KR20120088315A - Radiation curable adhesive composition - Google Patents

Radiation curable adhesive composition Download PDF

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KR20120088315A
KR20120088315A KR1020110009582A KR20110009582A KR20120088315A KR 20120088315 A KR20120088315 A KR 20120088315A KR 1020110009582 A KR1020110009582 A KR 1020110009582A KR 20110009582 A KR20110009582 A KR 20110009582A KR 20120088315 A KR20120088315 A KR 20120088315A
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meth
acrylate
polymerizable unsaturated
unsaturated compound
acid
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KR101740057B1 (en
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엄준필
성동묵
홍범선
이동현
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엘지이노텍 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
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups

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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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

PURPOSE: A photocurable adhesive composition is provided to additionally include a polymerizable unsaturated compound having isocyanate group, thereby inducing enhancement of curing speed increase, adhesive strength for substrates, and surface roughness by volumetric shrinkage. CONSTITUTION: A photocurable adhesive composition comprises a polymerizable unsaturated compound having an acidic functional group, a polymerizable unsaturated compound having an annular ring, a polymerizable unsaturated compound having a hydroxy group, a polymerizable unsaturated compound having aliphatics, and a polymerizable unsaturated compound having an isocyanate group. The polymerizable unsaturated compound is a mixture of more than one or two selected from (meth) acrylic acid, acrylic acid dimer, β-styryl acrylic acid, β-furfuryl acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, mesaconic acid, itaconic acid.

Description

광경화성 접착제 조성물{Radiation curable adhesive composition}Photocurable adhesive composition

본 발명은 체적수축이 적고 경화밀도가 높으며 다양한 고분자와의 접착특성을 가지는 광경화성 접착제의 조성물에 관한 것이다.
The present invention relates to a composition of a photocurable adhesive having a low volume shrinkage, a high curing density, and adhesive properties with various polymers.

광경화를 이용한 재료들은 이미 여러 산업에 널리 응용되고 있다. 특히 자외선(UV) 개시 경화의 분야에서는 (메트)아크릴레이트 및 불포화 폴리에스테르 등을 이용한 중합이 널리 검토되어, 도료, 잉크, 접착제, 코팅제, 광 조형 및 레지스트 잉크 등 많은 분야에서 공업적으로 이용되고 있다.Photocuring materials are already widely used in many industries. Particularly in the field of ultraviolet (UV) initiation curing, polymerization using (meth) acrylates and unsaturated polyesters and the like has been widely studied and industrially used in many fields such as paints, inks, adhesives, coating agents, photo-forming and resist inks. have.

접착제의 분야에서도 마찬가지로 광경화성 수지를 이용한 광경화형 접착제가 널리 이용되고 있다. 광경화 과정은 광에 의해 유도된 광개시제가 자유 라디칼이나 산 유도물을 형성하면서 경화 반응이 진행되게 된다.Similarly, in the field of adhesives, photocurable adhesives using photocurable resins are widely used. In the photocuring process, the curing reaction proceeds while the photoinitiator induced by light forms free radicals or acid derivatives.

그런데, 기존의 광경화성 접착제는 체적수축이 크며 기타 다른 형태의 접착제보다 경화밀도가 작다. 또한 기재가 되는 고분자의 종류에 따라 사용되는 접착제를 달리 사용해야 하는 어려움이 있다.
However, conventional photocurable adhesives have a large volume shrinkage and a lower curing density than other types of adhesives. In addition, there is a difficulty in using a different adhesive used according to the type of the polymer to be a substrate.

본 발명은 종래의 문제점을 해결하기 위한 것으로, 본 발명의 과제는 체적수축이 적고 경화밀도가 높으며 다양한 고분자와의 접착특성을 갖는 광경화성 접착제의 조성물을 제공하는 것이다.
The present invention is to solve the conventional problems, the object of the present invention is to provide a composition of a photocurable adhesive having a low volume shrinkage, high curing density, and adhesive properties with various polymers.

상술한 과제를 달성하기 위하여, 본 발명에서는 (a) 산성 관능기를 갖는 중합성 불포화 화합물, (b) 환형 고리를 가지는 중합성 불포화 화합물, (c) 하이드록시기를 가지는 중합성 불포화 화합물, (d) 지방족(탄소 chain 4개 이상)을 가지는 중합성 불포화 화합물, (e) 이소시아네이트기를 가지는 중합성 불포화 화합물을 포함하는 광경화성 접착제가 제공된다.
In order to achieve the above object, in the present invention, (a) a polymerizable unsaturated compound having an acidic functional group, (b) a polymerizable unsaturated compound having a cyclic ring, (c) a polymerizable unsaturated compound having a hydroxy group, (d) There is provided a photocurable adhesive comprising a polymerizable unsaturated compound having an aliphatic (4 or more carbon chains) and (e) a polymerizable unsaturated compound having an isocyanate group.

