JP2003342350A - High molecular weight epoxy resin, resin composition for electric laminate, and electric laminate - Google Patents

Abstract

(57) [Object] To provide a high molecular weight epoxy resin excellent in flexibility, heat resistance, low water absorption, electric characteristics, and moldability, a composition for an electric laminate, and an electric laminate. The present invention provides a high-molecular-weight epoxy resin represented by the following general formula (1) and having a weight-average molecular weight of 10,000 to 200,000. General formula (1) (Wherein A is a chemical structure represented by the following general formula (2) or (3), and the proportion of A represented by the general formula (3) is 5 mol% or more in the general formula (1);
Is a hydrogen atom or a group represented by the following general formula (4), and n is a number of 25 to 500 on average. )

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a high molecular weight epoxy resin characterized by containing a bisphenolacetophenone structure as an essential component, a resin composition for electric laminates containing the high molecular weight epoxy resin, and The present invention relates to an electric laminate. The high molecular weight epoxy resin of the present invention provides a resin composition for electric laminates having high flexibility, high glass transition temperature, low water absorption and low dielectric constant. The electric laminated plate referred to here is a laminated plate used for an insulating substrate including a printed wiring board, a build-up laminated board, a flexible laminated board, and the like.

[0002]

2. Description of the Related Art Epoxy resins are widely used in paints, civil engineering adhesion, and electrical applications. In particular, bisphenol A type high molecular weight epoxy resins are mainly used as base resins for paint varnishes and film moldings. It is used as a fluidity modifier added to base resins and epoxy resin varnishes, or as an additive for improving the toughness of cured products, and high molecular weight epoxy resins containing bromine atoms are blended with thermoplastic resins. Used as a flame retardant. On the other hand, printed wiring boards used in electrical and electronic equipment are becoming smaller, lighter and more sophisticated, especially in comparison with multilayer printed wiring boards, where the number of layers is higher, the density is higher, and the thickness is thinner. There is a demand for higher efficiency, lighter weight, high reliability, and moldability. In response to this demand, a new method for manufacturing a multilayer printed wiring board such as a build-up method has been developed, and a high-performance epoxy resin suitable for these has been demanded. As a resin-coated copper foil for a build-up wiring board and a resin for an adhesive film, a high molecular weight epoxy resin has been studied because of its advantageous film forming property. As a performance requirement for this high molecular weight epoxy resin, it has been strongly demanded to lower the dielectric constant and lower the dielectric loss of the resin in accordance with the recent demand for higher transmission rate of electric signals. There is also a demand for high heat resistance and low water absorption from the viewpoint of improving reliability. As the high molecular weight epoxy resin which has been conventionally studied, bisphenol A type epoxy resin,
There are bisphenol F type epoxy resin, brominated epoxy resin, etc., and there are also JP-A-11-269264 and JP-A-11-2792.
No. 60, JP-A No. 11-302373, etc. describes thermoplastic polyhydroxypolyether resins having a fluorene skeleton introduced, but with these resins, strict high reliability and low dielectric constant as described above are obtained. It is not possible to meet the requirements at the same time.

[0003]

When a known high molecular weight epoxy resin is used in a resin composition for electric laminates, it is possible to improve moldability, flexibility, impact resistance and adhesiveness. Yes, but heat resistance when used as a printed wiring board,
Low water absorption and poor insulation and dielectric properties. The problem to be solved by the present invention is to solve various problems of conventional high molecular weight epoxy resins, and to provide flexibility, heat resistance, low water absorption, and electrical characteristics (especially, low dielectric constant and low dielectric loss). ), A high molecular weight epoxy resin and a resin composition for electric laminates necessary for obtaining a resin composition for electric laminates excellent in moldability, impact resistance and adhesiveness.

