KR101921720B1 - Resin composition and adhesive - Google Patents

Resin composition and adhesive Download PDF

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KR101921720B1
KR101921720B1 KR1020137028975A KR20137028975A KR101921720B1 KR 101921720 B1 KR101921720 B1 KR 101921720B1 KR 1020137028975 A KR1020137028975 A KR 1020137028975A KR 20137028975 A KR20137028975 A KR 20137028975A KR 101921720 B1 KR101921720 B1 KR 101921720B1
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component
adhesive
meth
resin composition
acrylate
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KR1020137028975A
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KR20140021643A (en
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유키 히샤
기미히코 요다
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덴카 주식회사
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    • 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
    • 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
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1403—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the type of electromagnetic or particle radiation
    • B29C65/1406—Ultraviolet [UV] radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1403—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the type of electromagnetic or particle radiation
    • B29C65/1409—Visible light radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/483—Reactive adhesives, e.g. chemically curing adhesives
    • B29C65/4845—Radiation curing adhesives, e.g. UV light curing adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/483—Reactive adhesives, e.g. chemically curing adhesives
    • B29C65/485—Multi-component adhesives, i.e. chemically curing as a result of the mixing of said multi-components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/82—Testing the joint
    • B29C65/8207—Testing the joint by mechanical methods
    • B29C65/8215—Tensile tests
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/20—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines
    • B29C66/21—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines said joint lines being formed by a single dot or dash or by several dots or dashes, i.e. spot joining or spot welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43—Joining a relatively small portion of the surface of said articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/94—Measuring or controlling the joining process by measuring or controlling the time
    • B29C66/949—Measuring or controlling the joining process by measuring or controlling the time characterised by specific time values or ranges
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (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
    • C09J115/00—Adhesives based on rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N19/00—Investigating materials by mechanical methods
    • G01N19/04—Measuring adhesive force between materials, e.g. of sealing tape, of coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/52—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate

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  • Adhesives Or Adhesive Processes (AREA)
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Abstract

본 발명은 높은 접착 강도를 나타내는 수지 조성물의 제공을 목적으로 하며, 하기 (A)∼(F)성분을 함유하여 이루어진 수지 조성물이다：(A)성분은 디시클로펜테닐기를 가진 (메타)아크릴레이트, (B)성분은 수산기를 가진 (메타)아크릴레이트, (C)성분은 디엔계의 골격 또는 수소 첨가된 디엔계의 골격을 가지고 또한 (메타)아크릴로일기를 가지지 않는 올리고머, (D)성분은 실란 커플링제, (E)성분은 광중합 개시제, (F)성분은 (메타)아크릴산이며, 또한 (G)성분으로서 폴리비닐알코올을 함유해도 좋다.The present invention provides a resin composition exhibiting a high adhesive strength and is a resin composition comprising the following components (A) to (F): (A) is a (meth) acrylate having a dicyclopentenyl group (B) is a (meth) acrylate having a hydroxyl group, (C) is an oligomer having a skeleton of a diene skeleton or a hydrogenated diene skeleton and also having no (meth) acryloyl group, (D) The component (E) is a photopolymerization initiator, the component (F) is a (meth) acrylic acid, and the component (G) may contain polyvinyl alcohol.

Description

수지 조성물 및 접착제{RESIN COMPOSITION AND ADHESIVE}RESIN COMPOSITION AND ADHESIVE [0001]

본 발명은 접착제에 관한 것이다.The present invention relates to an adhesive.

시클로올레핀 폴리머는 전자 재료, 광학 렌즈 및 의료 재료 등의 용도로 사용되고 있다. 시클로올레핀 폴리머는 극성이 작고 표면에 많은 관능기를 가지지 않기 때문에 난(難)피착체로서 알려져 있다. 이러한 시클로올레핀계 수지를 접착하는 접착제로서는 용제형 접착제나 핫멜트 접착제를 들 수 있다.Cycloolefin polymers are used for electronic materials, optical lenses and medical materials. The cycloolefin polymer is known as an abrasive because it has a small polarity and does not have many functional groups on its surface. As adhesives for bonding such cycloolefin-based resins, there can be mentioned solvent-type adhesives and hot-melt adhesives.

올레핀계 수지를 접착하는 방법으로서 특허문헌 1에 개시되어 있는 바와 같이 프라이머에 의한 처리를 한 후 순간 접착제에 의해 접착하는 방법이 있다. 특허문헌 2에 개시된 것처럼 (메타)아크릴레이트를 함유하는 것을 특징으로 하는 에너지선 경화성 수지 조성물이 개시되어 있다.As a method for adhering an olefin resin, there is a method in which after treatment with a primer as described in Patent Document 1, the adhesive is bonded with an instant adhesive. Discloses an energy ray curable resin composition comprising (meth) acrylate as disclosed in Patent Document 2.

특허문헌 1:일본 특개소62-18485호 공보Patent Document 1: Japanese Patent Application Laid-Open No. 62-18485 특허문헌 2: 일본 특개2007-77321호 공보Patent Document 2: Japanese Patent Application Laid-Open No. 2007-77321 특허문헌 3: WO2010/027041호Patent Document 3: WO2010 / 027041

용제형 접착제는 용제를 사용한다. 용제형 접착제는 인체에 유해한데다가 용제의 휘발에 시간이 걸리고 접착 강도 자체도 충분한 것을 얻을 수 없다.The solvent type adhesive is a solvent. The solvent type adhesive is harmful to the human body, and it takes time to volatilize the solvent and the adhesive strength itself is not sufficient.

핫멜트 접착제는 접착제를 용해시키는 수고 및 장치가 필요하다. 또 이 접착제의 경우에도 충분한 접착 강도를 얻을 수 없다. 아울러 핫멜트 접착제를 이용할 경우 시클로올레핀 폴리머를 미리 가열해 두면 접착 강도는 향상되지만 수지가 변형되어버린다는 새로운 문제가 발생한다.The hot melt adhesive requires labor and equipment to dissolve the adhesive. Further, even in the case of this adhesive, sufficient adhesive strength can not be obtained. If a hot melt adhesive is used, a new problem arises that if the cycloolefin polymer is heated in advance, the bonding strength is improved but the resin is deformed.

특허문헌 1에 개시되어 있는 접착 방법에 의하면 프라이머 처리에 수고가 든다는 문제가 있는 데다가 접착 강도도 충분한 것을 얻을 수 없다.According to the bonding method disclosed in Patent Document 1, there is a problem in that the primer treatment is labor-intensive and the bonding strength is not sufficient.

특허문헌 2는 (메타)아크릴레이트를 함유하는 것을 특징으로 하는 에너지선 경화성 수지 조성물이 개시되어 있다. 그러나 디시클로펜테닐기를 가진 (메타)아크릴레이트에 대해서는 기재가 없다.Patent Document 2 discloses an energy ray curable resin composition comprising (meth) acrylate. However, (meth) acrylates having a dicyclopentenyl group are not described.

특허문헌 3은 폴리이소프렌, 폴리부타디엔, 폴리우레탄 골격을 가진 (메타)아크릴레이트 올리고머 및 유연화 성분을 포함한 광경화형 접착 조성물이 개시되어 있다. 그러나 (메타)아크릴산에 대해서는 기재가 없다.Patent Document 3 discloses a photocurable adhesive composition comprising a polyisoprene, a polybutadiene, a (meth) acrylate oligomer having a polyurethane skeleton and a softening component. However, there is no description for (meth) acrylic acid.

