KR20130086134A - Composition and adhesive - Google Patents

Composition and adhesive Download PDF

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KR20130086134A
KR20130086134A KR1020127029224A KR20127029224A KR20130086134A KR 20130086134 A KR20130086134 A KR 20130086134A KR 1020127029224 A KR1020127029224 A KR 1020127029224A KR 20127029224 A KR20127029224 A KR 20127029224A KR 20130086134 A KR20130086134 A KR 20130086134A
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acrylate
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KR101667000B1 (en
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유키 히샤
기미히코 요다
준 와타나베
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덴끼 가가꾸 고교 가부시키가이샤
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
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    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

높은 접착 강도와 높은 내수성을 나타내는 조성물의 제공. 하기 (A)~(D)성분을 함유하여 이루어지는 조성물. (A)성분은 일반식〔1〕에서 나타나는 이소시아눌환 유도체, (B)성분은 수산기를 갖는 (메타)아크릴레이트, (C)성분은 실란 커플링제, (D)성분은 광중합 개시제를 함유하는 조성물. 알킬기를 갖는 (메타)아크릴레이트를 더 함유해도 된다. 편광 필름용, 시클로올레핀 폴리머용, 폴리카보네이트용, 트리아세틸셀룰로오스용, 폴리비닐알코올용, 유리용의 접착제로서 사용해도 된다.

Figure pct00007
Provision of a composition exhibiting high adhesive strength and high water resistance. The composition containing following (A)-(D) component. (A) component is isocyanuryl ring derivative represented by General formula [1], (B) component has (meth) acrylate which has a hydroxyl group, (C) component contains silane coupling agent, (D) component contains photoinitiator Composition. You may further contain the (meth) acrylate which has an alkyl group. You may use as an adhesive agent for polarizing films, a cycloolefin polymer, a polycarbonate, a triacetyl cellulose, a polyvinyl alcohol, and a glass.
Figure pct00007

Description

조성물 및 접착제{Composition and adhesive}Composition and Adhesives

본 발명은 조성물에 관한 것으로, 특히 그 조성물로 이루어지는 접착제에 관한 것이다.TECHNICAL FIELD This invention relates to a composition. Specifically, It is related with the adhesive which consists of this composition.

시클로올레핀 폴리머는 전자 재료, 광학 렌즈 및 의료 재료 등의 용도로 사용되고 있다. 시클로올레핀 폴리머는 극성이 작고 표면에 많은 관능기를 가지지 않기 때문에 난피착체로서 알려져 있다. 이러한 시클로올레핀계 수지를 접착하는 접착제로서는 용제형 접착제나 핫멜트 접착제를 들 수 있다.Cycloolefin polymers are used for applications such as electronic materials, optical lenses and medical materials. Cycloolefin polymers are known as oocyte adhering bodies because of their low polarity and do not have many functional groups on their surfaces. As an adhesive agent which adheres such cycloolefin resin, a solvent type adhesive agent and a hot melt adhesive agent are mentioned.

올레핀계 수지를 접착하는 방법으로서는 특허문헌 1에 개시되어 있는 바와 같이 프라이머에 의한 처리를 하고 나서 순간 접착제에 의해 접착한다는 방법을 들 수 있다.As a method of adhering an olefin resin, the method of adhering with an instantaneous adhesive agent after processing with a primer is disclosed, as disclosed in patent document 1.

특허문헌 2에는 유리, 금속, 폴리페닐렌설파이드와 같은 결정성 엔지니어링 플라스틱, 폴리카보네이트와 같은 투명성 엔지니어링 플라스틱 등의 각종 플라스틱 재료 등 다양한 피착체에 대해 똑같이 높은 접착강도를 가지고 내열성 및 내습성이 양호하며 강성도 뛰어난 에너지 선경화성 수지 조성물이 개시되어 있다. 그 수지 조성물은 분자량이 500~5000인 디엔계 혹은 수소 첨가된 디엔계의 (메타)아크릴레이트, 특정 구조의 포화 탄화 수소를 에스테르 결합을 개재하여 갖는 단관능 (메타)아크릴레이트, 수산기 함유 (메타)아크릴레이트, 다관능성 (메타)아크릴레이트, 광중합 개시제 및 산화 방지제를 함유한다.Patent Document 2 has the same high adhesive strength for various adherends such as glass, metal, crystalline engineering plastics such as polyphenylene sulfide, and transparent plastics such as polycarbonate, and has good heat resistance and moisture resistance. An energy precurable resin composition excellent in rigidity is also disclosed. The resin composition contains a monofunctional (meth) acrylate having a molecular weight of 500 to 5000 or a hydrogenated diene (meth) acrylate and a saturated hydrocarbon having a specific structure through an ester bond, and a hydroxyl group-containing (meth ) Acrylate, polyfunctional (meth) acrylate, photoinitiator, and antioxidant.

액정 표시 관련 분야 등에 이용되는 편광 필름은 통상 폴리비닐알코올(PVA)에 요오드나 안료를 흡착시킨 것을 일축 연신하여 제조된다. 이 폴리비닐알코올계 편광 필름은 열이나 수분에 의해 수축되어 편광 성능의 저하를 초래하기 때문에 그 표면에 보호 필름이 첩합된 것이 편광판이다.The polarizing film used for a liquid crystal display related field etc. is manufactured by uniaxially stretching what adsorbed iodine and a pigment to polyvinyl alcohol (PVA) normally. Since this polyvinyl alcohol-type polarizing film shrink | contracts by heat and water and causes the fall of polarization performance, it is a polarizing plate in which the protective film was bonded to the surface.

편광판의 보호 필름에는 통상 트리아세틸셀룰로오스가 사용되고 있다.Triacetyl cellulose is normally used for the protective film of a polarizing plate.

편광 필름에 보호 필름을 첩합하기 위한 접착제로서는 종래부터 폴리비닐알코올계의 수용액이 널리 사용되고 있다(특허문헌 3).As an adhesive agent for bonding a protective film to a polarizing film, the polyvinyl alcohol-type aqueous solution is widely used conventionally (patent document 3).

특허문헌 4는 반도체 소자와 반도체 소자 탑재용 지지 부재를 접착하기 위한 접착제에 관한 것으로, 알칼리 현상액에 의한 패턴 형성성이 뛰어나고 노광 후의 충분한 재접착성을 가지며, 필름상으로 형성한 경우에는 저온 첩부성도 뛰어난 감광성 접착제 조성물을 제공하는 것을 목적으로 하여 (A)알칼리 가용성 폴리머와 (B)열경화성 수지와 (C)1종 또는 복수의 방사선 중합성 화합물과 (D)광 개시제를 함유하고, 조성물 중의 전방사선 중합성 화합물의 혼합물의 5%중량 감소 온도가 200℃이상인 감광성 접착제 조성물이 개시되어 있다. 그리고, 방사선 중합성 화합물로서 이소시아눌산 에틸렌 옥사이드 변성 디 또는 트리아크릴레이트를 들 수 있고, 이에 의해 경화 후의 접착성 및 내열성을 특히 양호한 것으로 하는 것이 기재되어 있다.Patent document 4 relates to an adhesive for bonding a semiconductor element and a support member for mounting a semiconductor element. The patent document 4 is excellent in pattern formability by an alkaline developer, has sufficient re-adhesion after exposure, and is formed at a low temperature when formed into a film. For the purpose of providing an excellent photosensitive adhesive composition, (A) an alkali-soluble polymer, (B) a thermosetting resin, (C) one or more radiation polymerizable compounds, and (D) a photoinitiator, A photosensitive adhesive composition is disclosed wherein a 5% weight loss temperature of a mixture of polymerizable compounds is at least 200 ° C. And isocyanuric acid ethylene oxide modified di or triacrylate is mentioned as a radiation polymeric compound, It is described by this that adhesiveness and heat resistance after hardening are especially favorable.

특허문헌 1: 일본특개소62-18485호 공보Patent Document 1: Japanese Patent Application Laid-Open No. 62-18485 특허문헌 2: 일본특개 2007-77321호 공보Patent Document 2: Japanese Patent Application Laid-Open No. 2007-77321 특허문헌 3: 일본특개 2008-065251호 공보Patent Document 3: Japanese Patent Application Laid-Open No. 2008-065251 특허문헌 4: 국제공개 제2008/149625호Patent Document 4: International Publication No. 2008/149625

용제형 접착제는 용제를 사용한다. 용제형 접착제는 인체에 유해한 데다가 용제의 휘발에 시간이 걸려 접착 강도 자체도 충분한 것을 얻을 수 없다.Solvent-type adhesive uses a solvent. Solvent-based adhesives are harmful to the human body and take time to volatilize the solvent to obtain sufficient adhesive strength.

핫멜트 접착제는 접착제를 용융시키는 수고 및 장치가 필요하다. 이 접착제도 충분한 접착 강도를 얻을 수 없다. 핫멜트 접착제를 이용하는 경우 시클로올레핀 폴리머를 미리 가열해 두면 접착 강도는 향상되지만 수지가 변형되어 버리는 새로운 문제가 발생한다.Hot melt adhesives require labor and apparatus to melt the adhesive. This adhesive cannot obtain sufficient adhesive strength. In the case of using a hot melt adhesive, when the cycloolefin polymer is preheated, the adhesive strength is improved, but a new problem occurs that the resin is deformed.

