JP2761403B2 - Heat resistant epoxy resin composition - Google Patents

Description

The present invention relates to a novel modified epoxy resin composition. More specifically, the present invention relates to a novel modified epoxy resin composition which is excellent in heat resistance, mechanical properties, water resistance and the like, and is suitable for paints, casting materials, molding materials for laminated boards and the like.

<Prior art> Bisphenol A type epoxy resin and bisphenol A type epoxy resin containing halogen are blended with various curing agents such as aromatic polyamine, aliphatic polyamine, amine adduct, dicyandiamide, acid anhydride, phenol novolak and the like. , Molding materials, casting materials and the like.

In addition, a reinforcing base material obtained by coating and impregnating a varnish of such a composition with a solvent is used as a laminate (printed wiring board).
Used for molding.

By the way, in recent years, especially in the electric and electronic fields,
Along with precision, in applications such as insulating coatings for electronic components, encapsulants, and laminates, heat resistance has been strongly improved in order to obtain reliability such as mechanical properties and electrical insulation at high temperatures. It has been demanded. However, conventionally used paints, sealing materials, laminates, and the like made of the epoxy resin compound have low glass transition temperatures and lack high-temperature reliability. Therefore, in order to increase the heat resistance, a polyfunctional epoxy resin such as an orthocresol novolak type epoxy resin or a phenol novolak type epoxy resin is often used in combination with the above-mentioned compound.

However, when a large amount of these polyfunctional epoxy resins are blended, heat resistance is improved, but heat shock resistance is reduced, and cracks are easily generated in paints, sealing materials, and the like.

In addition, when used in laminates, water resistance is required, and if water resistance is inferior, when soldering electric and electronic parts, the laminated board will have a quality called swelling, peeling, The defect phenomenon easily occurs.

<Problems to be Solved by the Invention> An object of the present invention is to provide an insulating paint for electronic parts which is excellent in heat resistance, does not deteriorate in mechanical properties and electric insulation even when used at high temperatures, and requires high-temperature reliability. Another object of the present invention is to provide a heat-resistant epoxy resin composition which can be suitably used for a sealing material, a laminate (printed wiring board), and the like.

The present inventor has determined that a polyfunctional epoxy resin (A) derived from a special trisphenol or a combination of a polyfunctional epoxy resin (A) and a bifunctional epoxy resin (B) can be used as a bisphenol ( Together with C), it was found that the modified epoxy resin composition obtained by reacting in the presence of a catalyst had excellent heat resistance and mechanical properties.

Therefore, an object of the present invention is to provide a novel modified epoxy resin composition which is excellent in heat resistance and mechanical properties by being cured, and is capable of producing an insulating paint, a sealing material, and a molded product. .

Another object of the present invention is to provide a novel modified epoxy resin composition which is excellent in heat resistance by curing, and can produce a laminate having improved mechanical strength and electrical insulation at high temperatures. It is to provide.

<Means for Solving the Problems> That is, the present invention provides a polyfunctional epoxy resin (A) and, if necessary, a bifunctional epoxy resin (B), and bisphenol A, bisphenol B, bisphenol F, or 1,1 A modified epoxy resin composition obtained by reacting any one or more bisphenols (C) of -bis (4-hydroxyphenyl) ethane in the presence of a catalyst, wherein the polyfunctional epoxy resin (A) Is 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -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- [α-methyl-α- (3,5-dibromo-
4-hydroxyphenyl) ethyl] -4- [α, α-bis (3,5-dibromo-4-hydroxyphenyl) ethyl] benzene and 1,1,3-tris (2-methyl-4
-Hydroxy-5-tert-butylphenyl) butane, which contains a condensate of at least one trisphenol compound selected from epichlorohydrin and / or β-methylepichlorohydrin, wherein the bifunctional epoxy resin (B) An object of the present invention is to provide a heat-resistant epoxy resin composition comprising a condensate of a bisphenol (C) with epichlorohydrin and / or β-methylepichlorohydrin.

Further, the modified epoxy resin composition, 200 ~ 1500g / e
It should have an epoxy equivalent of q.

The weight ratio of the polyfunctional epoxy resin (A) to the bifunctional epoxy resin (B) is preferably in the range of 90:10 to 30:70.

