KR101768287B1 - Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same - Google Patents

Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same Download PDF

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KR101768287B1
KR101768287B1 KR1020140169213A KR20140169213A KR101768287B1 KR 101768287 B1 KR101768287 B1 KR 101768287B1 KR 1020140169213 A KR1020140169213 A KR 1020140169213A KR 20140169213 A KR20140169213 A KR 20140169213A KR 101768287 B1 KR101768287 B1 KR 101768287B1
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epoxy resin
resin composition
curing
formula
substituted
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KR20160065413A (en
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천진민
권기혁
김민겸
이동환
정주영
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삼성에스디아이 주식회사
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Priority to PCT/KR2015/010729 priority patent/WO2016085115A1/en
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    • 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
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    • C08G59/68—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 catalysts used
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Abstract

본 발명은 하기 화학식 1로 표시되는 포스포늄계 화합물에 관한 것이다:
[화학식 1]

Figure 112014116183593-pat00028

(상기 화학식 1에서, R1, R2, R3, 및 R4 는 각각 독립적으로 치환 또는 비치환된 C1~C30의 지방족 탄화수소기, 치환 또는 비치환된 C6~C30의 방향족 탄화수소기, 또는 헤테로 원자를 포함하는 치환 또는 비치환된 C1~C30의 탄화수소기이고, X1 및 X2는 각각 독립적으로 치환 또는 비치환된 C1~C30의 지방족 탄화수소기, 치환 또는 비치환된 C6~C30의 방향족 탄화수소기, 또는 헤테로 원자를 포함하는 치환 또는 비치환된 C1~C30의 탄화수소기이고, Y1, Y2, Y3 및 Y4 는 각각 독립적으로 산소원자(O), 황원자(S) 또는 치환된 질소원자(N)이다).The present invention relates to a phosphonium compound represented by the following formula (1)
[Chemical Formula 1]
Figure 112014116183593-pat00028

(Wherein R 1 , R 2 , R 3 and R 4 each independently represents a substituted or unsubstituted C 1 -C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C6-C30 aromatic hydrocarbon group, or a hetero And X 1 and X 2 each independently represent a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, a substituted or unsubstituted C1 to C30 hydrocarbon group, group, or a substituted or unsubstituted C1 ~ C30 containing hetero atom a hydrocarbon group, Y 1, Y 2, Y 3 and Y 4 are each independently oxygen atom (O), sulfur (S) or substituted nitrogen, Atom (N)).

Description

포스포늄계 화합물, 이를 포함하는 에폭시수지 조성물, 및 이를 사용하여 제조된 반도체 소자{PHOSPHONIUM COMPOUND, EPOXY RESIN COMPOSITION COMPRISING THE SAME AND SEMICONDUCTOR DEVICE PREPARED FROM USING THE SAME}TECHNICAL FIELD [0001] The present invention relates to a phosphonium compound, an epoxy resin composition containing the same, and a semiconductor device manufactured using the same. BACKGROUND OF THE INVENTION [0002]

본 발명은 포스포늄계 화합물, 이를 포함하는 에폭시수지 조성물 및 이를 사용하여 제조된 반도체 소자에 관한 것이다. The present invention relates to a phosphonium compound, an epoxy resin composition containing the same, and a semiconductor device manufactured using the same.

IC(integrated circuit), LSI(large scale integration) 등의 반도체 소자를 포장하고 반도체장치를 얻는 방법으로, 에폭시수지 조성물을 이용한 트랜스퍼(transfer) 성형이 저비용, 대량 생산에 적합하다는 점에서 널리 사용되고 있다. 에폭시수지나 경화제인 페놀 수지의 개량에 의하여 반도체 소자의 특성 및 신뢰성의 향상이 도모될 수 있다. BACKGROUND ART [0002] Transfer molding using an epoxy resin composition is widely used as a method of packaging semiconductor devices such as an IC (integrated circuit) and an LSI (large scale integration) and obtaining a semiconductor device because of its low cost and suitable for mass production. Improvement of the characteristics and reliability of the semiconductor device can be achieved by improving the phenolic resin which is an epoxy resin or a curing agent.

이러한 에폭시수지 조성물은 에폭시수지, 경화제, 경화촉매 등을 포함한다. 상기 경화촉매로 통상 이미다졸계 촉매, 아민계 촉매, 포스핀계 촉매가 사용되어 왔다. Such an epoxy resin composition includes an epoxy resin, a curing agent, a curing catalyst and the like. As the curing catalyst, an imidazole-based catalyst, an amine-based catalyst, and a phosphine-based catalyst have usually been used.

그러나 전자기기가 점차 소형화, 경량화, 고성능화되는 추세에 따라 반도체의 고집적화도 매년 가속화되고 있고 또 반도체 소자의 표면 실장화에 대한 요구도 늘어감에 따라 종래의 에폭시수지 조성물로는 해결할 수 없는 문제들이 생기고 있다. 또한 근래의 반도체 소자의 포장에 사용되는 재료에는 생산성의 향상을 목적으로 한 속경화성과 물류, 보관시의 취급성 향상을 목적으로 한 보존 안정성이 요구되고 있다.However, due to the tendency of electronic devices to be gradually reduced in size, weight, and performance, the high integration of semiconductors is accelerating every year, and as the demand for surface mounting of semiconductor devices increases, problems that can not be solved by conventional epoxy resin compositions occur have. In recent years, materials used for packaging semiconductor devices are required to have fast curability for the purpose of improving productivity and storage stability for the purpose of improving handling and handling during storage.

트리페닐포스핀(triphenylphosphine)과1,4-벤조퀴논(1,4-benzoquinone)의 부가생성물을 에폭시수지 조성물의 경화촉매에 포함하여 사용하는 방법이 알려져 있다. 그러나, 이 경우 비교적 저온에서도 경화촉진 효과가 나타나서 경화 이전에 에폭시수지 등과 혼합될 때 발생하는 열 또는 외부로부터 더해지는 열에 의해 에폭시수지 조성물의 경화를 일부 진행시킬 수 있고 수지 조성물의 각 성분을 혼합한 후 에폭시수지 조성물을 상온에서 보관하는 경우에도 경화를 촉진시킴으로써 저장안정성이 떨어진다는 문제점이 있다. 이러한 경화반응의 진행은 에폭시수지 조성물이 액체인 경우 점도의 상승, 유동성 저하를 가져올 수 있고, 에폭시수지 조성물이 고체인 경우 점성을 발현시킬 수 있으며, 이러한 상태의 변화는 에폭시수지 조성물 내에서 균일하게 나타나지 않는다. 따라서, 실제로 에폭시수지 조성물을 고온에서 경화반응 시켰을 때 유동성 저하에 따른 성형성 저하, 성형 제품의 기계적, 전기적, 화학적 특성이 저하될 수 있다.There is known a method in which an adduct of triphenylphosphine and 1,4-benzoquinone is used as a curing catalyst for an epoxy resin composition. However, in this case, the effect of accelerating the curing is exhibited even at a relatively low temperature so that the curing of the epoxy resin composition can be partially progressed by the heat generated when mixing with the epoxy resin or the like or the heat from the outside before curing, Even when the epoxy resin composition is stored at room temperature, there is a problem that storage stability is deteriorated by accelerating the curing. The progress of the curing reaction may lead to an increase in viscosity and a decrease in fluidity when the epoxy resin composition is a liquid, and when the epoxy resin composition is solid, it may manifest viscous property, and such a change in state may occur uniformly in the epoxy resin composition It does not appear. Therefore, when the epoxy resin composition is actually subjected to a curing reaction at a high temperature, the moldability may deteriorate due to the lowering of fluidity, and the mechanical, electrical and chemical properties of the molded product may be deteriorated.

이와 관련하여, 일본공개특허 제2007-262238호는 포스포늄 실리케이트 화합물을 사용한 에폭시수지 경화촉매를 개시하고 있다.
In this regard, Japanese Patent Laid-Open No. 2007-262238 discloses an epoxy resin curing catalyst using a phosphonium silicate compound.

본 발명의 목적은 에폭시수지의 경화를 촉진할 수 있고, 몰딩시 유동성이 우수하고, 높은 경화 강도를 나타내고, 짧은 경화시간에서도 경화가 가능한 경화촉매용 화합물을 제공하는 것이다.An object of the present invention is to provide a curing catalyst compound capable of accelerating curing of an epoxy resin, exhibiting excellent flowability upon molding, exhibiting a high curing strength, and being able to be cured even in a short curing time.

본 발명의 다른 목적은 저온에서도 에폭시수지의 경화를 촉진할 수 있는 경화촉매용 화합물을 제공하는 것이다.Another object of the present invention is to provide a compound for a curing catalyst which can accelerate the curing of the epoxy resin even at low temperatures.

본 발명의 또 다른 목적은 원하는 경화온도가 될 때에만 경화를 촉매시키고 원하는 경화온도가 아닐 때에는 경화촉매 활성이 없게 하는 저장안정성이 높은 경화촉매용 화합물을 제공하는 것이다.It is a further object of the present invention to provide a compound for a curing catalyst having high storage stability which catalyzes curing only when the desired curing temperature is reached and no curing catalyst activity when not the desired curing temperature.

본 발명의 또 다른 목적은 상기 에폭시수지 조성물을 포함하는 반도체 소자를 제공하는 것이다.It is still another object of the present invention to provide a semiconductor device comprising the epoxy resin composition.

본 발명의 포스포늄계 화합물은 하기 화학식 1로 표시될 수 있다: The phosphonium-based compound of the present invention may be represented by the following formula (1)

[화학식 1][Chemical Formula 1]

Figure 112014116183593-pat00001
Figure 112014116183593-pat00001

(상기 화학식 1에서, R1, R2, R3, R4, X1, X2, Y1, Y2, Y3, 및 Y4 는 하기 상세한 설명에서 정의한 바와 같다).Wherein R 1 , R 2 , R 3 , R 4 , X 1 , X 2 , Y 1 , Y 2 , Y 3 and Y 4 are as defined in the following description.

상기 포스포늄계 화합물은 하기 화학식 1a 내지 1e 중의 하나로 표시될 수 있다.The phosphonium-based compound may be represented by one of the following formulas (1a) to (1e).

[화학식 1a][Formula 1a]

Figure 112014116183593-pat00002
Figure 112014116183593-pat00002

[화학식 1b][Chemical Formula 1b]

Figure 112014116183593-pat00003
Figure 112014116183593-pat00003

[화학식 1c][Chemical Formula 1c]

Figure 112014116183593-pat00004
Figure 112014116183593-pat00004

[화학식 1d]≪ RTI ID = 0.0 &

Figure 112014116183593-pat00005
Figure 112014116183593-pat00005

[화학식 1e][Formula 1e]

Figure 112014116183593-pat00006
Figure 112014116183593-pat00006

본 발명의 다른 관점인 에폭시수지 조성물은 에폭시수지, 경화제, 무기충전제 및 경화촉매를 포함하고, 상기 경화촉매에는 경화촉진제로서 작용하는 상기 포스포늄계 화합물을 포함할 수 있다. Another aspect of the present invention is an epoxy resin composition comprising an epoxy resin, a curing agent, an inorganic filler, and a curing catalyst, and the curing catalyst may include the phosphonium-based compound serving as a curing accelerator.

상기 에폭시수지는 비스페놀 A형 에폭시수지, 비스페놀 F형 에폭시수지, 페놀노볼락형 에폭시수지, tert-부틸 카테콜형 에폭시수지, 나프탈렌형 에폭시수지, 글리시딜아민형 에폭시수지, 크레졸노볼락형 에폭시수지, 비페닐형 에폭시수지, 선형지방족에폭시수지, 지환식에폭시수지, 복소환식 에폭시수지, 스피로환 함유 에폭시수지, 시클로헥산디메탄올형 에폭시수지, 트리메틸올형 에폭시수지, 할로겐화 에폭시수지 중 하나 이상을 포함할 수 있다. The epoxy resin may be at least one selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, tert-butyl catechol epoxy resin, naphthalene epoxy resin, glycidylamine epoxy resin, , A biphenyl type epoxy resin, a linear aliphatic epoxy resin, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spirocyclic epoxy resin, a cyclohexanedimethanol type epoxy resin, a trimethylol type epoxy resin and a halogenated epoxy resin .

