JP3446164B2 - Epoxy resin and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin whose cured product has a low water absorption and a low stress and which is suitable mainly for the electric and electronic industries, and a method for producing the same. More specifically, the amount of bis is based on 1 mol of dicyclopentadiene.
0.2 to 3 mol of phenol A and 2,6 xylenol
It is in the range of 0.5 to 10 mol, and bisphenol A
And the total weight of 2,6 xylenol is dicyclopenta
The present invention relates to an epoxy resin obtained by epoxidizing a co-condensed phenol resin obtained by reacting the diene in an amount exceeding the weight thereof .

[0002]

2. Description of the Related Art Conventionally, epoxy compounds have been widely used in many fields because of their excellent properties.
In recent years, with the rapid development of the electronic / electrical industry, it has come to be used as a base material which constitutes an electronic device or an electronic component represented by an LSI, a laminated board or the like. In particular, it is used as a sealing material for ICs in the field of electronics, where technological innovation is intense. Generally, the epoxy resin composition used for these epoxy resin molding materials is prepared by mixing an epoxy resin, a curing agent, a curing accelerator, a filler, a flame retardant, and a colorant, and kneading these. And is used as a molding material. Conventionally, an ortho-cresol novolac type epoxy resin has been widely used as an epoxy resin for these molding materials because of its excellent balance in heat resistance, moldability, electrical characteristics and the like. However, in recent years, high integration of semiconductor devices, miniaturization and thinning of packages,
The number of layers in laminated boards is increasing, and epoxy resins suitable for these applications are required to have higher heat resistance, lower water absorption, and lower stress.

[0003]

Therefore, the present inventors have completed the present invention as a result of earnest research to obtain an epoxy resin composition excellent in high heat resistance, low water absorption and low stress. Thus, an object of the present invention is to provide an epoxy resin that provides an epoxy resin composition excellent in high heat resistance, low water absorption, and low stress, which cannot be achieved by conventional techniques in the fields of electricity and electronics. is there.

[0004]

The summary of the present invention is as follows.
Bisphenol A to 1 mol of dicyclopentadiene
Is 0.2 to 3 mol and 2,6 xylenol is 0.5 to 10 mol.
In the molar range, and bisphenol A and 2,6
The total weight of xylenol is the weight of dicyclopentadiene.
The co-condensed phenolic resin obtained by reacting the
It is an epoxy resin represented by the general formula (I), which is poxylated ,

[0005]

[Chemical 3]

In the formula (I), n and m represent integers of n ≧ 1 and m ≧ 1. Further, bisphenol A is contained in an amount of 0.2 to 3 mol per mol of dicyclopentadiene,
2,6 xylenol is in the range of 0.5 to 10 moles,
Further, the total weight of bisphenol A and 2,6 xylenol exceeds the weight of dicyclopentadiene, and the cocondensed phenol tree represented by the general formula (II) is obtained.
Fat

[0007]

[Chemical 4]

In the formula (II), n and m represent an integer of n ≧ 1 and an integer of m ≧ 1 . Is a method for producing an epoxy resin, which comprises epoxidizing by reacting with epichlorohydrin in the presence of an alkali metal hydroxide.

[0009] These phenol represented by the raw material is the formula of the epoxy resin (II) in the present invention - Le resins, 2,
It is a cocondensation product of 3 components of 6-xylenol, dicyclopentadiene and bisphenol A. Since 2,6-xylenol is a monofunctional component, 2,6-xylenol / dicyclopentadiene / bisphenol- It is possible to synthesize a wide range from low viscosity to high viscosity by adjusting the charged molar ratio of le A.

[0010] Then, 該Fu E Bruno - by epoxidizing Le cocondensates, resulting epoxy resin in the molecule, can be introduced dicyclopentadiene skeleton, whereby the low water absorption of, Enables low stress,
Further, by introducing the bisphenol A skeleton, it is possible to impart flexibility and to obtain high heat resistance by polyfunctionalization.
Furthermore, the heat resistance and water resistance of the resin could be improved by introducing a 2,6 xylenol skeleton.