[0004]

MEANS FOR SOLVING THE PROBLEMS The present invention provides "1. High molecular weight epoxy resin represented by the following general formula (1) having a weight average molecular weight of 10,000 to 200,000. General formula (1)

[0005]

[Chemical 5]

(In the formula, A is a chemical structure represented by the following general formula (2) or (3), and A is the general formula (3))
Is 5 mol% or more in the general formula (1), B
Is a hydrogen atom or a group represented by the following general formula (4), and n is an average value of 25 to 500. ) General formula (2)

[0007]

[Chemical 6]

(In the formula, R _{1 s} may be the same or different from each other and are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements, X is a single bond,
A divalent hydrocarbon group having 1 to 7 carbon atoms, -O-, -S-, -SO _2- ,
Alternatively, it is a group selected from -CO-. ) General formula (3)

[0009]

[Chemical 7]

(In the formula, R ₁ 'may be the same or different from each other and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements, R ₂ is a hydrogen atom, It is a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements, and R ₃ is a hydrogen atom or 1 to 10 carbon atoms.
And m is an integer of 0-5. )] General formula (4)

[0011]

[Chemical 8]

2. The epoxy equivalent of the high molecular weight epoxy resin is 5,000 g / equivalent or more,
The high molecular weight epoxy resin described in item 1. 3. Li and Na contained in high molecular weight epoxy resin
And the total amount of K is 5 ppm or less and the content of phosphorus is 150 ppm or less, the high molecular weight epoxy resin as described in the item 1 or 2. 4. The high molecular weight described in any one of 1 to 3 above, characterized by reacting a dihydric phenol compound having the chemical structure of the general formula (2) or (3) with epihalohydrin in the presence of an alkali. Method for producing epoxy resin. 5. A difunctional epoxy resin containing the chemical structure of general formula (2) or (3) is reacted with a dihydric phenol compound containing the chemical structure of general formula (2) or (3) in the presence of a catalyst. A method for producing the high molecular weight epoxy resin described in any one of 1 to 3 above. 6. The method for producing a high molecular weight epoxy resin according to item 5, wherein the reaction temperature is in the range of 50 ° C to 230 ° C. 7. A resin composition for an electric laminate, which comprises the high molecular weight epoxy resin described in any one of 1 to 3 above. 8. Item 7. The resin composition for electric laminates described in Item 7, which contains the high molecular weight epoxy resin described in any one of Items 1 to 3, a thermosetting resin, a curing agent, and a curing accelerator as essential components. 9. A resin composition for an electric laminate, wherein the thermosetting resin is an epoxy resin other than the high molecular weight epoxy resin according to any one of items 1 to 3. 10. An electric laminate obtained from the resin composition for electric laminates according to any one of 7 to 9. Regarding

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The constituent component of the high molecular weight epoxy resin represented by the general formula (1) of the present invention is the chemical structure represented by the general formula (2) or (3), and A is the general formula ( The ratio of 3) is preferably 5 mol% or more in the general formula (1), more preferably 10 mol% or more, and further preferably 15 mol% or more. When the content of the component having the chemical structure represented by the general formula (3) is less than 5 mol%, heat resistance and low water absorption become insufficient. Further, if the weight average molecular weight of the high molecular weight epoxy resin is less than 10,000, the heat resistance is insufficient, and if it exceeds 200,000, the resin becomes extremely high in viscosity and it becomes difficult to handle the resin, which is not preferable.
In terms of heat resistance and resin handling, preferably,
The weight average amount of the high molecular weight epoxy resin is 10,000 to
90,000, more preferably 12,000 to 8
10,000, more preferably 15,000 to 7
It is 10,000. The epoxy equivalent of the high molecular weight epoxy resin in the present invention may be 5,000 g / equivalent or more. Incidentally, when the epoxy group is not contained, the epoxy equivalent becomes an infinite value. If it is less than 5,000 g / equivalent, heat resistance becomes insufficient, which is not preferable. When it is 5,000 g / equivalent or more, heat resistance is improved, which is preferable.

