JP3533973B2 - Phosphorus-containing epoxy resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for producing a copper clad laminate used for an electronic circuit board and a sealing material, a molding material, a casting material, an adhesive, an electrically insulating paint used for an electronic component. The present invention relates to a phosphorus-containing epoxy resin composition useful as a material for materials.

[0002]

2. Description of the Related Art Epoxy resins are widely used in electronic parts, electric devices, automobile parts, FRP, sports equipment and the like because of their excellent adhesiveness, heat resistance and moldability. Above all, copper-clad laminates and encapsulants used in electronic parts and electrical equipment are strongly required to have safety such as fire prevention and delay. Is used. Although it has a problem that the specific gravity is large, flame retardancy is imparted by introducing halogen, especially bromine into the epoxy resin, and an excellent cured product having a high reactivity of the epoxy group can be obtained. Therefore, brominated epoxy resins are positioned as useful electronic and electric materials. However, when looking at recent electric devices, the tendency to attach importance to so-called light, thin, short, and small devices is gradually increasing. Halides, which have a large specific gravity under such social requirements, are unfavorable materials from the viewpoint of the recent tendency toward weight reduction, and when used at high temperature for a long time, dissociation of halides occurs, which causes wiring corrosion. May occur. Furthermore, harmful substances such as halides are generated during the burning of used electronic parts and electrical equipment, and the use of halogen is becoming a problem from the viewpoint of environmental safety, and alternative materials are being researched. Is starting to appear. Therefore, the development of halogen-free flame-retardant epoxy resin and its commercialization meet the demands of the times.

[0003]

DISCLOSURE OF THE INVENTION The present inventor has earnestly studied to develop a flame-retardant epoxy resin which does not use halogen, and is written by Hitoshi Nishizawa, supplemented new edition "Polymer Flame Retardant" Co., Ltd. Focusing on the basic principle of the flame retardant action of phosphorus and phosphorus compounds outlined on page 49, pages 52 to 59, published by Taiseisha (1989), a new phosphorus-containing flame retardant that applies this basic principle. The epoxy resin composition is obtained by using a specific epoxy resin, that is, a novolac type epoxy resin in a specific amount or more, and the obtained resin composition has excellent flame retardancy and physical properties of a cured product thereof. Therefore, the present invention has been completed and the present invention has been completed. In particular, to provide a phosphorus-containing epoxy resin composition suitable for a copper clad laminate used for an electronic circuit board and a sealing material, a molding material, a casting material, an adhesive, a material for an electric insulating paint used for an electronic component, etc. With the goal.

[0004]

The summary of the present invention is as follows.
Epoxy resins containing 20% by weight or more of novolac type epoxy resin, quinone compound and bond to phosphorus atom 1
Phosphorus-containing epoxy obtained by reacting an organic phosphorus compound having 1 active hydrogen with an organic phosphorus compound having active hydrogen obtained by reacting the quinone compound with the molar ratio of the quinone compound to the organic phosphorus compound is greater than 0 and less than 1 Flame Retardant Phosphorus-Containing Epoxy Resin Composition Using Resin, Especially Flame Retardant Phosphorus-Containing Epoxy Resin Using Compound Represented by General Formula (1) and / or General Formula (2) as Organic Phosphorus Compound In composition.

Further, the flame-retardant phosphorus-containing epoxy resin composition is used as a resin composition for producing a copper-clad laminate used for electronic circuit boards and sealing materials, molding materials, casting materials and adhesives used for electronic parts. It is intended to be used as an agent, a material for electrical insulating paints, and the like.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail. The epoxy resin in the present invention means a curable epoxy resin, and the epoxy resin may be a single kind or a mixture of two or more kinds, but in the present invention, the epoxy resin contains 20% by weight or more, Preferably 40% by weight
It is necessary that the above novolac type epoxy resin is present. When the content of the novolac type epoxy resin is less than 20% by weight, it is not preferable because it is difficult to impart flame retardancy and the heat resistance is deteriorated. When the epoxy resins are a mixture, examples of the resin other than the novolac type epoxy resin include, for example, bisphenol type epoxy resin, resorcin type epoxy resin, polyglycol type epoxy resin, fluorene type epoxy resin, and the like, two or more epoxies in one molecule. Examples thereof include, but are not limited to, those having a group.

