JPH02311513A - Heat-resistant, flame-retarding epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition improved in heat resistance and does not decrease in its mechanical properties and electrical insulation properties even at high temperatures by mixing a specified polyepoxy resin with a lowly halogenated bisphenol epoxy resin. CONSTITUTION:A trisphenol compound (a) of formula I (wherein R<1> <to> <3> are each H or 4C or lower alkyl; (n) is 0 or 1; Y is either of formulas II and III; and R<4> <to> <7> are each R<1>) is condensed with (beta-methyl)epihalohydrin (b) to obtain a normally (semi)solid polyepoxy resin (A) having a softening point <=130 deg.C and an epoxy equivalent of 154 to 380. Separately a bisphenol epoxy resin obtained by condensing a bisphenol (c) with component (b) is reacted with a halogenated bisphenol (d) to obtain a lowly halogenated bisphenol epoxy resin (B). Component A is mixed with component B in a ratio of (10 to 70):(90 to 10).

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to novel epoxy resin compositions.

More specifically, the present invention relates to a novel epoxy resin composition whose cured product has excellent heat resistance, mechanical properties, water resistance, etc., and is suitable for paints, casting materials, laminate molding materials, and the like.

<Prior art> Epoxy resin with aromatic polyamine, aliphatic polyamine,
Compounds of various curing agents such as amine adducts, dicyandiamide, acid anhydrides, and phenol novolacs are used as adhesives, paints, molding materials, casting materials, and the like.

Further, a reinforcing base material coated and impregnated with a varnish made of such a compound with a solvent is used for forming a laminate (printed wiring board).

By the way, in recent years, with the miniaturization and precisionization especially in the electrical and electronic fields, in applications such as insulating paints, sealants, and laminates for electronic parts, there has been a rise in the In order to obtain reliability, there is a strong demand for improved heat resistance. However, paints, sealants, laminates (printed wiring boards), etc. made from the above-mentioned epoxy resin formulations that have been conventionally used have low glass transition temperatures and lack high-temperature reliability. Therefore, in order to improve heat resistance, a polyfunctional epoxy resin such as an orthocresol novolac type epoxy resin or a phenol novolac type epoxy resin is often used in combination with the above-mentioned epoxy resin.

However, when a large amount of these polyfunctional epoxy resins is added, although the heat resistance is improved, the heat shock resistance is reduced and cracks are likely to occur in paints, sealants, etc.

In addition, when epoxy resin is used in laminates (printed wiring boards), water resistance is required, and if water resistance is poor, electricity
When soldering electronic components, the laminate may bulge.
Product defects such as peeling, measling, and crazing are more likely to occur.

<Problems to be Solved by the Invention> The purpose of the present invention is to provide an insulating coating for electronic parts that has excellent heat resistance, does not deteriorate mechanical properties and electrical insulation properties even when used at high temperatures, and requires high-temperature reliability. An object of the present invention is to provide a heat-resistant and flame-retardant epoxy resin composition that can be suitably applied to sealing materials, laminates (printed wiring boards), and the like.

The present inventor conducted extensive studies in order to achieve the above object.

As a result, by mixing a multifunctional epoxy resin derived from special trisphenols with a low bromine-containing bisphenol type epoxy resin, it has far superior heat resistance compared to cured products obtained from conventionally known epoxy resins. It has been found that it is possible to obtain an epoxy resin composition which has improved reliability such as mechanical properties and electrical properties.

In addition, if it is desired to impart sufficient flame retardancy as required, a high bromine-containing bisphenol type epoxy resin can be added and mixed into the above composition to create an epoxy resin that has sufficient flame retardancy without reducing heat resistance. It has been found that a composition can be obtained.

Therefore, by laminating and molding the epoxy resin composition of the present invention with, for example, glass cloth to form a cured product, it has excellent heat resistance and flame retardancy, and is particularly useful as an electronic component with improved reliability at high temperatures. laminates can be obtained.

A first aspect of the present invention is (A) the following general formula [1], in which RI, R2 and R3 are each independently a hydrogen atom or an alkyl group having 4 or less carbon atoms. , n is a number of 0 or 1, and Y is the general formula [1b] or the general formula [1c] R6, where R4, R8, Re and R7 are each independently a hydrogen atom or a carbon number of 4 or less. A polyfunctional epoxy resin obtained by condensation of a trisphenol compound represented by an alkyl group with shrimp halohydrin or β-methyl shrimp halohydrin, and (E) bisphenols and shrimp halohydrin or β-
A heat-resistant and flame-retardant product characterized by containing a low-halogenated bisphenol-type epoxy resin obtained by the reaction of a bisphenol-type epoxy resin obtained by condensation with methylevihalohydrin and a halogenated bisphenol. It is an epoxy resin composition.

