KR101571084B1 - Novel flame-retardant epoxy resin epoxy resin composition essentially containing the epoxy resin and cured product thereof - Google Patents

Novel flame-retardant epoxy resin epoxy resin composition essentially containing the epoxy resin and cured product thereof Download PDF

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KR101571084B1
KR101571084B1 KR1020097023341A KR20097023341A KR101571084B1 KR 101571084 B1 KR101571084 B1 KR 101571084B1 KR 1020097023341 A KR1020097023341 A KR 1020097023341A KR 20097023341 A KR20097023341 A KR 20097023341A KR 101571084 B1 KR101571084 B1 KR 101571084B1
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카즈오 이시하라
테츠야 나카니시
노리코 키시
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신닛테츠 수미킨 가가쿠 가부시키가이샤
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
    • C08G59/1422—Polycondensates modified by chemical after-treatment with inorganic compounds containing phosphorus
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • H05K1/03—Use of materials for the substrate
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Abstract

Flame retardant epoxy resin suitable for sealing materials, molding materials, moldings, adhesives, and electric insulating coating materials used for copper clad laminate and electronic parts used for electronic circuit boards which are flame retardant and have high heat resistance and high reactivity, And a cured product of the epoxy resin composition. A novel flame retardant epoxy resin containing nitrogen and phosphorus represented by a specific formula, a novel flame retardant epoxy resin composition containing the flame retardant epoxy resin as an essential component, and a novel flame retardant epoxy resin composition obtained by heating and curing the novel flame retardant epoxy resin composition .

Flame retardant epoxy resin

Description

TECHNICAL FIELD [0001] The present invention relates to a novel flame retardant epoxy resin, an epoxy resin composition containing the epoxy resin, and a cured product thereof. [0002]

The present invention relates to a novel flame retardant resin composition useful as a resin composition for producing a copper clad laminate, a film material, a resin-coated copper foil, etc. used for an electronic circuit board and a sealing material, a molding material, a mold material, an adhesive, An epoxy resin composition, and a cured product thereof.

Epoxy resins are widely used for electronic parts, electric appliances, automobile parts, FRP, and sports goods because they have excellent adhesiveness, heat resistance and moldability. Among them, copper-clad laminated plates and sealing materials used for electronic parts and electric devices are required to have safety such as fire prevention and delay, so that brominated epoxy resins having these characteristics have been used so far. There is a problem that the specific gravity is large. However, bromine epoxy resin is used as a useful electronic and electric material because flame retardancy is imparted by introducing halogen, especially bromine, into the epoxy resin and epoxy group has high reactivity and excellent cured product is obtained have.

However, in recent electric apparatuses, the tendency to put the so-called thin-and-thin short-lived weight more and more is becoming stronger. Under such a social demand, halides having a large specific gravity are undesirable materials from the viewpoint of recent lightweight tendency, and when used over a long period of time at a high temperature, halide dissociation occurs, thereby causing wire corrosion There is a concern. Further, harmful substances such as halides are generated at the time of burning of used electronic parts and electric devices, and the use of halogen at the point of environmental safety becomes a problem, and a material to replace them has been researched. The inventors of the present invention have made an effort to solve this problem by inventing a phosphorus-containing epoxy resin which is free from the problem of thinning, wiring corrosion and generation of harmful halides of electronic devices (Japanese Patent Laid-Open Publication No. H11-166035, Japanese Patent Laid- -279258). However, improvement in heat resistance and flame retardancy of the cured product is further demanded.

The inventors of the present invention have conducted intensive researches to achieve a further improvement in heat resistance and flame retardancy of a phosphorus-containing epoxy resin imparting flame retardancy without using halogen, and found that a new flame retardant epoxy resin containing phosphorus and nitrogen can improve heat resistance and flame retardancy And has completed the present invention. The present invention relates to a novel flame-retardant epoxy resin suitable for sealing materials, molding materials, moldings, adhesives, electric insulating paint materials, and electric insulating films used for copper clad laminate and electronic parts used for electronic circuit boards , A novel flame retardant epoxy resin composition and a cured product thereof.

That is, the gist of the present invention is a novel flame retardant epoxy resin composition comprising a novel flame retardant epoxy resin containing nitrogen and phosphorus represented by the general formula (1) and an epoxy resin as essential components, and a cured product thereof.

Specifically, there is provided a novel flame retardant epoxy resin containing nitrogen and phosphorus having a specific structure represented by the general formula (1).