The novolac type epoxy resin in the present invention is obtained by epoxidizing a hydroxyl group of a phenol novolac resin obtained by condensing a phenol and an aldehyde with epichlorohydrin or the like.
Specific examples thereof include Epotote YDPN-638 (Tono Kasei Co., Ltd. phenol novolac type epoxy resin), Epotote YDCN-701, YDCN-70.
2, YDCN-703, YDCN-704 (Cresol novolac type epoxy resin manufactured by Tohto Kasei Co., Ltd.), Epotote ZX-1071T, ZX-1270, ZX-1.
342 (Toruto Kasei Co., Ltd. alkyl novolac type epoxy resin), Epotote ZX-1247 (Toto Kasei Co., Ltd. styrenated phenol novolac type epoxy resin), Epototo ZX-1142L (Toto Kasei Co., Ltd. naphthol novolac type epoxy resin), Examples thereof include bisphenol novolac type epoxy resin, aralkylphenol novolac type epoxy resin, and phenylphenol novolac type epoxy resin. You may use these epoxy resins individually or in mixture of 2 or more types. Any novolac type epoxy resin may be used, and it is not limited to the above.

The novolac type epoxy resin also includes those obtained by reacting the above novolac type epoxy resin with phenols, amines and carboxylic acids. Furthermore, what reacted various epoxy resins and a novolak type phenol resin is also contained in a novolak type epoxy resin. In order to obtain the flame-retardant phosphorus-containing epoxy resin composition of the present invention, it is necessary to contain 20% by weight or more of these novolac type epoxy resins as epoxy resins.

The organic phosphorus compound having one active hydrogen bonded to the phosphorus atom used in the present invention means that active hydrogen capable of reacting with a functional group such as a quinone or a glycidyl group or a vinyl group is bonded to the phosphorus atom. The organic phosphorus compounds described above are specifically the organic phosphorus compounds represented by the general formula (1) and the general formula (2). Specific examples of the phosphorus compound represented by the general formula (1) include HCA (Sanko Chemical Co., Ltd. 9,
10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide). Specific examples of the phosphorus compound represented by the general formula (2) include diphenylphosphine oxide.

Specific examples of the quinones to be reacted with the phosphorus compounds represented by the general formulas (1) and (2) are 1,4
-Benzoquinone, 1,2-benzoquinone, toluquinone,
1,4-naphthoquinone and the like can be mentioned. These quinones may be used alone or in combination of two or more, and
It is not limited to these.

The phosphorus compounds and quinone compounds represented by the general formulas (1) and (2) are disclosed in, for example, JP-A-5-214.
No. 068, a general Russian magazine (Zh. Obshc
H. Khim.), 42 (11), pages 2415--21418 (1972), JP-A-60-126293, and JP-A-61-23678.
The reaction is carried out by the methods described in JP-A No. 7 and JP-A No. 5-331179. However, in the present invention, the molar ratio of the quinone compound and the phosphorus compound represented by the general formula (1) or the general formula (2) is more than 0 and less than 1, and the stoichiometrically general formula (1 ) And the compound of the general formula (2) are left. As a result, the reaction product becomes a mixture of the compounds represented by the general formulas (1) and (2) and the compounds represented by the general formulas (3) and (4). Since the hydrogen of the hydroxyl group of the compounds of the general formulas (3) and (4) has reactivity, these compounds are referred to in the present specification as
It is supposed to be included in the category of organic phosphorus compounds having active hydrogen. As a result, the phosphorus-containing epoxy resin of the present invention can increase the phosphorus content and can impart excellent flame retardancy. Here, when the phosphorus compounds of the general formulas (1) and (2) are reacted with epoxy resins without using the quinone compound, that is, when the molar ratio is 0.0, the epoxy which is the cross-linking point of the epoxy resin is used. Since a reaction with the group occurs and the crosslink density of the cured product decreases, the physical properties such as heat resistance are adversely affected. When an attempt is made to react a quinone compound and a phosphorus compound at a molar ratio of 1.0,
These two reactions do not proceed as intended and the phosphorus compound or quinone compound remains. In particular, when a sublimable quinone compound remains, it does not have a reactive group that reacts with the epoxy resin, which adversely affects the physical properties such as heat resistance. In order to obtain only the compounds of the general formula (3) and the general formula (4), the molar ratio of the quinone compound and the phosphorus compound having one active hydrogen bonded to the phosphorus atom, which is the method of the present invention, is larger than 0 and 1 After the reaction is performed for less than 1, the crude reaction product is preferably filtered or recrystallized. 1
When the compounds of the general formulas (3) and (4), which are organic phosphorus compounds having two active hydrogens in the molecule, are reacted with the epoxy resin, the obtained phosphorus-containing epoxy resin has high viscosity and impregnability and When the workability such as flowability is affected, it is possible to prevent the workability from being affected by using low-viscosity epoxy resins. However, it is necessary to contain the novolac type epoxy resin as an epoxy resin in an amount of 20% by weight or more.

