KR20130052509A - Thermosetting composition - Google Patents

Thermosetting composition Download PDF

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KR20130052509A
KR20130052509A KR1020120117789A KR20120117789A KR20130052509A KR 20130052509 A KR20130052509 A KR 20130052509A KR 1020120117789 A KR1020120117789 A KR 1020120117789A KR 20120117789 A KR20120117789 A KR 20120117789A KR 20130052509 A KR20130052509 A KR 20130052509A
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thermosetting composition
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radically polymerizable
polymer
polymerizable compound
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KR101929862B1 (en
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유우키 키무라
토모히로 에토우
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제이엔씨 주식회사
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    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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    • C08F216/36—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by a ketonic radical
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    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/12—Esters of monohydric alcohols or phenols
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    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
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    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

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Abstract

PURPOSE: A thermosetting composition is provided to be spread on a substrate with low critical surface tension, and to obtain an organic film with excellent heat resistance, transparency, and adhesion to a substrate. CONSTITUTION: A thermosetting composition contains a polymer and an organic solvent. The polymer is formed by copolymerizing a radical polymerizable compound represented by chemical formula 1, a radical polymerizable compound which has at least one selected from epoxy and alkoxysilyl, and another radical polymerizable compound. In the chemical formula 1, R1 is hydrogen or methyl, R2-R5 is a C1-5 alkyl, R6 is a C1-10 alkyl, m is an integer from 1-10, and n is an integer from 1-150.

Description

열경화성 조성물{THERMOSETTING COMPOSITION}Thermosetting Composition {THERMOSETTING COMPOSITION}

본 발명은, 전자 부품에 있어서의 절연 재료, 반도체 장치에 있어서의 패시베이션막, 버프 코트막, 층간 절연막 또는 평탄화막, 액정 표시 소자에 있어서의 층간 절연막 또는 컬러 필터용 보호막 등의 형성에 적용할 수 있으며, 동시에 낮은 임계 표면 장력을 갖는 기판에도 도포가 가능한 열경화성 조성물, 이에 의한 투명막 및 이러한 막을 갖는 전자 부품에 관한 것이다. INDUSTRIAL APPLICABILITY The present invention can be applied to formation of insulating materials in electronic components, passivation films in semiconductor devices, buff coat films, interlayer insulating films or planarization films, interlayer insulating films in liquid crystal display elements, protective films for color filters, and the like. And a thermosetting composition which can be applied to a substrate having a low critical surface tension at the same time, a transparent film thereby, and an electronic component having such a film.

전자 기기에 따라서는, 유기막을 형성하는 바탕이 낮은 표면 에너지를 갖는 경우가 있다. 이 경우, 종래의 열경화성 조성물에서는, 스핀 코트, 슬릿 코트 또는 인쇄 등에 의한 도포 시에 열경화성 조성물 용액이 튕겨져서, 코팅 불량이 생겨버린다고 하는 문제가 있었다. 한편, 전자 기기 제조 프로세스의 저비용화를 위해서, 각종 미세 가공을 위한 광 리소그래피 공정을 생략하기 위해 인쇄법에 의한 직접 패터닝이 시도되고 있다. 이들 중에는 여러 가지 방법이 있는데, 예를 들면, 반전 오프셋 인쇄법의 경우, 실리콘계 블랭킷 실린더의 전면에 슬릿 코터 등으로 열경화성 조성물(잉크)을 도포하여, 상기 블랭킷을 미리 표면에 요철이 패터닝된 유리 등의 기판(클리쉐)에 불필요한 부분을 전사하고, 그 후 블랭킷에 남은 잉크를 기판에 전사해서 패터닝한다. 이 때의 블랭킷 재질에는 실리콘계의 낮은 임계 표면 장력을 갖는 재료가 사용되므로, 종래의 잉크를 그대로 도포하면 블랭킷에 잉크를 도포하는 단계에서 튕겨져 버려, 인쇄할 수 없다고 하는 문제가 있었다. Depending on the electronic device, the ground for forming the organic film may have low surface energy. In this case, in the conventional thermosetting composition, there existed a problem that the thermosetting composition solution jumps out at the time of application | coating by a spin coat, a slit coat, printing, etc., and a coating defect arises. On the other hand, in order to reduce the cost of the electronic device manufacturing process, direct patterning by the printing method has been attempted in order to omit the optical lithography process for various fine processing. Among these, there are various methods. For example, in the case of the reverse offset printing method, a thermosetting composition (ink) is applied to a front surface of a silicon blanket cylinder with a slit coater or the like, and the blanket is patterned on the surface in advance. The unnecessary portion is transferred to the substrate (cliché) of the substrate, and then the ink remaining on the blanket is transferred to the substrate and patterned. In this case, since the material having a low critical surface tension of silicon-based is used as the blanket material, there is a problem that if the conventional ink is applied as it is, it is thrown off at the step of applying the ink to the blanket and cannot be printed.

특허 문헌 1에는, 유기 반도체 잉크를 반전 오프셋 인쇄하기 위한 기술이 개시되어 있다. 불소계 계면 활성제를 첨가하는 것으로 블랭킷으로의 도포성을 부여하는 것이 가능하다. Patent Document 1 discloses a technique for reverse offset printing an organic semiconductor ink. By adding a fluorochemical surfactant, it is possible to give applicability | paintability to a blanket.

선행 기술 문헌Prior art literature

특허 문헌 1: 국제 공개 특허 제2010/113931호 팸플릿Patent Document 1: International Publication No. 2010/113931 Pamphlet

조성물의 도포성은 그 표면 장력의 값에 좌우된다. 종래의 조성물의 표면 장력은 용매의 표면 장력이 지배적이어서, 도포성을 확보하면서 표면 장력을 컨트롤하는 것은 어려웠다. 또한, 계면 활성제로 조절하려고 해도 통상적으로 사용하는 양으로는 표면 장력을 저하시킬 수 없었고, 계면 활성제를 다량 첨가하면 도포 균일성이나 신뢰성에 문제가 발생할 가능성이 있기 때문에 현실적이지 않았다. The applicability of the composition depends on the value of its surface tension. The surface tension of the conventional composition is dominated by the surface tension of the solvent, it was difficult to control the surface tension while securing the applicability. Moreover, even if it was going to adjust with surfactant, surface tension could not be reduced by the quantity normally used, and it was unrealistic because adding a large amount of surfactant may cause a problem in application uniformity and reliability.

본 발명의 과제는, 낮은 임계 표면 장력을 갖는 기판에도 도포할 수 있으면서, 또한 내열성·투명성·기판에 대한 밀착성이 양호한 유기막을 얻기 위한 열경화성 조성물, 이러한 열경화성 조성물로 형성되는 유기막 및 이와 같은 유기막을 갖는 전자 부품을 제공하는 것이다. An object of the present invention is a thermosetting composition for obtaining an organic film which can be applied to a substrate having a low critical surface tension and also has good heat resistance, transparency, and adhesion to a substrate, an organic film formed of such a thermosetting composition, and such an organic film. It is to provide an electronic component having.

본 발명자들은 상기 과제를 해결하기 위해서 예의 검토한 결과, 디메틸실록산 구조를 갖는 아크릴 폴리머 재료를 사용함으로써 전술한 과제를 해결할 수 있는 조성물을 완성하게 되었다. MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors completed the composition which can solve the above-mentioned subject by using the acrylic polymer material which has a dimethylsiloxane structure.

본 발명은 이하의 구성을 포함한다. The present invention includes the following configuration.

[1] 하기 화학식(1)으로 나타내는 라디칼 중합성 화합물(a1), 에폭시 및 알콕시실릴 중에서 적어도 하나를 갖는 라디칼 중합성 화합물(a2), 그리고 기타 라디칼 중합성 화합물(a3)을 라디칼 공중합하여 형성되는 폴리머(A) 및 유기 용제(B)를 함유하는 열경화성 조성물. [1] formed by radical copolymerization of a radically polymerizable compound (a1) represented by the following formula (1), a radically polymerizable compound (a2) having at least one of epoxy and alkoxysilyl, and other radically polymerizable compound (a3) A thermosetting composition containing a polymer (A) and an organic solvent (B).

[화학식 1][Formula 1]

Figure pat00001
Figure pat00001

(R1은 수소 또는 메틸이고, R2 내지 R5는 탄소수 1 내지 5의 알킬이며, R6은 탄소수 1 내지 10의 알킬이고, m은 1 내지 10의 정수이며, n은 1 내지 150의 정수이다)(R 1 is hydrogen or methyl, R 2 to R 5 are alkyl of 1 to 5 carbon atoms, R 6 is alkyl of 1 to 10 carbon atoms, m is an integer of 1 to 10, n is an integer of 1 to 150 to be)

[2] 표면 장력이 24mN/m이하인 상기 [1]에 기재된 열경화성 조성물. [2] The thermosetting composition according to the above [1], wherein the surface tension is 24 mN / m or less.

[3] 유기 용제(B)가 수산기를 갖는 화합물인 상기 [1] 또는 상기 [2]에 기재된 열경화성 조성물. [3] The thermosetting composition according to the above [1] or [2], wherein the organic solvent (B) is a compound having a hydroxyl group.

[4] 화학식(1)으로 나타내는 라디칼 중합성 화합물(a1)이, R1이 메틸, R2 내지 R5가 메틸, R6이 탄소 1 내지 10의 알킬, m이 1 내지 5의 정수, n이 1 내지 150의 정수인 상기 [1] 내지 상기 [3] 중에서 어느 하나에 기재된 열경화성 조성물. [4] The radically polymerizable compound (a1) represented by the formula (1) is a compound in which R 1 is methyl, R 2 to R 5 is methyl, R 6 is carbon 1 to 10 alkyl, m is an integer of 1 to 5, n The thermosetting composition in any one of said [1]-[3] which is an integer of 1-150.

[5] 에폭시 및 알콕시실릴 중에서 적어도 하나를 갖는 라디칼 중합성 모노머(a2)가, 글리시딜(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트글리시딜에테르, 3-(메타)아크릴옥시프로필트리메톡시실란, 3-(메타)아크릴옥시프로필트리에톡시실란, 3-(메타)아크릴옥시프로필메틸디메톡시실란, 3-(메타)아크릴옥시프로필메틸디에톡시실란, 비닐트리메톡시실란, 비닐트리에톡시실란 및 p-스티릴트리메톡시실란으로 이루어지는 그룹에서 선택되는 적어도 하나인 상기 [1] 내지 상기 [4] 중에서 어느 하나에 기재된 열경화성 조성물. [5] The radically polymerizable monomer (a2) having at least one of epoxy and alkoxysilyl is glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3- (meth) Acryloxypropyl trimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltrimeth The thermosetting composition according to any one of the above [1] to [4], which is at least one selected from the group consisting of oxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane.

[6] 그 외의 라디칼 중합성 화합물(a3)이 벤질, 시클로헥실, 트리스-트리메틸실록시실릴, 디시클로펜타닐, 말레이미드, 히드록시카보닐 또는 히드록시페닐을 갖는 라디칼 중합성 화합물 중에서 적어도 하나인 상기 [1] 내지 상기 [5] 중에서 어느 하나에 기재된 열경화성 조성물. [6] The other radically polymerizable compound (a3) is at least one of radically polymerizable compounds having benzyl, cyclohexyl, tris-trimethylsiloxysilyl, dicyclopentanyl, maleimide, hydroxycarbonyl or hydroxyphenyl. The thermosetting composition in any one of said [1]-[5].

[7] 그 외의 라디칼 중합성 화합물(a3)이, 벤질(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, (메타)아크릴로일옥시프로필-트리스-트리메틸실록시실란, 디시클로펜타닐(메타)아크릴레이트, N-시클로헥실말레이미드, N-페닐말레이미드, (메타)아크릴산, 및 4-히드록시페닐비닐케톤으로 이루어지는 그룹에서 선택되는 적어도 하나인 상기 [1] 내지 상기 [6] 중에서 어느 하나에 기재된 열경화성 조성물. [7] Other radically polymerizable compounds (a3) are benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryloyloxypropyl-tris-trimethylsiloxysilane, dicyclopentanyl (meth) ) Acrylic acid, N-cyclohexyl maleimide, N-phenylmaleimide, (meth) acrylic acid, and at least one selected from the group consisting of 4-hydroxyphenyl vinyl ketone, any one of the above [1] to [6] The thermosetting composition of one.