시클로올레핀 폴리머는 저흡수성, 고투명성, 저비중을 특징으로 하고 있다. 따라서 시클로올레핀 폴리머는 유리 대체 재료, 투명 플라스틱 대체 재료로서 전자 재료, 광학 렌즈 및 의료 재료 등의 용도로 사용되고 있다.Cycloolefin polymers are characterized by low absorption, high transparency and low specific gravity. Therefore, the cycloolefin polymer is used as a glass substitute material, an electronic material as an alternative to transparent plastic, an optical lens, and a medical material.

그러나 시클로올레핀 폴리머는 극성은 작고 표면에 많은 관능기를 가지지 않기 때문에 접착되기 어렵다는 과제가 있었다.However, the cycloolefin polymer has a problem in that it is difficult to be bonded because the polarity is small and the polymer does not have many functional groups on its surface.

본 발명은 그러한 실정을 감안하여 이루어진 것이다. 본 발명은, 예를 들면 시클로올레핀 폴리머에 대해서 단시간에 충분한 접착 강도를 발현할 수 있고 또한 무용제형으로 친환경적인 시클로올레핀 폴리머용 접착제의 제공을 목적으로 한다.The present invention has been made in view of such circumstances. An object of the present invention is to provide an adhesive for a cycloolefin polymer which is capable of exhibiting sufficient adhesive strength to a cycloolefin polymer in a short period of time and is environmentally friendly as a solventless formulation.

본 발명자는 상기 과제를 해결하기 위해 예의 연구를 거듭하여 본 발명에 이른 것이다.Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems and have reached the present invention.

즉, 본 발명은 일측면에서,That is, in one aspect,

하기 (A)∼(F)성분을 함유하여 이루어진 수지 조성물이다.(A) to (F) described below.

(A)성분은 디시클로펜테닐기를 가진 (메타)아크릴레이트(A) is a (meth) acrylate having a dicyclopentenyl group

(B)성분은 수산기를 가진 (메타)아크릴레이트(B) component is a (meth) acrylate having a hydroxyl group

(C)성분은 디엔계의 골격 또는 수소 첨가된 디엔계의 골격을 가지고 또한 (메타)아크릴로일기를 가지지 않은 올리고머(C) is an oligomer having a diene skeleton or a hydrogenated diene skeleton and also having no (meth) acryloyl group

(D)성분은 실란 커플링제(D) is a silane coupling agent

(E)성분은 광중합 개시제(E) is a photopolymerization initiator

(F)성분은 (메타)아크릴산(F) is a copolymer of (meth) acrylic acid

본 발명에 관한 수지 조성물은 일실시형태에서 추가적으로 (G)성분으로서 폴리비닐알코올을 함유하여 이루어진다.The resin composition according to the present invention further comprises polyvinyl alcohol as a component (G) in one embodiment.

본 발명에 관한 수지 조성물은 일실시형태에서 (A)성분이 디시클로펜테닐(메타)아크릴레이트이다.In the resin composition according to the present invention, the component (A) is dicyclopentenyl (meth) acrylate in one embodiment.

본 발명에 관한 수지 조성물은 일실시형태에서 추가적으로 (C)성분의 수평균 분자량이 500∼50000이다.In the resin composition according to the present invention, the number average molecular weight of the component (C) is in the range of 500 to 50000 in one embodiment.

본 발명에 관한 수지 조성물은 일실시형태에서 두께 1mm로서 파장 365nm, 적산광량 2000mJ/cm2의 조건에서 15초간 조사함으로써 경화시켰을 때에 경화물의 저장탄성률이 0.1∼100000MPa(23℃)의 범위내가 된다.The resin composition of the present invention is within the range of a 1mm thick in one embodiment the wavelength 365nm, the accumulated light quantity 2000mJ / cm 2 under the conditions of 15 seconds by irradiating the cured product storage modulus when cured sikyeoteul 0.1~100000MPa (23 ℃).

본 발명에 관한 수지 조성물은 일실시형태에서 산화방지제를 더 함유하여 이루어진다.The resin composition according to the present invention further comprises an antioxidant in one embodiment.

본 발명은 다른 일측면에서 본 발명에 관한 해당 수지 조성물로 이루어진 접착제이다.Another aspect of the present invention is an adhesive comprising the resin composition according to the present invention.

본 발명에 관한 접착제는 일실시형태에서 시클로올레핀 폴리머용 접착제이다.The adhesive according to the present invention is an adhesive for a cycloolefin polymer in one embodiment.

본 발명에 관한 접착제는 일실시형태에서 디시클로펜타디엔 고리구조를 가진 시클로올레핀 폴리머용 접착제이다.The adhesive according to the present invention is an adhesive for a cycloolefin polymer having a dicyclopentadiene ring structure in one embodiment.

본 발명은 또 다른 일측면에서 본 발명에 관한 해당 접착제를 이용하여 피착체끼리 접착된 접착체이다.In another aspect, the present invention is an adhesive body which is adhered to adherends using the adhesive according to the present invention.

본 발명에 관한 접착체는 일실시형태에서 피착체가 시클로올레핀 폴리머, 폴리카보네이트, 셀룰로오스 트리아세테이트, 폴리비닐알코올 및 유리로 이루어진 군에서 선택되는 1종 이상이다.In the adhesive material according to the present invention, in one embodiment, the adherend is at least one selected from the group consisting of cycloolefin polymer, polycarbonate, cellulose triacetate, polyvinyl alcohol and glass.

본 발명은 또 다른 일측면에서, 피착체 표면에 본 발명에 관한 해당 접착제를 두께 0.0001∼5mm가 되도록 도포하여 피착체끼리 맞붙이고 파장 200∼500nm, 적산광량 200∼6000J/cm2, 조사 시간 1∼60초의 조건하에서 접착제를 경화시키는 것을 포함한 접착체의 제조 방법이다.The invention in another aspect, to the adhesive of the present invention to an adherend surface coating so as to have a thickness 0.0001~5mm worked between adherends is 200~500nm wavelength, the accumulated light quantity 200~6000J / cm 2, irradiation time 1 And curing the adhesive under the condition of a temperature of 60 to 60 seconds.

본 발명의 수지 조성물은, 예를 들면 시클로올레핀 폴리머에 대해 높은 접착 강도를 나타내고 내습성도 우수하다는 특징을 가진다.The resin composition of the present invention is characterized in that it exhibits a high adhesive strength to a cycloolefin polymer and is excellent in moisture resistance, for example.

도 1은 실시예에서의 인장 접착 강도의 측정 순서를 도시한 모식도다.Fig. 1 is a schematic diagram showing a procedure for measuring the tensile bond strength in the examples. Fig.

본 발명에서의 (A)성분은 디시클로펜테닐기를 가진 (메타)아크릴레이트이다. 보다 구체적으로는 (A)성분은 분자의 말단 또는 측쇄에 1개 이상의 디시클로펜테닐기를 함유하는 (메타)아크릴레이트이다. (A)성분의 (메타)아크릴레이트로서는 디시클로펜테닐옥시에틸(메타)아크릴레이트, 디시클로펜테닐옥시프로필(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트 등을 들 수 있다. 이들 중에서는 디시클로펜테닐(메타)아크릴레이트가 바람직하다.The component (A) in the present invention is a (meth) acrylate having a dicyclopentenyl group. More specifically, the component (A) is a (meth) acrylate containing at least one dicyclopentenyl group at the terminal or side chain of the molecule. (Meth) acrylate of the component (A) include dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate and dicyclopentenyl (meth) acrylate. Of these, dicyclopentenyl (meth) acrylate is preferred.