본 발명에 의한 광경화성 접착제는 이소시아네이트기를 갖는 중합성 불포화 화합물을 더 포함함으로써 경화 속도의 향상, 기재에 대한 접착 강도 증가 및 체적수축 감소를 통한 표면조도 향상의 효과를 유도할 수 있다.
The photocurable adhesive according to the present invention may further include the polymerizable unsaturated compound having an isocyanate group, thereby inducing the effect of improving the curing rate, increasing the adhesive strength to the substrate, and improving the surface roughness by reducing the volume shrinkage.

이하에서는 본 발명에 의한 광경화성 접착제 조성물의 바람직한 실시예를 설명한다.Hereinafter, a preferred embodiment of the photocurable adhesive composition according to the present invention will be described.

본 발명의 광경화성 접착제는 (a) 산성 관능기를 갖는 중합성 불포화 화합물 (이하, 「(a) 중합성 불포화 화합물」이라고 함), (b) 환형 고리를 가지는 중합성 불포화 화합물(이하, 「(b) 중합성 불포화 화합물」이라고 함), (c) 하이드록시기를 가지는 중합성 불포화 화합물(이하, (c) 중합성 불포화 화합물」이라고 함), (d) 지방족(탄소 chain 4개 이상)을 가지는 중합성 불포화 화합물(이하, (d) 중합성 불포화 화합물」이라고 함), (e) 이소시아네이트기를 가지는 중합성 불포화 화합물(이하, (e) 중합성 불포화 화합물」이라고 함)을 포함하는 공중합체이다.
The photocurable adhesive agent of this invention is (a) polymeric unsaturated compound which has an acidic functional group (henceforth "(a) polymeric unsaturated compound"), (b) polymeric unsaturated compound which has a cyclic ring (henceforth "( b) a polymerizable unsaturated compound), (c) a polymerizable unsaturated compound having a hydroxy group (hereinafter referred to as (c) a polymerizable unsaturated compound), and (d) an aliphatic (4 or more carbon chains) It is a copolymer containing a polymerizable unsaturated compound (henceforth (d) polymerizable unsaturated compound "), and (e) a polymerizable unsaturated compound which has an isocyanate group (henceforth (e) polymerizable unsaturated compound").

[화학식1]

Figure pat00001

[Chemical Formula 1]
Figure pat00001

(a) 중합성 불포화 화합물에 있어서, 산성 관능기의 예로는 카르복실기, 불포화 디카르복실산 또는 산무수물류 등을 들 수 있고, 특히 카르복실기가 사용되는 것이 바람직하다.In the (a) polymerizable unsaturated compound, examples of the acidic functional group include carboxyl groups, unsaturated dicarboxylic acids or acid anhydrides, and particularly preferably a carboxyl group is used.

카르복실기를 갖는 (a) 중합성 불포화 화합물의 예로는 (메트)아크릴산, 아크릴산 이합체, β-스티릴아크릴산, β-푸르푸릴아크릴산, 크로톤산, α-시아노신남산, 신남산 등의 불포화 모노카르복실산류; 불포화 디카르복실산 또는 산무수물류을 갖는 (a) 중합성 불포화 화합물의 예로는 말레산, 무수 말레산, 푸마르산, 시트라콘산, 메사콘산, 이타콘산 등이 있다.Examples of the (a) polymerizable unsaturated compound having a carboxyl group include unsaturated monocarboxyl such as (meth) acrylic acid, acrylic acid dimer, β-styrylacrylic acid, β-furfuryl acrylic acid, crotonic acid, α-cyanocinnamic acid and cinnamic acid. Acid; Examples of the (a) polymerizable unsaturated compound having unsaturated dicarboxylic acid or acid anhydride include maleic acid, maleic anhydride, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.

본 발명에 있어서 (a) 중합성 불포화 화합물은 단독으로 사용할 수도 있고 또는 2종 이상을 혼합하여 사용할 수도 있지만, (메트)아크릴산 또는 무수말레산을 사용하는 것이 바람직하다.In the present invention, the (a) polymerizable unsaturated compound may be used alone or in combination of two or more thereof, but it is preferable to use (meth) acrylic acid or maleic anhydride.

