TWI631199B - Adhesive composition - Google Patents

Adhesive composition Download PDF

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TWI631199B
TWI631199B TW103124477A TW103124477A TWI631199B TW I631199 B TWI631199 B TW I631199B TW 103124477 A TW103124477 A TW 103124477A TW 103124477 A TW103124477 A TW 103124477A TW I631199 B TWI631199 B TW I631199B
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meth
weight
parts
adhesive composition
acrylate
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TW103124477A
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TW201510146A (en
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崔漢永
柳智熙
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韓商東友精細化工有限公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062Copolymers with monomers not covered by C09J133/06
    • C09J133/064Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/16Anti-static materials

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本發明提供一種黏著劑組合物,包含:一丙烯酸系共聚物,在以所有單體為100重量份的基礎下,藉由將包含1至10重量份具有一羧基的(甲基)丙烯酸酯系單體及0.1至2重量份具有含以羥基來取代4個或多個碳原子的線性或環狀烷基的(甲基)丙烯酸酯系單體之單體進行共聚來製備;三官能基或更高之甲苯二異氰酸酯系交聯劑;及具有Na+或K+離子之離子型抗靜電劑,使得該黏著劑組合物可在不畏物理特性隨著時間改變(高溫或高溫及高濕環境之改變)而變差的情況下,同時改善抗靜電特性及耐久性、及縮短固化期間。 The present invention provides an adhesive composition comprising: an acrylic copolymer, based on 100 parts by weight of all monomers, by including 1 to 10 parts by weight of a (meth) acrylic ester system having a carboxyl group A monomer and 0.1 to 2 parts by weight of a monomer having a linear or cyclic alkyl (meth) acrylate monomer containing 4 or more carbon atoms substituted with a hydroxyl group are prepared by copolymerization; a trifunctional group or Higher toluene diisocyanate cross-linking agents; and ionic antistatic agents with Na + or K + ions, making the adhesive composition change over time without fear of physical characteristics (high temperature or high temperature and high humidity environment) In the case of deterioration, the antistatic properties and durability are improved, and the curing period is shortened.

Description

黏著劑組合物 Adhesive composition

本發明關於一種黏著劑組合物,其具有良好的抗靜電特性與液體穩定性及較短的固化期間。 The invention relates to an adhesive composition, which has good antistatic properties, liquid stability and short curing period.

一般來說,液晶顯示器(LCD)包含偏光板及具有液晶的液晶晶胞,其中使用一適用於將液晶晶胞與偏光板結合在一起的黏著層。對於黏著劑,廣泛使用了包括具有良好的黏著性及透明度之丙烯酸系聚合物作為基底材料之丙烯酸系黏著劑。 Generally, a liquid crystal display (LCD) includes a polarizing plate and a liquid crystal cell having a liquid crystal. An adhesive layer suitable for combining the liquid crystal cell and the polarizing plate is used. As the adhesive, an acrylic adhesive including an acrylic polymer having good adhesiveness and transparency as a base material is widely used.

在將偏光板結合到液晶晶胞的過程當中,離型膜從黏著層剝離會造成靜電。靜電會影響液晶的配向,導致液晶缺陷,或誘發靜電吸引,使得異物流入液晶晶胞與黏著劑之間而造成污染。 During the process of bonding the polarizing plate to the liquid crystal cell, the release film may peel off from the adhesive layer and cause static electricity. Static electricity will affect the alignment of the liquid crystal, cause liquid crystal defects, or induce electrostatic attraction, so that foreign matter flows into the liquid crystal cell and the adhesive and causes pollution.

為了解決那些問題,將一離子型抗靜電劑與黏著劑組合物混合。然而,因離子型抗靜電劑遷移到表面而溢出所造成的滲出現象,將造成捲曲、起泡、脫層、及之類。更明確的說,那些缺陷可能會在高溫或高溫濕下更嚴重。 To solve those problems, a monoionic antistatic agent is mixed with an adhesive composition. However, the bleeding phenomenon caused by the overflow of the ionic antistatic agent to the surface will cause curling, blistering, delamination, and the like. More specifically, those defects may be more severe under high temperature or high temperature and humidity.

同時,習知揭示了一種黏著劑組合物,其包括藉由含氧化烯基之單體進行共聚來取得的丙烯酸系共聚物[韓國專利公開號第2012-0073093號及第2009-0055576號]。然而,其有可能會 隨著時間的增加而讓丙烯酸系共聚物的黏性也跟著增加,因此,量產時,該丙烯酸系共聚物將很難保存。 At the same time, a conventionally disclosed adhesive composition includes an acrylic copolymer obtained by copolymerizing an oxyalkylene group-containing monomer [Korean Patent Publication Nos. 2012-0073093 and 2009-0055576]. However, it is possible that As time goes on, the viscosity of the acrylic copolymer also increases. Therefore, during mass production, the acrylic copolymer will be difficult to preserve.

此外,針對該黏著劑組合物,除了抗靜電特性及耐久性,固化期間也扮演影響生產率的一個重要的因素之一,更明確的說,其可影響儲存容量、庫存管理、緊急出貨的處理、及之類。 In addition, for this adhesive composition, in addition to antistatic properties and durability, it also plays an important role in productivity during curing. More specifically, it can affect storage capacity, inventory management, and emergency shipment handling. , And the like.

因此,習知針對了各種可增加交聯反應速度以縮短固化期之催化劑進行介紹[韓國專利公開號第2012-0091549號及第2010-0039274號]。然而,控制交聯反應所使用的催化劑含量是很重要的,更明確的說,若添加過多的催化劑,將導致設備堵塞的風險或之類。 Therefore, conventionally, various catalysts which can increase the crosslinking reaction speed to shorten the curing period are introduced [Korean Patent Publication Nos. 2012-0091549 and 2010-0039274]. However, it is important to control the amount of catalyst used in the cross-linking reaction. More specifically, if too much catalyst is added, there will be a risk of equipment clogging or the like.