Formula 1

Figure 112009068624829-pct00001

(Wherein X represents at least one chemical structure selected from the group consisting of the following formulas (2) to (5), and Y represents at least one chemical structure selected from the group consisting of the following formulas (6) to (9) And n represents an integer of 1 to 10)

(2) to (28) cited above have the following structures.

(2)

Figure 112009068624829-pct00002

(Wherein R1 represents hydrogen or a hydrocarbon group, which may be the same or different from each other, may be linear, branched or cyclic, and a represents an integer of 0, 1, 2, 3, 4 or 5)

(3)

Figure 112009068624829-pct00003

(A) represents an integer of 0, 1, 2, 3, 4 or 5, and Z represents a hydrogen atom or a hydrocarbon group, Oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any of the following formulas (10) to (19)

Formula 4

Figure 112009068624829-pct00004

(Wherein R1 represents hydrogen or a hydrocarbon group, which may be the same or different from each other, may be linear, branched or cyclic, and a represents an integer of 0, 1, 2, 3, 4 or 5)

Formula 5

Figure 112009068624829-pct00005

And b is an integer of 0, 1, 2, 3, 4, 5, 6 or 7, and R < 1 > is hydrogen or a hydrocarbon group, Lt; / RTI &

6

Figure 112009068624829-pct00006

Branched or cyclic, c represents an integer of 0, 1, 2, 3 or 4, and G represents a hydrogen atom or a hydrocarbon group, which may be the same or different, Wherein at least one of the molecules has the formula (21) or (22) described below, d represents an integer of 1, 2, 3, 4 or 5, and c + d? 5 to be)

Formula 7

Figure 112009068624829-pct00007

Branched or cyclic, c1 and c2 represent integers of 0, 1, 2, 3 or 4, and d represents an integer of 1 to 3, provided that R 1 and R 2 are the same or different and each represents a hydrogen atom or a hydrocarbon group, E is an integer of 0, 1, 2, 3 or 4, c1 + e? 4, c2 + d? 5, and G represents an integer of 1, 2, 3, 4 or 5, 20 to 23, and at least one of the molecules has the following general formula (21) or (22)

8

Figure 112009068624829-pct00008

R 2 represents hydrogen or a hydrocarbon group, which may be the same or different from each other, may be a linear, branched or cyclic form, c 1 and c 2 represent an integer of 0, 1, 2, 3 or 4, F is an integer of 1, 2, 3 or 4, c1 + e? 4, c2 + f? 4, and G is a group represented by the following general formulas Z represents at least one of methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or a group represented by the following formulas (10) to 19, and m represents an integer of 1, 2, 3, ...)

Formula 9

Figure 112009068624829-pct00009

(Wherein R 2 represents hydrogen or a hydrocarbon group and may be the same or different, and may be linear, branched or cyclic, and G represents any one of the following formulas (20) to (22) G is an integer of 0, 1, 2, 3, 4, 5 or 6, h1 and h2 are integers of 0, 1, 2, 3, 4 or 5, I is an integer of 1, 2, 3, 4, 5 or 6, g + h1? 6, i + h2? 6, Z is methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene , Biphenyl, or any one of the following formulas (10) to (19), and 1 represents an integer of 1, 2, 3,

10

Figure 112009068624829-pct00010

Formula 11

Figure 112009068624829-pct00011

Formula 12

Figure 112009068624829-pct00012

Formula 13

Figure 112009068624829-pct00013

Formula 14

Figure 112009068624829-pct00014

Formula 15

Figure 112009068624829-pct00015

Formula 16

Figure 112009068624829-pct00016

Formula 17

Figure 112009068624829-pct00017

(Wherein D represents benzene, naphthalene, anthracene, phenanthrene or biphenyl)

18

Figure 112009068624829-pct00018

(Wherein q represents an integer of 0, 1, 2, 3, ...)

Formula 19

Figure 112009068624829-pct00019

(Wherein W represents methylene, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of formulas (10) to (17)

20

Figure 112009068624829-pct00020

Formula 21

Figure 112009068624829-pct00021

(Wherein j is 0 or 1 and R 3 and R 4 represent hydrogen or a hydrocarbon group, which may be the same or different, may be a straight chain, a branched chain or a ring, or a combination of R 3 and R 4, Structure)

Formula 22

Figure 112009068624829-pct00022

(Wherein j represents 0 or 1, and R 3 and R 4 represent hydrogen or a hydrocarbon group, which may be the same or different, may be linear, branched or cyclic, or R 3 and R 4 may combine to form a cyclic structure , B represents benzene, naphthalene, anthracene, phenanthrene, and hydrocarbon substituents thereof, and Y represents any one of formulas (6) to (9)