(B)성분은 수산기를 함유하는 (메타)아크릴레이트이다. 보다 구체적으로는, (B)성분은 분자의 말단 또는 측쇄에 1개 이상의 수산기를 함유하는 (메타)아크릴레이트이다. 수산기를 함유하는 (메타)아크릴레이트로서는 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 2-히드록시-3-페녹시프로필(메타)아크릴레이트, 2-(메타)아크릴로일옥시에틸-2-히드록시프로필프탈레이트, 4-히드록시시클로헥실(메타)아크릴레이트 등을 들 수 있다. 이들 중에서는 접착성의 관점에서 2-히드록시-3-페녹시프로필(메타)아크릴레이트가 더욱 바람직하다.(B) is a (meth) acrylate containing a hydroxyl group. More specifically, the component (B) is a (meth) acrylate containing at least one hydroxyl group at the terminal or side chain of the molecule. Examples of the (meth) acrylate containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl Acrylate, phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate and 4-hydroxycyclohexyl (meth) acrylate. Of these, 2-hydroxy-3-phenoxypropyl (meth) acrylate is more preferable from the viewpoint of adhesiveness.

(C)성분은 디엔계의 골격 또는 수소 첨가된 디엔계의 골격을 가진 올리고머이다. (C)성분은 (메타)아크릴레로일기를 갖지 않는 것이 바람직하다. (C)성분은 수지의 유연성 부여의 관점에서 이하와 같은 성분을 들 수 있다.(C) is an oligomer having a diene skeleton or a hydrogenated diene skeleton. The component (C) preferably has no (meth) acryloyl group. The component (C) includes the following components from the viewpoint of imparting flexibility to the resin.

올리고머의 주쇄 골격은 디엔계의 골격 또는 수소 첨가된 디엔계의 골격이다. 디엔계의 골격 또는 수소 첨가된 디엔계의 골격으로서는 폴리부타디엔, 폴리이소프렌, 폴리부타디엔의 수소 첨가물 및 폴리이소프렌의 수소 첨가물로 이루어진 군에서 선택되는 1종 이상의 골격을 들 수 있다. 이들 중에서는 폴리이소프렌 및 폴리이소프렌의 수소 첨가물로 이루어진 군에서 선택되는 1종 이상이 바람직하고, 폴리이소프렌이 더욱 바람직하다.The main chain skeleton of the oligomer is a diene skeleton or a hydrogenated diene skeleton. Examples of the diene skeleton or the hydrogenated diene skeleton include at least one skeleton selected from the group consisting of hydrogenated products of polybutadiene, polyisoprene, polybutadiene, and hydrogenated polyisoprene. Of these, at least one selected from the group consisting of hydrogenated products of polyisoprene and polyisoprene is preferable, and polyisoprene is more preferable.

(C)성분의 올리고머의 수평균 분자량은 500∼50000이 바람직하고, 5000∼45000이 보다 바람직하고, 8000∼40000이 가장 바람직하다. 수평균 분자량이 500이상이면 본 발명의 접착제에 에너지선을 조사하여 얻을 수 있는 경화체의 경도가 높기 때문에 접착제층을 형성하기 쉬워진다. 수평균 분자량이 50000 이하이면 얻을 수 있는 접착제의 점도가 작기 때문에 제조 과정에서의 혼합 등의 작업성이나 실용 용도에서 해당 접착제를 이용할 때의 작업성이 양호하다.The number average molecular weight of the oligomer of the component (C) is preferably 500 to 50000, more preferably 5000 to 45000, and most preferably 8000 to 40000. When the number average molecular weight is 500 or more, the adhesive layer of the present invention is easily formed because the hardness of the cured product obtained by irradiating the energy ray to the adhesive of the present invention is high. When the number average molecular weight is 50,000 or less, the viscosity of the obtainable adhesive is small, so that workability such as mixing in the production process and workability when the adhesive is used for practical use are good.

(C)성분의 올리고머로서는 쿠라레이사제「LIR-50」(이소프렌올리고머), 쿠라레이사제「LIR-30」(이소프렌올리고머), 쿠라레이사제「LBR-307」(부타디엔올리고머), 쿠라레이사제「LBR-305」(부타디엔올리고머), 쿠라레이사제「LBR-300」(부타디엔올리고머)을 들 수 있다. 이들 중에서는 이소프렌올리고머 및/또는 부타디엔올리고머의 1종 이상이 유연성과 접착성의 관점에서 더욱 바람직하다.LBR-307 " (butadiene oligomer) manufactured by Kuraray Co., Ltd., and " LIR-50 " manufactured by Kuraray Co., LBR-305 "(butadiene oligomer), and" LBR-300 "(butadiene oligomer) manufactured by Kuraray Co., Ltd. Among them, at least one of isoprene oligomer and / or butadiene oligomer is more preferable from the viewpoint of flexibility and adhesiveness.

(D)성분은 실란 커플링제이다. 실란 커플링제로서는 γ-클로로프로필트리메톡시실란, 비닐트리메톡시실란, 비닐트리클로로실란, 비닐트리에톡시실란, 비닐프로필트리메톡시실란, 비닐-트리스(β-메톡시에톡시)실란, γ-(메타)아크릴록시프로필트리메톡시실란, β-(3,4-에폭시시클로헥실)에틸트리메톡시실란, γ-글리시독시프로필트리메톡시실란, γ-메르캅토프로필트리메톡시실란, γ-아미노프로필트리에톡시실란, N-β-(아미노에틸)-γ-아미노프로필트리메톡시실란, N-β-(아미노에틸)-γ-아미노프로필메틸디메톡시실란, γ-유레이도프로필트리에톡시실란, 히드록시에틸(메타)아크릴레이트인산에스테르, (메타)아크릴록시옥시에틸애시드포스페이트, (메타)아크릴록시옥시에틸애시드포스페이트모노에틸아민하프솔트 등을 들 수 있다. 이들 중에서는 유리 등에 대한 밀착성 관점에서 γ-글리시독시프로필트리메톡시실란, γ-(메타)아크릴록시프로필트리메톡시실란 및 비닐프로필트리메톡시실란으로 이루어진 군 중 1종 이상이 바람직하다.(D) is a silane coupling agent. Examples of the silane coupling agent include? -Chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinylpropyltrimethoxysilane, vinyltris (? -Methoxyethoxy) silane, ? - (meth) acryloxypropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -glycidoxypropyltrimethoxysilane,? -mercaptopropyltrimethoxysilane ,? - (aminoethyl) -? - aminopropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropylmethyldimethoxysilane,? - Hydroxyethyl (meth) acrylate phosphate ester, (meth) acryloxyoxyethyl acid phosphate, (meth) acryloxyoxyethyl acid phosphate monoethylamine half salt and the like. Of these, at least one of the group consisting of? -Glycidoxypropyltrimethoxysilane,? - (meth) acryloxypropyltrimethoxysilane and vinylpropyltrimethoxysilane is preferable from the viewpoint of adhesiveness to glass and the like.

(E)성분은 광중합 개시제이다. 광중합 개시제로서는 자외선 중합 개시제나 가시광 중합 개시제 등을 들 수 있는데, 어느 것이든 제한 없이 이용된다. 자외선 중합 개시제로서는 벤조인계, 벤조페논계, 아세토페논계 등을 들 수 있다. 가시광 중합 개시제로서는 아실포스핀옥사이드계, 티옥산톤계, 메탈로센계, 퀴논계, α-아미노알킬페논계 등을 들 수 있다.Component (E) is a photopolymerization initiator. Examples of the photopolymerization initiator include an ultraviolet polymerization initiator and a visible light polymerization initiator, and any of them may be used without limitation. Examples of the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone. Examples of the visible light polymerization initiator include acylphosphine oxide-based, thioxanthone-based, metallocene-based, quinone-based, and -aminoalkylphenone based.