공중합체에서 차지하는 (a) 중합성 불포화 화합물의 함유율은 0.02 내지 2몰%이고, 바람직하게는 0.05 내지 0.5몰%이다. 여기서, (a) 불포화 화합물의 함유율이 0.02몰% 미만인 경우에는 얻어지는 공중합체의 기재 접착력이 떨어지게 되고, 0.5몰%를 초과할 경우에는 저장안정성이 다소 떨어질 수 있으며, 인쇄 시 뭉침 현상 등이 일어날 수 있다.
The content of the polymerizable unsaturated compound (a) in the copolymer is 0.02 to 2 mol%, preferably 0.05 to 0.5 mol%. Here, when the content of the unsaturated compound (a) is less than 0.02 mol%, the substrate adhesive strength of the copolymer is decreased, and when the content of the unsaturated compound is more than 0.5 mol%, the storage stability may be slightly decreased, and agglomeration may occur when printing. have.

(b) 중합성 불포화 화합물의 예로는 테트라하이드로 퍼퓨릴 (메트)아크릴레이트, 이소보닐 (메트)아크릴레이트, 2-메틸사이클로헥실(메트)아크릴레이트, 테트라하이드로퍼퓨란-3-일 (메트)아크릴레이트, 퍼퓨릴 (메트)아크릴레이트, 이소보닐 에톡시 (메트)아크릴레이트(isobornyl ethoxy (meth)acrylate), 2-페닐에틸 (메트)아크릴레이트(2-phenylethyl (meth)acrylate), 디사이클로펜타닐 (메트)아크릴레이트(dicyclopentanyl (meth)acrylate), 디사이클로펜타닐 에테르 (메트)아크릴레이트(dicyclopentenyl ether (meth)acrylate), 에틸렌 글리콜 디사이클로펜타닐 에테르 (메트)아크릴레이트(Ethylene glycol dicyclopentenyl ether (meth)acrylate) 등을 들 수 있다.(b) Examples of the polymerizable unsaturated compound include tetrahydro perfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tetrahydroperfuran-3-yl (meth) Acrylate, perfuryl (meth) acrylate, isobornyl ethoxy (meth) acrylate, 2-phenylethyl (meth) acrylate, dicyclo Dicyclopentanyl (meth) acrylate, dicyclopentenyl ether (meth) acrylate, ethylene glycol dicyclopentanyl ether (meth) acrylate ) acrylate).

이들 (b) 중합성 불포화 화합물 중에서도 특히 이중 환형 고리를 가지는 디사이클로펜타닐 (메트)아크릴레이트(dicyclopentanyl (meth)acrylate)가 바람직하다.Among these (b) polymerizable unsaturated compounds, dicyclopentanyl (meth) acrylate which has a bicyclic ring is especially preferable.

본 발명에 있어서, (b) 중합성 불포화 화합물은 기재와의 접착성 및 도막의 물리적 특성 등에 영향을 주는 부분으로서, 단독으로 사용할 수도 있고 또는 2종 이상을 혼합하여 사용할 수도 있다.In the present invention, the polymerizable unsaturated compound (b) may be used alone or in combination of two or more kinds as a part that affects the adhesion to the substrate, the physical properties of the coating film, and the like.

공중합체에서 차지하는 (b) 중합성 불포화 화합물의 함유율은 0.02 내지 2몰%이다. 바람직하게는 0.04 내지 1몰%이다. (b) 중합성 불포화 화합물이 0.02몰% 미만일 경우 접착성이 저하될 우려가 있고, 2몰%가 초과되면 도막이 매우 불안정(brittle)해질 수 있다.
The content rate of (b) polymerizable unsaturated compound in a copolymer is 0.02-2 mol%. Preferably it is 0.04-1 mol%. (b) When the polymerizable unsaturated compound is less than 0.02 mol%, there is a fear that the adhesiveness is lowered, and when 2 mol% is exceeded, the coating film may become very unstable.

(c) 중합성 불포화 화합물의 예로는 2-하이드록시 에틸(메트)아크릴레이트, 카프로락톤 (메트)아크릴레이트, 4-하이드록시 부틸 (메트)아크릴레이트, 디에틸렌 글리콜 (메트)아크릴레이트, 트리에틸렌 글리콜 (메트)아크릴레이트 등을 들 수 있다.(c) Examples of the polymerizable unsaturated compound include 2-hydroxy ethyl (meth) acrylate, caprolactone (meth) acrylate, 4-hydroxy butyl (meth) acrylate, diethylene glycol (meth) acrylate, tri Ethylene glycol (meth) acrylate etc. are mentioned.

