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TW201702344A - Adhesive composition for polarizing plate, adhesive layer and adhesive sheet, and adhesive layer attached polarizing plate - Google Patents

Adhesive composition for polarizing plate, adhesive layer and adhesive sheet, and adhesive layer attached polarizing plate Download PDF

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Publication number
TW201702344A
TW201702344A TW105118350A TW105118350A TW201702344A TW 201702344 A TW201702344 A TW 201702344A TW 105118350 A TW105118350 A TW 105118350A TW 105118350 A TW105118350 A TW 105118350A TW 201702344 A TW201702344 A TW 201702344A
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Taiwan
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adhesive layer
polarizing plate
meth
adhesive
mass
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TW105118350A
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Chinese (zh)
Inventor
室井佐知
大久保貴啓
近藤恵子
黒澤翔
田中□祐
紺野雄太
三角忠史
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綜研化學股份有限公司
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Publication of TW201702344A publication Critical patent/TW201702344A/en

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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • 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
    • C09J11/06Non-macromolecular additives organic
    • 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
    • C09J133/10Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J133/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)

Abstract

The purpose of the invention is to provide an adhesive composition for a polarizing pate, the adhesive composition is capable of applying to a structure thatomits at least one of protective films for a polarizer, whterin the protective films usually formed on two sides of the polarizer. The durability of the adhesive composition under high temperature and humility environment is excellent and the ability to inhibit contraction of a polarizing plate is outstanding. The technical solution of the invention is to provide an adhesive composition used for forming an adhesive payer directly contacting with a polarizer. The adhesive composition comprises (A) (methyl) acrylic copolymers and (B) crosslinking agent. The (methyl) acrylic copolymers are obtained by polymerization of monomers, the monomers comprise alkyl methacrylate (a1) with glass transition temperature (Tg) of homopolymer less than -10 DEG C, and cross linkable functional group-containing monomers (a2) having 0.5 mass % or more and less than 10 mass %. The alkyl of a1 contains eight carbons or more, and a1 has 50 mass % or more and 99 mass % or less.

Description

偏光板用的黏著劑組成物、黏著劑層及黏著片以及附黏著劑層的偏光板 Adhesive composition for polarizing plate, adhesive layer and adhesive sheet, and polarizing plate with adhesive layer

本發明係關於偏光板用黏著劑組成物、黏著劑層及黏著片以及附黏著劑層的偏光板。 The present invention relates to an adhesive composition for a polarizing plate, an adhesive layer and an adhesive sheet, and a polarizing plate with an adhesive layer.

液晶單元(liquid crystal cell)係具有在2片基板(例:玻璃板)之間夾住液晶層之構造。在構成液晶單元之基板的表面,係透過黏著劑層而貼附有偏光板。先前,偏光板係為了提升力學性質及光學耐久性,通常係採用於具有偏光功能之偏光片的兩面上,積層有三乙酸纖維素膜等偏光片保護膜之構造。 A liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates (for example, a glass plate). On the surface of the substrate constituting the liquid crystal cell, a polarizing plate is attached through the adhesive layer. In order to improve the mechanical properties and optical durability, the polarizing plate is usually used on both sides of a polarizing plate having a polarizing function, and has a structure in which a polarizer protective film such as a cellulose triacetate film is laminated.

近年來係要求液晶單元的薄型化及偏光板的薄型化,對應偏光板之薄型要求,係嘗試省略形成於偏光片兩面之偏光片保護膜。但不具有偏光片保護膜之偏光板中,偏光片容易受水分影響,在高濕熱環境下容易產生偏光片的裂痕(破裂)、顯著收縮、光學性能劣化等的不良情形。 In recent years, the thickness of the liquid crystal cell and the thickness reduction of the polarizing plate have been demanded, and in response to the demand for the thin type of the polarizing plate, attempts have been made to omit the polarizer protective film formed on both sides of the polarizing plate. However, in the polarizing plate which does not have a polarizer protective film, the polarizer is easily affected by moisture, and it is easy to cause a crack (fracture) of the polarizer, a significant shrinkage, and deterioration of optical performance in a high-humidity heat environment.

專利文獻1記載一種含有單體成分聚合所得之(甲基)丙烯酸系聚合物的黏著劑,該單體成分含有在酯基末端具有碳數10至24的分支烷基之(甲基)丙烯酸烷酯19至99.5質量%。但並未特別提及省略偏光片保護膜並將黏著劑層直接積層於偏光片時之上述裂痕、收縮等問題。 Patent Document 1 describes an adhesive containing a (meth)acrylic polymer obtained by polymerization of a monomer component containing a (meth)acrylic acid having a branched alkyl group having 10 to 24 carbon atoms at the ester group terminal. The ester is 19 to 99.5% by mass. However, there is no particular mention of the above-mentioned cracking, shrinkage, and the like when the polarizer protective film is omitted and the adhesive layer is directly laminated on the polarizer.

