JP2788927B2 - New epoxy compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel epoxy compound, particularly an epoxy compound having excellent heat resistance. When the epoxy compound of the present invention is used alone or as a mixture with another epoxy compound, it has excellent heat resistance, water resistance, thermal shock resistance and dielectric properties, a matrix resin for electronic circuit boards and FRP, a sealing material for electronic parts, It can be used in a wide range such as mold materials, coating materials, adhesives, and paints.

"Prior art" Epoxy resins are widely used in a wide range such as electronic parts, electric devices, automobile parts and sports goods because of their excellent adhesive properties, electric properties, heat resistance and the like. As the epoxy resin, bisphenol A diglycidyl ether type, for example, YD-128 (Epoxy equivalent: 187 g / eq) manufactured by Toto Kasei Co., Ltd. is used as a general-purpose product.
Polyfunctional epoxy resins such as phenol novolak epoxy resin, cresol novolak epoxy resin, and tetraglycidyl ether of diaminodiphenylmethane are used as heat-resistant epoxy resins because of their inferior high heat resistance, which is a current technical need. However, even though these epoxy resins are excellent in heat resistance and the like, they are hard and brittle cured products and have insufficient heat shock resistance and water resistance. For example, for semiconductor encapsulation, cresol novolak epoxy resin and phenol novolak resin are used in view of heat resistance, water resistance, adhesion, electrical characteristics, and price in order to protect a semiconductor integrated circuit. However, epoxy resin is required to have higher heat resistance, water resistance and thermal shock resistance than ever before due to the improvement of the integration degree of the IC, the miniaturization of the wiring, the enlargement of the chip, and the thinning of the package. In addition, for electronic circuit boards, high heat resistance due to the increase in heat generation due to the thinning of the circuit and the high density of ICs, capacitors and resistors on the board,
There is a demand for a high thermal shock resistance and an improvement in the adhesion of the circuit when hot.

"Problems to be Solved by the Invention" The present invention is not satisfactory with phenol novolak epoxy resin or cresol novolak epoxy resin,
An object of the present invention is to provide a novel epoxy compound having excellent thermal shock resistance, water resistance, and dielectric properties, and an epoxy resin composition containing the epoxy compound.

"Means for Solving the Problems" The present invention has solved the above problems, and (1) an epoxy compound represented by the following structural formula [I].

(2) The epoxy compound represented by the formula [I] according to claim (1) alone or a mixture of the epoxy compound and another epoxy compound, a curing agent or a filler commonly used in an epoxy resin composition. A curable epoxy resin composition, characterized by having added thereto.

It is.

That is, the present invention relates to an epoxy compound represented by the formula [I] and an epoxy resin composition containing the compound. The compound of the present invention is obtained by reacting 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane represented by the formula [II] with epihalohydrin, Depending on the reaction conditions, an epoxy oligomer represented by the formula [III] can also be obtained.

And n represents a number from 0 to 5. (Where R represents an oxygen atom or a glycidyl ether group, Represents cyclohexane. To produce the desired epoxy compound, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane represented by the formula [II] is reacted with epihalohydrin in the presence of a catalyst. To produce epihalohydrin ether, followed by a dehydrohalogenation reaction with an alkali metal hydroxide.

The compound represented by the formula [II] is 2-cyclohexyl-
It is generally obtained by condensing 5-methylphenol and crotonaldehyde, which is an unsaturated aldehyde, in the presence of an acidic catalyst such as oxalic acid or p-toluenesulfonic acid, but the method is not limited thereto. The compound represented by the formula [II] can be obtained from Adeka Argus Chemical Co., Ltd.

Examples of the epihalohydrin used in the present invention include epichlorohydrin, epibromohydrin and the like, and the use amount thereof is in the range of 2 to 30 mol per 1 equivalent of phenolic hydroxyl group.

Examples of the catalyst used in the present invention include tetramethylammonium chloride, tetraethylammonium bromide, and benzyltrimethylammonium chloride.
Quaternary ammonium salts, onium compounds such as n-butyltriphenylphosphonium bromide, tertiary amines such as triethylamine, phosphines such as triphenylphosphine, lithium hydroxide, potassium hydroxide, sodium hydroxide And the like. The use amount of these catalysts is 5 to 0.01% by weight based on the phenol compound represented by the formula [II].

The epihalohydrin etherification reaction in the present invention is carried out at room temperature to 120 ° C, preferably at 30 to 80 ° C for 1 to 20 hours.

The dehydrohalogenation reaction in the present invention is performed using an alkali metal hydroxide. As the alkali metal hydroxide, potassium hydroxide and sodium hydroxide are preferable, and the amount of use is 0.8 to 1.2 equivalents to 1 equivalent of the phenolic hydroxyl group of the phenol compound represented by the formula [II]. Condensed water is produced during the dehydrohalogenation reaction, but it is preferable to proceed with the reaction while removing the condensed water from the system to accelerate the reaction and suppress abnormal reactions and obtain an epoxy compound with a high yield. A technique is used in which epihalohydrin and produced water are azeotropically removed below. The temperature is 30-110 ° C, and the degree of vacuum is 20-200 mmHg.