특허문헌 1에 개시되어 있는 접착 방법에 의하면 프라이머 처리에 수고가 드는 문제가 있는데다가 접착 강도도 충분한 것을 얻을 수 없다.According to the bonding method disclosed in Patent Literature 1, there is a problem in that the primer treatment is troublesome and sufficient adhesive strength cannot be obtained.

특허문헌 2는 (메타)아크릴레이트를 함유하는 것을 특징으로 하는 에너지 선경화성 수지 조성물이 개시되어 있다. 그러나, 이소시아눌산 유도체를 함유하는 기재는 되어 있지 않고, 또한 트리아세틸셀룰로오스를 피착체로 한 기재는 되어 있지 않다.Patent Literature 2 discloses an energy precurable resin composition characterized by containing (meth) acrylate. However, there is no base material containing an isocyanuric acid derivative, and no base material using triacetyl cellulose as an adherend.

특허문헌 3에는 각종 광학 필름에 대해 침투성을 갖는 기재 침투성 모노머를 사용한 접착제 조성물이 개시되어 있다. 이러한 조성물은 기재 필름을 침입하여 광학 특성 저하의 점에서 바람직하지 않다.In patent document 3, the adhesive composition using the base material permeable monomer which has permeability with respect to various optical films is disclosed. Such a composition penetrates a base film and is unpreferable in the point of optical characteristic fall.

특허문헌 4는 트리아세틸셀룰로오스를 피착체로 한 기재는 되어 있지 않고, 또한 본 발명에서 필수적인 실란 커플링제를 필수로 하지 않는다. 본 발명은 열경화성 수지와 알칼리 가용성 폴리머를 필수로 하지 않는다. 열경화성 수지와 알칼리 가용성 폴리머를 필수로 한 경우, 자외선에 의한 경화 저해 및 접착성의 점에서 바람직하지 않다. 본 발명은 수산기를 갖는 (메타)아크릴레이트를 접착성을 향상시키기 위해 필수로 하고 있다.Patent Literature 4 does not describe the triacetyl cellulose as an adherend and does not require a silane coupling agent essential in the present invention. The present invention does not require a thermosetting resin and an alkali-soluble polymer. When the thermosetting resin and the alkali-soluble polymer are essential, they are not preferable in terms of curing inhibition by ultraviolet rays and adhesiveness. This invention makes the (meth) acrylate which has a hydroxyl group essential for improving adhesiveness.

본 발명은 이러한 실정을 감안하여 이루어진 것이다. 본 발명은 예를 들면 시클로올레핀 폴리머, 폴리카보네이트, 트리아세틸셀룰로오스, 폴리비닐알코올 및 유리에 대해 단시간에 충분한 접착 강도를 발현할 수 있고, 높은 내수성을 갖는 무용제형으로 환경 친화적인 접착제의 제공을 목적으로 한다.The present invention has been made in view of such circumstances. SUMMARY OF THE INVENTION The present invention aims to provide an environmentally friendly adhesive that can express sufficient adhesive strength in a short time to cycloolefin polymer, polycarbonate, triacetylcellulose, polyvinyl alcohol and glass, and is a solvent-free type having high water resistance. It is done.

본 발명자는 상기 과제를 해결하기 위해 면밀히 연구를 거듭하여 본 발명에 이른 것이다.MEANS TO SOLVE THE PROBLEM This inventor earnestly researched in order to solve the said subject, and came to this invention.

즉, 본 발명은 일측면에 있어서 하기 (A)~(D)성분을 함유하여 이루어지는 조성물이다.That is, this invention is a composition which contains the following (A)-(D) component in one side.

(A)성분은 일반식〔1〕에서 나타나는 이소시아눌환 유도체(일반식〔1〕 중의 X1 및 X2는 (메타)아크릴로일 옥시기를 나타내고, X3은 히드록실기 또는 (메타)아크릴로일 옥시기를 나타내며, R1, R2 및 R3은 탄소수 1~4의 탄화수소기를 나타낸다.)(A) A component isocyanuryl ring derivative represented by General formula [1] (X <1> and X <2> in General formula [1] represent a (meth) acryloyl oxy group, X <3> is a hydroxyl group or (meth) acryl Represents a loyloxy group, and R 1 , R 2, and R 3 represent a hydrocarbon group having 1 to 4 carbon atoms.)

Figure pct00001
Figure pct00001

(B)성분은 수산기를 갖는 (메타)아크릴레이트(B) component (meth) acrylate which has a hydroxyl group

(C)성분은 실란 커플링제(C) component is a silane coupling agent

(D)성분은 광중합 개시제(D) component is a photoinitiator

본 발명에 관한 조성물의 일실시형태에서는 (E)성분으로서 일반식〔2〕에서 나타나는 (메타)아크릴레이트를 더 함유한다.In one Embodiment of the composition which concerns on this invention, (E) component further contains the (meth) acrylate represented by General formula [2].

일반식〔2〕 R-O-R′General formula [2] R-O-R '

(식 중, R은 (메타)아크릴로일기를 나타내고, R′는 탄소수 5~18개의 알킬기를 나타낸다.)(In formula, R represents a (meth) acryloyl group and R 'represents a C5-C18 alkyl group.)

본 발명에 관한 조성물의 다른 일실시형태에서는 조성물의 경화물의 저장 탄성률(E′)이 0.000001~10000MPa(23℃)의 범위 내이다.In another embodiment of the composition concerning this invention, the storage elastic modulus (E ') of the hardened | cured material of a composition exists in the range of 0.000001-10000 Mpa (23 degreeC).

본 발명에 관한 조성물의 또 다른 일실시형태에서는 (A)성분이 이소시아눌산 에틸렌 옥사이드 변성 트리(메타)아크릴레이트, 이소시아눌산 에틸렌 옥사이드 변성 디(메타)아크릴레이트, 이소시아눌산 에틸렌 옥사이드 변성 트리/디(메타)아크릴레이트 혼합물, 이소시아눌산 프로필렌 옥사이드 변성 트리(메타)아크릴레이트, 이소시아눌산 프로필렌 옥사이드 변성 디(메타)아크릴레이트, 이소시아눌산 부틸 옥사이드 변성 트리(메타)아크릴레이트 및 이소시아눌산 부틸 옥사이드 변성 디(메타)아크릴레이트로 이루어지는 군에서 선택되는 1종 또는 2종 이상이다.In another embodiment of the composition according to the present invention, the component (A) is isocyanuric acid ethylene oxide modified tri (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified tri / Di (meth) acrylate mixture, isocyanuric acid propylene oxide modified tri (meth) acrylate, isocyanuric acid propylene oxide modified di (meth) acrylate, isocyanuric acid butyl oxide modified tri (meth) acrylate and isocyanate It is 1 type, or 2 or more types chosen from the group which consists of butyl oxide modified | denatured di (meth) acrylate.

본 발명에 관한 조성물의 또 다른 일실시형태에서는 (A)성분이 조성물의 5~80질량%를 차지하고, (A)성분 및 (B)성분의 합계 100질량부 중에서 (A)성분:(B) 성분=10~99:1~90(질량비)이며, (C)성분의 사용량은 (A)성분 및 (B)성분의 합계 100질량부에 대해 0.001~10질량부이고, (D)성분의 사용량은 (A)성분 및 (B)성분의 합계 100질량부에 대해 0.001~30질량부이다.In another embodiment of the composition according to the present invention, (A) component comprises 5 to 80% by mass of the composition, and (A) component in the total of 100 parts by mass of the component (A) and (B): (B) Component = 10-99: 1-90 (mass ratio), and the usage-amount of (C) component is 0.001-10 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, and the usage-amount of (D) component Is 0.001-30 mass parts with respect to a total of 100 mass parts of (A) component and (B) component.

본 발명에 관한 조성물의 또 다른 일실시형태에서는 (E)성분이 2-에틸헥실(메타)아크릴레이트, 노닐(메타)아크릴레이트, 이소데실(메타)아크릴레이트, n-라우릴(메타)아크릴레이트 및 트리데실(메타)아크릴레이트로 이루어지는 군 중의 1종 또는 2종 이상이다.In another embodiment of the composition according to the present invention, (E) component is 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acryl It is 1 type, or 2 or more types in the group which consists of a rate and a tridecyl (meth) acrylate.

본 발명에 관한 조성물의 또 다른 일실시형태에서는 (A)성분이 조성물의 5~80질량%를 차지하고, (A)성분 및 (B)성분의 합계 100질량부 중에서 (A)성분:(B)성분=10~99:1~90(질량비)이며, (A)성분, (B)성분 및 (E)성분의 합계 100질량부 중에서 (A)성분:(B)성분:(E)성분=10~80:1~70:15~80(질량비)이고, (C)성분의 사용량은 (A)성분, (B)성분 및 (E)성분의 합계 100질량부에 대해 0.001~10질량부이며, (D)성분의 사용량은 (A)성분, (B)성분 및 (E)성분의 합계 100질량부에 대해 0.001~30질량부이다.In another embodiment of the composition according to the present invention, (A) component comprises 5 to 80% by mass of the composition, and (A) component in the total of 100 parts by mass of the component (A) and (B): (B) It is component = 10-99: 1-90 (mass ratio), and in 100 mass parts of total of (A) component, (B) component, and (E) component, (A) component: (B) component: (E) component = 10 It is -80: 1-70: 15-80 (mass ratio), and the usage-amount of (C) component is 0.001-10 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (E) component, The usage-amount of (D) component is 0.001-30 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (E) component.

