JPS62127318A - Epoxy resin composition for laminated sheet - Google Patents

Abstract

PURPOSE:To obtain the titled resin composition excellent in heat resistance and drillability, by mixing bisphenol A glycidyl ether with a poly(isoprope nylphenyl glycidyl ether) and a curing agent. CONSTITUTION:A resin composition comprising 50-99pts.wt. bisphenol A glycidyl ether, 1-50pts.wt. poly(isopropenylphenyl glycidyl ether) of formula I and a curing agent. In the formula, R1-R4 are each H, a 1-10C alkyl or a halogen and n is 2-50. As the bisphenol A glycidyl ether, an adduct obtained by using tetrabromobisphenol A is preferable, especially, for use where flame retardancy is required. Examples of the curing agents used include dicyandiamide and diphenyldiaminomethane.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an epoxy resin composition for laminates that has excellent heat resistance and drill workability.

<Prior Art> In recent years, the electronic equipment industry centered on ICs, LSIs, etc. has been rapidly developing, and these electronic equipments have been incorporated in large quantities not only into computers but also into home appliances, automobiles, and the like. Epoxy resin laminates are mainly used for S boards and the like to which these electronic devices are attached.

The physical properties required for this type of laminate are simply heat resistance, ease of drilling, dimensional stability, and chemical resistance. In particular, in recent years heavy density wiring has become commonplace, and requirements for drill workability have become stricter. That is, it is required to have sufficient heat resistance to withstand the frictional heat during drilling, and to have less cracking during drilling. Currently, Epoquin resin compositions for laminates use a combination of bisphenol A type glycidyl ether and glycidyl ether of 0-cresol novolac or glycidyl ether of phenol novolac to improve stickiness. It is being

<Problems to be solved by the invention> However, by adding glycidyl ether of O-cresol novolak or phenol novolak to improve heat resistance, the glass transition temperature increases and heat resistance increases, but the elastic modulus also increases. There is a need for a balanced composition that is not prone to cracking during processing.

Means for Solving the Problems> The present invention provides bisphenol A type glinozyl ether 50
~99 parts by weight General formula (1) (wherein R3-R1 is a group selected from hydrogen, an alkyl group having 1-1° of carbon atoms, and a halogen, and n is an average of 2 to 50
is the number of This is an epoxy resin composition for a laminate, comprising 1 to 50 parts by weight of a poly(isopropenylphenyl glycidyl ether) represented by the following formula and a curing agent.

The bisphenol A-type glycicin ether used in the present invention refers to the glycidyl ether of bisphenol A obtained from bisphenol A and epichlorohydrin, and the resulting glycidyl ether of bisphenol A to bisphenol A or mono-halogenated bisphenol such as tetrabromobisphenol. It further includes glycidyl ethers of bisphenol A and monohalogenated bisphenols to mixed bisphenols. t
1. For applications requiring high flammability, adducts obtained using this tetrabromobisphenol A and the above-mentioned glycidyl ethers of mixed bisphenol A are desirable.

-C Poly(isopropenylphenyl glycidyl ether>m represented by formula (1) is exemplified by 0-3m-
1P-13 types of poly(isopropenylphenyl glycidyl ether), poly(2,6-dimethyl-4-isopropenylphenyl glycidyl ether), poly(2,
6-dipromo-4-isopropenylphenyl glycidyl ether), and copolymers thereof.

These production methods can be obtained by converting the isopropenylphenol into a polymer by cationic polymerization or thermal polymerization under an alkali catalyst, and then reacting the isopropenylphenol with epichlorohydrin to form a glycidyl ether. It can also be obtained by reacting the isopropenylphenol with epichlorohydrin to convert it into glycidyl ether, which is then subjected to canon polymerization using a specific catalyst such as hydrogen iodide or a mixed catalyst of hydrogen iodide and a halogen.

In 100 parts by weight of the mixture of bisphenol A type glycidyl ether and the poly(isopropenylphenyl glycidyl ether), the poly(isopropenylphenyl glycidyl ether) is present in an amount of 1 to 50 parts by weight, preferably 5 parts by weight.
~30 parts by weight.

A small amount of another type of glycidyl ether may be added to the glycidyl ether mixture in this proportion.

The curing agent in the present invention is not particularly limited,
Various conventionally known curing agents can be used in an amount that is stoichiometrically equal to or about half of the amount of the epoxy present in glinozyl ether. As a hardening agent, for example, "Printed wiring materials and processing technology J CMC technical report 1"
K17 (Publisher: Somc Co., Ltd.), etc., and the like are used.