本發明解決了上述習知所發生的問題,本發明一目的為提供一種黏著劑組合物,其可在不畏黏性隨著時間而增加的情況下,同時改善抗靜電特性及耐久性,並在不使用交聯催化劑的情況下,縮短固化期間。 The present invention solves the problems occurring in the conventional knowledge, and an object of the present invention is to provide an adhesive composition, which can improve antistatic properties and durability at the same time without fear of increasing viscosity over time, and Without using a crosslinking catalyst, the curing period is shortened.

依據本發明一目的,在此提供一種黏著劑組合物,包含:一丙烯酸系共聚物,在以所有單體為100重量份的基礎下,藉由將包含1至10重量份具有一羧基的(甲基)丙烯酸酯系單體及0.1至2重量份具有含以羥基來取代4個或多個碳原子的線性或環狀烷基的(甲基)丙烯酸酯系單體之單體進行共聚來製備;三官能基或更高之甲苯二異氰酸酯系交聯劑;及具有Na+或K+離子之離子型抗 靜電劑。 According to an object of the present invention, there is provided an adhesive composition including: an acrylic copolymer, based on 100 parts by weight of all monomers, by including 1 to 10 parts by weight of a carboxyl group ( (Meth) acrylic acid ester-based monomer and 0.1 to 2 parts by weight of a monomer having a (meth) acrylic acid ester-based monomer having a linear or cyclic alkyl group having 4 or more carbon atoms substituted with a hydroxyl group are copolymerized to Preparation; trifunctional or higher toluene diisocyanate cross-linking agents; and ionic antistatic agents with Na + or K + ions.

具有含以羥基來取代4個或多個碳原子的線性或環狀烷基之(甲基)丙烯酸酯系單體可為至少一選自由4-羥基丁基丙烯酸酯、6-羥基己基(甲基)丙烯酸酯、8-羥基(甲基)丙烯酸辛酯、及所組成的群組。 The (meth) acrylate-based monomer having a linear or cyclic alkyl group having 4 or more carbon atoms substituted with a hydroxyl group may be at least one selected from the group consisting of 4-hydroxybutyl acrylate, 6-hydroxyhexyl (methyl Acrylate), octyl 8-hydroxy (meth) acrylate, and A group of people.

用以製備丙烯酸系共聚物的單體可進一步包含具有一芳香環之(甲基)丙烯酸酯系單體。 The monomer used to prepare the acrylic copolymer may further include a (meth) acrylate monomer having an aromatic ring.

該抗靜電劑可為一含氟陰離子。 The antistatic agent may be a fluorine-containing anion.

該含氟陰離子可為OTF()、TFSI()、或FSI()。 The fluorine-containing anion may be OTF ( ), TFSI ( ), Or FSI ( ).

在以所有單體為100重量份的基礎下,該丙烯酸系共聚物可藉由將包含:1)88至98重量份具有1-12個碳原子的烷基之(甲基)丙烯酸酯單體;2)1至10重量份具有一羧基的(甲基)丙烯酸酯系單體;及3)0.1至2重量份具有含以羥基來取代4個或多個碳原子的線性或環狀烷基之(甲基)丙烯酸酯系單體之單體進行共聚來製備。 Based on 100 parts by weight of all monomers, the acrylic copolymer may contain: (1) 88 to 98 parts by weight of a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms 2) 1 to 10 parts by weight of a (meth) acrylate-based monomer having a carboxyl group; and 3) 0.1 to 2 parts by weight having a linear or cyclic alkyl group containing a hydroxyl group to replace 4 or more carbon atoms The monomer of (meth) acrylate type monomer is copolymerized and prepared.

在以丙烯酸系共聚物為100重量份的基礎下,該黏著劑組合物可包含0.1至1重量份的三官能基或更高之甲苯二異氰酸酯系交聯劑;及0.5至5重量份具有Na+或K+離子的離子型抗靜電劑。 Based on 100 parts by weight of the acrylic copolymer, the adhesive composition may include 0.1 to 1 part by weight of a trifunctional or higher toluene diisocyanate-based crosslinking agent; and 0.5 to 5 parts by weight of Na + Or K + ion ionic antistatic agent.

該黏著劑組合物的固化期間,在基於23℃及65%RH不隨著時間改變之時間點下,可為48小時或更短,且該黏著劑組合物在放置於室溫24小時之前與之後的黏度變化可為50%或更少。 The curing period of the adhesive composition may be 48 hours or less at a time point based on 23 ° C. and 65% RH that does not change with time, and the adhesive composition is left to stand at room temperature for 24 hours with Later viscosity changes can be 50% or less.

本發明揭示一種黏著劑組合物,其具有良好的抗靜電特性與液體穩定性及較短的固化期間。 The invention discloses an adhesive composition, which has good antistatic properties, liquid stability and short curing period.

接下來,本發明詳細內容將描述於下。 Next, the details of the present invention will be described below.

本發明的黏著劑組合物包括:一丙烯酸系共聚物,在以所有單體為100重量份的基礎下,藉由將包含1至10重量份具有一羧基的(甲基)丙烯酸酯系單體及0.1至2重量份具有含以羥基來取代4個或多個碳原子的線性或環狀烷基的(甲基)丙烯酸酯系單體之單體進行共聚來製備;三官能基或更高之甲苯二異氰酸酯系交聯劑;及具有Na+或K+離子之離子型抗靜電劑。 The adhesive composition of the present invention includes: an acrylic copolymer, based on 100 parts by weight of all monomers, by including 1 to 10 parts by weight of a (meth) acrylate monomer having a carboxyl group And 0.1 to 2 parts by weight of a monomer having a (meth) acrylic acid ester-based monomer having a linear or cyclic alkyl group substituted with 4 or more carbon atoms by a hydroxyl group; trifunctional group or higher Toluene diisocyanate cross-linking agent; and ionic antistatic agent with Na + or K + ions.