조성물의 도포성의 좋고 나쁨은, 도포 대상인 기판의 임계 표면 장력과 도포하는 조성물의 표면 장력과의 밸런스에 의해 결정된다. 조성물의 표면 장력이 어느 값보다 높을 경우는, 조성물은 기판 위로 번지는 것보다도 조성물 스스로 응집해버리는 힘이 강하여 기판 위에서는 튕겨져 버린다. 낮은 임계 표면 장력을 갖는 실리콘계 기판으로의 도포 실험에서는, 표면 장력이 24mN/m이하의 값일 때, 조성물이 튕기는 일없이 균일한 도막이 형성되어 도포성이 양호해진다. 낮은 임계 표면 장력을 갖는 실리콘계 기판에서 도포성이 양호하면, 실리콘계 기판보다도 임계 표면 장력이 높은 다른 기판에서의 도포성은 양호해지므로, 실질적으로 표면 장력이 24mN/m이하라면, 그 조성물의 도포성은 양호하다고 할 수 있다. The applicability of the composition is determined by the balance between the critical surface tension of the substrate to be applied and the surface tension of the composition to be applied. When the surface tension of the composition is higher than any value, the composition tends to have a stronger force of aggregation of the composition itself than to spread onto the substrate, and bounces off the substrate. In the application experiment to the silicon-based substrate having a low critical surface tension, when the surface tension is a value of 24 mN / m or less, a uniform coating film is formed without the composition splashing and the applicability is improved. If the applicability is good in a silicon-based substrate having a low critical surface tension, the applicability in other substrates having a higher critical surface tension is better than that of the silicon-based substrate. Therefore, if the surface tension is substantially 24 mN / m, the applicability of the composition is good. It can be said.

본 발명의 열경화성 조성물을 사용해서 형성되는 투명막, 절연막 등의 (패턴 형상)투명막은 내열성, 투명성, 표면과의 밀착성, 내약품성 등에 있어서 우수하다. 그 결과, 본 발명의 열경화성 조성물을 사용한 투명막 등의 막을 사용한 표시 소자로 표시 품위가 향상된다. (Pattern-shaped) transparent films, such as a transparent film and an insulating film formed using the thermosetting composition of this invention, are excellent in heat resistance, transparency, adhesiveness with a surface, chemical-resistance, etc. As a result, display quality improves with the display element using films, such as a transparent film using the thermosetting composition of this invention.

1. 본 발명의 열경화성 조성물1.The thermosetting composition of the present invention

본 발명의 열경화성 조성물은 화학식(1)로 나타내는 라디칼 중합성 화합물(a1), 에폭시, 알콕시실릴 중에서 적어도 하나를 갖는 라디칼 중합성 화합물(a2), 기타 라디칼 중합성 화합물(a3)을 라디칼 공중합하여 형성되는 폴리머(A), 유기 용제(B)를 포함한다. The thermosetting composition of the present invention is formed by radical copolymerization of a radically polymerizable compound (a1) represented by formula (1), a radically polymerizable compound (a2) having at least one of epoxy, alkoxysilyl, and other radically polymerizable compound (a3). It contains the polymer (A) and the organic solvent (B) which become.

또한, 본 발명의 열경화성 조성물은 본 발명의 효과를 얻을 수 있는 범위 내에서 상기 이외의 다른 성분을 추가적으로 함유하여도 좋다. In addition, the thermosetting composition of this invention may contain other components other than the above within the range which can obtain the effect of this invention.

본 발명의 열경화성 조성물은 라디칼 공중합하여 형성되는 폴리머(A) 100 중량부에 대하여, 유기 용제(B)를 10 중량부 내지 10,0000 중량부 사용하는 것이 본 발명의 열경화성 조성물로부터 얻을 수 있는 유기막의 코팅성을 높이는 관점에서 바람직하다. The thermosetting composition of the present invention is based on 100 parts by weight of the polymer (A) formed by radical copolymerization of the organic film obtainable from the thermosetting composition of the present invention using 10 parts by weight to 10,0000 parts by weight of an organic solvent (B). It is preferable from a viewpoint of improving coating property.

또한, 폴리머(A) 이외에도, 그 외의 폴리머를 배합해도 좋다.
In addition to the polymer (A), other polymers may be blended.

1-1. 라디칼 공중합으로 형성되는 폴리머(A)1-1. Polymer (A) formed by radical copolymerization

상기 라디칼 공중합 폴리머(A)에 있어서의 라디칼 중합성 화합물의 혼합 비율(중량비)은 (a1)이 0.1 중량% 내지 5 중량% 정도이고, (a2)가 4.9 중량% 내지 95 중량% 정도이며, (a3)가 4.9 중량% 내지 95 중량% 정도인 것이 바람직하다.
The mixing ratio (weight ratio) of the radically polymerizable compound in the said radical copolymer polymer (A) is about 0.1 to 5 weight% of (a1), (a2) is about 4.9 to 95 weight%, ( It is preferable that a3) is about 4.9 to 95 weight%.

1-1-1. 라디칼 중합성 화합물(a1)1-1-1. The radical polymerizing compound (a1)

본 발명에서는, 폴리머(A)를 얻기 위한 원료로서, 하기 화학식(1)으로 나타내는 라디칼 중합성 화합물(a1)을 사용한다. In this invention, the radically polymerizable compound (a1) represented by following General formula (1) is used as a raw material for obtaining a polymer (A).

[화학식 1][Formula 1]

Figure pat00002
Figure pat00002

(R1은 수소 또는 메틸이고, R2 내지 R5는 탄소수 1 내지 5의 알킬이며, R6은 탄소수 1 내지 10의 알킬이고, m은 1 내지 10의 정수이며, n은 1 내지 150의 정수이다)(R 1 is hydrogen or methyl, R 2 to R 5 are alkyl of 1 to 5 carbon atoms, R 6 is alkyl of 1 to 10 carbon atoms, m is an integer of 1 to 10, n is an integer of 1 to 150 to be)

본 발명에 있어서, 상기 화학식(1)로 나타내는 라디칼 중합성 화합물 중에서, R1은 수소 또는 메틸, R2 내지 R5는 메틸, R6은 탄소 1 내지 10의 알킬, m이 1 내지 5의 정수, n이 1 내지 150의 정수인 화합물이 바람직하다. R1이 메틸, R2 내지 R5가 메틸, R6이 부틸, m이 3, n이 1 내지 150의 정수인 화합물이 보다 바람직하며, 또한 n이 30 내지 70의 정수인 것이 더욱 바람직하다.
In the present invention, in the radically polymerizable compound represented by the formula (1), R 1 is hydrogen or methyl, R 2 to R 5 is methyl, R 6 is carbon 1-10 alkyl, m is an integer of 1 to 5 Preference is given to compounds wherein n is an integer from 1 to 150. More preferably, a compound in which R 1 is methyl, R 2 to R 5 is methyl, R 6 is butyl, m is 3 and n is an integer of 1 to 150, and more preferably n is an integer of 30 to 70.

1-1-2. 라디칼 중합성 화합물(a2)1-1-2. Radically polymerizable compound (a2)

본 발명에서는, 폴리머(A)를 얻기 위한 원료로서, 에폭시 및 알콕시실릴 중에서 적어도 하나를 갖는 라디칼 중합성 모노머(a2)를 사용한다. 바람직한 라디칼 중합성 화합물(a2)은, 글리시딜(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트글리시딜에테르, 3-(메타)아크릴옥시프로필트리메톡시실란, 3-(메타)아크릴옥시프로필트리에톡시실란, 3-(메타)아크릴옥시프로필메틸디메톡시실란, 3-(메타)아크릴옥시프로필메틸디에톡시실란, 비닐트리메톡시실란, 비닐트리에톡시실란 및 p-스티릴트리메톡시실란으로 이루어지는 그룹에서 선택된다.
In the present invention, a radical polymerizable monomer (a2) having at least one of epoxy and alkoxysilyl is used as a raw material for obtaining the polymer (A). Preferable radically polymerizable compound (a2) is glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3- (meth) acryloxypropyl trimethoxysilane, 3- ( Meta) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and p- It is selected from the group which consists of styryl trimethoxysilane.

1-1-3. 라디칼 중합성 화합물(a3)1-1-3. Radically polymerizable compound (a3)

본 발명에서는, 폴리머(A)를 얻기 위한 원료로서, 그 외의 라디칼 중합성 모노머(a3)를 사용한다. 그 외의 라디칼 중합성 화합물(a3)은 라디칼 중합성 화합물(a1) 및 라디칼 중합성 화합물(a2) 이외의 라디칼 중합성 화합물이다. 바람직한 라디칼 중합성 화합물(a3)은, 벤질, 시클로헥실, 트리스-트리메틸실록시실릴, 디시클로펜타닐, 말레이미드, 히드록시카보닐 및 히드록시페닐을 갖는 라디칼 중합성 화합물 중에서 적어도 하나를 포함하는 라디칼 중합성 화합물이다. 구체적으로는, 예를 들면, 벤질(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, (메타)아크릴로일옥시프로필-트리스-트리메틸실록시실란, 디시클로펜타닐(메타)아크릴레이트, N-시클로헥실말레이미드, N-페닐말레이미드, (메타)아크릴산 및 4-히드록시페닐비닐케톤으로 이루어지는 그룹에서 선택된다.
In this invention, another radically polymerizable monomer (a3) is used as a raw material for obtaining a polymer (A). The other radically polymerizable compound (a3) is a radically polymerizable compound other than the radically polymerizable compound (a1) and the radically polymerizable compound (a2). Preferred radically polymerizable compounds (a3) are radicals comprising at least one of radically polymerizable compounds having benzyl, cyclohexyl, tris-trimethylsiloxysilyl, dicyclopentanyl, maleimide, hydroxycarbonyl and hydroxyphenyl It is a polymeric compound. Specifically, for example, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryloyloxypropyl- tris-trimethylsiloxysilane, dicyclopentanyl (meth) acrylate, N- Cyclohexyl maleimide, N-phenylmaleimide, (meth) acrylic acid and 4-hydroxyphenylvinylketone.

1-1-4. 폴리머(A)의 제조 방법1-1-4. Manufacturing method of polymer (A)

폴리머(A)는, 상기 화학식(1)으로 나타내는 라디칼 중합성 화합물(a1), 에폭시 및 알콕시실릴 중에서 적어도 하나를 갖는 라디칼 중합성 화합물(a2) 및 그 외의 라디칼 중합성 화합물(a3)을 라디칼 공중합하여 얻을 수 있다. 폴리머(A)의 제조 방법은 특별히 제한되지 않으나, 폴리머(A)는 상기 라디칼 중합성 화합물류를 라디칼 개시제의 존재 하에 가열하여 제조하는 것이 가능하다. 상기 라디칼 개시제로서는, 유기 과산화물, 아조 화합물 등을 사용할 수 있다. 라디칼 공중합의 반응 온도는 특별히 한정되지는 않지만, 통상적으로 50℃ 내지 150℃ 정도의 범위이다. 반응 시간 역시 특별히 한정되지는 않지만, 통상적으로 1시간 내지 48시간 정도의 범위이다. 또한, 해당 반응은 가압, 감압 또는 대기압 중 어느 압력 하에서도 수행될 수 있다. The polymer (A) is a radical copolymerization of the radically polymerizable compound (a2) having at least one of the radically polymerizable compound (a1), epoxy and alkoxysilyl represented by the general formula (1) and the other radically polymerizable compound (a3). Can be obtained. Although the manufacturing method of a polymer (A) is not specifically limited, A polymer (A) can be manufactured by heating the said radically polymerizable compounds in presence of a radical initiator. As said radical initiator, an organic peroxide, an azo compound, etc. can be used. Although the reaction temperature of radical copolymerization is not specifically limited, Usually, it is the range of about 50 degreeC-150 degreeC. Although reaction time is not specifically limited, either, Usually, it is the range of about 1 hour to about 48 hours. In addition, the reaction can be carried out under any pressure such as pressurization, reduced pressure or atmospheric pressure.