본 발명은 다른 일측면에 있어서 본 발명에 관한 조성물로 이루어지는 접착제이다.This invention is an adhesive agent which consists of a composition which concerns on this invention in another aspect.

본 발명에 관한 접착제는 일실시형태에 있어서 편광 필름용 접착제이다.The adhesive agent concerning this invention is an adhesive agent for polarizing films in one Embodiment.

본 발명에 관한 접착제는 다른 일실시형태에 있어서 시클로올레핀 폴리머용 접착제이다.The adhesive agent which concerns on this invention is an adhesive agent for cycloolefin polymer in another embodiment.

본 발명에 관한 접착제는 또 다른 일실시형태에 있어서 시클로올레핀 폴리머, 폴리카보네이트, 트리아세틸셀룰로오스, 폴리비닐알코올 및 유리로 이루어지는 군에서 선택되는 1종 또는 2종 이상의 기재용으로 사용된다.In another embodiment, the adhesive according to the present invention is used for one or two or more substrates selected from the group consisting of a cycloolefin polymer, polycarbonate, triacetyl cellulose, polyvinyl alcohol and glass.

본 발명은 또 다른 일측면에 있어서 본 발명에 관한 접착제를 이용하여 피착체끼리를 접착하여 만들어진 접착체이다.This invention is an adhesive body formed by adhering adherends using the adhesive agent which concerns on this invention in another one side.

본 발명에 관한 접착체는 일실시형태에 있어서 피착체가 시클로올레핀 폴리머, 폴리카보네이트, 트리아세틸셀룰로오스, 폴리비닐알코올 및 유리로 이루어지는 군에서 선택되는 1종 또는 2종 이상이다.In one embodiment, the adherend according to the present invention is one or two or more selected from the group consisting of cycloolefin polymer, polycarbonate, triacetyl cellulose, polyvinyl alcohol and glass.

본 발명의 조성물은 시클로올레핀 폴리머, 폴리카보네이트, 트리아세틸셀룰로오스, 폴리비닐알코올 및 유리에 대해 단시간에 충분한 높은 접착 강도와 높은 내수성을 나타낸다는 특징을 가진다. 그리고, 본 발명의 조성물은 무용제형이기 때문에 환경 친화적이다.The composition of the present invention is characterized by exhibiting high adhesive strength and high water resistance sufficient for a short time to cycloolefin polymer, polycarbonate, triacetylcellulose, polyvinyl alcohol and glass. And since the composition of this invention is a solvent-free type, it is environmentally friendly.

(A)성분은 일반식〔1〕에서 나타나는 이소시아눌환 유도체(일반식〔1〕 중의 X1 및 X2는 (메타)아크릴로일 옥시기를 나타내고, X3은 히드록실기 또는 (메타)아크릴로일 옥시기를 나타내며, R1, R2 및 R3은 탄소수 1~4의 탄화수소기, 전형적으로는 알킬렌기를 나타낸다.)이다.(A) A component isocyanuryl ring derivative represented by General formula [1] (X <1> and X <2> in General formula [1] represent a (meth) acryloyl oxy group, X <3> is a hydroxyl group or (meth) acryl A loyloxy group, R 1 , R 2 and R 3 represent a hydrocarbon group having 1 to 4 carbon atoms, typically an alkylene group.).

Figure pct00002
Figure pct00002

(A)이소시아눌산 유도체로서는 이소시아눌산 에틸렌 옥사이드 변성 트리(메타)아크릴레이트, 이소시아눌산 에틸렌 옥사이드 변성 디(메타)아크릴레이트, 이소시아눌산 에틸렌 옥사이드 변성 트리/디(메타)아크릴레이트 혼합물(즉, 이소시아눌산 에틸렌 옥사이드 변성 트리(메타)아크릴레이트와 이소시아눌산 에틸렌 옥사이드 변성 디(메타)아크릴레이트의 혼합물), 이소시아눌산 프로필렌 옥사이드 변성 트리(메타)아크릴레이트, 이소시아눌산 프로필렌 옥사이드 변성 디(메타)아크릴레이트, 이소시아눌산 부틸렌 옥사이드 변성 트리(메타)아크릴레이트 및 이소시아눌산 부틸렌 옥사이드 변성 디(메타)아크릴레이트 등을 들 수 있다.(A) As the isocyanuric acid derivative, isocyanuric acid ethylene oxide modified tri (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified tri / di (meth) acrylate mixture ( That is, a mixture of isocyanuric acid ethylene oxide modified tri (meth) acrylate and isocyanuric acid ethylene oxide modified di (meth) acrylate), isocyanuric acid propylene oxide modified tri (meth) acrylate, isocyanuric acid propylene oxide modified Di (meth) acrylate, isocyanurate butylene oxide modified tri (meth) acrylate, isocyanurate butylene oxide modified di (meth) acrylate, and the like.

이소시아눌산 유도체 중에서는 내수성의 점에서 이소시아눌산 에틸렌 옥사이드 변성 디(메타)아크릴레이트, 이소시아눌산 에틸렌 옥사이드 변성 트리(메타)아크릴레이트, 이소시아눌산 에틸렌 옥사이드 변성 트리/디(메타)아크릴레이트 혼합물로 이루어지는 군 중의 1종 또는 2종 이상이 바람직하다.Among the isocyanuric acid derivatives, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, and isocyanuric acid ethylene oxide modified tri / di (meth) acrylate in terms of water resistance 1 type, or 2 or more types in the group which consists of mixtures is preferable.

(B)수산기 함유 (메타)아크릴레이트로서는 1개 이상의 (메타)아크릴로일기를 갖는 모노머 중에서 수산기를 함유하는 것을 들 수 있다.As (B) hydroxyl group containing (meth) acrylate, what contains a hydroxyl group in the monomer which has one or more (meth) acryloyl groups is mentioned.

수산기 함유 모노머로서는 2-히드록시에틸(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 지방족 에폭시(메타)아크릴레이트(다이셀 UCB사 제품「Ebecryl111」「Ebecryl112」), 에피클로로히드린(이하, ECH라고 함) 변성 알릴(메타)아크릴레이트(나가세 화성사 제품「데코날 아크릴레이트 DA-111」), 부탄디올모노(메타)아크릴레이트, 수산기 함유 카프로락톤(메타)아크릴레이트, 디프로필렌글리콜(메타)아크릴레이트, ECH 변성 페녹시(메타)아크릴레이트, 폴리프로필렌글리콜(메타)아크릴레이트(n=5-13), 에틸렌 옥사이드(이하, EO라고 함) 변성 숙신산 (메타)아크릴레이트, β-카르복시에틸(메타)아크릴레이트, 수산기 함유 디아크릴화 이소시아누레이트, ECH 변성 프탈산 디(메타)아크릴레이트, ECH 변성 프로필렌글리콜 디(메타)아크릴레이트, 프로필렌 옥사이드(이하, PO변성이라고 함) 비스페놀 A 디글리시딜에테르 디(메타)아크릴레이트, ECH 변성 글리세롤 트리(메타)아크릴레이트, EO 변성 인산 메타크릴레이트, 폴리에틸렌글리콜-폴리프로필렌글리콜 메타크릴레이트, 2-히드록시-3-페녹시프로필 (메타)아크릴레이트 등을 들 수 있다. 이들 1종 또는 2종 이상을 사용해도 된다.As hydroxyl-containing monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, aliphatic epoxy (Meth) acrylate ("Ebecryl 111" and "Ebecryl 112" by Daicel UCB Co., Ltd.), epichlorohydrin (hereinafter referred to as ECH) modified allyl (meth) acrylate ("Deconal acrylate DA-111 by Nagase Chemical Co., Ltd.") ), Butanediol mono (meth) acrylate, hydroxyl-containing caprolactone (meth) acrylate, dipropylene glycol (meth) acrylate, ECH modified phenoxy (meth) acrylate, polypropylene glycol (meth) acrylate (n = 5-13), ethylene oxide (hereinafter referred to as EO) modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, hydroxyl-containing diacrylated isocyanurate, ECH modified phthalic acid di (meth) arc Latex, ECH modified propylene glycol di (meth) acrylate, propylene oxide (hereinafter referred to as PO modified) bisphenol A diglycidyl ether di (meth) acrylate, ECH modified glycerol tri (meth) acrylate, EO modified phosphoric acid Methacrylate, polyethyleneglycol polypropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. You may use these 1 type, or 2 or more types.

수산기 함유 (메타)아크릴레이트 중에서는 접착성의 점에서 2-히드록시에틸(메타)아크릴레이트, ECH 변성 페녹시(메타)아크릴레이트, 2-히드록시-3-페녹시프로필 (메타)아크릴레이트로 이루어지는 군 중의 1종 이상이 바람직하고, 2-히드록시에틸(메타)아크릴레이트 및/또는 2-히드록시-3-페녹시프로필 (메타)아크릴레이트가 보다 바람직하다.In hydroxyl-containing (meth) acrylate, it is 2-hydroxyethyl (meth) acrylate, ECH modified phenoxy (meth) acrylate, and 2-hydroxy-3- phenoxypropyl (meth) acrylate from an adhesive point. At least 1 type in the group which consists of is preferable, and 2-hydroxyethyl (meth) acrylate and / or 2-hydroxy-3- phenoxypropyl (meth) acrylate are more preferable.

