KR20060055755A - Uv-crosslinkable acrylic pressure sensitive adhesives - Google Patents

Uv-crosslinkable acrylic pressure sensitive adhesives Download PDF

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KR20060055755A
KR20060055755A KR1020040094901A KR20040094901A KR20060055755A KR 20060055755 A KR20060055755 A KR 20060055755A KR 1020040094901 A KR1020040094901 A KR 1020040094901A KR 20040094901 A KR20040094901 A KR 20040094901A KR 20060055755 A KR20060055755 A KR 20060055755A
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sensitive adhesive
adhesive
pressure
acrylic
photoinitiator
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KR1020040094901A
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KR100659748B1 (en
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김현중
도현성
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재단법인서울대학교산학협력재단
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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
    • 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
    • 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
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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

Abstract

본 발명은 자외선 가교형 아크릴계 점착제에 관한 것으로, 특히 불포화기를 포함하는 벤조페논 유도체, 수소공여기를 포함하는 아크릴계 모노머, 및 점착고분자로 중합되는 최소한 하나 이상의 모노머 혼합물을 용액 중합하며, 생성된 공중합체를 자외선에 노출·가교하여 제조되는, 광중합효율이 개선된 자외선 가교형 아크릴계 점착제에 관한 것으로, 점착고분자 자체에 광개시제 및 수소공여체를 측쇄에 도입하여 점착제를 완성함으로써, 낮은 UV 조사량에도 혹은 단시간에 점착제 경화를 달성할 수 있어 생산성이 개선된 자외선 가교형 아크릴계 점착제를 제공하는 것이다.The present invention relates to an ultraviolet crosslinkable acrylic pressure sensitive adhesive, and in particular, solution copolymerization of at least one monomer mixture polymerized with a benzophenone derivative including an unsaturated group, an acrylic monomer including a hydrogen donor group, and an adhesive polymer, and a resulting copolymer. The present invention relates to an ultraviolet-ray cross-linked acrylic pressure-sensitive adhesive produced by exposing and cross-linking to ultraviolet rays, wherein the pressure-sensitive adhesive is prepared by introducing a photoinitiator and a hydrogen donor into the side chain in the adhesive polymer itself to complete the pressure-sensitive adhesive. It is possible to provide a UV cross-linking acrylic pressure-sensitive adhesive can be achieved by curing can be improved.

자외선, 가교형, 수소공여기, 광개시제, 점착제UV light, crosslinking type, hydrogen donating group, photoinitiator, adhesive

Description

자외선 가교형 아크릴계 점착제{UV-crosslinkable acrylic pressure sensitive adhesives} UV crosslinkable acrylic pressure sensitive adhesive {UV-crosslinkable acrylic pressure sensitive adhesives}             

도1은 본 발명에 따른 점착고분자 측쇄에 결합된 벤조페논 유도체 화학식을 도시한 것이다.Figure 1 shows the chemical formula of the benzophenone derivative bonded to the adhesive polymer side chain according to the present invention.

도2는 UV 조사에 따른 이중결합 변화도를 나타내는 FT-IR ATR 측정도를 도시한 것이며,Figure 2 shows the FT-IR ATR measurement showing the degree of change in the double bond according to the UV irradiation,

도3 및 도4는 UV 조사에 따른 이중결합 변화량을 도시한 것이며,3 and 4 show the amount of double bond changes according to UV irradiation,

도5 및 도6은 UV 조사에 따른 겔함량 변화를 도시한 것이며,5 and 6 show the gel content change according to the UV irradiation,

도7 및 도8은 UV 조사에 따른 프로브 택 변화를 도시한 것이며,7 and 8 show the change in probe tack according to the UV irradiation,

도9 및 도10은 UV 조사에 따른 접착력 변화를 도시한 것이며,9 and 10 show the change in adhesion force according to the UV irradiation,

도11 및 도12는 UV 조사에 따른 SAFT 변화를 도시한 것이다.11 and 12 show changes in SAFT according to UV irradiation.

본 발명은 자외선 가교형 아크릴계 점착제에 관한 것으로, 특히 불포화기를 포함하는 벤조페논 유도체, 수소공여기를 포함하는 아크릴계 모노머, 및 점착고분자로 중합되는 최소한 하나 이상의 모노머 혼합물을 용액 중합하며, 생성된 공중합체를 자외선에 노출·가교하여 제조되는, 광중합효율이 개선된 자외선 가교형 아크릴계 점착제에 관한 것이다.The present invention relates to an ultraviolet crosslinkable acrylic pressure sensitive adhesive, and in particular, solution copolymerization of at least one monomer mixture polymerized with a benzophenone derivative including an unsaturated group, an acrylic monomer including a hydrogen donor group, and an adhesive polymer, and a resulting copolymer. The present invention relates to an ultraviolet-ray crosslinkable acrylic pressure-sensitive adhesive produced by exposing and crosslinking to ultraviolet rays, wherein the photopolymerization efficiency is improved.

점착제(pressure sensitive adhesives, PSA)는 테이프, 라벨, 의학용품 등과 같은 다양한 산업분야에서 사용되고 있다. 점착제는 점탄성 물질로 구성되어 있기 때문에 택(tack), 접착력(peel strength), 응집력(shear strength)의 방법으로 물성이 측정되는 반고상의 물질특성을 보인다. 점착제를 구성하는 원료 가운데서 아크릴계 모노머(monomer)를 사용하여 중합한 것은 충분한 응집력을 나타내기에는 분자량이 그다지 높지 않으므로 응용되는 점착제 대부분의 경우 화학적인 가교가 필요하다. 점착제의 가교 방법 중 UV에 의한 경화방법이 경제성과 환경적인 이점으로 최근 활발한 연구가 진행되고 있다. Pressure sensitive adhesives (PSA) are used in a variety of industries such as tapes, labels, medical supplies and the like. Since the pressure-sensitive adhesive is composed of a viscoelastic material, the physical properties of the adhesive are measured by the method of tack, peel strength, and shear strength. Polymerization using an acrylic monomer among the raw materials constituting the pressure-sensitive adhesive is not high enough to exhibit sufficient cohesion, so most of the applied pressure-sensitive adhesives require chemical crosslinking. UV curing among the crosslinking method of the pressure-sensitive adhesive is an active research in recent years due to economic and environmental advantages.

