KR20120000103A - Epoxy resin, epoxy resin composition, and cured object - Google Patents

Epoxy resin, epoxy resin composition, and cured object Download PDF

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KR20120000103A
KR20120000103A KR1020117025323A KR20117025323A KR20120000103A KR 20120000103 A KR20120000103 A KR 20120000103A KR 1020117025323 A KR1020117025323 A KR 1020117025323A KR 20117025323 A KR20117025323 A KR 20117025323A KR 20120000103 A KR20120000103 A KR 20120000103A
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epoxy resin
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resin composition
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아츠히코 카타야마
니란잔 쿠마르 스레스타
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신닛테츠가가쿠 가부시키가이샤
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    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

염소 함유량이 낮고, 내열성, 기계 강도가 뛰어나며, 도료, 적층판, 접착제 등에 유용한 에폭시수지, 에폭시수지 조성물, 및 경화물을 제공한다.
디에폭시에틸벤젠과 페놀성 수산기를 2개 가지는 화합물을 반응시켜 얻어지는 에폭시수지이며, 식(1)로 표시되는 에폭시수지 또는 이것을 주성분으로 하는 에폭시수지에 따른 것이다. 식(1)에 있어서, A는 페놀성 수산기를 2개 가지는 화합물에 유래하는 잔기이다. 또한 이 에폭시수지와 경화제를 포함하는 에폭시수지 조성물에 따른 것이다.Provided is an epoxy resin, an epoxy resin composition, and a cured product having low chlorine content, excellent heat resistance and mechanical strength, and are useful for paints, laminates, adhesives, and the like.
It is an epoxy resin obtained by making diepoxyethylbenzene and the compound which has two phenolic hydroxyl groups react, It depends on the epoxy resin represented by Formula (1), or the epoxy resin which has this as a main component. In Formula (1), A is a residue derived from the compound which has two phenolic hydroxyl groups. The present invention also relates to an epoxy resin composition containing the epoxy resin and a curing agent.

Description

에폭시수지, 에폭시수지 조성물 및 경화물{EPOXY RESIN, EPOXY RESIN COMPOSITION, AND CURED OBJECT}Epoxy resin, epoxy resin composition and cured product {EPOXY RESIN, EPOXY RESIN COMPOSITION, AND CURED OBJECT}

본 발명은 도료, 적층판, 접착제 등에 유용한 에폭시수지, 에폭시수지 조성물, 및 경화물에 관한 것이다.The present invention relates to epoxy resins, epoxy resin compositions, and cured products useful for paints, laminates, adhesives, and the like.

종래부터 도료, 적층판, 접착제 등에 사용되고 있는 에폭시수지는 에폭시 당량이 낮고, 경화물의 밀착성이나 인성(靭性)이 좋지 않기 때문에, 비스페놀A형 에폭시수지 혹은 비스페놀F형 에폭시수지를 비스페놀A, 비스페놀F 혹은 테트라브롬비스페놀A 등으로 고분자화한 이른바 고분자 에폭시수지가 일반적으로 사용되고 있다.Epoxy resins conventionally used in paints, laminates and adhesives have a low epoxy equivalent and poor adhesion and toughness of the cured product. So-called polymer epoxy resins polymerized with bromine bisphenol A or the like are generally used.

그러나 이 고분자 에폭시수지는 액상 수지에 비해 밀착성은 뛰어나지만 내열성, 기계 강도가 떨어진다는 결점을 가지고 있다. 이들의 개선책으로서, 특허문헌 1에는 2관능 에폭시수지와 2관능 페놀류를 촉매로서 알칼리 금속 화합물과 이미다졸류를 병용하고, 합성 용매로서 비점 130℃이상의 용매를 사용하여, 합성시의 고형분 농도를 50중량%이하로 함으로써, 분지(分枝)가 적은 고분자량 에폭시 중합체로 하여, 강도를 높이는 방법을 개시하고 있다. 사용하는 2관능 에폭시수지에는 제한이 없다고 하고 있지만, 예시되어 있는 에폭시수지는 비스페놀A형 에폭시수지, 비스페놀F형 에폭시수지, 비스페놀S형 에폭시수지, 지환식 에폭시수지, 지방족 쇄상 에폭시수지, 그 외에 2관능 페놀류의 디글리시딜에테르화물, 2관능 알코올류의 디글리시딜에테르화물, 및 그들의 할로겐화물, 수소 첨가물 등의 일반적인 것이며, 에폭시수지의 구조에 착목하고 있지 않다.However, this polymer epoxy resin has excellent adhesiveness compared to liquid resin, but has the disadvantage of poor heat resistance and mechanical strength. As these improvement measures, Patent Document 1 uses an alkali metal compound and imidazole as a catalyst as a bifunctional epoxy resin and a bifunctional phenol, and uses a solvent having a boiling point of 130 ° C. or higher as a synthetic solvent to obtain a solid content concentration at the time of synthesis. By setting it as weight% or less, the method of making high molecular weight epoxy polymer with few branches, and improving strength is disclosed. Although there is no restriction | limiting in the bifunctional epoxy resin to be used, the illustrated epoxy resin is bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, etc. It is a general thing, such as diglycidyl ether compound of functional phenols, the diglycidyl ether compound of bifunctional alcohol, these halides, hydrogenated substance, etc., and does not take the structure of an epoxy resin.

또한 특허문헌 2에는 2관능 에폭시수지(X)와 2가 페놀화합물(Y)을 촉매의 존재하에 반응시켜 얻어지고, 하기 (a)~(d)의 요건:In addition, Patent Document 2 obtains by reacting a bifunctional epoxy resin (X) and a divalent phenol compound (Y) in the presence of a catalyst, and the requirements of the following (a) to (d):

(a)질량평균 분자량이 30,000~200,000(a) Mass average molecular weight is 30,000-200,000

(b)에폭시 당량이 5,000~20,000g/당량(b) epoxy equivalent 5,000-20,000 g / equivalent

(c)잔존 2관능 에폭시수지(X) 함유량이 1000ppm이하(c) Content of residual bifunctional epoxy resin (X) is 1000 ppm or less

(d)잔존 2가 페놀화합물(Y) 함유량이 100ppm이하(d) Content of residual dihydric phenolic compound (Y) is 100ppm or less

를 만족시키는 고분자량 에폭시수지와, 에폭시기와 반응하는 경화제로 이루어지는 고분자량 에폭시수지 조성물이, 저용출성이며, 내약품성, 내용제성, 내열성, 성형성, 가요성(可撓性), 내충격성, 밀착성, 접착성이 뛰어난 경화물을 부여하는 것을 개시하고 있다.The high molecular weight epoxy resin composition comprising a high molecular weight epoxy resin and a curing agent reacting with the epoxy group has low elution, and has chemical resistance, solvent resistance, heat resistance, moldability, flexibility, impact resistance, It discloses to provide hardened | cured material excellent in adhesiveness and adhesiveness.