이들 (c) 중합성 불포화 화합물 중에서도 특히 2-하이드록시 에틸 (메트)아크릴레이트가 바람직하다.Especially among these (c) polymerizable unsaturated compounds, 2-hydroxy ethyl (meth) acrylate is preferable.

본 발명에 있어서, (d) 중합성 불포화 화합물은 단독으로 사용할 수도 있고 또는 2종 이상을 혼합하여 사용할 수도 있다.In the present invention, the polymerizable unsaturated compound (d) may be used alone or in combination of two or more thereof.

공중합체에서 차지하는 (c) 중합성 불포화 화합물의 함유율은 0.05 내지 5몰%이다. 바람직하게는 0.1 내지 2몰%이다. 여기서, (d) 불포화 화합물의 함유율이 0.05% 미만인 경우에는 얻어지는 공중합체의 기재 접착력이 떨어지게 되고 경화 시 중합도가 떨어지게 되며, 5몰% 초과일 경우 바인더 자체의 뭉침 현상 등이 발생할 수 있다.
The content rate of (c) polymerizable unsaturated compound in a copolymer is 0.05-5 mol%. Preferably it is 0.1-2 mol%. Here, when the content of the unsaturated compound (d) is less than 0.05%, the substrate adhesive strength of the copolymer is lowered and the degree of polymerization is lowered during curing. When the content of the unsaturated compound is greater than 5 mol%, aggregation of the binder itself may occur.

(d) 중합성 불포화 화합물은 바인더의 물리적 특성 및 점도 특성에 영향을 주는 것으로, 그 예로는 데실 (메트)아크릴레이트(decyl (meth)acrylate), 라우릴 (메트)아크릴레이트(lauryl (meth)acrylate), 이소데실 (메트)아크릴레이트(Isodecyl (meth)acrylate), 스테아릴 (메트)아크릴레이트(stearyl (meth)acrylate), 옥틸 (메트)아크릴레이트(octyl (meth)acrylate), 미리스틸 (메트)아크릴레이트(myristyl (meth)acrylate), 세틸 (메트)아크릴레이트(cetyl (meth)acrylate) 등을 들 수 있다.(d) polymerizable unsaturated compounds affect the physical and viscosity properties of the binder, such as decyl (meth) acrylate, lauryl (meth) acrylate), isodecyl (meth) acrylate, stearyl (meth) acrylate, octyl (meth) acrylate, myristyl ( Meth) acrylate (myristyl (meth) acrylate), cetyl (meth) acrylate (cetyl (meth) acrylate) and the like.

이들 (d) 중합성 불포화 화합물 중에서도 특히 라우일 (메트)아크릴레이트(lauryl (meth)acrylate)가 바람직하다.Especially among these (d) polymerizable unsaturated compounds, lauryl (meth) acrylate is preferable.

공중합체에서 차지하는 (d) 중합성 불포화 화합물의 함유율은 0.1 내지 10몰%이다. 바람직하게는 0.1 내지 3몰%이다. 여기서, (d) 불포화 화합물의 함유율이 0.1% 미만인 경우에는 얻어지는 공중합체의 기재 접착력이 떨어지게 되고, 10몰% 초과일 경우 도막이 형성이 안 되거나 매우 소프트(soft)해질 수 있다.
The content rate of the (d) polymerizable unsaturated compound in a copolymer is 0.1-10 mol%. Preferably it is 0.1-3 mol%. Here, if the content of the unsaturated compound (d) is less than 0.1%, the substrate adhesive strength of the copolymer obtained is lowered, and if it is more than 10 mol%, the coating film may not be formed or may be very soft.

(e) 중합성 불포화 화합물의 예로는 2-Acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl) ethyl isocyanate 등을 들 수 있다.(e) Examples of the polymerizable unsaturated compound include 2-Acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and the like.

이들 (e) 중합성 불포화 화합물 중에서도 특히 2-methacryloyloxyethyl isocyanate가 바람직하다.Among these (e) polymerizable unsaturated compounds, 2-methacryloyloxyethyl isocyanate is particularly preferable.