A second aspect of the present invention further provides, in addition to the first aspect, (D) a highly halogenated bisphenol type epoxy obtained by condensing a halogenated bisphenol with shrimp halohydrin or β-methyl shrimp halohydrin; This is an epoxy resin composition containing a heat-resistant and flame-retardant epoxy resin composition characterized by containing a resin.

Further, the present invention is a heat-resistant and flame-retardant epoxy resin composition containing 10 to 80% by weight, preferably 30 to 70% by weight of a polyfunctional epoxy resin.

Furthermore, the present invention is a heat-resistant and flame-retardant epoxy resin composition having a bromine content of 5 to 30% by weight, preferably 15 to 25% by weight.

The present invention will be explained in detail below.

The trisphenol compound used in the present invention is represented by the following general formula [I].

In the formula, each of R1, R2 and R3 is independently a hydrogen atom or an alkyl group having 4 or less carbon atoms, and may be the same or different, n is a number of 0 or 1, and Y is a general formula [1b or general formula [1c] [1c] ■ -CH2-C- Here, R4, R5, all and R7 are each independently a hydrogen atom or an alkyl group having 4 or less carbon atoms, and may be the same or different. good.

It is particularly preferred that R1 to R7 are all hydrogen atoms.

A particularly preferable substance as the trisphenol compound represented by the above general formula [I] is, for example, 1-[α-methyl-
α-(4′-hydroxyphenyl)ethyl]-4-[α
', α'-bis(4″-hydroxyphenyl)ethyl]
Benzene, 1,1,3-tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane, 1-[α-
Methyl-α-(3′,5′-dimethyl-4′-hydroxyphenyl)ethyl]-4′-[α′,α′-bis(3
'', 5''-dimethyl-45-hydroxyphenyl)ethyl]benzene, and the like.

These trisphenol compounds and shrimp halohydrin or β-methyl shrimp halohydrin, preferably epichlorohydrin or β-methyl epichlorohydrin, are etherified in the presence of a suitable etherification catalyst, and then dehydrohalogenated, etc. by a conventionally known reaction. A multifunctional epoxy resin can be obtained. Used in the present invention (
A) The polyfunctional epoxy resin is semi-solid to solid at room temperature, and has a softening point of 130°C or lower, preferably 80°C.
℃ or less, the epoxy equivalent is 154 to 380, preferably 1
90-230.

(E) Low halogenated bisphenol type epoxy resin used in the present invention is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol such as 1,1-bis(glycidoxyphenyl)ethane, and shrimp halohydrin or β-methyl It is a resin obtained by reacting a bisphenol type epoxy resin obtained by condensation with shrimp halohydrin and a halogenated bisphenol in the presence of a catalyst, and has an epoxy equivalent of 250 to 600, preferably 400 to 500. 5-30, preferably 15-25
It has a halogen content of % by weight.

As the halogenated bisphenols, brominated bisphenols are preferred, particularly tetrabromobisphenol A, tetrabromobisphenol F, 1,1-bis(
3,5-dibromo-4-hydroxyphenylethane is preferred.

As the highly halogenated bisphenol type epoxy resin (D) used in the present invention, the halogenated bisphenols and epihalohydrin or β-methylepihalohydrin, preferably epichlorohydrin or β-methylepichlorohydrin are combined with a known suitable etherification catalyst. It is a highly halogenated bisphenol type epoxy resin obtained by etherification in the presence of and then dehydrohalogenation. ,5-dibromo-4-hydroxyphenyl)ethane type epoxy resin is preferred;
Preference is given to those having an epoxy equivalent weight of 00 to 600, especially 300 to 400, and a bromine content of 45 to 54, especially 47 to 50% by weight.

In the composition of the present invention, the polyfunctional epoxy resin and the low halogenated bisphenol epoxy resin contain 10:
90-70:30, preferably 20:80-5
It is preferable to use the ratio of 0:50.

When used in the above ratio, a cured epoxy resin product having excellent mechanical properties and heat resistance can be obtained.

Adding and mixing a polyfunctional epoxy resin to a low-halogenated bisphenol type epoxy resin improves heat resistance, but
Flame retardancy decreases. Generally, to improve flame retardancy, a halogen-containing bisphenol type epoxy resin is used which is reacted with a large amount of halogenated bisphenols. However, in this case, the molecular weight of the halogen-containing bisphenol-type epoxy resin becomes too large, and the heat resistance of the cured product deteriorates.