[0012]

[Chemical 3]

[Chemical 4]

X in the above formula is a compound having the general formula (5) or the general formula (6), which is a reaction residue of a quinone compound.

[0014]

[Chemical 5]

[Chemical 6]

The reaction between the phosphorus compounds represented by the general formulas (1) and (2) and the quinone compounds is carried out by first dissolving the phosphorus compound in an inert solvent, adding the quinone compounds, and stirring the mixture by heating. To do. Examples of the inert solvent include methanol, ethanol, isopropanol, chloroform, N, N-dimethylformamide, dioxane, ethylene glycol, methoxypropanol, ethyl cellosolve, benzene, toluene, xylene and the like, but the general formula (1), Any solvent in which the phosphorus compound of the general formula (2) can be dissolved may be used, but the solvent is not limited thereto. In the reaction, quinone compounds are added in the form of powder or dissolved in a solvent. At this time, since heat is generated, quinone compounds are added by divided charging or a dropping method according to the addition amount so as not to cause sudden heat generation. 1 to 50 ℃ to 150 ℃ after addition
The reaction is carried out while holding for 4 hours. As the reaction progresses, the general formulas (3) and (4) are precipitated.

Epoxy resins are added to the mixture obtained by reacting the quinone compound and the phosphorus compound by the above-mentioned method to carry out the reaction. This reaction can be carried out by a known method, and the reaction is carried out at a reaction temperature of 100 ° C to 200 ° C, more preferably 120 ° C to 180 ° C with stirring. If the rate of this reaction is slow, a catalyst can be used as needed to improve productivity. Specifically, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, triphenylphosphine, tris (2,6-dimethoxyphenyl)
Various catalysts such as phosphines such as phosphine, phosphonium salts such as ethyltriphenylphosphonium bromide, 2methylimidazole, imidazoles such as 2ethyl-4-methylimidazole can be used.

As the curing agent for the composition of the present invention, it is possible to use a generally used curing agent for epoxy resins such as various phenolic resins, acid anhydrides, amines, hydrazides and acidic polyesters. These curing agents are 1
You may use only 1 type and may use 2 or more types.

A curing accelerator such as a tertiary amine, a quaternary ammonium salt, phosphines and imidazoles may be added to the composition of the present invention, if necessary. If necessary, an inorganic filler, a reinforcing material such as glass cloth / aramid fiber, a filler, a pigment, etc. may be added.

As a result of evaluating the characteristics of the epoxy resin composition used and the laminate obtained by using the composition, epoxy resins containing 20% by weight or more of a novolac type epoxy resin as an epoxy resin and quinone. Phosphorus-containing compound obtained by reacting a compound and an organophosphorus compound at a molar ratio of a quinone compound to an organophosphorus compound less than a stoichiometric amount of more than 0 and less than 1 By using an epoxy resin, a halide-free composition is obtained, and it is possible to obtain an epoxy resin composition that is lightweight, has no halogen dissociation at high temperatures, and is flame-retardant. The epoxy resin composition is a resin composition for producing a copper clad laminate used for an electronic circuit board, a sealing material used for electronic parts, and a molding material. It was found to be useful as a casting material, an adhesive, a material for electrical insulating paints, etc.

[0020]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The specific gravity of the synthesized epoxy resin is JIS-K-
The measurement was performed according to 0061. Flame retardancy is UL (Und
The measurement was carried out according to the erwriter Laboratories standard. Copper foil peel strength is JIS C 64
81 Measured according to 5.7. Further, the thermogravimetric reduction start temperature and the glass transition temperature of the cured product were measured by Exter6000 manufactured by Seiko Instruments Inc.