상기 경화제는 페놀아랄킬형 페놀수지, 페놀노볼락형 페놀수지, 자일록형 페놀수지, 크레졸 노볼락형 페놀수지, 나프톨형 페놀수지, 테르펜형 페놀수지, 다관능형 페놀수지, 디시클로펜타디엔계 페놀수지, 비스페놀 A와 레졸로부터 합성된 노볼락형 페놀수지, 트리스(하이드록시페닐)메탄, 디하이드록시바이페닐을 포함하는 다가 페놀 화합물, 무수 말레인산 및 무수 프탈산을 포함하는 산무수물, 메타페닐렌디아민, 디아미노디페닐메탄, 디아미노디페닐설폰 중 하나 이상을 포함할 수 있다.The curing agent may be at least one selected from the group consisting of a phenol aralkyl type phenol resin, a phenol novolac type phenol resin, a xylock type phenol resin, a cresol novolak type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, , Novolac phenolic resins synthesized from bisphenol A and resole, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, metaphenylenediamine, Diaminodiphenylmethane, diaminodiphenylsulfone, and the like.

상기 경화촉매는 상기 에폭시수지 조성물 중 0.01 내지 5중량%로 포함될 수 있다.The curing catalyst may be contained in an amount of 0.01 to 5 wt% of the epoxy resin composition.

상기 포스포늄계 화합물은 상기 경화촉매 중 10 내지 100중량%로 포함될 수 있다.The phosphonium-based compound may be contained in an amount of 10 to 100% by weight of the curing catalyst.

상기 에폭시수지 조성물은 상기 에폭시수지 조성물 중 상기 에폭시수지 2 내지 17중량%, 상기 경화제 0.5 내지 13중량%, 상기 무기 충전제 70 내지 95중량%, 상기 경화촉매 0.01 내지 5중량%를 포함할 수 있다. The epoxy resin composition may contain 2 to 17 wt% of the epoxy resin, 0.5 to 13 wt% of the curing agent, 70 to 95 wt% of the inorganic filler, and 0.01 to 5 wt% of the curing catalyst in the epoxy resin composition.

상기 에폭시수지 조성물은 72시간 경과 후 저장안정성이 80% 이상일 수 있다.The storage stability of the epoxy resin composition after 72 hours may be 80% or more.

상기 에폭시수지 조성물은 하기 식 1의 경화수축률이 0.4% 미만일 수 있다:The epoxy resin composition may have a curing shrinkage ratio of less than 0.4% of the following formula 1:

<식 1><Formula 1>

경화수축률= ｜C - D｜/C x 100Cure shrinkage rate = | C - D | / C x 100

(상기 식 1에서, C는 에폭시수지 조성물을 175℃, 70kgf/㎠에서 트랜스퍼 몰딩 프레스하여 얻은 시편의 길이, D는 상기 시편을 170~180℃에서 4시간 후경화(PMC:post molding cure)하고, 냉각시킨 후 얻은 시편의 길이이다).(C represents the length of the specimen obtained by transfer molding pressing the epoxy resin composition at 175 DEG C and 70 kgf / cm &lt; 2 &gt;, and D is the post cure of the specimen at 170 to 180 DEG C for 4 hours , And the length of the specimen obtained after cooling).

본 발명의 또 다른 관점인 반도체 소자는 상기 에폭시수지 조성물로 밀봉될 수 있다.The semiconductor device, which is another aspect of the present invention, can be sealed with the above epoxy resin composition.

본 발명은 에폭시수지의 경화를 촉진할 수 있고, 저온에서도 에폭시수지의 경화를 촉진할 수 있는 경화촉매용 화합물을 제공하며, 에폭시수지, 경화제 등을 포함하는 혼합물에서 소정 범위의 시간 및 온도 조건에서도 점도 변화를 최소화하여 에폭시수지 조성물을 고온에서 경화반응 시켰을 때 유동성 저하에 따른 성형성 저하, 성형 제품의 기계적, 전기적, 화학적 특성이 저하가 없게 하고, 저장안정성이 높은 경화촉매용 화합물을 제공하였다.The present invention provides a compound for a curing catalyst capable of promoting curing of an epoxy resin and capable of accelerating the curing of the epoxy resin even at a low temperature, and is useful for a mixture containing an epoxy resin, a curing agent, It is possible to provide a compound for a curing catalyst having a low storage stability due to a decrease in moldability and mechanical, electrical and chemical properties of a molded product due to a decrease in fluidity when the epoxy resin composition is cured at a high temperature by minimizing viscosity change.

도 1은 본 발명 일 실시예의 반도체 소자의 단면도이다.
도 2는 본 발명 다른 실시예의 반도체 소자의 단면도이다.1 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention.
2 is a cross-sectional view of a semiconductor device according to another embodiment of the present invention.

본 명세서에서 "치환 또는 비치환된"에서 "치환된"은 해당 작용기 중 하나 이상의 수소 원자가 수산기, 할로겐, 아미노기, 니트로기, 시아노기, C1~C20의 알킬기, C1~C20의 할로알킬기, C6~C30의 아릴기, C3~C30의 헤테로아릴기, C3~C10의 시클로알킬기, C3~C10의 헤테로시클로알킬기, C7~C30의 아릴알킬기, C1~C30의 헤테로알킬기로 치환된 것을 의미하고, '할로'는 불소, 염소, 요오드 또는 브롬을 의미한다.As used herein, the term "substituted or unsubstituted" means that at least one hydrogen atom of the functional group is a hydroxyl group, a halogen atom, an amino group, a nitro group, a cyano group, a C 1 to C 20 alkyl group, a C 1 to C 20 haloalkyl group, C30 aryl group, C3-C30 heteroaryl group, C3-C10 cycloalkyl group, C3-C10 heterocycloalkyl group, C7-C30 arylalkyl group, C1-C30 heteroalkyl group, Means fluorine, chlorine, iodine or bromine.

본 명세서에서 "아릴기"는 환형인 치환기의 모든 원소가 p-오비탈을 가지며 p-오비탈이 공액을 형성하는 치환기를 의미하고, 모노 또는 융합 (즉, 탄소 원자들이 인접한 쌍들을 나눠 가지는 고리) 작용기를 포함하고, "비치환된 아릴기"는 C6 내지 C30의 단일 또는 융합된(fused) 다환(polycyclic) 아릴기를 의미하고, 예를 들면 페닐기, 비페닐기, 나프틸기, 나프톨기, 안트라세닐기 등을 의미할 수 있지만 이에 제한되지 않는다."Aryl group" means a substituent group in which all the elements of a cyclic substituent have p-orbital and p-orbital forms a conjugate, and mono or fused (i.e., a ring in which carbon atoms divide adjacent pairs) Quot; unsubstituted aryl group "means a single or fused polycyclic aryl group of C6 to C30, for example, a phenyl group, a biphenyl group, a naphthyl group, a naphthol group, an anthracenyl group, etc. , But is not limited thereto.

본 명세서에서 "헤테로아릴기"는 C6 내지 C30의 아릴기 내에 질소, 산소, 황 및 인으로 이루어진 군에서 선택되는 원자가 1 내지 3개 포함되고 나머지는 탄소인 것을 의미하고, 예를 들면 피리디닐, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐, 퀴놀리닐, 이소퀴놀리닐, 퀴녹살리닐, 아크리디닐, 퀴나졸리닐, 신노리닐, 프탈라지닐, 티아졸릴, 벤조티아졸릴, 이속사졸릴, 벤즈이속사졸릴, 옥사졸릴, 벤즈옥사졸릴, 피라졸릴, 인다졸릴, 이미다졸릴, 벤즈이미다졸릴, 퓨리닐, 티오페닐, 벤조티오페닐, 푸라닐, 벤조푸라닐, 이소벤조푸라닐을 의미할 수 있지만 이에 제한되지 않는다. In the present specification, the "heteroaryl group" means that the aryl group of C6 to C30 contains 1 to 3 atoms selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus, and the others are carbon. Examples thereof include pyridinyl, Pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, acridinyl, quinazolinyl, cinnolinyl, phthalazinyl, thiazolyl, benzothiazolyl, Isothiazolyl, isoxazolyl, benzisoxazolyl, benzisoxazolyl, oxazolyl, benzoxazolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, purinyl, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, But is not limited to.

본 명세서에서 '헤테로시클로알킬기', '헤테로아릴기', '헤테로시클로알킬렌기', '헤테로아릴렌기'에서 '헤테로'는 질소, 산소, 황 또는 인 원자를 의미한다.In the present specification, "hetero" in the context of "heterocycloalkyl group", "heteroaryl group", "heterocycloalkylene group" and "heteroarylene group" means nitrogen, oxygen, sulfur or phosphorus atom.

본 발명의 포스포늄계 화합물은 포스포늄계 양이온과 아연(Zn) 중심 금속의 고리형 계열 구조의 음이온을 포함하고, 하기 화학식 1로 표시될 수 있다:The phosphonium-based compound of the present invention includes anions of a cyclic series structure of a phosphonium-based cation and a zinc (Zn) center metal, and can be represented by the following formula (1)

[화학식 1][Chemical Formula 1]

Figure 112014116183593-pat00007
Figure 112014116183593-pat00007

(상기 화학식 1에서, R1, R2, R3 및 R4 는 각각 독립적으로 치환 또는 비치환된 C1~C30의 지방족 탄화수소기, 치환 또는 비치환된 C6~C30의 방향족 탄화수소기, 또는 헤테로 원자를 포함하는 치환 또는 비치환된 C1~C30의 탄화수소기이고, (Wherein R 1 , R 2 , R 3 and R 4 each independently represent a substituted or unsubstituted C 1 -C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C6-C30 aromatic hydrocarbon group, or a hetero atom A substituted or unsubstituted C1 to C30 hydrocarbon group,

X1 및 X2는 각각 독립적으로 치환 또는 비치환된 C1~C30의 지방족 탄화수소기, 치환 또는 비치환된 C6~C30의 방향족 탄화수소기, 또는 헤테로 원자를 포함하는 치환 또는 비치환된 C1~C30의 탄화수소기이고, Y1, Y2, Y3, 및 Y4 는 각각 독립적으로 산소원자(O), 황원자(S) 또는 치환된 질소원자(N)이다).X 1 and X 2 each independently represents a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, or a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group containing a hetero atom And Y 1 , Y 2 , Y 3 and Y 4 are each independently an oxygen atom (O), a sulfur atom (S) or a substituted nitrogen atom (N).

본 발명의 포스포늄계 화합물은 하기 화학식 1a 내지 1e 로 표시될 수 있다. The phosphonium compounds of the present invention can be represented by the following formulas (1a) to (1e).

[화학식 1a][Formula 1a]

Figure 112014116183593-pat00008
Figure 112014116183593-pat00008

[화학식 1b][Chemical Formula 1b]

Figure 112014116183593-pat00009
Figure 112014116183593-pat00009

[화학식 1c][Chemical Formula 1c]

Figure 112014116183593-pat00010
Figure 112014116183593-pat00010

[화학식 1d]&Lt; RTI ID = 0.0 &

Figure 112014116183593-pat00011
Figure 112014116183593-pat00011

[화학식 1e][Formula 1e]

Figure 112014116183593-pat00012
Figure 112014116183593-pat00012

포스포늄계 화합물은 유리전이온도가 100 내지 130℃, 예를 들면 123 내지 125℃가 될 수 있다. 포스포늄계 화합물은 수불용성 화합물이 될 수 있다. 상기 범위에서, 저온 경화의 효과가 있을 수 있다. The phosphonium-based compound may have a glass transition temperature of 100 to 130 캜, for example, 123 to 125 캜. The phosphonium-based compound may be a water-insoluble compound. Within this range, there may be an effect of low temperature curing.

