JP3287594B2 - Epoxy resin and composition thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel epoxy resin and a composition thereof, and more particularly to an epoxy resin having excellent heat resistance and water resistance of a cured product and a composition thereof.

[0002]

2. Description of the Related Art Epoxy resin has the mechanical strength of a cured product,
It has excellent properties such as chemical resistance and adhesiveness, and is used in a wide range of fields such as electric and electronic materials, paints, and composite materials.
However, bisphenol A, which is most commonly used for powder coatings, electric laminates, electric wire varnishes, etc.
The resin composition using the mold solid epoxy resin has a problem that the heat resistance of the cured product is not sufficient.

On the other hand, when a polyfunctional epoxy resin such as orthocresol novolak type epoxy resin is added for the purpose of improving the heat resistance of the bisphenol A type solid epoxy resin,
Although the heat resistance is improved, there is a disadvantage that the water resistance is deteriorated, and an epoxy resin and a composition thereof which provide a cured product excellent in both the heat resistance and the water resistance have been desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an epoxy resin excellent in heat resistance and water resistance of a cured product and a composition thereof.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by introducing a fluorene skeleton into an epoxy resin, the cured product has excellent heat resistance and water resistance. It was found that an epoxy resin composition was obtained, and the present invention was completed.

That is, according to the present invention, 9,9-bis (4-hydroxyphenyl) fluorene and a bisphenol A type epoxy resin are prepared by adding a phenolic hydroxyl group to an epoxy group at a molar ratio of 0.2: 1 to 0.9: 1. is obtained by reacting at a ratio is, epoxy equivalent is the 444~949g / eq, and, the epoxy equivalent weight of from 2.39 to 5.10 times the epoxy equivalent of the bisphenol a type epoxy resin Epo
An epoxy resin composition consisting of a
Used for impregnating loss into electrical laminate materials
Epoxy resin composition.

The epoxy resin composition of the present invention has the following general
Equation (1)

Embedded image It contains an epoxy resin represented by For convenience of explanation
The epoxy resin represented by the above general formula (1) is used in the present invention.
Also referred to as epoxy resin.

The epoxy resin of the present invention can be synthesized by an addition reaction between an excess bisphenol A type epoxy resin and 9,9'-bis (4-hydroxyphenyl) fluorene.

[0009] The epoxy resin of the present invention is prepared at the time of its production in consideration of industrial utility and productivity.
A phenol having two phenolic hydroxyl groups in a molecule other than bis (4-hydroxyphenyl) fluorene and an epoxy resin having two epoxy groups in a molecule other than the bisphenol A type epoxy resin are used in combination. ,
It can also be manufactured as a mixed epoxy resin composition. In that case, the composition must be 9,9'-bis (4-hydroxyphenyl) fluorene at least 50% by weight of the total phenols. By introducing such a fluorene skeleton, a resin having excellent heat resistance and water resistance can be obtained.

Examples of phenols other than 9,9'-bis (4-hydroxyphenyl) fluorene include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S and the like.

The epoxy resin used as a raw material of the epoxy resin composition of the present invention must be at least 50% by weight of bisphenol A type epoxy resin. Epoxy resin raw materials other than bisphenol A type epoxy resin include bisphenol F, bisphenol S, resorcinol, ethylene glycol, propylene glycol,
One or more diglycidyl ethers synthesized from 4-butanediol, 1,6-hexanediol, etc. and epichlorohydrin can be used.

The epoxy resin and the composition of the present invention are synthesized by an addition reaction of the phenols and the epoxy resin. The molar ratio of the phenolic hydroxyl group to the epoxy group in the raw material is 0.2: It is limited to the range of 1 to 0.9: 1. The reason is that when the molar ratio is 0.2 or less, the effect of introducing the fluorene skeleton is not sufficient, and when the molar ratio is 0.9 or more, the epoxy resin composition to be synthesized has a high softening point and is inferior in processability. It is. In order to balance the effect of the introduction of the fluorene skeleton and the processability, the molar ratio of the phenolic hydroxyl group to the epoxy group in the raw material should be 0.3: 1.
And more preferably in the range of 0.8: 1.