具有一羧基的(甲基)丙烯酸酯系單體可抑制因離子型抗靜電劑遷移到表面而溢出所產生的滲出現象,並藉由增強與玻璃的黏著力來改善耐久性。具有一羥基的(甲基)丙烯酸酯單體可藉由增加交聯反應來縮短黏著劑組合物的固化期間。 The (meth) acrylic acid ester monomer having a carboxyl group can suppress the appearance of bleeding caused by the migration of the ionic antistatic agent to the surface, and improve the durability by enhancing the adhesion with glass. The (meth) acrylate monomer having a monohydroxy group can shorten the curing period of the adhesive composition by increasing the crosslinking reaction.

此外,該離子型抗靜電劑之Na+或K+離子會與羥基形成一配位鍵,從而抑制羥基及異氰酸酯之反應,進而改善該黏著劑組合物的液體穩定性。 In addition, Na + or K + ions of the ionic antistatic agent will form a coordination bond with the hydroxyl group, thereby inhibiting the reaction between the hydroxyl group and the isocyanate, thereby improving the liquid stability of the adhesive composition.

此外,該三官能基或更高之甲苯二異氰酸酯系交聯劑為一芳香族異氰酸酯,其與具有一羥基的(甲基)丙烯酸酯單體有良好的反應性,從而可縮短該黏著劑組合物的固化期間。 In addition, the trifunctional or higher toluene diisocyanate-based cross-linking agent is an aromatic isocyanate, which has good reactivity with a (meth) acrylate monomer having a hydroxyl group, thereby shortening the adhesive combination. During the curing of the material.

換句話說,本發明特徵在於,具有一羧基的(甲基)丙烯酸酯系單體及具有含以羥基來取代4個或多個碳原子的線性或環狀烷基之(甲基)丙烯酸酯系單體皆包含於用以製備丙烯酸系共聚物之單體中;使用了三官能基或更高之甲苯二異氰酸酯系交聯劑及具有Na+及K+離子之離子型抗靜電劑;且用以製備丙烯酸系共聚物之單體也採取最佳的混合比例,以同時改善抗靜電特性、耐久性、固化期間、及液體穩定性。 In other words, the present invention is characterized by a (meth) acrylate monomer having a carboxyl group and a (meth) acrylate having a linear or cyclic alkyl group containing 4 or more carbon atoms substituted with a hydroxyl group. All monomers are included in the monomers used to prepare acrylic copolymers; trifunctional or higher toluene diisocyanate crosslinkers and ionic antistatic agents with Na + and K + ions are used; and The monomers used to prepare acrylic copolymers are also optimally mixed to improve antistatic properties, durability, curing period, and liquid stability.

在以所有單體為100重量份的基礎下,本發明的丙烯酸系共聚物較佳為藉由將包含:88至98重量份具有1-12個碳原子的烷基之(甲基)丙烯酸酯單體;1至10重量份具有一羧基的(甲基)丙烯酸酯系單體;及0.1至2重量份具有含以羥基來取代4個或多個碳原子的線性或環狀烷基之(甲基)丙烯酸酯系單體之單體進行共聚來製備。 Based on 100 parts by weight of all monomers, the acrylic copolymer of the present invention is preferably a (meth) acrylic acid ester containing: 88 to 98 parts by weight of an alkyl group having 1 to 12 carbon atoms. Monomer; 1 to 10 parts by weight of a (meth) acrylate-based monomer having a carboxyl group; and 0.1 to 2 parts by weight of a linear or cyclic alkyl group containing a hydroxyl group to replace 4 or more carbon atoms ( A monomer of a meth) acrylate-based monomer is prepared by copolymerization.

具有1-12個碳原子的烷基之(甲基)丙烯酸酯單體之例子有(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、n-(甲基)丙烯酸丁酯、2-(甲基)丙烯酸丁酯、t-(甲基)丙烯酸丁酯、2-(甲基)丙烯酸乙基己酯、(甲基)丙烯酸乙酯、n-(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸戊酯、n-(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬 酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯、及之類。在這當中,較佳為n-丙烯酸丁酯、2-丙烯酸乙基己酯、或其混和物。其可單獨使用或兩個以上混合使用。 Examples of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) Butyl acrylate, n- (meth) acrylate, butyl 2- (meth) acrylate, t- (meth) acrylate, ethylhexyl 2- (meth) acrylate, (meth) Ethyl acrylate, propyl n- (meth) acrylate, isopropyl (meth) acrylate, amyl (meth) acrylate, octyl n- (meth) acrylate, isooctyl (meth) acrylate, (Meth) acrylic acid Esters, decyl (meth) acrylate, lauryl (meth) acrylate, and the like. Among these, n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture thereof is preferred. They can be used alone or in combination of two or more.

在以所有單體為100重量份的基礎下,該具有1-12個碳原子的烷基之(甲基)丙烯酸酯單體的含量可為88至98重量份。若(甲基)丙烯酸酯單體少於88重量份,將造成黏著力不足,但若其超過98重量份,則將造成凝聚力降低。 The content of the (meth) acrylate monomer of the alkyl group having 1 to 12 carbon atoms may be 88 to 98 parts by weight based on 100 parts by weight of all monomers. If the (meth) acrylate monomer is less than 88 parts by weight, insufficient adhesion will be caused, but if it exceeds 98 parts by weight, cohesion will be reduced.

具有一羧基的(甲基)丙烯酸酯系單體可使用丙烯酸或甲基丙烯酸。 As the (meth) acrylate monomer having a carboxyl group, acrylic acid or methacrylic acid can be used.

在以所有單體為100重量份的基礎下,該具有一羧基的(甲基)丙烯酸酯系單體的含量較佳為1至10重量份。若其含量少於1重量份,抑制離子型抗靜電劑之滲出現象的效果將不大,使得耐久性變差,或其作為交聯反應之催化劑作用將變弱,造成固化期間無法縮短。若其含量超過10重量份,將因過多的交聯反應而導致該黏著劑組合物的液體穩定性變差。 The content of the (meth) acrylate monomer having a carboxyl group is preferably 1 to 10 parts by weight based on 100 parts by weight of all monomers. If its content is less than 1 part by weight, the effect of suppressing the appearance of ionic antistatic agents will be small, resulting in poor durability, or its role as a catalyst for cross-linking reactions will be weakened, and the curing period cannot be shortened. If the content exceeds 10 parts by weight, the liquid stability of the adhesive composition is deteriorated due to excessive crosslinking reaction.