점착제 가교 UV 경화기술은 UV 중합과 UV 가교 방법으로 나누어질 수 있다. UV 중합형 점착제는 올리고머(oligomer), 모노머(monomer), 점착부여수지(tackifier), 광개시제(photoinitiator)로 구성되며 승온된 반응기 안에서 블렌딩(blending)되어 다양한 종류의 기재(PVC, PET, PE, 종이 등)에 코팅된 형태로 UV 조사를 통해 고분자로 중합된다. 한편, UV 가교형 점착제는 광개시제가 점착제의 고분자 사슬내부에 직접 중합되어 있어 추가적인 광개시제의 투여없이 바로 기재에 코팅하여 UV 조사를 통해 가교를 이룰 수 있다. 종래 공개된 자외선 가교형 아크릴계 점착제는 상당 UV 조사량을 통하여 가교되는 점착제이므로, 광 가교효율이 개선된 아크릴계 점착제 개발의 필요성이 대두되고 있다.Adhesive crosslinking UV curing technology can be divided into UV polymerization and UV crosslinking method. UV polymerized adhesives consist of oligomers, monomers, tackifiers, and photoinitiators, and are blended in a heated reactor to produce various types of substrates (PVC, PET, PE, paper). And the like to polymerize the polymer through UV irradiation. On the other hand, the UV cross-linked pressure-sensitive adhesive can be directly cross-polymerized through UV irradiation by coating the photoinitiator directly polymerized inside the polymer chain of the pressure-sensitive adhesive without the administration of additional photoinitiator. Since the UV crosslinkable acrylic pressure sensitive adhesive disclosed in the related art is crosslinked through a significant amount of UV radiation, there is a need for developing an acrylic pressure sensitive adhesive having improved light crosslinking efficiency.

본 발명의 목적은 광 가교효율이 개선된 자외선 가교형 점착제를 제공하는 것이며, 그러므로 점착제 가공시 생산성이 향상된 자외선 가교형 점착제를 공개하는 것이다.
SUMMARY OF THE INVENTION An object of the present invention is to provide an ultraviolet crosslinked pressure-sensitive adhesive having improved light crosslinking efficiency, and thus to disclose an ultraviolet crosslinked pressure-sensitive adhesive having improved productivity in adhesive processing.

상기 목적은 불포화기를 포함하는 벤조페논 유도체, 수소공여기를 포함하는 아크릴계 모노머, 및 점착고분자로 중합되는 최소한 하나 이상의 모노머 혼합물을 용액 중합하며, 생성된 공중합체를 자외선에 노출시켜 가교하여 제조되는, 광중합효율이 개선된 자외선 가교형 아크릴계 점착제에 의하여 달성된다. 이하 구체적으로 설명하고자 한다.The above object is prepared by solution polymerization of a benzophenone derivative including an unsaturated group, an acrylic monomer including a hydrogen donor group, and at least one monomer mixture polymerized with an adhesive polymer, and crosslinking by exposing the resulting copolymer to ultraviolet rays. It is achieved by an ultraviolet crosslinked acrylic pressure-sensitive adhesive with improved photopolymerization efficiency. It will be described in detail below.

본 발명에서의 정의된 '점착고분자'는 점착성능을 보이는 모노머 중합체이며, 바람직하게는 아크릴계 고분자이며, '점착제'는 상기 점착고분자와 더욱 중합된 광개시제 및 수소탈환능을 촉진시키는 모노머가 더더욱 중합된 점착고분자를 언급하는 것이다.The 'adhesive polymer' as defined in the present invention is a monomer polymer showing adhesive performance, preferably an acrylic polymer, and the 'adhesive' is a polymerized photoinitiator and a monomer that promotes hydrogen desorption ability. It refers to adhesive polymers.

본 발명에서 점착고분자와 중합되는 광개시제는 점착고분자 사슬내부에 중합되어야 하므로, 불포화기를 포함하며, 바람직하게는 4-acryloyloxy benzophenone(ABP), O-acryloyle acetophenone oxime(AAPO) 등 불포화기를 포함하는 벤조페논 유도체를 사용할 수 있다. 상기 고분자 측쇄에 결합되는 광개시제, 특히 ABP는 불포화기(C=C 이중결합) 및 벤조페논(benzophenone;광 개시 성분)으로 구성되므로 점착고분자를 구성하는 아크릴 모노머와 공중합이 가능하고, 따라서 점착고분자의 측쇄에 도1에 도시된 바와 같이 벤조페논기가 부여된 형태를 이루고 있다. 따라서, 점착제 측쇄의 벤조페논기는 UV 조사시 수소공여기를 포함하는 아크릴계 모노머로부터 수소를 탈환하는 과정에서 가교가 이루어진다. 바람직한 광개시제 조성은 점착고분자 100 중량부에 대하여 0.5 내지 2 중량부 투여된다. In the present invention, since the photoinitiator to be polymerized with the adhesive polymer should be polymerized in the adhesive polymer chain, it contains an unsaturated group, preferably 4-acryloyloxy benzophenone (ABP), O-acryloyle acetophenone oxime (AAPO) containing a benzophenone Derivatives can be used. The photoinitiator, especially ABP, bound to the polymer side chain is composed of an unsaturated group (C = C double bond) and benzophenone (benzophenone; photoinitiating component), so that it is copolymerizable with an acrylic monomer constituting the adhesive polymer, and thus As shown in FIG. 1, the side chain has a benzophenone group. Therefore, the benzophenone group of the pressure-sensitive adhesive side chain is crosslinked in the process of recapture of hydrogen from an acrylic monomer including a hydrogen donor group during UV irradiation. Preferred photoinitiator composition is administered 0.5 to 2 parts by weight based on 100 parts by weight of the adhesive polymer.