그러나 잔존 원료를 저감시키는 것이 경화물의 물성을 향상시키는 것은 주지의 사실이다. 또한 사용하는 2관능 에폭시수지에는 제한이 없다고 하고 있지만, 예시되어 있는 에폭시수지는 비스페놀A형 에폭시수지, 비스페놀F형 에폭시수지, 비스페놀S형 에폭시수지, 테트라브로모비스페놀A형 에폭시수지 등의 비스페놀형 에폭시수지, 4,4'-비페놀, 3,3',5,5'-테트라메틸-4,4'-비페놀과 에피할로히드린의 축합 반응에 의해 얻어지는 비페놀형 에폭시수지, 카테콜, 레조르신, 하이드로퀴논 등의 단환 2가 페놀의 디글리시딜에테르, 디히드록시나프탈렌의 디글리시딜에테르, 상기 방향족 에폭시수지의 방향환을 수소 첨가한 에폭시수지, 2가 알코올의 디글리시딜에테르, 지환식 에폭시수지, 프탈산, 이소프탈산, 테트라하이드로프탈산, 헥사하이드로프탈산 등의 2가 카르본산의 디글리시딜에스테르 등의 일반적인 것으로, 에폭시수지의 구조에 착목하고 있지 않다.However, it is well known that reducing the remaining raw material improves the physical properties of the cured product. Although there is no restriction on the bifunctional epoxy resin to be used, the illustrated epoxy resins are bisphenol-type epoxy resins such as bisphenol-A epoxy resin, bisphenol-F epoxy resin, bisphenol-S epoxy resin and tetrabromobisphenol-A epoxy resin. Epoxy resin, 4,4'-biphenol, 3,3 ', 5,5'-tetramethyl-4,4'-biphenol and a biphenol type epoxy resin obtained by condensation reaction of epihalohydrin, cate Diglycidyl ether of monocyclic dihydric phenol, diglycidyl ether of dihydroxy naphthalene, epoxy resin which hydrogenated the aromatic ring of the said aromatic epoxy resin, diol of dihydric alcohol, such as chol, resorcinol, hydroquinone, etc. It is common to diglycidyl ester of dihydric carboxylic acid such as glycidyl ether, alicyclic epoxy resin, phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, etc. It is not.

또한 특허문헌 1, 2에 예시되어 있는 에폭시수지는 에피클로로히드린을 원료로서 사용하기 때문에, 수십에서 수천 ppm의 염소를 포함하고 있다. 전기·전자부품 용도에서는 염소 농도가 낮은 에폭시수지가 요망되고 있어, 염소 함유량이 낮으면서, 내열성을 가지는 고분자 에폭시수지의 출현이 기대되고 있다.In addition, since the epoxy resin illustrated by patent documents 1 and 2 uses epichlorohydrin as a raw material, it contains chlorine of several tens to thousands ppm. Epoxy resins with low chlorine concentrations are desired in electrical and electronic component applications, and high-temperature epoxy resins with low chlorine content are expected.

일본국 공개특허공보 평11-147930호Japanese Patent Laid-Open No. 11-147930 일본국 공개특허공보 2006-36801호Japanese Laid-Open Patent Publication 2006-36801

따라서, 본 발명이 해결하고자 하는 과제는, 염소 함유량이 낮고, 내열성, 기계 강도가 뛰어나며, 도료, 적층판, 접착제 등에 유용한 에폭시수지, 에폭시수지 조성물, 및 경화물을 제공하는 것에 있다.Accordingly, an object of the present invention is to provide an epoxy resin, an epoxy resin composition, and a cured product having low chlorine content, excellent heat resistance and mechanical strength, and are useful for paints, laminates, adhesives, and the like.

본 발명자 등은 상술한 종래기술에서의 실상에 비추어, 염소 함유량이 낮고, 내열성이 뛰어나며, 도료, 적층판, 접착제 등에 유용한 에폭시수지를 얻기 위해 예의 연구한 결과, 에폭시수지로서 디에폭시에틸벤젠과 페놀성 수산기를 2개 가지는 화합물을 반응시켜 얻어지는 에폭시수지를 사용함으로써, 상기의 과제가 해결되는 것을 찾아내어, 본 발명을 완성하기에 이르렀다.In light of the above-described conventional state of the art, the present inventors have made diepoxyethylbenzene and phenolic properties as epoxy resins as a result of diligent research to obtain epoxy resins having low chlorine content, excellent heat resistance, and useful for paints, laminates and adhesives. By using the epoxy resin obtained by making the compound which has two hydroxyl groups react, it discovered that the said subject was solved and came to complete this invention.

본 발명은 하기 일반식(1)로 표시되는 에폭시수지에 관한 것이다.The present invention relates to an epoxy resin represented by the following general formula (1).

Figure pct00001
Figure pct00001

여기서, A는 치환기를 가지고 있어도 되는 2가의 방향족기를 나타내고, n은 1에서 15의 수를 나타낸다.Here, A represents the bivalent aromatic group which may have a substituent, n shows the number of 1-15.

또한 본 발명은 디에폭시에틸벤젠과 페놀성 수산기를 2개 가지는 화합물을 반응시켜 얻어지고, 상기 일반식(1)로 표시되는 에폭시수지를 주성분으로서 포함하는 에폭시수지이다. 이 에폭시수지는 부성분을 포함할 수 있고, 부성분으로서 하기 일반식(2)로 표시되는 에폭시수지를 포함하는 것이 바람직하다.In addition, the present invention is an epoxy resin obtained by reacting a diepoxyethylbenzene with a compound having two phenolic hydroxyl groups, and containing the epoxy resin represented by the general formula (1) as a main component. This epoxy resin can contain a subcomponent, and it is preferable to contain the epoxy resin represented by following General formula (2) as a subcomponent.

Figure pct00002
Figure pct00002

여기서, A 및 n은 일반식(1)과 동의(同意)이다. B1은 하기 식(3) 또는 하기 식(4)로 표시되는 2가의 기이며, B2는 하기 식(5) 또는 하기 식(6)으로 표시되는 2가의 기인데, B1이 식(3)으로 표시되는 2가의 기이면서, B2가 (5)로 표시되는 2가의 기인 경우를 제외한다.Here, A and n are synonymous with General formula (1). B 1 is a divalent group represented by the following formula (3) or (4), B 2 is a divalent group represented by the following formula (5) or the following formula (6), and B 1 is a formula (3 Except for the divalent group represented by), B 2 is a divalent group represented by (5).

Figure pct00003
Figure pct00003

또한 본 발명은 디에폭시에틸벤젠과 페놀성 수산기를 2개 가지는 화합물을 반응시키는 것을 특징으로 하는 에폭시수지의 제조방법에 관한 것이다. 이 제조방법으로 얻어지는 에폭시수지는 상기 일반식(1)로 표시되는 에폭시수지를 주성분으로서 포함하는 에폭시수지이며, 부성분으로서 상기 일반식(2)로 표시되는 에폭시수지를 포함하는 것이 바람직하다.The present invention also relates to a method for producing an epoxy resin, characterized by reacting a diepoxyethylbenzene with a compound having two phenolic hydroxyl groups. The epoxy resin obtained by this manufacturing method is an epoxy resin containing the epoxy resin represented by the said General formula (1) as a main component, and it is preferable to include the epoxy resin represented by the said General formula (2) as a subcomponent.

상기 에폭시수지의 제조방법에 있어서, 페놀성 수산기를 2개 가지는 화합물로서는, 비스페놀계 화합물 또는 비페놀계 화합물을 바람직하게 들 수 있다.In the manufacturing method of the said epoxy resin, a bisphenol type compound or a biphenol type compound is mentioned preferably as a compound which has two phenolic hydroxyl groups.