The epoxy compound generated after the completion of the dehydrohalogenation reaction coexists with a metal halide salt by-produced during the reaction. Therefore, after removing the metal halide salt by excess in a state of being dissolved in the epihalohydrin, remove the extra epihalohydrin by a conventional method, or remove the extra epihalohydrin by the usual method while coexisting with the metal halide. After removing the epihalohydrin, the compound is dissolved in an organic solvent to remove a salt or washed with water and separated, and then the organic solvent is removed by heat and vacuum to obtain the desired compound of the formula [I]. The organic solvent used at this time has a good solubility of the epoxy resin, and it is desirable that the organic solvent has a small loss at the time of washing with water.
Examples thereof include aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and alcohols such as isopropanol and n-butanol. These can be used alone or in combination.

In the epoxy resin composition using the epoxy compound according to the present invention, all commonly used curing agents can be used. Specifically, aliphatic polyamines such as diethylenetriamine and isophoronediamine, aromatic polyamines such as diaminodiphenylmethane, polyamideamines composed of dimer acid and ethyleneamine, acid anhydrides such as phthalic anhydride and pyromellitic anhydride, and polyhydric phenols such as phenol novolak And the like.

Further, in the epoxy resin composition using the epoxy compound according to the present invention, various compounding agents such as a filler, a flame retardant, a coupling agent, and a curing accelerator can be used, if necessary, in addition to the curing agent.

"Action" Since the novel epoxy compound represented by the formula [I] has three epoxy groups in one molecule, it has high heat resistance (Tg) and has a cyclohexane ring and a methyl group in each benzene ring, Since an alkyl group having 4 carbon atoms, which is a crotonaldehyde residue, is present in the main chain, the epoxy resin composition using the epoxy compound of the present invention has a small water absorption and a small internal stress at the time of curing, that is, at the time of cold heat. Provides a cured product with high crack resistance (thermal shock resistance).

Usually, the internal stress of the cured epoxy resin is represented by the following general formula.

σ: internal stress K: constant E: elastic modulus of matrix resin
α ₂ , α ₁ : Coefficient of linear expansion of resin (matrix) and sealing material (substrate) T: Temperature T ₀ : Reference temperature Therefore, it is possible to reduce internal stress by lowering elastic modulus E Becomes

"Examples and Comparative Examples" Next, the present invention will be specifically described with reference to Examples and Comparative Examples.

Example 1. Synthesis of 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane triglycidyl ether.

1,1,3-Tris (1,1,3-tris) was added to a 1-liter flask equipped with a stirrer, thermometer, continuous dropping device, and a device for cooling and condensing azeotropic vapor of epichlorohydrin and water under reduced pressure and returning only epichlorohydrin to the reaction system. 207.3 g of 2-methyl-4-hydroxy-5-cyclohexylphenyl) butane (1 gram equivalent of phenolic hydroxyl group), epichlorohydrin 46
2.5 g (5 mol) was added and dissolved, and 1 g of tetramethylammonium chloride was added, followed by stirring at 40 ° C. for 5 hours.

Next, the pressure inside the reaction system was reduced to 100 mmHg, and the temperature was adjusted to 50 ± 2 ° C., and then 82.4 g (1.01 mol) of 49% strength sodium hydroxide was added.
The reaction was added dropwise over time. During this time, the produced water was sequentially removed from the system by azeotropic distillation with epichlorohydrin. After the reaction was completed, the pressure in the system was reduced to 10 ± 2 mmHg, and the temperature was raised to 150 ° C. to recover excess epichlorohydrin. The product was dissolved in 500 g of methyl isobutyl ketone, salt by-produced was removed by washing with water, and methyl isobutyl ketone was distilled off with a rotary evaporator to obtain 250 g (yield 94.9%) of a pale yellow solid epoxy compound. . The obtained epoxy compound had an epoxy equivalent of 270.3 g / eq and a softening point of 92.5 ° C. Fig. 1 shows the molecular weight distribution, Fig. 2 shows the infrared absorption spectrum, and Fig. 3 shows the mass spectrum chart. FIG. 3 shows that the mass of the main component is 789 and 790. From these data, it can be seen that the epoxy compound obtained is a compound represented by the chemical structural formula [I], which is consistent with the molecular weight of 790 calculated from the formula [I].

Example 2 Measurement of Physical Properties of Cured Product 4,4'-Diamino-3,3'-diethylmethane (Kayahard A-A manufactured by Nippon Kayaku Co., Ltd.) was used as a curing agent for 100 g of the epoxy compound of the present invention obtained in Example 1. The epoxy resin composition blended at a rate of 23.5 g was heated and uniformly dissolved, and then poured into a predetermined mold to prepare a cured product under the conditions of 110 ° C. × 2 hours + 170 ° C. × 2 hours. The physical properties of the cured product of this casting were measured according to JIS K 6911. The results are shown in Table 1.