具有含以羥基來取代4個或多個碳原子的線性或環狀烷基之(甲基)丙烯酸酯系單體可為至少一選自由4-羥基丁基(甲基)丙烯酸酯、6-羥基己基(甲基)丙烯酸酯、8-羥基(甲基)丙烯酸辛酯、及所組成的群組。考量到固化期間,較佳為4-羥基丁基丙烯酸酯或The (meth) acrylate-based monomer having a linear or cyclic alkyl group having 4 or more carbon atoms substituted with a hydroxyl group may be at least one selected from the group consisting of 4-hydroxybutyl (meth) acrylate, 6- Hydroxyhexyl (meth) acrylate, octyl 8-hydroxy (meth) acrylate, and A group of people. Considering the curing period, 4-hydroxybutyl acrylate or .

在以所有單體為100重量份的基礎下,具有含以羥基來取代4個或多個碳原子的線性或環狀烷基之(甲基)丙烯酸酯系單體的含量較佳為0.1至2重量份。若其含量少於0.1重量份,固化期間可能只會稍微縮短。若其含量超過2重量份,將因過多的交聯反應而導致該黏著劑組合物的液體穩定性變差。 The content of the (meth) acrylic acid ester-based monomer having a linear or cyclic alkyl group containing 4 or more carbon atoms substituted with a hydroxyl group on the basis of 100 parts by weight of all monomers is preferably 0.1 to 2 parts by weight. If it is less than 0.1 part by weight, the curing period may be shortened only slightly. If the content exceeds 2 parts by weight, the liquid stability of the adhesive composition is deteriorated due to excessive crosslinking reaction.

此外,為了防止漏光,本發明用以製備丙烯酸系共聚物之單體可進一步包含一具有芳香環基之(甲基)丙烯酸酯單體。 In addition, in order to prevent light leakage, the monomer used to prepare the acrylic copolymer of the present invention may further include a (meth) acrylate monomer having an aromatic ring group.

具有芳香環基之(甲基)丙烯酸酯單體之例子可為至少一選自由2-乙基苯氧基(甲基)丙烯酸酯、2-乙基硫代苯基(甲基)丙烯酸酯、苯基(甲基)丙烯酸酯、芐基(甲基)丙烯酸酯、2-苯基(甲基)丙烯酸乙酯、3-苯基(甲基)丙烯酸丙酯、4-苯基(甲基)丙烯酸丁酯、2-2-甲基苯基(甲基)丙烯酸乙酯、2-3-甲基苯基(甲基)丙烯酸乙酯、2-4-甲基苯基(甲基)丙烯酸乙酯、2-(4-丙基苯基)(甲基)丙烯酸乙酯、2-(4-(1-甲基乙基)苯基)(甲基)丙烯酸乙酯、2-(4-甲氧基苯基)(甲基)丙烯酸乙酯、2-(4-環己基苯基)(甲基)丙烯酸乙酯、2-(2-氯苯)(甲基)丙烯酸乙酯、2-(3-氯苯)(甲基)丙烯酸乙酯、2-(4-氯苯)(甲基)丙烯酸乙酯、2-(4-溴苯)(甲基)丙烯酸乙酯、2-(3-苯基苯)(甲基)丙烯酸乙酯、及2-(4-芐基苯基)(甲基)丙烯酸乙酯所組成的群組。考量到共聚反應性,較佳為2-乙基苯氧基(甲基)丙烯酸酯或芐基(甲基)丙烯酸酯。 Examples of the (meth) acrylate monomer having an aromatic ring group may be at least one selected from the group consisting of 2-ethylphenoxy (meth) acrylate, 2-ethylthiophenyl (meth) acrylate, Phenyl (meth) acrylate, benzyl (meth) acrylate, ethyl 2-phenyl (meth) acrylate, propyl 3-phenyl (meth) acrylate, 4-phenyl (meth) Butyl acrylate, ethyl 2-2-methylphenyl (meth) acrylate, ethyl 2-2-3methylphenyl (meth) acrylate, ethyl 2-2-4methylphenyl (meth) acrylate Ester, 2- (4-propylphenyl) (meth) acrylate, 2- (4- (1-methylethyl) phenyl) (meth) acrylate, 2- (4-formyl (Oxyphenyl) ethyl (meth) acrylate, ethyl 2- (4-cyclohexylphenyl) (meth) acrylate, ethyl 2- (2-chlorobenzene) (ethyl) acrylate, 2- ( 3-chlorobenzene) ethyl (meth) acrylate, ethyl 2- (4-chlorobenzene) (meth) acrylate, ethyl 2- (4-bromobenzene) (meth) acrylate, 2- (3- A group consisting of ethyl phenylbenzene) (meth) acrylate and ethyl 2- (4-benzylphenyl) (meth) acrylate. In consideration of copolymerization reactivity, 2-ethylphenoxy (meth) acrylate or benzyl (meth) acrylate is preferred.

在具有1-12個碳原子的烷基之(甲基)丙烯酸酯單體、具有一羧基的(甲基)丙烯酸酯系單體、及具有含以羥基來取代4個 或多個碳原子的線性或環狀烷基之(甲基)丙烯酸酯系單體為100重量份的情況下,具有芳香環基之(甲基)丙烯酸酯單體添加的含量較佳為6至12重量份。若其添加量少於6重量份或超過12重量份,將出現漏光。 (Meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms, (meth) acrylic acid ester monomer having a carboxyl group, and having 4 hydroxyl groups When the (meth) acrylate monomer of a linear or cyclic alkyl group having a plurality of carbon atoms is 100 parts by weight, the content of the (meth) acrylate monomer having an aromatic ring group is preferably 6 To 12 parts by weight. If it is added in an amount of less than 6 parts by weight or more than 12 parts by weight, light leakage will occur.