그리고 또한 본 발명은 상기의 에폭시수지와, 경화제를 함유하는 것을 특징으로 하는 에폭시수지 조성물에 관한 것이다. 이 에폭시수지 조성물은 또한 경화 촉진제를 함유하는 것이 좋다. 또한 본 발명은 이 에폭시수지 조성물을 성형 경화시켜 이루어지는 것을 특징으로 하는 에폭시수지 경화물에 관한 것이다.The present invention also relates to an epoxy resin composition comprising the above epoxy resin and a curing agent. It is preferable that this epoxy resin composition also contains a hardening accelerator. Moreover, this invention relates to the epoxy resin hardened | cured material formed by shape-hardening this epoxy resin composition.

본 발명에 의하면, 염소 함유량이 낮고, 내열성, 기계 강도가 뛰어나며, 도료, 적층판, 접착제 등에 유용한 에폭시수지, 에폭시수지 조성물, 및 경화물을 제공할 수 있다.ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin, epoxy resin composition, and hardened | cured material which are low in chlorine content, are excellent in heat resistance and mechanical strength, and are useful for a coating material, a laminated board, an adhesive agent, etc. can be provided.

도 1은 본 발명의 에폭시수지(A)의 1H-NMR 스펙트럼을 나타낸다.1 shows the 1 H-NMR spectrum of the epoxy resin (A) of the present invention.

우선, 본 발명의 에폭시수지에 대하여 설명한다.First, the epoxy resin of this invention is demonstrated.

본 발명의 에폭시수지는 상기 일반식(1)로 표시된다. 여기서, A는 치환기를 가지고 있어도 되는 2가의 방향족기이며, 페놀성 수산기를 2개 가지는 화합물(이하, 2가의 페놀화합물이라고도 칭함)로부터 생기는 기이므로, 후술하는 2가의 페놀화합물로부터도 이해된다.The epoxy resin of this invention is represented by the said General formula (1). Here, since A is a divalent aromatic group which may have a substituent and is formed from a compound having two phenolic hydroxyl groups (hereinafter also referred to as a divalent phenol compound), it is also understood from the divalent phenol compound described below.

이들 바람직한 2가의 방향족기로서는 페닐렌기, 나프틸렌기, 안트라센기, 디페닐메탄기, 1,1-디페닐에탄기, 1,1,1-메틸디페닐에탄기, 디페닐에테르기, 디페닐술피드기, 디페닐술폭시드기, 디페닐술폰기, 디페닐케톤기, 페닐벤조에이트기, 비페닐기, 스틸벤기, 디아조벤젠기, 아닐린벤질리덴기 및 이들의 유도체 등이 예시된다. 여기서, 안트라센기는 안트라센으로부터 2개의 수소가 제거되어 생기는 기를 말하고, 디페닐메탄기, 1,1-디페닐에탄기, 1,1,1-메틸디페닐에탄기, 디페닐에테르기, 디페닐술피드기, 디페닐술폭시드기, 디페닐술폰기, 디페닐케톤기, 페닐벤조에이트기, 비페닐기, 스틸벤기, 디아조벤젠기, 아닐린벤질리덴기는 -Ph-X-Ph-로 표시되는 기를 말하고, Ph는 벤젠환이며, X는 CH2, C2H4, C3H6, O, S, SO, SO2, CO, COO, 단결합, C2H2, N2 또는 CHN이다.As these preferable bivalent aromatic groups, a phenylene group, a naphthylene group, an anthracene group, a diphenylmethane group, a 1, 1- diphenyl ethane group, a 1, 1, 1- methyl diphenyl ethane group, a diphenyl ether group, diphenyl Sulfide group, diphenyl sulfoxide group, diphenyl sulfone group, diphenyl ketone group, phenyl benzoate group, biphenyl group, stilbene group, diazobenzene group, aniline benzylidene group, derivatives thereof and the like. Here, the anthracene group refers to a group formed by removing two hydrogens from anthracene, and refers to a diphenylmethane group, a 1,1-diphenylethane group, a 1,1,1-methyldiphenylethane group, a diphenylether group, and a diphenylsulfur. Feed group, diphenyl sulfoxide group, diphenyl sulfone group, diphenyl ketone group, phenyl benzoate group, biphenyl group, stilbene group, diazobenzene group, aniline benzylidene group refers to the group represented by -Ph-X-Ph- , Ph is a benzene ring, X is CH 2 , C 2 H 4 , C 3 H 6 , O, S, SO, SO 2 , CO, COO, single bond, C 2 H 2 , N 2 or CHN.

상기 2가의 방향족기는 치환기를 가질 수 있고, 바람직한 치환기로서는 메틸기, 에틸기, 알릴기, 프로파르길기, 페닐기, 벤질기 등의 탄화수소기, 메톡시기, 에톡시기, 알릴옥시기, 페녹시기 등의 알콕시기, 불소, 염소, 브롬 등의 할로겐기 등을 들 수 있다. 바람직하게는 탄소수 1~6의 알킬기, 탄소수 1~6의 알콕시기, 탄소수 6~8의 방향족 탄화수소기 또는 염소, 브롬 등의 할로겐이다.The divalent aromatic group may have a substituent, and preferred substituents include alkoxy groups such as hydrocarbon groups such as methyl group, ethyl group, allyl group, propargyl group, phenyl group and benzyl group, methoxy group, ethoxy group, allyloxy group and phenoxy group. And halogen groups such as fluorine, chlorine and bromine. Preferably they are a C1-C6 alkyl group, a C1-C6 alkoxy group, a C6-C8 aromatic hydrocarbon group, or halogen, such as chlorine and a bromine.

그 중에서도, 2가의 방향족기로서는 고내열성, 저열팽창성, 저흡습성의 관점에서, 입체 장해가 적으면서, 대칭성이 뛰어난 구조를 가지는 것이 바람직하고, 특히 2,6-나프틸렌기, 1,5-나프틸렌기, 4,4'-디페닐메탄기, 4,4'-디페닐에테르기 또는 4,4'-비페닐기가 적합하게 선택된다.Especially, as a divalent aromatic group, it is preferable to have a structure excellent in symmetry with few steric hindrances from a viewpoint of high heat resistance, low thermal expansion, and low hygroscopicity, and especially a 2, 6- naphthylene group and a 1, 5- nap Tylene group, 4,4'- diphenylmethane group, 4,4'- diphenyl ether group, or 4,4'-biphenyl group is suitably selected.

일반식(1)에 있어서, n은 1에서 15의 수를 나타내고, 바람직한 n의 값은 적용하는 용도에 따라 다르다. 이 수는 평균값(수 평균)이다. 예를 들면, 필러의 고충전율화가 요구되는 반도체 봉지재의 용도에는, 저점도인 것이 바람직하고, n의 값은 1~5, 바람직하게는 1~3, 더욱 바람직하게는 n이 1인 것이 30wt%이상 포함되는 것이다.In General formula (1), n represents the number of 1 to 15, and a preferable value of n changes with the use to apply. This number is an average value (number average). For example, it is preferable that it is low viscosity for the use of the semiconductor sealing material which requires high filling rate of a filler, The value of n is 1-5, Preferably it is 1-3, More preferably, it is 30 wt% that n is 1. That is to be included.