專利文獻2記載一種黏著型偏光板,係具有偏光板、及設置於該偏光板之黏著劑層,其構成係前述偏光板僅在偏光片的一側具有透明保護膜,前述黏著劑層係設置於不具有前述透明保護膜側的偏光片上。但並未特別提及省略前述透明保護膜時之上述裂痕、收縮、光學性能等問題。 Patent Document 2 discloses an adhesive polarizing plate comprising a polarizing plate and an adhesive layer provided on the polarizing plate, wherein the polarizing plate has a transparent protective film only on one side of the polarizing plate, and the adhesive layer is provided. On the polarizer without the aforementioned transparent protective film side. However, the above-mentioned problems such as cracking, shrinkage, and optical properties when the transparent protective film is omitted are not particularly mentioned.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2012-246477號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-246477

[專利文獻2]日本特開2012-247574號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-247574

本發明的課題在於提供一種偏光板用黏著劑組成物,係可應用於省略通常在偏光片兩面形成之偏光片保護膜之至少一面的構成,且即使在高濕熱環境下亦可形成耐久性優異、且抑制偏光片之收縮為優異的黏著劑層。 An object of the present invention is to provide an adhesive composition for a polarizing plate which can be applied to a configuration in which at least one surface of a polarizer protective film which is usually formed on both surfaces of a polarizer is omitted, and excellent durability can be obtained even in a high-humidity heat environment. Further, the shrinkage of the polarizer is suppressed to be an excellent adhesive layer.

本發明人等為解決上述課題而努力研究。其 結果發現藉由使用具有以下特定構成之偏光板用黏著劑組成物,而可解決上述課題,從而完成本發明。 The inventors of the present invention have diligently studied to solve the above problems. its As a result, it has been found that the above problems can be solved by using an adhesive composition for a polarizing plate having the following specific constitution, and the present invention has been completed.

本發明例如為以下[1]至[5]。 The present invention is, for example, the following [1] to [5].

[1]一種偏光板用黏著劑組成物,係用以形成與偏光片直接相接之黏著劑層,並含有:(A)(甲基)丙烯酸系共聚物,係單體成分共聚所得,該單體成分含有均聚物的玻璃轉移溫度(Tg)未滿-10℃且烷基之碳數為8以上的甲基丙烯酸烷酯(a1)50質量%以上99.5質量%以下、及含有交聯性官能基的單體(a2)0.5質量%以上且未滿10質量%的量;以及(B)交聯劑。 [1] An adhesive composition for a polarizing plate for forming an adhesive layer directly in contact with a polarizer, and comprising: (A) a (meth)acrylic copolymer obtained by copolymerizing a monomer component, The monomer component contains a homopolymer having a glass transition temperature (Tg) of less than -10 ° C and an alkyl group having a carbon number of 8 or more, and the alkyl methacrylate (a1) is 50% by mass or more and 99.5% by mass or less, and contains cross-linking. The amount of the functional group-based monomer (a2) is 0.5% by mass or more and less than 10% by mass; and (B) the crosslinking agent.

[2]一種偏光板用黏著劑層,係前述[1]所記載的黏著劑組成物所形成。 [2] An adhesive layer for a polarizing plate, which is formed by the adhesive composition described in the above [1].

[3]如前述[2]所記載的偏光板用黏著劑層,其中水蒸氣透過率為800g/m2.day以下。 [3] The adhesive layer for a polarizing plate according to the above [2], wherein a water vapor transmission rate is 800 g/m 2 . Below day.

[4]一種偏光板用黏著片,係具有前述[2]或[3]所記載的黏著劑層。 [4] An adhesive sheet for a polarizing plate, comprising the adhesive layer according to [2] or [3] above.

[5]一種附黏著劑層的偏光板,係具有直接積層於偏光片的至少一面之前述[2]或[3]所記載的黏著劑層。 [5] A polarizing plate with an adhesive layer comprising an adhesive layer as described in [2] or [3] directly laminated on at least one surface of the polarizer.

根據本發明可提供一種偏光板用黏著劑組成物,係可應用於省略通常在偏光片兩面形成之偏光片保護膜之至少一面的構成,即使在高濕熱環境下亦可形成耐久性優異、且抑制偏光片之收縮為優異者。又,可提供由前述組成物所形成之偏光板用黏著劑層、具有前述黏著劑層 之偏光板用黏著片、及具有前述黏著劑層之附黏著劑層的偏光板。 According to the present invention, it is possible to provide an adhesive composition for a polarizing plate which can be applied to a configuration in which at least one surface of a polarizer protective film which is usually formed on both surfaces of a polarizer is omitted, and excellent durability can be formed even in a high-humidity heat environment. It is preferable to suppress the shrinkage of the polarizer. Further, an adhesive layer for a polarizing plate formed of the above composition can be provided, and the adhesive layer can be provided The polarizing plate for polarizing plates and the polarizing plate having the adhesive layer of the above-mentioned adhesive layer.