The epoxy resin composition of the present invention further includes, if necessary,
A curing accelerator, filler, surface treatment agent, etc. may be added.

The curing accelerator can be appropriately selected from known ones depending on the type of curing agent used. For example, when the curing agent is dicyandiamide, 2-ethyl-4-methylimidazur, hensyldimethylamine, etc. Illustrated.

As the filler, phosphor, alumina, aluminum hydroxide, talc, mica, etc. are used.

Examples of the surface treatment agent include T-glysodoquinopropyltrimethoxosilane, β-(3°4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-aminopropyltrimethoxysilane.

The laminate can be manufactured, for example, by the method described in the above-mentioned "Materials and processing techniques for printed wiring," and the base material for the laminate can be made of organic or inorganic natural fibers, glass fibers, or synthetic fibers. These include cloth, nonwoven fabric, mat, etc., and specific examples include glass cloth, polyester cloth, paper, and Tetoron cloth.

<Effects of the Invention> Epoxy resins used for laminates have conventionally been mixed with O-cresol novolac glycidyl ether or phenol novolac glycidyl ether in order to improve the heat resistance of general-purpose bisphenol A type glycidyl ether. There is.

However, in these novolaphtaglycidyl ethers,
Although heat resistance can be increased, the modulus of elasticity also increases,
It bends and breaks easily, making drilling workability worse.

The composition of the present invention consists of a mixture of poly(isopropenylphenyl glycidyl ether)s and bisphenol A glycidyl ether.

Excellent workability.

<Execution seconds 0 Epoxy current is defined as Durham equivalent per mole of glycidyl ether group. In addition, the average polymerization weight is calculated from the number average molecular weight measured by the osmotic pressure method (manufactured by Corona, Molecular Weight Analyzer Model 117). Further, the glass transition temperature and elastic modulus were measured using Rheolograph Solid (manufactured by Toyo Seiki ■).

Reference Example 1 (1) Synthesis of polymer of isopropenylphenol Bisphenol A was thermally decomposed according to the description in Example 1 of Japanese Patent Publication No. 38-1368, and the obtained mixture '1F+(+)-
Isopropenylphenol 43wt%, phenol 42
wt%, p-isopropenylphenol oligomer I
To 300 g of 43 wt% N a O
After the polymerization was completed by keeping the temperature at 50° C. for 6 hours, the reactant was poured into a large amount of dilute MCI aqueous solution to precipitate the polymer, thereby obtaining a p-isopropenylphenol polymer.

(2) Synthesis of poly(isopropenylphenylglycidyl ether) le equipped with a thermometer, separation tube, dropping funnel, and stirrer
Add 135 g of the p-inopropenylphenol obtained in (1) to Fufusco and add 7 g of epichlorohydrin.
0 moles (8 liters) Change 73°C 1 Pressure 250mmH
[X and 48% NaO)I aqueous solution was added continuously for 8 hours. During this time, epichlorohydrin and water were azeotropically liquefied and separated into an organic layer and an aqueous layer in a separation tube, the aqueous layer was removed from the system and the organic layer was circulated into the system. After the reaction 1
After keeping it warm for a while and removing unreacted epichlorohydrin from the stalks,
The reaction product was dissolved in methyl isobutyl ketone. Next, after separating the by-product salt with F, methyl isobutyl ketone was suddenly removed to obtain poly(p-isopropenylphenyl glycidyl ether) H"4. Met.

Reference example 2 Reference example 1 except that the polymerization temperature was changed from 150°C to 180°C
Poly(p-isopropenylphenyl glycidyl ether) was obtained in the same manner as above. The epoxy equivalent was 217 and the number average degree of polymerization was 6.3.

Reference Example 3 (1) Synthesis of isopropenylphenyl glycidyl ether Instead of p-isopropenylphenol polymer, p-
Except for using 1°0 mole of isopropenylphenol.
The reaction was carried out under the same conditions as in Reference Example 1 (2) to obtain p-isopropenylphenyl glycidyl ether.

(2) Synthesis of poly(isopropenylphenyl glycidyl ether) 19 g of p-isopropenylphenyl glycidyl ether obtained in (1) was dissolved in 181 g of methylene chloride dehydrated with molecular sieves 4A, and cooled to -20°C. Add 0.128g of hydrogen iodide and 2.5g of toluene,
It was kept warm for 15 minutes. After adding 100 g of methanol to stop the reaction, 1Qwt% sodium thiosulfate aqueous solution 1
After washing with 00 g, the solvent and remaining monomers were removed by distillation to obtain poly(p-isopropenylphenyl glycidyl ether). The epoxy equivalent was 209 and the number average degree of polymerization was 9.1.