본 발명의 에폭시수지는, 디에폭시에틸벤젠과 페놀성 수산기를 2개 가지는 2가의 페놀화합물을 반응시킴으로써 제조할 수 있다. 이 반응에서는, 디에폭시에틸벤젠의 에폭시기가 개환하여 2가의 페놀화합물과 에테르 결합을 생기게 해 결합하여 중합한다. 이 개환은 α위치와 β위치의 어느 쪽으로부터도 개환이 일어날 수 있는데, 식(1)의 에폭시수지가 주성분이 되고, 일반식(2)의 에폭시수지가 부성분이 된다. 또한 n이 늘어나면 α위치와 β위치에서 개환한 구조 단위의 양쪽을 포함하는 에폭시수지도 소량 부성분으로서 포함된다. α위치 또는 β위치에서 개환한 구조 단위는 식(3)~식(6)에 표시된다. 여기서, 일반식(2)의 B1 및 B2가 동시에 식(3) 및 식(5)의 구조 단위를 가질 경우는 일반식(1)과 같아지므로, 그 경우는 제외된다.The epoxy resin of this invention can be manufactured by making diepoxy ethylbenzene and the bivalent phenol compound which has two phenolic hydroxyl groups react. In this reaction, an epoxy group of diepoxyethylbenzene is ring-opened to form a divalent phenol compound and an ether bond to bond and polymerize. The ring-opening can occur from either the α-position or the β-position, but the epoxy resin of formula (1) is the main component, and the epoxy resin of the general formula (2) is the minor component. When n is increased, an epoxy resin containing both of the structural units ring-opened at the α position and the β position is also included as a minor component. The structural unit ring-opened at the α position or the β position is represented by the formulas (3) to (6). Here, when the B 1 and B 2 of formula (2) at the same time have a structural unit of formula (3) and equation (5) becomes equal to the formula (1), the case is excluded.

본 발명의 에폭시수지는 식(1)의 에폭시수지 또는 이 에폭시수지를 주성분으로 하는 에폭시수지이다. 식(1)의 에폭시수지를 주성분으로 하는 에폭시수지인 경우, 부성분으로서는 식(2)의 에폭시수지가 포함된다. 또한 경우에 따라 α위치와 β위치에서 개환한 구조 단위를 포함하는 에폭시수지(이하, 에폭시수지(3)이라고도 칭함)가 포함된다. 식(1)의 에폭시수지를 주성분으로 하는 에폭시수지인 경우, 통상 식(1)의 에폭시수지는 50%이상, 바람직하게는 60%이상 포함된다. 식(2)의 에폭시수지는 50%미만, 바람직하게는 10~40% 포함된다. 또한 에폭시수지(3)의 양은 n수에 따라 변화하지만, α위치와 β위치에서 개환하는 확률이 상기 범위이므로, 대체로 그것으로부터 계산 가능하다. 그러나 많아도 50%미만이다. 또한 식(1)의 에폭시수지, 식(2)의 에폭시수지 및 에폭시수지(3)은 모두 조성식이 같고, 에폭시기 및 히드록시를 가지므로, 유사한 성질을 나타낸다.The epoxy resin of this invention is an epoxy resin of Formula (1) or an epoxy resin which has this epoxy resin as a main component. In the case of the epoxy resin which has the epoxy resin of Formula (1) as a main component, the epoxy resin of Formula (2) is contained as a subcomponent. Moreover, the epoxy resin (henceforth also called epoxy resin 3) containing the structural unit ring-opened at the (alpha) position and the (beta) position as needed is contained. In the case of the epoxy resin containing the epoxy resin of the formula (1) as a main component, the epoxy resin of the formula (1) is usually 50% or more, preferably 60% or more. The epoxy resin of Formula (2) is less than 50%, Preferably it contains 10 to 40%. In addition, although the quantity of the epoxy resin 3 changes with n numbers, since the probability of ring opening in the alpha position and the beta position is the said range, it can be calculated from it substantially. But at most it is less than 50%. Further, the epoxy resin of formula (1), the epoxy resin of formula (2), and the epoxy resin (3) all have the same compositional formula and have similar epoxy groups and hydroxy.

디에폭시에틸벤젠과 2가의 페놀화합물을 필요에 따라 촉매의 존재하, 50~200℃로 1~20시간 반응함으로써 본 발명의 에폭시수지가 얻어진다.The epoxy resin of this invention is obtained by reacting diepoxyethylbenzene and a bivalent phenolic compound at 50-200 degreeC for 1 to 20 hours in presence of a catalyst as needed.

디에폭시에틸벤젠과 2가의 페놀화합물의 반응 비율은, 디에폭시에틸벤젠과 2가의 페놀화합물의 몰비로 100/10~100/95, 바람직하게는 100/15~100/70이 되는 반응 비율이 바람직하다. 이 몰비를 조정함으로써 n수를 제어할 수 있다. 또한 디에폭시에틸벤젠을 과잉하게 사용함으로써 말단을 에폭시기로 할 수 있다.The reaction ratio of diepoxyethylbenzene and the divalent phenolic compound is preferably a reaction ratio of 100/10 to 100/95, preferably 100/15 to 100/70 in the molar ratio of diepoxyethylbenzene and the divalent phenolic compound. Do. By adjusting this molar ratio, the number of n can be controlled. Moreover, the terminal can be made into an epoxy group by using diepoxyethylbenzene excessively.

이때에 사용할 수 있는 촉매로서는, 예를 들면 수산화나트륨, 수산화칼륨 등의 알칼리 금속 수산화물, 트리에틸아민, 벤질디메틸아민 등의 제3급 아민, 테트라메틸암모늄클로라이드 등의 제4급 암모늄염, 이미다졸화합물, 트리페닐포스핀 등의 포스핀류, 테트라-n-부틸포스포늄테트라페닐보레이트 등의 포스포늄염 등을 들 수 있다. 촉매 사용량으로서는, 사용하는 촉매에 따라 다르지만, 디에폭시에틸벤젠의 중량에 대하여 0.001~3%인 것이 바람직하고, 더욱 바람직하게는 0.01%~2%이다.As the catalyst which can be used at this time, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, tertiary amines such as triethylamine and benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, and imidazole compounds And phosphonium salts such as phosphine such as triphenylphosphine and tetra-n-butylphosphonium tetraphenylborate. Although the amount of the catalyst used varies depending on the catalyst to be used, the amount of the catalyst is preferably 0.001 to 3%, more preferably 0.01% to 2% based on the weight of diepoxyethylbenzene.

반응을 행할 때에는 필요에 따라 유기 용매를 사용해도 된다. 유기 용매로서는, 예를 들면 톨루엔, 크실렌 등의 방향족 탄화수소계 용매, MIBK, MEK 등의 케톤계 용매 등을 들 수 있다. 용매의 사용량으로서는, 디에폭시에틸벤젠 및 2가의 페놀화합물의 합계 중량 100중량부에 대하여 통상 10~1000중량부, 바람직하게는 20~200중량부이다.When performing reaction, you may use an organic solvent as needed. As an organic solvent, aromatic hydrocarbon solvents, such as toluene and xylene, ketone solvents, such as MIBK and MEK, etc. are mentioned, for example. As a usage-amount of a solvent, it is 10-1000 weight part normally with respect to 100 weight part of total weights of diepoxy ethylbenzene and a bivalent phenolic compound, Preferably it is 20-200 weight part.