The epoxy resin and the composition of the present invention can be made into a resin composition by which a cured product excellent in heat resistance and water resistance can be obtained by blending an epoxy resin curing agent. The epoxy resin curing agent is not particularly limited as long as it is known as a curing agent for an epoxy resin. For example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ′, 4,4′- Examples thereof include acid anhydrides such as benzophenonetetracarboxylic dianhydride, aromatic amines such as phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone, and phenols such as phenol novolak, orthocresol novolak, and phloroglicinol.

In addition, the resin and the composition of the present invention may appropriately use components such as a filler, a pigment, a curing accelerator, a coupling agent, and a solvent, in addition to the epoxy resin and the epoxy resin curing agent.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below more specifically based on embodiments. Synthesis Example 1 146 g of 9,9′-bis (4-hydroxyphenyl) fluorene and a bisphenol A type liquid epoxy resin (trade name YD-12 manufactured by Toto Kasei Co., Ltd.) are placed in a 1-liter flask.
8, 354 g of epoxy equivalent (186 g / eq) and melt-mixed at 150 ° C. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 0.43: 1. Thereafter, 0.073 g of triphenylphosphine was added, and stirring was continued at 150 ° C. for 4 hours to complete the addition reaction, thereby obtaining a fluorene skeleton-containing epoxy resin composition having an epoxy equivalent of 444 g / eq. FIG. 1 shows an IR spectrum diagram.

Synthesis Example 2 168 g of 9,9'-bis (4-hydroxyphenyl) fluorene and a bisphenol A type liquid epoxy resin (trade name YD-12 manufactured by Toto Kasei Co., Ltd.) are placed in a 1-liter flask.
8, 332 g of epoxy equivalent (186 g / eq) and melt-mixed at 150 ° C. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 0.53: 1. Thereafter, 0.084 g of triphenylphosphine was added, and stirring was continued at 150 ° C. for 4 hours to complete the addition reaction, thereby obtaining a fluorene skeleton-containing epoxy resin composition having an epoxy equivalent of 630 g / eq.

Synthesis Example 3 193 g of 9,9'-bis (4-hydroxyphenyl) fluorene and bisphenol A were placed in a one-liter flask.
Type liquid epoxy resin (trade name YD-1 manufactured by Toto Kasei Co., Ltd.)
28, and 307 g of epoxy equivalent (186 g / eq) were charged and melt-mixed at 150 ° C. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 0.66: 1. Thereafter, 0.096 g of triphenylphosphine was added, and stirring was continued at 150 ° C. for 4 hours to complete the addition reaction, thereby obtaining a fluorene skeleton-containing epoxy resin composition having an epoxy equivalent of 949 g / eq.

Example 1 10 g of an epoxy resin composition (hereinafter referred to as epoxy resin 1) synthesized by the method of Synthesis Example 1, 3, 3 ′,
2.9 g of 4,4′-benzophenonetetracarboxylic dianhydride and 0.05 g of 2-ethyl-4-methylimidazole as a curing accelerator are dissolved in 19.4 g of dimethylformamide, and impregnated into a 10 cm × 10 cm glass cloth. After drying in an oven at 150 ° C. for 2 hours to remove dimethylformamide, the mixture was cured at 200 ° C. for 2 hours to obtain a cured product. 10cm x 5c from the obtained cured product
m was cut out and poured into boiling water for 24 hours, and the weight before and after the charging was measured. Thereafter, the test piece was removed in an electric furnace at 700 ° C. to remove organic components, and the weight of the glass cloth was measured. Was determined. The glass transition temperature of the cured product was measured by DSC. Table 1 shows the results.

Example 2 10 g of an epoxy resin composition (hereinafter referred to as epoxy resin 2) synthesized by the method of Synthesis Example 2 as an epoxy resin, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride as a curing agent The water absorption and the glass transition temperature of the cured product were determined in the same manner as in Example 1 except that 2.04 g of the cured product was used. Table 1 shows the results.