[0011] If the this error epoxy resin, an epoxy resin composition containing at least 10 wt.% Or more as an essential component in the epoxy resin component was used as a molding material,
Compared with the conventional epoxy resin molding materials, it was possible to achieve higher heat resistance, lower water absorption, and lower stress. Next, the present invention will be described in detail.

Synthesis of Co-Condensed Phenol The co-condensed phenol resin of 2,6 xylenol, dicyclopentadiene and bisphenol A represented by the general formula ( II ) is 2,6 xylenol. Obtained by co-condensing dicyclopentadiene and bisphenol A in the presence of a Lewis acid catalyst. The molar ratio of each component at the time of synthesizing this co-condensed phenol resin is dicyclopentadiene 1
Bisphenol A is 0.2 to 3 moles, 2,
6-xylenol is 0.5 to 10 mol. The catalyst is preferably a Lewis acid, and specific examples thereof include boron trifluoride and its complex salts, aluminum chloride, tin chloride, iron chloride, sulfuric acid, phosphoric acid and the like. The amount of these catalysts is preferably 0.001 to 0.5 mol per mol of dicyclopentadiene.

The reaction method is preferably such that a catalyst is added to a molten mixture of 2,6 xylenol and bisphenol A, and then dicyclopentadiene is added dropwise over 1 to 10 hours. The reaction temperature is 50 to 200 ° C., preferably 8
The temperature is preferably 0 to 160 ° C., and the reaction time is 1 to 15 hours, preferably 5 to 10 hours. After the completion of the reaction, hydroxides of alkali metals such as sodium hydroxide and calcium hydroxide and hydroxides of alkaline earth metals were added to deactivate the catalyst, and then unreacted 2,6 xylenol was recovered under reduced pressure. Then, a reaction product is dissolved by adding a solvent such as toluene, xylene, methyl ethyl ketone, and methyl isobutyl ketone. Thereafter, washing with water is repeated several times, and the solvent is recovered under reduced pressure to obtain the desired co-condensed phenol resin (compound represented by formula I). In the reaction, a solvent such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, ethylene glycol or diethylene glycol may be used if necessary.

Synthesis of Epoxy Resin Epoxy resin from 2,6 xylenol, bisphenol A and dicyclopentadiene co-condensed phenol resin represented by the general formula (II) is obtained by the above method. It is obtained by reacting a condensed phenol resin with epichlorohydrin. This reaction is performed according to a conventionally known method. For example, a co-condensed phenol resin is dissolved in an excess amount of epichlorohydrin with respect to its hydroxyl equivalent, an alkali metal hydroxide such as sodium hydroxide is added as a solid or concentrated aqueous solution, and the reaction temperature is 30 to 120.
There is a method of reacting at a temperature of 50 to 760 mmHg for 0.5 to 10 hours.

On the other hand, the co-condensed phenol resin is dissolved in an excess amount of epichlorohydrin with respect to the hydroxyl group equivalent, and a quaternary ammonium salt such as tetraethylammonium chloride is added as a catalyst at a reaction temperature of 50 to 150.
There is also a method in which the reaction is performed at a temperature of 50 to 760 mmHg for 0.5 to 10 hours. In the above-mentioned reaction method, the amount of epichlorohydrin used is 3 to 20 times, preferably 4 to 20 times the molar amount of the hydroxyl groups of the co-condensed phenol resin.
The amount of the alkali metal hydroxide used is 8 times the molar amount, and the amount of the alkali metal hydroxide used is 0.8 with respect to the hydroxyl groups of the co-condensed phenol resin.
It is in the range of 5 to 1.1 times the molar amount. The epoxidized product of the co-condensed phenol obtained by these reactions contains unreacted epichlorohydrin and a reaction by-product, an alkali metal chloride. Unreacted epichlorohydrin is removed by distillation, and alkali metal chlorides are removed by extraction with water or filtration to remove the desired co-condensed pheno-phenol.
It is possible to obtain an epoxidized resin.