공중합체에서 차지하는 (e) 중합성 불포화 화합물의 함유율은 0.04 내지 4몰%이다. 바람직하게는 0.07 내지 1몰%이다. 여기서, (e) 불포화 화합물의 함유율이 0.04% 미만인 경우에는 얻어지는 공중합체의 경화속도, 접착력, 표면조도 등이 떨어지게 되고, 4몰% 초과일 경우 저장안정성이 떨어지며 도막이 매우 불안정(brittle)하게 된다.
The content rate of (e) polymerizable unsaturated compound in a copolymer is 0.04-4 mol%. Preferably it is 0.07-1 mol%. Here, when the content of the unsaturated compound (e) is less than 0.04%, the curing rate, adhesive strength, surface roughness, etc. of the copolymer obtained are lowered. When the content of the unsaturated compound is higher than 4 mol%, the storage stability is poor and the coating film becomes very unstable.

(e) 중합성 불포화 화합물이 첨가될 경우 기존에 비해 경화 속도가 향상되고, 유리, 금속, 수지 등의 기재에 대한 접착 강도 역시 현저하게 증가된다. 또한, 접착시 수축을 작게 하여 표면 조도를 향상시키는 이점이 있다.
(e) When the polymerizable unsaturated compound is added, the curing rate is improved compared with the conventional one, and the adhesive strength to substrates such as glass, metal, and resin is also significantly increased. In addition, there is an advantage of improving the surface roughness by reducing the shrinkage during adhesion.

공중합체의 폴리스티렌 환산 중량 평균 분자량 (이하, 「Mw」라고 함)은 바람직하게는 50,000 내지 200,000, 더욱 바람직하게는 100,000 내지 150,000이다. 여기서, 분자량이 50,000 이하인 경우 기재와의 접착력이 떨어지게 된다.The polystyrene reduced weight average molecular weight (hereinafter, referred to as "Mw") of the copolymer is preferably 50,000 to 200,000, more preferably 100,000 to 150,000. Here, when the molecular weight is 50,000 or less, the adhesive strength with the substrate is lowered.

또한, 공중합체의 Mw와 폴리스티렌 환산 수평균 분자량 (이하, 「Mn」이라고 함)과의 비율 (Mw/Mn)은 통상적으로 1.0 내지 5.0, 바람직하게는 1.0 내지 3.0이다.
Moreover, the ratio (Mw / Mn) of Mw of a copolymer and polystyrene conversion number average molecular weight (henceforth "Mn") is 1.0-5.0 normally, Preferably it is 1.0-3.0.

공중합체는 (a) 중합성 불포화 화합물, (b) 중합성 불포화 화합물, (c) 중합성 불포화 화합물, (d) 중합성 불포화 화합물, (e) 중합성 불포화 화합물을 예를 들어 적당한 용제 중에서 라디칼 중합 개시제의 존재 하에 중합함으로써 제조할 수 있다.The copolymer may be (a) a polymerizable unsaturated compound, (b) a polymerizable unsaturated compound, (c) a polymerizable unsaturated compound, (d) a polymerizable unsaturated compound, or (e) a polymerizable unsaturated compound, for example, in a suitable solvent. It can manufacture by superposing | polymerizing in presence of a polymerization initiator.

상기 중합에 사용되는 용제의 예로는 톨루엔, PGMEA(Propylene Glycol Monomethyl Ether Acetate), 에틸 아세테이트(ethyl acetate), 부틸 아세테이트(butyl acetate), 아세톤(acetone), 메탄올(methanol), 부틸 카비톨(butyl carbitol), 부틸 카비톨 아세테이트(butyl carbitol acetate), 테르피네올(terpineol) 등을 사용할 수 있다.Examples of the solvent used for the polymerization include toluene, Propylene Glycol Monomethyl Ether Acetate (PGMEA), ethyl acetate, butyl acetate, acetone, methanol, methanol, butyl carbitol ), Butyl carbitol acetate, terpineol and the like can be used.

이들 용제는 단독으로 사용할 수도 있고 또는 2종 이상을 혼합하여 사용할 수도 있다.
These solvents may be used alone or in combination of two or more thereof.