디에폭시에틸벤젠은 디비닐벤젠을 과산화물에 의해 에폭시화한 것을 사용할 수 있다. 에피클로로히드린을 사용하지 않기 때문에 얻어지는 화합물은 염소 함유량이 적다. 과산화물로서는, 통상의 방법에 의해 얻어지는 과산, 과산화수소, 또는 유기 과산화물을 사용할 수 있다. 디비닐벤젠이 이성체 혼합물인 경우, 이 에폭시화합물도 이성체 혼합물이 되지만 지장은 없다.Diepoxy ethylbenzene can use what epoxidized divinylbenzene with peroxide. Since epichlorohydrin is not used, the compound obtained has little chlorine content. As the peroxide, peracid, hydrogen peroxide, or organic peroxide obtained by a conventional method can be used. When divinylbenzene is an isomer mixture, this epoxy compound also becomes an isomer mixture, but it does not interfere.

본 발명의 제조방법에서 사용되는 2가의 페놀화합물은 공지의 것을 모두 사용할 수 있고, 상기한 A에 페놀성 수산기가 결합한 A(OH)2로 표시되는 2가의 페놀화합물이 사용된다. 바람직하게는 비스페놀계 화합물 또는 비페놀계 화합물이다.As the divalent phenolic compound used in the production method of the present invention, any known one can be used, and a divalent phenolic compound represented by A (OH) 2 having a phenolic hydroxyl group bonded to A can be used. Preferably, it is a bisphenol type compound or a biphenol type compound.

본 발명의 제조방법에서 얻어지는 에폭시수지는, 식(1)의 에폭시수지 또는 이 에폭시수지와 식(2)의 에폭시수지를 주성분으로 하는 에폭시수지이다. 그리고 에폭시수지(3) 소량 성분으로서 포함할 수 있다.The epoxy resin obtained by the manufacturing method of this invention is an epoxy resin which has the epoxy resin of Formula (1) or this epoxy resin and the epoxy resin of Formula (2) as a main component. And a small amount of the epoxy resin (3).

본 발명의 에폭시수지 조성물에서 사용하는 경화제로서는, 공지 관용의 화합물을 모두 사용할 수 있는데, 그 중에서도 대표적인 것으로서는 디시안디아미드, 이미다졸, BF3-아민 착체, 구아니딘 유도체 등의 잠재성 경화제, 페놀, 치환 페놀류 및 비스페놀류로부터 유도되는 각종 노볼락수지와 그 변성물, 메타페닐렌디아민, 디아미노디페닐메탄, 디아미노디페닐술폰 등의 방향족 아민류, 폴리아미드수지 및 이들의 변성물, 무수 말레산, 무수 프탈산, 무수 헥사히드로프탈산, 무수 피로멜리트산 등의 산 무수물계 경화제 등을 들 수 있다. 이들 경화제는 단독이어도 2종 이상의 병용이어도 된다. 경화제는 상온 경화용인 것과 가열 경화용인 것을 용도에 따라 구분하여 사용하는 것이 바람직하다.As the curing agent used in the epoxy resin composition of the present invention, all known and conventional compounds can be used. Among them, latent curing agents such as dicyandiamide, imidazole, BF 3 -amine complex, guanidine derivative, phenol, Various novolac resins and their modified products derived from substituted phenols and bisphenols, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone, polyamide resins and modified products thereof, and maleic anhydride And acid anhydride curing agents such as phthalic anhydride, hexahydrophthalic anhydride and pyromellitic anhydride. These curing agents may be used alone or in combination of two or more. It is preferable to use a hardening | curing agent separately for what is for normal temperature hardening, and for heat-hardening according to a use.

이들 경화제의 사용량은 특별히 제한되는 것은 아니지만, 에폭시수지의 고형분 100중량부에 대하여 2~70중량부이다. 단, 이 혼합비는 사용하는 경화제의 종류에 따라 크게 변화하므로 최적 조건을 적당히 결정하는 것이 필요하다.Although the usage-amount of these hardening | curing agents is not specifically limited, It is 2-70 weight part with respect to 100 weight part of solid content of an epoxy resin. However, since this mixing ratio changes greatly with the kind of hardening | curing agent to be used, it is necessary to determine optimal conditions suitably.

상기의 각 화합물을 경화제로서 사용할 때는 경화 촉진제를 적당히 사용할 수 있다. 경화 촉진제로서는 공지 관용의 것을 모두 사용할 수 있는데, 예를 들면 제3급 아민, 이미다졸, 유기산 금속염, 루이스산, 아민 착염(錯鹽) 등을 들 수 있고, 이들은 단독 뿐 아니라 2종 이상의 병용도 가능하다.When using each said compound as a hardening | curing agent, a hardening accelerator can be used suitably. As a hardening accelerator, all well-known and conventional things can be used, For example, tertiary amine, imidazole, an organic acid metal salt, Lewis acid, an amine complex salt, etc. are mentioned, These are not only single, but also 2 or more types of combined use. It is possible.

본 발명의 에폭시수지 조성물에는, 필요에 따라 충전제, 섬유, 커플링제, 난연제, 이형제, 발포제 등의 그 밖의 성분을 첨가할 수 있다. 이때의 충전제로서는, 예를 들면 폴리에틸렌 분말, 폴리프로필렌 분말, 석영, 실리카, 규산염, 탄산칼슘, 탄산마그네슘, 석고, 벤토나이트, 형석(螢石), 이산화티탄, 카본블랙, 흑연, 산화철, 알루미늄 분말, 철분, 탤크, 마이카, 카올린 클레이 등이, 섬유로서는 예를 들면 셀룰로오스 섬유, 유리 섬유, 탄소 섬유, 아라미드 섬유 등이, 커플링제로서는 예를 들면 실란커플링제, 티탄커플링제 등이, 난연제로서는 예를 들면 브롬화비스페놀A, 3산화안티몬, 인계 화합물 등이, 이형제로서는 예를 들면 스테아린산염, 실리콘, 왁스 등이, 발포제로서는 예를 들면 프레온, 디클로로에탄, 부탄, 펜탄, 디니트로펜타메틸렌테트라민, 파라톨루엔술포닐히드라지드, 혹은 프레온, 디클로로에탄, 부탄, 펜탄 등이 염화비닐-염화비닐리덴 공중합체나 스티렌-(메타)아크릴산에스테르 공중합체의 껍데기 내에 충전되어 있는 팽창성 열가소성 수지 입자 등을 들 수 있다.Other components, such as a filler, a fiber, a coupling agent, a flame retardant, a mold release agent, a foaming agent, can be added to the epoxy resin composition of this invention as needed. As the filler at this time, for example, polyethylene powder, polypropylene powder, quartz, silica, silicate, calcium carbonate, magnesium carbonate, gypsum, bentonite, fluorspar, titanium dioxide, carbon black, graphite, iron oxide, aluminum powder, Examples of the fiber include iron, talc, mica, kaolin clay, and the like, such as cellulose fiber, glass fiber, carbon fiber, aramid fiber, and the like. As the coupling agent, for example, a silane coupling agent, a titanium coupling agent, and the like, are examples of the flame retardant. For example, bisphenol A, antimony trioxide, a phosphorus compound, etc., as a mold release agent, for example, stearic acid salt, silicone, wax, etc., As a blowing agent, Freon, dichloroethane, butane, pentane, dinitropentamethylenetetramine, para Toluenesulfonylhydrazide, or freon, dichloroethane, butane, pentane, etc. may be used for vinyl chloride-vinylidene chloride copolymer or styrene- (meth) acrylic acid. Expandable thermoplastic resin particles etc. which are filled in the shell of an ester copolymer are mentioned.