상기의 라디칼 공중합 반응에 사용하는 용제는, 사용하는 라디칼 중합성 화합물류, 그리고 생성하는 중합체가 용해되는 용제가 바람직하다. 해당 용제의 구체적인 예는, 메탄올, 에탄올, 1-프로파놀, 2-프로파놀, 1-부탄올, 2-부탄올, 이소부탄올, tert-부틸알코올, 아세톤, 2-부타논, 초산에틸, 초산프로필, 테트라히드로푸란, 아세토니트릴, 디옥산, 톨루엔, 크실렌, 시클로헥사논, 에틸렌글리콜모노에틸에테르, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르, 3-메톡시프로피온산메틸, 3-에톡시프로피온산에틸 등이다. 상기 용제는, 이들 중에서 1종이어도 좋고, 이들 중에서 2종 이상의 혼합물이어도 좋다. The solvent used for the said radical copolymerization reaction is preferably a solvent in which the radically polymerizable compounds to be used and the polymer to be produced are dissolved. Specific examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butyl alcohol, acetone, 2-butanone, ethyl acetate, propyl acetate, Tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and the like. One kind of these solvents may be used, or a mixture of two or more kinds thereof may be used.

폴리머(A)는 폴리스티렌을 표준으로 한 GPC분석으로 구한 중량 평균 분자량이 약 500 내지 100,000 정도의 범위이면, 막의 성막성이 양호하여 바람직하다. 나아가, 중량 평균 분자량이 약 1,500 내지 50,000 정도의 범위이면, 기판 밀착성이 양호하여 더욱 바람직하다. The polymer (A) is preferable because the film-forming property of the film is good as long as the weight average molecular weight determined by GPC analysis based on polystyrene is in the range of about 500 to 100,000. Furthermore, when the weight average molecular weight is in the range of about 1,500 to 50,000, the substrate adhesion is good and more preferable.

폴리머(A)의 중량 평균 분자량은, 예를 들면, 표준 폴리스티렌에는 분자량이 약 645 내지 132,900 정도의 폴리스티렌(예를 들면, VARIAN사 제품의 폴리스틸렌 캐리브레이션키트 PL2010-0102), 칼럼에는 PLgel MIXED-D(VARIAN사 제품)를 사용하고, 이동상으로서 THF를 사용하여 측정할 수 있다.
The weight average molecular weight of the polymer (A) is, for example, polystyrene having a molecular weight of about 645 to 132,900 in standard polystyrene (for example, polystyrene calibration kit PL2010-0102 manufactured by VARIAN, PLgel MIXED-D) (VARIAN Co., Ltd.) can be used, and it can measure using THF as a mobile phase.

1-2. 용제(B)1-2. Solvent (B)

본 발명에서 사용되는 용제(B)는, 끓는점이 100℃ 내지 300℃ 정도인 화합물이 바람직하다. 끓는점이 100℃ 내지 300℃ 정도인 상기 용제의 구체적인 예로는, 초산부틸, 프로피온산부틸, 젖산에틸, 히드록시초산메틸, 히드록시초산에틸, 히드록시초산부틸, 메톡시초산메틸, 메톡시초산에틸, 메톡시초산부틸, 에톡시초산메틸, 에톡시초산에틸, 3-옥시프로피온산메틸, 3-히드록시프로피온산에틸, 3-메톡시프로피온산메틸, 3-메톡시프로피온산에틸, 3-에톡시프로피온산메틸, 3-에톡시프로피온산에틸, 2-히드록시프로피온산메틸, 2-히드록시프로피온산프로필, 2-메톡시프로피온산메틸, 2-메톡시프로피온산에틸, 2-메톡시프로피온산프로필, 2-에톡시프로피온산메틸, 2-에톡시프로피온산에틸, 2-히드록시-2-메틸프로피온산메틸, 2-히드록시-2-메틸프로피온산에틸, 2-메톡시-2-메틸프로피온산메틸, 2-에톡시-2-메틸프로피온산에틸, 피루브산메틸, 피루브산에틸, 피루브산프로필, 아세토초산메틸, 아세토초산에틸, 2-옥소부탄산메틸, 2-옥소부탄산에틸, 디옥산, 에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 프로필렌글리콜, 디프로필렌글리콜, 트리프로필렌글리콜, 1,4-부탄디올, 에틸렌글리콜모노이소프로필에테르, 에틸렌글리콜모노부틸에테르, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노프로필에테르아세테이트, 에틸렌글리콜모노부틸에테르아세테이트, 시클로헥사논, 시클로펜타논, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노메틸에테르아세테이트, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜모노부틸에테르, 디에틸렌글리콜모노부틸에테르아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜메틸에틸에테르, 톨루엔, 크실렌, γ-부티롤락톤, 또는 N,N-디메틸아세트아미드를 들 수 있다. 이들은 단독으로 사용해도 좋고, 2개 이상을 조합하여 사용해도 좋다. As for the solvent (B) used by this invention, the compound whose boiling point is about 100 degreeC-about 300 degreeC is preferable. Specific examples of the solvent having a boiling point of about 100 ° C to 300 ° C include butyl acetate, butyl propionate, ethyl lactate, methyl hydroxy acetate, ethyl hydroxy acetate, butyl hydroxy acetate, methyl methoxy acetate, ethyl methoxy acetate, Methoxy butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 Ethyl ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyruvic acid Methyl, ethyl pyruvate, Propyl pyruvate, methyl aceto acetate, ethyl aceto acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl Ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene Glycol monobutyl ether There may be mentioned the three lactate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, γ- butyrolactone, or N, N- dimethylacetamide. These may be used independently and may be used in combination of 2 or more.

본 발명에서 사용되는 용제는, 이들의 끓는점이 100℃ 내지 300℃ 정도인 용제를 20중량%이상 함유하는 혼합 용제이어도 좋다. 혼합 용제에 있어서의 끓는점이 100℃ 내지 300℃ 정도인 용제 이외의 용제에는, 공지의 용제 중 하나 또는 둘 이상을 사용할 수 있다. The solvent used in the present invention may be a mixed solvent containing 20% by weight or more of a solvent having a boiling point of about 100 ° C to 300 ° C. One or two or more of the well-known solvents can be used for solvents other than the solvent whose boiling point in a mixed solvent is about 100 to 300 degreeC.

본 발명의 열경화성 조성물에 포함되는 용제로서 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 3-메톡시프로피온산메틸, 3-에톡시프로피온산에틸, 디에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜모노부틸에테르아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르, 젖산에틸 및 초산부틸에서 선택되는 적어도 하나를 사용하면, 도포 균일성이 높아지므로 보다 바람직하다. 나아가 프로필렌글리콜모노메틸에테르아세테이트, 3-메톡시프로피온산메틸, 3-에톡시프로피온산에틸, 디에틸렌글리콜메틸에틸에테르, 젖산에틸 및 초산부틸에서 선택되는 적어도 하나를 사용하면, 열경화성 조성물의 도포 균일성을 높아지면서 또한 인체에 대한 안전성의 관점에서 더욱 더 바람직하다. As the solvent contained in the thermosetting composition of the present invention, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropionate methyl, 3-ethoxypropionate, diethylene glycol monoethyl ether The use of at least one selected from acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethyl lactate and butyl acetate is more preferable since the coating uniformity is increased. Furthermore, by using at least one selected from propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methylethyl ether, ethyl lactate and butyl acetate, the uniformity of the coating composition of the thermosetting composition It is also higher and more preferable from the viewpoint of safety to the human body.

또한, 본 발명의 열경화성 조성물에 있어서, 폴리머(A) 및 용제(B)의 총량에 대하여, 고형분인 폴리머(A)가 0.1 중량% 내지 80중량% 정도가 되도록 배합되는 것이 바람직하다.
Moreover, in the thermosetting composition of this invention, it is preferable to mix | blend so that the polymer (A) which is solid content may be about 0.1 to 80 weight% with respect to the total amount of a polymer (A) and a solvent (B).

1-3. 기타 성분1-3. Other ingredients

본 발명의 열경화성 조성물에는, 도포 균일성, 접착성을 향상시키기 위해 각종 첨가제를 첨가할 수 있다. 첨가제에는, 음이온계, 양이온계, 노니온계, 불소계 또는 실리콘계의 레벨링제·계면 활성제, 실란커플링제 등의 밀착성 향상제, 알콕시벤조페논류 등의 자외선 흡수제, 에폭시 화합물, 멜라민 화합물 또는 비스아지드화합물 등의 가교제, 다가카복실산, 페놀 화합물 등의 에폭시 경화제, 힌다드페놀계, 힌다드아민계, 인(燐)계, 유황계 화합물 등의 산화 방지제를 주로 들 수 있다.
Various additives can be added to the thermosetting composition of this invention in order to improve coating uniformity and adhesiveness. The additive may be an anionic, cationic, nonionic, fluorine or silicone leveling agent or surfactant, a silane coupling agent such as adhesion improving agents, ultraviolet absorbers such as alkoxybenzophenones, epoxy compounds, melamine compounds, or bisazide compounds. And antioxidants such as epoxy curing agents such as crosslinking agents, polycarboxylic acids, and phenol compounds, hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds.

1-3-1. 계면 활성제1-3-1. Surfactants

본 발명의 열경화성 조성물에는 도포 균일성을 향상시키기 위해서 계면 활성제를 첨가할 수 있다. 상기 계면 활성제로서는, 예를 들면, 폴리프로우 No.45, 폴리프로우KL-245, 폴리프로우 No.75, 폴리프로우 No.90, 폴리프로우 No.95(이상, 모두 상품명; 쿄에이샤(共榮社) 화학(주)(KYOEISHA CHEMICAL CO., LTD)), BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346(이상, 모두 상품명; 빅크 케미 재팬(주)(BYK Japan KK)), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS(이상, 모두 상품명; 신에츠 화학 공업(주)(Shin-Etsu Chemicla Co., Ltd)), 사후론SC-101, 사후론KH-40(이상, 모두 상품명; AGC세이미케미컬(주)(AGC SEIMI CHEMICAL CO., LTD.)), 후타젠트222F, 후타젠트251, FTX-218(이상, 모두 상품명; (주)네오스(NEOS COMPANY Ltd.)), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802(이상, 모두 상품명; 미츠비시 머티리얼즈(주)(Mitsubishi Materials Corporation)), 메가팩F-171, 메가팩F-177, 메가팩F-475, 메가팩F-556, 메가팩R-30(이상, 모두 상품명DIC(주)), 플루오르알킬벤젠술폰산염, 플루오르알킬카복실산염, 플루오르알킬폴리옥시에틸렌에테르, 플루오르알킬암모늄요오드화물, 플루오르알킬베타인, 플루오르알킬술폰산염, 디글리세린테트라키스(플루오르알킬폴리옥시에틸렌에테르), 플루오르알킬트리메틸암모늄염, 플루오르알킬아미노술폰산염, 폴리옥시에틸렌노닐페닐에테르, 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌알킬에테르, 폴리옥시에틸렌라우릴에테르, 폴리옥시에틸렌오레일에테르, 폴리옥시에틸렌트리데실에테르, 폴리옥시에틸렌세틸에테르, 폴리옥시에틸렌스테아릴에테르, 폴리옥시에틸렌라우레이트, 폴리옥시에틸렌올리에이트, 폴리옥시에틸렌스테아레이트, 폴리옥시에틸렌라우릴아민, 소르비탄라우레이트, 소르비탄팔미테이트, 소르비탄스테아레이트, 소르비탄올리에이트, 소르비탄지방산에스테르, 폴리옥시에틸렌소르비탄라우레이트, 폴리옥시에틸렌소르비탄팔미테이트, 폴리옥시에틸렌소르비탄스테아레이트, 폴리옥시에틸렌소르비탄올리에이트, 폴리옥시에틸렌나프틸에테르, 알킬벤젠술폰산염, 또는 알킬디페닐에테르디술폰산염을 들 수 있다. 이들로부터 선택되는 적어도 하나를 상기 첨가제에 사용하는 것이 바람직하다. Surfactant can be added to the thermosetting composition of this invention in order to improve coating uniformity. As said surfactant, For example, polyprou No.45, polyprou KL-245, polyprou No.75, polyprou No.90, polyprou No.95 (all are brand names; Kyoko) Eisha Chemical Co., Ltd. (KYOEISHA CHEMICAL CO., LTD), BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346 (above, all trade names; BIC Chemi Japan Co., Ltd.) (BYK Japan KK )), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (above, all trade names; Shin-Etsu Chemicla Co., Ltd), Safron SC-101, Safron KH-40 (above, all trade names; AGC SEIMI CHEMICAL CO., LTD.), Futagent 222F, Futagent 251, FTX-218 (above, NEOS COMPANY Ltd., EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (above, all trade names; Mitsubishi Materials, Ltd.) (Mitsubishi Materials Corporation)), mega pack F-171, mega pack F-177, mega pack F-475, mega pack F-556, mega pack R-30 (more than all products) DIC Corporation), fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene Ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonic acid salt, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxy Ethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan Palmitate, sorbitan stearate, sorbitan Liate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonic acid Salt or alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these in the additive.