Synthesis Example 1 HCA 14 was placed in a 4-neck glass separable flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introducing device.
Charge 1 part by weight and 173 parts by weight of ethyl cellosolve,
It was heated and dissolved. Then 1,4-naphthoquinone 8
7.5 parts by weight were added in portions while paying attention to the temperature rise due to the heat of reaction. At this time, the molar ratio of 1,4-naphthoquinone and HCA was 1,4-naphthoquinone / HCA = 0.85. After the reaction, Epotote YDPN-638 771.
5 parts by weight were charged, the mixture was stirred while introducing nitrogen gas, and heated to 120 ° C. to dissolve. 0.23 parts by weight of triphenylphosphine was added and reacted at 150 ° C. for 4 hours. The epoxy equivalent of the obtained epoxy resin is 32.
6.9 g / eq, phosphorus content 2% by weight, specific gravity 1.2
It was 6.

Synthesis Example 2 155 parts by weight of HCA, 1,4-naphthoquinone 99.
0 parts by weight, toluene 330 parts by weight, Epotote YDP
The same operation as in Synthesis Example 1 was performed except that N-638 was 746.0 parts by weight and triphenylphosphine was 0.25 parts by weight. The molar ratio is 1,4-naphthoquinone / HCA = 0.
It was 87. The epoxy equivalent of the obtained epoxy resin was 360.3 g / eq, the phosphorus content was 2.2% by weight, and the specific gravity was 1.26.

Synthesis Example 3 141 parts by weight of HCA, 1,4-benzoquinone 41.
9 parts by weight, xylene 430 parts by weight, Epotote YDP
The same operation as in Synthesis Example 1 was performed except that N-638 844.3 parts by weight and triphenylphosphine 0.23 parts by weight were used. The molar ratio is 1,4-benzoquinone / HCA = 0.
It was 59. The epoxy equivalent of the obtained epoxy resin was 300.9 g / eq, the phosphorus content was 2.0% by weight, and the specific gravity was 1.25.

Synthesis Example 4 141 parts by weight of HCA, 1,4-naphthoquinone 25.
7 parts by weight, toluene 300 parts by weight, Epotote YDC
The same operation as in Synthesis Example 1 was performed except that N-701 was 833.3 parts by weight and triphenylphosphine was 0.17 parts by weight. The molar ratio is 1,4-naphthoquinone / HCA = 0.
It was 25. The epoxy equivalent of the obtained epoxy resin was 316.6 g / eq, the phosphorus content was 2.0% by weight, and the specific gravity was 1.25.

Synthesis Example 5 55.0 parts by weight of diphenylphosphine oxide, 1,
4-naphthoquinone 74.1 parts by weight, dioxane 13
0 parts by weight, Epotote YDCN-701 870.9
The same operation as in Synthesis Example 1 was performed except that the amount of triphenylphosphine was 0.13 parts by weight. Molar ratio is 1,4
-Naphthoquinone / diphenylphosphine oxide = 0.
It was 58. The epoxy equivalent of the obtained epoxy resin was 309.1 g / eq, the phosphorus content was 2.5% by weight, and the specific gravity was 1.26.

Synthesis Example 6 141 parts by weight of HCA, 1,4-naphthoquinone 96.
3 parts by weight, toluene 300 parts by weight, Epotote YDP
N-638 262.7 parts by weight, YDF-170 40
The same operation as in Synthesis Example 1 was carried out except that 9.6 parts by weight and 0.24 parts by weight of triphenylphosphine were used. The molar ratio was 1,4-naphthoquinone / HCA = 0.93. The epoxy equivalent of the obtained epoxy resin is 323.0 g / e.
q, the phosphorus content was 2.0% by weight, and the specific gravity was 1.26.

Synthesis Example 7 In the same apparatus as in Synthesis Example 1, 256 parts by weight of diphenylphosphine oxide and 600 parts by weight of ethyl cellosolve were charged and heated to dissolve. Then, 48.6 parts by weight of 1,4-benzoquinone was added portionwise while paying attention to the temperature rise due to the heat of reaction. At this time, the molar ratio of 1,4-benzoquinone and diphenylphosphine oxide was 1,4-benzoquinone / diphenylphosphine oxide = 0.89. The crystals formed after the reaction were separated by filtration and recrystallized from methyl alcohol. When the powder obtained by drying was confirmed by liquid chromatography, there were no peaks for diphenylphosphine oxide and 1,4-benzoquinone, and the molecular weight indicated that diphenylphosphine oxide had 1,2
It was identified as a bifunctional phenol compound reacted with 4-benzoquinone. 200 parts by weight of this powder, YDPN-
638 300 parts by weight and YD-128 (BPA type epoxy resin manufactured by Tohto Kasei Co., Ltd.) 500 parts by weight were charged.
The mixture was heated and melted and charged with 0.20 part by weight of triphenylphosphine to carry out a reaction. The epoxy equivalent of the obtained epoxy resin was 308.4 g / eq, the phosphorus content was 2.0% by weight, and the specific gravity was 1.25.