A known curing agent may be added to the epoxy resin synthesized as described above to prepare an epoxy resin molding composition. Examples of curing agents that can be used include amines, acid anhydrides, aminopolyamide resins, polysulfide resins, and novolac resins such as phenol novolac,
Examples thereof include boron trifluoride amine complex and dicyandiamide. Also, 2,6 xylenol,
It is also possible to use a co-condensation type phenol resin composed of bisphenol A and dicyclopentadiene together with another curing agent.
In particular, a co-condensed phenol resin composed of 2,6 xylenol, bisphenol A and dicyclopentadiene is used as a curing agent component in the composition, and an epoxy resin obtained by epoxidizing the co-condensed phenol resin is used as an epoxy resin. By using it as a component, an extremely excellent epoxy resin composition can be obtained.

When the epoxy resin of the present invention is used as a molding material for sealing, it is preferably cured with a novolac resin, and among them, a phenol novolac resin is preferable.
It is also preferable to use a co-condensation type phenol resin composed of 2,6 xylenol, bisphenol A and dicyclopentadiene together. When used as a material for a printed circuit board laminate, it is often cured with dicyandiamide.
The amount of these curing agents used is amines, polyamide resin,
In the case of polysulfide resin, boron trifluoride amine complex, and novolac resin, the amount of active hydrogen in these curing agents is 0.5 to 0.9 equivalent with respect to the amount of epoxy groups in the epoxy resin component. Thus, in the case of dicyandiamide, the active hydrogen equivalent is preferably 0.3 to 0.7 equivalent.

[0018] In the compositions using d epoxy resin of the present invention, it is possible to use a curing accelerator if necessary. Examples of the curing accelerator include tertiary amines such as triethylamine and diethylbenzylamine, quaternary ammonium salts such as tetraethylammonium chloride and benzyltrimethylammonium chloride, phosphines such as triethylphosphine and triphenylphosphine, and n- Examples thereof include phosphonium salts such as butyltriphenylphosphonium bromide, imidazoles such as 2-ethyl-4-methylimidazole, and organic salts thereof such as acetic acid. Among these, preferred curing accelerators are imidazoles and phosphines.

The epoxy resin composition of the present invention can be cured as it is by adding a curing accelerator if necessary.
Dissolve epoxy resin and curing agent in ketones such as acetone and methyl ethyl ketone, cyclic ethers such as dioxane and tetrahydrofuran, amides such as dimethylformamide and dimethylacetamide, aromatic hydrocarbons such as benzene, toluene and xylene. If necessary, a curing accelerator may be added to uniformly disperse or dissolve the compound, and then the solvent may be removed for curing.

When the composition using the epoxy resin of the present invention is used as a sealing resin, silica powder, alumina, antimony trioxide, talc, in addition to the epoxy resin, the epoxy curing agent and, if necessary, the curing accelerator, Inorganic fillers such as calcium carbonate, natural wax, paraffins,
A release agent such as a metal salt of a straight-chain fatty acid, a flame retardant such as chlorinated paraffin, hexabromene benzene, a coloring agent such as titanium white, carbon black and red iron oxide, a silane coupling agent, and the like may be appropriately added and blended. good.

The cured product of d epoxy resin composition of the present invention has a small water absorption, low stress reduction, from where is excellent in high heat resistance, is suitable sealing molding material, the laminated material for printed circuit. Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples.

[0022]

[Examples and Comparative Examples]

Reference Example 1 2,6 xylenol 366 parts by weight (hereinafter, "parts" means "parts by weight") Bisphenol A 135 parts, BF
11 parts of 3 ether complex was placed in a glass separable flask and heated to 115 ° C. with stirring to dissolve. While maintaining the temperature of 110 ° C to 120 ° C, 366 parts of dicyclopentadiene was added dropwise over 5 hours. Further 120
After reacting at a temperature of ℃ to 130 ℃ for 5 hours, it was neutralized with calcium hydroxide until pH 7.0. afterwards,
Unreacted 2,6-xyleno was heated to 200 ℃ under reduced pressure.
The solvent was removed by evaporation.