포스포늄계 화합물은 에폭시수지, 경화제, 무기 충전제 중 하나 이상을 포함하는 조성물에 첨가되어 잠재성 경화촉매로 사용될 수 있다. The phosphonium-based compound may be added to a composition comprising at least one of an epoxy resin, a curing agent, and an inorganic filler, and used as a latent curing catalyst.

생성된 포스핀 화합물이 에폭시수지 내 에폭사이드기와 반응하여 개환 반응을 하게 되고, 개환 반응 후 에폭시수지 내 수산기와의 반응에 의한 에폭사이드기의 개환 반응, 활성화된 에폭시수지의 사슬 말단과 에폭사이드의 반응 등으로 인해 경화반응을 촉매하게 된다. The resulting phosphine compound reacts with the epoxide group in the epoxy resin to perform ring-opening reaction. After the ring-opening reaction, the ring-opening reaction of the epoxide group by reaction with the hydroxyl group in the epoxy resin, the chain terminal of the activated epoxy resin and the epoxide Reaction and so on.

생성된 포스핀 화합물이 에폭시수지 내 에폭사이드기와 반응하여 개환 반응을 하게 되고, 개환 반응 후 에폭시수지 내 수산기와의 반응에 의한 에폭사이드기의 개환 반응, 활성화된 에폭시수지의 사슬 말단과 에폭사이드의 반응 등으로 인해 경화반응을 촉매하게 된다. The resulting phosphine compound reacts with the epoxide group in the epoxy resin to perform ring-opening reaction. After the ring-opening reaction, the ring-opening reaction of the epoxide group by reaction with the hydroxyl group in the epoxy resin, the chain terminal of the activated epoxy resin and the epoxide Reaction and so on.

포스포늄계 화합물은 에폭시수지와 경화제의 경화반응을 촉매함과 동시에 저온 경화성과 저장안정성이 높고, 에폭시수지, 경화제 등을 포함하는 혼합물에서 소정 범위의 시간 및 온도 조건에서도 점도 변화를 최소화할 수 있는 에폭시수지 조성물을 제공할 수 있는 효과가 있다. 저장 안정성은 원하는 경화온도가 될 때에만 경화를 촉매시키고 원하는 경화온도가 아닐 때에는 경화촉매 활성이 없는 활성으로서, 그 결과 점도 변화 없이도 에폭시수지 조성물을 장시간 동안 저장할 수 있게 한다. 일반적으로 경화반응의 진행은 에폭시수지 조성물이 액체인 경우 점도의 상승, 유동성 저하를 가져올 수 있고, 에폭시수지 조성물이 고체인 경우 점성을 발현시킬 수 있다.The phosphonium compound catalyzes the curing reaction between the epoxy resin and the curing agent and at the same time has a low temperature curability and a high storage stability and is capable of minimizing the change in viscosity even in a predetermined range of time and temperature conditions in a mixture containing an epoxy resin, There is an effect that an epoxy resin composition can be provided. The storage stability catalyzes curing only when the desired curing temperature is reached, and when not the desired curing temperature, there is no curing catalytic activity, so that the epoxy resin composition can be stored for a long time without viscosity change. In general, the progress of the curing reaction may lead to an increase in the viscosity and a decrease in the fluidity when the epoxy resin composition is a liquid, and to develop viscosity when the epoxy resin composition is solid.

포스포늄계 양이온 함유 화합물은 용매 하에 포스핀계 화합물과 알킬 할라이드, 아릴 할라이드 또는 아랄킬 할라이드 등을 결합시켜 제조되거나, 포스포늄계 양이온 함유 염(예: 테트라페닐포스포늄 할라이드)이 될 수 있다. 포스핀계 화합물로는 트리페닐포스핀, 메틸디페닐포스핀, 디메틸페닐포스핀, 에틸디페닐포스핀, 디페닐프로필포스핀, 이소프로필디페닐포스핀, 디에틸페닐포스핀 등이 될 수 있지만, 이에 제한되지 않는다. 음이온 함유 화합물은 음이온 함유 염이 될 수 있다.The phosphonium-based cation-containing compound may be prepared by bonding an alkyl halide, an aryl halide, or an aralkyl halide with a phosphine-based compound in a solvent, or may be a phosphonium-based cation-containing salt (e.g., tetraphenylphosphonium halide). Examples of the phosphine-based compound include triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldiphenylphosphine, diethylphenylphosphine and the like , But is not limited thereto. The anion-containing compound may be an anion-containing salt.

포스포늄계 양이온 함유 화합물: 아연(Zn) 중심 금속의 고리형 계열 구조의 음이온 함유 화합물은 2:1의 몰수비로 반응할 수 있다. 본 발명의 일 실시예의 에폭시수지 조성물은 에폭시수지, 경화제, 무기충전제, 경화촉매 중 하나 이상을 포함할 수 있다. Phosphonium-based cation-containing compound: The anion-containing compound of the cyclic series structure of the zinc (Zn) center metal can react at a molar ratio of 2: 1. The epoxy resin composition of one embodiment of the present invention may include at least one of an epoxy resin, a curing agent, an inorganic filler, and a curing catalyst.

에폭시수지Epoxy resin

에폭시수지는 분자 중에 2개 이상의 에폭시기를 갖는 것으로, 비스페놀 A형 에폭시수지, 비스페놀 F형 에폭시수지, 페놀노볼락형 에폭시수지, tert-부틸 카테콜형 에폭시수지, 나프탈렌형 에폭시수지, 글리시딜아민형 에폭시수지, 크레졸노볼락형 에폭시수지, 비페닐형 에폭시수지, 선형지방족에폭시수지, 지환식에폭시수지, 복소환식 에폭시수지, 스피로환 함유 에폭시수지, 시클로헥산디메탄올형 에폭시수지, 트리메틸올형 에폭시수지, 할로겐화 에폭시수지 등이 될 수 있고, 이들은 단독 또는 2종 이상 혼합하여 포함될 수도 있다. 예를 들면, 에폭시수지는 분자 중에 2개 이상의 에폭시기 및 1개 이상의 수산기를 갖는 에폭시수지일 수 있다. 에폭시수지는 고상의 에폭시수지, 액상의 에폭시수지, 중 하나 이상을 포함할 수 있고 바람직하게는 고상의 에폭시수지를 사용할 수 있다.The epoxy resin is an epoxy resin having two or more epoxy groups in the molecule, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, tert-butyl catechol type epoxy resin, naphthalene type epoxy resin, Epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, Halogenated epoxy resins, and the like, which may be used alone or in combination of two or more. For example, the epoxy resin may be an epoxy resin having two or more epoxy groups in the molecule and at least one hydroxyl group. The epoxy resin may include at least one of a solid phase epoxy resin and a liquid phase epoxy resin, and preferably a solid phase epoxy resin may be used.

일 구체예에서, 에폭시수지는 하기 화학식 2의 비페닐형 에폭시수지, 하기 화학식 3의 페놀아랄킬형 에폭시수지가 될 수 있다:In one embodiment, the epoxy resin may be a biphenyl type epoxy resin of the following formula 2, a phenol aralkyl type epoxy resin of the formula 3:

[화학식 2](2)

Figure 112014116183593-pat00013
Figure 112014116183593-pat00013

(상기 화학식 2에서, R은 탄소수 1 내지 4의 알킬기, n의 평균치는 0 내지 7이다.)(Wherein R is an alkyl group having 1 to 4 carbon atoms and the average value of n is 0 to 7).

[화학식 3](3)

Figure 112014116183593-pat00014

Figure 112014116183593-pat00014

(상기 화학식 3에서, n의 평균치는 1 내지 7이다).(In the above formula (3), the average value of n is 1 to 7).

에폭시수지는 조성물 중 고형분 기준으로 2 내지 17중량%, 예를 들면 3 내지 15중량%, 예를 들면 3 내지 12중량% 포함될 수 있다. 상기 범위에서, 조성물의 경화성이 저하되지 않을 수 있다.The epoxy resin may be included in the composition in an amount of from 2 to 17% by weight, for example, from 3 to 15% by weight, for example, from 3 to 12% by weight, based on the solid content. Within this range, the curability of the composition may not be deteriorated.

경화제Hardener

경화제는 페놀아랄킬형 페놀수지, 페놀노볼락형 페놀수지, 자일록형 페놀수지, 크레졸 노볼락형 페놀수지, 나프톨형 페놀수지, 테르펜형 페놀수지, 다관능형 페놀수지, 디시클로펜타디엔계 페놀수지, 비스페놀 A와 레졸로부터 합성된 노볼락형 페놀수지, 트리스(하이드록시페닐)메탄, 디하이드록시바이페닐을 포함하는 다가 페놀 화합물, 무수 말레인산 및 무수 프탈산을 포함하는 산무수물, 메타페닐렌디아민, 디아미노디페닐메탄, 디아미노디페닐설폰등의 방향족 아민 등을 들수 있다. 바람직하게는, 경화제는 1개 이상의 수산기를 갖는 페놀수지일 수 있다. The curing agent is selected from the group consisting of phenol aralkyl type phenol resin, phenol novolac type phenol resin, xylock type phenol resin, cresol novolak type phenol resin, naphthol type phenol resin, terpene type phenol resin, Novolak type phenol resins synthesized from bisphenol A and resole, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, metaphenylenediamine, di Aminodiphenylmethane, diaminodiphenylsulfone, and other aromatic amines. Preferably, the curing agent may be a phenolic resin having at least one hydroxyl group.

일 구체예에서, 경화제는 하기 화학식 4의 자일록형 페놀수지, 하기 화학식 5의 페놀아랄킬형 페놀수지를 사용할 수 있다:In one embodiment, the curing agent may be a xylyl phenolic resin of formula 4, a phenol aralkyl phenolic resin of formula 5:

<화학식 4>&Lt; Formula 4 >

Figure 112014116183593-pat00015
Figure 112014116183593-pat00015

(상기 화학식 4에서 n의 평균치는 0 내지 7이다.)(The average value of n in the above formula (4) is 0 to 7.)

<화학식 5>&Lt; Formula 5 >

Figure 112014116183593-pat00016
Figure 112014116183593-pat00016

(상기 화학식 5에서 n의 평균치는 1 내지 7이다)(The average value of n in Formula 5 is 1 to 7)

경화제는 에폭시수지 조성물 중 고형분 기준으로 0.5 내지 13중량%, 예를 들면 1 내지 10중량%, 예를 들면 2 내지 8중량% 포함될 수 있다. 상기 범위에서, 조성물의 경화성이 저하되지 않을 수 있다. The curing agent may be contained in an amount of 0.5 to 13% by weight, for example, 1 to 10% by weight, for example, 2 to 8% by weight, based on the solid content in the epoxy resin composition. Within this range, the curability of the composition may not be deteriorated.

무기충전제Inorganic filler

에폭시수지 조성물은 무기충전제를 더 포함할 수 있다. 무기충전제는 조성물의 기계적 물성의 향상과 저응력화를 높일 수 있다. 무기충전제의 예로는 용융실리카, 결정성실리카, 탄산칼슘, 탄산마그네슘, 알루미나, 마그네시아, 클레이(clay), 탈크(talc), 규산칼슘, 산화티탄, 산화안티몬, 유리섬유 중 하나 이상을 포함할 수 있다. The epoxy resin composition may further include an inorganic filler. The inorganic filler can improve mechanical properties and low stress of the composition. Examples of the inorganic filler may include at least one of fused silica, crystalline silicate, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, have.

