JPH11166035A - Epoxy resin composition including phosphorus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition suitable for copper-clad laminate of fire-resistant and light weight electronic circuit board, sealant for electronic parts, molding material, cast molding material, adhesive, electrical insulating material and the like. SOLUTION: This composition consists of a hardening epoxy rein including at least 20 wt.% of a novolac type epoxy resin as the epoxy resin and a phosphorus compound of the formula (R is hydrogen or an aliphatic group, or an aromatic group and may be the same or not) set to react and included in amount of 0.8-8 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a copper-clad laminate used for an electronic circuit board and a sealing material used for an electronic component.
The present invention relates to a phosphorus-containing epoxy resin composition suitable for a molding material, a casting material, an adhesive, an electric insulating paint, and the like.

[0002]

2. Description of the Related Art Epoxy resins are excellent in adhesiveness, heat resistance and moldability, so that they are used in electronic parts, electric equipment, automobile parts,
Widely used such as FRP and sports equipment. Of these, brominated epoxy resins are particularly used for copper-clad laminates and sealing materials used for electronic components and electric equipment for safety reasons such as prevention and delay of fire. Flame retardancy is imparted by introducing a halogen such as bromine into an epoxy resin, and an excellent cured product is obtained due to the high reactivity of the epoxy group. However, environmental problems such as generation of harmful substances such as hydrogen halides during combustion have been reported. In order to solve such problems, there is an increasing demand for flame-retardant epoxy resins that do not use halides.

[0003]

The present inventors have made intensive studies to develop epoxy resins having flame retardancy without using halogens, and as a result, have completed the present invention.
The present invention is suitable for sealing materials, molding materials, casting materials, adhesives, electric insulating paints, etc. used for copper-clad laminates used for electronic circuit boards and electronic components. An object of the present invention is to provide a phosphorus-containing epoxy resin composition provided.

[0004]

According to the present invention, a phosphorus compound represented by the general formula (1) is added to an epoxy resin composition containing 20% by weight or more of a novolak type epoxy resin as an epoxy resin in a curable epoxy resin. Phosphorus content is 0.
A phosphorus-containing epoxy resin composition characterized by being reacted so as to be from 8% by weight to 8% by weight.

[0005]

Embedded image

R is a hydrogen atom, an aliphatic group, or an aromatic group, and may be the same or different.

That is, the present invention relates to an epoxy resin composition comprising an epoxy resin, a curing agent and, if necessary, a curing accelerator, wherein at least 20% by weight of the epoxy resin is a curable epoxy resin composed of a novolak type epoxy resin. In addition, a phosphorus compound represented by the general formula (1) is made an essential element, and the phosphorus compound is reacted with the epoxy resin so that the content as a phosphorus element derived from the phosphorus compound becomes 0.8% by weight to 8% by weight. It is a phosphorus-containing epoxy resin composition characterized by the above-mentioned.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail. The curable epoxy resin in the present invention means a curable epoxy resin, and the epoxy resin may be a single resin or a mixture of two or more resins. However, in the present invention, it is essential that 20% by weight or more of a novolak type epoxy resin is present in the curable epoxy resin. When the novolak type epoxy resin is less than 20% by weight, not only the heat resistance, adhesiveness and curability are deteriorated due to a decrease in the crosslinking density of the cured epoxy resin, but also the flame retardancy is adversely affected. . The object of the present invention can be achieved only by reacting a predetermined amount of a novolak type epoxy resin of 20% by weight or more with a phosphorus compound. When the curable epoxy resin is a mixture, the epoxy resin mixed with the novolak type epoxy resin includes, for example, bisphenol type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, resorcinol type epoxy resin, polyglycol type epoxy resin. There are resins and the like, but there is no particular limitation.

The novolak type epoxy resin in the present invention is obtained by subjecting a hydroxyl group of a phenol novolak resin obtained by condensing a phenol and an aldehyde to epoxidation by the action of epichlorohydrin or the like. As Epototh YDPN-638
(Phenol novolak type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YDCN-701, YDCN-7
02, YDCN-703, YDCN-704 (cresol novolak type epoxy resin manufactured by Toto Kasei Co., Ltd.),
Epotote ZX-1071T, ZX-1270, ZX-
1342 (Alkynovolak type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo ZX-1247 (Styrene phenol novolak type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo ZX-1142L (Naphthol novolak type epoxy resin manufactured by Toto Kasei Co., Ltd.), Bisphenol novolak type epoxy resin, aralkylphenol novolak type epoxy resin and the like may be mentioned, but these epoxy resins may be used alone or in combination of two or more types. Absent.