본 발명의 에폭시수지 조성물은 종래 알려져 있는 방법과 동일한 방법으로 용이하게 에폭시수지 조성물의 경화물로 할 수 있다. 예를 들면 본 발명의 에폭시수지와 경화제, 필요에 따라 경화 촉진제 및 그 외의 첨가제를 필요에 따라 압출기, 니더, 롤 등을 사용하여 균일해질 때까지 충분히 혼합하여 에폭시수지 조성물을 얻고, 그 에폭시수지 조성물을 용융 후 주형 혹은 트랜스퍼 성형기 등을 사용하여 성형하고, 또한 80~200℃로 가열함으로써 경화물을 얻을 수 있다.The epoxy resin composition of this invention can be easily made into the hardened | cured material of an epoxy resin composition by the method similar to the method known conventionally. For example, the epoxy resin and the curing agent of the present invention, if necessary, a curing accelerator and other additives, if necessary, by using an extruder, kneader, roll or the like until the mixture is sufficiently mixed to obtain an epoxy resin composition, the epoxy resin composition After melt | dissolution, it shape | molds using a mold or a transfer molding machine, etc., and can harden | cure a cured | cured material by heating at 80-200 degreeC.

또한 본 발명의 에폭시수지 조성물을 용제에 용해시켜, 유리 섬유, 카본 섬유, 폴리에스테르 섬유, 폴리아미드 섬유, 알루미나 섬유, 종이 등의 기재에 함침시켜 가열 건조하여 얻은 프리 프레그를 열 프레스 성형하여 경화물을 얻는 것 등도 할 수 있다. 예를 들면 본 발명의 에폭시수지와 경화제, 희석용 용제 등을 균일해질 때까지 가열, 교반하고, 이것을 유리 크로스에 함침시켜 가열 반건조하여 용제분을 날린 프리 프레그를, 필요 매수 겹쳐 80~200℃로 1시간 이상 가열 프레스함으로써 유리 크로스 적층판을 제작할 수 있다.In addition, the prepreg obtained by dissolving the epoxy resin composition of the present invention in a solvent, impregnating a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, or the like by heating and drying, is cured by hot press molding. It can also be obtained. For example, the epoxy resin of the present invention, a curing agent, a dilution solvent, and the like are heated and stirred until uniform, impregnated in a glass cross, heated and semi-dried, and a prepreg containing a solvent powder is overlapped with the required number of sheets at 80 to 200 ° C. The glass cross laminated board can be produced by heat-pressing for 1 hour or more.

이때 사용할 수 있는 희석용 용제의 구체예로서는 톨루엔, 크실렌, 메틸에틸케톤, 메틸이소부틸케톤, 메틸셀로솔브 등이 바람직하고, 그 사용량은 에폭시수지 조성물과 상기 희석용 용제의 합계 중량에 대하여, 10~70중량%, 바람직하게는 15~65중량%이다.As a specific example of the dilution solvent which can be used at this time, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, etc. are preferable, The usage-amount is 10 with respect to the total weight of an epoxy resin composition and the said dilution solvent. 70 weight%, Preferably it is 15-65 weight%.

이렇게 얻어지는 경화물은 염소 함유량이 낮고, 높은 내열성을 가지고 있기 때문에, 본 발명의 에폭시수지 조성물은 광범위한 분야에서 사용할 수 있다. 구체적으로는 성형 재료, 주형 재료, 적층 재료, 도료, 접착제, 레지스트 등 광범위한 용도로 사용할 수 있다.Since the hardened | cured material obtained in this way has low chlorine content and high heat resistance, the epoxy resin composition of this invention can be used in a wide range of fields. Specifically, it can be used for a wide range of applications such as molding materials, casting materials, laminated materials, paints, adhesives, and resists.

<실시예><Examples>

다음으로 본 발명의 특징을 더욱 명확히 하기 위해 실시예를 들어 구체적으로 설명한다. 또한 본문 중의 "부", "%"는 모두 중량 기준을 나타내는 것이다.Next, examples will be described in detail to clarify the features of the present invention. In addition, all "part" and "%" in a main body show a basis of weight.

(합성예 1)Synthesis Example 1

3L 반응기에 디비닐벤젠(신닛테츠가가쿠 제품 DVB-960 디비닐벤젠 함유량 97%, m-체/p-체=62:38) 300부, 아세트산에틸 1200부를 장입(裝入)하여 교반하였다. 이어서, 과아세트산 30% 함유 아세트산에틸 용액 1640부를 3시간 동안 적하하였다. 적하 중은 반응 온도가 30℃가 되도록 제어를 행하였다. 적하 후 또한 30℃에서 3시간 교반을 행하였다. 반응액을 실온까지 냉각한 후, 20% NaOH 수용액 1208부를 첨가하고, 1시간 교반 후, 수층을 분리하여, 미반응의 과아세트산 및 생성된 아세트산의 제거를 행하였다. 에바포레이터로 아세트산에틸을 감압 증류 제거한 후, 정제 증류(유출(留出) 온도 10torr 150℃)를 행하고, 디에폭시에틸벤젠 151.6부를 얻었다. 얻어진 디에폭시에틸벤젠의 에폭시 당량은 81g/eq, 25℃에서의 점도는 18mPa·s, 순도는 97.1%(가스 크로마토그래피 면적%), m-체/p-체=64:36(1H-NMR 적분비)이었다.300 parts of divinylbenzene (97% of DVB-960 divinylbenzene from Shin-Nitetsu Chemical Co., Ltd. content, m-body / p-body = 62: 38), and 1200 parts of ethyl acetate were charged and stirred in the 3 L reactor. Subsequently, 1640 parts of ethyl acetate solution containing 30% of peracetic acid were added dropwise for 3 hours. During dripping, it controlled so that reaction temperature might be 30 degreeC. After dripping was further performed at 30 ° C. for 3 hours. After cooling the reaction solution to room temperature, 1208 parts of 20% aqueous NaOH solution was added, and after stirring for 1 hour, the aqueous layer was separated and unreacted peracetic acid and acetic acid produced were removed. After distilling off ethyl acetate under reduced pressure with an evaporator, purified distillation (outflow temperature of 10 torr 150 ° C) was performed to obtain 151.6 parts of diepoxyethylbenzene. The epoxy equivalent of the obtained diepoxy ethylbenzene was 81 g / eq, the viscosity in 25 degreeC was 18 mPa * s, the purity was 97.1% (gas chromatography area%), m-form / p-form = 64:36 (1H-NMR) Integral ratio).