이들 첨가제 중에서도, 플루오르알킬벤젠술폰산염, 플루오르알킬카복실산염, 플루오르알킬폴리옥시에틸렌에테르, 플루오르알킬암모늄요오드화물, 플루오르알킬베타인, 플루오르알킬술폰산염, 디글리세린테트라키스(플루오르알킬폴리옥시에틸렌에테르), 플루오르알킬트리메틸암모늄염, 또는 플루오르알킬아미노술폰산염 등의 불소계의 계면 활성제, BYK306, BYK346, KP-341, KP-358, 또는 KP-368 등의 실리콘계 첨가제 중에서 선택되는 적어도 1종이 첨가되면, 열경화성 조성물의 도포 균일성이 높아지므로 바람직하다. Among these additives, fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate and diglycerin tetrakis (fluoroalkyl polyoxyethylene ether) Thermosetting composition when at least one selected from a fluorine-based surfactant such as fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate salt, silicone-based additives such as BYK306, BYK346, KP-341, KP-358, or KP-368 is added Since application uniformity of is high, it is preferable.

또한, 본 발명의 열경화성 조성물에 있어서의 계면 활성제의 함유량은 통상적으로 0.01 중량% 내지 10중량%인 것이 바람직하다.
In addition, it is preferable that content of surfactant in the thermosetting composition of this invention is 0.01 weight%-10 weight% normally.

1-3-2. 밀착성 향상제1-3-2. Adhesion Enhancer

본 발명의 열경화성 조성물은, 형성되는 경화막과 기판과의 밀착성을 더 향상시킨다는 관점에서 밀착성 향상제를 추가적으로 함유하여도 좋다. 이러한 관점에서, 밀착성 향상제의 함유량은, 열경화성 조성물 전량에 대하여 10중량% 이하인 것이 바람직하다. 한편으로는, 0.01중량% 이상인 것이 바람직하다. The thermosetting composition of this invention may contain an adhesive improving agent further from a viewpoint of further improving adhesiveness of the cured film formed and a board | substrate formed. From such a viewpoint, it is preferable that content of an adhesive improving agent is 10 weight% or less with respect to the thermosetting composition whole quantity. On the other hand, it is preferable that it is 0.01 weight% or more.

이러한 밀착성 향상제로서는, 예를 들면, 실란계, 알루미늄계 또는 티타네이트계의 커플링제를 사용할 수 있고, 구체적으로는, 3-글리시딜옥시프로필디메틸에톡시실란, 3-글리시딜옥시프로필메틸디에톡시실란, 및 3-글리시딜옥시프로필트리메톡시실란 등의 실란계 커플링제, 아세트알콕시알루미늄디이소프로필레이트 등의 알루미늄계 커플링제 및 테트라이소프로필비스(디옥틸포스파이트)티타네이트 등의 티타네이트계 커플링제를 들 수 있다. As such an adhesion improving agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used, and specifically, 3-glycidyloxypropyldimethylethoxysilane and 3-glycidyloxypropylmethyl Silane coupling agents such as diethoxysilane and 3-glycidyloxypropyltrimethoxysilane, aluminum coupling agents such as acetalkoxyaluminum diisopropylate, tetraisopropylbis (dioctylphosphite) titanate and the like And titanate coupling agents.

이들 중에서도 3-글리시딜옥시프로필트리메톡시실란이 밀착성을 향상시키는 효과가 크기 때문에 바람직하다.
Among these, 3-glycidyloxypropyl trimethoxysilane is preferable because the effect of improving adhesiveness is large.

1-3-3. 자외선 흡수제1-3-3. Ultraviolet absorber

본 발명의 열경화성 조성물은, 경화막의 열화 방지 능력을 더욱 향상시킨다는 관점에서 자외선 흡수제를 추가적으로 함유하여도 좋다. 상기 자외선 흡수제의 함유량은 열경화성 조성물 전량에 대하여 0.01 중량% 내지 10 중량%인 것이 바람직하고, 0.05 중량% 내지 8 중량%인 것이 보다 바람직하며, 0.1 중량% 내지 5 중량%인 것이 더욱 더 바람직하다. The thermosetting composition of this invention may further contain a ultraviolet absorber from a viewpoint of further improving the ability to prevent deterioration of a cured film. It is preferable that content of the said ultraviolet absorber is 0.01 weight%-10 weight% with respect to whole quantity of a thermosetting composition, It is more preferable that it is 0.05 weight%-8 weight%, It is further more preferable that it is 0.1 weight%-5 weight%.

이러한 자외선 흡수제로서는, 예를 들면, TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, TINUVIN 765(이상, 모두 상품명; BASF재팬(주))를 들 수 있다. 이들 중에서도, TINUVIN P, TINUVIN 120, TINUVIN 326이 투명성, 상용성(相溶性) 등의 관점에서 바람직하다.
As such a ultraviolet absorber, TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, TINUVIN 765 (all are brand names; BASF Japan Co., Ltd.) are mentioned, for example. Among these, TINUVIN P, TINUVIN 120, and TINUVIN 326 are preferable from a viewpoint of transparency, compatibility, and the like.

1-3-4. 가교제1-3-4. Cross-linking agent

본 발명의 열경화성 조성물은, 내열성, 내약품성, 막면 내의 균일성, 가요성, 유연성, 탄성을 더욱 향상시킨다는 관점에서 가교제를 추가적으로 함유해도 좋다. 이러한 관점에서는, 가교제의 함유량은 상기 열경화성 조성물 전량에 대하여, 30중량% 이하인 것이 바람직하다. 한편으로는, 0.01중량% 이상인 것이 바람직하다. 또한, 가교제는 열로 가교하는 열가교제라도 광조사로 가교하는 광가교제라도 좋다. The thermosetting composition of the present invention may further contain a crosslinking agent from the viewpoint of further improving heat resistance, chemical resistance, uniformity in film surface, flexibility, flexibility and elasticity. From such a viewpoint, it is preferable that content of a crosslinking agent is 30 weight% or less with respect to the said thermosetting composition whole quantity. On the other hand, it is preferable that it is 0.01 weight% or more. In addition, the crosslinking agent may be a thermal crosslinking agent which crosslinks by heat, or an optical crosslinking agent which crosslinks by light irradiation.

이러한 열가교제로서는, 예를 들면, jER807, jER815, jER825, jER827, jER828, jER190P 및 jER191P, jER1004, jER1256, YX8000(상품명; 미쓰비시화학(주)(Mitsubishi Chemical Corporation)), 애럴다이트CY177, 애럴다이트CY184(상품명; 헌츠만 재팬(주)), 세록사이드2021P, EHPE-3150(상품명; 다이세루화학공업(주)(DAICEL CHEMICAL INDUSTRIES,LTD.)), 텍모어VG3101L(상품명; (주)프린테크), 니카락MW-30HM, 니카락MW-100LM, 니카락MW-270, 니카락MW-280, 니카락MW-290, 니카락MW-390, 니카락MW-750LM(상품명; (주)산와 케미컬(Sanwa Chemical Co., Ltd.)) 등을 들 수 있다. As such a thermal crosslinking agent, jER807, jER815, jER825, jER827, jER828, jER190P and jER191P, jER1004, jER1256, YX8000 (brand name; Mitsubishi Chemical Corporation), Araldite CY177, Aralddie TYY184 (brand name; Huntsman Japan Co., Ltd.), Ceroxide 2021P, EHPE-3150 (brand name; DAICEL CHEMICAL INDUSTRIES, LTD.), Tekmore VG3101L (brand name; Principe) TECH), Nikarak MW-30HM, Nikarak MW-100LM, Nikarak MW-270, Nikarak MW-280, Nikarak MW-290, Nikarak MW-390, Nikarak MW-750LM (brand name) Sanwa Chemical Co., Ltd.) etc. are mentioned.

또한, 이러한 광가교제로서는, 예를 들면, 4,4'-디아지도스틸벤-2,2'-이나트륨술포네이트, 4,4'-디아지도벤잘아세톤-2,2'-디술포네이트 이나트륨염, 1,3-비스(4'-아지도-2'-술포벤질리덴)부타논 이나트륨염, 2,6-비스(4'-아지도-2'-술포벤질리덴)시클로헥사논 이나트륨염, 2,6-비스(4'-아지도-2'-술포벤질리덴)-4-메틸시클로헥사논 이나트륨염, 2,5-비스(4'-아지도-2'-술포벤질리덴)시클로펜타논 이나트륨염, 4,4'-디아지도신나밀리덴아세톤-2,2'-이소디움 술포네이트, 2,6-비스(4'-아지도-2'-술포신나밀리덴)시클로헥사논 이나트륨염, 2,5-비스(4'-아지도-2'-술포신나밀리덴)시클로펜타논 이나트륨염 등을 들 수 있다.
As such a photocrosslinking agent, for example, 4,4'-diazidostilbene-2,2'-disosulfonate and 4,4'-diazidobenzalacetone-2,2'-disulfonate include Sodium salt, 1,3-bis (4'-azido-2'-sulfobenzylidene) butanone disodium salt, 2,6-bis (4'-azido-2'-sulfobenzylidene) cyclohexanone Disodium salt, 2,6-bis (4'-azido-2'-sulfobenzylidene) -4-methylcyclohexanone disodium salt, 2,5-bis (4'-azido-2'-sulfo Benzylidene) cyclopentanone disodium salt, 4,4'-diazidocinnamylideneacetone-2,2'-isodium sulfonate, 2,6-bis (4'-azido-2'-sulfocinnamil Den) cyclohexanone disodium salt, 2, 5-bis (4'-azido-2'- sulfoscinamilidene) cyclopentanone disodium salt, etc. are mentioned.

1-3-5. 경화제1-3-5. Hardener

본 발명의 열경화성 조성물은 열경화성을 조정하는 관점에서, 경화제를 추가적으로 함유하여도 좋다. 이와 같은 관점에서, 경화제의 함유량은 열경화성 조성물 전량에 대하여 30중량% 이하인 것이 바람직하다. 한편으로는, 0.01중량% 이상인 것이 바람직하다. The thermosetting composition of this invention may contain a hardening | curing agent further from a viewpoint of adjusting thermosetting. From such a viewpoint, it is preferable that content of a hardening | curing agent is 30 weight% or less with respect to the thermosetting composition whole quantity. On the other hand, it is preferable that it is 0.01 weight% or more.