Reference example 4 0.128 g of hydrogen iodide, 0.128 g of hydrogen iodide instead of 2.5 g of toluene, 2.5 g of toluene and 0 iodine
．． Polymerization was carried out in the same manner as in Reference Example 3 except that 254 g of toluene and 2.5 g of toluene were used to obtain poly(p-isopropenylphenyl glycidyl ether). Epoxy equivalent is 213
, the number average degree of polymerization was 37.

Examples 1 and 2 Commercially available Sumiepoxy ESA-011 (Epoxy 1490 manufactured by Sumisho Chemical Co., Ltd.) of glycidyl ether of bisphenol A and poly(isopropenylphenyl glycidyl ether) were added in the amounts shown in Table 1 to 25 g of methyl ethyl ketone. It was melted and made into Evokin resin face.

For this festival, 4.0g of dicyandiamide.

0.1 g of 2-ethyl-4-methylimidazole and 40 g of methyl cellosolve were added and mixed uniformly.

Subsequently, the mixture was poured into a mold, and after drying and removing the solvent, it was press-molded at 160° C. and 100 kg/− for 10 minutes.

Further, it was cured at 180° C. for 1 hour to obtain a molded product.

The glass transition temperature and elastic modulus of the molded product at 20°C were measured. The results are shown in Table 1.

Comparative Example 1 Poly (isopropenylphenyl glycidyl ether)
The same procedure as in Example 1 was carried out except that . Table 1 shows the results.
Shown below.

Comparative Examples 2-3 Sumie epoxy of glycidyl ether ESCN-220
The same procedure as in Example 1 was carried out except that epoxy equivalent (epoxy equivalent: 215, number average degree of polymerization: 4.8, manufactured by Sumitomo Chemical Co., Ltd.) was used. The results are shown in Table 1.

Examples 3 to 7 Sumiboxy ■ to glycidyl ether to bisphenol
ESB-500 (manufactured by Sumisho Chemical Co., Ltd. Epoquin equivalent weight 489
Table 1 shows the type and content of poly(isopropenylphenyl glycidyl ether).
The same procedure as in Example 1 was carried out except for the changes shown in . The results are shown in Table 1.

Comparative Examples 4 to 6 Sumipoxy ■ to glycidyl ether of bisphenol A
The same procedure as Comparative Example 3 was carried out except that ESB-500 was used. The results are shown in Table 1.

Procedural amendment 3 (voluntary) June 2q, 1985 Patent Application No. 269163 2, Title of invention: Epoxy resin composition for laminates 3, Address related to the case of the person making the amendment: 5 Kitahama, Higashi-ku, Osaka City 15-chome name (
209) Sumitomo Chemical Co., Ltd. Representative: Hideo Mori 4, Agent Address: Sumitomo Chemical Co., Ltd. 1, 5-15 Kitahama, Higashi-ku, Osaka Name: Patent Attorney (8597) Mitsuhiro Moroishi Contact Information
(06) 220-34045, Description subject to amendment 1, Title of the invention: Epoxy resin composition for laminates 2, Claims ill: 50 to 99 parts by weight of glass phenol A type grindyl ether, general formula ( 1) (In the formula, R1-R4 are hydrogen, an alkyl group having 1 to 10 carbon atoms, and a halogen group, and n is an average of 2 to 50
is the number of An epoxy resin composition for a laminate, comprising 111 to 50 parts by weight of poly(isobropenyl phenylcricidyl ether) represented by the following formula and a curing agent.

3. Detailed Description of the Invention <<Industrial Application Field>> The present invention relates to an epoxy resin composition for laminates that has excellent heat resistance and drill workability.

(Prior Art) In recent years, the electronic equipment industry centered on ICs, LSIs, etc. has been rapidly developing, and these electronic equipments are being incorporated in large quantities not only into computers but also into home appliances, automobiles, and the like.

Epoxy resin laminates are commonly used for substrates and the like on which these electronic devices are attached.

Physical properties required for this type of laminate include not only earth resistance but also drill workability, dimensional stability, and chemical resistance.

In particular, as high-density wiring has become more common in recent years, requirements for drill workability have become stricter.

That is, it is required to have sufficient heat resistance to withstand IIj heat during drilling, and to have less peeling and cracking during drilling.