As a method for producing the high molecular weight epoxy resin of the present invention, an epihalohydrin such as epichlorohydrin or epibromhydrin is reacted with a dihydric phenol compound containing the chemical structure of the general formula (2) or (3) in the presence of an alkali. And a one-step method of producing, and at least one kind of a bifunctional epoxy resin containing a chemical structure of general formula (2) or (3) and a dihydric phenol containing a chemical structure of general formula (2) or (3) There is a two-step process in which at least one compound is generally reacted in the presence of a catalyst to produce. The above-mentioned weight average molecular weight and epoxy equivalent are the charged molar ratio of epihalohydrin and dihydric phenol compound, or difunctional epoxy and difunctional epoxy compound.
By adjusting the charged molar ratio of the hydric phenol compound, it is possible to produce a compound having a desired value. The bifunctional epoxy resin used as the raw material for the two-step method is an epoxy resin represented by the general formula (6) or (7), but other resins may be used as long as they do not impair the object of the present invention. Any compound having two epoxy groups may be used together. Examples of the bifunctional epoxy resin represented by the general formula (6) include bisphenol A type epoxy resin and bisphenol F.
Type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resin, biphenol type epoxy resin and the like. Particularly preferred among these epoxy resins are bisphenol A, bisphenol F, 4,4'-biphenol and 3,3 ', 5,5'-tetramethyl-
It is a diglycidyl ether of 4,4'-biphenol. Examples of the bifunctional epoxy resin represented by the general formula (7) include a bisphenolacetophenone type epoxy resin, and a diglycidyl ether of bisphenolacetophenone is particularly preferable. Other bifunctional epoxy resins that may be used in combination include alicyclic epoxy resins, diglycidyl ethers of monocyclic dihydric phenols such as catechol, resorcin, and hydroquinone, diglycidyl ethers of dihydroxynaphthalene, dihydric alcohols. And diglycidyl ester of divalent carboxylic acid such as phthalic acid, isophthalic acid, tetrahydrophthalic acid and hexahydrophthalic acid. These epoxy resins may be substituted with a substituent having no adverse effect such as an alkyl group, an aryl group, an ether group or an ester group.
These epoxy resins may be used in combination of plural kinds. General formula (6)

[0015]

[Chemical 9]

(In the formula, R _{1 s} may be the same as or different from each other and are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements, X is a single bond,
A divalent hydrocarbon group having 1 to 7 carbon atoms, -O-, -S-, -SO _2- ,
Or, it is a group selected from -CO-, and n is an integer of 0-10. ) General formula (7)

[0017]

[Chemical 10]

(In the formula, R ₁ 'may be the same or different from each other and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements, and R ₂ is a hydrogen atom. , A group selected from a hydrocarbon group having 1 to 10 carbon atoms or a halogen element, and R ₃ is a hydrogen atom or a group having 1 to 10 carbon atoms.
10 hydrocarbon groups, m is an integer from 0 to 5, k
Is an integer of 0 to 10. )

The dihydric phenol compound used in the production of the one-step method and the two-step method of the high molecular weight epoxy resin of the present invention is a divalent phenol compound represented by the general formula (8) or (9), Compounds having two hydroxyl groups bonded to the aromatic ring in the other molecule may be used in combination unless the object of the present invention is impaired. Examples of the divalent phenol compound of the general formula (8) include bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, biphenols, and the like, and particularly bisphenol A, bisphenol F, 4,4′- Biphenol and 3,3 ', 5,5'-tetramethyl-4,4'-biphenol are preferred. Examples of the dihydric phenol compound of the general formula (9) include bisphenolacetophenones, but bisphenolacetophenone is particularly preferable. Other than these, it may be used in combination with two hydroxyl groups bonded to the aromatic ring in the molecule.
Examples of the individual compound include catechol, resorcin, hydroquinone, dihydroxynaphthalene and the like. Further, these may be substituted with a substituent having no adverse effect, such as an alkyl group, an aryl group, an ether group or an ester group. These dihydric phenol compounds can be used in combination of two or more kinds. General formula (8)