이와 같은 경화제로서는, 다가 카복실산, 산무수물, 페놀 화합물 등을 들 수 있다. 구체적으로는, 다가 카복실산으로서 SMA17352(상품명; SARTOMER(주)) 등을 들 수 있고, 산무수물로서 SMA1000, SMA2000, SMA3000(상품명; SARTOMER(주)), 무수말레인산, 테트라히드로프탈산무수물, 헥사히드로프탈산, 메틸테트라히드로프탈산무수물, 메틸헥사히드로프탈산무수물, 무수프탈산, 메틸테트라히드로무수프탈산, 트리멜리틱산무수물, 헥사히드로트리멜리틱산무수물, 무수메틸나딕산, 수소화메틸나딕산무수물, 도데세닐 무수호박산, 피로멜리틱산 이무수물, 헥사히드로피로멜리틱산 이무수물, 벤조페논테트라카복실산 이무수물, TMEG, TMTA-C, TMEG-500, TMEG-600(상품명: 신니혼리카(新日本理化)(주)(New Japan Chemical co., ltd.)), EpiclonB-4400(상품명; DIC(주)), YH-306, YH-307, YH-309(상품명; 미쓰비시화학(주)(Mitsubishi Chemical Corporation)), SL-12AH, SL-20AH, IPU-22AH(상품명; 오카무라세이유(岡村製油)(주)), OSA-DA, DSA 및 PDSA-DA(상품명; 산요카세이(三洋化成)(주))을 들 수 있고, 페놀 화합물로서 2,3,4-트리히드록시벤조페논, 2,4,6-트리히드록시벤조페논, 2,2',4,4'-테트라히드록시벤조페논, 2,3,3',4-테트라히드록시벤조페논, 2,3,4,4'-테트라히드록시벤조페논, 비스(2,4-디히드록시페닐)메탄, 비스(p-히드록시페닐)메탄, 트리(p-히드록시페닐)메탄, 1,1,1-트리(p-히드록시페닐)에탄, 비스(2,3,4-트리히드록시페닐)메탄, 2,2-비스(2,3,4-트리히드록시페닐)프로판, 1,1,3-트리스(2,5-디메틸-4-히드록시페닐)-3-페닐프로판, 4,4'-[1-[4-[1-[4-히드록시페닐]-1-메틸에틸]페닐]에틸렌]비스페놀, 비스(2,5-디메틸-4-히드록시페닐)-2-히드록시페닐메탄, 3,3,3',3'-테트라메틸-1,1'-스피로비인덴-5,6,7,5',6',7'-헥산올 및 2,2,4-트리메틸-7,2',4'-트리히드록시플라반을 들 수 있다. As such a hardening | curing agent, polyhydric carboxylic acid, an acid anhydride, a phenol compound etc. are mentioned. Specifically, SMA17352 (brand name; SARTOMER Co., Ltd.) etc. are mentioned as polyhydric carboxylic acid, SMA1000, SMA2000, SMA3000 (brand name; SARTOMER Co., Ltd.), maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic acid are mentioned as acid anhydride. , Methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, hexahydrotrimelitic anhydride, methylnadic anhydride, methylhydric hydride anhydride, dodecenyl anhydride, Pyromellitic dianhydride, hexahydropyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, TMEG, TMTA-C, TMEG-500, TMEG-600 (brand name: Shin-Nihon Rika Co., Ltd. (New Japan Chemical co., Ltd.)), Epiclon B-4400 (trade name; DIC Corporation), YH-306, YH-307, YH-309 (trade name; Mitsubishi Chemical Corporation), SL- 12AH, SL-20AH, IPU-22AH (trade name; Okamura Seyou ( OSA-DA, DSA, and PDSA-DA (brand name; Sanyokasei Co., Ltd.) are mentioned, As a phenolic compound, 2,3, 4- trihydroxy benzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,3', 4-tetrahydroxybenzophenone, 2,3,4,4 '-Tetrahydroxybenzophenone, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p -Hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2 , 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol, Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7, 5 ', 6', 7'-hexanol and 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan.

본 발명의 열경화성 조성물에 상기 다가 카복실산이나 페놀 화합물이 첨가되면 열경화성을 조정하는 것이 가능하다. 경화성을 향상시키는 것으로 내열성, 내약품성을 더욱 향상시킬 수 있다.
When the said polyhydric carboxylic acid and a phenol compound are added to the thermosetting composition of this invention, it is possible to adjust thermosetting. By improving curability, heat resistance and chemical resistance can be further improved.

1-3-6. 산화 방지제1-3-6. Antioxidant

본 발명의 열경화성 조성물에는 힌다드페놀계, 힌다드아민계, 인(燐)계, 유황계 화합물 등의 산화 방지제를 첨가할 수 있다. 이 중에서도 힌다드페놀계가 내후성의 관점에서 바람직하다. 구체적인 예로서는, Irganox1010, IrganoxFF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295(상품명; BASF재팬(주)), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80(상품명; (주)ADEKA)을 들 수 있다. 이 중에서도 ADK STAB AO-60이 보다 바람직하다. Antioxidants, such as a hindered phenol type, a hindered amine type, a phosphorus type, and a sulfur type compound, can be added to the thermosetting composition of this invention. Among these, a hindered phenol type is preferable from the viewpoint of weather resistance. Specific examples include Irganox1010, IrganoxFF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1425 WL, Irganox1520L, IroxDox, 245gan Irgan 245, Irgan2452 Irgan ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80 (brand name; ADEKA Co., Ltd.) Can be. Among these, ADK STAB AO-60 is more preferable.

산화 방지제의 함유량은 열경화성 조성물 전량에 대하여, 0.01 내지 10중량%인 것이 바람직하다.
It is preferable that content of antioxidant is 0.01 to 10 weight% with respect to the thermosetting composition whole quantity.

1-4. 열경화성 조성물의 표면 장력1-4. Surface Tension of Thermosetting Compositions

본 발명의 열경화성 조성물의 표면 장력은, 바람직하게는 24mN/m 이하이고, 보다 바람직하게는 23mN/m 이하이며, 더욱 바람직하게는 22mN/m이하다. 상기 표면 장력이 이러한 범위 내에 있으면, 낮은 임계 표면 장력을 갖는 기판에 대해서도 조성물이 튕기는 일없이, 균일한 도막이 형성되며, 양호한 도포성을 얻을 수 있다.
The surface tension of the thermosetting composition of this invention becomes like this. Preferably it is 24 mN / m or less, More preferably, it is 23 mN / m or less, More preferably, it is 22 mN / m or less. If the surface tension is within this range, even a substrate having a low critical surface tension can be formed without uniform composition, and a uniform coating can be obtained.

1-5. 열경화성 조성물의 보존1-5. Preservation of Thermosetting Compositions

본 발명의 열경화성 조성물은, 온도가 -30℃ 내지 25℃ 정도인 범위에서 보존하면, 조성물의 경시(經時) 안정성이 양호해져서 바람직하다. 보존 온도가 -20℃ 내지 10℃라면, 석출물이 없어 더욱 바람직하다.
When the thermosetting composition of this invention is stored in the range whose temperature is about -30 degreeC-about 25 degreeC, time-lapse stability of a composition becomes favorable and it is preferable. If storage temperature is -20 degreeC-10 degreeC, there is no precipitate and it is more preferable.

1-6. 열경화성 조성물의 사용1-6. Use of Thermosetting Compositions

본 발명의 열경화성 조성물은 투명한 막을 형성함에 있어 적합하고, 투명 절연막을 형성함에 있어서 최적이다. 여기서, 절연막이라는 것은, 예를 들면, 층 형상으로 배치되는 배선들 간을 절연하기 위해서 마련하는 막(층간 절연막) 등을 말한다. The thermosetting composition of the present invention is suitable for forming a transparent film and is optimal for forming a transparent insulating film. Here, an insulating film means the film | membrane (interlayer insulation film) etc. which are provided in order to insulate between the wiring arrange | positioned in layer shape, for example.

본 발명의 열경화성 조성물을 사용하여 낮은 임계 표면 장력을 갖는 기판에 투명막을 형성하는 방법은, 예를 들면, 다음과 같다. The method of forming a transparent film on the board | substrate which has a low critical surface tension using the thermosetting composition of this invention is as follows, for example.

우선, 본 발명의 열경화성 조성물을 스핀 코트, 롤 코트, 슬릿 코트 등의 공지의 방법으로, 낮은 임계 표면 장력을 갖는 바탕 표면에 도포한다. 바탕으로서는, 예를 들면, 실리콘계 재료나 불소계 재료가 코팅된 기판이나, 인쇄용 실리콘제 블랭킷 실린더 등을 들 수 있다. First, the thermosetting composition of this invention is apply | coated to the base surface which has a low critical surface tension by well-known methods, such as a spin coat, a roll coat, and a slit coat. Examples of the substrate include a substrate coated with a silicon material or a fluorine material, a blanket cylinder made of silicon for printing, and the like.

예를 들면, 실리콘계 재료를 도포한 기판의 경우, 해당 기판에 열경화성 조성물을 도포한 후, 핫플레이트나 오븐으로 80℃ 내지 120℃ 정도에서 1분 내지 5분 정도 처리하여 용매를 증발시켜 건조시킨다. For example, in the case of a substrate coated with a silicon-based material, the thermosetting composition is applied to the substrate, and then treated with a hot plate or oven at about 80 ° C. to 120 ° C. for about 1 to 5 minutes to evaporate and dry the solvent.

건조 후의 막은 오븐에서 150℃ 내지 250℃로 10분 내지 60분 정도 처리하여 열경화시킨다. 이와 같이 하여 투명 유기막을 얻을 수 있다. The film after drying is heat-processed in oven at 150 to 250 degreeC for 10 to 60 minutes. In this way, a transparent organic film can be obtained.

한편, 반전 오프셋 인쇄의 경우, 실리콘제 블랭킷 실린더에 슬릿 코트로 열경화성 조성물을 도포하고, 용제를 소정의 레벨까지 건조시키기 위해서 대기 시간(웨이팅(waiting) 타임)을 둔다. 그 후, 표면에 요철 패턴이 형성된 유리제의 클리쉐에 블랭킷을 가압하여, 불필요한 부분을 클리쉐 위에 전사하여 제거한다. 블랭킷 위에 남은 패턴형상의 열경화성 조성물을 유리 기판 등에 더 전사한다. On the other hand, in the case of reverse offset printing, a thermosetting composition is applied to a blanket cylinder made of silicone with a slit coat, and a waiting time (waiting time) is set in order to dry the solvent to a predetermined level. Thereafter, the blanket is pressed against a glass cliché having a concave-convex pattern formed on the surface, and the unnecessary portion is transferred onto the cliché and removed. The patterned thermosetting composition remaining on the blanket is further transferred to a glass substrate or the like.

이렇게 하여 얻은 패턴 형상의 투명막을 핫플레이트나 오븐에서 80℃ 내지 120℃로 1분 내지 5분 정도 처리하여 용매를 증발시켜 건조시킨다. The patterned transparent film thus obtained is treated at 80 ° C. to 120 ° C. for about 1 to 5 minutes in a hot plate or an oven to evaporate and dry the solvent.

건조 후의 막은 오븐에서 150℃ 내지 250℃로 10분 내지 60분 정도 처리하여 열경화시킨다. 이렇게 하여 패턴 형상의 투명 유기막을 얻을 수 있다. The film after drying is heat-processed in oven at 150 to 250 degreeC for 10 to 60 minutes. In this way, a patterned transparent organic film can be obtained.

상술한 바와 같이 형성된 (패턴 형상)유기막은, 그 후에 상기 유기막 위에 투명 전극을 형성하고 식각으로 패터닝을 실행한 후, 배향 처리를 실행하는 막을 형성시켜도 좋다. 해당 유기막은 내스퍼터성이 높기 때문에, 투명 전극을 형성해도 절연막에 주름이 발생하지 않으며, 높은 투명성을 유지할 수 있다. The (pattern-shaped) organic film formed as mentioned above may form a film | membrane which performs an orientation process after forming a transparent electrode on the said organic film after that and performing patterning by etching. Since the organic film has high sputter resistance, wrinkles do not occur in the insulating film even when a transparent electrode is formed, and high transparency can be maintained.

상기 (패턴 형상)투명 유기막은, 액정 등을 채용하는 표시 소자에 사용할 수 있다. 예를 들면, 액정 표시 소자는, 상술한 바와 같이 하여 기판 위에 패터닝된 투명막이 마련된 소자 기판과 대향기판인 컬러 필터 기판을 위치를 맞추어서 압착하고, 그 후 열처리하여 조합, 대향하는 기판 사이에 액정을 주입하여 주입구를 밀봉함으로써 제조된다. The (pattern) transparent organic film can be used for a display element employing a liquid crystal or the like. For example, the liquid crystal display device, as described above, compresses the element substrate provided with the transparent film patterned on the substrate and the color filter substrate, which is the opposite substrate, in a position, and then heat-treats the liquid crystal between the combined and opposing substrates. It is prepared by sealing the inlet by injection.