(C)성분은 실란 커플링제이다. 실란 커플링제로서는 γ-클로로프로필 트리메톡시실란, 비닐트리메톡시실란, 비닐트리클로로실란, 비닐트리에톡시실란, 비닐프로필 트리메톡시실란, 비닐-트리스(β-메톡시에톡시)실란, γ-메타크릴록시프로필 트리메톡시실란, γ-아크릴록시프로필 트리메톡시실란, β-(3,4-에폭시시클로헥실)에틸트리메톡시실란, γ-글리시독시프로필 트리메톡시실란, γ-메르캅토프로필 트리메톡시실란, γ-아미노프로필 트리에톡시실란, N-β-(아미노에틸)-γ-아미노프로필 트리메톡시실란, N-β-(아미노에틸)-γ-아미노프로필메틸 디메톡시실란, γ-유레이도프로필 트리에톡시실란, 히드록시에틸(메타)아크릴레이트 인산 에스테르, (메타)아크릴록시옥시에틸애시드포스페이트, (메타)아크릴록시옥시에틸애시드포스페이트 모노에틸아민하프솔트 등을 들 수 있다. 이들 중에서는 접착성의 점에서 γ-글리시독시프로필 트리메톡시실란, γ-(메타)아크릴록시프로필 트리메톡시실란 및 비닐프로필 트리메톡시실란으로 이루어지는 군 중의 1종 또는 2종 이상이 바람직하고, γ-글리시독시프로필 트리메톡시실란이 보다 바람직하다.(C) component is a silane coupling agent. Examples of the silane coupling agent include γ-chloropropyl trimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinylpropyl trimethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyl trimethoxysilane, γ-acryloxypropyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ Mercaptopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, N-β- (aminoethyl) -γ-aminopropyl trimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyl Dimethoxysilane, γ-ureidopropyl triethoxysilane, hydroxyethyl (meth) acrylate phosphate ester, (meth) acryloxyoxyethyl acid phosphate, (meth) acryloxyoxyethyl acid phosphate monoethylamine half salt, etc. Can be mentioned. In these, 1 type (s) or 2 or more types are preferable in the group which consists of (gamma)-glycidoxy propyl trimethoxysilane, (gamma)-(meth) acryloxypropyl trimethoxysilane, and vinyl propyl trimethoxysilane from an adhesive point, , γ-glycidoxypropyl trimethoxysilane is more preferred.

(D)성분은 광중합 개시제이다.(D) component is a photoinitiator.

광중합 개시제로서는 자외선 중합 개시제나 가시광 중합 개시제 등을 들 수 있다. 자외선 중합 개시제로서는 벤조인계, 벤조페논계, 아세토페논계 등을 들 수 있다. 가시광 중합 개시제로서는 아실포스핀옥사이드계, 티옥산톤계, 메탈로센계, 퀴논계, α-아미노알킬페논계 등을 들 수 있다.As a photoinitiator, an ultraviolet-ray polymerization initiator, a visible light polymerization initiator, etc. are mentioned. Examples of the ultraviolet polymerization initiators include benzoin, benzophenone, acetophenone and the like. As a visible light polymerization initiator, an acyl phosphine oxide type, a thioxanthone type, a metallocene type, a quinone type, the (alpha)-aminoalkyl phenone type, etc. are mentioned.

광중합 개시제로서는 벤조페논, 4-페닐벤조페논, 벤조일 안식향산, 2,2-디에톡시아세토페논, 비스디에틸아미노벤조페논, 벤질, 벤조인, 벤조일이소프로필에테르, 벤질디메틸케탈, 1-히드록시시클로헥실페닐케톤, 티옥산톤, 2-메틸티옥산톤, 2,4-디메틸티옥산톤, 이소프로필티옥산톤, 2,4-디에틸티옥산톤, 2,4-디이소프로필티옥산톤, 1-(4-이소프로필페닐)2-히드록시-2-메틸프로판-1-온, 1-(4-(2-히드록시에톡시)-페닐)-2-히드록시-2-메틸-1-프로판-1-온, 2-히드록시-2-메틸-1-페닐프로판-1-온, 캠퍼퀴논, 2,4,6-트리메틸벤조일 디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드, 2-메틸-1-(4-(메틸티오)페닐)-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-1-부타논-1,2-디메틸아미노-2-(4-메틸-벤질)-1-(4-모르폴린-4-일-페닐)-부탄-1-온, 비스(2,6-디메톡시벤조일)-2,4,4-트리메틸-펜틸포스핀옥사이드 등을 들 수 있다. 이들 중에서는 벤질디메틸케탈 및/또는 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드가 바람직하다.Examples of the photopolymerization initiator include benzophenone, 4-phenylbenzophenone, benzoyl benzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclo Hexylphenyl ketone, thioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone , 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl- 1-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, camphorquinone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6 -Trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -1-butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like. Among them, benzyldimethyl ketal and / or bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferable.

본 발명의 접착제는 각종 기재의 밀착성을 한층 더 향상시키는 것을 목적으로 (A)성분, (B)성분 이외의 단관능 (메타)아크릴레이트를 더 함유할 수 있다.The adhesive of this invention can further contain monofunctional (meth) acrylates other than (A) component and (B) component for the purpose of further improving the adhesiveness of various base materials.

(A)성분이나 (B)성분 이외의 단관능 (메타)아크릴레이트로서는 (E)일반식〔2〕에서 나타나는 (메타)아크릴레이트를 들 수 있다.As monofunctional (meth) acrylates other than (A) component and (B) component, the (meth) acrylate represented by (E) General formula [2] is mentioned.

일반식〔2〕 R-O-R′General formula [2] R-O-R '

(식 중, R은 (메타)아크릴로일기를 나타내고, R′는 탄소수 5~18개의 알킬기를 나타낸다.)(In formula, R represents a (meth) acryloyl group and R 'represents a C5-C18 alkyl group.)

(E)성분의 단관능 (메타)아크릴레이트로서는 2-에틸헥실(메타)아크릴레이트, 노닐(메타)아크릴레이트, 이소데실(메타)아크릴레이트, n-라우릴(메타)아크릴레이트 및 트리데실(메타)아크릴레이트 등을 들 수 있다. 이들 중에서는 접착성의 점에서 n-라우릴(메타)아크릴레이트가 바람직하다.As monofunctional (meth) acrylate of (E) component, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, and tridecyl (Meth) acrylate etc. are mentioned. In these, n-lauryl (meth) acrylate is preferable at an adhesive point.

식 중, R′의 탄소수는 5~18개가 바람직하고, 6~18개가 보다 바람직하다. 5개 이상이면 내수성이 향상되고, 18개 이하이면 조성물이 석출되지 않아 접착성이 향상된다.In formula, 5-18 pieces are preferable and, as for carbon number of R ', 6-18 pieces are more preferable. If it is five or more, water resistance will improve, and if it is 18 or less, a composition will not precipitate and adhesiveness improves.

본 발명의 각 구성 성분의 사용량은 예를 들면 접착제의 시클로올레핀 폴리머에 대한 접착성이 특별히 높아지고, 또한 다른 피착체에 대해서도 높은 접착 강도를 갖게 되는 점에서 이하의 사용량이 바람직하다.As for the usage-amount of each structural component of this invention, adhesiveness with respect to the cycloolefin polymer of an adhesive agent especially becomes high, for example, and since it has a high adhesive strength with respect to another adherend, the following usage-amount is preferable.

(A)성분은 조성물의 5~80질량%를 차지하는 것이 바람직하고, 10~70질량%를 차지하는 것이 보다 바람직하다.(A) It is preferable to occupy 5-80 mass% of a composition, and, as for a component, it is more preferable to occupy 10-70 mass%.

(A)성분, (B)성분의 배합 비율은 (A)성분 및 (B)성분의 합계 100질량부 중에서 (A)성분:(B)성분=10~99:1~90(질량비)이 바람직하고, 20~98:2~80(질량비)이 보다 바람직하며, 55~95:5~45(질량비)가 가장 바람직하다.As for the mixture ratio of (A) component and (B) component, (A) component: (B) component = 10-99: 1-90 (mass ratio) are preferable in 100 mass parts of total of (A) component and (B) component. 20-98: 2-80 (mass ratio) are more preferable, and 55-95: 5-45 (mass ratio) are the most preferable.

(E)성분을 사용하는 경우, (A)성분, (B)성분, (E)성분의 사용량은 (A)성분, (B)성분 및 (E)성분의 합계 100질량부 중에서 (A)성분:(B)성분:(E)성분=10~80:1~70:15~80(질량비)이 바람직하고, 15~50:2~60:25~65(질량비)가 보다 바람직하며, 20~45:3~45:35~60(질량비)이 가장 바람직하다.When using (E) component, the usage-amount of (A) component, (B) component, and (E) component is (A) component in 100 mass parts of total of (A) component, (B) component, and (E) component. : (B) component: (E) component = 10-80: 1-70: 15-80 (mass ratio) are preferable, 15-50: 2-60: 25-65 (mass ratio) are more preferable, 20- 45: 3-45: 35-60 (mass ratio) are the most preferable.