한편, 여기된 광개시제로 수소를 공여함으로써 광 가교효율이 향상될 수 있으며, 따라서 가교효율은 수소공여기를 포함하는 아크릴계 모노머에 의해 촉진되며, 상기 수소공여기를 포함하는 아크릴계 모노머는 점착고분자 측쇄에 중합될 수 있다. 따라서, 본 발명에 의한 점착제의 광 가교효율 촉진은 점착고분자와 중합된 수소공여기를 포함하는 아크릴계 모노머에 의해 달성될 수 있다. 상기 수소공여기는 하이드록시(hydroxy, -OH), 에테르(ether), 아민(amine)기를 포함할 수 있으며, 특히 바람직하게는 2-hydroxyethyl methacrylate (2-HEMA)를 선택할 수 있다. 바람직한 모노머 조성은 점착고분자 100 중량부에 대하여 3 내지 6 중량부 첨가되는 것이다.On the other hand, the light crosslinking efficiency can be improved by donating hydrogen with the excited photoinitiator, and thus the crosslinking efficiency is promoted by an acryl-based monomer including a hydrogen donor group, and the acryl-based monomer including the hydrogen donor group is attached to the adhesive polymer side chain. Can be polymerized. Therefore, the optical crosslinking efficiency of the pressure-sensitive adhesive according to the present invention can be achieved by an acrylic monomer containing a pressure-sensitive adhesive polymer and a hydrogen donor group polymerized. The hydrogen donating group may include a hydroxy (hydroxy, -OH), ether (ether), amine (amine) group, particularly preferably 2-hydroxyethyl methacrylate (2-HEMA) can be selected. The preferred monomer composition is 3 to 6 parts by weight based on 100 parts by weight of the adhesive polymer.

따라서 본 발명의 목적은 낮은 UV 조사량에서 경화가 빠르게 이루어지는 UV 가교형 아크릴 점착제를 제공하는 것이며, 상기 점착제는 점착고분자에 중합가능한 광개시제 및 상기 광개시제에 수소를 공여하며 점착고분자에 중합가능한 모노머를 포함한다.Accordingly, an object of the present invention is to provide a UV cross-linked acrylic pressure-sensitive adhesive that is cured at a low UV irradiation rate, wherein the pressure-sensitive adhesive comprises a photoinitiator polymerizable to the adhesive polymer and a monomer that is capable of donating hydrogen to the photoinitiator and polymerizing the adhesive polymer. .

이하 실시예에 의하여 상세히 설명한다.It will be described in detail by the following examples.

점착능력을 나타내는 다양한 점착고분자를 대상할 수 있으나, 바람직하게는 2-에틸헥실 아크릴레이트(2-EHA), 비닐아세테이트(VAc), 및 아크릴산(AA)으로 구성되는 아크릴계 점착고분자를 선택하며, 상기 고분자와 중합될 수 있는 수소공여기를 포함하는 모노머로서 2-하이드록시에틸메타그릴레이트(2-HEMA), 및 광개시제로서 불포화 벤조페논 유도체(P-36)를 사용하여 용액 중합을 통하여 합성하고, 2-HEMA와 P-36의 함량을 변화시키면서 점착제의 경화거동은 FT-IR ATR을 사용하여 관찰하고 접착물성은 UV 조사량에 따라 택(tack), 접착력(peel strength), SAFT(shear adhesion failure temperature)의 방법을 사용하여 관찰하였다.Although it can target a variety of adhesive polymers exhibiting the adhesive ability, it is preferable to select an acrylic adhesive polymer consisting of 2-ethylhexyl acrylate (2-EHA), vinyl acetate (VAc), and acrylic acid (AA), Synthesized through solution polymerization using 2-hydroxyethyl methacrylate (2-HEMA) as a monomer containing a hydrogen donor group capable of polymerization with a polymer, and an unsaturated benzophenone derivative (P-36) as a photoinitiator, The curing behavior of the adhesive was observed using FT-IR ATR while varying the contents of 2-HEMA and P-36, and the adhesive properties were tack, peel strength and shear adhesion failure temperature depending on the UV irradiation dose. Observation using the method of).

2-ethylhexyl acrylate(2-EHA), vinyl acetate(VA), acrylic acid (AA), 2-hydroxyethyl methacrylate (2-HEMA), benzophenone 유도체(P-36)를 사용하여 2-HEMA와 P-36의 함량을 변화시키면서 용액 중합법을 통해 UV 가교형 아크릴 점착제 를 합성하였다. 2-HEMA and P-36 using 2-ethylhexyl acrylate (2-EHA), vinyl acetate (VA), acrylic acid (AA), 2-hydroxyethyl methacrylate (2-HEMA), and benzophenone derivatives (P-36) UV cross-linking acrylic pressure-sensitive adhesive was synthesized by solution polymerization while varying the content.

실시예 1.Example 1.