Then, the phenolic hydroxyl group of the bisphenols (C) is 0.03 or more per epoxy group of the polyfunctional epoxy resin (A) and the bifunctional epoxy resin (B).
It is better to react within the range of 0.5.

 Hereinafter, the present invention will be described in detail.

The trisphenol compound used to obtain the modified epoxy resin composition of the present invention is 1- [α-methyl-α-
(4-hydroxyphenyl) ethyl] -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- [α-methyl-α- (3,5-dibromo-4-hydroxyphenyl) ethyl] -4- [α, α-bis (3,5-
Dibromo-4-hydroxyphenyl) ethyl] benzene and 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.

A polyfunctional epoxy resin is produced by a conventionally known reaction such as etherification of these trisphenol compounds and epichlorohydrin and / or β-methylepichlorohydrin in the presence of a suitable etherification catalyst, followed by dehydrohalogenation. You.

In the present invention, the above trisphenol compounds may be used as a mixture of a plurality of types.

Hereinafter, the reaction of the polyfunctional epoxy resin (A), which is a main component of the epoxy resin composition of the present invention, will be described. The same applies to the above-described polyfunctional epoxy resin mixture.

Trisphenol compound and epihalohydrin or β
The reaction with -methyl epihalohydrin can be carried out by various methods following this type of conventionally known reaction.
One method is to equilibrate an alkali compound, for example, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide, preferably sodium hydroxide, to 1 equivalent of the phenolic hydroxyl group of the trisphenol compound. The etherification step and the dehalogenated hydroxylation step at the same time, in the presence of water, at a temperature of about 60-90 ° C., preferably at least 1.02 to 1.05 times the amount,
After completion of the reaction, unreacted halohydrins from the reaction mixture,
This is a method (one-step method) of removing water and generated salts, and drying and obtaining a trifunctional epoxy compound as a reaction product.

However, if a method of sequentially performing the etherification step and the dehydrohalogenation step (two-step method) is employed, an epoxy compound of stable quality can be obtained, which is a more preferable method.

In the etherification step, about 0.005 to 5 mol% of an etherification catalyst, for example, a tertiary amine such as trimethylamine or triethylamine, a tertiary phosphine such as triphenylphosphine or tributylphosphine, is used. The fourth such as tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, choline chloride;
Ammonium salts, tetramethylphosphonium bromide, tetramethylphosphonium iodide, quaternary phosphonium salts such as triphenylpropylphosphonium bromide, benzyldibutylsulfonium chloride,
The reaction is carried out in the presence of a tertiary sulfonium salt such as benzyldimethylsulfonium chloride, preferably a quaternary ammonium salt.

In this etherification step, the reaction is carried out until at least about 50%, preferably about 80% or more of the hydroxyl groups of the trisphenol compound are etherified. This reaction is
Generally, the reaction is carried out at a temperature of about 60 to 110 ° C. for about 1 to 12 hours, wherein the water is controlled to be 3.0% by weight or less.

In the subsequent dehydrohalogenation step, the reaction product of the etherification step is subjected to the reaction as it is, that is, while containing unreacted epichlorohydrin. As a catalyst for this reaction, the same alkali compound as used in the first method, for example, an alkali metal hydroxide, preferably sodium hydroxide, is used in an amount of 0.5 times mol per equivalent of the phenolic hydroxyl group of the trisphenol compound. It is used in an amount of preferably at least 0.8 times the molar amount. However, this use ratio is desirably 1 mol or less to avoid inconvenience such as gelation.

Epichlorohydrin or β-methyl epichlorohydrin is added in an amount of 3 to 30 per mol of the trisphenol compound.
It is preferred to use molar.

After completion of the reaction, unreacted epichlorohydrin is removed by distillation under reduced pressure, by-product salts are removed by washing with water, and, if necessary, phosphoric acid and neutralization with a weak acid such as sodium dihydrogen phosphate are performed. The target epoxy compound is obtained.

The multifunctional epoxy resin (A) in the present invention has a softening point of 130 ° C. or less from a semisolid at room temperature, and an epoxy equivalent of 160 to 600 g / eq.