<실시예 1>&Lt; Example 1 >

교반기, 콘덴서, 온도계를 부착한 분리가능 플라스크에, 합성예 1에서 제조한 디에폭시에틸벤젠을 61부, 비스페놀A(도쿄 카세이 고교 가부시키가이샤 제품)를 41부, 메틸이소부틸케톤(도쿄 카세이 고교 가부시키가이샤 제품) 102부를 투입해 80℃로 가열하여 교반하에서 완전히 용해한 후, 촉매로서 트리페닐포스핀 0.07부를 첨가하고, 130℃까지 승온하여 6시간 반응을 행하였다. 반응 종료 후 5torr의 감압하, 120℃에서 탈휘(脫揮)를 행하였다. 에폭시 당량 259g/eq, 담황색 투명한 점조 액체인 에폭시수지(A) 100부를 얻었다. 실린더 연소법에 의한 전 염소 함유량은 0.5ppm미만이었다. 에폭시수지(A)의 1H-NMR 스펙트럼을 도 1에 나타낸다.In a detachable flask equipped with a stirrer, a condenser and a thermometer, 61 parts of diepoxyethylbenzene prepared in Synthesis Example 1, 41 parts of bisphenol A (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and methyl isobutyl ketone (Tokyo Kasei Kogyo Co., Ltd.) 102 parts of Co., Ltd. products were added, and the mixture was heated to 80 ° C and completely dissolved under stirring. Then, 0.07 part of triphenylphosphine was added as a catalyst, and the reaction was carried out for 6 hours by heating up to 130 ° C. After completion | finish of reaction, devolatilization was performed at 120 degreeC under reduced pressure of 5torr. 100 parts of epoxy resins (A) which are epoxy equivalent 259g / eq and a pale yellow transparent viscous liquid were obtained. The total chlorine content by the cylinder combustion method was less than 0.5 ppm. 1H-NMR spectrum of the epoxy resin (A) is shown in FIG. 1.

<실시예 2><Example 2>

교반기, 콘덴서, 온도계를 부착한 분리가능 플라스크에, 합성예 1에서 제조한 디에폭시에틸벤젠을 61부, 비스페놀F(혼슈 가가쿠 고교 가부시키가이샤 제품)를 41부, 메틸이소부틸케톤 101부를 투입하여 80℃로 가열하여 교반하에서 완전히 용해한 후, 촉매로서 트리페닐포스핀 0.07부를 첨가하고, 130℃까지 승온하여 6시간 반응을 행하였다. 반응 종료 후 5torr의 감압하, 120℃에서 탈휘를 행하였다. 에폭시 당량 298g/eq, 담황색 투명한 점조 액체인 에폭시수지(B) 100부를 얻었다. 전 염소 함유량은 0.5ppm미만이었다.Into a detachable flask equipped with a stirrer, a condenser and a thermometer, 61 parts of diepoxyethylbenzene prepared in Synthesis Example 1, 41 parts of bisphenol F (manufactured by Honshu Chemical Co., Ltd.) and 101 parts of methyl isobutyl ketone were added. The mixture was heated to 80 ° C and completely dissolved under stirring. Then, 0.07 part of triphenylphosphine was added as a catalyst, and the temperature was raised to 130 ° C to carry out the reaction for 6 hours. After completion | finish of reaction, devolatilization was performed at 120 degreeC under reduced pressure of 5torr. 100 parts of epoxy resins (B) which are an epoxy equivalent of 298 g / eq and a pale yellow transparent viscous liquid were obtained. The total chlorine content was less than 0.5 ppm.

<실시예 3><Example 3>

교반기, 콘덴서, 온도계를 부착한 분리가능 플라스크에, 합성예 1에서 제조한 디에폭시에틸벤젠을 61부, 4,4'-디히드록시비페닐에테르(도쿄 카세이 가가쿠 고교 가부시키가이샤 제품)를 38부, 메틸이소부틸케톤 75부를 투입해 80℃로 가열하여 교반하에서 완전히 용해한 후, 촉매로서 트리페닐포스핀 0.07부를 첨가하고, 130℃까지 승온하여 6시간 반응을 행하였다. 반응 종료 후 5torr의 감압하, 120℃에서 탈휘를 행하였다. 에폭시 당량 279g/eq, 담황색 투명한 점조 액체인 에폭시수지(C) 82부를 얻었다. 전 염소 함유량은 0.5ppm미만이었다.To a detachable flask equipped with a stirrer, a condenser and a thermometer, 61 parts of diepoxyethylbenzene prepared in Synthesis Example 1 and 4,4'-dihydroxybiphenyl ether (manufactured by Tokyo Kasei Kagaku Kogyo Co., Ltd.) 38 parts and 75 parts of methyl isobutyl ketones were added, and it heated at 80 degreeC, melt | dissolving completely under stirring, and added 0.07 part of triphenylphosphines as a catalyst, it heated up to 130 degreeC, and reacted for 6 hours. After completion | finish of reaction, devolatilization was performed at 120 degreeC under reduced pressure of 5torr. 82 parts of epoxy resins (C) which are an epoxy equivalent of 279 g / eq and a pale yellow transparent viscous liquid were obtained. The total chlorine content was less than 0.5 ppm.

<실시예 4><Example 4>

교반기, 콘덴서, 온도계를 부착한 분리가능 플라스크에, 합성예 1에서 제조한 디에폭시에틸벤젠을 82부, 9,9-비스(4-히드록시페닐)플루오렌(도쿄 카세이 가가쿠 고교 가부시키가이샤 제품)을 88부, 메틸이소부틸케톤 80부를 투입해 80℃로 가열하여 교반하에서 완전히 용해한 후, 촉매로서 트리페닐포스핀 0.09부를 첨가하고, 130℃까지 승온하여 6시간 반응을 행하였다. 반응 종료 후 5torr의 감압하, 120℃에서 탈휘를 행하였다. 에폭시 당량 342g/eq, 담황색 고체인 에폭시수지(D) 165부를 얻었다. 전 염소 함유량은 0.5ppm미만이었다.82 parts of 9,9-bis (4-hydroxyphenyl) fluorene (Tokyo Kasei Kagaku Kogyo Co., Ltd.) of diepoxyethylbenzene prepared in Synthesis Example 1 was added to a detachable flask equipped with a stirrer, a condenser and a thermometer. 88 parts of products and 80 parts of methyl isobutyl ketones were added, and it heated at 80 degreeC, melt | dissolving completely under stirring, 0.09 parts of triphenylphosphines were added as a catalyst, it heated up to 130 degreeC, and reaction was performed for 6 hours. After completion | finish of reaction, devolatilization was performed at 120 degreeC under reduced pressure of 5torr. 165 parts of epoxy resins (D) which are epoxy equivalent 342g / eq and light yellow solid were obtained. The total chlorine content was less than 0.5 ppm.

실시예 1~4에서 얻어진 에폭시수지(A)~(D)는, 모두 일반식(1)로 표시되는 에폭시수지를 주성분으로 하고, 그 비율은 약 70wt%이며, 일반식(2)로 표시되는 에폭시수지를 약 30wt% 포함하는 것이었다.Epoxy resins (A) to (D) obtained in Examples 1 to 4 all have an epoxy resin represented by the general formula (1) as a main component, and the ratio thereof is about 70 wt%, which is represented by the general formula (2). The epoxy resin contained about 30 wt%.

<실시예 5~8><Examples 5-8>

실시예 1~4에서 얻은 에폭시수지 A~D에, 리카시드 MH-700(4-메틸헥사히드로 무수 프탈산/헥사히드로 무수 프탈산 혼합물(70/30) 신니혼 리카 가부시키가이샤 제품)을 당량비가 1.0이 되도록 혼합하였다. 혼합물에 대하여, 0.3%의 2-에틸-4-메틸이미다졸(시코쿠 카세이 고교 가부시키가이샤 제품)을 첨가하여 균일하게 혼합한 후, 120℃ 1시간+150℃ 3시간 가열 경화시켜 경화물을 얻었다.To epoxy resins A to D obtained in Examples 1 to 4, lycaside MH-700 (4-methylhexahydro phthalic anhydride / hexahydro phthalic anhydride mixture (70/30) manufactured by Shin-Nihon Rika Co., Ltd.) has an equivalent ratio of 1.0. Mix so as to. 0.3% 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added to the mixture and mixed uniformly, followed by heat curing at 120 ° C for 1 hour + 150 ° C for 3 hours. Got it.