In the present invention, heat resistance is achieved by adding and mixing the minimum amount of highly halogenated bisphenol epoxy resin necessary for flame retardancy to the above-mentioned combination of polyfunctional epoxy resin and low halogenated bisphenol epoxy resin. Sufficient flame retardancy can be imparted without reducing the flame retardancy.

In the present invention, when making an epoxy resin composition with sufficient flame retardancy, there is no regulation on the amount of highly halogenated bisphenol type epoxy resin to be used, but polyfunctional epoxy resin,
The weight percent of the polyfunctional epoxy resin in the resin composition obtained from the combination of a low halogenated bisphenol epoxy resin and a highly halogenated bisphenol epoxy resin is preferably 10 to 25.

The method for producing the composition of the present invention is not particularly limited as long as the above components can be mixed homogeneously. They may be mixed in a molten state, or may be mixed using a solvent such as methyl ethyl ketone. The order of the components to be mixed is not particularly limited either, and they may be mixed sequentially or simultaneously.

The epoxy resin composition of the present invention may optionally contain other epoxy resins known per se, such as bisphenol-type epoxy resins, within a range that does not impair the purpose of the present invention.
It can be used in combination with phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, etc. When used, curing agents such as aliphatic amine type, aromatic amine type, amine adduct, dicyandiamide, phenol novolac resin, ortho-cresol novolac resin, acid anhydride, etc., which are generally known as curing agents for ordinary epoxy resins, are mixed. electrical insulating paints, in the form of compositions with
It can be used in the production of molding materials, sealants, laminates, etc.

The amount of curing agent used varies depending on the type of curing agent, but for example, when polyamines are used, it is based on the ratio of epoxy equivalent to active hydrogen equivalent. Also,
Curing accelerators can also be used if necessary.

When used as a paint, it is prepared by blending general-purpose colorants (pigments), fillers, solvents, antifoaming agents, etc. When used as a sealant for molding materials, various fillers are used. I can do it. When used as an epoxy resin composition for laminates, it is generally prepared into a varnish using a solvent such as aromatic hydrocarbons such as toluene and xylene, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. The prepared epoxy resin composition was impregnated into a reinforcing base material such as glass cloth, carbon fiber, glass fiber, paper, asbestos, polyester fiber, aromatic polyamide fiber (trademark Kevlar), and this was made into a prepreg. After that, it is heated and pressed in a press to form a laminate.

<Examples> The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

(Example 1) 462.5 g of epichlorohydrin, 1-[α-methyl-
α(4′-hydroxyphenyl)ethyl]-4-[α′
, 141.3 g of α'-bis(4'-hydroxyphenyl)ethyl]benzene was charged into a 1°C glass flask equipped with a stirrer and a reflux device, and the temperature was raised to 70'C while stirring. . At the same temperature, while reducing the pressure to 300 mmHg, add 79 g of 48% sodium hydroxide aqueous solution to 3
It was added dropwise continuously over time. Water within this time series was continuously taken out of the system. Thereafter, unreacted epichlorohydrin was distilled out of the system. 230 g of methyl isobutyl ketone and 230 g of water were added to the residue and stirred to transfer the generated common salt to the aqueous phase, which was then allowed to stand and the separated aqueous phase was removed. Next, add 48% sodium hydroxide aqueous solution 1 to the oil phase.
0 g was added and stirred at 85° C. for 2 hours to perform a second dehydrochlorination reaction. The oil phase is then separated from the aqueous phase,
76 g of a 30% aqueous sodium dihydrogen phosphate solution was added thereto for neutralization, followed by water removal by azeotropic distillation and salt filtration using a G4 glass filter.

5mm) Ig, methyl isobutyl ketone was completely removed from the oil phase under reduced pressure at 150°C, and the epoxy equivalent was 212,
A polyfunctional epoxy resin (A-1) having a softening point of 60°C was obtained.

351 g of this polyfunctional epoxy resin (A-1), low brominated epoxy resin epoxy equivalent 487, brome content 21.
1wt%) 340g1 Highly brominated bisphenol A epoxy resin (D-1) C epoxy equivalent 356 Nippon Kayaku ■registered trademark ETBA-100, brome content 48.1wt%)
207 g and 300 g of methyl ethyl ketone were completely dissolved at 50°C. This epoxy resin methyl ethyl ketone solution had an epoxy equivalent of 405, a solid content of 75.1%, and a bromine content of 14.2 wt%.

This epoxy resin methyl ethyl ketone solution (100 parts by weight as solid content), 15 parts by weight of ethylene glycol monomethyl ether, 15 parts by weight of dimethylformamide,
Dicyandiamide (active hydrogen group/epoxy group = 0.65
/1 equivalent amount) and 0.2 parts by weight of 2-ethyl-4-methylimidazole were mixed to prepare a varnish.