UV 가교형 아크릴 점착제 합성에 사용된 2-EHA, VAc, AA, 2-HEMA는 Junsei Chemcals에서 공급받아 별도의 정제없이 사용하였다. 불포화 벤조페논 유도체(P-36)은 SK UCB에서 공급받아 사용하였다. UV 가교형 아크릴 점착제는 고형분 50%로 에틸아세테이트를 용제로 사용하여 500ml 4구 플라스크에 2-EHA, VAc, AA , 2-HEMA, P-36을 혼합하여 heating mantle에서 6시간동안 80℃에서 합성하였다. 점착제의 합성 성분조건은 표 1과 같다.2-EHA, VAc, AA, 2-HEMA used for the synthesis of UV crosslinkable acrylic pressure-sensitive adhesive was supplied from Junsei Chemcals and used without further purification. Unsaturated benzophenone derivative (P-36) was supplied from SK UCB. UV crosslinkable acrylic pressure sensitive adhesive was synthesized at 80 ℃ for 6 hours in heating mantle by mixing 2-EHA, VAc, AA, 2-HEMA, P-36 in 500ml four-necked flask using 50% solids ethyl acetate as solvent. It was. Synthetic composition conditions of the pressure-sensitive adhesive is shown in Table 1.

표 1. 점착제 조성Table 1. Adhesive composition

CodeCode 2-EHA (wt%)2-EHA (wt%) VAc (wt%)VAc (wt%) AA (wt%)AA (wt%) 2-HEMA (phr)2-HEMA (phr) P-36 (phr)P-36 (phr) SH0P1SH0P1 8080 1515 55 00 1One SH3P1SH3P1 8080 1515 55 33 1One SH6P1SH6P1 8080 1515 55 66 1One SH9P1SH9P1 8080 1515 55 99 1One SH3P05SH3P05 8080 1515 55 33 0.50.5 SH3P2SH3P2 8080 1515 55 33 22

UV 가교형 아크릴 점착제는 코로나 처리된 PET 필름(두께 25㎛, SK Chemical)에 26번 코팅 (K-26 bar)바로 실온에서 코팅한 후 80℃에서 1시간동안 건조시켰다. 건조된 필름은 테스트 전 22℃, 60%에서 24시간동안 보관한 후 고압수은램프(100W/cm2 : 주파장대 365nm)가 장착된 컨베이어벨트타입의 UV 경화장치에서 조 사량을 0, 210, 630, 1050, 1470, 1890, 2310, 2730 mJ/cm2으로 변화시키면서 경화시켰다. 제조된 점착제에 대한 측정방법은 다음과 같다.UV cross-linked acrylic pressure-sensitive adhesive was coated on a corona treated PET film (thickness 25㎛, SK Chemical) 26 times (K-26 bar) immediately at room temperature and then dried at 80 ℃ for 1 hour. The dried film was stored at 22 ° C and 60% for 24 hours before testing, and then the irradiation amount was 0, 210, 630 in a conveyor belt type UV curing machine equipped with a high-pressure mercury lamp (100W / cm 2 : 365nm wavelength band). , 1050, 1470, 1890, 2310, 2730 mJ / cm 2 was cured while changing. The measurement method for the prepared pressure-sensitive adhesive is as follows.

1) FT-IR ATR 측정 : UV 조사량에 따른 IR 스펙트럼을 관찰하기 위해 ATR이 장착된 Nicolet Magna 550 Series II FT-IR (Midac Co.,USA)로 IR 스펙트럼을 관찰하였다. 1) FT-IR ATR Measurement: In order to observe the IR spectrum according to the UV irradiation dose, the IR spectrum was observed by Nicolet Magna 550 Series II FT-IR equipped with ATR (Midac Co., USA).

2) 겔 함량 : UV 조사량을 변화시키면서 제조된 점착제 샘플은 톨루엔에 넣고 40℃에서 4일간 보관한 뒤 일정한 중량에 이를 때까지 건조하여 다음 식으로 계산하였다. Wt는 톨루엔 침투 후 무게, W0은 침투 전 무게이다. 2) Gel content : The pressure-sensitive adhesive sample prepared while changing the UV irradiation amount was put in toluene and stored for 4 days at 40 ℃ and dried until a constant weight was calculated by the following equation. W t is the weight after toluene penetration and W 0 is the weight before penetration.

Gel contents (%) = (Wt / W0)×100 Gel contents (%) = (W t / W 0 ) × 100

3) 접착 물성 : 접착 물성은 프로브 택(probe tack), 180°접착력(180°peel strength), SAFT(shear adhesion failure temperature) 방법으로 측정한다. 택과 접착력 테스트는 texture analyzer (Stable Micro Systems, TA-XT2i)를 이용하였다. 지름 5mm의 원통형 스테인리스스틸 프로브를 박리속도 0.5mm/sec 일정한 압력 100gf/cm2 하에 프로브 택을 측정하였고 접착력은 180ㅀ 각도에서 crosshead 속도를 300 mm/min로 하여 측정하였다. SAFT(shear adhesion failure temperature)는 점착제 샘플을 SUS 판에 25mm x 25mm의 면적으로 붙인 뒤 2kg 고무롤러로 두 번 압착한 뒤 1kg의 추를 끝에 매달고 분당 0.4℃씩 승온시키면서 점착제 샘플이 SUS에서 떨 어지는 온도를 측정하였다. 통상 가교되지 않거나 수소결합만으로 가교된 아크릴 점착제는 고온에서 응집력이 급격하게 감소하므로 화학적인 가교를 통해 고온에서도 높은 응집력을 나타내도록 하고 있다. 점착제의 응집력은 동적 혹은 정적 방법으로 측정된다. 정적인 방법은 일정한 온도에서 테스트 기재에 붙어있는 점착 샘플을 일정한 하중을 주어 기재에서 점착 샘플이 떨어지는 시간을 측정하지만 동적인 방법인 SAFT는 온도를 상승시키면서 테스트 기재에 붙어있는 점착 샘플에 일정하중을 주어 떨어지는 온도를 측정하는 방법이다.3) Adhesion Properties : Adhesion properties are measured by probe tack, 180 ° peel strength, and SAFT (shear adhesion failure temperature) method. Tack and adhesion tests were performed using a texture analyzer (Stable Micro Systems, TA-XT2i). Cylindrical stainless steel probes with a diameter of 5 mm were measured at a probe tack of 0.5 mm / sec at a constant pressure of 100 g f / cm 2 , and the adhesive force was measured at a crosshead speed of 300 mm / min at 180 ° angle. SAFT (shear adhesion failure temperature) is a sample of 25mm x 25mm attached to the SUS plate and pressed twice with a 2kg rubber roller, and then the adhesive sample drops from the SUS while hanging the 1kg weight at the end and raising the temperature by 0.4 ℃ per minute. The temperature was measured. Usually, the acrylic pressure-sensitive adhesive which is not crosslinked or crosslinked only by hydrogen bonds has a high decrease in cohesion at high temperature, and thus high cohesion at high temperature through chemical crosslinking. Cohesion of the pressure-sensitive adhesive is measured by a dynamic or static method. The static method gives a constant load on the adhesive sample attached to the test substrate at a constant temperature to measure the time when the adhesive sample falls from the substrate.However, the dynamic method SAFT increases the temperature and applies a constant load to the adhesive sample attached to the test substrate. It is a way to measure the falling temperature.