Next, 880 parts of methyl isobutyl ketone was added to dissolve the product, and 300 parts of warm water at 80 ° C. was added to wash with water, and the lower aqueous layer was separated and removed. Then, the mixture was heated to 200 ° C. under reduced pressure to evaporate and remove methyl isobutyl ketone to obtain 377 parts of a target co-condensation type phenol resin. This was a reddish brown, brittle solid. Table 1 shows the softening point, hydroxyl equivalent, and melt viscosity of this resin. The resin obtained in this reference example was designated as a phenol resin (I).

Reference Example 2 The same operation as in Reference Example 1 was carried out except that 153 parts of bisphenol A was used to obtain 395 parts of a cocondensed phenol resin. Table 1 shows the softening point, hydroxyl group equivalent and melt viscosity of this resin. The resin obtained in this reference example was named phenol resin (II).

Reference Example 3 244 parts of 2,6 xylenol and 2 parts of bisphenol A
The same operation as in Reference Example 1 was carried out except that 28 parts were used to obtain 468 parts of a cocondensation type phenol resin. Table 1 shows the softening point, hydroxyl group equivalent and melt viscosity of this resin. The resin obtained in this reference example was named phenol resin (III).

[0026]

[Table 1]

Example 1 The phenol resin (I) 194.4 synthesized in Reference Example 1
Parts, epichlorohydrin 462.5 parts, and diethylene glycol dimethyl ether 92.5 parts were placed in a glass separable flask and heated to 60 ° C. with stirring to dissolve. Next, under a reduced pressure of 110 mmHg, the temperature is adjusted to 58-
While maintaining the temperature at 62 ° C., 80 parts of a 49 wt% sodium hydroxide aqueous solution was added dropwise over 4 hours. During this period, epichlorohydrin and water that azeotropically distilled off were statically separated, water was sequentially removed from the system, and epichlorohydrin was sequentially returned to the system.

After completion of the reaction, epichlorohydrin was recovered under reduced pressure at 180 ° C., and methyl isobutyl ketone 5
60 parts was added and the reaction was carried out at a temperature of 80 to 90 ° C. for 2 hours, and 230 parts of water was added to dissolve the by-produced sodium chloride, which was separated and separated. After neutralizing with a phosphoric acid aqueous solution,
Water washing was repeated several times, and filtration was performed. Under reduced pressure, 180
The methyl isobutyl ketone was removed by evaporation under the condition of ° C to obtain 243 parts of the desired co-condensation type phenol resin epoxy resin. The resin was a reddish brown, brittle solid. Table 2 shows the softening point, epoxy equivalent, melt viscosity, and hydrolyzable chlorine of this resin. The resin obtained in this example was designated as epoxy resin (I).

Example 2 239 parts of an epoxy resin (II) was obtained in the same manner as in Example 1 except that 190 parts of the phenol resin (II) synthesized in Reference Example 2 was used. Table 2 shows the softening point, epoxy equivalent, melt viscosity and hydrolyzed chlorine of this resin.

Example 3 The phenol resin (III) synthesized in Reference Example 3 was added to 184.
The same operation as in Example 1 was carried out except that 6 parts were used to obtain 233 parts of an epoxy resin (III). Table 2 shows the softening point, epoxy equivalent, melt viscosity and hydrolyzed chlorine of this resin.