[0020]

[Chemical 11]

(In the formula, R _{1 s} may be the same or different from each other and are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements, X is a single bond,
A divalent hydrocarbon group having 1 to 7 carbon atoms, -O-, -S-, -SO _2- ,
Alternatively, it is a group selected from -CO-. ) General formula (9)

[0022]

[Chemical 12]

(In the formula, R ₁ 'may be the same or different from each other and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements, and R ₂ is a hydrogen atom. , A group selected from a hydrocarbon group having 1 to 10 carbon atoms or a halogen element, and R ₃ is a hydrogen atom or a group having 1 to 10 carbon atoms.
10 is a hydrocarbon group and m is an integer of 0-5. )

In the two-step process for producing the high molecular weight epoxy resin of the present invention, a catalyst can be used and has a catalytic ability to promote the reaction between the epoxy group and the phenolic hydroxyl group, alcoholic hydroxyl group or carboxyl group. Any compound may be used as long as it is a compound. Examples thereof include alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines and imidazoles. Specific examples of the alkali metal compound include sodium hydroxide, lithium hydroxide, potassium hydroxide, alkali metal hydroxides such as sodium carbonate, sodium bicarbonate,
Alkali metal salts such as sodium chloride, lithium chloride, potassium chloride, etc., alkali metal alkoxides such as sodium methoxide, sodium ethoxide, etc., alkali metal phenoxides, sodium hydride, lithium hydride,
Etc., alkali metal salts of organic acids such as sodium acetate, sodium stearate and the like. Specific examples of the organic phosphorus compound include tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, Trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium bromide, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium bromide, triphenylethylphosphonium bromide, Triphenylethylphosphonium iodide , Triphenyl benzyl phosphonium chloride,
And triphenylbenzylphosphonium bromide. Specific examples of the tertiary amine include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine and the like. Specific examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, Tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride Id, phenyl trimethyl ammonium chloride, and the like. Specific examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like. Specific examples of cyclic amines include 1,8-diazabicyclo (5,4,0) undecene-
7,1,5-diazabicyclo (4,3,0) nonene-5 and the like can be mentioned. These catalysts can be used in combination. Usually, the amount of the catalyst used is 0.001 to 1% by weight based on the reaction solid content. When using an alkali metal compound as a catalyst,
The total content of Li, Na and K in the high molecular weight epoxy resin is preferably 5 ppm or less, since alkali metal remains in the high molecular weight epoxy resin and deteriorates the insulation characteristics of the printed wiring board using the same. Yes, more preferably 4 ppm or less, still more preferably 3 ppm or less. If it is 5 ppm or more, the insulating property is deteriorated, which is not preferable. Also, when an organic phosphorus compound is used as a catalyst, it remains as a catalyst residue in the high molecular weight epoxy resin,
The phosphorus content in the high molecular weight epoxy resin is preferably 150 pp because it deteriorates the insulation characteristics of the printed wiring board.
m or less, more preferably 140 ppm or less, still more preferably 100 ppm or less. 150p
When it is pm or more, the insulating property is deteriorated, which is not preferable.

The high molecular weight epoxy resin of the present invention is
A solvent may be used in the step of the synthetic reaction during the production, and a high molecular weight epoxy resin is dissolved as the solvent,
Any substance may be used as long as it does not adversely affect the reaction. Examples thereof include aromatic hydrocarbons, ketones, amide solvents, glycol ethers and the like. Specific examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like. As the ketones, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, dioxane and the like can be mentioned. Specific examples of the amide solvent include formamide,
N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-
Dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like can be mentioned. Specific examples of glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-
Examples include n-butyl ether and propylene glycol monomethyl ether acetate. Two or more of these solvents can be used in combination. The amount of the solvent used can be appropriately selected according to the reaction conditions, but for example, in the case of the two-step process, it is preferable that the solid content concentration is 35% to 95%. When a highly viscous product is produced during the reaction, the reaction can be continued by adding a solvent during the reaction. After the completion of the reaction, the solvent may be removed by distillation or the like, if necessary, and further added. The reaction temperature during the two-step process for producing the high molecular weight epoxy resin of the present invention is within a temperature range in which the catalyst used does not decompose. The reaction temperature is preferably 50 to 230 ° C, more preferably 120 to 200 ° C. When using a low boiling solvent such as acetone or methyl ethyl ketone,
The reaction temperature can be secured by carrying out the reaction under high pressure using an autoclave.