Formula 23

Figure 112009068624829-pct00023

(Wherein R represents an integer of 0, 1, 2, 3, ..., E represents benzene, naphthalene, anthracene, phenanthrene, biphenyl and hydrocarbon substituents thereof, (6) to (9)

24

Figure 112009068624829-pct00024

Branched or cyclic, c1 and c2 represent an integer of 0, 1, 2, 3 or 4, and Z represents a hydrogen atom or a hydrocarbon group, And m represents an integer of 1, 2, 3, ..., and the like), or an alkylene group having 1 to 3 carbon atoms,

25

Figure 112009068624829-pct00025

(Wherein R 2 represents hydrogen or a hydrocarbon group, which may be the same or different from each other, may be linear, branched or cyclic, h 1 and h 2 are integers of 0, 1, 2, 3, 4 or 5, Z represents any one of the following formulas (10) to (19), and l represents an integer of 1, 2, 3, ..., and Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene,

The present invention also provides a novel flame retardant epoxy resin containing an amine compound represented by the formula (26), a compound according to claim 1 obtained by reacting an epoxy resin and an organic phosphorus compound represented by the formula (27) and / or the formula (28) . Here, the formulas (26) to (28) are represented by the following formulas.

26

Figure 112009068624829-pct00026

(Wherein X represents any one of formulas (2) to (5), and n represents an integer of 1, 2, 3, ...)

27

Figure 112009068624829-pct00027

(Wherein j is 0 or 1, and R 3 and R 4 are hydrogen or a hydrocarbon group, and they may be the same or different, and may be linear, branched or cyclic, or R3 and R4 may combine to form a ring Structure)

28

Figure 112009068624829-pct00028

(Wherein j is 0 or 1 and R 3 and R 4 represent hydrogen or a hydrocarbon group, which may be the same or different, may be a straight chain, a branched chain or a ring, or a combination of R 3 and R 4, And B represents benzene, naphthalene, anthracene, phenanthrene, and hydrocarbon substituents thereof)

The epoxy resin preferably has an epoxy equivalent of 200 g / eq to 1000 g / eq, a phosphorus content of 0.2% to 8.0%, and a nitrogen content of 0.1% to 4.0%.

The present invention also provides a novel flame retardant epoxy resin composition comprising the novel flame retardant epoxy resin as an essential component and a curing agent.

The present invention also provides an epoxy resin laminate obtained by using the novel flame retardant epoxy resin composition.

The present invention also provides an epoxy resin sealing material obtained using the novel flame retardant epoxy resin composition.

The present invention also provides an epoxy resin mold material obtained using the novel flame retardant epoxy resin composition.

The present invention also provides a novel flame-retardant epoxy resin cured product obtained by curing the flame-retardant epoxy resin composition.

The novel flame-retardant epoxy resin, epoxy resin composition and cured product thereof are useful as sealants, moldings, moldings, adhesives, and materials for electrical insulation paints used for resin compositions for production of copper clad laminate used for electronic circuit boards and electronic components useful.

As is clear from comparison with Examples and Comparative Examples to be described later, the novel flame retardant epoxy resin and the novel flame retardant epoxy resin composition of the present invention have flame retardancy at a low phosphorus content and excellent physical properties such as heat resistance and reactivity, It is most suitable for electrical insulating materials including copper clad laminate used in electronic circuit boards, and is suitable for sealing materials, molding materials, mold materials, adhesives, and film materials used in electronic parts, and is also effective as a material for electrical insulation paints.

Fig. 1 shows a GPC diagram of the epoxy resin obtained in Example 1. Fig.

Fig. 2 shows the FTIR diagram of the epoxy resin obtained in Example 1. Fig.

3 shows a GPC diagram of the epoxy resin obtained in Example 4. Fig.

4 shows the FTIR diagram of the epoxy resin obtained in Example 4. Fig.

The present invention will be described in detail. The novel epoxy resin represented by the general formula (1) has high flame retardancy because it contains phosphorus and nitrogen in the same molecule. In addition, as an effect of introducing nitrogen, the heat resistance was also increased, and the reactivity was also remarkably improved. Such a method for synthesizing a novel epoxy resin can be obtained by reacting an amine compound represented by the formula (26) with an organic phosphorus-containing compound represented by the formula (27) and / or an epoxy resin.