바람직하게는 저응력화를 위해서는 선팽창계수가 낮은 용융실리카를 사용한다. 용융실리카는 진비중이 2.3 이하인 비결정성 실리카를 의미하는 것으로 결정성 실리카를 용융하여 만들거나 다양한 원료로부터 합성한 비결정성 실리카도 포함된다. 용융실리카의 형상 및 입경은 특별히 한정되지는 않지만, 평균 입경 5 내지 30㎛의 구상 용융실리카를 50 내지 99중량%, 평균입경 0.001 내지 1㎛의 구상 용융실리카를 1 내지 50중량%를 포함한 용융실리카 혼합물을 전체 충전제에 대하여 40 내지 100중량%가 되도록 포함하는 것이 좋다. 또한, 용도에 맞춰 그 최대 입경을 45㎛, 55㎛ 및 75㎛ 중 어느 하나로 조정해서 사용할 수가 있다. 상기 구상 용융실리카에는 도전성의 카본이 실리카 표면에 이물질로서 포함되는 경우가 있으나 극성 이물질의 혼입이 적은 물질을 선택하는 것이 중요하다.Preferably, fused silica having a low linear expansion coefficient is used for low stress. The fused silica refers to amorphous silica having a true specific gravity of 2.3 or less and includes amorphous silica obtained by melting crystalline silica or synthesized from various raw materials. Although the shape and the particle diameter of the fused silica are not particularly limited, the fused silica containing 50 to 99% by weight of spherical fused silica having an average particle diameter of 5 to 30 탆 and the spherical fused silica having an average particle diameter of 0.001 to 1 탆 in an amount of 1 to 50% It is preferable that the mixture is contained in an amount of 40 to 100% by weight based on the total filler. The maximum particle diameter can be adjusted to any one of 45 탆, 55 탆 and 75 탆 according to the application. In the spherical fused silica, conductive carbon may be contained on the surface of the silica as a foreign substance, but it is important to select a substance having a small amount of polar foreign substances.

무기충전제의 사용량은 성형성, 저응력성, 및 고온강도 등의 요구 물성에 따라 다르다. 구체예에서는 무기충전제는 에폭시수지 조성물 중 70 내지 95중량%, 예를 들면 75 내지 92중량%로 포함될 수 있다. 상기 범위에서, 에폭시수지 조성물의 난연성, 유동성 및 신뢰성을 확보할 수 있다.The amount of the inorganic filler to be used varies depending on required properties such as moldability, low stress, and high temperature strength. In an embodiment, the inorganic filler may be included in the epoxy resin composition in an amount of 70 to 95% by weight, for example, 75 to 92% by weight. Within the above range, flame retardancy, fluidity and reliability of the epoxy resin composition can be secured.

경화촉매Curing catalyst

에폭시수지 조성물은 상기 화학식 1 구조의 포스포늄계 화합물을 포함하는 경화촉매를 포함할 수 있다. 포스포늄계 화합물은 에폭시수지 조성물 중 0.01 내지 5중량%, 예를 들면 0.02 내지 1.5중량%, 예를 들면 0.05 내지 1.5중량%로 포함될 수 있다. 상기 범위에서, 경화 반응 시간이 지연되지 않고, 조성물의 유동성이 확보될 수 있다. The epoxy resin composition may include a curing catalyst containing a phosphonium compound having the above-described formula (1). The phosphonium-based compound may be contained in an amount of 0.01 to 5% by weight, for example, 0.02 to 1.5% by weight, for example, 0.05 to 1.5% by weight in the epoxy resin composition. Within this range, the curing reaction time is not delayed and the fluidity of the composition can be ensured.

에폭시수지 조성물은 포스포늄을 포함하지 않는 비-포스포늄계 경화촉매를 더 포함할 수 있다. 비-포스포늄계 경화촉매는 3급 아민 경화촉매, 유기금속화합물 경화촉매, 유기인화합물 경화촉매, 이미다졸 경화촉매 및 붕소화합물 경화촉매 등이 사용 가능하다. 3급 아민 경화촉매에는 벤질디메틸아민, 트리에탄올아민, 트리에틸렌디아민, 디에틸아미노에탄올, 트리(디메틸아미노메틸)페놀, 2-2-(디메틸아미노메틸)페놀, 2,4,6-트리스(디아미노메틸)페놀과 트리-2-에틸헥실산염 등이 있다. 유기 금속화합물 경화촉매에는 크로뮴아세틸아세토네이트, 징크아세틸아세토네이트, 니켈아세틸아세토네이트 등이 있다. 유기인화합물 경화촉매에는 트리스-4-메톡시포스핀, 트리페닐포스핀, 트리페닐포스핀트리페닐보란, 트리페닐포스핀-1,4-벤조퀴논 부가물 등이 있다. 이미다졸류 경화촉매에는 2-메틸이미다졸,　2-페닐이미다졸, 2-아미노이미다졸, 2-메틸-1-비닐이미다졸, 2-에틸-4-메틸이미다졸, 2-헵타데실이미다졸 등이 있다. 붕소화합물 경화촉매에는 트리페닐포스핀 테트라페닐보레이트, 테트라페닐보론염, 트리플루오로보란-n-헥실아민, 트리플루오로보란모노에틸아민, 테트라플루오로보란트리에틸아민, 테트라플루오로보란아민 등이 있다. 이외에도 1,5-디아자바이시클로[4.3.0]논-5-엔(1,5-diazabicyclo[4.3.0]non-5-ene: DBN), 1,8-디아자바이시클로[5.4.0]운덱-7-엔(1,8-diazabicyclo[5.4.0]undec-7-ene: DBU) 및 페놀노볼락 수지염 등을 사용할 수 있다. 특히 바람직한 경화촉매로는 유기인화합물 경화촉매, 붕소화합물 경화촉매, 아민계 경화촉매, 또는 이미다졸계 경화촉매를 단독 혹은 혼합하여 사용하는 것을 들 수 있다. 경화촉매는 에폭시수지 또는 경화제와 선반응하여 만든 부가물을 사용하는 것도 가능하다. The epoxy resin composition may further comprise a non-phosphonium-based curing catalyst that does not contain phosphonium. As the non-phosphonium curing catalyst, a tertiary amine curing catalyst, an organometallic compound curing catalyst, an organic phosphorus compound curing catalyst, an imidazole curing catalyst and a boron compound curing catalyst can be used. Tertiary amine curing catalysts include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri (dimethylaminomethyl) phenol, 2-2- (dimethylaminomethyl) phenol, 2,4,6-tris Minomethyl) phenol and tri-2-ethylhexyl acid salt. Organometallic compound curing catalysts include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, and the like. Organic phosphorus compound curing catalysts include tris-4-methoxyphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzoquinone adduct, and the like. The imidazole curing catalysts include, but are not limited to, 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, 2 - methyl-1-vinylimidazole, 2- Heptadecyl imidazole, and the like. Examples of the boron compound curing catalyst include triphenylphosphine tetraphenyl borate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroboron monoethylamine, tetrafluoroborantriethylamine, tetrafluoroborane amine . In addition, 1,5-diazabicyclo [4.3.0] non-5-ene (1,5-diazabicyclo [4.3.0] non-5-ene: DBN), 1,8-diazabicyclo [5.4. 1,8-diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolak resin salts. Particularly preferable examples of the curing catalysts include organic phosphorus compound curing catalysts, boron compound curing catalysts, amine curing catalysts, and imidazole curing catalysts, either singly or in combination. As the curing catalyst, it is also possible to use an adduct formed by the reaction with an epoxy resin or a curing agent.

전체 경화촉매 중 본 발명의 포스포늄계 화합물은 10 내지 100중량%, 예를 들면 60 내지 100중량%로 포함될 수 있고, 상기 범위에서 경화 반응 시간이 지연되지 않고, 조성물의 유동성이 확보 효과가 있을 수 있다. Of the total curing catalysts, the phosphonium compound of the present invention may be contained in an amount of 10 to 100% by weight, for example, 60 to 100% by weight. In this range, the curing reaction time is not delayed, .

경화촉매는 에폭시수지 조성물 중 0.01 내지 5중량%, 예를 들면 0.02 내지 1.5중량%, 예를 들면 0.05 내지 1.5중량%로 포함될 수 있다. The curing catalyst may be included in the epoxy resin composition in an amount of 0.01 to 5 wt%, for example, 0.02 to 1.5 wt%, for example, 0.05 to 1.5 wt%.

상기 범위에서, 경화 반응 시간이 지연되지 않고, 조성물의 유동성이 확보될 수 있다.Within this range, the curing reaction time is not delayed and the fluidity of the composition can be ensured.

본 발명의 조성물은 조성물에 포함되는 통상의 첨가제를 더 포함할 수 있다. 구체예에서, 첨가제는 커플링제, 이형제, 응력 완화제, 가교 증진제, 레벨링제, 착색제 중 하나 이상을 포함할 수 있다.The composition of the present invention may further include conventional additives included in the composition. In embodiments, the additive may include at least one of a coupling agent, a release agent, a stress relieving agent, a crosslinking enhancer, a leveling agent, and a colorant.

커플링제는 에폭시실란, 아미노실란, 머캡토실란, 알킬실란 및 알콕시실란으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있지만, 이에 제한되지 않는다. 커플링제는 에폭시수지 조성물 중 0.1 내지 1중량%로 포함될 수 있다.The coupling agent may be at least one selected from the group consisting of epoxy silane, aminosilane, mercaptosilane, alkylsilane and alkoxysilane, but is not limited thereto. The coupling agent may be contained in an amount of 0.1 to 1% by weight in the epoxy resin composition.

이형제는 파라핀계 왁스, 에스테르계 왁스, 고급 지방산, 고급 지방산 금속염, 천연 지방산 및 천연 지방산 금속염으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다. 이형제는 에폭시수지 조성물 중 0.1 내지 1중량%로 포함될 수 있다.As the releasing agent, at least one selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt can be used. The release agent may be contained in an amount of 0.1 to 1% by weight in the epoxy resin composition.

응력 완화제는 변성 실리콘 오일, 실리콘 엘라스토머, 실리콘 파우더 및 실리콘 레진으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있지만, 이에 제한되지 않는다. 응력 완화제는 에폭시수지 조성물 중 0 내지 6.5중량%, 예를 들면 0 내지 1중량%, 예를 들면 0.1 내지 1중량%로 함유되는 것이 바람직한데, 선택적으로 함유될 수도 있고, 양자 모두 함유될 수도 있다. 이때, 변성 실리콘 오일로는 내열성이 우수한 실리콘 중합체가 좋으며, 에폭시 관능기를 갖는 실리콘 오일, 아민 관능기를 갖는 실리콘 오일 및 카르복실 관능기를 갖는 실리콘 오일 등을 1종 또는 2종 이상 혼합하여 전체 에폭시수지 조성물에 대해 0.05 내지 1.5 중량% 사용할 수 있다. 다만, 실리콘 오일을 1.5 중량% 이상 초과할 경우에는 표면 오염이 발생하기 쉽고 레진 블리드(bleed)가 길어질 우려가 있으며, 0.05 중량% 미만으로 사용 시에는 충분한 저탄성률을 얻을 수가 없게 되는 문제점이 있을 수 있다. 또한, 실리콘 파우더는 중심입경이 15㎛ 이하인 것이 성형성 저하의 원인으로 작용하지 않기에 특히 바람직하며, 전체 수지 조성물에 대하여 0 내지 5중량%, 예를 들면 0.1 내지 5중량%로 함유될 수 있다.The stress relieving agent may be at least one selected from the group consisting of modified silicone oil, silicone elastomer, silicone powder, and silicone resin, but is not limited thereto. The stress relieving agent is preferably contained in the epoxy resin composition in an amount of 0 to 6.5% by weight, for example, 0 to 1% by weight, for example, 0.1 to 1% by weight, and may be contained selectively or both . As the modified silicone oil, a silicone polymer having excellent heat resistance is preferable, and a silicone oil having an epoxy functional group, a silicone oil having an amine functional group, and a silicone oil having a carboxyl functional group, or the like, 0.05 to 1.5% by weight based on the total weight of the composition. However, when the amount of the silicone oil is more than 1.5% by weight, surface contamination is liable to occur and the resin bleed may be prolonged. When the silicone oil is used in an amount of less than 0.05% by weight, a sufficient low elastic modulus may not be obtained have. The silicone powder having a median particle diameter of 15 탆 or less is particularly preferable because it does not act as a cause of degradation in moldability and may be contained in an amount of 0 to 5% by weight, for example, 0.1 to 5% by weight, based on the whole resin composition .