The resin composition for electric laminates containing the high molecular weight epoxy resin of the present invention as an essential component includes an epoxy resin other than the high molecular weight epoxy resin, a thermosetting resin other than the epoxy resin, a curing agent, and a curing accelerator. Various materials such as a solvent, an inorganic filler, and a fiber base material can be used in combination. Examples of the epoxy resin that can be used in combination include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin,
Cresol novolac type epoxy resins, condensation of phenols with aldehydes such as glyoxal, hydroxybenzaldehyde, crotonaldehyde, etc. Glycidyl ether type epoxy resins such as epoxy resins obtained by reacting epihalohydrin with novolaks, glycidyl ester type epoxy resins, glycidyl Examples include various epoxy resins such as amine type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. As the thermosetting resin other than the epoxy resin, a polyimide resin, a thermosetting polyphenylene ether resin, a cyanate ester resin, or the like can be used. Examples of the curing agent include aromatic polyamines, dicyandiamide, acid anhydrides, various phenol novolac resins, and the like. Examples of the curing accelerator include benzyldimethylamine, amines such as various imidazole compounds, and tertiary phosphines such as triphenylphosphine. As the solvent, for example, acetone,
Methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, N, N
-Dimethylacetamide, methanol, ethanol and the like can be mentioned, and these solvents can be used by appropriately mixing two or more kinds. In addition, UV inhibitors, plasticizers, etc. for storage stability, aluminum hydroxide, alumina, calcium carbonate, silica, etc. as inorganic fillers, silane coupling agents, titanate coupling agents, etc. can be used as coupling agents. Is. Examples of the fiber substrate include inorganic fiber cloth such as glass cloth, glass fiber non-woven fabric,
Examples include organic fiber nonwoven fabrics. Further, in order to impart flame retardancy, halogen-based, P-based, N-based, silicon-based, etc. flame retardants may be added. These resin compositions can be used for conventional multilayer electric laminates and new printed wiring boards such as build-up methods. In particular, it is preferably used in the form of a resin-coated copper foil, an adhesive film or the like used as a material for build-up method printed wiring boards. Explain the build-up method. 40 ~ on the inner layer circuit board laminated with glass prepreg
This is a method of stacking a 90 μm film (insulating layer) or a film with a copper foil (copper foil: 9 to 18 μm) as a build-up layer. or drill) process / desmear /
It becomes a plating process. And if it has the same performance as the conventional laminated board, the mounting area and weight are about 1/4, which is an excellent method for downsizing and weight reduction. In particular, the high molecular weight epoxy resin of the present invention is suitable for forming a film and can be preferably used as a build-up insulating layer.

[0027]