상기 라디칼 중합 개시제의 예로는 2,2¡?-아조비스이소부티로 니트릴, 2,2¡?-아조비스(2,4-디메틸발레로니트릴), 2,2¡?-아조비스(4-메톡시-2,4-디메틸발레로니트릴) 등의 아조 화합물; 벤조일퍼옥시드, 라우로일퍼옥시드, t-부틸퍼옥시피발레이트, 1,1¡?-비스(t-부틸퍼옥시)시클로헥산 등의 유기 과산화물 또는 과산화수소 등을 들 수 있다. 라디칼 중합 개시제로서 과산화물을 사용하는 경우에는 환원제를 병용하여 산화 환원형 개시제로 할 수도 있다.
Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (4- Azo compounds such as methoxy-2,4-dimethylvaleronitrile); Organic peroxides, such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis (t-butyl peroxy) cyclohexane, hydrogen peroxide, etc. are mentioned. When using a peroxide as a radical polymerization initiator, it can also be set as a redox initiator by using a reducing agent together.

[실시예][Example]

바인더 수지로서 상기 화학식 1로 표시되는 아크릴 공중합체를 60중량% 포함하고, 접착제용 모노머로서 디사이클로펜타닐 (메트)아크릴레이트(dicyclopentanyl (meth)acrylate) 30 중량%, 경화촉진제로 덴드리틱 아크릴레이트 3중량%, 기타 첨가제로 소포제 및 분산제를 2중량%를 50℃에서 1시간 동안 교반하면서 용해한 다음, 광중합 개시제로 Ciba社의 Irgacure 651 5중량%를 첨가하여 광경화형 접착제 조성물을 제조하였다.
60 wt% of the acrylic copolymer represented by Formula 1 as the binder resin, 30 wt% of dicyclopentanyl (meth) acrylate as the monomer for the adhesive, dendritic acrylate as a curing accelerator 3 weight%, other weight defoamer and dispersant were dissolved by stirring at 50 ° C. for 1 hour at 50 ° C., and then 5% by weight of Irgacure 651 manufactured by Ciba was added as a photopolymerization initiator to prepare a photocurable adhesive composition.

[비교예][Comparative Example]

바인더 수지로서 하기 화학식 2로 표시되는 아크릴 공중합체를 60중량% 포함하고, 접착제용 모노머로서 디사이클로펜타닐 (메트)아크릴레이트 (dicyclopentanyl (meth)acrylate) 30중량%, 경화촉진제로 덴드리틱 아크릴레이트 3중량%, 기타 첨가제로 소포제 및 분산제를 2중량%를 50℃에서 1시간 동안 교반하면서 용해한 다음, 광중합 개시제로 Ciba社의 Irgacure 651 5중량%를 첨가하여 광경화형 접착제 조성물을 제조하였다.
60 wt% of an acrylic copolymer represented by Formula 2 as a binder resin, 30 wt% of dicyclopentanyl (meth) acrylate as a monomer for an adhesive, and a dendritic acrylate as a curing accelerator 3 weight%, other weight defoamer and dispersant were dissolved by stirring at 50 ° C. for 1 hour at 50 ° C., and then 5% by weight of Irgacure 651 manufactured by Ciba was added as a photopolymerization initiator to prepare a photocurable adhesive composition.

[화학식2](2)

Figure pat00002

Figure pat00002

접착력평가Adhesion Evaluation

바인더를 PET, PC, PMMA plate에 두께 20㎛ 이하로 코팅하여 아래 2가지 종류의 접착제를 사용하여 cross-cut tape test(ASTM D3359)를 실시하여 코팅층과 PET 필름, PC 필름, PMMA plate와의 접착성을 조사하여 아래의 [표 1]에 그 결과를 나타내었다.A binder is coated on PET, PC and PMMA plates with a thickness of 20 ㎛ or less and cross-cut tape test (ASTM D3359) is carried out using the following two types of adhesives to bond the coating layer with PET film, PC film and PMMA plate. Examining the results are shown in [Table 1] below.

#1 (PET film)# 1 (PET film) #2 (PC film)# 2 (PC film) #3 (PMMA plate)# 3 (PMMA plate) 본 발명 binderInvention binder 100%100% 100%100% 100%100% 비교군 binderComparative group binder 70%70% 65%65% 70%70%

외형변형평가External deformation evaluation

binder를 PET film에 두께 20㎛ 이하로 코팅하여 코팅 전후, PET film의 네 방향의 모서리 부분의 휨 정도를 측정하여 아래의 [표 2]에 그 결과를 나타내었다.The binder was coated on a PET film with a thickness of 20 μm or less, and before and after coating, the warpage degree of four corners of the PET film was measured, and the results are shown in [Table 2] below.