<비교예 1>Comparative Example 1

비스페놀A형 에폭시수지(YD-134 에폭시 당량 246g/eq 전 염소 함유량 1700ppm)와 리카시드 MH-700을 당량비가 1.0이 되도록 혼합하였다. 혼합물에 대하여, 0.3%의 2-에틸-4-메틸이미다졸을 첨가하여 균일하게 혼합한 후, 120℃ 1시간+150℃ 3시간 가열 경화시켜 경화물을 얻었다.The bisphenol A type epoxy resin (YD-134 epoxy equivalent 246 g / eq total chlorine content 1700 ppm) and lycaside MH-700 were mixed so that an equivalent ratio might be 1.0. To the mixture, 0.3% 2-ethyl-4-methylimidazole was added and uniformly mixed, followed by heat curing at 120 ° C for 1 hour + 150 ° C for 3 hours to obtain a cured product.

<비교예 2>Comparative Example 2

비스페놀F형 에폭시수지(YDF-170 에폭시 당량 246g/eq 전 염소 함유량 1600ppm)와 리카시드 MH-700을 등량비가 1.0이 되도록 혼합하였다. 혼합물에 대하여, 0.3%의 2-에틸-4-메틸이미다졸을 첨가하여 균일하게 혼합한 후, 120℃ 1시간+150℃ 3시간 가열 경화시켜 경화물을 얻었다.Bisphenol F type epoxy resin (YDF-170 epoxy equivalent 246 g / eq total chlorine content 1600 ppm) and lycaside MH-700 were mixed so that an equivalent ratio might be 1.0. To the mixture, 0.3% 2-ethyl-4-methylimidazole was added and uniformly mixed, followed by heat curing at 120 ° C for 1 hour + 150 ° C for 3 hours to obtain a cured product.

실시예 5~8 및 비교예 1~2에서 얻은 경화물에 대하여, Tg(TMA법), 구부림 탄성율, 구부림 강도를 측정하였다. 측정 조건은 다음과 같다.About the hardened | cured material obtained in Examples 5-8 and Comparative Examples 1-2, Tg (TMA method), bending elastic modulus, and bending strength were measured. Measurement conditions are as follows.

Tg: TMA법Tg: TMA method

구부림 탄성율, 구부림 강도; 3점 구부림법Bending elastic modulus, bending strength; 3-point bend

Figure pct00004
Figure pct00004

본 발명의 에폭시수지는 종래 일반적으로 사용되어 온 에폭시수지와 비교하여, 염소 함유량이 낮고, 내열성, 기계 강도가 뛰어나, 도료, 적층판, 접착제 등에 유용한 에폭시수지, 에폭시수지 조성물, 및 경화물을 부여할 수 있다.The epoxy resin of the present invention has a lower chlorine content, excellent heat resistance and mechanical strength than epoxy resins generally used in the past, and can provide epoxy resins, epoxy resin compositions, and cured products useful for paints, laminates, adhesives, and the like. Can be.

Claims (9)

하기 일반식(1)로 표시되는 것을 특징으로 하는 에폭시수지.
Figure pct00005

여기서, A는 치환기를 가지고 있어도 되는 2가의 방향족기를 나타내고, n은 1에서 15의 수를 나타낸다.Epoxy resin, characterized by the following general formula (1).
Figure pct00005

Here, A represents the bivalent aromatic group which may have a substituent, n shows the number of 1-15. 디에폭시에틸벤젠과 페놀성 수산기를 2개 가지는 화합물을 반응시켜 얻어지고, 하기 일반식(1)로 표시되는 에폭시수지를 주성분으로서 포함하는 것을 특징으로 하는 에폭시수지.
Figure pct00006

여기서, A는 치환기를 가지고 있어도 되는 2가의 방향족기를 나타내고, n은 1에서 15의 수를 나타낸다.An epoxy resin obtained by reacting a diepoxyethylbenzene with a compound having two phenolic hydroxyl groups, and containing an epoxy resin represented by the following general formula (1) as a main component.
Figure pct00006

Here, A represents the bivalent aromatic group which may have a substituent, n shows the number of 1-15. 제2항에 있어서,
부성분으로서 하기 일반식(2)로 표시되는 에폭시수지를 포함하는 것을 특징으로 하는 에폭시수지.
Figure pct00007

여기서, A는 치환기를 가지고 있어도 되는 2가의 방향족기를 나타내고, n은 1에서 15의 수를 나타낸다. B1은 하기 식(3) 또는 하기 식(4)로 표시되는 2가의 기이고, B2는 하기 식(5) 또는 하기 식(6)으로 표시되는 2가의 기인데, B1이 식(3)으로 표시되는 2가의 기이면서, B2가 (5)로 표시되는 2가의 기인 경우를 제외한다.
Figure pct00008
The method of claim 2,
Epoxy resin characterized by including the epoxy resin represented by following General formula (2) as a subcomponent.
Figure pct00007

Here, A represents the bivalent aromatic group which may have a substituent, n shows the number of 1-15. B 1 is a divalent group represented by the following formula (3) or (4), B 2 is a divalent group represented by the following formula (5) or (6), and B 1 is a formula (3 Except for the divalent group represented by), B 2 is a divalent group represented by (5).
Figure pct00008
 디에폭시에틸벤젠과 페놀성 수산기를 2개 가지는 화합물을 반응시키는 것을 특징으로 하는 에폭시수지의 제조방법.A method for producing an epoxy resin, wherein diepoxyethylbenzene and a compound having two phenolic hydroxyl groups are reacted. 제4항에 있어서,
페놀성 수산기를 2개 가지는 화합물이 비스페놀계 화합물인 것을 특징으로 하는 에폭시수지의 제조방법.The method of claim 4, wherein
A method for producing an epoxy resin, wherein the compound having two phenolic hydroxyl groups is a bisphenol compound. 제4항에 있어서,
페놀성 수산기를 2개 가지는 화합물이 비페놀계 화합물인 것을 특징으로 하는 에폭시수지의 제조방법.The method of claim 4, wherein
A method for producing an epoxy resin, wherein the compound having two phenolic hydroxyl groups is a biphenol compound. 제1항 내지 제3항 중 어느 한 항에 기재된 에폭시수지와, 경화제를 함유하는 것을 특징으로 하는 에폭시수지 조성물.An epoxy resin composition comprising the epoxy resin according to any one of claims 1 to 3 and a curing agent. 제7항에 있어서,
또한 경화 촉진제를 함유하는 것을 특징으로 하는 에폭시수지 조성물.The method of claim 7, wherein
Furthermore, the epoxy resin composition containing a hardening accelerator. 제7항에 기재된 에폭시수지 조성물을 성형 경화시켜 이루어지는 것을 특징으로 하는 에폭시수지 경화물.A cured epoxy resin product obtained by molding and curing the epoxy resin composition according to claim 7.
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