첨가제는 에폭시수지 조성물 중 0.1 내지 10중량%, 예를 들면 0.1 내지 3중량%로 포함될 수 있다.The additive may be included in the epoxy resin composition in an amount of 0.1 to 10% by weight, for example, 0.1 to 3% by weight.

에폭시수지 조성물은 EMMI-1-66에서 175℃, 70kgf/㎠에서 트랜스퍼 몰딩 프레스에 의한 유동길이가 59 내지 75inch가 될 수 있다. 상기 범위에서, 에폭시수지 조성물의 용도로 사용될 수 있다.The epoxy resin composition may have a flow length of 59 to 75 inches by transfer molding press at 175 DEG C and 70 kgf / cm &lt; 2 &gt; in EMMI-1-66. Within this range, it can be used for the use of epoxy resin composition.

에폭시수지 조성물은 하기 식 1에 의해 측정된 경화수축률이 0.4% 미만, 예를 들면 0.01 내지 0.39%가 될 수 있다. 상기 범위에서, 경화수축률이 낮아 에폭시수지 조성물의 용도로 사용될 수 있다:The epoxy resin composition may have a curing shrinkage of less than 0.4%, for example, from 0.01 to 0.39%, as measured by the following formula (1). Within this range, the curing shrinkage is low and can be used for epoxy resin composition applications:

<식 1> <Formula 1>

경화수축률= ｜C - D｜/C x 100Cure shrinkage rate = | C - D | / C x 100

(상기 식 1에서, C는 에폭시수지 조성물을 175℃, 70kgf/㎠에서 트랜스퍼 몰딩 프레스하여 얻은 시편의 길이, D는 상기 시편을 170~180℃에서 4시간 후경화(PMC:post molding cure)하고, 냉각시킨 후 얻은 시편의 길이이다).(C represents the length of the specimen obtained by transfer molding pressing the epoxy resin composition at 175 DEG C and 70 kgf / cm &lt; 2 &gt;, and D is the post cure of the specimen at 170 to 180 DEG C for 4 hours , And the length of the specimen obtained after cooling).

상기 범위에서, 경화수축률이 낮아 에폭시수지 조성물의 용도로 사용될 수 있다.Within this range, the curing shrinkage is low and can be used as an epoxy resin composition.

에폭시수지 조성물 중 에폭시수지는 단독으로 사용되거나, 경화제, 경화촉매, 이형제, 커플링제, 및 응력완화제 등의 첨가제와 멜트 마스터 배치(melt master batch)와 같은 선반응을 시켜 만든 부가 화합물로도 포함될 수 있다. 에폭시수지 조성물을 제조하는 방법은 특별히 제한되지 않지만, 조성물에 포함되는 각 구성성분을 헨셀 믹서나 뢰디게 믹서를 이용하여 균일하게 혼합한 후, 롤 밀이나 니이더로 90~120℃에서 용융 혼련하고, 냉각 및 분쇄 과정을 거쳐 제조될 수 있다.
The epoxy resin in the epoxy resin composition may be used alone or as an additive compound prepared by a linear reaction such as a curing agent, a curing catalyst, an additive such as a releasing agent, a coupling agent, a stress relaxation agent, and a melt master batch have. The method for producing the epoxy resin composition is not particularly limited, but the components contained in the composition are homogeneously mixed using a Henschel mixer or a Lodige mixer, and then melt-kneaded at 90 to 120 캜 in a roll mill or kneader , Cooling and milling processes.

본 발명의 수지 조성물의 용도는 반도체 소자 밀봉용도, 접착필름, 프리프레그 등의 절연수지시트, 회로기판, 솔더레지스트, 언더필제, 다이본딩재, 부품 보충 수지 용도 등의 에폭시수지 조성물이 필요로 하는 광범위한 용도에 적용될 수 있으며, 이에 제한되는 것은 아니다.The use of the resin composition of the present invention is not limited to the use of the epoxy resin composition such as an insulating resin sheet such as an adhesive film or prepreg, a circuit board, a solder resist, an underfill, a die bonding material, But it is not limited thereto.

반도체 소자 밀봉Semiconductor device sealing

본 발명의 에폭시수지 조성물은 반도체 소자 밀봉용도로 사용될 수 있고, 에폭시수지, 경화제, 포스포늄계 화합물 함유 경화촉매, 무기충진제, 첨가제를 포함할 수 있다.The epoxy resin composition of the present invention can be used for sealing semiconductor devices and can include an epoxy resin, a curing agent, a curing catalyst containing a phosphonium compound, an inorganic filler, and an additive.

본 발명의 반도체 소자는 상기 에폭시수지 조성물을 사용하여 밀봉될 수 있다. The semiconductor device of the present invention can be sealed using the above epoxy resin composition.

도 1은 본 발명 일 실시예의 반도체 소자의 단면도이다. 도 1을 참조하면, 본 발명 일 실시예의 반도체 소자(100)는 배선기판(10), 배선기판(10) 위에 형성된 범프(30), 범프(30) 위에 형성된 반도체칩(20)을 포함하고, 배선기판(10)과 반도체칩(20) 간의 갭은 에폭시수지 조성물(40)로 봉지될 수 있고, 에폭시수지 조성물은 본 발명 실시예의 에폭시수지 조성물이 될 수 있다.1 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention. 1, a semiconductor device 100 according to an embodiment of the present invention includes a wiring board 10, a bump 30 formed on the wiring board 10, and a semiconductor chip 20 formed on the bump 30, The gap between the wiring board 10 and the semiconductor chip 20 can be sealed with the epoxy resin composition 40 and the epoxy resin composition can be the epoxy resin composition of the embodiment of the present invention.

도 2는 본 발명 다른 실시예의 반도체 소자의 단면도이다. 도 2를 참조하면, 본 발명 다른 실시예의 반도체 소자(200)는 배선기판(10), 배선기판(10) 위에 형성된 범프(30), 범프(30) 위에 형성된 반도체칩(20)을 포함하고, 배선기판(10)과 반도체칩(20) 간의 갭과 반도체칩(30) 상부면 전체가 에폭시수지 조성물(40)로 봉지될 수 있고, 에폭시수지 조성물은 본 발명 실시예의 반도체 소자 밀봉용 에폭시수지 조성물을 포함할 수 있다.2 is a cross-sectional view of a semiconductor device according to another embodiment of the present invention. 2, a semiconductor device 200 according to another embodiment of the present invention includes a wiring board 10, a bump 30 formed on the wiring board 10, and a semiconductor chip 20 formed on the bump 30, The gap between the wiring substrate 10 and the semiconductor chip 20 and the entire upper surface of the semiconductor chip 30 can be sealed with the epoxy resin composition 40. The epoxy resin composition can be used as the epoxy resin composition for sealing semiconductor devices . &Lt; / RTI &gt;

도 1과 도 2에서 배선기판, 범프, 반도체 칩의 각각의 크기, 범프의 개수는 임의의 도시된 것으로서, 변경될 수 있다.In Figs. 1 and 2, the size of each of the wiring board, the bump, and the semiconductor chip, and the number of bumps are arbitrary and can be changed.

본 발명의 조성물을 이용하여 반도체 소자를 밀봉하는 방법은 저압 트랜스퍼 성형 방법이 가장 일반적으로 사용될 수 있다. 그러나, 인젝션(injection) 성형 방법이나 캐스팅(casting) 방법 등의 방법으로도 성형될 수 있다. 상기 방법에 의해 구리 리드프레임, 철 리드프레임, 또는 상기 리드프레임에 니켈 및 구리로 팔라듐으로 이루어진 군으로부터 선택되는 1종 이상의 물질로 프리플레이팅된 리드프레임, 또는 유기계 라미네이트 프레임의 반도체 소자를 제조할 수 있다.
A method of sealing a semiconductor device using the composition of the present invention is most commonly used for a low pressure transfer molding method. However, it can also be formed by a method such as an injection molding method or a casting method. According to the above method, a lead frame pre-plated with a copper lead frame, an iron lead frame, or at least one material selected from the group consisting of nickel and palladium on the lead frame, or a semiconductor element of an organic laminate frame is manufactured .

이하, 본 발명을 실시예에 의거 더욱 상세히 설명하나, 실시예에 의거 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

실시예 및 비교예에서 사용된 성분의 구체적인 사양은 다음과 같다.Specific specifications of the components used in Examples and Comparative Examples are as follows.

(A) 에폭시수지(A) an epoxy resin

비페닐형 에폭시수지인 NC-3000(Nippon Kayaku)를 사용하였다.NC-3000 (Nippon Kayaku), a biphenyl type epoxy resin, was used.

(B) 경화제(B) Curing agent

자일록형 페놀수지인　HE100C-10(Air Water)를 사용하였다.And HE100C-10 (Air Water), which is a xylock type phenol resin, was used.

(C) 경화촉매(C) Curing catalyst

(C1)1.7g 의 2,3-dihydroxynaphtalene을 메탄올 50㎖ 에 녹이고 Potassium hydroxide 1M을 10㎖ 첨가 하여 이 혼합물을 1시간 동안 실온에서 교반시킨 후 0.9 g 의 Zinc acetate를 첨가하였다. 이 혼합물을 실온에서 3시간 교반시킨 후 4.2　g의 Tetraphenylphosphonium bromide를 용액 메탄올 5.0㎖에 녹여 첨가한 후 상온에서 약 2시간 정도 반응시켰다. 반응이 끝난 뒤에 불용인 고체를 필터링으로 제거한 후 얻어진 용액의 용매를 저압에서 제거하여 화학식 1a의 화합물　을 얻어냈다(수율: 85 %). NMR 데이타로 하기 화학식 1a 의 화합물임을 확인하였다.(C1) 1.7 g of 2,3-dihydroxynaphthalene was dissolved in 50 ml of methanol, 10 ml of 1M potassium hydroxide was added, and the mixture was stirred at room temperature for 1 hour, and then 0.9 g of Zinc acetate was added. After the mixture was stirred at room temperature for 3 hours, 4.2 g of Tetraphenylphosphonium bromide was dissolved in 5.0 ml of methanol solution and reacted at room temperature for about 2 hours. After the reaction was completed, the insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at a low pressure to obtain the compound of formula (Ia) (yield: 85%). It was confirmed by NMR data that the compound represented by the following formula (1a).