Example 3 10 g of an epoxy resin composition (hereinafter referred to as epoxy resin 2) synthesized by the method of Synthesis Example 3 as an epoxy resin, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride as a curing agent The water absorption and glass transition temperature of the cured product were determined in the same manner as in Example 1 except that 1.36 g of the cured product was used. Table 1 shows the results.

Comparative Example 1 10 g of bisphenol A type epoxy resin (trade name: YD-014, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 973 g / eq) as an epoxy resin, and 3,3 ′, 4, as a curing agent
4'-benzophenonetetracarboxylic dianhydride 1.3
The water absorption and the glass transition temperature of the cured product were determined in the same manner as in Example 1 except that 3 g was used. Table 1 shows the results.

Comparative Example 2 8.5 g of bisphenol A type epoxy resin (trade name: YD-014, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 973 g / eq) as an epoxy resin, and orthocresol novolak type epoxy resin (Toto Kasei Co., Ltd.) Made, trade name YD
CN-704, epoxy equivalent 211 g / eq) 1.5
g, and the water absorption and glass transition temperature of the cured product were determined in the same manner as in Example 1 except that 2.04 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was used as a curing agent. . Table 1 shows the results.

Comparative Example 3 As an epoxy resin, 7.0 g of bisphenol A type epoxy resin (trade name: YD-014, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 973 g / eq), and orthocresol novolak type epoxy resin (Toto Kasei Co., Ltd.) Made, trade name YD
CN-704, epoxy equivalent 211 g / eq) 3.0
g, and 2.76 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride were used as a curing agent, and the water absorption and glass transition temperature of the cured product were determined in the same manner as in Example 1. . Table 1 shows the results.

Comparative Example 4 5.5 g of bisphenol A type epoxy resin (trade name: YD-014, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 973 g / eq) as an epoxy resin, and orthocresol novolak type epoxy resin (Toto Kasei Co., Ltd.) Made, trade name YD
CN-704, epoxy equivalent 211 g / eq) 4.5
g, and 3.48 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride as a curing agent, and the water absorption and the glass transition temperature of the cured product were determined in the same manner as in Example. Table 1 shows the results.

[0025]

[Table 1]

As shown in Table 1 above, the composition using the epoxy resin composition of the present invention as a raw material was compared with the epoxy resin composition using bisphenol A type solid epoxy resin and orthocresol novolak type epoxy resin as raw materials. However, it has a much higher glass transition temperature at the same water absorption or gives a cured product excellent in both water absorption and glass transition temperature.

[0027]

The epoxy resin composition of the present invention and the resin composition containing this epoxy resin composition give a cured product having a low water absorption and an extremely high glass transition temperature, and are particularly useful for paints and electrical applications. It is useful as an epoxy resin and a resin composition used for applications such as laminates and wire varnishes.

[Brief description of the drawings]

FIG. 1 shows the IR of the epoxy resin obtained in Synthesis Example 1.
It is a spectrum diagram.

──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Ryusuke Hayashi 5-6-16-504 Yokodai, Isogo-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Kazuo Ishihara 3-17-14, Higashikasai, Edogawa-ku, Tokyo, Tokyo Metropolitan Kasei Stock Hiroshi Nakanishi (72) Inventor Hiroshi Nakanishi 3-17-14 Higashikasai, Edogawa-ku, Tokyo; Central Research Laboratory, Toto Kasei Co., Ltd. (56) References JP-A 2-1790 (JP, A) Masaki Shinbo, Epoxy Resin Handbook, Japan, Nikkan Kogyo Shimbun, December 25, 1987, pp. 34-36 (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/14 C08G 59/62 C08J 5/24

Claims (1)

(57) [Claims] 1. A method in which 9,9-bis (4-hydroxyphenyl) fluorene and a bisphenol A type epoxy resin are mixed at a molar ratio of phenolic hydroxyl groups to epoxy groups of from 0.2: 1 to 0.9: 1. in obtained by reacting an epoxy equivalent weight of 444~949g / eq, and, an epoxy resin the epoxy equivalent weight of from 2.39 to 5.10 times the epoxy equivalent of the bisphenol a type epoxy resin d
A epoxy resin composition that is impregnated in glass cloth and
Epoxy resin composition used for obtaining laminated board materials
object.