Specific examples of the amine compound represented by the formula (26) used in the present invention include aniline, phenylenediamine, toluidine, xylidine, diethyltoluenediamine and the like as examples of the formula (2). (X) is represented by the formula (3) and the formula (4) is exemplified by diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenylketone, diaminodiphenylsulfide, diaminodiphenylsulfone, bis Aminophenyl) fluorene, diamino diethyl dimethyldiphenyl methane, diaminodiphenyl ether, diaminobenzanilide, diaminobiphenyl, dimethyldiaminobiphenyl, biphenyltetramine, bisaminophenylanthracene, bisaminophenox Cyanobenzene, bisaminophenoxyphenyl ether, bisaminophenoxybiphenyl, bisaminophenoxyphenylsulfone, bisaminophenoxyphenylpropane, and the like. And diaminonaphthalene (X) is an example of the formula (5). Further, these compounds and isomers having hydrocarbon substituents can also be mentioned. Further, the present invention is not limited to these, and it may represent two or more kinds of amine compounds represented by the general formula (26).

Organic anthraquinone represented by the formula (27) used in the present invention is an organic phosphorus compound in which hydrogen which is reactive with a functional group such as quinone, glycidyl and vinyl group is bonded to a phosphorus atom. Specifically, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), diphenylphosphine oxide, CPHO (manufactured by Nippon Kagaku Kogyo K.K., Phosphine oxide) and the like.

The organic phosphorus compounds represented by the formula (28) used in the present invention are phosphorus-containing phenol compounds obtained by reacting hydrogen and quinones, which are the activities of organic phosphorus compounds represented by the formula (27). Specifically, HCA-HQ 10- (2,5-dihydroxyphenyl) -10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), 10- (2,7- 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, PPQ (diphenylphosphinylhydroquinone, manufactured by Hokka Kagaku Kogyo K.K.), diphenylphosphinylnaphthoquinone , CPHO-HQ (cyclooctylenephosphinyl-1,4-benzenediol, manufactured by Nippon Kagaku Kogyo K.K.), cyclooctylenephenylphosphinyl-1,4-naphthalenediol, and JP-A-2002-265562 Containing phosphorus-containing phenol compounds and the like. In the present invention, any of those represented by Chemical Formula (27) and / or Chemical Formula (28) may be used, but not limited thereto, and two or more kinds may be used.

The phosphorus-containing phenol compounds obtained by reacting quinones with active hydrogen bonded to phosphorus atoms are disclosed, for example, in Japanese Patent Laid-Open Publication No. H05-214068, Zh.Obshch. Khim. , Pp. 2415 to 2418 (1972), Japanese Patent Application Laid-Open No. S60-126293, Japanese Patent Application Laid-Open No. S61-236787, and Japanese Patent Application Laid-Open No. H05-331179. At this time, operations such as purification and recrystallization are required to extract only the produced polyfunctional phosphorus-containing phenol compounds. However, if an organic phosphorus compound in which an active hydrogen atom is bonded to a phosphorus atom is adequately left, such an operation is not required, and the viscosity of the epoxy resin after the reaction may be lowered while increasing the phosphorus content of the epoxy resin.

The epoxy resin which reacts with the amine compound represented by the formula (26) and the organic phosphorous compound represented by the formula (27) and / or the formula (28) is preferably a glycidyl ether group.

Specific examples of the epoxy resin include Epototo YDC-1312, ZX-1027 (a hydroquinone type epoxy resin manufactured by Toto Kasei Corporation), ZX-1251 (a biphenol type epoxy resin manufactured by Toto Kasei Kabushiki Kaisha) Eptoto YD-900, Eptoto YD-8125, Eptoto YD-825GS, Eptoto YD-011, Eptoto YD-900 and Eptoto YD-901 Eptotol YDF-870GS, Eptotol YDF-2001 (BPF type epoxy resin, product of Tohto Kasei Kabushiki Kaisha), epoxy resin (BPF type epoxy resin) (Phenol novolak type epoxy resin, manufactured by Toto Kasei Kabushiki Kaisha), Ecotto YDCN-701 (cresol novolak type epoxy resin, manufactured by Toto Kasei K.K.), ZX-1201 Bisphenol fluorene type epoxy resin), NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkylphe ESN-155, Epoxy Resin Epoxy Resin), EPPN-501H, EPPN-502H (polyfunctional epoxy resin manufactured by Nippon Kayaku K.K.), ZX-1355 (naphthalene diol type epoxy resin manufactured by Toto Kasei Kabushiki Kaisha) ESN-355, ESN-375 (a dinaphthol aralkyl type epoxy resin, product of Tohto Kasei Co., Ltd.), ESN-475V, ESN-485 (alpha naphthol aralkyl type epoxy resin, manufactured by Toto Kasei K.K.), and the like, but not limited to these, and two or more kinds may be used in combination.