1. FT-IR ATR 측정 결과 및 해석1.FT-IR ATR Measurement Results and Interpretation

도2에 SH3P2의 점착제 샘플에 조사량이 0, 2730mJ/cm2일 FT-IR ATR 측정도가 도시된다. 광개시제로 중합된 벤조페논의 벤젠 고리의 C=C 이중결합 피크(peak)가 소멸되는 것을 나타내었다. 이것은 벤조페논의 C=O기가 UV 조사량이 증가할수록 주변의 수소를 탈환하여 벤조페논의 벤젠 고리의 C=C 이중결합의 공액(conjugation)이 사라졌기 때문에 나타나는 현상이다. 특히, 수소공여체로서 하이드록시(hydroxy)를 가지는 2-HEMA가 중합체에 포함되어 있어 벤조페논의 벤젠 고리의 C=C 이중결합 소멸 속도가 빠르게 진행된다. Figure 2 shows the FT-IR ATR measurement of 0, 2730mJ / cm 2 irradiation amount to the pressure-sensitive adhesive sample of SH3P2. It was shown that the C = C double bond peak of the benzene ring of benzophenone polymerized with the photoinitiator disappears. This phenomenon occurs because the conjugation of the C = C double bond of the benzene ring of benzophenone disappears as the C = O group of the benzophenone increases the amount of UV irradiation. In particular, 2-HEMA having a hydroxy (hydroxy) as a hydrogen donor is included in the polymer, so the rate of C = C double bond disappearance of the benzene ring of benzophenone proceeds rapidly.

UV 조사량에 따른 벤조페논의 C=C 이중결합의 농도는 1585~1600/cm-1 사이의 면적을 적분하여 계산이 가능하고 이의 결과를 도3 및 도4에 나타내었다. 도3은 UV 조사량이 증가함에 따라 2-HEMA의 함유량이 다른 SH3P1과 SH0P1의 벤조페논의 C=C 이중결합의 상대농도 변화를 나타낸 것이다. UV 조사 초기에는 SH3P1의 C=C 이중결합 농도가 급격하게 증가하다가 UV 조사량이 630mJ/cm2을 초과한 후에는 C=C 이중결합의 감소속도에 차이가 없어지는 현상을 나타내었다. 이는 SH3P1에 hydroxy기가 있는 2-HEMA로부터 벤조페논이 수소를 더 잘 탈환하기 때문이다. 도4에는 광개시제 농도의 증가에 따른 UV 조사량의 영향을 나타낸 것이다. UV 조사 초기에는 SH3P2의 벤조페논의 C=C 이중결합의 소멸속도가 SH3P1보다 빠른 현상을 나타내었다. 이는 광개시제의 농도가 증가할수록 경화속도가 증가한다고 해석된다. 한편, 초기에는 반응속도가 광개시제의 농도가 증가함에 따라 증가하지만 나중에는 그 감소속도가 비슷하게 된다는 것을 알 수 있다.The concentration of C = C double bond of benzophenone according to the UV irradiation amount can be calculated by integrating the area between 1585 ~ 1600 / cm -1 and the results are shown in FIGS. 3 and 4. Figure 3 shows the change in the relative concentration of C = C double bonds of the benzophenone of SH3P1 and SH0P1 with different 2-HEMA content as the UV irradiation amount increases. In the early stage of UV irradiation, the C = C double bond concentration of SH3P1 increased rapidly, but after the UV irradiation amount exceeded 630mJ / cm 2 , there was no difference in the decrease rate of C = C double bond. This is because benzophenone better recaptures hydrogen from 2-HEMA having a hydroxy group in SH3P1. Figure 4 shows the effect of the UV irradiation amount with the increase of the photoinitiator concentration. At the initial stage of UV irradiation, the disappearance rate of C = C double bond of benzophenone of SH3P2 was faster than that of SH3P1. It is interpreted that the curing rate increases as the concentration of the photoinitiator increases. On the other hand, the reaction rate initially increases as the concentration of the photoinitiator increases, but later it can be seen that the decrease rate is similar.

따라서, 광개시제 포함 및/또는 수소공여기가 있는 모노머를 포함하는 점착제는 광 가교효율이 그렇지 않은 경우보다 높다고 판단할 수 있다.Therefore, the pressure-sensitive adhesive containing a photoinitiator and / or a monomer having a hydrogen donor group can be determined that the photo-crosslinking efficiency is higher than otherwise.