共聚物的製備方法並沒有特別的限制。共聚物可由習知諸如本體聚合、溶液聚合、乳液聚合、及懸浮聚合的方法來製備。在這當中,較佳為溶液聚合。此外,亦可使用習知聚合所常用的溶劑、聚合引發劑、用以控制分子量的鏈轉移劑及之類。 The method for preparing the copolymer is not particularly limited. Copolymers can be prepared by conventional methods such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization. Among these, solution polymerization is preferred. In addition, solvents, polymerization initiators, chain transfer agents for controlling molecular weight, and the like commonly used in conventional polymerization can also be used.

該共聚物的重量平均分子量(以聚苯乙烯來計,Mw),以膠體滲透層析法來測量,為50,000至2,000,000,且較佳為400,000至2,000,000。若共聚物的重量平均分子量少於50,000,與共聚物之間的凝聚力將不足,導致黏著耐久性的問題。若共聚物的重量平均分子量超過200,000,塗佈時將需大量的稀釋溶劑來確保加工性。 The weight average molecular weight (in terms of polystyrene, Mw) of the copolymer, as measured by colloidal permeation chromatography, is 50,000 to 2,000,000, and preferably 400,000 to 2,000,000. If the weight average molecular weight of the copolymer is less than 50,000, the cohesive force with the copolymer will be insufficient, resulting in a problem of adhesion durability. If the weight average molecular weight of the copolymer exceeds 200,000, a large amount of a diluent solvent will be required during coating to ensure processability.

該交聯劑可改善黏著性及耐久性、保有高溫下的可靠性、及保有黏著劑的形狀。更明確的說,考量到與具有一羧基的(甲基)丙烯酸酯系單體及具有含以羥基來取代4個或多個碳原子的線性或環狀烷基之(甲基)丙烯酸酯系單體之反應性、耐久性、及防止漏光,較佳使用三官能基或更高之甲苯二異氰酸酯系交聯劑。 This cross-linking agent can improve adhesion and durability, maintain reliability at high temperatures, and retain the shape of the adhesive. More specifically, considering the (meth) acrylic acid ester monomer having a carboxyl group and the (meth) acrylic acid ester group having a linear or cyclic alkyl group having 4 or more carbon atoms substituted with a hydroxyl group For monomer reactivity, durability, and prevention of light leakage, a trifunctional or higher toluene diisocyanate-based crosslinking agent is preferably used.

三官能基或更高之甲苯二異氰酸酯系交聯劑的例子有甲苯二異氰酸酯(Urethane公司,日本,CORONATE-L)之三羥甲基丙烷加成物及甲苯二異氰酸酯三聚合物(Aekyung Chemical公 司,AKNATE TR-50)。 Examples of trifunctional or higher toluene diisocyanate-based cross-linking agents are trimethylolpropane adduct of toluene diisocyanate (Urethane, Japan, CORONATE-L) and toluene diisocyanate terpolymer (Aekyung Chemical Corporation) Division, AKNATE TR-50).

在以所有單體為100重量份的基礎下,三官能基或更高之甲苯二異氰酸酯系交聯劑的含量可為0.1至1重量份。若其含量少於0.1重量份,交聯度將不足,導致凝聚力降低,從而讓耐久性變差,諸如剝離、及可切割性變弱。若其含量超過1.0重量份,將很難確保液體的穩定性。 The content of the trifunctional or higher toluene diisocyanate-based crosslinking agent may be 0.1 to 1 part by weight based on 100 parts by weight of all the monomers. If the content is less than 0.1 parts by weight, the degree of cross-linking will be insufficient, resulting in a decrease in cohesive force, which will result in poor durability, such as peeling and poor cuttability. If it exceeds 1.0 part by weight, it will be difficult to ensure the stability of the liquid.

為了改善液體穩定性,本發明可包括一具有Na+及K+離子之離子型抗靜電劑,其可減少丙烯酸系共聚物中羥基及異氰酸酯基之反應速率。 In order to improve the liquid stability, the present invention may include an ionic antistatic agent having Na + and K + ions, which can reduce the reaction rate of hydroxyl and isocyanate groups in the acrylic copolymer.

該離子型抗靜電劑之陰離子,可使用含氟陰離子或碘離子。含氟陰離子可為三氟甲磺酸()、雙(三氟磺酰)亞胺()、及雙(氟磺酰基)亞胺()。 As the anion of the ionic antistatic agent, a fluorine-containing anion or an iodine ion can be used. The fluorine-containing anion may be trifluoromethanesulfonic acid ( ), Bis (trifluorosulfonyl) imine ( ), And bis (fluorosulfonyl) imine ( ).

在以丙烯酸系共聚物為100重量份的基礎下,離子型抗靜電劑的含量為0.5至5重量份。若該離子型抗靜電劑的含量少於0.5重量份,將造成抗靜電特性不足,而若該離子型抗靜電劑的含量超過5重量份,則將無法保有其耐久性。 The content of the ionic antistatic agent is 0.5 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer. If the content of the ionic antistatic agent is less than 0.5 parts by weight, the antistatic properties will be insufficient, and if the content of the ionic antistatic agent exceeds 5 parts by weight, its durability cannot be maintained.

此外,本發明的黏著劑組合物可進一步包含一矽烷偶聯劑。 In addition, the adhesive composition of the present invention may further include a silane coupling agent.