Synthetic Example 8 282 parts by weight of HCA and 660 parts by weight of ethyl cellosolve were placed in the same apparatus as in Synthetic Example 1 and heated to dissolve. After that, 192.6 parts by weight of 1,4-naphthoquinone was dividedly charged while paying attention to the reaction exotherm. At this time 1,
The molar ratio of 4-naphthoquinone to HCA was 1,4-naphthoquinone / HCA = 0.93. The crystals formed after the reaction were separated by filtration and recrystallized from methyl alcohol.
When the powder obtained by drying was confirmed by liquid chromatography, there were no peaks for HCA and 1,4-naphthoquinone, and it was identified from the molecular weight as a bifunctional phenol compound in which HCA was reacted with 1,4-naphthoquinone.
243.9 parts by weight of this powder, YDPN-638 30
0 parts by weight and 300 parts by weight of YDF-170 were charged, heated and melted, and 0.24 parts by weight of triphenylphosphine was charged and reacted. The epoxy equivalent of the obtained epoxy resin was 337.0 g / eq, the phosphorus content was 2.0% by weight, and the specific gravity was 1.26.

Synthesis Example 9 209 parts by weight of HCA, 30 parts by weight of bisphenol A, and 761 parts by weight of Epotote YDPN-638 were mixed, and after dissolution, 0.2 part by weight of triphenylphosphine was added to carry out a reaction. The epoxy equivalent of the obtained epoxy resin was 350.8 g / eq, the phosphorus content was 3.0% by weight, and the specific gravity was 1.26. Synthesis example 10 141 parts by weight of HCA, 1,4-benzoquinone 56.
6 parts by weight, 150 parts by weight of Epototo YDCN-702, 652.4 parts by weight of YD-128, and 0.20 part by weight of triphenylphosphine were used, and the same operation as in Synthesis Example 1 was performed. Molar ratio is 1,4-naphthoquinone / HCA
= 0.80. The epoxy equivalent of the obtained epoxy resin was 327.1 g / eq, the phosphorus content was 2.0% by weight, and the specific gravity was 1.24.

Synthesis Example 11 141 parts by weight of HCA, 1,4-naphthoquinone 10
4.3 parts by weight, toluene 400 parts by weight, Epotote Y
The same operation as in Synthesis Example 1 was performed, except that 754.7 parts by weight of DPN-638 and 0.25 part by weight of triphenylphosphine were used. The molar ratio is 1,4-naphthoquinone / HCA =
There was 1.01. The epoxy equivalent of the obtained epoxy resin was 340.5 g / eq, the phosphorus content was 2.0% by weight,
The specific gravity was 1.25. Moreover, when the obtained epoxy resin was confirmed by liquid chromatography, it was found that
There are peaks for A and 1,4-naphthoquinone, especially 1,
It was confirmed that a large amount of 4-naphthoquinone remained.

Example 1 100.0 parts by weight of the epoxy resin obtained in Synthesis Example 1, 3.21 parts by weight of dicyandiamide (manufactured by Nippon Carbide Co., Ltd.) as a curing agent, and 2E4MZ as a curing accelerator.
(2 ethyl 4 methyl imidazole manufactured by Shikoku Kasei Co., Ltd.) 0.01 part by weight was uniformly dissolved in solvents such as methyl ethyl ketone, methyl cellosolve, and dimethylformamide. The obtained resin varnish is glass cloth WEA 762.
8 XS13 (Nitto Boseki Co., Ltd. 0.18 mm thick)
Impregnated in. The impregnated glass cloth was dried in a hot air circulation oven at 150 ° C for 4 minutes to obtain a prepreg. 8 sheets of the obtained prepregs are piled up and 130 ℃ × 15 minutes and 170 ℃
Heat and pressure were applied under the condition of × 20 kg / cm 2 × 70 minutes to obtain a laminated plate. Table 1 shows the physical properties of the obtained laminate.