The reaction of the epoxy resin with the amine compound represented by the formula (26) and the organic phosphorus compound represented by the formula (27) and / or the formula (28) can be carried out by a known method and the reaction temperature is preferably from 100 ° C to 200 ° C, Can be carried out under stirring at 120 ° C to 180 ° C. An epoxy resin or an amine compound or an organic phosphorus compound may be reacted and then the remaining amine compound or an organic phosphorus compound may be reacted or an epoxy resin and an amine compound and an organic phosphorus compound may be simultaneously reacted.

The reaction time can be determined by measuring the epoxy equivalence. The measurement can be performed by the JIS K7236 method. The epoxy equivalent is increased by the reaction of the epoxy resin with the amine compound and the organic phosphorus-containing compound, and the end point of the reaction can be determined by comparison with the theoretical epoxy equivalent.

In addition, when the reaction rate is low, productivity can be improved by using a catalyst as needed. Specific examples thereof include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, Phosphonium salts such as phenylphosphonium bromide, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole.

In the reaction, a modifying agent such as polyhydric phenols may be used at the same time so long as the physical properties of the present invention are not impaired. Examples of the polyhydric phenols include divalent phenols such as bisphenol A, bisphenol F, bisphenol C, bisphenol Z, bisphenol S and biphenol, phenol novolac resins, cresol novolac resins, naphthol novolak resins, naphthol aralkyl resins, And the like.

Examples of the curing agent of the composition of the present invention include curing agents for commonly used epoxy resins such as various polyhydric phenol resins and acid anhydrides typified by phenol novolac resins, amines represented by DICY, hydrazides, and acidic polyesters These curing agents may be used alone or in combination of two or more.

In the composition of the present invention, a curing accelerator such as a tertiary amine, a quaternary ammonium salt, a phosphine, an imidazole or the like may be added as necessary. If necessary, a reinforcing material such as an inorganic filler, glass cloth or aramid fiber, a filler, a pigment and the like may be blended.

The properties of the laminate obtained using the novel flame retardant epoxy resin of the present invention were evaluated, and it was found that the flame retardancy was high and the heat resistance was high. The epoxy resin, the epoxy resin composition and the cured product thereof can be used as a resin composition for producing a copper clad laminate used for an electronic circuit board, an electronic component Moldings, moldings, adhesives, film materials, materials for electrical insulation paints, and the like.

Example

General

The present invention is specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The laminate was prepared under the following conditions. A resin varnish having the composition shown in Table 1 was prepared using the obtained epoxy resin, a curing agent and, if necessary, a curing accelerator, and this resin varnish was impregnated with glass cloth (WEA7628, manufactured by Nitto Boseki Co., Ltd.) , And dried by heating at 150 DEG C for 5 minutes to obtain a prepreg.

Four sheets of these prepregs were laminated, and a copper foil (3EC-III, manufactured by Mitsui Kinzoku Kogyo K.K.) having a thickness of 35 탆 was disposed on both sides thereof to prepare a laminate. The laminate was heated and pressed under the conditions of 170 DEG C and 20 kgf / cm < 2 > for 70 minutes to produce a laminate. The flame retardancy was measured according to UL (Underwriter Laboratorics) standard. The peeling strength of the copper foil was measured in accordance with JIS C 6481 5.7. Further, the glass transition temperature of the cured product was measured with an Exster 6000 DSC manufactured by SSI Nanotechnology Co., Ltd. at a rate of 10 ° C / min.

Example 1

575.5 parts by weight of YDPN-638, 140.0 parts by weight of YDF-170 250.0, 140.0 parts by weight of HCA, 100 parts by weight of Ethacure 100 (trade name, manufactured by Nippon Shokubai Co., Ltd.) were added to a glass separable flask equipped with a stirrer, a thermometer, (Manufactured by Ethyl Corporation, diethyltoluene diamine), and the mixture was stirred while heating with nitrogen gas and dissolved by heating. 0.1 part by weight of triphenylphosphine was added and reacted at 150 DEG C for 4 hours. The obtained epoxy resin had an epoxy equivalent of 275.9 g / eq and a phosphorus content of 2.0 wt%. GPC and FTIR of the obtained epoxy resin are shown in Fig. 1 and Fig. The curing agent (DICY) and the curing accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate was evaluated by the method described in the general description of the examples. The evaluation results of the laminate are shown in Table 1.