Further, the novolak type epoxy resin includes those obtained by reacting the above novolak type epoxy resin with phenols, amines and carboxylic acids. Further, those obtained by reacting various epoxy resins with a novolak type phenol resin are also included in the novolak type epoxy resin in the present invention. It is essential that these novolak type epoxy resins be contained in the epoxy resin composition in an amount of 20% by weight or more. Specific examples of the phosphorus compound represented by the general formula (1) include HCA (9,8-dihydro-9 manufactured by Sanko Chemical Co., Ltd.).
-Oxa-10-phosphaphenanthrene-10-oxide).

As a method of reacting the phosphorus compound represented by the general formula (1) with an epoxy resin, a known method can be used. 100 ° C to 200 ° C as the reaction temperature,
More preferably, the reaction is carried out at 120 ° C. to 180 ° C. with stirring. Active hydrogen directly bonded to the phosphorus atom of the phosphorus compound represented by the general formula (1) reacts with the epoxy group of the epoxy resin. The end point of the reaction is confirmed to be 99% or more of the theoretical epoxy equivalent by tracking the epoxy equivalent. Or
The residual amount of the phosphorus compound represented by the general formula (1) is traced as the acid value of the epoxy resin, and the residual amount is represented by the general formula (1) by a method for confirming the end point of the reaction or instrumental analysis represented by liquid chromatography or the like. There is a method of tracking the phosphorus compound to be used. Either method may be used, but it is necessary to sufficiently react the epoxy resin with the phosphorus compound represented by the general formula (1). A catalyst is used as necessary in consideration of the reaction rate. Specifically, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, and ethyltriphenylphosphonium Various catalysts such as phosphonium salts such as bromide, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used. However, it is necessary to react the phosphorus compound represented by the general formula (1) in the epoxy resin composition such that the phosphorus content is in the range of 0.8 to 8 parts by weight. If the phosphorus content of the epoxy resin composition is less than 0.8 parts by weight, sufficient flame retardancy cannot be obtained, and if it is more than 8 parts by weight, the crosslink density of the cured epoxy resin decreases. Since the physical properties such as heat resistance and adhesiveness are reduced, it is necessary to control the phosphorus content of the epoxy resin composition to be in the range of 0.8 to 8 parts by weight.

The phosphorus compounds represented by the general formula (1) have already been disclosed in JP-A-57-205418 and JP-A-62-704.
No. 14, there is a report that a transparent cured product can be obtained without discoloration by being incorporated into an epoxy resin composition. JP-A-61-166822 also reports that a sealing epoxy resin composition having a high thermal conductivity, a low coefficient of thermal expansion, a high humidity resistance and a good moldability is obtained. Further, Japanese Patent Application Laid-Open No. 1-165618 reports that a partial reaction is carried out to prevent discoloration and discoloration of coloring by a dye. According to the present invention, an epoxy resin composition having flame retardancy can be obtained without using a halide, which is the object of the present invention, by completely reacting a phosphorus compound represented by the general formula (1) with an epoxy resin. However, the method of merely blending or partially reacting as described in the above patents cannot achieve the object of the present invention because physical properties such as heat resistance, adhesiveness and moisture resistance are deteriorated. From the above, it is clear that the above patents use the phosphorus compound represented by the general formula (1), but none of them is used for the purpose of imparting flame retardancy.

As the curing agent for the composition of the present invention, commonly used curing agents for epoxy resins such as various phenolic resins, acid anhydrides, amines, hydrazides and acidic polyesters can be used. These curing agents are 1
Only one type or two or more types may be used. The composition of the present invention may optionally contain a curing accelerator such as a tertiary amine, a quaternary ammonium salt, a phosphine or an imidazole. In addition, a reinforcing material such as an inorganic filler or glass cloth / aramid fiber, a filler, a pigment, and the like are used as needed.