광중합 개시제로서는 벤조페논, 4-페닐벤조페논, 벤조일안식향산, 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-트리메틸벤조일디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드, 2-메틸-1-(4-(메틸티오)페닐)-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-1-부탄온-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 벤질디메틸케탈이 바람직하다.Examples of the photopolymerization initiator include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropylether, benzyldimethylketal, 1-hydroxycyclo Hexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone 2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy- 2-methyl-1-phenylpropan-1-one, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6 2-methyl-1- (4-methylthio) phenyl) -2-morpholinopropane- -Morpholinophenyl) -1-butanone- 1,2-dimethylamino-2- (4-methyl-benzyl)Switch (2, 6-dimethoxybenzoyl) -2,4,4- trimethyl-pentyl, and the like phosphine oxide. Of these, benzyl dimethyl ketal is preferred.

(F)성분은 (메타)아크릴산(아크릴산 또는 메타크릴산)이다. 이것은 특히 내습성 등의 내구성 관점에서 사용한다.(F) is (meth) acrylic acid (acrylic acid or methacrylic acid). This is used particularly in view of durability such as moisture resistance.

본 발명의 수지 조성물은 상기 (A)∼(F)성분을 필수 성분으로서 함유한다. 상기 (A)∼(F)성분을 함유하는 수지 조성물은 여기에 광이 조사됨으로써 경화된다. 경화물은 시클로올레핀 폴리머에 대해 접착성이 양호함과 동시에 상기 경화시에 표면 경화성이 높은 특징을 나타낸다. 본 발명의 수지 조성물은, 예를 들면 폴리카보네이트, 셀룰로오스트리아세테이트, 폴리비닐알코올 등의 범용 플라스틱 수지, 유리 피착체에 대해서도 높은 접착 강도를 나타낸다.The resin composition of the present invention contains the above components (A) to (F) as essential components. The resin composition containing the components (A) to (F) is cured by being irradiated with light. The cured product exhibits good adhesiveness to the cycloolefin polymer and exhibits high surface hardenability at the time of curing. The resin composition of the present invention exhibits high adhesive strength even to general-purpose plastic resins such as polycarbonate, cellulose triacetate, polyvinyl alcohol, and glass adherends.

본 발명의 수지 조성물에는 (G)성분으로서 폴리비닐알코올을 함유할 수 있다. 이것은 폴리비닐알코올 수지로 이루어진 피착체에 대한 밀착성 관점에서 이하와 같은 성분을 들 수 있다.The resin composition of the present invention may contain polyvinyl alcohol as a component (G). These are the following components from the viewpoint of adhesion to an adherend made of a polyvinyl alcohol resin.

상기 폴리비닐알코올은 폴리초산비닐을 비누화하여 얻을 수 있는 폴리비닐알코올 유도체라면 특별히 한정되는 것은 아니다. 폴리비닐알코올의 평균 중합도는 100∼5000이 바람직하고, 1000∼4000이 더욱 바람직하다. 폴리비닐알코올의 평균 비누화도는 85∼100몰%가 바람직하고, 90∼100몰%가 더욱 바람직하다.The polyvinyl alcohol is not particularly limited as long as it is a polyvinyl alcohol derivative obtained by saponifying polyvinyl acetate. The average degree of polymerization of the polyvinyl alcohol is preferably 100 to 5000, more preferably 1000 to 4000. The average saponification degree of the polyvinyl alcohol is preferably 85 to 100 mol%, more preferably 90 to 100 mol%.

본 발명의 수지 조성물의 사용량은 접착제의 시클로올레핀 폴리머에 대한 접착성이 특단적으로 높아지고, 또한 다른 피착체에 대해서도 높은 접착 강도를 갖게 되는 관점에서 이하와 같다.The amount of the resin composition of the present invention is as follows from the viewpoint that the adhesiveness of the adhesive to the cycloolefin polymer is particularly high and the adhesive strength to other adherends is also high.

(A)성분, (B)성분 및 (C)성분의 사용량은 (A)성분, (B)성분 및 (C)성분의 합계 100질량부 중 (A)성분：(B)성분：(C)성분=40∼90：1∼20：5∼45(질량비)가 바람직하고, (A)성분：(B)성분：(C)성분=55∼85：3∼10：10∼40(질량비)이 더욱 바람직하다.The amount of the component (A), the component (B), and the amount of the component (C) used is from 100 parts by mass in total of the components (A), (B) and (C) (A): (B) Component: (C) Component = 55 to 85: 3 to 10: 10 to 40 (mass ratio) More preferable.

(D)성분의 사용량은 (A)성분, (B)성분, (C)성분 및 (F)성분의 합계량 100질량부에 대해 0.01∼10질량부가 바람직하고, 0.1∼5질량부가 더욱 바람직하고, 전형적으로는 0.5∼1.0질량부이다.The amount of the component (D) to be used is preferably from 0.01 to 10 parts by mass, more preferably from 0.1 to 5 parts by mass, more preferably from 0.1 to 5 parts by mass based on 100 parts by mass of the total amount of the components (A), (B), (C) Typically, it is 0.5 to 1.0 part by mass.

(E)성분의 사용량은 (A)성분, (B)성분, (C)성분 및 (F)성분의 합계량 100질량부에 대해 0.01∼30질량부가 바람직하고, 0.1∼20질량부가 더욱 바람직하고, 전형적으로는 5∼10질량부이다.The amount of the component (E) to be used is preferably from 0.01 to 30 parts by mass, more preferably from 0.1 to 20 parts by mass, per 100 parts by mass of the total amount of the component (A), the component (B), the component (C) And typically 5 to 10 parts by mass.

(F)성분의 사용량은 (A)성분, (B)성분, (C)성분 및 (F)성분의 합계량 100질량부 중 0.1∼30질량부가 바람직하고, 1∼20질량부가 더욱 바람직하고, 전형적으로는 10∼15질량부이다.The amount of the component (F) to be used is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, in a total amount of 100 parts by mass of the components (A), (B), (C) Is 10 to 15 parts by mass.

(G)성분의 사용량은 (A)성분, (B)성분, (C)성분 및 (F)성분의 합계량 100질량부에 대해 0.01∼50질량부가 바람직하고, 0.1∼30질량부가 더욱 바람직하고, 전형적으로는 0.5∼1.0질량부이다.The amount of the component (G) to be used is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, per 100 parts by mass of the total amount of the component (A), the component (B), the component (C) Typically, it is 0.5 to 1.0 part by mass.

아울러 본 발명의 수지 조성물은 본 발명의 목적을 손상시키지 않는 범위에서 그래프트 공중합체, 용제, 증량재, 보강재, 가소제, 증점제, 염료, 안료, 난연제, 산화방지제 및 계면활성제 등의 첨가제를 사용할 수 있다.Additives such as a graft copolymer, a solvent, an increasing agent, a reinforcing agent, a plasticizer, a thickener, a dye, a pigment, a flame retardant, an antioxidant and a surfactant may be used in the resin composition of the present invention so long as the object of the present invention is not impaired .

본 발명의 수지 조성물의 경화물은 0.1∼100000MPa(23℃)의 저장탄성률을 갖는 것이 바람직하고, 10∼10000MPa의 저장탄성률을 갖는 것이 더욱 바람직하고, 전형적으로는 500∼5000MPa이다. 수지 조성물의 경화물의 저장탄성률이 0.1MPa이상인 경우, 경화물이 경화되어 미반응 성분이 남지 않는다. 저장탄성률이 100000MPa이하인 경우, 경화물이 지나치게 강직되지 않아 접착력이 저하되지 않는다.The cured product of the resin composition of the present invention preferably has a storage elastic modulus of 0.1 to 100,000 MPa (23 DEG C), more preferably 10 to 10000 MPa, and more preferably 500 to 5000 MPa. When the storage elastic modulus of the cured product of the resin composition is 0.1 MPa or more, the cured product is cured and unreacted components are not left. When the storage elastic modulus is 100000 MPa or less, the cured product is not excessively rigid and the adhesive strength is not lowered.