This varnish was impregnated into a glass cloth (WE-18-BZ2 manufactured by Nitto Boseki ■) and heated at 150° C. for 5 minutes to obtain a semi-cured prepreg.

9 sheets of this prepreg are stacked at 180℃ and 10kgf/c.
rr? A glass cloth laminate was produced under molding conditions of , 60 minutes. The formed laminate has a glass transition temperature (Tg
) was 188°C, and the flame retardancy was UL-94 VO.

The results are shown in Table 1.

(Examples 2 to 5) Glass cloth laminates were created in the same manner as in Example 1, but using the amounts of raw materials shown in Table 1. Example 1
The same measurements as above were carried out and the results are shown in Table 1.

<Effects of the Invention> The present invention is a composition containing a polyfunctional epoxy resin that is inferior to special trisphenols and a low halogenated bisphenol type epoxy resin, and the cured product has excellent heat resistance and is resistant to heat at high temperatures. There is no deterioration in mechanical properties or electrical insulation properties even after use.

Moreover, the composition of the present invention containing a highly halogenated bisphenol type epoxy resin in the above composition can provide a cured product having sufficient flame retardancy without reducing heat resistance.

Claims (7)

[Claims] (1) (A) The following general formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] In the formula, R^1, R^2 and R^3 are each independently a hydrogen atom or a carbon number of 4 or less. It is an alkyl group, n is a number of 0 or 1, and Y is a general formula [1b] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [1b] or general formula [1c] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼[1c] Here, R^4, R^5, R^6 and R^7 are each independently a hydrogen atom or an alkyl group having 4 or less carbon atoms, and the trisphenol compound and epihalohydrin or β - Multifunctional epoxy resin obtained by condensation with methyl epihalohydrin and (E) bisphenols and epihalohydrin or β-
A heat-resistant and flame-retardant epoxy resin composition characterized by containing a low-halogenated bisphenol-type epoxy resin obtained by reacting a bisphenol-type epoxy resin obtained by condensation with methyl epihalohydrin and a halogenated bisphenol. (2) (A) The following general formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] In the formula, R^1, R^2 and R^3 are each independently a hydrogen atom or a carbon number of 4 or less. It is an alkyl group, n is a number of 0 or 1, and Y is a general formula [1b] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [1b] or general formula [1c] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼[1c] Here, R^4, R^5, R^6 and R^7 are each independently a hydrogen atom or an alkyl group having 4 or less carbon atoms, and the trisphenol compound and epihalohydrin or β - Multifunctional epoxy resin obtained by condensation with methyl epihalohydrin and (E) bisphenols and epihalohydrin or β-
A heat-resistant and flame-retardant epoxy resin composition characterized by containing a low-halogenated bisphenol-type epoxy resin obtained by the reaction of a bisphenol-type epoxy resin obtained by condensation with methyl epihalohydrin and a halogenated bisphenol, and ( D) A heat-resistant and flame-retardant epoxy resin composition containing a highly halogenated bisphenol-type epoxy resin obtained by condensation of halogenated bisphenols and epihalohydrin or β-methylepihalohydrin. (3) The halogenated bisphenols are tetrabrominated bisphenol A, tetrabrominated bisphenol B
, tetrabrominated bisphenol F, or 1,1-bis(3,5-dibromo-4-hydroxyphenyl)ethane. (4) The trisphenol compound is 1-[α-methyl-α-(4′-hydroxyphenylethyl]-4-[α′,α′-bis(4″-hydroxyphenyl)ethyl]benzene, 1-[ α-methyl-α-(3′
,5'-dimethyl-4'-hydroxyphenyl)ethyl]-4'-[α',α'-bis(3″,5″-dimethyl-4″hydroxyphenyl)ethyl]benzene, 1,1
, 3-tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane.
The heat-resistant and flame-retardant epoxy resin composition according to any one of the above. (5) The bisphenol according to any one of claims 1 to 4, wherein the bisphenol is at least one selected from the group consisting of bisphenol A, bisphenol B, bisphenol F, and 1,1-bis(4-hydroxy)ethane. Heat-resistant and flame-retardant epoxy resin composition. (6) Claims 1 to 4, wherein the polyfunctional epoxy resin is present in an amount of 10 to 80% by weight in the heat-resistant and flame-retardant epoxy resin composition.
5. The heat-resistant and flame-retardant epoxy resin composition according to any one of 5. (7) The heat-resistant and flame-retardant epoxy resin composition according to any one of claims 1 to 6, wherein the halogen content in the heat-resistant and flame-retardant epoxy resin composition is 5 to 30% by weight.