As a result of evaluation of the laminate of the epoxy resin composition, novolak type epoxy resin was contained in an amount of 20% by weight or more as an epoxy resin, and the phosphorus compound represented by the general formula (1) was defined as the phosphorus content in the cured resin. The use of an epoxy resin composition obtained by reacting from 0.8% by weight to 8% by weight makes it possible to obtain an epoxy resin composition which is lightweight and imparts flame retardancy. This epoxy resin composition is used not only for copper-clad laminates used for electronic circuit boards, but also for sealing materials, molding materials, casting materials,
It can be suitably used for adhesives, electric insulating paints and the like.

[0015]

Next, the present invention will be described specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. The peel strength of the copper foil is JIS C 6481.
It measured according to 5.7. Flame retardancy is UL (Underw
(Reter Laboratorics) standard. The glass transition temperature of the cured product was measured using Exter6000 TMA manufactured by Seiko Instruments Inc. Flexural strength and flexural modulus are JIS K6911
It measured at room temperature according to. As for the water absorption, the test piece was allowed to stand in a thermo-hygrostat at 85 ° C. and a humidity of 85% for 72 hours, and the rate of weight increase was taken as the water absorption. The novolak-type epoxy resin content shown in Tables 1, 2, and 3 indicates the novolak-type epoxy resin content in the epoxy resin when reacting with the phosphorus compound. In the present invention, the novolak-type epoxy resin content Is 20% by weight or more.

Synthesis Example 1 A four-neck glass separable flask equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen gas introducing device was charged with an epototo.
YDCN-701P 843.0 parts, bisphenol A
16.0 parts were charged, stirred while introducing nitrogen gas, and dissolved by heating. After adding 0.02 parts of triphenylphosphine as a catalyst and reacting at 150 ° C. for 3 hours, 141.0 parts of the above-mentioned HCA was added to further react. At this time, the content of the novolak-type epoxy resin was 85.6% by weight. The epoxy equivalent of the obtained epoxy resin was a theoretical epoxy equivalent of 30 which was completely reacted.
298.6 g / eq for 0.0 g / eq;
It was confirmed that CA completely reacted with the epoxy resin. The phosphorus content was 2.0% by weight.

Synthesis Example 2 791 parts of epototo YDCN-701P, HCA
The same operation as in Synthesis Example 1 was performed except that 209 parts and 0.02 part of triphenylphosphine were used. At this time, the content of the novolak-type epoxy resin was 79.1% by weight. The epoxy equivalent of the obtained epoxy resin is 34 with respect to the theoretical epoxy equivalent of 345.0 g / eq which is completely reacted.
It was 6.5 g / eq, and it was confirmed that HCA was completely reacted with the epoxy resin. The phosphorus content is 3.
It was 0% by weight.

Synthesis Example 3 547.5 parts of epototo YDPN-638, 542.5 parts of epotote YDF-170250.0 parts, 62.5 parts of BRG-85 (phenol novolak resin, softening point 85 ° C., manufactured by Gunei Chemical Co., Ltd.), 140 parts of HCA, The same operation as in Synthesis Example 1 was performed, except that 0.02 part of triphenylphosphine was used. At this time, the content of the novolak-type epoxy resin was 60.0% by weight. The epoxy equivalent of the obtained epoxy resin was 306.7 g / eq with respect to the theoretical epoxy equivalent of 300.0 g / eq, which was completely reacted, and it was confirmed that HCA was completely reacted with the epoxy resin. The phosphorus content was 2.0% by weight.

Synthesis Example 4 The same operation as in Synthesis Example 1 was carried out except that 804.0 parts of Epotohto YDPN-638, 55 parts of bisphenol F, 141 parts of HCA and 0.02 parts of triphenylphosphine were used. At this time, the content of the novolak-type epoxy resin was 85.9% by weight. The epoxy equivalent of the obtained epoxy resin was the theoretical epoxy equivalent 2 which was completely reacted.
304.1 g / eq for 99.7 g / eq,
It was confirmed that HCA was completely reacted with the epoxy resin. The phosphorus content was 2.0% by weight.

Synthesis Example 5 Epotote YDPN-638 859 parts, HCA 1
The same operation as in Synthesis Example 1 was performed except that 41 parts and 0.02 part of triphenylphosphine were used. At this time, the content of the novolak-type epoxy resin was 85.9% by weight. The epoxy equivalent of the obtained epoxy resin was 237.1 g / eq of epoxy equivalent to 236.3 g / eq of theoretical epoxy equivalent which was completely reacted, and it was confirmed that HCA was completely reacted with epoxy resin. The phosphorus content was 2.0% by weight. This resin was measured for its softening point and ICI viscosity in order to evaluate it as a sealing material. As a result, the softening point was 56 ° C. and the ICI melt viscosity at 150 ° C. was 0.14 Pa · sec.