본 발명의 수지 조성물은 접착제로서 사용할 수 있다. 본 발명의 접착제는 예를 들면 시클로올레핀 폴리머, 폴리카보네이트, 셀룰로오스트리아세테이트(트리아세틸셀룰로오스), 폴리비닐알코올 및 유리로 이루어진 군에서 선택되는 1종 이상에 대해 높은 접착 강도를 나타낸다. 즉, 이들 수지를 피착체로서 유용한 접착제로서 이용할 수 있다. 본 발명의 접착제는 이들 피착체 중에서도 특히 시클로올레핀 폴리머에 대해 높은 접착 강도를 나타낸다.The resin composition of the present invention can be used as an adhesive. The adhesive of the present invention exhibits a high adhesive strength to at least one selected from the group consisting of, for example, cycloolefin polymer, polycarbonate, cellulose triacetate (triacetyl cellulose), polyvinyl alcohol and glass. That is, these resins can be used as an adhesive useful as an adherend. The adhesive of the present invention exhibits a high adhesive strength particularly to the cycloolefin polymer among these adherends.

본 발명의 용도로서의 접착제를 적용 가능한 피착체의 시클로올레핀 폴리머란, 예를 들면 노르보넨이나 다환 노르보넨계 모노머 등의 고리형 올레핀(시클로올레핀) 모노머 유래의 구성 단위를 가진 열가소성 수지이다. 시클로올레핀 폴리머로서는, 예를 들면 시클로올레핀의 개환 집합체, 2종 이상의 시클로올레핀을 이용한 개환 공중합체의 수소 첨가물, 사슬형 올레핀이나 비닐기를 가진 방향족 화합물과 시클로올레핀과의 부가 공중합체 등을 들 수 있으며, 본 발명에 관한 접착제는 특히 디시클로펜타디엔 고리구조를 가진 시클로올레핀 폴리머에 유효하다. 또 시클로올레핀 폴리머에 극성기를 도입해도 좋다.The cycloolefin polymer of an adherend to which an adhesive for the purpose of the present invention can be applied is a thermoplastic resin having a constituent unit derived from a cyclic olefin (cycloolefin) monomer such as norbornene or a polycyclic norbornene monomer. Examples of the cycloolefin polymer include ring-opening aggregates of cycloolefins, hydrogenated products of ring-opening copolymers using two or more kinds of cycloolefins, addition copolymers of aromatic compounds having a chain olefin or vinyl group and cycloolefins, and the like , The adhesive relating to the present invention is particularly effective for a cycloolefin polymer having a dicyclopentadiene ring structure. The polar group may be introduced into the cycloolefin polymer.

시판되는 시클로올레핀 폴리머로서는, 예를 들면 독일 Ticona사제의 「Topas」, 제이에스알사제의 「아톤」, 일본 제온사제의 「제오노아(ZEONOR)」나 「제오넥스(ZEONEX)」, 미쓰이 화학사제의 「아펠」등을 들 수 있다.Examples of commercially available cycloolefin polymers include "Topas" manufactured by Ticona of Germany, "Aton" manufactured by JSR Corporation, "ZEONOR" and "ZEONEX" manufactured by Japan Xion, &Quot; Apples " and the like.

본 발명의 접착제의 접착 방법은, 예를 들면 이하와 같다. 피착체 2장 중 적어도 1장의 피착체 표면에 접착제를 두께 0.0001∼5mm, 전형적으로는 0.01∼0.50mm가 되도록 도포하고 그 후 피착체끼리 맞붙여 파장 200∼500nm, 전형적으로는 350∼420nm, 적산광량 200∼6000mJ/cm2, 전형적으로는 300∼2000mJ/cm2, 조사 시간 1∼60초, 전형적으로는 2∼30초의 조건하에서 접착제를 경화하여 피착체를 접착하는 방법이 바람직하다.The method for adhering the adhesive of the present invention is, for example, as follows. The adhesive is applied to the surface of at least one adherend of two adherends so as to have a thickness of 0.0001 to 5 mm, typically 0.01 to 0.50 mm, and adhered to each other to form a film having a wavelength of 200 to 500 nm, typically 350 to 420 nm, intensity 200~6000mJ / cm 2, typically 300~2000mJ / cm 2, irradiation time 1-60 seconds, typically to cure the adhesive under conditions 2 to 30 seconds is preferred a method of adhering an adherend.

본 발명은 기타 성분으로서 산화방지제를 사용해도 좋다. 산화방지제로서는 페놀계, 하이드로퀴논계를 사용할 수 있으며, 바람직하게는 페놀계가 이용된다. 산화방지제로서는 β-나프토퀴논, 2-메톡시-1,4-나프토퀴논, 메틸하이드로퀴논, 하이드로퀴논, 2,2-메틸렌비스(4-메틸-6-터셔리부틸페놀), 카테콜, 하이드로퀴논모노메틸에테르, 모노터셔리부틸하이드로퀴논, 2,5-디터셔리부틸하이드로퀴논, p-벤조퀴논, 2, 5-디페닐-p-벤조퀴논, 2, 5-디터셔리부틸-p-벤조퀴논, 피크린산, 구연산, 페노티아진, 터셔리부틸카테콜, 2-부틸-4-히드록시아니솔 및 2,6-디터셔리부틸-p-크레졸 등을 예시할 수 있다. 이들 중에서는 2,2-메틸렌-비스(4-메틸-6-터셔리부틸페놀)가 바람직하다.An antioxidant may be used as the other component of the present invention. As the antioxidant, a phenol-based or hydroquinone-based antioxidant may be used, preferably a phenol-based antioxidant. Examples of the antioxidant include? -Naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, 2,2-methylenebis (4-methyl- , Hydroquinone monomethyl ether, mono tertiary butyl hydroquinone, 2,5-ditertiary butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5- -Benzoquinone, picric acid, citric acid, phenothiazine, tertiary butyl catechol, 2-butyl-4-hydroxy anisole and 2,6-ditertiary butyl-p-cresol. Of these, 2,2-methylene-bis (4-methyl-6-tert-butylphenol) is preferred.

산화방지제의 사용량은 (A)성분, (B)성분, (C)성분 및 (F)성분의 합계량 100질량부에 대해 0.01∼10질량부가 바람직하고, 0.1∼8질량부가 더욱 바람직하고, 2.0∼8.0질량부가 더욱 바람직하다.The amount of the antioxidant to be used is preferably from 0.01 to 10 parts by mass, more preferably from 0.1 to 8 parts by mass, more preferably from 2.0 to 10 parts by mass, per 100 parts by mass of the total amount of the components (A), (B), (C) 8.0 parts by mass is more preferable.

<실시예><Examples>

이하 실험예를 들어 본 발명을 더욱 상세히 설명하는데 본 발명은 이들로 한정되지는 않는다. 아울러 실험예에 기재된 접착제 중의 각 성분으로는 이하의 화합물을 선택했다.Hereinafter, the present invention will be described in more detail with reference to Experimental Examples, but the present invention is not limited thereto. The following compounds were selected for each component in the adhesive described in the Experimental Example.