In the present invention, the bifunctional epoxy resin (B) used simultaneously with the polyfunctional epoxy resin (A) includes:
Biciphenols (C) and epichlorohydrin and / or
Alternatively, a bifunctional bisphenol-type epoxy resin obtained by the same condensation reaction as described above with β-methylepichlorohydrin is preferable, and bisphenol A-type epoxy resin, bisphenol B-type epoxy resin, bisphenol F-type epoxy resin, 1,1-bis (4-hydroxyphenyl) ethane type epoxy resin and the like.
Those having an epoxy equivalent of 50 g / eq are preferred for improving heat resistance.

In the present invention, as the polyfunctional epoxy resin (A) or the bisphenol (C) for reacting the polyfunctional epoxy resin (A) with the bifunctional epoxy resin (B), bisphenol A, bisphenol B, bisphenol One or more selected from F and 1,1-bis (4-hydroxyphenyl) ethane are used.

In the present invention, the reaction of the polyfunctional epoxy resin (A) or the polyfunctional epoxy resin (A) with the bifunctional epoxy resin (B) and the bisphenol (C) may be carried out without a solvent or as necessary. Accordingly, the reaction is performed in the presence of a catalyst using a solvent such as an aromatic hydrocarbon such as toluene or xylene or a ketone such as methyl isobutyl ketone.

As the above-mentioned catalyst, any known catalyst used for a polyaddition reaction between an epoxy group and a phenolic hydroxyl group can be used. Examples of such a catalyst include basic catalysts such as sodium hydroxide and sodium carbonate, and fourth catalysts such as tetraalkylammonium halide and aralkyltrialkylammonium halide.
Examples include a quaternary ammonium salt catalyst, and a phosphorus-based catalyst such as triphenylphosphine and ethyltriphenylphosphonium halide. The catalyst is preferably used in an amount of about 10 to 400 ppm based on the epoxy resin used.

The above reaction is carried out at a temperature of about 120-200 ° C. and usually under normal pressure for about 3
It can be carried out under stirring from a molten state to a solution state for up to 20 hours.

Depending on the desired epoxy equivalent weight, softening point or glass transition temperature of the cured product of the modified epoxy resin composition, the proportions of the polyfunctional epoxy resin (A) and the bifunctional epoxy resin (B) used in the above reaction and the epoxy resin The use ratio with the bisphenol (C) can be arbitrarily selected. However, in order to achieve the object of the present invention, a polyfunctional epoxy resin (A) and a bifunctional epoxy resin (B)
Is preferably present in a weight ratio of 90:10 to 30:70, especially 80:20 to 50:50.

An epoxy group 1 comprising a multifunctional epoxy resin (A) and, if necessary, a bifunctional epoxy resin (B).
The phenolic hydroxyl group of the bisphenol (C) per unit is preferably from 0.03 to 0.5, particularly preferably from 0.05 to 0.4.

In addition, the final modified epoxy resin composition is generally 200
It is desirable for the purposes of the present invention to have an epoxy equivalent in the range of 〜1500 g / eq, especially 250-500 g / eq.

That is, when the epoxy equivalent of the modified epoxy resin composition is within the above range, it has sufficient heat resistance, and has good melt viscosity, good softening point, etc., and has by-products such as gel. No good epoxy resin can be obtained.

In addition, such a material has a suitable solution viscosity even when varnished with a solvent, and good workability can be obtained in the coating and coating steps. Furthermore, even when a powder coating is used, the melt fluidity is low, and good coating performance can be obtained.

The modified epoxy resin composition of the present invention thus obtained has excellent heat resistance at high temperatures, as shown in Examples described later, and is used, for example, as a coating material, a casting material, and a forming material for forming a laminate. In this case, highly reliable ones such as mechanical strength and electrical insulation at high temperatures can be obtained.

The modified epoxy resin composition of the present invention, if necessary,
As long as the object of the present invention is not impaired, it can be used in combination with other known epoxy resins and various resins.

In such a case, it is of course possible to use together with a phenol novolak type epoxy resin, an orthocresol novolak type epoxy resin or the like.

When the epoxy resin composition of the present invention is used in combination with various resins such as other epoxy resins, the type and mixing ratio of the resins may be appropriately determined according to the intended use of the epoxy resin.

When used, the epoxy resin composition of the present invention may be used in various forms such as aliphatic amines, aromatic amines, amine adducts, acid anhydrides, phenolic resins, etc., which are generally known as ordinary epoxy resin curing agents. In the form of a composition containing the curing agent of the present invention, the composition can be used for producing, for example, an electrical insulating paint, a sealing material, a laminate, and the like.