矽烷偶聯劑的種類並沒有特別的限制。矽烷偶聯劑的例子有乙烯基氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-(3,4-環氧樹脂環己基)乙基三甲氧基矽烷、3-環氧丙氧基 丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯酰氧基丙基三乙氧基矽烷、3-甲基丙烯酰氧基丙基三甲氧基矽烷、3-甲基丙烯酰氧基甲基二甲氧基矽烷、3-甲基丙烯酰氧基丙基甲基二乙氧基矽烷、3-丙烯酰氧基丙基三甲氧基矽烷、N-2-(氨基乙基)-3-氨丙基甲基二甲氧基矽烷、N-2-(氨基乙基)-3-氨基丙基三甲氧基矽烷、N-2-(氨基乙基)-3-氨丙基三乙氧基矽烷、3-氨基丙基三甲氧基矽烷、3-氨基丙基三乙氧基矽烷、3-三乙氧基甲矽烷基-N-(1,3-二甲基-亞丁基)丙胺、N-苯基-3-氨基丙基三甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、雙(三乙氧基甲矽烷丙基)四硫化物、3-異氰酸酯丙基三乙氧基矽烷、及之類。其可單獨使用或兩個以上混合使用。 The type of the silane coupling agent is not particularly limited. Examples of the silane coupling agent are vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-cyclo Oxypropoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methyl Acryloyloxymethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N-2- (aminoethyl ) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane Silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, and others . They can be used alone or in combination of two or more.

該黏著劑組合物除了上述組成可進一步包含,諸如增黏劑樹脂、抗氧化劑、流平劑、表面潤滑劑、染料、顏料、消泡劑、填料及光穩定劑之加成物,以控制黏著力、凝聚力、黏性、彈性模量、玻璃轉換溫度、及之類。 The adhesive composition may further include, in addition to the above composition, adducts such as a tackifier resin, an antioxidant, a leveling agent, a surface lubricant, a dye, a pigment, an antifoaming agent, a filler, and a light stabilizer to control adhesion. Force, cohesion, viscosity, elastic modulus, glass transition temperature, and the like.

添加劑的含量可在不讓本發明的效果變差的範圍內進行適當的控制。 The content of the additives can be appropriately controlled within a range that does not deteriorate the effects of the present invention.

本發明的黏著劑組合物可用來作為偏光板與液晶晶胞結合的黏著劑,或用於表面保護膜的黏著劑。此外,本發明的黏著劑組合物可用於保護膜、反射片、用於成型的黏著片、用於 攝影的黏著片、用於標示土地的黏著片、用於光學黏著劑產品、及用於電子產品的黏著劑,以及用於一般廣告產品的黏著片產品。 The adhesive composition of the present invention can be used as an adhesive for combining a polarizing plate and a liquid crystal cell, or an adhesive for a surface protection film. In addition, the adhesive composition of the present invention can be used for a protective film, a reflective sheet, an adhesive sheet for molding, and Photographic adhesives, adhesives for marking land, adhesives for optical products, adhesives for electronic products, and adhesive products for general advertising products.

在此所提供的較佳實施例是為了幫助了解本發明,以下所述之實例也僅為了呈現本發明,而非用以限定本發明。任何所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 The preferred embodiments are provided to help understand the present invention, and the examples described below are only for presenting the present invention and not for limiting the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the scope of the attached patent application.

製備實例:丙烯酸系共聚物 Preparation example: acrylic copolymer

製備實例1至11及比較製備實例1至5 Preparation Examples 1 to 11 and Comparative Preparation Examples 1 to 5

將依據表1所示之組成而製備之單體混和物放入一個具有冷卻裝置的1公升反應器中,以促進氮氣的回流及溫度的控制,再將100重量份的乙酸乙酯作為溶劑加入其中。在那之後,以氮氣吹淨1小時以去除氧氣,並將溫度維持在78℃。再將混和物攪拌均勻。然後,將0.03重量份的偶氮二異丁腈(AIBN)作為反應引發劑予以加入,再進行8小時的反應,從而製備一重量平均分子量約為780,000之丙烯酸共聚物。 The monomer mixture prepared according to the composition shown in Table 1 was placed in a 1 liter reactor with a cooling device to promote the reflux of nitrogen and control the temperature, and then 100 parts by weight of ethyl acetate was added as a solvent. among them. After that, it was purged with nitrogen for 1 hour to remove oxygen, and the temperature was maintained at 78 ° C. Stir the mixture evenly. Then, 0.03 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and the reaction was further performed for 8 hours to prepare an acrylic copolymer having a weight average molecular weight of about 780,000.

實例1至18及比較實例1至12 Examples 1 to 18 and Comparative Examples 1 to 12

具有15%固體含量的各黏著劑組合物乃藉由將丙烯酸系共聚物、離子型抗靜電劑、及交聯劑依表2所示進行混合來製備,再將混和物以乙酸乙酯稀釋。 Each adhesive composition having a solid content of 15% was prepared by mixing an acrylic copolymer, an ionic antistatic agent, and a cross-linking agent as shown in Table 2, and then diluting the mixture with ethyl acetate.

將如上所製備的各個黏著劑組合物塗佈於一塗有矽脫模劑的離型膜上,以具有25μm之厚度,接著以100℃乾燥1分鐘, 從而形成一黏著層。在於其上層壓另一個離型膜,從而製造一黏著片。 Each of the adhesive compositions prepared as described above was coated on a release film coated with a silicon release agent to have a thickness of 25 μm, followed by drying at 100 ° C. for 1 minute. Thereby, an adhesive layer is formed. Another release film was laminated thereon, thereby producing an adhesive sheet.

將所製造的黏著片之離型膜剝離,然後,透過黏著處理將所形成的黏著層層壓到一185μm厚的碘系偏光板,以製造一附黏著劑偏光板。將所製造出來的偏光板存放於23℃及60%RH的條件下。 The release film of the manufactured adhesive sheet was peeled off, and then the formed adhesive layer was laminated to a 185 μm-thick iodine-based polarizing plate through an adhesive treatment to manufacture an adhesive-attached polarizing plate. The manufactured polarizing plate was stored under the conditions of 23 ° C and 60% RH.

測試實例 Test case

藉由該實例及比較實例所取得的黏著劑組合物、黏著片、及附黏著劑偏光板之物理特性,係藉由下列方法來測量,並將測量結果記錄於表3。 The physical properties of the adhesive composition, the adhesive sheet, and the adhesive-attached polarizing plate obtained by this example and the comparative example were measured by the following methods, and the measurement results are recorded in Table 3.