(A)성분, 디시클로펜테닐기를 함유하는 (메타)아크릴레이트로서 디시클로펜테닐아크릴레이트(히타치 화성사제「FA-511AS」)(A), dicyclopentenyl acrylate (FA-511AS manufactured by Hitachi Chemical Co., Ltd.) as a (meth) acrylate containing a dicyclopentenyl group,

(A)성분, 디시클로펜테닐기를 함유하는 (메타)아크릴레이트로서 디시클로펜테닐옥시에틸메타크릴레이트(히타치 화성사제「FA-512MT」)(A), dicyclopentenyloxyethyl methacrylate (FA-512MT manufactured by Hitachi Chemical Co., Ltd.) as a (meth) acrylate containing a dicyclopentenyl group,

(B)성분, 수산기를 함유하는 (메타)아크릴레이트로서 2-히드록시-3-페녹시프로필아크릴레이트(동아합성사제「M-5700」)(B), 2-hydroxy-3-phenoxypropyl acrylate ("M-5700" manufactured by TOAGOSEI CO., LTD.) As a (meth) acrylate containing a hydroxyl group,

(B)성분, 수산기를 함유하는 (메타)아크릴레이트로서 2-히드록시에틸메타크릴레이트(교에이샤 화학사제「라이트에스테르HO」)(B), 2-hydroxyethyl methacrylate ("Wight Ester HO" manufactured by Kyoeisha Chemical Co., Ltd.) as the (meth) acrylate containing a hydroxyl group,

(C)성분, 올리고머, 이소프렌올리고머(쿠라레이사제「LIR-30」)(GPC에 의한 폴리스티렌 환산의 수평균분자량 28000)(C) component, an oligomer, an isoprene oligomer ("LIR-30" manufactured by Kuraray Co., Ltd.) (number average molecular weight of 28,000 in terms of polystyrene by GPC)

(C)성분, 올리고머, 부타디엔올리고머(쿠라레이사제「LBR-307」)(GPC에 의한 폴리스티렌 환산의 수평균분자량 8000)(C) component, oligomer, butadiene oligomer ("LBR-307" manufactured by Kuraray Co., Ltd. (number average molecular weight 8000 in terms of polystyrene by GPC)

(D)성분, 실란 커플링제, γ-글리시독시프로필트리메톡시실란(신에츠 화학 사제「KBM-403」)(D), a silane coupling agent,? -Glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)

(D)성분, 실란 커플링제, 비닐프로필트리메톡시실란(신에츠 화학사제「KBM-1003」)(D), a silane coupling agent, vinylpropyltrimethoxysilane (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.)

(D)성분, 실란 커플링제, γ-메타크릴록시프로필트리메톡시실란(신에츠 화학사제「KBM-503」)(D), a silane coupling agent,? -Methacryloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd.)

(E)성분, 광개시제로서 벤질디메틸케탈(치바ㆍ스페셜티ㆍ케미컬즈사제「IRGACURE651」)(E), benzyl dimethyl ketal ("IRGACURE651" manufactured by Chiba Specialty Chemicals Co., Ltd.) as a photoinitiator,

(E)성분, 광개시제로서 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드(치바ㆍ스페셜티ㆍ케미컬즈사제「IRGACURE819」)(E), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819, manufactured by Ciba Specialty Chemicals) as a photoinitiator,

(F)성분, 메타크릴산(미츠비시 레이온사제「AM」)(F), methacrylic acid ("AM" manufactured by Mitsubishi Rayon Co., Ltd.)

(F)성분, 아크릴산(니혼쇼쿠바이사제「아크릴산메틸AM」)(F), acrylic acid ("Methyl Acrylate AM" manufactured by Nippon Shokubai Co., Ltd.)

(G)성분, 폴리비닐알코올(덴키화학 공업사제「덴카포발H-17」)(평균 중합도 1200, 평균 비누화도 97몰%)(Average polymerization degree: 1200, average degree of saponification: 97 mol%) of polyvinyl alcohol ("DENKAPO VAL H-17" manufactured by Denki Kagaku Kogyo Co., Ltd.)

(G)성분, 폴리비닐알코올(덴키화학 공업사제「덴카포발F-12」)(평균 중합도 1200, 평균 비누화도 99몰%)(Average polymerization degree: 1200, average degree of saponification: 99 mol%) of polyvinyl alcohol ("DENKAWO F-12" manufactured by Denki Kagaku Kogyo Co., Ltd.)

산화방지제, (D-1) 2,2-메틸렌-비스(4-메틸-6-터셔리부틸페놀)(스미토모 화학 사제「스밀라이저MDP-S」)Antioxidant, (D-1) 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol) (Sumilite MDP-S,

각종 물성은 다음과 같이 측정했다.Various physical properties were measured as follows.

〔광경화성〕[Photocurable property]

온도 23℃에서 측정했다. 광경화성에 관하여는 ZEONEX480R(일본 제온사제) 시험편(폭25mm×길이25mm×두께2.0mm) 표면에 접착제를 두께0.03mm가 되도록 도포했다. 두께는 0.03mm 유리 비드에 의해 제어했다. 그 후 무전극 방전 램프를 사용한 퓨전사제 경화 장치를 이용하여 파장 365nm, 적산광량 2000mJ/cm2의 조건에서 15초간 조사하여 경화시켰다. 광경화성으로서 경화율을 기재했다. 경화율은 FT-IR를 사용하여 이하의 식에 의해 산출했다.And the temperature was measured at 23 캜. Regarding the photo-curability, an adhesive was applied to the surface of a test piece (25 mm wide × 25 mm long × 2.0 mm thick) of ZEONEX 480R (manufactured by Japan Xionics Co., Ltd.) so as to have a thickness of 0.03 mm. The thickness was controlled by 0.03 mm glass beads. Thereafter, the mixture was irradiated for 15 seconds at a wavelength of 365 nm and a cumulative light quantity of 2000 mJ / cm 2 using a Fusion-type curing apparatus using a non-electrode discharge lamp, and cured. The curing rate is described as photocurability. The curing rate was calculated by the following equation using FT-IR.

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

〔시클로올레핀 폴리머 접착성 평가(시클로올레핀 폴리머(ZEONEX) 시험편간의 인장 접착 강도)〕[Evaluation of Cycloolefin Polymer Adhesion (Tensile Adhesion Strength Between Cycloolefin Polymer (ZEONEX) Test Specimen]]

ZEONEX480R(일본 제온사제) 시험편(12a)(폭25mm×길이100mm×두께2.0mm)의 길이 방향의 끝단 부분에, 중앙에 0.5cm2 크기의 구멍(11)이 뚫린 테플론(등록상표) 테이프(10)(두께80㎛×폭25mm×길이25mm)를 접착제 두께 제어를 위해 붙였다. 해당 구멍(11)에 접착제(13)를 두께80㎛가 되도록 공급한 후, 해당 구멍(11)을 덮도록 하여 테플론(등록상표) 테이프(10) 위에, 다른 하나의 ZEONEX480R(일본 제온사제) 시험편(12b)(폭25mm×길이100mm×두께2.0mm)의 끝단 부분을 맞붙였다. 이 때의 모습을 도 1에 도시한다. 경화 후, 접착제로 접착한 해당 시험편을 이용하여 도 1의 화살표의 좌우로 잡아당겨 인장 접착 강도를 측정했다. 경화 조건은 〔광경화성〕에 기재된 방법에 따랐다.A Teflon (registered trademark) tape 10 (manufactured by Nippon Zeon Co., Ltd.) having a hole 11 having a size of 0.5 cm 2 in the center is formed in the longitudinal end portion of a test piece 12a (25 mm in width x 100 mm in length x 2.0 mm in thickness) ) (80 占 퐉 in thickness 占 25 mm in width 占 25 mm in length) was attached for controlling the adhesive thickness. The adhesive 13 was supplied to the hole 11 so as to have a thickness of 80 mu m and then another Teflon tape 10 was coated with another ZEONEX480R (12 mm in width and 20 mm in width x 100 mm in length x 2.0 mm in thickness). The state at this time is shown in Fig. After curing, the tensile bonding strength was measured by pulling the test piece from the left and right of the arrow in Fig. 1 using the test piece adhered with an adhesive. The curing conditions were according to the method described in [Photocuring property].