(C)성분의 사용량은 (A)성분, (B)성분 및 필요에 따라 사용하는 (E)성분의 합계 100질량부에 대해 0.001~10질량부가 바람직하고, 0.01~5질량부가 보다 바람직하며, 0.1~3질량부가 가장 바람직하다.0.001-10 mass parts is preferable with respect to a total of 100 mass parts of (A) component, (B) component, and (E) component used as needed, and, as for the usage-amount of (C) component, 0.01-5 mass parts is more preferable, 0.1-3 mass parts is the most preferable.

(D)성분의 사용량은 (A)성분, (B)성분 및 필요에 따라 사용하는 (E)성분의 합계 100질량부에 대해 0.001~30질량부가 바람직하고, 0.1~20질량부가 보다 바람직하며, 0.5~15질량부가 가장 바람직하다.0.001-30 mass parts is preferable with respect to a total of 100 mass parts of (A) component, (B) component, and (E) component used as needed, and, as for the usage-amount of (D) component, 0.1-20 mass parts is more preferable, 0.5-15 mass parts is the most preferable.

본 발명의 조성물은 본 발명의 목적을 손상시키지 않는 범위에서 그래프트 공중합체, 용제, 증량재, 보강재, 가소제, 증점제, 염료, 안료, 난연제, 산화 방지제 및 계면 활성제 등의 첨가제를 사용할 수 있다.The composition of the present invention may be used additives such as graft copolymers, solvents, extenders, reinforcing agents, plasticizers, thickeners, dyes, pigments, flame retardants, antioxidants and surfactants within a range that does not impair the object of the present invention.

열경화성 수지와 알칼리 가용성 폴리머의 함유량은 접착성이나 탄성률의 점에서 수지 조성물 100질량부 중에서 5질량부 이하가 바람직하고, 3질량부 이하가 보다 바람직하며, 1질량부 이하가 가장 바람직하고, 열경화성 수지와 알칼리 가용성 폴리머를 함유하지 않는 것이 더 바람직하다.As for content of a thermosetting resin and an alkali-soluble polymer, 5 mass parts or less are preferable in 100 mass parts of resin compositions from an adhesive point or an elasticity modulus, 3 mass parts or less are more preferable, 1 mass part or less is the most preferable, and a thermosetting resin More preferably no alkali-soluble polymer.

본 발명의 조성물의 경화물은 경화성 및 접착성이 양립할 수 있다는 점에서 0.000001~10000MPa(23℃)의 저장 탄성률(E′)을 갖는 것이 바람직하고, 0.00001~5000MPa의 저장 탄성률(E′)을 갖는 것이 보다 바람직하며, 0.001~1000MPa의 저장 탄성률(E′)을 갖는 것이 가장 바람직하다. 조성물의 경화물의 저장 탄성률(E′)이 0.000001MPa 이상이면 경화물이 경화되어 미반응 성분이 남지 않는 경우가 있다. 10000MPa 이하이면 경화물이 과동하게 강직하게 되지 않아 접착성이 저하되지 않는 경우가 있다.The cured product of the composition of the present invention preferably has a storage modulus (E ′) of 0.000001 to 10000 MPa (23 ° C.) in that both curability and adhesiveness are compatible, and has a storage modulus (E ′) of 0.00001 to 5000 MPa. It is more preferable to have, and it is most preferable to have storage elastic modulus (E ') of 0.001-1000 Mpa. When the storage elastic modulus (E ') of the hardened | cured material of a composition is 0.000001 Mpa or more, hardened | cured material may harden | cure and an unreacted component may not remain. If it is 10000 MPa or less, hardened | cured material may not become rigid too much and adhesiveness may not fall.

본 발명의 조성물은 접착제로서 사용할 수 있다. 본 발명의 접착제는 예를 들면 시클로올레핀 폴리머, 폴리카보네이트, 트리아세틸셀룰로오스, 폴리비닐알코올 및 유리로 이루어지는 군에서 선택되는 1종 이상에 대해 높은 접착 강도를 나타내고, 바람직하게는 전부에 대해 높은 접착 강도를 나타낸다. 특히, 시클로올레핀 폴리머나 트리아세틸셀룰로오스에 대해 높은 접착 강도를 나타낸다.The composition of the present invention can be used as an adhesive. The adhesive of the present invention exhibits high adhesive strength to at least one selected from the group consisting of, for example, cycloolefin polymers, polycarbonates, triacetylcelluloses, polyvinyl alcohols and glass, and preferably high adhesive strength to all Indicates. In particular, it shows high adhesive strength with respect to a cycloolefin polymer and a triacetyl cellulose.

본 발명의 시클로올레핀 폴리머란, 예를 들면 노르보르넨이나 다환 노르보르넨계 모노머 등의 환상 올레핀(시클로올레핀) 모노머 유래의 구성 단위를 갖는 열가소성 수지이다. 시클로올레핀 폴리머로서는 예를 들면 시클로올레핀의 개환 중합체, 2종 이상의 시클로올레핀을 이용한 개환 공중합체의 수소 첨가물, 쇄상 올레핀이나 비닐기를 갖는 방향족 화합물과 시클로올레핀의 부가 공중합체 등을 들 수 있다. 또한, 시클로올레핀 폴리머에 극성기를 도입해도 된다.The cycloolefin polymer of this invention is a thermoplastic resin which has a structural unit derived from cyclic olefin (cycloolefin) monomers, such as a norbornene and a polycyclic norbornene-type monomer, for example. As a cycloolefin polymer, the ring-opening polymer of cycloolefin, the hydrogenated substance of the ring-opening copolymer using 2 or more types of cycloolefin, the addition copolymer of the aromatic compound which has a linear olefin, a vinyl group, and cycloolefin, etc. are mentioned, for example. Moreover, you may introduce a polar group into a cycloolefin polymer.

시판의 시클로올레핀 폴리머로서는 예를 들면 독일　Ticona사 제품의 「Topas」, JSR사 제품의 「아톤」, 일본 제온사 제품의 「제오노아(ZEONOR)」나 「제오넥스(ZEONEX)」, 미츠이 화학사 제품의 「아펠」 등을 들 수 있다.Commercially available cycloolefin polymers include, for example, "Topas" manufactured by Germany's Ticona Corporation, "Aton" manufactured by JSR Corporation, "ZEONOR" and "ZEONEX" manufactured by Japan Xeon Corporation, and Mitsui Chemicals. "Apel" etc. are mentioned.

트리아세틸셀룰로오스란, 예를 들면 셀룰로오스를 무수 아세트산 등과 반응시켜 셀룰로오스의 3개의 수산기를 전부 아세틸화한 것을 말한다.A triacetyl cellulose means what acetylated all three hydroxyl groups of a cellulose by making cellulose react with acetic anhydride etc., for example.

본 발명의 접착제의 접착 방법은 예를 들면 이하와 같다. 피착체 2장 중에서 적어도 1장의 피착체 표면에 접착제를 두께 0.0001~5mm가 되도록 도포하고, 그 후 피착체끼리를 첩합하며, 파장 200~500nm, 적산 광량 200~6000mJ/㎠, 조사 시간 1~60초의 조건 하에서 접착제를 경화하여 피착체를 접착하는 방법이 바람직하다.The adhesion method of the adhesive agent of this invention is as follows, for example. An adhesive is applied to at least one of the adherend surfaces of the two adherends so as to have a thickness of 0.0001 to 5 mm, and then the adherends are bonded together, and the wavelengths are 200 to 500 nm, the accumulated light amount is 200 to 6000 mJ / cm2, and the irradiation time is 1 to 60. The method of hardening | curing an adhesive agent and bonding an adherend on an initial condition is preferable.

실시예Example

이하, 실험예를 들어 본 발명을 더 상세하게 설명한다. 본 발명은 이들에 한정되는 것은 아니다. 실험예에 기재된 접착제 중의 각 성분에는 이하의 화합물을 선택하고, 표 1 내지 3에 기재된 배합 비율로 각 성분을 혼합하여 각 실험예의 조성물로 하였다.Hereinafter, the present invention will be described in more detail with reference to experimental examples. The present invention is not limited to these. The following compounds were selected for each component in the adhesive agent described in the experiment example, and each component was mixed at the compounding ratio of Tables 1-3, and it was set as the composition of each experiment example.