또는, 상기 소자 기판 위에 액정을 산포한 후, 소자 기판을 겹쳐서 액정이 새지 않도록 밀봉함으로써도 제작할 수 있고, 상기 표시 소자는 이와 같이 제작된 표시 소자라도 좋다. Or after spreading a liquid crystal on the said element substrate, it can also manufacture by overlapping an element substrate and sealing so that a liquid crystal may not leak, and the said display element may be a display element produced in this way.

이와 같이 하여 본 발명의 열경화성 조성물로 형성된 뛰어난 내열성과 투명성을 갖는 유기막을 액정 표시 소자에 적용할 수 있다. 한편, 본 발명의 액정 표시소자로 적용될 수 있는 액정, 다시 말해 액정 화합물 및 액정 조성물에 대해서는 특별히 한정되지는 않으며, 액정 화합물 및 액정 조성물 중에서 어느 것을 사용해도 좋다. Thus, the organic film which has the outstanding heat resistance and transparency formed from the thermosetting composition of this invention can be applied to a liquid crystal display element. The liquid crystal which can be applied to the liquid crystal display device of the present invention, that is, the liquid crystal compound and the liquid crystal composition is not particularly limited, and any of the liquid crystal compound and the liquid crystal composition may be used.

본 발명이 바람직한 양태에 따른 열경화성 조성물은, 예를 들면, 투명막에 대하여 일반적으로 요구되고 있는 고 내용제성, 고 내수성, 고 내산성, 고 내알칼리성, 고 내열성, 고 투명성, 바탕과의 밀착성 등의 각종 특성들을 가진다. 그 결과, 본 발명이 바람직한 양태에 따른 열경화성 조성물을 사용한 투명막 등을 채용한 표시 소자 등으로 제품의 표시 품위를 향상시킬 수 있다. The thermosetting composition according to the preferred embodiment of the present invention includes, for example, high solvent resistance, high water resistance, high acid resistance, high alkali resistance, high heat resistance, high transparency, adhesion to a substrate, and the like, which are generally required for a transparent membrane. It has various characteristics. As a result, the display quality of a product can be improved by the display element etc. which employ | adopted the transparent film etc. which used the thermosetting composition which concerns on a preferable aspect of this invention.

또한, 본 발명이 바람직한 양태에 따른 열경화성 조성물은, 내용제성, 내산성, 내알칼리성, 내열성, 투명성에 있어 뛰어나며, 해당 열경화성 조성물을 채용한 투명막, 표시 소자 등은, 그 투명막 형성 후의 후공정에 있어서 용제, 산, 알칼리 용액 등에 침지, 접촉, 열처리 등이 행하여지더라도 막에 표면 러프니스가 용이하게 발생되지 않는다.
Moreover, the thermosetting composition which concerns on this aspect of this invention is excellent in solvent resistance, acid resistance, alkali resistance, heat resistance, and transparency, and the transparent film, display element, etc. which employ | adopted this thermosetting composition are a post process after formation of the transparent film. Therefore, even when immersion, contact, and heat treatment are performed on a solvent, an acid, an alkaline solution, or the like, surface roughness does not easily occur in the film.

실험예Experimental Example

이하, 예시적인 실험예들에 의해 본 발명을 더 설명하지만, 본 발명이 이들에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be further described by way of exemplary experimental examples, but the present invention is not limited thereto.

합성예 1: 폴리머(A1)의 합성Synthesis Example 1 Synthesis of Polymer (A1)

교반기가 부착된 4구 플라스크에, 중합 용제로서 디에틸렌글리콜메틸에틸에테르, 라디칼 중합성 화합물(a1)로서 FM-0721(JNC(주) 제품), 라디칼 중합성 화합물(a2)로서 글리시딜메타크릴레이트, 3-메타크릴옥시프로필트리메톡시실란, 라디칼 중합성 화합물(a3)로서 디시클로펜타닐메타크릴레이트(히타치카세이(日立化成)공업(주) 제품 FA-513M), 4-히드록시페닐비닐케톤을 하기 중량으로 투입하고, 중합 개시제로서 V-601(와코우쥰야쿠 공업(주)(Wako Pure Chemical Industries, Ltd.) 제품)을 하기 중량으로 더 투입하여, 90℃에서 2시간 동안 가열하였다. In a four-necked flask with a stirrer, diethylene glycol methylethyl ether as the polymerization solvent, FM-0721 (manufactured by JNC Corporation) as the radical polymerizable compound (a1), and glycidyl meta as the radical polymerizable compound (a2) Dicyclopentanyl methacrylate (Hitachi Chemical Co., Ltd. FA-513M), 4-hydroxyphenyl as a acrylate, 3-methacryloxypropyl trimethoxysilane, and a radically polymerizable compound (a3). Vinyl ketone was added to the following weight, and V-601 (Wako Pure Chemical Industries, Ltd. product) was further added to the following weight as a polymerization initiator, and it heated at 90 degreeC for 2 hours. .

디에틸렌글리콜메틸에틸에테르 20g20 g of diethylene glycol methyl ethyl ether

FM-0721 0.1gFM-0721 0.1 g

글리시딜메타크릴레이트 3.5gGlycidyl methacrylate 3.5 g

3-메타크릴옥시프로필트리메톡시실란 3.5g3.5 g of 3-methacryloxypropyltrimethoxysilane

디시클로펜타닐메타크릴레이트 2.0g2.0 g of dicyclopentanyl methacrylate

4-히드록시페닐비닐케톤 0.9g4-hydroxyphenyl vinyl ketone 0.9 g

V-601 1.0gV-601 1.0 g

용액을 실온까지 냉각하여 폴리머(A1)용액을 얻었다. The solution was cooled to room temperature to obtain a polymer (A1) solution.

용액의 일부를 샘플링하여, GPC분석(폴리스티렌 표준)으로 중량 평균 분자량을 측정하였다. 그 결과, 얻어진 폴리머(A1)의 중량 평균 분자량은 7,100이었다.
A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A1) was 7,100.

합성예 2: 폴리머(A2)의 합성Synthesis Example 2 Synthesis of Polymer (A2)

합성예 1과 같이 수행하고, 하기 성분을 하기 중량으로 투입하고, 중합을 실시하였다.It carried out like the synthesis example 1, the following component was added to the following weight, and superposition | polymerization was performed.

디에틸렌글리콜메틸에틸에테르 20g20 g of diethylene glycol methyl ethyl ether

FM-0721 0.1gFM-0721 0.1 g

글리시딜메타크릴레이트 3.9gGlycidyl methacrylate 3.9g

N-시클로헥실말레이미드 3.0g3.0 g of N-cyclohexylmaleimide

디시클로펜타닐메타크릴레이트 3.0g3.0 g of dicyclopentanyl methacrylate

V-601 1.0g V-601 1.0 g

합성예 1과 같은 처리를 실시하여 폴리머(A2)용액을 얻었다. 얻어진 폴리머(A2)의 GPC분석(폴리스티렌 표준)으로 구한 중량 평균 분자량은 7,500이었다.
The same treatment as in Synthesis example 1 was carried out to obtain a polymer (A2) solution. The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (A2) was 7,500.

합성예 3: 폴리머(A3)의 합성Synthesis Example 3: Synthesis of Polymer (A3)

합성예 1과 같이 수행하고, 하기 성분을 하기 중량으로 투입하고 중합을 실시하였다. It carried out like the synthesis example 1, the following component was added to the following weight, and superposition | polymerization was performed.

디에틸렌글리콜메틸에틸에테르 20g20 g of diethylene glycol methyl ethyl ether

FM-0721 0.1gFM-0721 0.1 g

3-메타크릴옥시프로필트리메톡시실란 3.9g3.9 g of 3-methacryloxypropyltrimethoxysilane

벤질메타크릴레이트 2.0gBenzyl methacrylate 2.0 g

메타크릴로일옥시프로필-트리스-트리메틸실록시실란 2.0g2.0 g of methacryloyloxypropyl-tris-trimethylsiloxysilane

시클로헥실메타크릴레이트 2.0g2.0 g of cyclohexyl methacrylate

V-601 1.0gV-601 1.0 g

합성예 1과 같은 처리를 수행하여 폴리머(A3) 용액을 얻었다. 얻어진 폴리머(A3)의 GPC분석(폴리스티렌 표준)으로 구한 중량 평균 분자량은 7,500이었다.
The same treatment as in Synthesis example 1 was carried out to obtain a polymer (A3) solution. The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (A3) was 7,500.

합성예 4: 폴리머(A4)의 합성Synthesis Example 4 Synthesis of Polymer (A4)

합성예 1과 같이 수행하고, 하기 성분을 하기 중량으로 투입하고, 중합을 실시하였다. It carried out like the synthesis example 1, the following component was added to the following weight, and superposition | polymerization was performed.

디에틸렌글리콜메틸에틸에테르 20g20 g of diethylene glycol methyl ethyl ether

FM-0721 1.0gFM-0721 1.0g

3-메타크릴옥시프로필트리메톡시실란 3.0g3.0 g of 3-methacryloxypropyl trimethoxysilane

메타크릴산 1.0g1.0 g of methacrylic acid

메타크릴로일옥시프로필-트리스-트리메틸실록시실란 3.0g3.0 g of methacryloyloxypropyl-tris-trimethylsiloxysilane

N-페닐말레이미드 2.0g2.0 g of N-phenylmaleimide

V-601 1.0gV-601 1.0 g

합성예 1과 같은 처리를 수행하여 폴리머(A4) 용액을 얻었다. 얻어진 폴리머(A4)의 GPC분석(폴리스티렌 표준)으로 구한 중량 평균 분자량은 7,800이었다.
The same treatment as in Synthesis example 1 was carried out to obtain a polymer (A4) solution. The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (A4) was 7,800.

합성예 5: 기타 폴리머(B1)의 합성Synthesis Example 5 Synthesis of Other Polymer (B1)

합성예 1과 같이 수행하고, 하기 성분을 하기 중량으로 투입하여, 중합을 실시하였다. It carried out similarly to the synthesis example 1, and added the following component at the following weight, and superposed | polymerized it.

디에틸렌글리콜메틸에틸에테르 20g20 g of diethylene glycol methyl ethyl ether

디시클로펜타닐메타크릴레이트 5.0g5.0 g of dicyclopentanyl methacrylate

N-시클로헥실말레이미드 2.5g2.5 g of N-cyclohexylmaleimide

메타크릴산 2.5gMethacrylic acid 2.5g

V-601 1.5gV-601 1.5 g

합성예 1과 같은 처리를 수행하여 폴리머(B1) 용액을 얻었다. 얻어진 폴리머(B1)의 GPC분석(폴리스티렌 표준)으로 구한 중량 평균 분자량은 3,300이었다.
The same treatment as in Synthesis example 1 was carried out to obtain a polymer (B1) solution. The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (B1) was 3,300.

합성예 6: 폴리머(A5)의 합성Synthesis Example 6 Synthesis of Polymer (A5)

합성예 1과 같이 수행하고, 하기 성분을 하기 중량으로 투입하여 중합을 실시하였다. The polymerization was carried out as in Synthesis Example 1, and the following components were added at the following weight.

디에틸렌글리콜메틸에틸에테르 20g20 g of diethylene glycol methyl ethyl ether

FM-0721 0.03g FM-0721 0.03 g

3-메타크릴옥시프로필트리메톡시실란 3.0g3.0 g of 3-methacryloxypropyl trimethoxysilane

메타크릴산 1.0g1.0 g of methacrylic acid

디시클로펜타닐메타크릴레이트 3.97gDicyclopentanyl methacrylate 3.97 g

N-페닐말레이미드 2.0g2.0 g of N-phenylmaleimide

V-601 1.0gV-601 1.0 g

합성예 1과 같은 처리를 수행하여 폴리머(A5) 용액을 얻었다. 얻어진 폴리머(A5)의 GPC분석(폴리스티렌 표준)으로 구한 중량 평균 분자량은 8,500이었다.
The same treatment as in Synthesis example 1 was carried out to obtain a polymer (A5) solution. The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (A5) was 8,500.

비교 합성예 1: 폴리머(C1)의 합성Comparative Synthesis Example 1 Synthesis of Polymer (C1)

합성예 1과 같이 수행하도, 하기 성분을 하기 중량으로 투입하여 중합을 실시하였다. In the same manner as in Synthesis example 1, the following components were added at the following weight to carry out polymerization.