〔내습성〕[Moisture resistance]

상기 시클로올레핀 폴리머 접착성 평가용 시험편을 85℃×85%RH에 24시간 폭로시키고 해당 시험편을 이용하여 인장 접착 강도를 측정했다.The test pieces for evaluating the cycloolefin polymer adhesiveness were exposed to 85 캜 x 85% RH for 24 hours, and tensile bond strengths were measured using the test pieces.

〔범용 폴리머 접착성 평가(폴리카보네이트(테이진사제) 시험편간의 인장 접착 강도)〕[General Polymer Adhesion Evaluation (Tensile Adhesive Strength Between Polycarbonate (Teijin) Test Specimens)]

팬라이트(테이진사제) 시험편(폭25mm×길이25mm×두께2.0mm)끼리를 두께80㎛×폭11.5mm×길이25mm의 테플론(등록상표) 테이프를 스페이서로서 이용하여 접착제를 접착시켰다(접착 면적 3.125cm2). 경화 후, 접착제로 접착한 해당 시험편을 이용하여 인장 접착 강도를 측정했다. 경화 조건은 〔광경화성〕에 기재된 방법에 따랐다.Adhesives were bonded to each other using a Teflon (registered trademark) tape having a thickness of 80 占 퐉, a width of 11.5 mm, and a length of 25 mm as test pieces (25 mm in width, 25 mm in length and 2.0 mm in thickness) 3.125 cm 2 ). After curing, the tensile bond strength was measured using the corresponding test piece bonded with an adhesive. The curing conditions were according to the method described in [Photocuring property].

〔범용 폴리머 접착성 평가(폴리비닐알코올(쿠라레이사제) 시험편간의 인장 접착 강도)〕[General polymer adhesive property evaluation (tensile bond strength between polyvinyl alcohol (manufactured by Kuraray Co., Ltd.) test piece)]

시험편(폭25mm×길이25mm×두께0.03mm)끼리를 두께80㎛×폭11.5mm×길이25mm의 테플론(등록상표) 테이프를 스페이서로서 이용하여 접착제를 접착시켰다(접착 면적 3.125cm2). 경화 후, 접착제로 접착한 해당 시험편을 이용하여 인장 접착 강도를 측정했다. 경화 조건은 〔광경화성〕에 기재된 방법에 따랐다.An adhesive was bonded (adhesive area: 3.125 cm 2 ) using Teflon (registered trademark) tape having a thickness of 80 탆, a width of 11.5 mm and a length of 25 mm as a spacer between test pieces (25 mm in width x 25 mm in length x 0.03 mm in thickness). After curing, the tensile bond strength was measured using the corresponding test piece bonded with an adhesive. The curing conditions were according to the method described in [Photocuring property].

〔범용 폴리머 접착성 평가(트리아세틸셀룰로오스(코니카 미놀타사제) 시험편간의 인장 접착 강도)〕[General-purpose polymer adhesive property evaluation (tensile adhesive strength between triacetyl cellulose (manufactured by Konica Minolta) test piece)]

시험편(폭25mm×길이25mm×두께0.03mm)끼리를 두께80㎛×폭11.5mm×길이25mm의 테플론(등록상표) 테이프를 스페이서로서 이용하여 접착제를 접착시켰다(접착 면적 3.125cm2). 경화 후, 접착제로 접착한 해당 시험편을 이용하여 인장 접착 강도를 측정했다. 경화 조건은 〔광경화성〕에 기재된 방법에 따랐다.An adhesive was bonded (adhesive area: 3.125 cm 2 ) using Teflon (registered trademark) tape having a thickness of 80 탆, a width of 11.5 mm and a length of 25 mm as a spacer between test pieces (25 mm in width x 25 mm in length x 0.03 mm in thickness). After curing, the tensile bond strength was measured using the corresponding test piece bonded with an adhesive. The curing conditions were according to the method described in [Photocuring property].

〔유리 접착성 평가(내열유리 시험편간의 인장 접착 강도)〕[Evaluation of glass adhesion property (Tensile adhesion strength between heat resistant glass test pieces)]

내열유리 시험편(25mm×25mm×2.0mm)끼리를 두께80㎛×폭11.5mm×길이25m의 테플론(등록상표) 테이프를 스페이서로서 이용하여 접착제를 접착시켰다(접착 면적 3.125cm2). 경화 조건은 〔광경화성〕에 기재된 방법에 따랐다. 상기 조건에서 접착제를 경화시킨 후, 추가로 시험편의 뒤편에 덴키화학공업사제 접착제 「G-55」를 사용하여 아연 도금 강판(100mm×25mm×2.0mm, 엔지니어링 테스트 서비스사제)을 접착시켰다. 23℃×50%RH×24시간 양생에 의해 경화 후, 접착제로 접착한 해당 시험편을 이용하여 인장 접착 강도를 측정했다. 인장 전단 접착 강도(단위：MPa)는 온도 23℃, 습도 50%의 환경하에서 인장 속도 10mm/분으로 측정했다.The adhesive was adhered (adhesive area: 3.125 cm 2 ) using a Teflon (registered trademark) tape having a thickness of 80 탆, a width of 11.5 mm and a length of 25 m as a spacer between heat resistant glass test pieces (25 mm x 25 mm x 2.0 mm). The curing conditions were according to the method described in [Photocuring property]. After the adhesive was cured under the above conditions, a galvanized steel sheet (100 mm x 25 mm x 2.0 mm, manufactured by Engineering Test Service) was adhered to the back of the test piece by using an adhesive "G-55" manufactured by Denki Kagaku Kogyo Co., After curing by curing at 23 占 폚 占 50% RH 占 24 hours, the tensile bond strength was measured using the corresponding test piece bonded with an adhesive. The tensile shear bond strength (unit: MPa) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 캜 and a humidity of 50%.

〔저장탄성률 평가〕[Evaluation of storage elastic modulus]

접착제를 경화시켜 길이20mm×폭5mm×두께1mm의 경화물 시료를 조제했다. 경화 조건은 〔광경화성〕에 기재된 방법에 따랐다. 이 경화물 시료를 평가했다. 세이코 전자공업(주)사제 텐션 모듈 DMS210을 사용하여 주파수 1Hz, 왜곡 0.05%의 조건으로 온도를 변경하고 인장 모드로 동적 점탄성 스펙트럼을 측정하여 23℃에서의 저장탄성률E＇의 값을 구했다.The adhesive was cured to prepare a cured sample having a length of 20 mm, a width of 5 mm and a thickness of 1 mm. The curing conditions were according to the method described in [Photocuring property]. This cured sample was evaluated. Using a tension module DMS210 manufactured by Seiko Denshi Kogyo Co., Ltd., the temperature was changed under the conditions of a frequency of 1 Hz and a distortion of 0.05%, and a dynamic viscoelastic spectrum was measured in a tensile mode to obtain a storage elastic modulus E 'at 23 ° C.

(실험예 1∼14)(Experimental Examples 1 to 14)

표 1에 나타내는 종류의 원재료를 표 1에 나타내는 조성으로 혼합하여 접착제를 조제했다. 얻어진 접착제에 대해 각종 물성의 측정을 실시했다. 그 결과를 표 1에 도시한다.The raw materials of the kind shown in Table 1 were mixed in the composition shown in Table 1 to prepare an adhesive. Various physical properties of the obtained adhesive were measured. The results are shown in Table 1.