EXAMPLES The present invention will be further described below based on examples, but the present invention is not limited thereto. In the examples, all "parts" indicate parts by weight. Examples 1 to 3 and Comparative Examples 1 to 4 Compound (X), compound (Y), catalyst and 55 parts by weight of cyclohexanone having the formulations shown in Table 1 were placed in a pressure resistant reaction vessel equipped with a stirrer and placed under a nitrogen gas atmosphere at 180 ° C. The reaction was carried out for 5 hours. After removing the solvent from the reaction product by a conventional method, the obtained resin was analyzed for its property value by the following method. Weight average molecular weight: Measured as a polystyrene conversion value by gel permeation chromatography. Epoxy equivalent: measured by potentiometric titration method and converted to a value as resin solid content. Li, Na, K content: measured by atomic absorption method and converted into a value as resin solid content. Phosphorus content: measured with a fluorescent X-ray apparatus and converted into a value as a resin solid content. ε (1MHz): Yokogawa Hewlett-Packard Company, HP4192A
Measured using. tanδ (1MHz): Yokogawa Hewlett Packard, HP419
Measured using 2A. Water absorption rate: Measured after 168 hours at 85 ° C./85% RH. 180 degree bending resistance of the high molecular weight resin film: When the obtained high molecular weight phenoxy resin is formed into a film and bent at 180 degrees, cracks are formed in the film, or cracking occurs.
I checked if it would break. Glass transition temperature: measured by DSC. The analysis results are shown in Table 1. As shown in Table 1, the high molecular weight epoxy resin of the present invention has a low dielectric constant (ε) and a low dielectric loss (t).
anδ), excellent in low water absorption.

[0028]

[Table 1]

(Note) A: Bisphenol A diglycidyl ether (epoxy equivalent: 186 g / eq, hydrolyzable chlorine concentration: 40 wtppm,
α glycol group concentration: 40 meq / kg, product name: Epikote 828 manufactured by Japan Epoxy Resin Co., Ltd. B: Bisphenol F diglycidyl ether (epoxy equivalent: 168 g / eq, hydrolyzable chlorine concentration: 50 wtppm,
α-glycol group concentration: 60 meq / kg, trade name: Japan Epoxy Resin Co., Ltd. Epicoat 806) C: 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol diglycidyl ether (epoxy equivalent: 185)
g / eq, hydrolyzable chlorine concentration: 40 wtppm, α glycol group concentration: 50 meq / kg, trade name: Japan Epoxy Resin Co., Ltd. Epicoat YX4000) D: Bisphenol A (phenolic hydroxyl equivalent: 114 g
/ eq) E: Bisphenolacetophenone (phenolic hydroxyl group: 145 g / eq) F: 50 wt% tetramethylammonium chloride aqueous solution G: 20 wt% sodium hydroxide aqueous solution (Na content: 11.
50wt%) H: 29wt% tetramethylammonium hydroxide (nitrogen content: 4.46wt%) I: triphenylphosphine (phosphorus content: 11.83wt
%)

Examples 4-6, Comparative Examples 5-6 Using the high molecular weight epoxy resins obtained in Examples 1, 2, 3 and Comparative Examples 3, 4 and commercially available epoxy resins, Table 2
After making a varnish with the compounding ratio shown in (1) and impregnating it with a glass cloth (Style 7628, treated AS750, thickness 0.180 mm, manufactured by Asahi Schebel Co., Ltd.), the impregnated cloth is dried for 8 minutes in a drying chamber at 150 ° C. Then, a B-stage prepreg was obtained. Eight prepregs obtained by cutting this prepreg and one copper foil (electrolytic copper foil CF-T8, thickness 35 μm, manufactured by Fukuda Metal Foil & Powder Co., Ltd.) were stacked, and pressed at 40 kgf / cm ² for 175. A laminated plate was obtained by heating under pressure at 120 ° C. for 120 minutes. Table 2 shows the physical properties of the thus obtained laminate. The laminate using the high molecular weight epoxy resin of the present invention is excellent in heat resistance (glass transition temperature), boiling water resistance and adhesiveness.

[0031]

[Table 2]