1.保存穩定性(黏度變化,%) 1. Storage stability (viscosity change,%)

利用黏度計(Brookfield LVDV-II+B型(轉子代號3,30rpm))來測量該黏著劑組合物的初始黏性及放置於室溫24小時後該黏著劑組合物的黏性,並計算黏度變化(△η)。 A viscometer (Brookfield LVDV-II + B (rotor code 3, 30 rpm)) was used to measure the initial viscosity of the adhesive composition and the viscosity of the adhesive composition after being left at room temperature for 24 hours, and calculate the viscosity Change (Δη).

<評估標準> <Evaluation criteria>

○:△η<50% ○: △ η <50%

△:50%△η<100% △: 50% △ η <100%

×:100%△η ×: 100% △ η

2.固化期間 2. During curing

當所製造的黏著片在23℃及65% RH下固化1至10天,凝膠率依如下所述每日進行測量。延長固化的天數直到凝膠率不再增加,意即,依此判定固化期間。 When the manufactured adhesive sheet was cured at 23 ° C and 65% RH for 1 to 10 days, the gel fraction was measured daily as described below. The number of days of curing is extended until the gelation rate no longer increases, that is, the curing period is judged accordingly.

大約0.25g的黏著片的黏著層被固定在精確秤重250目的金屬絲網(100mm X 100mm),再將金屬絲網包起來使得凝膠不會從中逸出。利用精密天平來精確測量其重量,再將金屬絲網浸泡在乙酸乙酯溶液中3天。將浸泡的金屬絲網取出,接著以少量的乙酸乙酯溶液沖洗,再以120℃乾燥24小時,接著秤重。所測量的重量是用來藉由方程式1計算凝膠率。基於所計算出來的凝膠率落入到70%至80%的範圍內且未觀察到其隨時間變化的時間點來判定固化期間:[方程式1]凝膠率(%)=(C-A)/(B-A) x 100 The adhesive layer of about 0.25g of adhesive sheet was fixed on a 250-mesh wire mesh (100mm X 100mm), and the wire mesh was wrapped so that the gel would not escape from it. The weight was accurately measured using a precision balance, and the wire mesh was immersed in an ethyl acetate solution for 3 days. The soaked wire mesh was taken out, rinsed with a small amount of ethyl acetate solution, dried at 120 ° C. for 24 hours, and then weighed. The measured weight is used to calculate the gel fraction by Equation 1. Determine the curing period based on the time point at which the calculated gel fraction falls within the range of 70% to 80% and no change with time is observed: [Equation 1] Gel fraction (%) = (CA) / (BA) x 100

其中在方程式1中,A為金屬絲網的重量(g);B為黏著層固定於金屬絲網的重量(B-A:黏著層的重量,g);及C為金屬絲網經浸泡與乾燥後的重量(C-A:凝膠樹脂的重量,g)]。 Wherein in Equation 1, A is the weight of the wire mesh (g); B is the weight of the adhesive layer fixed to the wire mesh (BA: weight of the adhesive layer, g); and C is the metal wire mesh after soaking and drying. Weight (CA: weight of gel resin, g)].

3.耐久性(耐熱性,耐濕熱性) 3.Durability (heat resistance, damp heat resistance)

將所製造的附黏著劑的偏光板切割成90mm×170mm的尺寸來製成樣品,再將離型膜從其上剝離,再將偏光板附著於玻璃基板的兩面(110mm×190mm×0.7mm)使得偏光板的光吸收軸彼此正交。在此,施加5kg/cm2的壓力,並在無塵室內進行以避免氣泡或異料產生。為了測量耐熱性,將樣品置放於80℃的溫度下1000小時,然後,觀察是否有起泡或剝離出現。為了測量耐濕熱性,將樣品置放於60℃及90% RH的條件下1000小時,再觀察是否有起泡或剝離出現。在此,在進行樣品評估前,先將樣品置 放於常溫下24小時。 The manufactured polarizer with an adhesive was cut into a size of 90 mm × 170 mm to prepare a sample, and the release film was peeled off therefrom, and then the polarizer was attached to both sides of the glass substrate (110 mm × 190 mm × 0.7 mm). The light absorption axes of the polarizing plates are made orthogonal to each other. Here, a pressure of 5 kg / cm 2 is applied, and it is performed in a clean room to avoid the generation of bubbles or foreign materials. In order to measure the heat resistance, the sample was left at a temperature of 80 ° C for 1000 hours, and then, it was observed whether blistering or peeling occurred. In order to measure the humidity and heat resistance, the samples were placed under the conditions of 60 ° C and 90% RH for 1000 hours, and then observed whether blistering or peeling occurred. Here, the sample is placed at room temperature for 24 hours before the sample is evaluated.

<評估標準> <Evaluation criteria>

◎:沒有氣泡或剝離: ◎: No bubbles or peeling:

○:氣泡或剝離的數量<5 ○: Number of bubbles or peeling <5

△:5氣泡或剝離的數量<10 △: 5 Number of bubbles or peeling <10

×:10氣泡或剝離的數量 ×: 10 Number of bubbles or peeling

4.抗靜電特性(表面電阻率,Ω/□) 4. Antistatic characteristics (surface resistivity, Ω / □)

在離型膜從黏著片剝離後,對三個點的表面電阻值分別進行10次測量,再將測量值進行平均。 After the release film was peeled from the adhesive sheet, the surface resistance values of the three points were measured 10 times respectively, and the measured values were averaged.

在此,利用表面電阻分析儀(MCP-HT450/MITSUBISHI CHEMICAL)、探頭(URS,UR100)、探頭檢驗片(用於URS,用於UR 100)來進行表面電阻的測量。 Here, a surface resistance analyzer (MCP-HT450 / MITSUBISHI CHEMICAL), a probe (URS, UR100), and a probe test piece (for URS, for UR 100) were used to measure the surface resistance.