2. 겔 함량 측정 결과2. Gel content measurement result

합성된 점착제 고분자 사슬에는 UV 가교가 가능하도록 벤조페논이 측쇄에 존재하고 있어서 UV가 조사되면 가교반응이 일어나게 된다. 따라서 겔 함량이 늘어났다는 것은 가교반응이 진행되어서 형성된 고분자 망상구조가 용제에 용해되지 않으므로 이의 양을 측정하면 점착제의 가교정도를 측정할 수 있다.In the synthesized pressure-sensitive adhesive polymer chain, benzophenone is present in the side chain so that UV crosslinking is possible. Therefore, the increased gel content means that the cross-linking reaction proceeds, so that the polymer network structure is not dissolved in the solvent, so that the degree of crosslinking of the pressure-sensitive adhesive can be measured by measuring the amount thereof.

도5는 UV 조사량에 따른 SH0P1, SH3P1, SH9P1의 겔함량의 변화를 나타낸 것 이다. UV 조사전에는 모든 샘플의 겔함량이 0%였으나, 2310mJ/cm2의 조사량에서는 60%로 증가하였다. 하지만 SH9P1은 UV 조사량이 210mJ/cm2에서의 겔함량이 SH0P1보다 3배가량 더 높았다. 이것은 수소공여기를 가지는 모노머가 상대적으로 많이 포함된 SH9P1의 가교반응속도가 SH0P1보다 빠르다는 것을 의미하는 것으로 FT-IR ATR 결과와도 일치한다. 겔 함량에 대한 광개시제의 농도의 영향을 도6에 나타내었다. 광개시제의 농도가 증가할수록 광중합속도가 증가하게 된다는 상기 FT-IR ATR 측정결과는 겔 함량의 결과에서도 동일하게 나타났는데 벤조페논의 함량이 높은 SH3P2가 SH3P1보다 낮은 조사량에서도 더 높은 겔 함량을 보여주고 조사량이 높을 때도 겔 함량이 높게 나타난다. SH9P1과 SH3P2의 결과를 비교하여 볼 때 SH9P1의 겔 함량이 UV 조사량이 210mJ/cm2일 때 더 높은 값을 보여주는 것으로 2-HEMA의 하이드록시기에 의한 영향이 광개시제에 의한 영향보다 높음을 알 수 있다. Figure 5 shows the change in the gel content of SH0P1, SH3P1, SH9P1 according to the UV irradiation dose. Before UV irradiation, the gel content of all samples was 0%, but increased to 60% at a dose of 2310mJ / cm 2 . However, SH9P1 had 3 times higher gel content at 210mJ / cm 2 UV radiation than SH0P1. This means that the crosslinking reaction rate of SH9P1 containing a relatively large number of hydrogen donor groups is faster than that of SH0P1, which is consistent with the FT-IR ATR results. The effect of the concentration of photoinitiator on the gel content is shown in FIG. 6. The FT-IR ATR measurement results showed that the photopolymerization rate increased as the concentration of the photoinitiator increased. The same result was found in the gel content. The SH3P2 having a high benzophenone content showed a higher gel content even at a lower dose than the SH3P1. The gel content is also high when this is high. Compared with the results of SH9P1 and SH3P2, the gel content of SH9P1 shows higher value when UV irradiation dose is 210mJ / cm2, indicating that the effect of hydroxyl group of 2-HEMA is higher than that of photoinitiator. .

3. 접착 물성 측정 결과3. Result of adhesive property measurement

3.1 택 (Tack)3.1 Tack

도7은 UV 조사량을 변화시키면서 2-HEMA의 함량변화에 따른 프로브 택(probe tack)의 변화를 보여준 것이다. SH0P1, SH3Pl, SH6Pl, SH9Pl의 택은 UV 조사량이 210mJ/㎠일 때 급격히 감소하지만 630mJ/cm2을 초과하면 조금씩 줄어드는 경향을 나타내었다. 2-HEMA의 함량에 따른 초기 택 감소를 살펴보고자 UV 조사전의 프로브 택값과 조사량이 210mJ/cm2일 때의 값을 다음 수식을 이용하여 감소폭을 계산하였다. Figure 7 shows the change in probe tack with the change in the amount of 2-HEMA while varying the UV irradiation amount. The tack of SH0P1, SH3Pl, SH6Pl, and SH9Pl decreased rapidly when the UV irradiation amount was 210 mJ / cm 2 , but decreased slightly when exceeding 630 mJ / cm 2 . In order to examine the initial tack reduction according to the content of 2-HEMA, the reduction width was calculated using the following equation using the probe tack value before UV irradiation and the value when the dose was 210mJ / cm 2 .