Example 2 100.0 parts by weight of the epoxy resin obtained in Synthesis Example 2, 2.91 parts by weight of dicyandiamide as a curing agent, and 0.01 parts by weight of 2E4MZ as a curing accelerator were used as solvent methyl ethyl ketone, methyl cellosolve, and dimethyl. It was uniformly dissolved in formamide. The obtained resin varnish was subjected to the same operations as in Example 1 to obtain a laminated board. Table 1 shows the physical properties of the obtained laminate.

Example 3 100.0 parts by weight of the epoxy resin obtained in Synthesis Example 3, 3.49 parts by weight of dicyandiamide as a curing agent, and 0.02 parts by weight of 2E4MZ as a curing accelerator were used as solvents methyl ethyl ketone, methyl cellosolve, and dimethyl. It was uniformly dissolved in formamide. The obtained resin varnish was subjected to the same operations as in Example 1 to obtain a laminated board. Table 1 shows the physical properties of the obtained laminate. Example 4 100.0 parts by weight of the epoxy resin obtained in Synthesis Example 4, 3.32 parts by weight of dicyandiamide as a curing agent, and 0.01 parts by weight of 2E4MZ as a curing accelerator were uniformly dispersed in methyl ethyl ketone, methyl cellosolve, and dimethylformamide as solvents. Dissolved in. The obtained resin varnish was subjected to the same operations as in Example 1 to obtain a laminated board. Table 1 shows the physical properties of the obtained laminate.

Example 5 100.0 parts by weight of the epoxy resin obtained in Synthesis Example 5, 3.40 parts by weight of dicyandiamide as a curing agent, and 0.01 parts by weight of 2E4MZ as a curing accelerator were used as solvents such as methyl ethyl ketone, methyl cellosolve, and dimethyl. It was uniformly dissolved in formamide. The obtained resin varnish was subjected to the same operations as in Example 1 to obtain a laminated board. Table 2 shows the physical properties of the obtained laminate. Example 6 100.0 parts by weight of the epoxy resin obtained in Synthesis Example 6, 3.25 parts by weight of dicyandiamide as a curing agent, and 0.15 parts by weight of 2E4MZ as a curing accelerator were uniformly added to methyl ethyl ketone, methyl cellosolve, and dimethylformamide as solvents. Dissolved in. The obtained resin varnish was subjected to the same operations as in Example 1 to obtain a laminated board. Table 2 shows the physical properties of the obtained laminate.

Example 7 100.0 parts by weight of the epoxy resin obtained in Synthesis Example 7, 3.40 parts by weight of dicyandiamide as a curing agent, and 0.05 parts by weight of 2E4MZ as a curing accelerator were uniformly dissolved in a solvent. The obtained resin varnish was subjected to the same operations as in Example 1 to obtain a laminated board. Table 2 shows the physical properties of the obtained laminate. Example 8 100.0 parts by weight of the epoxy resin obtained in Synthesis Example 8, 3.11 parts by weight of dicyandiamide as a curing agent, and 0.15 parts by weight of 2E4MZ as a curing accelerator were uniformly dissolved in a solvent. The obtained resin varnish was subjected to the same operations as in Example 1 to obtain a laminated board. Table 2 shows the physical properties of the obtained laminate.

Comparative Example 1 90 parts by weight of Epotote YDB-500 (Brominated epoxy resin manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 499.5 g / eq, bromine content 21.7% by weight) and Epotote YD
CN-704 10 parts by weight, didiandiamide 2.38
By weight, 2E4MZ (0.06 parts by weight) was dissolved in a solvent such as methyl ethyl ketone, methyl cellosolve, or dimethylformamide to prepare a resin varnish. Using this resin varnish, the same operation as in Example 1 was performed to obtain a laminated plate. Table 3 shows the physical properties of the obtained laminate. The specific gravity of the mixture of epoxy resins used was 1.39.

Comparative Example 2 100.0 parts by weight of the epoxy resin obtained in Synthesis Example 9, 3.00 parts by weight of dicyandiamide as a curing agent, and 0.55 parts by weight of 2E4MZ as a curing accelerator were uniformly dissolved in a solvent. The obtained resin varnish was subjected to the same operations as in Example 1 to obtain a laminated board. Table 3 shows the physical properties of the obtained laminate.