由表3可知,依據本發明實例1至18之黏著劑組合物的固化期間縮短到12至36小時,相較於比較實例1至12之黏著劑組合物,其同時改善了抗靜電特性及耐久性,且不畏物理特性隨著時間改變(高溫或高溫及高濕環境之改變)而變差。 It can be seen from Table 3 that the curing period of the adhesive compositions according to Examples 1 to 18 of the present invention is shortened to 12 to 36 hours, and compared with the adhesive compositions of Comparative Examples 1 to 12, it also improves antistatic properties and durability. Properties, and not afraid of physical characteristics change with time (high temperature or changes in high temperature and high humidity environment) will deteriorate.

如上所述,本發明的黏著劑組合物可同時改善抗靜電特性及耐久性且不畏物理特性隨著時間改變(高溫或高溫及高濕環境之改變)而變差。 As described above, the adhesive composition of the present invention can simultaneously improve antistatic properties and durability without fear of physical properties changing with time (changes in high temperature or high temperature and high humidity environment).

再者,依據本發明的黏著劑組合物,其固化期間相較於習知顯著縮短到48小時或更短,且較佳為36小時或更短。因此,可抑制使用過多常用以縮短固化期間之添加劑,從而改善習知問題,諸如設備的堵塞及之類。 Furthermore, the curing time of the adhesive composition according to the present invention is significantly shortened to 48 hours or less, and preferably 36 hours or less, as compared with the conventional one. Therefore, excessive use of additives commonly used to shorten the curing period can be suppressed, thereby improving conventional problems such as blockage of equipment and the like.

Claims (7)

一種黏著劑組合物,包括:一丙烯酸系共聚物,在以所有單體為100重量份的基礎下,藉由將包含1至10重量份具有一羧基的(甲基)丙烯酸酯系單體及0.1至2重量份具有含以羥基來取代4個或多個碳原子的線性或環狀烷基的(甲基)丙烯酸酯系單體之單體進行共聚來製備;三官能基或更高之甲苯二異氰酸酯系交聯劑;及具有Na+或K+離子之離子型抗靜電劑,其中該黏著劑組合物的固化期間,在基於23℃及65%RH不隨著時間改變之時間點下,為48小時或更短,且該黏著劑組合物在放置於室溫24小時之前與之後的黏度變化為50%或更少。An adhesive composition includes: an acrylic copolymer, based on 100 parts by weight of all monomers, by including 1 to 10 parts by weight of a (meth) acrylate monomer having a carboxyl group and 0.1 to 2 parts by weight of a monomer having a (meth) acrylic acid ester-based monomer containing a linear or cyclic alkyl group substituted with 4 or more carbon atoms by a hydroxyl group; copolymerized by tri-functional group or higher Toluene diisocyanate-based cross-linking agent; and an ionic antistatic agent having Na + or K + ions, wherein the curing period of the adhesive composition is at a time point based on 23 ° C. and 65% RH that does not change with time. Is 48 hours or less, and the viscosity change of the adhesive composition before and after being left at room temperature for 24 hours is 50% or less. 如申請專利範圍第1項所述之黏著劑組合物,其中具有含以羥基來取代4個或多個碳原子的線性或環狀烷基之(甲基)丙烯酸酯系單體為至少一選自由4-羥基丁基丙烯酸酯、6-羥基己基(甲基)丙烯酸酯、8-羥基(甲基)丙烯酸辛酯、及所組成的群組。The adhesive composition according to item 1 of the scope of patent application, wherein the (meth) acrylate monomer having a linear or cyclic alkyl group containing 4 or more carbon atoms substituted with a hydroxyl group is at least one option Free 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy (meth) acrylate octyl, and A group of people. 如申請專利範圍第1項所述之黏著劑組合物,其中用以製備丙烯酸系共聚物的單體進一步包含具有一芳香環之(甲基)丙烯酸酯系單體。The adhesive composition according to item 1 of the scope of patent application, wherein the monomer used to prepare the acrylic copolymer further comprises a (meth) acrylate monomer having an aromatic ring. 如申請專利範圍第1項所述之黏著劑組合物,其中該抗靜電劑為一含氟陰離子。The adhesive composition according to item 1 of the patent application scope, wherein the antistatic agent is a fluorine-containing anion. 如申請專利範圍第4項所述之黏著劑組合物,其中該含氟陰離子為三氟甲磺酸()、雙(三氟磺醯)亞胺()、或雙(氟磺醯基)亞胺()。The adhesive composition according to item 4 of the scope of patent application, wherein the fluorine-containing anion is trifluoromethanesulfonic acid ( ), Bis (trifluorosulfonium) imine ( ), Or bis (fluorosulfonyl) imine ( ). 如申請專利範圍第1項所述之黏著劑組合物,其中該丙烯酸系共聚物在以所有單體為100重量份的基礎下,藉由將包含:1)88至98重量份具有1-12個碳原子的烷基之(甲基)丙烯酸酯單體;2)1至10重量份具有一羧基的(甲基)丙烯酸酯系單體;及3)0.1至2重量份具有含以羥基來取代4個或多個碳原子的線性或環狀烷基之(甲基)丙烯酸酯系單體之單體進行共聚來製備。The adhesive composition according to item 1 of the patent application range, wherein the acrylic copolymer is based on 100 parts by weight of all monomers, and will include: 1) 88 to 98 parts by weight having 1-12 (Meth) acrylic acid ester monomer of alkyl group having 1 carbon atom; 2) 1 to 10 parts by weight of (meth) acrylic acid ester monomer having a carboxyl group; and 3) 0.1 to 2 parts by weight A monomer of a linear or cyclic alkyl (meth) acrylate monomer substituted with 4 or more carbon atoms is prepared by copolymerization. 如申請專利範圍第1項所述之黏著劑組合物,在以丙烯酸系共聚物為100重量份的基礎下,包括0.1至1重量份的三官能基或更高之甲苯二異氰酸酯系交聯劑;及0.5至5重量份具有Na+或K+離子的離子型抗靜電劑。The adhesive composition according to item 1 of the scope of patent application, based on 100 parts by weight of the acrylic copolymer, including 0.1 to 1 part by weight of a trifunctional or higher toluene diisocyanate-based crosslinking agent. And 0.5 to 5 parts by weight of an ionic antistatic agent having Na + or K + ions.
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