Figure 112004053845317-PAT00001
Figure 112004053845317-PAT00001

SH0P1, SH3Pl, SH6Pl, SH9Pl의 감소폭은 각각 0.56%, 7.23%, 8.38%, 11.81%로 나타나 2-HEMA의 함량이 많은 점착제의 택이 초기 UV 조사량에 따라 급격하게 감소하는 결과를 나타냈다. 이는 2-HEMA의 함량이 많을수록 초기 UV 조사에서 가교 반응이 빠르게 진행되어 분자의 유동성이 감소하여 택을 감소시킨 것으로 상기 FT-IR ATR 및 겔 함량의 결과와도 일치한다. 또한, 광개시제의 농도가 높은 SH3P2는 SH3P05보다 UV 조사량이 낮아도 반응이 빠르게 일어나서 분자의 움직임을 빠르게 감소시키므로 UV 조사 전후 택의 감소 폭이 커진다. 이러한 결과는 도8에 도시되며 광개시제의 함량이 적은 SH3P05는 210mJ/cm2일 때 1.15% 감소한 반면 SH3P2는 15.68% 감소하였다.The reductions of SH0P1, SH3Pl, SH6Pl, and SH9Pl were 0.56%, 7.23%, 8.38%, and 11.81%, respectively, indicating that the tackiness of the 2-HEMA-containing adhesive rapidly decreased with the initial UV dose. This is in line with the results of the FT-IR ATR and gel content as the content of 2-HEMA reduced crosslinking reaction in the early UV irradiation to decrease the fluidity of the molecule to reduce the tack. In addition, SH3P2, which has a high photoinitiator concentration, has a lower UV irradiation amount than SH3P05, so that the reaction occurs quickly, thereby rapidly reducing the movement of molecules. These results are shown in Figure 8, the SH3P05 with a small amount of photoinitiator was reduced by 1.15% at 210mJ / cm 2 while SH3P2 was reduced by 15.68%.

3.2 접착력 (Peel strength)3.2 Peel strength

SH0P1, SH3P1, SH6P1, SH9P1의 UV 조사량에 따른 접착력의 변화를 도9에 나타내었다. 모든 점착제 샘플은 UV 조사량이 630mJ/cm2이상일 때는 접착력이 거의 일정하게 유지되지만 조사량이 210mJ/cm2일 때는 각기 다른 거동을 보였다. 2-HEMA의 함량이 높은 SH6P1, SH9P1의 접착력은 UV 조사 전보다 각각 52.74%, 53.34% 감소한 반면 SH0P1, SH3P1의 접착력은 각각 8.94%, 15.09%만큼 감소하였다. 이 결과는 프로브 택과 같은 결과를 나타내는 것으로 2-HEMA의 함량이 증가하면 점착제는 UV 조사량이 낮아도 가교밀도가 높아져서 저장 탄성율의 증가로 인해 접착력이 감소하는 결과를 나타내는 것이다. 도10은 광개시제의 함량에 따른 접착력의 변화를 나타낸 것으로 광개시제의 함량이 높은 SH3P2의 접착력은 UV 조사 전보다 조사량이 210mJ/cm2일 때 69.47% 감소한 반면 SH3P05의 접착력은 같은 조사량에서 9.09% 감소하는 결과를 나타내었다.The change in adhesion force according to the UV irradiation amount of SH0P1, SH3P1, SH6P1, and SH9P1 is shown in FIG. All the adhesive samples showed almost constant adhesion when the UV irradiation amount was 630 mJ / cm 2 or higher, but showed different behavior when the irradiation dose was 210 mJ / cm 2 . Adhesion of SH6P1 and SH9P1 with high 2-HEMA content was reduced by 52.74% and 53.34%, respectively, compared to before UV irradiation, while that of SH0P1 and SH3P1 was decreased by 8.94% and 15.09%, respectively. This result shows the same result as the probe tack. When the content of 2-HEMA is increased, the pressure-sensitive adhesive shows a result that the adhesive strength decreases due to the increase of the storage modulus due to the increase in the crosslinking density even though the UV irradiation amount is low. Figure 10 shows the change in the adhesion strength according to the content of the photoinitiator, the adhesion of SH3P2 content of the high photoinitiator was reduced 69.47% when the irradiation dose 210mJ / cm2 than before UV irradiation, while the adhesion of SH3P05 was reduced by 9.09% at the same dose Indicated.

3.3 SAFT(Shear adhesion failure temperature)3.3 SAFT (Shear adhesion failure temperature)

2-HEMA의 함량을 변화시켜서 제조된 점착제의 UV 조사량에 따른 SAFT 결과를 도11에 나타내었다. 모든 샘플에 대해서 UV 조사에 의해 가교 밀도가 증가함에 따라 SAFT가 증가하는 결과를 나타내었다. 하지만 2-HEMA의 함량이 높은 SH3P1은 UV 조사량에서도 높은 SAFT를 보였고 SH3P1과 SH0P1보다 빨리 SAFT가 150??에 이르렀다. 이것은 2-HEMA가 벤조페논에 대해서 수소를 잘 공여했기 때문에 나타난 결과로 이로 인해 가교밀도 증가속도가 빨라서 SAFT가 높게 나타난 것이다. 도12에 광개시제의 농도를 변화하면서 UV 조사량에 따른 점착제의 SAFT 결과를 나타내었다. 모든 범위의 UV 조사량에 대해서 SH3P2의 SAFT가 SH3P1보다 더 높은 값을 나타내었다. 이러한 현상도 마찬가지로 광중합 속도는 광개시제의 농도와 비례하므로 증가된 광개시제는 낮은 UV 조사량에서 높은 가교밀도를 나타내기 때문이다.SAFT results according to the UV irradiation amount of the pressure-sensitive adhesive prepared by changing the content of 2-HEMA is shown in FIG. For all samples, SAFT increased as the crosslink density increased by UV irradiation. However, SH3P1, which has high 2-HEMA content, showed high SAFT at UV irradiation, and SAFT reached 150 ?? faster than SH3P1 and SH0P1. This is because 2-HEMA was well donated hydrogen to benzophenone, which resulted in a high SAFT due to the rapid increase in crosslink density. 12 shows the SAFT results of the pressure-sensitive adhesive according to the UV irradiation amount while changing the concentration of the photoinitiator. The SAFT of SH3P2 showed higher values than SH3P1 for all ranges of UV radiation. This is also because the photopolymerization rate is proportional to the concentration of the photoinitiator, so the increased photoinitiator shows high crosslink density at low UV radiation.