Example 2

300.0 parts by weight of YD-128, 500.4 parts by weight of YDPN-638, 154.6 parts by weight of HCA, 15.0 parts by weight of BPA (bisphenol A, manufactured by Shin-Ten Tetsu Kagaku K.K.) and 30.0 parts by weight of ETHACURE 100 , And triphenylphosphine (0.2 part by weight). The obtained epoxy resin had an epoxy equivalent of 299.8 g / eq and a phosphorus content of 2.2% by weight. The curing agent (DICY) and the curing accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate was evaluated by the method described in the general description of the examples. The evaluation results of the laminate are shown in Table 1.

Example 3

299.6 parts by weight of YD-128, 504.5 parts by weight of YDPN-638, 143.7 parts by weight of HCA, 16.0 parts by weight of HCA-HQ, 15.0 parts by weight of BPA, 21.2 parts by weight of Ethacure 100, The procedure of Example 1 was otherwise repeated. The obtained epoxy resin had an epoxy equivalent of 301.8 g / eq and a phosphorus content of 2.2 wt%. The curing agent (DICY) and the curing accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate was evaluated by the method described in the general description of the examples. The evaluation results of the laminate are shown in Table 1.

Example 4

42.0 parts by weight of HCA and 98.0 parts by weight of toluene were placed in the same apparatus as in Example 1 and heated to dissolve. And 27.7 parts by weight of 1,4-naphthoquinone were added in portions while paying attention to the exothermic reaction. After almost no reaction heat was generated, the temperature was raised, and the reaction was maintained at the reflux temperature for 2 hours. 895.3 parts by weight of ESN-485 and 35.0 parts by weight of TSB-HB (3,3'-dimethyl-4,4'-diaminobiphenyl, manufactured by Wakayama Seika Kogyo K.K.) were melted while removing the solvent. And 0.1 part by weight of triphenylphosphine were mixed and reacted at 160 DEG C for 4 hours. The obtained epoxy resin had an epoxy equivalent of 458.3 g / eq and a phosphorus content of 0.6 wt%. GPC and FTIR of the obtained epoxy resin are shown in Fig. 3 and Fig. The curing agent (DICY) and the curing accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate was evaluated by the method described in the general description of the examples. The evaluation results of the laminate are shown in Table 1.

Comparative Example 1

250.0 parts by weight of YDF-170, 547.5 parts by weight of YDPN-638, 140.0 parts by weight of HCA, 62.5 parts by weight of BRG-557 (phenol novolak resin available from Showa Kobunshi Co., Ltd.) Phosphine was changed to 0.2 part by weight. The obtained epoxy resin had an epoxy equivalent of 297.5 g / eq and a phosphorus content of 2.0 wt%. The curing agent (DICY) and the curing accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate was evaluated by the method described in the general description of the examples. The evaluation results of the laminate are shown in Table 1.

Comparative Example 2

The same procedure as in Example 1 was conducted except that 761.0 parts by weight of YDPN-638, 209.0 parts by weight of HCA, 30.0 parts by weight of BPA and 0.2 parts by weight of triphenylphosphine were used in the same apparatus as in Example 1. [ The obtained epoxy resin had an epoxy equivalent of 327.4 g / eq and a phosphorus content of 3.0 wt%. The curing agent (DICY) and the curing accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate was evaluated by the method described in the general description of the examples. The evaluation results of the laminate are shown in Table 1.

Comparative Example 3

42.0 parts by weight of HCA and 98.0 parts by weight of toluene were placed in the same apparatus as in Example 1 and heated to dissolve. And 27.7 parts by weight of 1,4-naphthoquinone were added in portions while paying attention to the exothermic reaction. After almost no reaction heat was generated, the temperature was raised, and the reaction was maintained at the reflux temperature for 2 hours. 930.3 parts by weight of ESN-485 were added and melted while removing the solvent. And 0.1 part by weight of triphenylphosphine were mixed and reacted at 160 DEG C for 4 hours. The obtained epoxy resin had an epoxy equivalent of 315.2 g / eq and a phosphorus content of 0.6 wt%. The curing agent (DICY) and the curing accelerator (2E4MZ) were added to the obtained epoxy resin in the ratio shown in Table 1, and the laminate was evaluated by the method described in the general description of the examples. The evaluation results of the laminate are shown in Table 1.

Table 1

Figure 112009068624829-pct00029

As is apparent from the test results of Examples and Comparative Examples and the physical properties described in Comparative Examples of Table 1, the use of the novel flame retardant epoxy resin of the present invention resulted in high flame retardancy and high heat resistance even when phosphorus content was equivalent. In the comparison between Example 1 and Comparative Example 1, the epoxy resin of the present invention obtained by reacting with Ethacure 100 had a high flame retardancy even though the phosphorus content was not changed, and the heat resistance was also high compared with the glass transition temperature. Also in Example 4 and Comparative Example 3, the epoxy resin of the present invention obtained by reacting TSB-HB was remarkably improved in flame retardancy and heat resistance.