[화학식 1a] [Formula 1a]

Figure 112014116183593-pat00017
Figure 112014116183593-pat00017

1H NMR (400 MHz, DMSO) 7.96 (t, J= 2.4Hz, 8H), 7.85-7.80 (m, 16H), 7.75-7.70 (m, 16H), 7.42-7.39 (d, 4H), 7.03-7.00 (d, 4H), 6.90 (s, 4H) ppm; 31P NMR (166 MHz, DMSO) 24.20 ppm 1 H NMR (400 MHz, DMSO ) 7.96 (t, J = 2.4Hz, 8H), 7.85-7.80 (m, 16H), 7.75-7.70 (m, 16H), 7.42-7.39 (d, 4H), 7.03- 7.00 (d, 4H), 6.90 (s, 4H) ppm; &Lt; 31 &gt; P NMR (166 MHz, DMSO) 24.20 ppm

(C2)1.1g 의 catechol 을 메탄올 50㎖ 에 녹이고 Potassium hydroxide 1M을 10㎖ 첨가 하여 이 혼합물을 1시간 동안 실온에서 교반시킨 후 Zinc acetate 0.9 g을 첨가하였다. 이 혼합물을 실온에서 3시간 교반시킨 후 4.2 g의 Tetraphenylphosphonium bromide를 메탄올 5.0㎖에 녹여 첨가한 후 상온에서 약 2시간 정도 반응시켰다. 반응이 끝난 뒤에 불용인 고체를 필터링으로 제거한 후 얻어진 용액의 용매를 저압에서 제거하여 화학식 1b의 화합물을 얻어냈다(수율: 83 %). NMR 데이타로 하기 화학식 1b의 화합물임을 확인하였다.(C2) 1.1 g of catechol was dissolved in 50 ml of methanol, 10 ml of 1M potassium hydroxide was added, and the mixture was stirred at room temperature for 1 hour. Then, 0.9 g of zinc acetate was added thereto. The mixture was stirred at room temperature for 3 hours, and 4.2 g of tetraphenylphosphonium bromide was dissolved in 5.0 ml of methanol, and the mixture was reacted at room temperature for about 2 hours. After the reaction was completed, the insoluble solid was removed by filtration, and the solvent of the resulting solution was removed under reduced pressure to obtain the compound of formula (Ib) (yield: 83%). It was confirmed by NMR data that the compound of formula (1b) was obtained.

[화학식 1b][Chemical Formula 1b]

Figure 112014116183593-pat00018
Figure 112014116183593-pat00018

1H NMR (400 MHz, DMSO) 7.97 (t, J　= 2.4Hz, 8H), 7.84-7.81 (m, 16H), 7.76-7.72 (m, 16H), 6.46 (s, 8H) ppm; 31P NMR (166 MHz, DMSO) 24.30 ppm 1 H NMR (400 MHz, DMSO ) 7.97 (t, J = 2.4Hz, 8H), 7.84-7.81 (m, 16H), 7.76-7.72 (m, 16H), 6.46 (s, 8H) ppm; &Lt; 31 &gt; P NMR (166 MHz, DMSO) 24.30 ppm

(C3)1.3g 의 2-hydroxybenzenethiol을 메탄올 50㎖에 녹이고 Potassium hydroxide 1M을 10㎖ 첨가 하여 이 혼합물을 1시간 동안 실온에서 교반시킨 후 0.9 g의 Zinc acetate 을 첨가하였다. 이 혼합물을 실온에서 3시간 교반시킨 후 4.2 g의 Tetraphenylphosphonium bromide을 메탄올 5.0㎖에 녹여 첨가한 후 상온에서 약 2시간 정도 반응시켰다. 반응이 끝난 뒤에 불용인 고체를 필터링으로 제거한 후 얻어진 용액의 용매를 저압에서 제거하여 화학식 1c의 화합물을 얻어냈다(수율: 86 %). NMR 데이타로 하기 화학식 1c의 화합물임을 확인하였다.(C3) 1.3 g of 2-hydroxybenzenethiol was dissolved in 50 ml of methanol, 10 ml of 1M potassium hydroxide was added, and the mixture was stirred at room temperature for 1 hour, and then 0.9 g of Zinc acetate was added thereto. After the mixture was stirred at room temperature for 3 hours, 4.2 g of tetraphenylphosphonium bromide was dissolved in 5.0 ml of methanol, and the mixture was reacted at room temperature for about 2 hours. After the reaction was completed, the insoluble solid was removed by filtration, and the solvent of the resulting solution was removed under reduced pressure to obtain the compound of formula (1c) (yield: 86%). It was confirmed by NMR data that the compound of the following formula (1c).

[화학식 1c][Chemical Formula 1c]

Figure 112014116183593-pat00019
Figure 112014116183593-pat00019

1H NMR (400 MHz, DMSO) 7.96 (t, J= 2.4Hz, 8H), 7.84-7.80 (m, 16H), 7.76-7.72 (m, 16H), 7.27-7.24 (dd, 2H), 7.05-7.01 (dt, 2H), 6.70-6.67 (dd, 2H), 6.56-6.51 (dt, 2H) ppm; 31P NMR (166 MHz, DMSO) 24.40 ppm 1 H NMR (400 MHz, DMSO ) 7.96 (t, J = 2.4Hz, 8H), 7.84-7.80 (m, 16H), 7.76-7.72 (m, 16H), 7.27-7.24 (dd, 2H), 7.05- 7.01 (dt, 2H), 6.70-6.67 (dd, 2H), 6.56-6.51 (dt, 2H) ppm; &Lt; 31 &gt; P NMR (166 MHz, DMSO) 24.40 ppm

(C4)1.6g 의 thiosalicylic acid 을 메탄올 50㎖ 에 녹이고　Potassium hydroxide 1M을 10㎖ 첨가 하여 이 혼합물을 1시간 동안 실온에서 교반시킨 후 0.9 g의 Zinc acetate을 첨가하였다. 이 혼합물을 실온에서 3시간 교반시킨 후 4.3 g의 (4-Hydroxy-phenyl)-triphenylphosphonium bromide를 메탄올 5.0㎖에 녹여 첨가한 후 상온에서 약 2시간 정도 반응시켰다. 반응이 끝난 뒤에 불용인 고체를 필터링으로 제거한 후 얻어진 용액의 용매를 저압에서 제거하여 화학식 1d의 화합물을 얻어냈다(수율: 92%). NMR 데이타로 하기 화학식 1d의 화합물임을 확인하였다.(C4) 1.6 g of thiosalicylic acid was dissolved in 50 mL of methanol, 10 mL of 1M potassium hydroxide was added, and the mixture was stirred at room temperature for 1 hour. Then 0.9 g of Zinc acetate was added. The mixture was stirred at room temperature for 3 hours, and then 4.3 g of (4-Hydroxy-phenyl) -triphenylphosphonium bromide was dissolved in 5.0 mL of methanol and reacted at room temperature for about 2 hours. After the reaction was completed, the insoluble solid was removed by filtration, and the solvent of the resulting solution was removed under reduced pressure to give the compound of formula (1d) (yield: 92%). It was confirmed by NMR data that the compound of the formula (1d) was obtained.

[화학식 1d]&Lt; RTI ID = 0.0 &

Figure 112014116183593-pat00020
Figure 112014116183593-pat00020

1H NMR (400 MHz, DMSO) 7.94 (t, J= 2.4Hz, 6H), 7.82-7.76 (m, 12H), 7.73-7.66 (m, 12H), 7.56-7.54 (dd, 2H), 7.48-7.41 (m, 4H), 7.21-7.18 (dd, 2H), 7.11-7.09 (dd, 4H), 6.87-6.82 (dt, 2H), 6.75-6.70 (dt, 2H) ppm; 31P NMR (166 MHz, DMSO) 24.40 ppm 1 H NMR (400 MHz, DMSO ) 7.94 (t, J = 2.4Hz, 6H), 7.82-7.76 (m, 12H), 7.73-7.66 (m, 12H), 7.56-7.54 (dd, 2H), 7.48- 7.41 (m, 4H), 7.21-7.18 (dd, 2H), 7.11-7.09 (dd, 4H), 6.87-6.82 (dt, 2H), 6.75-6.70 (dt, 2H) ppm; &Lt; 31 &gt; P NMR (166 MHz, DMSO) 24.40 ppm

(C5)2.2g의 2-Hydroxy-N-phenyl-benzamide을 메탄올 50㎖ 에 녹이고 Potassium hydroxide 1M을 10㎖ 첨가하여 이 혼합물을 1시간 동안 실온에서 교반시킨 후 0.9 g의 Zinc acetate를 첨가하였다. 이 혼합물을 실온에서 3시간 교반시킨 후 4.3 g의 (3-Hydroxy-phenyl)-triphenylphosphonium bromide을 메탄올 5.0㎖에 녹여 첨가한 후 상온에서 약 2시간 정도 반응시켰다. 반응이 끝난 뒤에 불용인 고체를 필터링으로 제거한 후 얻어진 용액의 용매를 저압에서 제거하여 화학식 1e의 화합물을 얻어냈다(수율: 90%). NMR 데이타로 하기 화학식 1e의 화합물임을 확인하였다.(C5) 2.2 g of 2-Hydroxy-N-phenyl-benzamide was dissolved in 50 ml of methanol, 10 ml of 1M potassium hydroxide solution was added, and the mixture was stirred at room temperature for 1 hour. Then 0.9 g of Zinc acetate was added. After the mixture was stirred at room temperature for 3 hours, 4.3 g of (3-Hydroxy-phenyl) -triphenylphosphonium bromide was dissolved in 5.0 ml of methanol and reacted at room temperature for about 2 hours. After the reaction was completed, the insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at a low pressure to obtain the compound of formula (1e) (yield: 90%). It was confirmed by NMR data that the compound represented by the following formula (1e).

[화학식 1e][Formula 1e]

Figure 112014116183593-pat00021
Figure 112014116183593-pat00021

1H NMR (400 MHz, DMSO) 7.94-7.89 (t, J= 2.4Hz, 6H),7.82-7.66 (m, 30H), 7.36-7.33 (dd, 2H), 7.31-7.26 (dt, 4H), 7.15-7.09 (m, 4H), 7.02-6.91 (m, 6H), 6.66-6.63 (dd, 2H), 6.47-6.42 (dt, 2H) ppm; 31P NMR (166 MHz, DMSO) 24.50 ppm 1 H NMR (400 MHz, DMSO ) 7.94-7.89 (t, J = 2.4Hz, 6H), 7.82-7.66 (m, 30H), 7.36-7.33 (dd, 2H), 7.31-7.26 (dt, 4H), 7.15-7.09 (m, 4H), 7.02-6.91 (m, 6H), 6.66-6.63 (dd, 2H), 6.47-6.42 (dt, 2H) ppm; &Lt; 31 &gt; P NMR (166 MHz, DMSO) 24.50 ppm

(C6) 트리페닐 포스핀 (Triphenyl phosphine)(C6) Triphenyl phosphine

(C7) 트리페닐 포스핀과 1,4-벤조퀴논의 부가 생성물(C7) adduct of triphenylphosphine with 1,4-benzoquinone

(D) 무기 충전제: 평균입경 18㎛의 구상 용융실리카와 평균입경 0.5㎛의 구상 용융실리카의 9:1(중량비) 혼합물을 사용하였다.(D) Inorganic filler: A 9: 1 (weight ratio) mixture of spherical fused silica having an average particle diameter of 18 μm and spherical fused silica having an average particle diameter of 0.5 μm was used.

(E) 커플링제(E) Coupling agent

(e1) 머캡토프로필트리메톡시실란인 KBM-803(Shinetsu)과 (e2) 메틸트리메톡시실란인 SZ-6070(Dow Corning chemical)을 혼합하여 사용하였다. (e1) was mixed with KBM-803 (Shinetsu), which is a mercaptopropyltrimethoxysilane, and SZ-6070 (Dow Corning chemical), which is e2) methyltrimethoxysilane.

(F) 첨가제 (F) Additive

(f1) 이형제로 카르나우바왁스 및 (f2) 착색제로 카본 블랙 MA-600(Matsusita Chemical)을 사용하였다.
Carbon black MA-600 (Matsusita Chemical) was used as (f1) carnauba wax and (f2) colorant.