(화합물)(compound)

(A)성분: 이소시아눌산 에틸렌 옥사이드 변성 트리/디아크릴레이트(토아 합성사 제품「M-313」, 트리/디아크릴레이트는 트리아크릴레이트와 디아크릴레이트의 혼합물)(A) component: isocyanuric acid ethylene oxide modified tri / diacrylate ("M-313" by the Toa synthesis company, tri / diacrylate is a mixture of triacrylate and diacrylate)

(A)성분: 이소시아눌산 에틸렌 옥사이드 변성 디아크릴레이트(토아 합성사 제품「M-215」)(A) Component: isocyanuric acid ethylene oxide modified diacrylate ("M-215" made by Toa synthesis company)

(A)성분: 이소시아눌산 에틸렌 옥사이드 변성 트리아크릴레이트(토아 합성사 제품「M-315」)(A) component: isocyanuric acid ethylene oxide modified triacrylate ("M-315" by Toa synthesis company)

(B)성분: 수산기를 함유하는 (메타)아크릴레이트로서 2-히드록시에틸메타크릴레이트(미츠비시 가스사 제품「GE-610」)(B) Component: 2-hydroxyethyl methacrylate ("GE-610" by Mitsubishi Gas Corporation) as a (meth) acrylate containing a hydroxyl group

(B)성분: 2-히드록시-3-페녹시프로필아크릴레이트(토아 합성사 제품「M-5700」)(B) Component: 2-hydroxy-3-phenoxypropyl acrylate ("M-5700" by Toa synthesis company)

(B)성분: 4-히드록시부틸아크릴레이트(오사카 유기화학공업사 제품「4-HBA」)(B) Component: 4-hydroxybutyl acrylate ("4-HBA" made by Osaka organic chemical industry company)

(C)성분: 실란 커플링제, γ-글리시독시프로필 트리메톡시실란(신에츠 화학사 제품「KBM-403」)(C) component: A silane coupling agent and (gamma)-glycidoxy propyl trimethoxysilane ("KBM-403" by Shin-Etsu Chemical Co., Ltd.)

(C)성분: 실란 커플링제, γ-메타크릴록시프로필 트리메톡시실란(신에츠 화학사 제품「KBM-503」)(C) component: A silane coupling agent and (gamma)-methacryloxypropyl trimethoxysilane ("KBM-503" by Shin-Etsu Chemical Co., Ltd.)

(D)성분: 광개시제, 벤질디메틸케탈(치바 스페셜티 케미컬즈사 제품「IRGACURE651」)(D) component: photoinitiator, benzyl dimethyl ketal ("IRGACURE651" from Chiba Specialty Chemicals)

(D)성분: 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드(치바 스페셜티 케미컬즈사 제품「IRGACURE819」)(D) component: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("IRGACURE819" by Chiba Specialty Chemicals)

(E)성분: 라우릴 메타크릴레이트(쿄에이샤 화학사 제품「L」)(E) Component: Lauryl methacrylate ("L" made by Kyoisha Chemical Co., Ltd.)

(E)성분: 노닐 아크릴레이트(오사카 유기화학공업사 제품「NOAA」)(E) Component: Nonyl acrylate (NOAA, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[비교 성분][Comparative component]

(A)성분이나 (E)성분의 비교로서 벤질메타크릴레이트(쿄에이샤 화학사 제품「라이트 에스테르 BZ」, 호모폴리머 유리 전이 온도 54℃)Benzyl methacrylate as a comparison of (A) component and (E) component ("Light ester BZ" by Kyisha Chemical Co., Ltd., homopolymer glass transition temperature 54 degreeC)

(B)성분의 비교로서 디에틸아미노에틸 메타크릴레이트(쿄에이샤 화학사 제품「라이트 에스테르 DE」)Diethylaminoethyl methacrylate ("light ester DE" by Kyoisha Chemical Co., Ltd.) as a comparison of (B) component

각종 물성은 다음과 같이 측정하였다. 온도 23℃로 측정하였다.Various physical properties were measured as follows. It measured at the temperature of 23 degreeC.

〔광 경화성〕광 경화성에 관해서는 ZEONEX480R(일본 제온사 제품) 시험편(폭 25mm×길이 25mm×두께 2.0mm) 표면에 접착제를 두께 0.08mm가 되도록 도포하였다. 그 후, 무전극 방전 램프를 사용한 퓨전사 제품 경화 장치를 이용하여 파장 375nm, 적산광량 2000mJ/㎠의 조건으로 15초간 조사하고 경화시켰다. 광 경화성으로서 경화율을 기재하였다. 경화율은 FT-IR를 사용하여 이하의 식에 의해 산출하였다.[Photocurability] About the photocurability, the adhesive agent was apply | coated so that the adhesive might become thickness 0.08mm on the surface of ZEONEX480R (made by Japan Zeon company) test piece (width 25mm x length 25mm x thickness 2.0mm). Then, it irradiated for 15 second and hardened | cured on the conditions of the wavelength 375nm and accumulated light amount 2000mJ / cm <2> using the fusion apparatus made from the fusion company using an electrodeless discharge lamp. The hardening rate was described as photocurability. The hardening rate was computed by the following formula | equation using FT-IR.

(경화율)=[100-((경화 후의 탄소와 탄소의 이중 결합의 흡수 스펙트럼의 강도)/(경화 전의 탄소와 탄소의 이중 결합의 흡수 스펙트럼의 강도))]×100(%)(Cure ratio) = [100-((intensity of absorption spectrum of carbon and carbon double bond after curing) / (intensity of absorption spectrum of carbon and carbon double bond before curing))] × 100 (%)

〔시클로올레핀 폴리머 접착성 평가(ZEONEX　시험편 간의 인장 접착 강도)〕ZEONEX480R(일본 제온사 제품) 시험편(폭 25mm×길이 25mm×두께 2.0mm)끼리를 두께 80㎛×폭 11.5mm×길이 25mm의 테프론(등록상표) 테이프를 스페이서로서 이용하여 접착제를 접착시켰다(접착 면적 3.125㎠). 경화 후 접착제로 접착한 그 시험편을 이용하여 인장 접착 강도를 측정하였다. 접착 조건은 〔광 경화성〕에 기재된 방법에 따랐다.[Cycloolefin polymer adhesive evaluation (tensile adhesive strength between ZEONEX 'test pieces)] Teflon of ZEONEX480R (product made in Japan Zion Corporation) test pieces (25mm in width X 25mm in length X thickness 2.0mm) thickness 80micrometer X width 11.5mm X 25mm in length Trademark) The adhesive was adhere | attached using a tape as a spacer (adhesion area 3.125 cm <2>). Tensile adhesive strength was measured using the test piece adhere | attached with the adhesive agent after hardening. Bonding conditions followed the method as described in [photocurability].

〔트리아세틸셀룰로오스 접착성 평가(트리아세틸셀룰로오스(후지 필름사 제품) 시험편 간의 박리 접착 강도)〕트리아세틸셀룰로오스(후지 필름사 제품) 시험편(폭 10mm×길이 50mm×두께 0.08mm)끼리를 바코터를 이용하여 두께 10㎛로 접착시켰다. 경화 후 접착제로 접착한 그 시험편을 이용하여 180°박리 강도를 측정하였다. 인장 속도는 50mm/분.[Triacetyl cellulose adhesion evaluation (peel adhesion strength between triacetyl cellulose (made by Fujifilm)) test pieces] Triacetyl cellulose (made by Fuji Film) test pieces (10 mm wide x 50 mm long x 0.08 mm thick) with a bar coater To a thickness of 10 μm. 180 degree peeling strength was measured using the test piece bonded with the adhesive agent after hardening. Tensile speed is 50mm / min.

〔폴리비닐알코올 접착성 평가(폴리비닐알코올(쿠라레사 제품) 시험편 간의 박리 접착 강도)〕폴리비닐알코올(쿠라레사 제품) 시험편(폭 10mm×길이 50mm×두께 0.08mm)끼리를 바코터를 이용하여 두께 10㎛로 접착시켰다. 경화 후 접착제로 접착한 그 시험편을 이용하여 180°박리 강도를 측정하였다. 인장 속도는 50mm/분.[Adhesion evaluation of polyvinyl alcohol (peel adhesion strength between polyvinyl alcohol (product of Kuraray Corporation))] Test piece of polyvinyl alcohol (product of Kuraray Corporation) (10 mm in width x 50 mm in length x 0.08 mm in thickness) using a bar coater Adhesion was carried out at a thickness of 10 mu m. 180 degree peeling strength was measured using the test piece bonded with the adhesive agent after hardening. Tensile speed is 50mm / min.

〔범용 폴리머 접착성 평가(폴리카보네이트(테이진사 제품) 시험편 간의 인장 접착 강도)〕팬라이트(테이진사 제품) 시험편(폭 25mm×길이 25mm×두께 2.0mm)끼리를 두께 80㎛×폭 11.5mm×길이 25mm의 테프론(등록상표) 테이프를 스페이서로서 이용하여 접착제를 접착시켰다(접착 면적 3.125㎠). 경화 후 접착제로 접착한 그 시험편을 이용하여 인장 접착 강도를 측정하였다. 접착 조건은 〔광 경화성〕에 기재된 방법에 따랐다.[Universal polymer adhesive evaluation (tensile adhesive strength between polycarbonate (made by Teijin Corporation) test pieces)] Plight (made by Teijin Co.) test pieces (width 25mm x length 25mm X thickness 2.0mm) comrades thickness 80micrometer X width 11.5mm X An adhesive was adhered using a 25 mm long Teflon® tape as a spacer (adhesive area 3.125 cm 2). Tensile adhesive strength was measured using the test piece adhere | attached with the adhesive agent after hardening. Bonding conditions followed the method as described in [photocurability].