Synthesis Example 6 A four-neck glass separable flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introducing device was placed in an epototo.
760 parts of YDPN-638 and 240 parts of HCA were charged, and the mixture was heated and melted and mixed while introducing nitrogen gas. At this time, the content of the novolak type epoxy resin was 7
It was 6.0% by weight. The epoxy equivalent of the obtained epoxy resin was a theoretical epoxy equivalent of 314.4 g after complete reaction.
It is 247.8 g / eq to / eq, and it seems that HCA partially remains. The phosphorus content is 3.4.
% By weight.

Synthesis Example 7 198 parts of Epototo YDPN-638, Epotote YD-128 (a bisphenol A type epoxy resin manufactured by Toto Kasei Co., Ltd. Epoxy equivalent: 186.8 g / e)
q) The same operation as in Synthesis Example 1 was performed, except that 502 parts, 300 parts of HCA, and 0.03 parts of triphenylphosphine were used. At this time, the content of the novolak type epoxy resin was 19.8% by weight. The epoxy equivalent of the obtained epoxy resin was a theoretical epoxy equivalent having completely reacted 416.
The epoxy equivalent was 417.0 g / eq with respect to 9 g / eq, and it was confirmed that HCA was completely reacted with the epoxy resin. The phosphorus content was 4.3% by weight.

Example 1 100.0 parts of the epoxy resin obtained in Synthesis Example 1 and dicyandiamide (manufactured by Nippon Carbide Co., Ltd.) as a curing agent
3.52 parts and 0.05 parts of 2E4MZ (2ethyl 4-methylimidazole manufactured by Shikoku Chemicals Co., Ltd.) as a curing accelerator were uniformly dissolved in a solvent of methyl ethyl ketone, methyl cellosolve, and N, N dimethylformamide. The obtained resin varnish was applied to glass cloth WEA 7628 XS13.
(0.18 mm thick, manufactured by Nitto Boseki Co., Ltd.).
The impregnated glass cloth was dried in a hot air circulating oven at 150 ° C. for 6 minutes to obtain a prepreg. The obtained prepreg 8
Stack the sheets, 130 ℃ × 15min and 170 ℃ × 20kg /
Heating and pressurization were performed at 70 cm ² × 70 minutes to obtain a laminate. Table 1 shows the physical properties of the obtained laminate.

Example 2 100.0 parts of the epoxy resin obtained in Synthesis Example 2, 3.03 parts of dicyandiamide as a curing agent, and 0.80 parts of 2E4MZ as a curing accelerator are uniformly dissolved in the same solvent as in Example 1. did. The obtained resin varnish was subjected to the same operation as in Example 1 to obtain a laminate. Table 1 shows the physical properties of the obtained laminate.

Example 3 100.0 parts of the epoxy resin obtained in Synthesis Example 3, 3.42 parts of dicyandiamide as a curing agent, and 0.01 part of 2E4MZ as a curing accelerator are uniformly dissolved in the same solvent as in Example 1. did. The obtained resin varnish was subjected to the same operation as in Example 1 to obtain a laminate. Table 1 shows the physical properties of the obtained laminate.
Shown in

Example 4 100.0 parts of the epoxy resin obtained in Synthesis Example 4, 3.45 parts of dicyandiamide as a curing agent, and 0.05 part of 2E4MZ as a curing accelerator are uniformly dissolved in the same solvent as in Example 1. did. The obtained resin varnish was subjected to the same operation as in Example 1 to obtain a laminate. Table 1 shows the physical properties of the obtained laminate.
Shown in

Example 5 208 parts of the epoxy resin obtained in Synthesis Example 5 and BRG-557 (phenol novolak resin manufactured by Showa Polymer Co., Ltd., phenolic hydroxyl equivalent: 105 g / e) as a curing agent
q, softening point 85 ° C) 92 parts, Hulex RD-8 (fused silica manufactured by Tatsumori Co., Ltd.) 700 parts as a filler,
5 parts of triphenylphosphine as a curing accelerator, MA-
8 (Carbon black manufactured by Mitsubishi Chemical Corporation), 4 parts of carnauba wax as a release agent, KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.) as a silane coupling agent
Five parts were blended, melt-mixed at 80 ° C. at a rate of 1 kg / 20 minutes using a biaxial kneader S1KRC kneader (manufactured by Kurimoto Tekko Co., Ltd.), quenched, and pulverized to obtain a molding material. The obtained molding material is pressed at 170 ° C. under a pressure of 65 kg using a mold.
/ Cm ² for 10 minutes. Thereafter, the sample was further heated at 180 ° C. for 6 hours to obtain a test piece for measuring physical properties. Table 3 shows the physical properties of the obtained cured product.