Currently, epoxy resin compositions for laminates use a mixture of bisphenol A type grindyl ether and glycidyl ether of O-talesol novolac or glycidyl ether of phenol novolak in order to improve heat resistance.

Problems to be Solved by the Invention> However, by adding glycidyl ether of 0-talesol novolak or phenol novolac to improve heat resistance, the glass transition temperature increases and heat resistance increases, but the elastic modulus also increases. Cracks are more likely to occur during drilling.

Therefore, a composition with a high glass transition temperature and a moderate elastic modulus is required.

<<Means for solving the problem>> The present invention provides bisphenol A type grindyl ether 50
~99 parts by weight General formula (1) (wherein R-~R'' is a group selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, and a halogen, and n is an average of 2 to 50
is the number of This is a temporary Evokin resin composition consisting of 11 to 50 parts by weight of poly (isopropenylphenyl glycidyl ether) represented by ) and a curing agent.

The bisphenol A type glycidyl ether used in the present invention refers to glycidyl ether of bisphenol A obtained from bisphenol A and epichlorohydrin, and halogen-substituted bisphenol A such as bisphenol A or tetrabromobisphenol A to the glycidyl ether of bisphenol obtained. It further includes glycidyl ethers of bisphenol A and mixed bisphenol A obtained from halogen-substituted bisphenol A and epichlorohydrin.

For applications requiring flame retardancy, adducts obtained using this tetrabromobisphenol A and the glycidyl ethers of mixed bisphenol A described above are desirable.

Examples of poly(isopropenylphenyl glycidyl ether) represented by general formula (1) include 0-1m-
1P-23 types of poly(isopropenylphenyl glycidyl ether), poly(2,6-dimethyl-4-isopropenylphenyl glycidyl ether), poly(2,
6-dipromo-4-isopropenylphenyl glycidyl ether), and copolymers thereof.

These production methods are obtained by cationic polymerization of cough isopropenylphenol into a polymer of the isopropenylphenol, which is further reacted with epichlorohydrin to form a glycidyl ether.

It can also be obtained by reacting the isopropenylphenol with epichlorohydrin to form a glycidyl ether, which is then cationically polymerized with a specific catalyst such as hydrogen iodide or a mixed catalyst of hydrogen iodide and a halogen.

In 100 parts by weight of the mixture of bisphenol A type glycidyl ether and the poly(isopropenylphenyl glycidyl ether), the poly(isopropenylphenyl glycidyl ether) is present in an amount of 1 to 50 parts by weight, preferably 5 parts by weight.
~30! It is a quantity part.

A small amount of another type of glycidyl ether may be mixed with the glycidyl ether mixture in this proportion.

The curing agent in the present invention is not particularly limited,
Various conventionally known curing agents can be used in an amount stoichiometrically equal to or about half the epoxy equivalent of the glycidyl ether.

Examples of hardening agents include dicyandiamide, diphenyldiaminomethane, diphenyldiamino sulfone, etc., as described in [Printed Wiring Materials and Processing Technology J CMC Technical Report 17 (Published by CMC Corporation). used.

The epoxy resin composition of the present invention further includes, if necessary,
A curing accelerator, filler, surface treatment agent, etc. may be added.

The curing accelerator can be appropriately selected from known ones depending on the curing agent used.

For example, when the curing agent is dicyandiamide, examples thereof include 2-ethyl-4-methylimidazole and hensyldimethylamine.

As the filler, silica, alumina, aluminum hydroxide, talc, mica, etc. are used.

Examples of the surface treatment agent include T-glycidquinpropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and T-aminopropyltrimethoxysilane.

The laminate can be manufactured, for example, by the method described in the above-mentioned "Materials and Processing Techniques for Printed Wiring," and the base material for the laminate may include organic fibers, inorganic natural fibers, glass fibers, and synthetic fibers. These include cloth, nonwoven fabric, mat, etc., and specific examples include glass cloth, polyester cloth, paper, and Tetoron cloth.

<Effects of the Invention> The epoxy equivalent used in the laminate is a mixture of conventional O-cresol novolak glycinol ether and phenol novolac glycinol ether in order to improve the heat resistance of general-purpose bisphenol A type glycinol ether. It is used as

However, in these novolanogrindyl ethers,
Although heat resistance can be increased, the modulus of elasticity also increases,
It becomes brittle and breaks easily, and has poor drillability.