#1 (PET film)# 1 (PET film) 본 발명 binderInvention binder 2mm / 2mm / 1mm / 2mm2mm / 2mm / 1mm / 2mm 비교군 binderComparative group binder 2mm / 2mm / 3mm / 2mm2mm / 2mm / 3mm / 2mm

이에 따르면, 본 발명의 광경화성 접착제는 이소시아네이트기를 갖는 중합성 불포화 화합물을 더 포함함으로써 경화 속도의 향상, 기재에 대한 접착 강도 증가 및 체적수축 감소를 통한 표면조도 향상의 효과를 유도할 수 있다.According to this, the photocurable adhesive of the present invention may further include the polymerizable unsaturated compound having an isocyanate group, thereby inducing the effect of improving the curing rate, increasing the adhesive strength to the substrate, and improving the surface roughness by reducing the volume shrinkage.

Claims (13)

(a) 산성 관능기를 갖는 중합성 불포화 화합물,
(b) 환형 고리를 가지는 중합성 불포화 화합물,
(c) 하이드록시기를 가지는 중합성 불포화 화합물,
(d) 지방족(탄소 chain 4개 이상)을 가지는 중합성 불포화 화합물,
(e) 이소시아네이트기를 가지는 중합성 불포화 화합물을 포함하는 공중합체인 것을 특징으로 하는 광경화성 접착제.
(a) a polymerizable unsaturated compound having an acidic functional group,
(b) a polymerizable unsaturated compound having a cyclic ring,
(c) a polymerizable unsaturated compound having a hydroxyl group,
(d) polymerizable unsaturated compounds having aliphatic (4 or more carbon chains),
(e) It is a copolymer containing the polymerizable unsaturated compound which has an isocyanate group, The photocurable adhesive characterized by the above-mentioned.
제1항에 있어서,
상기 (a) 중합성 불포화 화합물은 (메트)아크릴산, 아크릴산 이합체, β-스티릴아크릴산, β-푸르푸릴아크릴산, 크로톤산, α-시아노신남산, 신남산, 말레산, 무수 말레산, 푸마르산, 시트라콘산, 메사콘산, 이타콘산 중 어느 하나 또는 둘 이상 혼합된 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
The (a) polymerizable unsaturated compound is (meth) acrylic acid, acrylic acid dimer, β-styryl acrylic acid, β-furfuryl acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, Photocurable adhesive, characterized in that any one or two or more of citraconic acid, mesaconic acid and itaconic acid are mixed.
제1항에 있어서,
상기 (a) 중합성 불포화 화합물은 0.02 내지 2몰%인 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
(A) The polymerizable unsaturated compound is a photocurable adhesive, characterized in that 0.02 to 2 mol%.
제1항에 있어서,
상기 (b) 중합성 불포화 화합물은 테트라하이드로 퍼퓨릴 (메트)아크릴레이트, 이소보닐 (메트)아크릴레이트, 2-메틸사이클로헥실(메트)아크릴레이트, 테트라하이드로퍼퓨란-3-일 (메트)아크릴레이트, 퍼퓨릴 (메트)아크릴레이트, 이소보닐 에톡시 (메트)아크릴레이트(isobornyl ethoxy (meth)acrylate), 2-페닐에틸 (메트)아크릴레이트(2-phenylethyl (meth)acrylate), 디사이클로펜타닐 (메트)아크릴레이트(dicyclopentanyl (meth)acrylate), 디사이클로펜타닐 에테르 (메트)아크릴레이트(dicyclopentenyl ether (meth)acrylate), 에틸렌 글리콜 디사이클로펜타닐 에테르 (메트)아크릴레이트(Ethylene glycol dicyclopentenyl ether (meth)acrylate) 중 어느 하나 또는 둘 이상 혼합된 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
The (b) polymerizable unsaturated compound is tetrahydro perfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tetrahydroperfuran-3-yl (meth) acrylic Latex, perfuryl (meth) acrylate, isobornyl ethoxy (meth) acrylate, 2-phenylethyl (meth) acrylate, dicyclopentanyl (Meth) acrylate (dicyclopentanyl (meth) acrylate), dicyclopentanyl ether (meth) acrylate (dicyclopentenyl ether (meth) acrylate), ethylene glycol dicyclopentanyl ether (meth) acrylate (Ethylene glycol dicyclopentenyl ether (meth) acrylate) or a mixture of two or more of the photocurable adhesive.
제1항에 있어서,
상기 (b) 중합성 불포화 화합물은 0.02 내지 2몰%인 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
(B) the polymerizable unsaturated compound is a photocurable adhesive, characterized in that 0.02 to 2 mol%.
제1항에 있어서,