디에틸렌글리콜메틸에틸에테르 20g20 g of diethylene glycol methyl ethyl ether

글리시딜메타크릴레이트 3.5gGlycidyl methacrylate 3.5 g

3-메타크릴옥시프로필트리메톡시실란 3.5g3.5 g of 3-methacryloxypropyltrimethoxysilane

디시클로펜타닐메타크릴레이트 2.0g2.0 g of dicyclopentanyl methacrylate

4-히드록시페닐비닐케톤 1.0g4-hydroxyphenyl vinyl ketone 1.0 g

V-601 1.0gV-601 1.0 g

합성예 1과 같은 처리를 수행하여 폴리머(C1) 용액을 얻었다. 얻어진 폴리머(C1)의 GPC분석(폴리스티렌 표준)으로 구한 중량 평균 분자량은 7,200이었다.
The same treatment as in Synthesis example 1 was carried out to obtain a polymer (C1) solution. The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (C1) was 7,200.

비교 compare 합성예Synthetic example 2:  2: 폴리머(C2)의Of polymer (C2) 합성 synthesis

합성예 1과 같이 수행하고, 하기 성분을 하기 중량으로 투입하여 중합을 실시하였다.The polymerization was carried out as in Synthesis Example 1, and the following components were added at the following weight.

디에틸렌글리콜메틸에틸에테르 20g20 g of diethylene glycol methyl ethyl ether

글리시딜메타크릴레이트 4.0gGlycidyl methacrylate 4.0 g

N-시클로헥실말레이미드 3.0g3.0 g of N-cyclohexylmaleimide

디시클로펜타닐메타크릴레이트 3.0g3.0 g of dicyclopentanyl methacrylate

V-601 1.0gV-601 1.0 g

합성예 1과 같은 처리를 수행하여 폴리머(C2) 용액을 얻었다. 얻어진 폴리머(C2)의 GPC분석(폴리스티렌 표준)으로 구한 중량 평균 분자량은 7,300이었다.
The same treatment as in Synthesis example 1 was carried out to obtain a polymer (C2) solution. The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (C2) was 7,300.

비교 합성예 3: 폴리머(C3)의 합성Comparative Synthesis Example 3: Synthesis of Polymer (C3)

합성예 1과 같이 수행하고, 하기 성분을 하기 중량으로 투입하여 중합을 실시하였다. The polymerization was carried out as in Synthesis Example 1, and the following components were added at the following weight.

디에틸렌글리콜메틸에틸에테르 20g20 g of diethylene glycol methyl ethyl ether

3-메타크릴옥시프로필트리메톡시실란 4.0g4.0 g of 3-methacryloxypropyl trimethoxysilane

벤질메타크릴레이트 2.0gBenzyl methacrylate 2.0 g

메타크릴로일옥시프로필-트리스-트리메틸실록시실란 2.0g2.0 g of methacryloyloxypropyl-tris-trimethylsiloxysilane

시클로헥실메타크릴레이트 2.0g2.0 g of cyclohexyl methacrylate

V-601 1.0gV-601 1.0 g

합성예 1과 같은 처리를 수행하여 폴리머(C3)용액을 얻었다. 얻어진 폴리머(C3)의 GPC분석(폴리스티렌 표준)으로 구한 중량 평균 분자량은 7,500이었다.
The same treatment as in Synthesis example 1 was carried out to obtain a polymer (C3) solution. The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (C3) was 7,500.

실험예 1: 열경화성 조성물의 제조Experimental Example 1 Preparation of Thermosetting Composition

희석 용제로서 프로필렌글리콜모노메틸에테르(이하에서는, "PGME"이라고도 한다), 합성예 1에서 얻어진 폴리머(A1)를 하기 중량으로 혼합 용해하여 고형분이 20 중량%인 열경화성 조성물을 얻었다. 폴리머의 합성에 사용한 용제와 희석 용제 이외의 성분을 고형분으로 하였다. Propylene glycol monomethyl ether (hereinafter also referred to as "PGME") and the polymer (A1) obtained in Synthesis Example 1 were mixed and dissolved as the diluting solvent in the following weights to obtain a thermosetting composition having a solid content of 20% by weight. Components other than the solvent and dilution solvent which were used for the synthesis | combination of a polymer were made into solid content.

프로필렌글리콜모노메틸에테르 2.0g2.0 g of propylene glycol monomethyl ether

폴리머(A1) 용액 3.0g
3.0 g of polymer (A1) solution

실험예 2 내지 실험예 6, 비교예 1 내지 비교예 6: 열경화성 조성물의 제조Experimental Example 2 to Experimental Example 6, Comparative Example 1 to Comparative Example 6: Preparation of the thermosetting composition

실험예 2 내지 실험예 6은, 실험예 1과 같이 표 1 또는 표 3에 따라 각 성분을 혼합 용해하고, 비교예 1 내지 비교예 6은, 실험예 1과 같이 표 2 또는 표 3에 따라 각 성분을 혼합 용해하여 각각 고형분 20%의 열경화성 조성물을 얻었다. 또한, 계면 활성제를 첨가할 경우는, 혼합한 조성물 전체량에 대하여 500ppm를 첨가하였다. Experimental Examples 2 to 6 were mixed and dissolved according to Table 1 or Table 3 as in Experimental Example 1, and Comparative Examples 1 to 6 were prepared according to Table 2 or Table 3 as in Experimental Example 1, respectively. The components were mixed and dissolved to obtain a thermosetting composition having a solid content of 20%, respectively. In addition, when surfactant was added, 500 ppm was added with respect to the mixed composition whole quantity.

실험예 1Experimental Example 1 실험예 2Experimental Example 2 실험예 3Experimental Example 3 실험예 4Experimental Example 4 실험예 5Experimental Example 5 폴리머Polymer A1A1 100100 5050 A2A2 100100 A3A3 100100 A4A4 100100 B1B1 5050 C1C1 C2C2 C3C3 첨가제additive S510S510 55 55 55 55 VG3101LVG3101L 2020 CY184CY184 1010 BYK342BYK342 500ppm500 ppm F－556F-556 500ppm500 ppm 희석용제Diluting solvent PGMEPGME 200200 300300 260260 220220 220220

비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 폴리머Polymer A1A1 A2A2 A3A3 A4A4 B1B1 C1C1 100100 100100 100100 C2C2 100100 C3C3 100100 첨가제additive S510S510 VG3101LVG3101L CY184CY184 BYK342BYK342 500ppm500 ppm F－556F-556 500ppm500 ppm 희석용제Diluting solvent PGMEPGME 200200 200200 200200 200200 200200

실험예 6Experimental Example 6 비교예 6Comparative Example 6 폴리머Polymer A1A1 A2A2 A3A3 A4A4 A5A5 100100 B1B1 C1C1 100100 C2C2 C3C3 첨가제additive S510S510 55 VG3101LVG3101L CY184CY184 BYK342BYK342 F－556F-556 10000ppm10000ppm 희석용제Diluting solvent PGMEPGME 220220 200200

상기 표 1 내지 표 3의 수치는, 계면 활성제 이외에는 중량부이다. 폴리머의 중량은 각 폴리머 용액의 고형분 농도를 33.3 중량%로 하여 계산한 고형분의 중량을 100 중량부로서 기재하였다. The numerical value of said Table 1-Table 3 is a weight part except surfactant. The weight of the polymer was described as 100 parts by weight of the weight of the solid content calculated by the solid content concentration of each polymer solution as 33.3% by weight.

상기 표 1 및 표 2의 첨가제 및 희석 용제에 있어서의 약호는 아래와 같다. The symbol in the additive of Table 1 and Table 2 and a diluting solvent is as follows.

실란 커플링제(밀착성 향상제)Silane Coupling Agent (Adhesive Enhancer)

S510: γ-글리시독시프로필트리메톡시실란(JNC(주))S510: γ-glycidoxypropyltrimethoxysilane (JNC Co., Ltd.)

에폭시 화합물(가교제)Epoxy compound (crosslinking agent)

VG3101L: 3관능 에폭시((주)프린테크)VG3101L: Trifunctional epoxy (Printech)

CY184: 2관능 에폭시(헌츠만 재팬(주))CY184: bifunctional epoxy (Huntsman Japan Co., Ltd.)

계면 활성제Surfactants

BYK342: 실리콘계 계면 활성제(빅크 케미 재팬(주))BYK342: silicone surfactant (Bik Chemi Japan Co., Ltd.)

F-556: 불소계 계면 활성제(DIC(주))F-556: Fluorine-based Surfactant (DIC Corporation)

희석 용제Dilution solvent

PGME: 프로필렌글리콜모노메틸에테르
PGME: Propylene Glycol Monomethyl Ether

열경화성 조성물의 평가 방법Evaluation method of thermosetting composition

(1) 표면 도포성(1) surface coating

낮은 임계 표면 장력을 갖는 표면에 대한 도포성을 반전 오프셋 인쇄용 실리콘제 블랭킷에 대한 도포성으로 확인하였다. 해당 블랭킷에 열경화성 조성물을 바코터로 도포하여 튕김 유무를 육안으로 확인하였다. 튕겼을 경우는 ×, 균일하게 도포된 경우는 ○로 하였다.
The applicability to the surface having a low critical surface tension was confirmed by the applicability to the blanket made of silicone for reverse offset printing. The thermosetting composition was applied to the blanket with a bar coater to visually check for the presence or absence of retraction. When it bounced, it was set as x and when it apply | coated uniformly.

(2) 투명막의 형성과 건조 후 막두께의 측정(2) Formation of transparent film and measurement of film thickness after drying

유리 기판 위에 열경화성 조성물을 500rpm으로 10초간 스핀 코트하고, 100℃의 핫플레이트 위에서 2분간 건조시켰다. 이 기판을 오븐에서 230℃에서 30분 포스트 베이크하여 막 두께 3.0㎛ ± 0.2㎛의 투명막을 형성하였다. 막 두께는 KLA-Tencor Japan(주) 제품의 촉침식 막후계 P-15를 사용하여, 3군데를 측정해서 평균값을 막 두께로 하였다.
The thermosetting composition was spin-coated at 500 rpm for 10 seconds on a glass substrate and dried for 2 minutes on a hot plate at 100 ° C. The substrate was post-baked at 230 ° C. for 30 minutes in an oven to form a transparent film having a film thickness of 3.0 μm ± 0.2 μm. The film thickness measured three places using the stylus type thickness gauge P-15 by KLA-Tencor Japan Co., Ltd., and made the average value into the film thickness.

(3) 도포 균일성(3) application uniformity

크롬 증착한 유리 기판 위에 열경화성 조성물을 스핀 코트하여, 100℃의 핫플레이트 위에서 2분간 건조시켰다. 그 후, 이 기판을 오븐에서 230℃로 30분 포스트 베이크하여, 막 두께 3.0㎛ ± 0.2㎛의 투명막을 형성하였다. 소성 후의 기판 표면을 육안에서 확인하여, 흐릿함, 얼룩 등이 확인된 경우는 ×, 확인되지 않은 경우를 ○로 하였다.
The thermosetting composition was spin-coated on the chromium-deposited glass substrate, and it dried for 2 minutes on a 100 degreeC hotplate. Thereafter, the substrate was post-baked at 230 ° C. for 30 minutes in an oven to form a transparent film having a film thickness of 3.0 μm ± 0.2 μm. The surface of the board | substrate after baking was visually confirmed, and when blurry, a stain, etc. were confirmed, x and the case where it was not confirmed were made into (circle).

(4) 투명성(4) transparency

니혼분코우(日本分光)(주)(JASCO Co.) 제품의 자외가시 근적외 분광 광도계 V-670을 사용하여 투명막을 형성하지 않은 유리 기판을 레퍼런스로하여 파장 400㎚에서의 광투과율을 측정하였다.
Using a UV-visible near-infrared spectrophotometer V-670 from Nippon Bunko Co., Ltd., the light transmittance at wavelength of 400 nm was measured with reference to a glass substrate without a transparent film. It was.