Comparative Example 3 100.0 parts by weight of the epoxy resin obtained in Synthesis Example 10, 3.21 parts by weight of dicyandiamide as a curing agent, and 0.05 parts by weight of 2E4MZ as a curing accelerator were used as solvents methyl ethyl ketone, methyl cellosolve, and dimethyl. It was uniformly dissolved in formamide. The obtained resin varnish was subjected to the same operations as in Example 1 to obtain a laminated board. Table 3 shows the physical properties of the obtained laminate.

Comparative Example 4 100.0 parts by weight of the epoxy resin obtained in Synthesis Example 11, 3.08 parts by weight of dicyandiamide as a curing agent, and 0.05 parts by weight of 2E4MZ as a curing accelerator were used as solvent methyl ethyl ketone, methyl cellosolve, and dimethyl. It was uniformly dissolved in formamide. The obtained resin varnish was subjected to the same operations as in Example 1 to obtain a laminated board. The physical properties of the obtained laminate are shown in Table 3, and two thermogravimetric reduction start temperatures were obtained.
It showed a low value.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

As is clear from the physical property values shown in the comparative examples of Table 3, a phosphorus-containing epoxy resin obtained by reacting a quinone with a phosphorus compound is partially adapted to the technical idea of the present invention. Even if there is 20% by weight or less of the novolac type epoxy resin, not only sufficient flame retardancy is not exhibited, but also physical properties such as heat resistance are adversely affected. Further, even if the novolac type epoxy resin is used in an amount of 20% by weight or more, the composition in which the reaction of the quinone and the phosphorus compound is carried out at a molar ratio of 0.0 gives flame retardancy, but the composition has no heat resistance or adhesiveness. The physical properties are deteriorating. Further, when the reaction between the quinones and the phosphorus compound is carried out at a molar ratio of 1.01, flame retardancy is obtained, but the remaining quinones adversely affect the adhesive strength and heat resistance. The specific gravity of the epoxy resin synthesized by the technique of the present invention is about 10% lighter than that of the conventional brominated epoxy resin, and the weight of the cured product is reduced. Further, not only the glass transition temperature is high, but also the thermogravimetric reduction start temperature is high, and the long-term heat resistance is excellent. Thus, the phosphorus-containing epoxy resin composition does not contain halogen, has flame retardancy, and has excellent physical properties such as heat resistance and adhesiveness. It is ideal for, and is used as an encapsulating material, molding material, casting material for electronic parts,
It is suitable as an adhesive and is also effective as a material for electrical insulating paints.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI H05K 1/03 610 B29K 63:00 // B29C 39/02 B29L 31:34 B29K 63:00 H01L 23/30 B29L 31:34 ( 56) References JP-A-11-166035 (JP, A) JP-A-4-11662 (JP, A) JP-A-5-214070 (JP, A) JP-A-5-39345 (JP, A) 50-113547 (JP, A) JP-A 5-214068 (JP, A) JP-A 60-126293 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 59 / 00-59/72 B32B 27/38 C09K 21/14 H01L 23/29 H01L 23/31 H05K 1/03 610

Claims (6)

(57) [Claims] 1. A novolac type epoxy resin in an amount of 20% by weight.
Stoichiometry in which the epoxy resin containing the above and the quinone compound and the organophosphorus compound having one active hydrogen bonded to a phosphorus atom have a molar ratio of the quinone compound to the organophosphorus compound of more than 0 and less than 1 A phosphorus-containing epoxy resin composition comprising a phosphorus-containing epoxy resin obtained by reacting an organic phosphorus compound having active hydrogen, which is obtained by reacting less than the amount. 2. The compound represented by the general formula (1) and / or the general formula (2) is used as the organic phosphorus compound having one active hydrogen bonded to a phosphorus atom. The phosphorus-containing epoxy resin composition of. [Chemical 1] [Chemical 2] 3. An organic phosphorus compound having active hydrogen, which is obtained by reacting a quinone compound with an organic phosphorus compound having one active hydrogen bonded to a phosphorus atom, in a molecule.
3. The phosphorus-containing epoxy resin composition according to claim 1, wherein the organic phosphorus compound having one active hydrogen is taken out and reacted with the epoxy resin. 4. An epoxy resin laminate comprising the phosphorus-containing epoxy resin composition according to claim 1, 2. 5. An epoxy resin encapsulant comprising the phosphorus-containing epoxy resin composition according to claim 1, 2. 6. An epoxy resin casting material comprising the phosphorus-containing epoxy resin composition according to claim 1, 2, or 3.