added thereto to stop the reaction. After that, it was washed three times with a 1 M aqueous hydrochloric acid solution and then washed with ion-exchanged water. The obtained solution was evaporated.
The mixture was concentrated in vacuo and dried under reduced pressure to obtain 113.2 g. This product had a number average molecular weight of 1050, a weight average molecular weight of 1490 and a hydroxyl group equivalent of 550.

(Preparation of Bifunctional OPE-2CN) A reactor equipped with a stirrer, a thermometer and a dropping funnel was cooled to -10 ° C, and 200 ml of a methylene chloride solution of chlorocyan (0.144 mol) was charged. Then, in advance 250 g of methyl ethyl ketone, "a" 52.8 g (hydroxyl group 0.096 mol) and triethylamine 14.6 g
A solution in which (0.144 mol) was dissolved was added dropwise from a dropping funnel over 60 minutes so that the temperature of the reaction solution was 10 ° C. or lower, and after the addition was completed, stirring was performed for 60 minutes. After that, washing with an 0.1 M hydrochloric acid aqueous solution three times, washing with ion-exchanged water, and filtration were performed to remove the produced salt and impurities. From the obtained solution, methylene chloride and methyl ethyl ketone were distilled off, and further dried under reduced pressure to obtain 53.0 g of a cyanate compound. In the obtained product, the absorption peak of the phenolic hydroxyl group (3600 cm-1) disappeared by IR analysis, and the absorption peak derived from the cyanate group
Since (2250 cm-1) was expressed, 100% conversion of the functional group was confirmed.

Example 1 30 parts of the above-mentioned bifunctional OPE-2CN, 30 parts of bisphenol A type cyanate prepolymer, tetrabromobisphenol A epoxy (manufactured by Dainippon Ink and Chemicals, Inc., trade name: EPIC)
LON-153) 20 parts, bisphenol A epoxy (manufactured by Dow Chemical Japan Ltd., trade name: DER-331L) 20 parts, iron acetylacetone 0.04 parts were dissolved in methyl ethyl ketone to prepare a varnish with a resin content of 60%. did. This varnish was impregnated into a glass cloth (NE glass product: product name WEX983 manufactured by Nitto Boseki) and treated with a hot air dryer to obtain a B-stage prepreg. 8 pieces of prepreg and copper foil (18 μm thick, Mitsui Kinzoku Co., Ltd., product name: 3EC-3) are piled up for 200
Vacuum hot pressing was performed at ℃ for 2 hours to obtain a 0.8 mm thick copper clad laminate. The physical properties of the obtained copper-clad laminate are shown in Table-2.

Comparative Examples 1 and 2 Copper-clad laminates were obtained in the same manner as in Example 1, except that the thermosetting resins were mixed in the mixing ratios shown in Table 1. Since Comparative Example 1 was insoluble in methyl ethyl ketone, toluene was used as a solvent.

[0044]

[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.

[0045]

[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. Moldability: Judgment was made based on whether or not the inner layer pattern of 70 μm thick copper foil could be embedded without voids.・ 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.・ Mechanical properties: Head speed: 1.0 mm / min, Distance between fulcrums: 20 mm, measured at room temperature

[0047]

INDUSTRIAL APPLICABILITY As described above, the resin composition containing the cyanate form of the polyphenylene ether oligomer of the present invention has high heat resistance and low dielectric properties, and is excellent in moldability and flexibility and is well balanced. Resin composition. A laminated board or a multilayer printed board using this resin is excellent in molding during multilayer molding, has high reliability, and enables high-speed processing of high-frequency signals and circuit design with low loss.

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) 4F100 AB17B AK54A BA02 BA07                       DH01 GB43 JG05 JJ03                 4J002 CD05Y CD06Y CD07Y CH07W                       CM02X GQ00 GQ01                 4J005 AA26 BA00 BD05

Claims (4)

[Claims] 1. A number average molecular weight of 700 to 3,0 as a constituent material.
A resin composition for laminates, comprising a cyanate body of polyphenylene ether oligomer represented by the structural formula (1) having a cyanate group at both ends of 00. [Chemical 1] (In the formula, -X- is represented by the structural formula (2), and R ¹ , R ² , R ⁷ and R ⁸ are
May be the same or different, halogen atom or carbon number
An alkyl group of 6 or less or a phenyl group. R ³ , R ⁴ , R
⁵ , 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. A is a linear or branched hydrocarbon having 20 or less carbon atoms, a phenyl group, or an organic group having a cyclic hydrocarbon. -(O-Y)-is one type of structure defined by structural formula (3) or defined by structural formula (3)
Two or more structures are randomly arranged.
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 ¹⁰ and R ¹¹ 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. 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 30, at least one of which is not 0. i independently represents an integer of 0 or 1. ) 2. A number average molecular weight of 700 to 3,0 as a constituent material.
Cyanate form of polyphenylene ether oligomer represented by structural formula (1) having a cyanate group at both ends of 00,
And another cyanate ester resin and an epoxy resin, which is a resin composition for laminated boards. 3. In the cyanate form of the polyphenylene ether oligomer having cyanate groups at both ends represented by the structural formula (1) of the constituent material, the structural formula represented by -X-
(2) at least R ¹ , R ² , R ³ , R ⁷ , and R ⁸ are methyl groups, or at least ^{one of} R ⁴ , R ⁵ , and R ⁶ is a methyl group, and-(O -Y)-is structural formula (4) or structural formula
2. The resin composition for a laminate according to claim 1, which has a structure in which (5) or structural formula (4) and structural formula (5) are randomly arranged. [Chemical 2] 4. Cyanide at both ends according to claim 1, 2, or 3.
A prepreg and a printed wiring board using a resin composition for a laminate, which contains a cyanate body of a polyphenylene ether oligomer having a group.