In the present invention, as the curing agent as described above, in particular, phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, Trimellitic anhydride, benzophenonetetracarboxylic anhydride, dodecylsuccinic anhydride, chlorendic anhydride, diaminodiphenylmethane, diaminodiphenylsulfone, triethylenetetramine, diethylenetriamine, mensendiamine, N-aminoethylpiperazine, isophoronediamine, 3, 9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5,5] undecane,
Metaxylylenediamine, dicyandiamide, ethylmethylimidazole and the like are preferably used.

The amount of the curing agent used varies depending on the type of the curing agent.
It is about 40 parts by weight.

When the epoxy resin composition of the present invention is used as a paint, it is adjusted by blending a general-purpose colorant (pigment), a filler, a solvent, an antifoaming agent, and the like.

Further, when the epoxy resin composition of the present invention is used as a resin for a laminate, usually, toluene, aromatic hydrocarbons such as xylene, acetone, methyl ethyl ketone,
It is adjusted to a varnish form using a solvent such as ketones such as methyl isobutyl ketone and dimethylformamide, and ethylene glycols such as methyl cellosolve. The epoxy resin composition adjusted to the varnish is impregnated with a reinforcing substrate such as glass cloth, carbon fiber, glass fiber, paper, asbestos, polyester fiber, aromatic polyamide fiber (Kevlar), and the like. Is made into a prepreg, and then heated and pressed by a press machine to form a laminate.

In addition, the epoxy resin composition of the present invention contains various fillers as necessary, silica, alumina, talc, mica, calcium bicarbonate, kaolin, diatomaceous earth, asbestos,
It goes without saying that graphite, boron, silicon carbide, carbon fiber, glass fiber, etc. may be added and used for various applications.

Using such an epoxy resin composition of the present invention, a cured coating, a casting, and a laminated board have preferable advantages as compared with a conventional bisphenol-type epoxy resin or a bromine-containing epoxy resin. While holding
It has high heat distortion temperature and glass transition temperature, improves mechanical strength at high temperature and electric insulation, and exhibits excellent water resistance.

<Examples> Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to these.

(Example 1) 1- [α-methyl-α- (4
-Hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene, a polyfunctional epoxy resin obtained by condensation reaction with epichlorohydrin (A) Epoxy equivalent 210 g / eq, softening point 60 ° C) 100g
And bisphenol A 11.8 g and xylene 20 g in a capacity of 300 ml
, And 0.4 ml of a 1% aqueous solution of tetramethylammonium chloride was further added.

The mixture was heated with stirring under a nitrogen atmosphere,
When the temperature was raised to 0 ° C., pressure reduction was started to remove xylene and water.

Thereafter, the pressure is once returned to normal pressure, and the mixture is
As a result of reacting at 150 ° C. for 6 hours, epoxy equivalent 340 g / eq,
An epoxy resin having a softening point of 98 ° C. was obtained.

This epoxy resin is adjusted to a resin concentration of 75%.
Diluted with methyl ethyl ketone to make resin solution 133
15 parts by weight of methyl cellosolve, 15 parts by weight of dimethylformamide, and 0.2 part by weight of dicyandiamide (active hydrogen equivalent / epoxy group = 0.65) and 2-ethyl-4-methylimidazole were mixed with each other, and a varnish-like epoxy resin composition was mixed. I adjusted things.

This composition is mixed with a glass cloth (Nitto Boseki WE-18K-BZ)
Impregnated into 2), and heated for 5 minutes at 0.99 ° C. to prepare a prepreg, produced this overlapping 9-ply, 170 ° C., 60 minutes heated and pressurized under a condition of 10 Kgf / mm ^2, a laminate having a thickness of 1.6mm did.

After the glass transition temperature (Tg) of the formed laminate by differential scanning calorimetry (DSC) and boiling water absorption, 10
After immersion for 2 seconds, the presence or absence of abnormalities such as "hagare" and "measling" was examined. Table 1 shows the results.