Comparative Example 1 100.0 parts of the epoxy resin in which HCA obtained in Synthesis Example 6 remained and dicyandiamide 4.23 as a curing agent
And 0.50 part of 2E4MZ as a curing accelerator were uniformly dissolved in the same solvent as in Example 1. The obtained resin varnish was subjected to the same operation as in Example 1 to obtain a laminate. Table 2 shows the physical properties of the obtained laminate. Comparative Example 2 100.0 parts of the epoxy resin obtained in Synthesis Example 7, 2.52 parts of dicyandiamide as a curing agent, and 1.10 parts of 2E4MZ as a curing accelerator were uniformly dissolved in the same solvent as in Example 1. The obtained resin varnish was subjected to the same operation as in Example 1 to obtain a laminate. Table 2 shows the physical properties of the obtained laminate.
Shown in

Comparative Example 3 90 parts of Epotote YDB-500 (brominated epoxy resin manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 498.5 g / eq, bromine content: 21.7% by weight) and Epotote YDCN
-704 10 parts, 2.38 parts of diiandiamide, 2E
Dissolve 0.06 parts of 4MZ in the same solvent as in Example 1,
A resin varnish was prepared. The same operation as in Example 1 was performed using this resin varnish to obtain a laminate. Table 2 shows the physical properties of the obtained laminate.

Comparative Example 4 Epototo YD-901 (BPA manufactured by Toto Kasei Co., Ltd.)
Type epoxy resin Epoxy equivalent 472.0g / eq) 1
00 parts and 2.67 parts of didiandiamide, 2E4MZ
0.10 parts was dissolved in the same solvent as in Example 1 to prepare a resin varnish. The same operation as in Example 1 was performed using this resin varnish to obtain a laminate. Table 2 shows the physical properties of the obtained laminate.

Comparative Example 5 Epototo YDCN-500 (a cresol novolak type epoxy resin manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 200.8 g / eq, IC at 150 ° C.)
I melt viscosity 0.28 Pa · sec, softening point 61.4 ° C)
180 parts, 100 parts of BRG-557 as a curing agent, and Epotote YDB-400 (a brominated epoxy resin manufactured by Toto Kasei Co., Ltd., epoxy equivalent 398.4 g, as a flame retardant)
/ Eq, bromine content: 48.8 wt%), 20 parts, and 13 parts of ATOX-S (antimony trioxide, manufactured by Nippon Seimitsu Co., Ltd.) as a flame retardant aid. A test piece for measurement was obtained. Table 3 shows the physical properties of the obtained cured product.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

As described above, the epoxy resin composition of the present invention does not contain halogen and has flame retardancy, and is particularly suitable for a copper-clad laminate used for an electronic circuit board. Sealing materials, molding materials, casting materials used for electronic components,
It is suitable for adhesives and is also effective as an electrical insulating paint.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H05K 1/03 630 (72) Inventor Seigo Takuwa 3-17-14 Higashikasai, Edogawa-ku, Tokyo Inside the Tokyo Metropolitan Chemical Research Institute

Claims (4)

[Claims] 1. A curable epoxy resin containing a novolak type epoxy resin as an epoxy resin in an amount of 20% by weight or more, and a phosphorus compound represented by the general formula (1) having a phosphorus content of 0.8% by weight to 8% by weight. %. A phosphorus-containing epoxy resin composition characterized in that the reaction is carried out so as to obtain a phosphorus-containing epoxy resin composition. Embedded image R is a hydrogen atom, an aliphatic group, or an aromatic group, and may be the same or different. 2. An epoxy resin laminate comprising the phosphorus-containing epoxy resin composition according to claim 1. 3. An epoxy resin sealing material using the phosphorus-containing epoxy resin composition according to claim 1. 4. An epoxy resin casting material comprising the phosphorus-containing epoxy resin composition according to claim 1.