(Note) (1) Molding conditions: 175 ° C. × 120 in both Examples and Comparative Examples
Min × 40 kgf / cm ² (2) Evaluation of storage stability of varnish ... Viscosity increase rate after 40 ° C. × 168 hours was measured. Viscosity measurement method, capillary viscometer:
Measured with a Canon Fenske viscometer (25 ° C). (3) Test method and evaluation method of cured physical properties 2-1: Measured by glass transition temperature DSC 2-2: Boiling water resistance (performed as an accelerated water resistance test) Disc-shaped cured material (diameter 50 mm x thickness 3 mm, Curing conditions 80 ° C x 10 hours + 120 ° C x 2 hours +175
After being dipped in boiling water of 98 ° C. or higher for 4 hours, the presence or absence of abnormality was visually determined and evaluated according to the following criteria. A: No abnormality B: Partly changed to white C: Totally changed to white 2-3: Peel strength JIS C 6481 (4) Commercially available epoxy resin and phenol resin used are as follows. Epicoat 1001: Japan Epoxy Resin Co., Ltd. product name, bisphenol A type epoxy resin, epoxy equivalent 470 (g / eq), saponifiable chlorine amount 150 (ppm) Epicoat 180S75: Japan Epoxy Resin Co., Ltd. product name, cresol novolac type epoxy resin , Epoxy equivalent 220 (g / eq), Saponifiable chlorine amount 70 (ppm) REGITOP PSM4261: Trade name of Gunei Chemical Co., phenol novolac resin, hydroxyl equivalent 103 (g / eq), softening point 8
5 (℃)

[0033]

The high molecular weight epoxy resin and the resin composition for electric laminates of the present invention have heat resistance (glass transition temperature), flexibility, low dielectric constant (ε), low dielectric loss (tan δ) and low water absorption. It has a high dielectric constant, and is particularly useful for electrical laminate applications that require low dielectric constant characteristics.

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Claims (10)

[Claims] 1. A high molecular weight epoxy resin represented by the following general formula (1) and having a weight average molecular weight of 10,000 to 200,000. General formula (1) (In the formula, A is a chemical structure represented by the following general formula (2) or (3), and the ratio of A being the general formula (3) is 5 mol% or more in the general formula (1), and B is Is a hydrogen atom or a group represented by the following general formula (4), and n is an average value of 25 to 500.) General formula (2) (In the formula, R _{1 s} may be the same or different from each other and are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements, and X is a single bond or 1 to 7 carbon atoms.
Is a divalent hydrocarbon group selected from -O-, -S-, -SO _2- , or -CO-. ) General formula (3) (In the formula, R ₁ ′ may be the same or different from each other and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements, and R ₂ is a hydrogen atom or a carbon number. It is a hydrocarbon group of 1 to 10 or a group selected from halogen elements, R ₃ is a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms, and m is an integer of 0 to 5.) General formula ( 4) [Chemical 4] 2. The high molecular weight epoxy resin according to claim 1, wherein the epoxy equivalent of the high molecular weight epoxy resin is 5,000 g / equivalent or more. 3. L contained in a high molecular weight epoxy resin
The high molecular weight epoxy resin according to claim 1 or 2, wherein the total amount of i, Na and K is 5 ppm or less and the phosphorus content is 150 ppm or less. 4. The dihydric phenol compound containing the chemical structure of the general formula (2) or (3) and epihalohydrin are reacted in the presence of an alkali, and the dihydric phenol compound is reacted. The method for producing a high molecular weight epoxy resin described in 1. 5. A bifunctional epoxy resin containing the chemical structure of general formula (2) or (3) and a divalent phenol compound containing the chemical structure of general formula (2) or (3) in the presence of a catalyst. The reaction is carried out according to
The method for producing a high molecular weight epoxy resin according to any one of 3 above. 6. The method for producing a high molecular weight epoxy resin according to claim 5, wherein the reaction temperature is in the range of 50 ° C. to 230 ° C. 7. A resin composition for an electric laminate, which is prepared by blending the high molecular weight epoxy resin according to any one of claims 1 to 3. 8. A resin composition for an electric laminate, which comprises, as essential components, the high molecular weight epoxy resin according to any one of claims 1 to 3, a thermosetting resin, a curing agent and a curing accelerator. 9. The resin composition for electric laminates according to claim 8, wherein the thermosetting resin is an epoxy resin other than the high molecular weight epoxy resin according to any one of claims 1 to 3. . 10. An electric laminate obtained from the resin composition for electric laminates according to claim 7.