As can be seen from the blending amount of the curing catalyst 2E4MZ used, the epoxy resin of the present invention is also improved in reactivity. As described above, the novel flame retardant epoxy resin and the novel flame retardant epoxy resin composition of the present invention have flame retardancy at a low content of phosphorus and excellent physical properties such as heat resistance and reactivity. Therefore, the electric insulation material And is suitable for sealing materials, molding materials, mold materials, adhesives, and film materials used in electronic parts, and is also effective as a material for electrical insulation paint.

The novel flame retardant epoxy resin and the novel flame retardant epoxy resin composition obtained by the present invention have flame retardancy at low phosphorus content and excellent physical properties such as heat resistance and reactivity. Therefore, electric insulating materials including copper clad laminate used for electronic circuit boards, Moldings, moldings, adhesives, and films used in electronic parts, and furthermore, it is suitable as a material for electrical insulation paints.

Claims (9)

A novel flame-retardant epoxy resin having an epoxy equivalent weight of 200 g / eq to 1000 g / eq containing nitrogen and phosphorus having a specific structure represented by formula (1) Formula 1
Figure 112015036230677-pct00030
 (Wherein X represents at least one chemical structure selected from the group consisting of the following formulas (2) to (5) Y represents at least one chemical structure selected from the group consisting of chemical formulas (6) to (9) described later, and n represents an integer of 1 to 6 in the case of X in the formula (2), X denotes an integer of 1 to 10 in the case of the formula (3) or 4, and X denotes an integer of 1 to 8 in the case of the formula (5)); (2)
Figure 112015036230677-pct00031
 (Wherein R1 represents hydrogen or a hydrocarbon group, which may be the same or different from each other, may be a linear, branched or cyclic form, and a represents an integer of 0, 1, 2, 3, 4 or 5); (3)
Figure 112015036230677-pct00032
 Branched or cyclic, a represents an integer of 0, 1, 2, 3 or 4, and Z represents methylene, , Oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any of the following formulas (10) to (19)); Formula 4
Figure 112015036230677-pct00033
 (Wherein R1 represents hydrogen or a hydrocarbon group, which may be the same or different from each other, may be in the form of a straight chain, branched or cyclic, and a represents an integer of 0, 1, 2, 3 or 4); Formula 5
Figure 112015036230677-pct00034
 And b is an integer of 0, 1, 2, 3, 4, 5, 6 or 7, and R < 1 > is hydrogen or a hydrocarbon group, Lt; / RTI > 6
Figure 112015036230677-pct00035
 Branched or cyclic, c represents an integer of 0, 1, 2, 3 or 4, and G represents a hydrogen atom or a hydrocarbon group, which may be the same or different, Wherein at least one of the molecules has the formula (21) or (22) described below, d represents an integer of 1, 2, 3, 4 or 5, and c + d? 5 to be); Formula 7
Figure 112015036230677-pct00036
 Branched or cyclic, c1 and c2 represent integers of 0, 1, 2, 3 or 4, and d represents an integer of 1 to 3, provided that R 1 and R 2 are the same or different and each represents a hydrogen atom or a hydrocarbon group, E is an integer of 0, 1, 2, 3 or 4, c1 + e? 4, c2 + d? 5, and G represents an integer of 1, 2, 3, 4 or 5, 20 to 23, and at least one of the molecules represents a formula 21 described later or a formula 22 described later); 8
Figure 112015036230677-pct00037
 R 2 represents hydrogen or a hydrocarbon group, which may be the same or different from each other, may be a linear, branched or cyclic form, c 1 and c 2 represent an integer of 0, 1, 2, 3 or 4, F is an integer of 1, 2, 3 or 4, c1 + e? 4, c2 + f? 4, and G is a group represented by the following general formulas Z represents at least one of methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or a group represented by the following formulas (10) to 19, and m represents an integer of 1, 2, 3, ...); Formula 9
Figure 112015036230677-pct00038
 Branched or cyclic, and G represents any one of the following general formulas (20) to (23), wherein at least one of R 1 and R 2 in the molecule is a hydrogen atom or a hydrocarbon group, and R 2 is hydrogen or a hydrocarbon group, G is an integer of 0, 1, 2, 3, 4, 5 or 6, h1 and h2 are integers of 0, 1, 2, 3, 4 or 5, I is an integer of 1, 2, 3, 4, 5 or 6, g + h1? 6, i + h2? 6, Z is methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene , Biphenyl or any one of the following formulas (10) to (19), and 1 represents an integer of 1, 2, 3, ...); 10