〔유리 접착성 평가(내열 유리 시험편 간의 인장 접착 강도)〕내열 유리의 파이렉스(등록상표) 시험편(폭 25mm×길이 25mm×두께 2.0mm)끼리를 두께 80㎛×폭 11.5mm×길이 25mm의 테프론(등록상표) 테이프를 스페이서로서 이용하여 접착제를 접착시켰다(접착 면적 3.125㎠). 접착 조건은 〔광 경화성〕에 기재된 방법에 따랐다. 상기 조건으로 접착제를 경화시킨 후, 추가로 시험편의 양 뒤쪽에 덴키카가쿠 산업사 제품 접착제「G-55」를 사용하여 아연 도금 강판(폭 100mm×길이 25mm×두께 2.0mm, 엔지니어링 테스트 서비스사 제품)을 접착시켰다. 경화 후 접착제로 접착한 그 시험편을 이용하여 인장 접착 강도를 측정하였다. 인장 전단 접착 강도(단위: MPa)는 온도 23℃, 습도 50%의 환경 하에서 인장 속도 10mm/분으로 측정하였다.[Glass Adhesion Evaluation (Tensile Adhesion Strength Between Heat-Resistant Glass Test Pieces)] Pyrex (registered trademark) test pieces (25 mm in width x 25 mm in length x 2.0 mm in thickness) of heat-resistant glass were made of Teflon (80 μm in thickness × 11.5 mm in width and 25 mm in length). Trademark) The adhesive was adhere | attached using a tape as a spacer (adhesion area 3.125 cm <2>). Bonding conditions followed the method as described in [photocurability]. After curing the adhesive under the above conditions, the galvanized steel sheet (100mm in width x 25mm in length x 2.0mm in thickness, product of engineering test service company) using the adhesive "G-55" made by Denki Kagaku Industries Co., Ltd. on both backs of the test pieces. Was bonded. Tensile adhesive strength was measured using the test piece adhere | attached with the adhesive agent after hardening. Tensile shear adhesive strength (unit: MPa) was measured at 10 mm / min of tensile velocity in the environment of the temperature of 23 degreeC, and 50% of humidity.

〔내수성(ZEONEX　시험편 간의 인장 접착 강도)〕상기 시클로올레핀 폴리머 접착성 평가용 시험편을 60℃ 온수에 24시간 침지하고, 그 시험편을 이용하여 인장 접착 강도를 측정하였다.[Water resistance (Tension adhesive strength between ZEONEX 'test pieces)] The test piece for cycloolefin polymer adhesion evaluation was immersed in hot water at 60 ° C. for 24 hours, and the tensile adhesive strength was measured using the test piece.

〔저장 탄성률 평가(저장 탄성률(23℃))〕온도 23℃로 측정하였다. 접착제를 경화시켜 길이 20mm×폭 5mm×두께 1mm의 경화물 시료를 조제하였다. 접착 조건은 〔광 경화성〕에 기재된 방법에 따랐다. 이 경화물 시료를 평가하였다. 세이코 전자공업(주) 제품 텐션 모듈 DMS210를 사용하여 주파수 1Hz, 왜곡 0.05%의 조건으로 온도를 변경하여 인장 모드로 동적 점탄성 스펙트럼을 측정하여 23℃에서의 저장 탄성률(E′)의 값을 구하였다.[Evaluation of Storage Modulus (Storage Modulus (23 ° C))] The temperature was measured at 23 ° C. The adhesive agent was hardened | cured and the hardened | cured material sample of length 20mm x width 5mm x thickness 1mm was prepared. Bonding conditions followed the method as described in [photocurability]. This hardened | cured material sample was evaluated. Using a tension module DMS210 manufactured by Seiko Electronics Co., Ltd., the temperature was changed under the condition of frequency 1 Hz and distortion 0.05%, and the dynamic viscoelastic spectrum was measured in tensile mode to obtain the value of storage modulus (E ′) at 23 ° C. .

Figure pct00003
Figure pct00003

Figure pct00004
Figure pct00004

Figure pct00005
Figure pct00005

표 1로부터 본 발명은 뛰어난 효과를 나타낸다. 시클로올레핀 폴리머에 대해 1.0MPa 이상의 인장 접착 강도를 나타낸다. 트리아세틸셀룰로오스에 대해 3.0N/cm이상의 박리 접착 강도를 나타낸다. 폴리비닐알코올에 대해 5.0N/cm이상의 박리 접착 강도를 나타낸다. 폴리카보네이트에 대해 4.0MPa이상의 인장 접착 강도를 나타낸다. 유리에 대해 5.0MPa이상의 인장 접착 강도를 나타낸다. 내수성 시험에 있어서, 0.3MPa이상의 인장 접착 강도를 나타낸다. 실험예 18은 (E)성분을 함유하고 있지 않지만, 내수성이나 폴리비닐알코올에의 접착성이 뛰어나다.From Table 1, this invention shows the outstanding effect. Tensile bond strength of at least 1.0 MPa is shown for the cycloolefin polymer. The peel adhesion strength of 3.0 N / cm or more is shown with respect to triacetyl cellulose. The peel adhesion strength of 5.0 N / cm or more with respect to polyvinyl alcohol is shown. Tensile adhesive strength of 4.0 MPa or more is shown with respect to the polycarbonate. Tensile adhesive strength of 5.0 MPa or more is shown for glass. In the water resistance test, a tensile adhesive strength of 0.3 MPa or more is shown. Experimental Example 18 does not contain the component (E), but is excellent in water resistance and adhesion to polyvinyl alcohol.

본 발명은 시클로올레핀 폴리머, 폴리카보네이트, 트리아세틸셀룰로오스, 폴리비닐알코올 및 유리에 대해 단시간에 충분한 접착성과 내수성을 가진다. 본 발명은 트리아세틸셀룰로오스에의 접착성이 뛰어나므로 편광 필름용 접착제로서 사용할 수 있다. 본 발명은 시클로올레핀 폴리머에의 접착성이 뛰어나므로 시클로올레핀 폴리머용 접착제로서 사용할 수 있다.The present invention has sufficient adhesion and water resistance in a short time to the cycloolefin polymer, polycarbonate, triacetyl cellulose, polyvinyl alcohol and glass. Since this invention is excellent in adhesiveness to triacetyl cellulose, it can be used as an adhesive agent for polarizing films. Since this invention is excellent in adhesiveness to a cycloolefin polymer, it can be used as an adhesive agent for cycloolefin polymers.

Claims (13)

하기 (A)~(D)성분을 함유하여 이루어지는 조성물:
(A)성분은 일반식〔1〕에서 나타나는 이소시아눌환 유도체(일반식〔1〕 중의 X1 및 X2는 (메타)아크릴로일 옥시기를 나타내고, X3은 히드록실기 또는 (메타)아크릴로일 옥시기를 나타내며, R1, R2 및 R3은 탄소수 1~4의 탄화수소기를 나타낸다.)
[화학식 1]
Figure pct00006

(B)성분은 수산기를 갖는 (메타)아크릴레이트,
(C)성분은 실란 커플링제,
(D)성분은 광중합 개시제.The composition containing the following (A)-(D) component:
(A) A component isocyanuryl ring derivative represented by General formula [1] (X <1> and X <2> in General formula [1] represent a (meth) acryloyl oxy group, X <3> is a hydroxyl group or (meth) acryl Represents a loyloxy group, and R 1 , R 2, and R 3 represent a hydrocarbon group having 1 to 4 carbon atoms.)
[Formula 1]
Figure pct00006