실시예 및 비교예Examples and Comparative Examples

상기 각 성분들을 하기 표 1의 조성(단위: 중량부)에 따라 각 성분들을 평량한 후 헨셀 믹서를 이용하여 균일하게 혼합하여 분말 상태의 1차 조성물을 제조하였다. 이후 연속 니이더를 이용하여 95℃에서 용융 혼련한 후 냉각 및 분쇄하여 반도체 소자 밀봉용 에폭시수지 조성물을 제조하였다.Each of the components was weighed according to the composition (unit: parts by weight) shown in the following Table 1, and then uniformly mixed using a Henschel mixer to prepare a powdery primary composition. Thereafter, the mixture was melt-kneaded at 95 DEG C using a continuous kneader, followed by cooling and pulverization, thereby preparing an epoxy resin composition for sealing semiconductor devices.


구 분
division 실시예Example 비교예Comparative Example 1One 22 33 44 55 1One 22 (A)(A) 8.98.9 8.98.9 8.98.9 8.98.9 8.98.9 8.98.9 8.98.9 (B)(B) 4.74.7 4.74.7 4.74.7 4.74.7 4.74.7 4.74.7 4.74.7


(C)


(C) (C1)(C1) 0.40.4 -- -- -- -- -- -- (C2)(C2) -- 0.40.4 -- -- -- -- -- (C3)(C3) -- -- 0.40.4 -- -- -- -- (C4)(C4) -- -- -- 0.40.4 -- -- -- (C5)(C5) -- -- -- -- 0.40.4 -- -- (C6)(C6) -- -- -- -- -- 0.40.4 -- (C7)(C7) -- -- -- -- -- -- 0.40.4 (D)(D) 8585 8585 8585 8585 8585 8585 8585 (E)(E) (e1)(e1) 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 (e2)(e2) 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 (F)(F) (f1)(f1) 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 (f2)(f2) 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3

실시예와 비교예에서 제조한 에폭시 조성물에 대해 이하에서 서술하는 측정방법을 통하여 하기 표 2의 물성을 평가하였다.The properties of the epoxy compositions prepared in Examples and Comparative Examples were evaluated in the following Table 2 through the measurement methods described below.

(1) 유동성(inch): EMMI-1-66에 준하여 평가용 금형을 사용하여 175℃, 70kgf/㎠ 에서 트랜스퍼 몰딩 프레스(transfer molding press)를 이용하여 유동 길이를 측정하였다. 측정값이 높을수록 유동성이 우수하다. (1) Fluidity (inch): Using an evaluation mold according to EMMI-1-66, the temperature was 175 ° C and 70 kgf / cm 2 The flow length was measured using a transfer molding press. The higher the measured value, the better the fluidity.

(2) 경화 수축율(%): 굴곡 강도 시편 제작용 금형을 사용하여 175℃, 70kgf/㎠에서 트랜스퍼 몰딩 프레스(transfer molding press)를 이용하여 성형시편(125 X 12.6 X 6.4mm)을 얻었다. 얻은 시편을 170~180℃의 오븐에 넣어 4시간 동안 후경화(PMC:post molding cure)시킨 다음 냉각한 후 시험편의 길이를 캘리퍼스로 측정하였다. 경화 수축율은 다음과 같은 식 1로부터 계산하였다.(2) Curing shrinkage (%): Flexural strength A molding specimen (125 X 12.6 X 6.4 mm) was obtained using a transfer molding press at 175 ° C and 70 kgf / cm 2 using a mold for preparing a specimen. The obtained specimens were post-cured (PMC) in an oven at 170 to 180 ° C for 4 hours, cooled, and the length of the specimens was measured with a caliper. The hardening shrinkage ratio was calculated from Equation 1 as follows.

<식 1> <Formula 1>

경화수축률= ｜C - D｜/ C x 100Cure shrinkage rate = | C - D | / C x 100

(상기 식 1에서, C는 에폭시수지 조성물을 175℃, 70kgf/㎠의 트랜스퍼 몰딩 프레스하여 얻은 시편의 길이, D는 상기 시편을 170~180℃에서 4시간 후경화하고 냉각시킨 후 얻은 시편의 길이이다.)C is the length of the specimen obtained by transfer molding the epoxy resin composition at 175 DEG C and 70 kgf / cm &lt; 2 &gt;, D is the length of the specimen obtained after curing the specimen at 170 to 180 DEG C for 4 hours to be.)

(3) 유리전이온도(℃): 열기계 분석기(Thermomechanical Analyzer, TMA)를 이용하여 측정하였다. 이 때 TMA는 25℃에서 분당 10℃씩 온도를 상승시켜 300℃까지 측정하는 조건으로 설정하였다.(3) Glass transition temperature (占 폚): Measured using a thermomechanical analyzer (TMA). At this time, the TMA was set to a condition of measuring up to 300 DEG C by raising the temperature by 10 DEG C per minute at 25 DEG C.

(4) 흡습율(%): 상기 실시예와 비교예에서 제조된 수지 조성물을 금형 온도 170~180℃, 클램프 압력 70kgf/㎠, 이송 압력 1000psi, 이송 속도 0.5~1cm/s, 경화 시간 120초의 조건으로 성형하여 직경 50mm, 두께 1.0mm의 디스크 형태의 경화 시편을 얻었다. 얻은 시편을 170~180℃의 오븐에 넣어 4시간 동안 후경화(PMC:post molding cure)시킨 직후 85℃, 85RH% 상대 습도 조건 하에서 168시간 동안 방치시킨 후 흡습에 의한 무게 변화를 측정하여 다음 식 2에 의하여 흡습율을 계산하였다.(4) Moisture absorption rate (%): The resin compositions prepared in the above Examples and Comparative Examples were heated at a mold temperature of 170 to 180 DEG C, a clamp pressure of 70 kgf / cm2, a feed pressure of 1000 psi, a feed rate of 0.5 to 1 cm / To obtain a disk-shaped cured specimen having a diameter of 50 mm and a thickness of 1.0 mm. The obtained specimens were placed in an oven at 170 to 180 ° C. and post-cured for 4 hours. The samples were allowed to stand for 168 hours at 85 ° C. and 85 RH% relative humidity, and the weight change due to moisture absorption was measured. 2, the moisture absorption rate was calculated.

<식 2><Formula 2>

흡습율 = (흡습 후 시험편의 무게 - 흡습 전 시험편의 무게)÷(흡습 전 시험편의 무게) X 100Moisture absorption rate = (weight of test piece after moisture absorption - weight of test piece before moisture absorption) ÷ (weight of test piece before moisture absorption) X 100

(5) 부착력(kgf): 구리 금속 소자를 부착 측정용 금형에 맞는 규격으로 준비하고,준비된 시험편에 상기 실시예와 비교예에서 제조된 수지 조성물을 금형 온도170~180℃, 클램프 압력 70kgf/㎠, 이송 압력 1000psi, 이송속도 0.5~1cm/s, 경화　시간 120초의 조건으로 성형하여 경화 시편을 얻었다. 얻은 시편을 170~180℃의 오븐에 넣어 4시간 동안 후경화(PMC:post molding cure)시켰다. 이때 시편에 닿는 에폭시수지 조성물의 면적은 40±1㎟이고, 부착력 측정은 각 측정 공정 당 12개의 시편에 대하여 UTM(Universal Testing Machine)을 이용하여 측정한 후 평균값으로 계산하였다.(5) Adhesive force (kgf): A copper metal element was prepared in accordance with the mold for measurement of adhesion, and the resin composition prepared in the above Examples and Comparative Examples was pressed into a prepared test piece at a mold temperature of 170 to 180 DEG C and a clamp pressure of 70 kgf / , A feed pressure of 1000 psi, a feed rate of 0.5 to 1 cm / s, and a curing time of 120 seconds to obtain a cured specimen. The obtained specimens were post-cured (PMC) in an oven at 170 to 180 ° C for 4 hours. In this case, the area of the epoxy resin composition contacting the specimen was 40 ± 1 mm 2, and the adhesion was measured by using a universal testing machine (UTM) for 12 specimens per each measuring step, and then the average value was calculated.

(6) 경화도(shore-D): 구리 금속 소자를 포함하는 가로 24mm, 세로 24mm, 두께 1mm인 eTQFP(exposed Thin Quad Flat Package) 패키지용 금형이 장착된 MPS(Multi Plunger System) 성형기를 이용하여 175℃에서 50, 60, 70, 80 그리고 90초간 평가하고자 하는 에폭시수지 조성물을 경화시킨 후 금형 위의 패지지에 직접 Shore-D형 경도계로 경화시간에 따른 경화물의 경도를 측정하였다. 값이 높을 수록 경화도가 우수하다. (6) Shore-D: Using an MPS (Multi Plunger System) molding machine equipped with a mold for an eTQFP (exposed Thin Quad Flat Package) package having a width of 24 mm, a length of 24 mm and a thickness of 1 mm including a copper metal element After curing the epoxy resin composition to be evaluated at 175 ° C for 50, 60, 70, 80 and 90 seconds, the hardness of the cured product was measured by a Shore-D type hardness meter directly on the lap on the mold. The higher the value, the better the degree of cure.

(7) 저장안정성: 에폭시수지 조성물을 25℃/50RH%로 설정된 항온항습기에 1주간 보존하면서 24시간 간격으로 상기 (1)의 유동성 측정과 같은 방법으로 유동길이를 측정하고, 제조 직후의 유동길이에 대한 백분율(%)을 구했다. 이 백분율의 수치가 클수록 저장안정성이 양호한 것을 나타낸다. (7) Storage stability: The flow length was measured at the intervals of 24 hours in the same manner as the fluidity measurement in the above (1) while the epoxy resin composition was stored in a thermostatic hygrostat set at 25 ° C / 50RH% for 1 week, (%) Was obtained. The larger this percentage value, the better the storage stability.

(8) 신뢰성: 상기 휨 특성 평가용 eTQFP 패키지를 125℃에서 24시간 동안 건조시킨 후 5 사이클(1 사이클은 패키지를 -65℃에서 10분, 25℃에서 10분, 150℃에서 10분씩 방치하는 것을 나타냄)의 열충격 시험을 수행하였다. 이후 패키지를 85℃, 60% 상대 습도 조건 하에서 168시간 동안 방치시킨 후 260℃에서 30초 동안 IR 리플로우를 1회 통과시키는 것을 3회 반복하는 프리컨디션 조건 이후에 패키지의 외관 크랙 발생 유무를 광학 현미경으로 관찰하였다. 이후 비파괴 검사인 C-SAM(Scanning Acoustic Microscopy)를 이용하여 에폭시수지 조성물과 리드프레임 간의 박리 발생 유무를 평가하였다.　패키지의 외관 크랙이 발생하거나 에폭시수지 조성물과 리드프레임간의 박리가 발생할 경우에는 패키지의 신뢰성을 확보할 수 없다.(8) Reliability: The eTQFP package for evaluating the flexural characteristics was dried at 125 DEG C for 24 hours, and then subjected to 5 cycles (one cycle was to leave the package at -65 DEG C for 10 minutes, 25 DEG C for 10 minutes, ) Were subjected to a thermal shock test. After the pre-conditioning condition in which the package is left for 168 hours at 85 ° C and 60% relative humidity and then passed once through the IR reflow for 30 seconds at 260 ° C, And observed with a microscope. Then, the occurrence of peeling between the epoxy resin composition and the lead frame was evaluated using a non-destructive inspection C-SAM (Scanning Acoustic Microscopy). When the appearance of the package is cracked or the peeling between the epoxy resin composition and the lead frame occurs, the reliability of the package can not be secured.