[표1-1][Table 1-1]

Figure 112013099226769-pct00001
Figure 112013099226769-pct00001

[표 1-2][Table 1-2]

Figure 112013099226769-pct00002
Figure 112013099226769-pct00002

본원발명은 시클로올레핀 폴리머, 폴리카보네이트, 폴리비닐알코올, 셀룰로오스 트리아세테이트 및 유리에 대해 충분한 접착 강도를 발현할 수 있다. 본원발명은 내습성을 가진다.The present invention can exhibit sufficient adhesive strength to cycloolefin polymers, polycarbonate, polyvinyl alcohol, cellulose triacetate and glass. The present invention has moisture resistance.

<산업상 이용 가능성>&Lt; Industrial applicability >

시클로올레핀 폴리머는 극성은 작고 표면에 많은 관능기를 가지지 않기 때문에 접착하기 어렵다는 과제가 있었다. 시클로올레핀 폴리머를 접착하기 위해서는 접착제를 사용한 후 추가로 프라이머 처리나 표면 코로나 처리를 병용할 필요가 있었다. 프라이머 처리나 표면 코로나 처리를 실시하는 것은 공정 증가가 될 우려가 있었다.The cycloolefin polymer has a problem that it is difficult to bond because the polarity is small and it does not have many functional groups on the surface. In order to bond the cycloolefin polymer, it is necessary to use an adhesive followed by a primer treatment or a surface corona treatment. There is a fear that the primer treatment or the surface corona treatment may increase the process.

본원발명은 접착제만으로 시클로올레핀 폴리머에 대해 높은 접착성을 나타낸다. 본원발명은, 프라이머 처리나 표면 코로나 처리를 병용하지 않아도 시클로올레핀 폴리머에 대해 높은 접착성을 나타내기 때문에 생력화(省力化)가 가능하다. 본원발명은 유용한 기술이다.The present invention exhibits high adhesiveness to the cycloolefin polymer only with an adhesive. INDUSTRIAL APPLICABILITY Since the present invention exhibits high adhesiveness to a cycloolefin polymer even when a primer treatment or a surface corona treatment is not used in combination, labor saving (labor saving) is possible. The present invention is a useful technique.

10　테이프
11　구멍
12a,12b　시험편
13　접착제10 tapes
11 holes
12a, 12b Test piece
13 Adhesive

Claims (14)

하기 (A)∼(F)성분을 함유하여 이루어진 수지 조성물로서,
(A)성분은 디시클로펜테닐기를 가진 (메타)아크릴레이트,
(B)성분은 수산기를 가진 (메타)아크릴레이트,
(C)성분은 디엔계의 골격 또는 수소 첨가된 디엔계의 골격을 가지고 또한 (메타)아크릴로일기를 가지지 않는 올리고머,
(D)성분은 실란 커플링제,
(E)성분은 광중합 개시제,
(F)성분은 (메타)아크릴산이며,
두께 1mm로 하여 파장365nm, 적산광량 2000mJ/cm2의 조건에서 15초간 조사함으로써 경화시켰을 때에 경화물의 저장탄성률이 0.1∼100000MPa(23℃)의 범위내가 되는 것을 특징으로 하는 수지 조성물.A resin composition comprising the following components (A) to (F)
(A) is a (meth) acrylate having a dicyclopentenyl group,
(B) is a (meth) acrylate having a hydroxyl group,
(C) is an oligomer having a diene skeleton or a hydrogenated diene skeleton and also having no (meth) acryloyl group,
(D) is a silane coupling agent,
(E) is a photopolymerization initiator,
(F) is (meth) acrylic acid,
Wherein the cured product has a storage elastic modulus in a range of 0.1 to 100000 MPa (23 캜) when irradiated for 15 seconds under the condition of a thickness of 1 mm and a wavelength of 365 nm and an accumulated light quantity of 2000 mJ / cm 2 . 청구항 1에 있어서, (G)성분으로서 폴리비닐알코올을 더 함유하여 이루어진 수지 조성물.The resin composition according to claim 1, further comprising polyvinyl alcohol as the component (G). 청구항 1 또는 청구항 2에 있어서, (A)성분, (B)성분 및 (C)성분의 사용량은 (A)성분, (B)성분 및 (C)성분의 합계 100질량부 중 (A)성분：(B)성분：(C)성분=40∼90：1∼20：5∼45(질량비)이며,
(D)성분의 사용량은 (A)성분, (B)성분, (C)성분 및 (F)성분의 합계량 100질량부에 대해 0.01∼10질량부이며,
(E)성분의 사용량은 (A)성분, (B)성분, (C)성분 및 (F)성분의 합계량 100질량부에 대해 0.01∼30질량부인 수지 조성물.The use amount of the component (A), the component (B) and the component (C) in the total amount of the components (A), (B) and (C) (B) component: (C) component = 40 to 90: 1 to 20: 5 to 45 (mass ratio)
(D) is used in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A), (B), (C) and (F)
(E) is used in an amount of 0.01 to 30 parts by mass based on 100 parts by mass of the total amount of the component (A), the component (B), the component (C) and the component (F). 청구항 1 또는 청구항 2에 있어서, (A)성분이 디시클로펜테닐(메타)아크릴레이트인 수지 조성물.The resin composition according to claim 1 or 2, wherein the component (A) is dicyclopentenyl (meth) acrylate. 청구항 1 또는 청구항 2에 있어서, (C)성분이 이소프렌올리고머 및/또는 부타디엔올리고머인 수지 조성물.The resin composition according to claim 1 or 2, wherein the component (C) is an isoprene oligomer and / or a butadiene oligomer. 청구항 1 또는 청구항 2에 있어서, (C)성분의 수평균 분자량이 500∼50000인 수지 조성물.The resin composition according to claim 1 or 2, wherein the component (C) has a number average molecular weight of 500 to 50000. 삭제delete 청구항 1 또는 청구항 2에 있어서, 산화방지제를 더 함유하여 이루어진 수지 조성물.The resin composition according to claim 1 or 2, further comprising an antioxidant. 청구항 1 또는 청구항 2에 기재된 수지 조성물로 이루어진 접착제.An adhesive comprising the resin composition according to claim 1 or 2. 청구항 9에 있어서, 시클로올레핀 폴리머용 접착제인 접착제.The adhesive according to claim 9, which is an adhesive for a cycloolefin polymer. 청구항 9에 있어서, 디시클로펜타디엔 고리구조를 가진 시클로올레핀 폴리머용 접착제인 접착제.The adhesive according to claim 9, which is an adhesive for a cycloolefin polymer having a dicyclopentadiene ring structure. 청구항 9에 기재된 접착제를 이용하여 피착체끼리 접착되어 있는 접착체.An adherend adhered between adherends using the adhesive according to claim 9. 청구항 12에 있어서, 피착체가 시클로올레핀 폴리머, 폴리카보네이트, 셀룰로오스트리아세테이트, 폴리비닐알코올 및 유리로 이루어진 군에서 선택되는 1종 이상인 접착체.The adhesive according to claim 12, wherein the adherend is at least one selected from the group consisting of a cycloolefin polymer, polycarbonate, cellulose triacetate, polyvinyl alcohol and glass. 피착체 표면에 청구항 9에 기재된 접착제를 두께 0.0001∼5mm가 되도록 도포하고 피착체끼리 맞붙여 파장 200∼500nm, 적산광량 200∼6000J/cm2, 조사 시간 1∼60초의 조건하에서 접착제를 경화하는 것을 포함하는 접착체의 제조 방법.The adhesive described in claim 9 is applied to the surface of the adherend so as to have a thickness of 0.0001 to 5 mm and adhered to each other to cure the adhesive under the conditions of a wavelength of 200 to 500 nm, a cumulative light quantity of 200 to 6000 J / cm 2 and an irradiation time of 1 to 60 seconds &Lt; / RTI &gt;
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