(5) 내열성(5) Heat resistance

상기 (1)에서 얻은 패턴 형상의 투명막의 기판을 230℃의 오븐에서 60분 동안 추가 베이크하여, 가열 전후에 있어서 상기 (4)와 동일하게 광투과율을 측정하고, 포스트 베이크 후(추가 베이크 전)의 광투과율을 T1이라 하고, 추가 베이크 후의 광투과율을 T2로 하였다. 포스트 베이크 후부터 추가 베이크 후의 광투과율의 저하가 적을수록 양호하다고 판정할 수 있다. 또한, 가열 전후에서 막 두께를 측정하여, 막 두께의 변화율을 다음 식으로 계산하였다. The substrate of the patterned transparent film obtained in the above (1) was further baked in an oven at 230 ° C. for 60 minutes, and the light transmittance was measured in the same manner as in the above (4) before and after heating, and after the post-baking (before the further baking) The light transmittance of T1 was called T1, and the light transmittance after further baking was set to T2. It can be judged that the smaller the decrease in the light transmittance after the post-baking and after the additional baking, the better. In addition, the film thickness was measured before and after heating, and the rate of change of the film thickness was calculated by the following equation.

(추가 베이크 후 막 두께/포스트 베이크 후 막 두께)× 100(%)
(Film thickness after additional bake / film thickness after post bake) × 100 (%)

(6) 밀착성(6) adhesion

상기 (1)에서 얻은 투명막의 기판을 바둑판눈 박리시험(크로스컷 시험)으로 평가하였다. 평가는 1㎜× 1㎜의 바둑판눈 100개 중에서 테이프 박리 후의 잔존 바둑판눈의 수를 나타내었다.
The board | substrate of the transparent film obtained by said (1) was evaluated by the board | substrate peeling test (cross cut test). The evaluation showed the number of remaining checkerboards after tape peeling among 100 checkerboards of 1 mm x 1 mm.

(7) 표면 장력(7) surface tension

조성물의 표면 장력은, 드롭마스터 DM-500(쿄와(協和) 계면화학(주)(Kyowa Interface Science CO., LTD.) 제품)을 사용하여, 펜던트 드롭법(현적법(懸滴法))으로 측정하였다. The surface tension of the composition was obtained by using the drop master DM-500 (manufactured by Kyowa Interface Science Co., Ltd.) and using the pendant drop method (preventive method). Measured by.

실험예 1 내지 실험예 6 및 비교예 1 내지 비교예 6에서 얻은 열경화성 조성물에 대하여, 상술한 평가 방법으로 얻은 결과를 표 4 내지 표 6에 나타낸다. About the thermosetting composition obtained by Experimental Example 1-Experimental Example 6 and Comparative Example 1-Comparative Example 6, the result obtained by the evaluation method mentioned above is shown to Tables 4-6.

실험예 1Experimental Example 1 실험예 2Experimental Example 2 실험예 3Experimental Example 3 실험예 4Experimental Example 4 실험예 5Experimental Example 5 표면 도포성Surface coating ○○ ○○ ○○ ○○ ○○ 건조 후 막 두께
(μm)Film thickness after drying
(μm) 3.11
3.11
3.20
3.20
3.02
3.02
3.12
3.12
3.20
3.20
도포균일성Coating uniformity ○○ ○○ ○○ ○○ ○○ 포스트베이크 후 막 두께
(μm)Film thickness after postbaking
(μm) 2.79
2.79
2.88
2.88
2.70
2.70
2.79
2.79
2.88
2.88
광투과율 T1
(%)Light transmittance T1
(%) 99
99
99
99
99
99
99
99
99
99
광투과율 T2
(%)Light transmittance T2
(%) 99
99
99
99
99
99
99
99
99
99
추가 베이크 후 막 두께
(μm)Film thickness after additional bake
(μm) 2.68
2.68
2.76
2.76
2.57
2.57
2.68
2.68
2.79
2.79
내열성
(막 두께 변화율 %)Heat resistance
(% Change in film thickness) 96
96
96
96
95
95
96
96
97
97
밀착성Adhesiveness 100100 100100 100100 100100 100100 표면 장력(mN/m)Surface tension (mN / m) 2222 2222 2222 2121 2222

비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 표면 도포성Surface coating ×× ×× ×× ×× ×× 건조 후 막 두께
(μm)Film thickness after drying
(μm) 3.10
3.10
3.01
3.01
3.02
3.02
3.22
3.22
3.11
3.11
도포 균일성Application Uniformity ○○ ○○ ×× ○○ ○○ 포스트베이크 후 막 두께
(μm)Film thickness after postbaking
(μm) 2.79
2.79
2.70
2.70
2.70
2.70
2.88
2.88
2.79
2.79
광투과율 T1
(%)Light transmittance T1
(%) 99
99
99
99
99
99
99
99
99
99
광투과율 T2
(%)Light transmittance T2
(%) 99
99
99
99
99
99
99
99
99
99
추가 베이크 후 막 두께
(μm)Film thickness after additional bake
(μm) 2.68
2.68
2.57
2.57
2.59
2.59
2.74
2.74
2.65
2.65
내열성
(막 두께 변화율 %)Heat resistance
(% Change in film thickness) 96
96
95
95
96
96
95
95
95
95
밀착성Adhesiveness 100100 100100 100100 100100 100100 표면 장력(mN/m)Surface tension (mN / m) 2828 2929 2828 2727 2626

실험예 6Experimental Example 6 비교예 6Comparative Example 6 표면 도포성Surface coating ○○ ×× 건조 후 막두께
(μm)Film thickness after drying
(μm) 3.09
3.09
3.11
3.11
도포 균일성Application Uniformity ○○ ×× 포스트베이크 후 막 두께
(μm)Film thickness after postbaking
(μm) 2.78
2.78
2.79
2.79
광투과율 T1
(%)Light transmittance T1
(%) 99
99
99
99
광투과율 T2
(%)Light transmittance T2
(%) 99
99
99
99
추가 베이크 후 막 두께
(μm)Film thickness after additional bake
(μm) 2.67
2.67
2.65
2.65
내열성
(막 두께 변화율 %)Heat resistance
(% Change in film thickness) 96
96
95
95
밀착성Adhesiveness 100100 100100 표면 장력(mN/m)Surface tension (mN / m) 2424 2525

비교예들에서는 표면 장력의 값이 크기 때문에(25mN/m이상), 실리콘계 기판에 튕겨지는(표면 도포성이 나쁨) 것에 반하여, 실험예들에서는 표면 장력의 값이 작기 때문에(24mN/m이하), 표면 도포성이 좋아져서 양호하게 도포된다. 나아가, 실험예들에서는 경화막으로서의 양호한 특성을 나타낸다. In the comparative examples, since the value of the surface tension is large (25 mN / m or more) and bounces on the silicon substrate (poor surface coating property), in the experimental examples, the value of the surface tension is small (24 mN / m or less). Surface applicability | paintability improves and it apply | coats favorably. Furthermore, the experimental examples show good characteristics as a cured film.

본 발명의 열경화성 조성물은, 예를 들면, 액정 표시 소자에 채용할 수 있는 절연막의 형성에 사용할 수 있다.The thermosetting composition of this invention can be used, for example in formation of the insulating film which can be employ | adopted for a liquid crystal display element.

Claims (7)

하기 화학식(1)로 나타내는 라디칼 중합성 화합물(a1), 에폭시 및 알콕시실릴 중에서 적어도 하나를 갖는 라디칼 중합성 화합물(a2) 및 기타 라디칼 중합성 화합물(a3)을 라디칼 공중합하여 형성되는 폴리머(A) 및 유기 용제(B)를 함유하는 열경화성 조성물.
[화학식 1]
Figure pat00003

(R1은 수소 또는 메틸이고, R2 내지 R5는 탄소수 1 내지 5의 알킬이며, R6은 탄소수 1 내지 10의 알킬이고, m은 1 내지 10의 정수이며, n은 1 내지 150의 정수이다.)Polymer (A) formed by radical copolymerization of a radically polymerizable compound (a1) represented by the following formula (1), a radically polymerizable compound (a2) having at least one of epoxy and alkoxysilyl, and other radically polymerizable compound (a3) And a thermosetting composition containing an organic solvent (B).
[Formula 1]
Figure pat00003

(R 1 is hydrogen or methyl, R 2 to R 5 are alkyl of 1 to 5 carbon atoms, R 6 is alkyl of 1 to 10 carbon atoms, m is an integer of 1 to 10, n is an integer of 1 to 150 to be.) 제 1 항에 있어서, 표면 장력이 24mN/m이하인 것을 특징으로 하는 열경화성 조성물. The thermosetting composition according to claim 1, wherein the surface tension is 24 mN / m or less. 제 1 항 또는 제 2 항에 있어서, 상기 유기 용제(B)가 수산기를 갖는 화합물인 것을 특징으로 하는 열경화성 조성물. The thermosetting composition according to claim 1 or 2, wherein the organic solvent (B) is a compound having a hydroxyl group. 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,
상기 화학식(1)로 나타내는 라디칼 중합성 화합물(a1)이, R1이 메틸, R2 내지 R5가 메틸, R6이 탄소 1 내지 10의 알킬, m이 1 내지 5의 정수, n이 1 내지 150의 정수인 것을 특징으로 하는 열경화성 조성물. The method according to any one of claims 1 to 3,
In the radically polymerizable compound (a1) represented by the general formula (1), R 1 is methyl, R 2 to R 5 is methyl, R 6 is carbon 1 to 10 alkyl, m is an integer of 1 to 5, n is 1 A thermosetting composition, characterized in that an integer of from 150 to 150. 제 1 항 내지 제 4 항 중 어느 한 항에 있어서,
에폭시 및 알콕시실릴 중에서 적어도 하나를 갖는 라디칼 중합성 모노머(a2)가, 글리시딜(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트글리시딜에테르, 3-(메타)아크릴옥시프로필트리메톡시실란, 3-(메타)아크릴옥시프로필트리에톡시실란, 3-(메타)아크릴옥시프로필메틸디메톡시실란, 3-(메타)아크릴옥시프로필메틸디에톡시실란, 비닐트리메톡시실란, 비닐트리에톡시실란 및 p-스티릴트리메톡시실란으로 이루어지는 그룹으로부터 선택되는 적어도 하나인 것을 특징으로 하는 열경화성 조성물. The method according to any one of claims 1 to 4,
The radically polymerizable monomer (a2) which has at least one among epoxy and alkoxy silyl is glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3- (meth) acryloxypropyl Trimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, A thermosetting composition, characterized in that it is at least one selected from the group consisting of vinyltriethoxysilane and p-styryltrimethoxysilane. 제 1 항 내지 제 5 항 중 어느 한 항에 있어서,
그 외의 라디칼 중합성 화합물(a3)이, 벤질, 시클로헥실, 트리스-트리메틸실록시실릴, 디시클로펜타닐, 말레이미드, 히드록시카보닐 및 히드록시페닐을 갖는 라디칼 중합성 화합물 중에서 적어도 하나인 것을 특징으로 하는 열경화성 조성물. 6. The method according to any one of claims 1 to 5,
The other radically polymerizable compound (a3) is at least one of radically polymerizable compounds having benzyl, cyclohexyl, tris-trimethylsiloxysilyl, dicyclopentanyl, maleimide, hydroxycarbonyl and hydroxyphenyl. Thermosetting composition to be. 제 1 항 내지 제 6 항 중 어느 한 항에 있어서,
그 외의 라디칼 중합성 화합물(a3)이, 벤질(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, (메타)아크릴로일옥시프로필-트리스-트리메틸실록시실란, 디시클로펜타닐(메타)아크릴레이트, N-시클로헥실말레이미드, N-페닐말레이미드, (메타)아크릴산 및 4-히드록시페닐비닐케톤으로 이루어지는 그룹으로부터 선택되는 적어도 하나인 것을 특징으로 하는 열경화성 조성물.7. The method according to any one of claims 1 to 6,
Other radically polymerizable compounds (a3) are benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryloyloxypropyl tris- trimethyl siloxysilane, and dicyclopentanyl (meth) acrylate And N-cyclohexylmaleimide, N-phenylmaleimide, (meth) acrylic acid and 4-hydroxyphenylvinyl ketone. The thermosetting composition characterized by the above-mentioned.
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