[0031]

[Table 2]

Evaluation as sealing molding materials Examples 4 to 6 Epoxy resins I to III obtained in Examples 1 to 3 and phenol novolac resin BRG-557 (Showa Polymer Co., Ltd.)
Made, hydroxyl equivalent 105 g / eq, softening point 86 ° C.), brominated epoxy resin YDB-400 (manufactured by Toto Kasei Co., Ltd., epoxy equivalent 400 g / eq, bromine content 49.3% by weight, softening point 66 ° C.), Triphenylphosphine (manufactured by Kishida Chemical Co., Ltd., reagent special grade), fused silica (manufactured by Tatsumori Co., Ltd., Hu-Rex RD-8), antimony trioxide (manufactured by Nippon Seiko Co., Ltd., ATOX-S), Table 3 shows calcium stearate (manufactured by Shodo Kagaku Co., Ltd.), carbon black (manufactured by Mitsubishi Kasei Co., Ltd., MA-100), and a silane coupling agent (manufactured by Nippon Unicar Co., Ltd., A-187). Using a twin-screw kneader SIKRC kneader (manufactured by Kurimoto Tekko Co., Ltd.), the components were melt-mixed at 80 to 100 ° C., rapidly cooled and pulverized to obtain a molding material. Next, using a mold, 65 kg /
It was compression molded and pre-cured under the conditions of cm ² , 120 ° C. and 10 minutes. Then, it was cured at 180 ° C. for 8 hours to obtain a test piece for measuring physical properties. Table 3 shows the results of physical property measurements.
Shown in. The physical property values were measured by the following methods. Glass transition temperature (Tg): Measured with a thermomechanical measuring device (TMA) TMC-30 manufactured by Shimadzu Corporation. Flexural strength and flexural modulus: In accordance with JIS K6911. Water absorption rate: Weight change after 72 hours under the condition of 85 ° C. and 85% RH in a disk-shaped molded product having a diameter of 100 mm and a thickness of 4 mm in a thermo-hygrostat.

Comparative Examples 1-2 As a comparative example, orthocresol-novolak epoxy resin YDCN-701P (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 200 g / eq, softening point 65 ° C.), YDCN-702P.
(Toto Kasei Co., Ltd., epoxy equivalent 203 g / eq, softening point 75 ° C.) was used, and the same operations as in Examples 7 to 9 were performed, and the results are shown in Table 3.

[0034]

[Table 3]

[0035]

The epoxy resin composition using the epoxy resin according to the present invention, when used as a molding material for sealing as shown in Table 3, has the effects of low water absorption, low stress and high heat resistance. .

[Brief description of drawings]

1 is a GPC chart of the co-condensed phenolic resin I obtained in Example 1.

2 is an FT-IR chart of the co-condensed phenolic resin I obtained in Example 1. FIG.

3 is a GPC chart of epoxy resin I obtained in Example 4. FIG.

FIG. 4 FT-I of epoxy resin I obtained in Example 4
R chart

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 62-70413 (JP, A) JP 4-342718 (JP, A) JP 61-291616 (JP, A) JP 7- 109338 (JP, A) JP-A-6-41273 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/32 C08G 61/02-61/10

Claims (2)

(57) [Claims] 1. Bisphenol A in an amount of 0.2 to 3 moles and 2,6 xylenol in an amount of 0.5 to 10 moles relative to 1 mole of dicyclopentadiene, and bisphenol A
And the total weight of 2,6 xylenol is more than the weight of dicyclopentadiene.
An epoxy resin represented by the general formula (I), characterized in that the co-condensed phenol resin represented by the formula (1) is reacted with epichlorohydrin in the presence of an alkali metal hydroxide to be epoxidized. The general formula (I) ## STR1 ## In the formula (I), n and m represent an integer of n ≧ 1 and an integer of m ≧ 1. The general formula (II) ## STR2 ## In the formula (II), n and m represent an integer of n ≧ 1 and an integer of m ≧ 1. 2. The epoxidation of the co-condensed phenolic resin represented by the general formula (II) according to claim 1, which is reacted with epichlorohydrin in the presence of an alkali metal hydroxide. 1. A method for producing an epoxy resin represented by the general formula (I) according to item 1.