본 발명은 광개시제 및 수소공여체를 점착고분자에 직접 중합시켜 측쇄를 형성하는 UV 경화형 점착제에 관한 것으로, 상기 측정결과로부터, FT-IR ATR을 사용하여 2-HEMA와 광개시제의 농도가 높은 점착제의 경화속도는 2-HEMA와 광개시제의 농도가 낮은 것보다 가교 속도가 빠른 결과를 얻었으며, 이러한 결과는 겔 함량 실험 결과에서도 동일하게 나타났는데 2-HEMA 및 광개시제의 농도가 높은 점착제의 겔 함량은 낮은 UV 조사량에서도 겔 함량이 높게 나타났다. 또한, 점착물성도 경화 속도의 영향을 받았는데 2-HEMA 및 광개시제의 농도가 증가함에 따라 택과 접착력은 UV 조사 초기에 급격히 감소하고 SAFT는 증가하였다. 상기 결과로부터 수소를 잘 공여하는 것이 UV 가교형 점착제에 적용되면 UV 조사량이 낮아도 경화속도가 빠르게 일어나서 광효율이 높은 점착제를 제조할 수 있다.The present invention relates to a UV curable pressure sensitive adhesive which polymerizes a photoinitiator and a hydrogen donor directly to an adhesive polymer to form side chains. From the above measurement results, the curing rate of a pressure sensitive adhesive having a high concentration of 2-HEMA and a photoinitiator using FT-IR ATR The crosslinking rate was faster than that of 2-HEMA and photoinitiator, and the same result was found in the gel content test. The gel content of the adhesive with high concentration of 2-HEMA and photoinitiator was low UV dose. The gel content was also high at. In addition, the tackiness was also affected by the curing rate. As the concentration of 2-HEMA and photoinitiator increased, the tack and adhesion decreased rapidly at the beginning of UV irradiation and SAFT increased. If the well-donating hydrogen from the above results is applied to the UV cross-linking pressure-sensitive adhesive, even if the amount of UV irradiation is low, the curing rate occurs quickly to produce a pressure-sensitive adhesive with high light efficiency.

통상의 아크릴 점착제는 충분한 응집력을 나타내기에는 분자량이 높지 않으므로 화학적인 가교를 위한 여러 수단이 제시될 수 있으나, 본 발명은 점착고분자 자체에 광개시제 및 수소공여체를 측쇄에 도입하여 점착제를 완성함으로써, 가교효율이 높은, 즉 낮은 UV 조사량에도 혹은 단시간에 점착제 경화를 달성할 수 있어 생산성이 개선된 자외선 가교형 아크릴계 점착제를 제공하는 것이다.
Conventional acrylic pressure-sensitive adhesives are not high molecular weight to show sufficient cohesive force, but various means for chemical crosslinking may be proposed. However, the present invention provides a photopolymerization agent and a hydrogen donor to the side chain to complete the pressure-sensitive adhesive by crosslinking. The present invention provides an ultraviolet crosslinkable acrylic pressure-sensitive adhesive having high productivity, that is, adhesive curing can be achieved even at a low UV irradiation dose or in a short time.

Claims (5)

불포화기를 포함하는 벤조페논 유도체 ; 수소공여기를 포함하는 아크릴계 모노머 ; 점착고분자로 중합되는 최소한 하나 이상의 모노머 혼합물을 용액 중합하여 생성된 공중합체를 자외선에 노출시켜 가교하여 제조되는, 광중합효율이 개선된 자외선 가교형 아크릴계 점착제.Benzophenone derivative containing an unsaturated group; Acrylic monomer containing a hydrogen donor group; An ultraviolet-ray crosslinking acrylic pressure-sensitive adhesive having improved photopolymerization efficiency, which is prepared by crosslinking a copolymer produced by solution polymerization of at least one monomer mixture polymerized into an adhesive polymer by ultraviolet rays. 제1항에 있어서, 상기 벤조페논 유도체는 4-acryloyloxy benzophenone(ABP) 또는 O-acryloyle acetophenone oxime(AAPO) 인 것을 특징으로 하는, 광중합효율이 개선된 자외선 가교형 아크릴계 점착제.According to claim 1, wherein the benzophenone derivative is 4-acryloyloxy benzophenone (ABP) or O-acryloyle acetophenone oxime (AAPO), characterized in that the UV cross-linking acrylic adhesive with improved photopolymerization efficiency. 제1항에 있어서, 상기 수소공여기를 포함하는 아크릴계 모노머는 2-HEMA 인 것을 특징으로 하는, 광중합효율이 개선된 자외선 가교형 아크릴계 점착제.The acrylic crosslinkable acrylic pressure-sensitive adhesive of claim 1, wherein the acrylic monomer including the hydrogen donor group is 2-HEMA. 제 1항 또는 제2항에 있어서, 상기 벤조페논 유도체는 상기 모노머 혼합물 100 중량부에 대하여 0.5 내지 2 중량부 투여되는 것을 특징으로 하는, 광중합효율이 개선된 자외선 가교형 아크릴계 점착제.According to claim 1 or claim 2, wherein the benzophenone derivative is 0.5 to 2 parts by weight based on 100 parts by weight of the monomer mixture, characterized in that the UV cross-linking acrylic pressure-sensitive adhesive with improved photopolymerization efficiency. 제 1항 또는 제2항에 있어서, 상기 수소공여기를 포함하는 아크릴계 모노머는 상기 모노머 혼합물 100 중량부에 대하여 3 내지 6 중량부 투여되는 것을 특징으로 하는, 광중합효율이 개선된 자외선 가교형 아크릴계 점착제.According to claim 1 or claim 2, wherein the acrylic monomer containing the hydrogen donating group is characterized in that administered 3 to 6 parts by weight based on 100 parts by weight of the monomer mixture, UV cross-linking acrylic adhesive with improved photopolymerization efficiency .
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