(B) component (meth) acrylate which has a hydroxyl group,
(C) component is a silane coupling agent,
(D) component is a photoinitiator. 청구항 1에 있어서,
(E)성분으로서 일반식〔2〕에서 나타나는 (메타)아크릴레이트를 더 함유하여 이루어지는 조성물:
일반식〔2〕　R-O-R′
(식 중, R은 (메타)아크릴로일기를 나타내고, R′는 탄소수 5~18개의 알킬기를 나타낸다.).The method according to claim 1,
The composition which further contains (meth) acrylate represented by General formula [2] as (E) component:
General formula [2] ROR '
(In formula, R represents a (meth) acryloyl group and R 'represents a C5-C18 alkyl group.). 청구항 1 또는 청구항 2에 있어서,
조성물의 경화물의 저장 탄성률(E′)이 0.000001~10000MPa(23℃)의 범위 내인 조성물.The method according to claim 1 or 2,
The storage elastic modulus (E ') of the hardened | cured material of a composition exists in the range of 0.000001-10000 Mpa (23 degreeC). 청구항 1 내지 청구항 3 중 어느 한 항에 있어서,
(A)성분이 이소시아눌산 에틸렌 옥사이드 변성 트리(메타)아크릴레이트, 이소시아눌산 에틸렌 옥사이드 변성 디(메타)아크릴레이트, 이소시아눌산 에틸렌 옥사이드 변성 트리/디(메타)아크릴레이트 혼합물, 이소시아눌산 프로필렌 옥사이드 변성 트리(메타)아크릴레이트, 이소시아눌산 프로필렌 옥사이드 변성 디(메타)아크릴레이트, 이소시아눌산 부틸 옥사이드 변성 트리(메타)아크릴레이트 및 이소시아눌산 부틸 옥사이드 변성 디(메타)아크릴레이트로 이루어지는 군에서 선택되는 1종 또는 2종 이상인 조성물.The method according to any one of claims 1 to 3,
(A) Component is isocyanuric acid ethylene oxide modified tri (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified tri / di (meth) acrylate mixture, isocyanuric acid Propylene oxide modified tri (meth) acrylate, isocyanuric acid propylene oxide modified di (meth) acrylate, isocyanuric acid butyl oxide modified tri (meth) acrylate and isocyanuric acid butyl oxide modified di (meth) acrylate One or two or more compositions selected from the group. 청구항 1, 청구항 3 또는 청구항 4 중 어느 한 항에 있어서,
(A)성분이 조성물의 5~80질량%를 차지하고, (A)성분 및 (B)성분의 합계 100질량부 중에서 (A)성분:(B)성분=10~99:1~90(질량비)이며, (C)성분의 사용량은 (A)성분 및 (B)성분의 합계 100질량부에 대해 0.001~10질량부이고, (D)성분의 사용량은 (A)성분 및 (B)성분의 합계 100질량부에 대해 0.001~30질량부인 조성물.The method of claim 1, 3, or 4,
(A) component occupies 5 to 80 mass% of a composition, and in 100 mass parts of total of (A) component and (B) component, (A) component: (B) component = 10-99: 1-90 (mass ratio) The usage-amount of (C) component is 0.001-10 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, and the usage-amount of (D) component is the sum total of (A) component and (B) component The composition which is 0.001-30 mass parts with respect to 100 mass parts. 청구항 2에 있어서,
(E)성분이 2-에틸헥실(메타)아크릴레이트, 노닐(메타)아크릴레이트, 이소데실(메타)아크릴레이트, n-라우릴(메타)아크릴레이트 및 트리데실(메타)아크릴레이트로 이루어지는 군 중의 1종 또는 2종 이상인 조성물.The method according to claim 2,
Group (E) component consists of 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, and tridecyl (meth) acrylate 1 or 2 or more types of composition. 청구항 2 또는 청구항 6에 있어서,
(A)성분이 조성물의 5~80질량%를 차지하고, (A)성분 및 (B)성분의 합계 100질량부 중에서 (A)성분:(B)성분=10~99:1~90(질량비)이며, (A)성분, (B)성분 및 (E)성분의 합계 100질량부 중에서 (A)성분:(B)성분:(E)성분=10~80:1~70:15~80(질량비)이고, (C)성분의 사용량은 (A)성분, (B)성분 및 (E)성분의 합계 100질량부에 대해 0.001~10질량부이며, (D)성분의 사용량은 (A)성분, (B)성분 및 (E)성분의 합계 100질량부에 대해 0.001~30질량부인 조성물.The method according to claim 2 or 6,
(A) component occupies 5 to 80 mass% of a composition, and in 100 mass parts of total of (A) component and (B) component, (A) component: (B) component = 10-99: 1-90 (mass ratio) (A) Component: (B) component: (E) component = 10-80: 1-70: 15-80 (mass ratio) in 100 mass parts of total of (A) component, (B) component, and (E) component ), The usage-amount of (C) component is 0.001-10 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (E) component, and the usage-amount of (D) component is (A) component, The composition which is 0.001-30 mass parts with respect to a total of 100 mass parts of (B) component and (E) component. 청구항 1 내지 청구항 7 중 어느 한 항에 기재된 조성물로 이루어지는 접착제.The adhesive agent which consists of a composition of any one of Claims 1-7. 청구항 1 내지 청구항 7 중 어느 한 항에 기재된 조성물로 이루어지는 편광 필름용 접착제.The adhesive agent for polarizing films which consists of a composition of any one of Claims 1-7. 청구항 1 내지 청구항 7 중 어느 한 항에 기재된 조성물로 이루어지는 시클로올레핀 폴리머용 접착제.Adhesive for cycloolefin polymer which consists of a composition of any one of Claims 1-7. 청구항 8에 있어서,
시클로올레핀 폴리머, 폴리카보네이트, 트리아세틸셀룰로오스, 폴리비닐알코올 및 유리로 이루어지는 군에서 선택되는 1종 또는 2종 이상의 기재용으로 사용하여 이루어지는 접착제.The method according to claim 8,
The adhesive agent used for the 1 type (s) or 2 or more types of base materials chosen from the group which consists of a cycloolefin polymer, polycarbonate, triacetyl cellulose, polyvinyl alcohol, and glass. 청구항 8에 기재된 접착제를 이용하여 피착체끼리를 접착하여 만들어진 접착체.The adhesive body which adhere | attached adherends using the adhesive agent of Claim 8. 청구항 12에 있어서,
피착체가 시클로올레핀 폴리머, 폴리카보네이트, 트리아세틸셀룰로오스, 폴리비닐알코올 및 유리로 이루어지는 군에서 선택되는 1종 또는 2종 이상인 접착체.The method of claim 12,
The adherend is one kind or two or more kinds selected from the group consisting of cycloolefin polymer, polycarbonate, triacetyl cellulose, polyvinyl alcohol and glass.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170026266A (en) 2015-08-27 2017-03-08 경희대학교 산학협력단 Composition for preventing or treating hearing loss comprising an extract of Candida Utilis

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6135118B2 (en) * 2011-12-21 2017-05-31 東洋インキＳｃホールディングス株式会社 Photopolymerizable oxirane resin composition, photopolymerizable coating agent, photopolymerizable adhesive, and optical film laminate
MY170959A (en) * 2012-04-10 2019-09-20 Sumitomo Bakelite Co Semiconductor device, die attach material, and method for manufacturing semiconductor device
JP6026205B2 (en) * 2012-09-28 2016-11-16 株式会社タムラ製作所 Adhesive composition, solar cell module, and method for connecting solar cell and wiring
JP6185947B2 (en) * 2014-03-31 2017-08-23 ミネベアミツミ株式会社 Ultraviolet curable resin composition, sliding member, and manufacturing method of sliding member

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6218485A (en) 1985-07-16 1987-01-27 Alpha Giken:Kk Primer for instantaneous adhesive
JPH05132534A (en) * 1991-11-13 1993-05-28 Dainippon Ink & Chem Inc Ultraviolet-curable resin composition
JPH08216320A (en) * 1995-02-14 1996-08-27 Bridgestone Corp Polarizing plate for liquid crystal display device
JP2007077321A (en) 2005-09-15 2007-03-29 Denki Kagaku Kogyo Kk Energy ray curable resin composition and adhesive using the same
JP2008065251A (en) 2006-09-11 2008-03-21 Dainippon Printing Co Ltd Polarizing plate
JP2008149625A (en) 2006-12-19 2008-07-03 Seiko Epson Corp Method for adjusting delivering timing, apparatus for adjusting delivering timing, and program
JP2008174667A (en) * 2007-01-19 2008-07-31 Okura Ind Co Ltd Active energy ray-curable adhesive composition and polarizing plate using the same
JP2009211057A (en) * 2008-02-04 2009-09-17 Sumitomo Chemical Co Ltd Polarization plate

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001019722A (en) * 1999-07-05 2001-01-23 Sumitomo Bakelite Co Ltd Die-attaching paste and semiconductor device using the same
JP3606260B2 (en) * 2002-01-18 2005-01-05 東亞合成株式会社 Active energy ray-curable coating composition
JP4280147B2 (en) * 2003-10-27 2009-06-17 Ｊｓｒ株式会社 Radiation curable resin composition
JP2008009329A (en) * 2006-06-30 2008-01-17 Jsr Corp Polarizing plate and method for manufacturing the same
JP5047636B2 (en) * 2007-01-18 2012-10-10 リンテック株式会社 Hard coat film
JP5228356B2 (en) * 2007-03-30 2013-07-03 大日本印刷株式会社 Polarizing plate adhesive and polarizing plate
JP5124406B2 (en) * 2008-09-24 2013-01-23 日東電工株式会社 Adhesive for polarizing plate, polarizing plate, method for producing the same, optical film, and image display device
JP5344224B2 (en) * 2009-02-10 2013-11-20 サイデン化学株式会社 Adhesive composition for polarizing plate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6218485A (en) 1985-07-16 1987-01-27 Alpha Giken:Kk Primer for instantaneous adhesive
JPH05132534A (en) * 1991-11-13 1993-05-28 Dainippon Ink & Chem Inc Ultraviolet-curable resin composition
JPH08216320A (en) * 1995-02-14 1996-08-27 Bridgestone Corp Polarizing plate for liquid crystal display device
JP2007077321A (en) 2005-09-15 2007-03-29 Denki Kagaku Kogyo Kk Energy ray curable resin composition and adhesive using the same
JP2008065251A (en) 2006-09-11 2008-03-21 Dainippon Printing Co Ltd Polarizing plate
JP2008149625A (en) 2006-12-19 2008-07-03 Seiko Epson Corp Method for adjusting delivering timing, apparatus for adjusting delivering timing, and program
JP2008174667A (en) * 2007-01-19 2008-07-31 Okura Ind Co Ltd Active energy ray-curable adhesive composition and polarizing plate using the same
JP2009211057A (en) * 2008-02-04 2009-09-17 Sumitomo Chemical Co Ltd Polarization plate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170026266A (en) 2015-08-27 2017-03-08 경희대학교 산학협력단 Composition for preventing or treating hearing loss comprising an extract of Candida Utilis

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