(Example 2) 200 g of the polyfunctional epoxy resin (A) used in Example 1
The reaction was carried out in the same manner as in Example 1 except that 200 g of a bifunctional epoxy resin (B) (epoxy equivalent: 188 g / eq) obtained by condensation of bisphenol A with epichlorohydrin and 111.4 g of bisphenol A were used. As a result, an epoxy resin having an epoxy equivalent of 440 g / eq and a softening point of 97 ° C. was obtained.

For this epoxy resin, a prepreg was prepared in the same manner as in Example 1, and physical properties were measured. The results are shown in Table 1.

(Comparative Example 1) Bifunctional epoxy resin (epoxy equivalent: 188 g / eq) 1053
g, and 307 g of bisphenol A were reacted in the same manner as in Example 1. As a result, an epoxy resin having an epoxy equivalent of 479 g / eq and a softening point of 69 ° C. was obtained.

For this epoxy resin, a prepreg was prepared in the same manner as in Example 1, and physical properties were measured. The results are shown in Table 1.

Comparative Example 2 The same reaction as in Example 1 was performed using 300 g of the bifunctional epoxy resin and 128 g of bisphenol A used in Comparative Example 1.
As a result, an epoxy resin having an epoxy equivalent of 921 g / eq and a softening point of 94 ° C. was obtained.

For this epoxy resin, a prepreg was prepared in the same manner as in Example 1, and physical properties were measured. The results are shown in Table 1.

<Effect of the Invention> The modified epoxy resin composition of the present invention comprises a polyfunctional epoxy resin (A) derived from a specific trisphenol compound, and optionally a bifunctional epoxy resin (B) and a bisphenol (C). The main component is an epoxy resin obtained by reacting with the above, so that a cured product having excellent heat resistance can be obtained.

Therefore, the modified epoxy resin composition of the present invention, for example, by laminating with a glass cloth to form a cured product, excellent heat resistance, mechanical strength at high temperatures, improved reliability such as electrical insulation, In particular, a laminate useful as an electronic component can be obtained.

Furthermore, the modified epoxy resin composition according to the present invention has a substantially linear, gel-free structure, such as being completely dissolved in an organic solvent such as methyl ethyl ketone while being derived from a trisphenol compound, and is used in various applications. In this case, the advantage of excellent workability and workability is also provided.

Continuation of the front page (72) Inventor Isao Kaneko 3 Chigusa Coast, Ichihara-shi, Chiba Mitsui Oil Chemical Industry Co., Ltd. (56) References JP-A-1-149822 (JP, A) JP-A-63-264623 (JP) JP-A-62-218412 (JP, A) JP-A-2-283717 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 59/00-59/72

Claims (4)

(57) [Claims] 1. A polyfunctional epoxy resin (A) and, if necessary, a bifunctional epoxy resin (B), and bisphenol A, bisphenol B, bisphenol F or 1,1
Any one of -bis (4-hydroxyphenyl) ethane
A modified epoxy resin composition obtained by reacting at least one kind of bisphenols (C) in the presence of a catalyst, wherein the polyfunctional epoxy resin (A) comprises 1- [α-methyl-α
-(4-hydroxyphenyl) ethyl] -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- [α-methyl-α- (3,5-dibromo-4-hydroxyphenyl) ethyl] -4- [α, α-bis (3,
5-dibromo-4-hydroxyphenyl) ethyl] benzene, and at least one trisphenol compound selected from 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; The bifunctional epoxy resin (B) contains a condensate of epichlorohydrin and / or β-methyl epichlorohydrin, and the bifunctional epoxy resin (B) contains a condensate of bisphenols (C) with epichlorohydrin and / or β-methyl epichlorohydrin. A heat-resistant epoxy resin composition, comprising: 2. The modified epoxy resin composition according to claim 2, wherein
The heat-resistant epoxy resin composition according to claim 1, which has an epoxy equivalent of 0 g / eq. 3. The heat resistance according to claim 1, wherein the polyfunctional epoxy resin (A) and the bifunctional epoxy resin (B) are in a weight ratio of 90:10 to 30:70. Epoxy resin composition. 4. The polyfunctional epoxy resins (A) and (2)
The phenolic hydroxyl group of the bisphenols (C) is 0.03 per epoxy group of the functional epoxy resin (B).
The heat-resistant epoxy resin composition according to any one of claims 1 to 3, which reacts in a range of from 0.5 to 0.5.