상기 (c) 중합성 불포화 화합물은 2-하이드록시 (메트)아크릴레이트, 카프로락톤 (메트)아크릴레이트, 4-하이드록시 부틸 (메트)아크릴레이트, 디에틸렌 글리콜 (메트)아크릴레이트, 트리에틸렌 글리콜 (메트)아크릴레이트 중 어느 하나 또는 둘 이상 혼합된 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
The (c) polymerizable unsaturated compound is 2-hydroxy (meth) acrylate, caprolactone (meth) acrylate, 4-hydroxy butyl (meth) acrylate, diethylene glycol (meth) acrylate, triethylene glycol Photocurable adhesive, characterized in that any one or two or more of (meth) acrylates are mixed.
제1항에 있어서,
상기 (c) 중합성 불포화 화합물은 0.05 내지 5몰%인 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
Said (c) polymerizable unsaturated compound is 0.05-5 mol%, The photocurable adhesive characterized by the above-mentioned.
제1항에 있어서,
상기 (d) 중합성 불포화 화합물은 데실 (메트)아크릴레이트(decyl (meth)acrylate), 라우릴 (메트)아크릴레이트(lauryl (meth)acrylate), 이소데실 (메트)아크릴레이트(Isodecyl (meth)acrylate), 스테아릴 (메트)아크릴레이트(stearyl (meth)acrylate), 옥틸 (메트)아크릴레이트(octyl (meth)acrylate), 미리스틸 (메트)아크릴레이트(myristyl (meth)acrylate), 세틸 (메트)아크릴레이트(cetyl (meth)acrylate) 중 어느 하나 또는 둘 이상 혼합된 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
The polymerizable unsaturated compound (d) may be decyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate (Isodecyl (meth) acrylate), stearyl (meth) acrylate, octyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) Photocurable adhesive, characterized in that any one or two or more of (cetyl (meth) acrylate) mixed.
제1항에 있어서,
상기 (d) 중합성 불포화 화합물은 0.1 내지 10몰%인 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
(D) the polymerizable unsaturated compound is a photocurable adhesive, characterized in that 0.1 to 10 mol%.
제1항에 있어서,
상기 (e) 중합성 불포화 화합물은 2-Acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl) ethyl isocyanate 중 어느 하나 또는 둘 이상 혼합된 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
The polymerizable unsaturated compound (e) is a photocurable adhesive, characterized in that any one or two or more of 2-Acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate is mixed.
제1항에 있어서,
상기 (e) 중합성 불포화 화합물은 0.04 내지 4몰%인 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
(E) The polymerizable unsaturated compound is a photocurable adhesive, characterized in that 0.04 to 4 mol%.
제1항에 있어서,
상기 광경화성 접착제에는 용제로서 톨루엔, PGMEA(Propylene Glycol Monomethyl Ether Acetate), 에틸 아세테이트(ethyl acetate), 부틸 아세테이트(butyl acetate), 아세톤(acetone), 메탄올(methanol), 부틸 카비톨(butyl carbitol), 부틸 카비톨 아세테이트(butyl carbitol acetate), 테르피네올(terpineol) 중 적어도 하나 이상 포함되는 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
The photocurable adhesive may include toluene, PGMEA (Propylene Glycol Monomethyl Ether Acetate), ethyl acetate, ethyl acetate, butyl acetate, acetone, methanol, methanol, butyl carbitol, A photocurable adhesive comprising at least one of butyl carbitol acetate and terpineol.
제1항에 있어서,
상기 광경화성 접착제에는 라디칼 중합 개시제로서, 2,2¡?-아조비스이소부티로 니트릴, 2,2¡?-아조비스(2,4-디메틸발레로니트릴), 2,2¡?-아조비스(4-메톡시-2,4-디메틸발레로니트릴), 벤조일퍼옥시드, 라우로일퍼옥시드, t-부틸퍼옥시피발레이트, 1,1¡?-비스(t-부틸퍼옥시)시클로헥산, 과산화수소 중 적어도 하나 이상 포함되는 것을 특징으로 하는 광경화성 접착제.
The method of claim 1,
The photocurable adhesive includes 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis as a radical polymerization initiator. (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis (t-butylperoxy) cyclohexane Photocurable adhesive, characterized in that it comprises at least one or more of hydrogen peroxide.
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