Comparative Example 1. Phenol novolak epoxy resin (Toto Kasei KK
Epototo YDPN-638P Epoxy equivalent 179 g / eq The same curing agent as in Example 2 was mixed with 100 g of the epoxy group (approximately 3.6) in one molecule, and 35.5 g of the same curing agent as in Example 2 was prepared. The results are shown in Table 1.

Comparative Example 2. Cresol novolak epoxy resin (manufactured by Toto Kasei KK
Epotote YDCN-701P Epoxy equivalent 205g / eq Softening point 65 ° C Number of epoxy groups in one molecule about 7) 100g Example 2
31 g of the same curing agent as above was blended to prepare a cured product under the same conditions, and the physical properties were measured. The results are shown in Table 1.

Example 3. Brominated epoxy resin (Epototo YD manufactured by Toto Kasei KK)
B-500 epoxy equivalent 515g / eq bromine content 21.7%) 85 parts,
Dicyandiamide (hereinafter referred to as DICY) as a curing agent and 2-ethyl-4 as a curing accelerator in a methyl ethyl ketone solution (solid content 80%) containing 15 parts of the epoxy compound of the present invention.
-Methyl imidazole (hereinafter referred to as 2E4MZ) at a ratio shown in Table-2 and glass cloth (WE-18K105BZ manufactured by Nitto Boseki Co., Ltd.)
2) impregnated and dried at 150 ° C. × 5 min to prepare a prepreg. A copper foil (3EC manufactured by Mitsui Kinzoku Kogyo Co., Ltd.) with a thickness of 35 microns is overlaid on the upper and lower sides of the obtained eight prepregs, and 170 ° C.
It was cured at Kg / cm ² × 2 hr to produce a copper-clad laminate having a resin thickness of 1.6 mm and a resin content of about 42%. The physical properties are shown in Table-2.

Comparative Example 3. Brominated epoxy resin epotote YDB-50085 parts,
Orthocresol novolak epoxy resin (Toto Kasei KK
Epototo YDCN-704 Epoxy equivalent 215 g / eq Softening point 92 ° C The number of epoxy groups in a molecule is about 11) Using a methyl ethyl ketone solution (solid content 80%) blended with 15 parts, a 1.6 mm thick resin as in Example 3 A copper-clad laminate of about 42% per minute was produced. The physical properties are shown in Table-2.

Example 4. To 100 parts of the epoxy compound of the present invention, 39 parts of a phenol novolak resin (softening point of 85 ° C.) as a curing agent, and 2-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.) as a curing accelerator
2MZ), quartz powder (Fuselex RD-8, manufactured by Tatsumori), silane coupling agent (A-187, manufactured by Nippon Unicar), and other additives in the proportions shown in Table 3 as fillers. After pre-curing at 120 ° C. × 10 min × 65 kg / cm ^{2 in} a mold, the mold was released and post-curing was performed at 170 ° C. × 3 hr. Table 3 shows the physical properties.

Comparative Example 4. Cresol novolak epoxy resin YDCN-701P 10
Except for using 0 parts, curing was performed in the same manner as in Example 4 in accordance with the mixing ratio shown in Table 3, and the physical properties were measured. The results are shown in Table-3.

[Effect of the Invention] The epoxy compound according to the present invention has three epoxy groups, hydrophobic cyclohexane and methyl groups in one molecule, and a methylene group in which a normal novolak epoxy resin is a formaldehyde residue. While the epoxy compound of the present invention is polyfunctionalized with crotonaldehyde residues, it is not only heat-resistant,
As can be seen from the above, since the water absorption rate is low and the elastic modulus is low, the internal stress of the cured product is reduced and the thermal shock resistance is excellent. In addition, the dielectric constant and tan δ are small, which is particularly preferable for use in electronic materials. As can be seen from Tables 2 and 3, the epoxy compound of the present invention shows excellent cured material properties when used in combination with other epoxy resins and fillers.

[Brief description of the drawings]

FIG. 1 is a gel permeation chromatogram of the epoxy compound of the present invention obtained in Example 1, showing the molecular weight distribution, FIG. 2 is an infrared absorption spectrum of the compound, and FIG. It is a bar graph of a spectrum.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C07D 303/18-303/27 C08G 59/02-59/06 C08G 59/32 CA (STN) REGISTRY (STN )

Claims (2)

(57) [Claims] 1. An epoxy compound represented by the following structural formula [I]. 2. An epoxy compound represented by the formula (I) according to claim 1 alone or a mixture of the epoxy compound and another epoxy compound, a curing agent or a filler commonly used in epoxy resin compositions. Curable epoxy resin composition characterized by adding an agent and the like.