The composition of the present invention consists of a mixture of poly(isopropenylphenyl glycidyl ether)s and bisphenol A glycidyl ether.

This composition has higher heat resistance, but has an appropriately suppressed modulus of elasticity, is less likely to crack, and has excellent drill workability.

<Example> Epoxy equivalent is defined as Durham equivalent per mole of glynodyl ether group.

In addition, the number average degree of polymerization is determined by the stem pressure immersion method (manufactured by Corona Corporation,
It is calculated from the number average molecular weight measured using a molecular weight measurement value (Model 117).

Further, the glass transition temperature and elastic modulus were measured using Rheolograph Solid (manufactured by Toyo Seiki ■).

Reference Example 1 +11 Synthesis of isopropenylphenyl glycidyl ether Bisphenol A was thermally decomposed according to the description in Example 1 of Japanese Patent Publication No. 38-1368, and the resulting mixture was purified to produce p-
Isopropenylphenol was obtained.

1 equipped with a thermometer, separation tube, dropping funnel, and stirrer!
In a flask, add 135 g of the p-isopropenylphenol.
was dissolved in 7°0 mol of epichlorohydrin and heated to 73°C.
The pressure was maintained at 250 mmHg, and a 48% NaOH aqueous solution was continuously added over 8 hours.

During this time, epichlorohydrin and water were azeotropically liquefied and separated into an organic layer and an aqueous layer in a separation tube, the aqueous layer was removed from the system and the organic layer was circulated into the system.

After completion of the reaction, keep warm for 1 hour to evaporate and remove unreacted epichlorohydrin, converting the reaction product to methyl isobutyl ketone)
I got a lot of customers.

Next, after the by-product salt was separated, methyl isobutyl ketone was boiled off and removed to obtain p-isopropenylphenyl glycidyl ether.

(2) Synthesis of poly(isopropenylphenyl glycidyl ether) 19 g of p-isopropenylphenyl glycidyl ether obtained by ill was dissolved in 181 g of methylene chloride dehydrated with molecular sieves 4A, cooled to -20°C, and iodized. Add 0.128g of hydrogen and 2.5g of toluene,
It was kept warm for 15 minutes.

After adding 100g of methanol to stop the reaction, 10w
t% sodium thiosulfate aqueous solution 100 g''?: After washing, the solvent and remaining monomers were removed by distillation, and the poly
(p-isopropenylphenyl glycidyl ether) was obtained.

The epoxy equivalent was 209 and the number average degree of polymerization was 9°1.

Reference example 2 Hydrogen iodide 0.128g, toluene 2.5g and iodine 0 instead of hydrogen iodide 0.128g and toluene 2.5g
．． Reference example except that 254 g and 2.5 g of toluene were used [
Polymerization was carried out in the same manner as above to obtain poly(p-isopropenylphenyl glycidyl ether).

The epoxy equivalent was 213 and the number average degree of polymerization was 37.

Examples 1 to 4 Sumiboxy ESB- which is an adduct of glycidyl ether of bisphenol A and tetrabromobisphenol A
Table 1
The amount shown in was used as methyl ethyl ketone resin face.

For this festival, 4.0g of non-andiamide.

0.1 g of 2-ethyl-4-methylimidazole and 40 g of methyl cellosolve were added and mixed uniformly.

Subsequently, the mixture was poured into a mold, and after drying and removing the solvent, it was press-molded at 160° C. for 10 minutes at I OOK g/cm2.

Further, it was cured at 180° C. for 1 hour to obtain a molded product.

The glass transition temperature and elastic modulus of the molded product at 20°C were measured.

The results are shown in Table 1.

Comparative Example 1 Poly (isopropenylphenyl glycidyl ether)
The same procedure as in Example 1 was carried out except that .

The results are shown in Table 1.

Comparative Examples 2-3 Poly (isopropenylphenyl glycidyl ether)
Sumiebokino of O-cresol noboranokurindyl ether ■ ESCN-220 (Susho Chemical Industry 1I
Epokin made by IT ff12+5, number average degree of polymerization 4.8)
The same procedure as in Examples 1 and 2 was carried out except that .

The results are shown in Table 1.

Claims (1)

[Claims] (1) Bisphenol A type glycidyl ether 50-9
9 parts by weight, General formula (1) ▲Mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, R_1 to R_4 are groups selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, and a halogen, n is average 2~
The number is 50. An epoxy resin composition for a laminate comprising 1 to 50 parts by weight of a poly(isopropenylphenylcricidyl ether) represented by the following formula and a curing agent.