평가 항목Evaluation items 실시예Example 비교예Comparative Example 1One 22 33 44 55 1One 22 기
본
물
성group
example
water
castle 유동성(inch)Flowability (inch) 7070 7171 7373 7676 7474 5252 5858 경화수축율(%)Cure shrinkage (%) 0.390.39 0.370.37 0.380.38 0.340.34 0.350.35 0.420.42 0.400.40 유리전이온도(℃)Glass transition temperature (캜) 123123 123123 124124 123123 124124 121121 122122 흡습율(%)Moisture absorption rate (%) 0.250.25 0.250.25 0.240.24 0.250.25 0.240.24 0.250.25 0.260.26 부착력(kgf)Adhesion (kgf) 7777 7474 7575 7777 7676 7272 7474

패
키
지

평
가

tile
key
G

Flat
end 경화
시간별
경화도 (Shore-D)Hardening
Hourly
Hardness (Shore-D) 50초50 seconds 7272 6969 7171 7373 6868 5252 6060 60초60 seconds 7373 7070 7373 7575 7272 6060 6464 70초70 seconds 7575 7373 7676 7777 7474 6464 6666 80초80 seconds 7676 7575 7676 7878 7676 6767 7070 90초90 seconds 7777 7676 7878 7979 7878 6767 7171 저장
안정성Save
stability 24 시간24 hours 96%96% 97%97% 97%97% 98%98% 98%98% 90%90% 92%92% 48 시간48 hours 94%94% 95%95% 92%92% 94%94% 94%94% 84%84% 88%88% 72 시간72 hours 92%92% 93%93% 90%90% 92%92% 90%90% 74%74% 79%79%
신뢰성
responsibility 외관크랙 발생수Exterior cracks can occur 00 00 00 00 00 00 00 박리 발생수Number of peeling occurrences 00 00 00 00 00 4545 2020 시험한 반도체수Number of tested semiconductors 8888 8888 8888 8888 8888 8888 8888

실시예 1 내지 5는 높은 유동성을 나타내며, 저장안정성의 경우 72 시간 후의 결과에서도 유동성의 차이가 거의 없는 것을 확인할 수 있고, 외관 크랙이 발생하지 않아 내크랙성이 양호하며 박리발생이 없는 것으로 볼 때 내습 신뢰성도 우수하다는 것을 알 수 있다.Examples 1 to 5 exhibited high fluidity, and in the case of storage stability, it was confirmed that there was almost no difference in fluidity even after 72 hours. In view of the fact that no external cracks occurred, crack resistance was good, and no peeling occurred It can be seen that the moisture resistance reliability is also excellent.

실시예 4 및 5는 비교예 1 및 2와 비교할 때, 높은 유동성을 나타내며 경화 수축률이 작다. 또한 경화시간별 경화도를 비교할 때 짧은 경화시간에서도 더 높은 경화도를 나타내고 있는 것을 확인할 수 있다. 또한 저장안정성의 경우 72시간 후의 결과에서도 유동성의 차이가 거의 없는 것을 확인할 수 있다.Examples 4 and 5 exhibit high fluidity and a low curing shrinkage ratio as compared with Comparative Examples 1 and 2. [ In addition, when the curing time of each curing time is compared, it can be confirmed that a higher curing degree is exhibited even in a short curing time. In the case of storage stability, there is no difference in fluidity even after 72 hours.

반면에, 본 발명의 포스포늄계 화합물을 포함하지 않는 비교예 1 및 2의 조성물은 저장안정성이 낮고, 경화수축률은 높고, 유동성은 낮으며, 부착력이 낮고, 신뢰성에 문제가 있으므로 패키지에 사용시 본 발명의 효과를 구현할 수 없음을 확인할 수 있다.On the other hand, the compositions of Comparative Examples 1 and 2, which do not contain the phosphonium compound of the present invention, have low storage stability, high curing shrinkage, low fluidity, low adhesion and reliability problems. It can be confirmed that the effect of the invention can not be realized.

이상 본 발명의 실시예들을 설명하였으나, 본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야 한다.While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (11)

하기 화학식 1a 내지 1e중의 하나로 표시되는 포스포늄계 화합물:
[화학식 1a]
Figure 112017034720536-pat00031

[화학식 1b]
Figure 112017034720536-pat00032

[화학식 1c]
Figure 112017034720536-pat00033

[화학식 1d]
Figure 112017034720536-pat00034

[화학식 1e]
Figure 112017034720536-pat00035
A phosphonium compound represented by one of the following formulas (1a) to (1e):
[Formula 1a]
Figure 112017034720536-pat00031

[Chemical Formula 1b]
Figure 112017034720536-pat00032

[Chemical Formula 1c]
Figure 112017034720536-pat00033

&Lt; RTI ID = 0.0 &
Figure 112017034720536-pat00034

[Formula 1e]
Figure 112017034720536-pat00035
 에폭시수지, 경화제, 무기충전제 및 경화촉매를 포함하고,
상기 경화촉매는 하기 화학식 1로 표시되는 포스포늄계 화합물을 포함하는 에폭시수지 조성물:
[화학식 1]
Figure 112017034720536-pat00036

(상기 화학식 1에서, R1, R2, R3 및 R4 는 각각 독립적으로 치환 또는 비치환된 C1~C30의 지방족 탄화수소기, 치환 또는 비치환된 C6~C30의 방향족 탄화수소기, 또는 헤테로 원자를 포함하는 치환 또는 비치환된 C1~C30의 탄화수소기이고,
X1 및 X2는 각각 독립적으로 치환 또는 비치환된 C1~C30의 지방족 탄화수소기, 치환 또는 비치환된 C6~C30의 방향족 탄화수소기, 또는 헤테로 원자를 포함하는 치환 또는 비치환된 C1~C30의 탄화수소기이고, Y1, Y2, Y3, 및 Y4 는 각각 독립적으로 산소원자(O), 황원자(S) 또는 치환된 질소원자(N)이다).An epoxy resin, a curing agent, an inorganic filler, and a curing catalyst,
Wherein the curing catalyst comprises a phosphonium compound represented by the following Formula 1:
[Chemical Formula 1]
Figure 112017034720536-pat00036

(Wherein R 1 , R 2 , R 3 and R 4 each independently represent a substituted or unsubstituted C 1 -C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C6-C30 aromatic hydrocarbon group, or a hetero atom A substituted or unsubstituted C1 to C30 hydrocarbon group,
X 1 and X 2 each independently represents a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, or a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group containing a hetero atom And Y 1 , Y 2 , Y 3 and Y 4 are each independently an oxygen atom (O), a sulfur atom (S) or a substituted nitrogen atom (N). 제2항에 있어서, 상기 포스포늄계 화합물은 하기 화학식 1a 내지 1e중의 하나로 표시되는 에폭시수지 조성물:
[화학식 1a]
Figure 112017034720536-pat00037

[화학식 1b]
Figure 112017034720536-pat00038

[화학식 1c]
Figure 112017034720536-pat00039

[화학식 1d]
Figure 112017034720536-pat00040

[화학식 1e]
Figure 112017034720536-pat00041
The epoxy resin composition according to claim 2, wherein the phosphonium compound is represented by one of the following formulas (1a) to (1e):
[Formula 1a]
Figure 112017034720536-pat00037

[Chemical Formula 1b]
Figure 112017034720536-pat00038

[Chemical Formula 1c]
Figure 112017034720536-pat00039

&Lt; RTI ID = 0.0 &
Figure 112017034720536-pat00040

[Formula 1e]
Figure 112017034720536-pat00041
 제2항에 있어서, 상기 에폭시수지는 비스페놀 A형 에폭시수지, 비스페놀 F형 에폭시수지, 페놀노볼락형 에폭시수지, tert-부틸 카테콜형 에폭시수지, 나프탈렌형 에폭시수지, 글리시딜아민형 에폭시수지, 크레졸노볼락형 에폭시수지, 비페닐형 에폭시수지, 선형지방족에폭시수지, 지환식에폭시수지, 복소환식 에폭시수지, 스피로환 함유 에폭시수지, 시클로헥산디메탄올형 에폭시수지, 트리메틸올형 에폭시수지, 할로겐화 에폭시수지 중 하나 이상을 포함하는 에폭시수지 조성물. The epoxy resin composition according to claim 2, wherein the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, tert-butyl catechol epoxy resin, naphthalene epoxy resin, glycidylamine epoxy resin, Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin &Lt; / RTI &gt; 제2항에 있어서, 상기 경화제는 페놀아랄킬형 페놀수지, 페놀노볼락형 페놀수지, 자일록형 페놀수지, 크레졸 노볼락형 페놀수지, 나프톨형 페놀수지, 테르펜형 페놀수지, 다관능형 페놀수지, 디시클로펜타디엔계 페놀수지, 비스페놀 A와 레졸로부터 합성된 노볼락형 페놀수지, 트리스(하이드록시페닐)메탄, 디하이드록시바이페닐을 포함하는 다가 페놀 화합물, 무수 말레인산 및 무수 프탈산을 포함하는 산무수물, 메타페닐렌디아민, 디아미노디페닐메탄, 디아미노디페닐설폰 중 하나 이상을 포함하는 에폭시수지 조성물.The curing agent according to claim 2, wherein the curing agent is selected from the group consisting of a phenol aralkyl type phenol resin, a phenol novolak type phenol resin, a xylock type phenol resin, a cresol novolak type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, A chloropentadiene-based phenol resin, a novolak-type phenol resin synthesized from bisphenol A and resole, a polyhydric phenol compound including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride , Metaphenylene diamine, diaminodiphenyl methane, and diaminodiphenyl sulfone. 제2항에 있어서, 상기 경화촉매는 상기 에폭시수지 조성물 중 0.01 내지 5중량%로 포함되는 에폭시수지 조성물.The epoxy resin composition according to claim 2, wherein the curing catalyst is contained in an amount of 0.01 to 5 wt% of the epoxy resin composition. 제2항에 있어서, 상기 포스포늄계 화합물은 상기 경화촉매 중 10 내지 100중량%로 포함되는 에폭시수지 조성물.The epoxy resin composition according to claim 2, wherein the phosphonium compound is contained in the curing catalyst in an amount of 10 to 100% by weight. 제2항에 있어서, 상기 에폭시수지 조성물은 상기 에폭시수지 조성물 중 상기 에폭시수지 2 내지 17중량%, 상기 경화제 0.5 내지 13중량%, 상기 무기 충전제 70 내지 95중량%, 상기 경화촉매 0.01 내지 5중량%를 포함하는, 에폭시수지 조성물.The epoxy resin composition according to claim 2, wherein the epoxy resin composition comprises 2 to 17 wt% of the epoxy resin, 0.5 to 13 wt% of the curing agent, 70 to 95 wt% of the inorganic filler, 0.01 to 5 wt% &Lt; / RTI &gt; 제2항에 있어서, 상기 에폭시수지 조성물은 72시간 경과 후 저장안정성이 80%이상인 에폭시수지 조성물. The epoxy resin composition according to claim 2, wherein the epoxy resin composition has a storage stability of 80% or more after 72 hours. 제2항에 있어서, 상기 에폭시수지 조성물은 하기 식 1의 경화수축률이 0.4% 미만인 것을 특징으로 하는 에폭시수지 조성물:
<식 1>
경화수축률= ｜C - D｜/C x 100
(상기 식 1에서, C는 에폭시수지 조성물을 175℃, 70kgf/㎠의 트랜스퍼 몰딩 프레스하여 얻은 시편의 길이, D는 상기 시편을 170~180℃에서 4시간 후경화하고 냉각시킨 후 얻은 시편의 길이이다).3. The epoxy resin composition according to claim 2, wherein the epoxy resin composition has a curing shrinkage ratio of less than 0.4%
<Formula 1>
Cure shrinkage rate = | C - D | / C x 100
C is the length of the specimen obtained by transfer molding the epoxy resin composition at 175 DEG C and 70 kgf / cm &lt; 2 &gt;, D is the length of the specimen obtained after curing the specimen at 170 to 180 DEG C for 4 hours, to be). 제2항의 에폭시수지 조성물을 사용하여 밀봉된 반도체 소자.A semiconductor element sealed by using the epoxy resin composition of claim 2.
KR1020140169213A 2014-11-28 2014-11-28 Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same KR101768287B1 (en)

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