Figure 112015036230677-pct00039
 Formula 11
Figure 112015036230677-pct00040
 Formula 12
Figure 112015036230677-pct00041
 Formula 13
Figure 112015036230677-pct00042
 Formula 14
Figure 112015036230677-pct00043
 Formula 15
Figure 112015036230677-pct00044
 Formula 16
Figure 112015036230677-pct00045
 Formula 17
Figure 112015036230677-pct00046
 (Wherein D represents benzene, naphthalene, anthracene, phenanthrene or biphenyl); 18
Figure 112015036230677-pct00047
 (Wherein q represents an integer of 0, 1, 2, 3, ...); Formula 19
Figure 112015036230677-pct00048
 (Wherein W represents methylene, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of formulas (10) to (17); 20
Figure 112015036230677-pct00049
 Formula 21
Figure 112015036230677-pct00050
 (Wherein j is 1, and R 3 and R 4 are hydrogen or a hydrocarbon group, which may be the same or different, may be a straight chain, branched chain or cyclic structure, or R 3 and R 4 may combine to form a cyclic structure ); Formula 22
Figure 112015036230677-pct00051
 (Wherein j is 1, and R 3 and R 4 are hydrogen or a hydrocarbon group, which may be the same or different, may be a straight chain, a branched chain or a ring, or a combination of R 3 and R 4 to form a cyclic structure B represents benzene, naphthalene, anthracene, phenanthrene, and hydrocarbon substituents thereof, and Y represents any one of formulas (6) to (9); Formula 23
Figure 112015036230677-pct00052
 (Wherein R represents an integer of 0, 1, 2, 3, ..., E represents benzene, naphthalene, anthracene, phenanthrene, biphenyl and hydrocarbon substituents thereof, (6) to (9); 24
Figure 112015036230677-pct00053
 Branched or cyclic, c1 and c2 represent an integer of 0, 1, 2, 3 or 4, and Z represents a hydrogen atom or a hydrocarbon group, And m represents an integer of 1, 2, 3, ...); and R < 2 > represents a hydrogen atom or an alkyl group; 25
Figure 112015036230677-pct00054
 (Wherein R 2 represents hydrogen or a hydrocarbon group, which may be the same or different from each other, may be linear, branched or cyclic, h 1 and h 2 are integers of 0, 1, 2, 3, 4 or 5, Z represents any of methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl or any one of formulas (10) to (19), and 1 represents an integer of 1, 2, 3,. A novel flame-retardant epoxy resin containing the epoxy resin according to claim 1 obtained by reacting an amine compound represented by the formula (26) with an epoxy resin and an organic phosphorus compound represented by the formula (27) or (28) 26
Figure 112015036230677-pct00055
 (Wherein X represents any one of formulas (2) to (5), and n represents an integer of 1, 2, 3, ...); 27
Figure 112015036230677-pct00056
 (Wherein j is 1, and R 3 and R 4 are hydrogen or a hydrocarbon group, which may be the same or different, may be a straight chain, a branched chain or a ring, or a combination of R 3 and R 4 to form a cyclic structure ); 28
Figure 112015036230677-pct00057
 (Wherein j is 1, and R 3 and R 4 are hydrogen or a hydrocarbon group, which may be the same or different, may be a straight chain, branched chain or cyclic structure, or R 3 and R 4 may combine to form a cyclic structure And B represents benzene, naphthalene, anthracene, phenanthrene, and hydrocarbon substituents thereof. The method according to claim 1, Wherein the epoxy equivalent is 200 g / eq to 1000 g / eq, the phosphorus content is 0.2% to 8.0%, and the nitrogen content is 0.1% to 4.0%. 3. The method of claim 2, Wherein the epoxy equivalent is 200 g / eq to 1000 g / eq, the phosphorus content is 0.2% to 8.0%, and the nitrogen content is 0.1% to 4.0%. A novel flame retardant epoxy resin composition comprising the novel flame retardant epoxy resin according to any one of claims 1 to 4 as an essential component and a curing agent. An epoxy resin laminate obtained by using the novel flame retardant epoxy resin composition according to claim 5. An epoxy resin encapsulant obtained by using the novel flame retardant epoxy resin composition according to claim 5. An epoxy resin mold material obtained by using the novel flame retardant epoxy resin composition according to claim 5. A novel flame retardant epoxy resin obtained by curing the flame-retardant epoxy resin composition according to claim 5.
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