以下,說明本發明的偏光板用黏著劑組成物、偏光板用黏著劑層、偏光板用黏著片及附黏著劑層之偏光板。以下,亦將本發明的偏光板用黏著劑組成物、偏光板用黏著劑層及偏光板用黏著片分別稱為「黏著劑組成物」、「黏著劑層」及「黏著片」。 Hereinafter, the adhesive composition for a polarizing plate, the adhesive layer for a polarizing plate, the adhesive sheet for a polarizing plate, and a polarizing plate with an adhesive layer will be described. In the following, the adhesive composition for a polarizing plate, the adhesive layer for a polarizing plate, and the adhesive sheet for a polarizing plate of the present invention are also referred to as "adhesive composition", "adhesive layer", and "adhesive sheet", respectively.

[偏光板用黏著劑組成物] [Adhesive Composition for Polarizing Plate]

本發明的偏光板用黏著劑組成物,係含有以下所說明之(甲基)丙烯酸系共聚物(A)及交聯劑(B)。前述組成物亦可按照必要而含有至少1種選自矽烷偶合劑(C)及抗靜電劑(D),亦可含有有機溶劑(E)。 The adhesive composition for a polarizing plate of the present invention contains the (meth)acrylic copolymer (A) and the crosslinking agent (B) described below. The composition may contain at least one selected from the group consisting of a decane coupling agent (C) and an antistatic agent (D) as necessary, and may also contain an organic solvent (E).

[(甲基)丙烯酸系共聚物(A)] [(Meth)acrylic copolymer (A)]

(甲基)丙烯酸系共聚物(A)係單體成分的共聚物,該單體成分含有均聚物的玻璃轉移溫度(Tg)未滿-10℃且烷基之碳數為8以上的甲基丙烯酸烷酯(a1)50質量%以上99.5質量%以下、及含有交聯性官能基的單體(a2)0.5質量%以上且未滿10質量%的量,亦即係前述單體成分共聚所得之共聚物。 (meth)acrylic copolymer (A) is a copolymer of a monomer component containing a homopolymer having a glass transition temperature (Tg) of less than -10 ° C and an alkyl group having a carbon number of 8 or more. The alkyl acrylate (a1) is 50% by mass or more and 99.5% by mass or less, and the crosslinking functional group-containing monomer (a2) is 0.5% by mass or more and less than 10% by mass, that is, the monomer component copolymerization. The resulting copolymer.

本明細書中將丙烯酸及甲基丙烯酸通稱為「(甲基)丙烯酸」。又,聚合物所含之源自一單體A之構成 單元係記載為「單體A單元」。又,前述(a1)、(a2)分別稱為「單體(a1)」、「單體(a2)」。 Acrylic acid and methacrylic acid are collectively referred to as "(meth)acrylic acid" in this specification. Moreover, the composition of the polymer derived from a monomer A The unit is described as "monomer A unit". Further, the above (a1) and (a2) are referred to as "monomer (a1)" and "monomer (a2)", respectively.

(甲基)丙烯酸烷酯的均聚物的玻璃轉移溫度(Tg)係採用Polymer Handbook Fourth Edition (Wiley-Interscience 2003)所記載的值。 The glass transition temperature (Tg) of the homopolymer of the (meth)acrylic acid alkyl ester is a value described in Polymer Handbook Fourth Edition (Wiley-Interscience 2003).

又,上述文獻未記載Tg之單體,例如可用以下條件測定以下條件所合成的均聚物之Tg。在具有攪拌機、迴流冷卻器、溫度計及氮導入管之反應裝置加入單體100質量份及乙酸乙酯100質量份,一邊導入氮氣一邊升溫至80℃。接著加入2,2’-偶氮雙異丁腈0.1質量份,在氮氣環境下以80℃進行6小時聚合反應。將所得單體之均聚物封入簡易密閉鍋。使用示差掃描熱量計(DSC),在氮氣流下以10℃/分鐘升溫並測定熱變化,描繪「吸放熱量」與「溫度」之圖表,以此時所觀測之特徵性拐點作為玻璃轉移。又,Tg係使用由DSC曲線以中點法所得的值。 Further, the above document does not describe a monomer of Tg, and for example, the Tg of the homopolymer synthesized under the following conditions can be measured under the following conditions. 100 parts by mass of a monomer and 100 parts by mass of ethyl acetate were added to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, and the temperature was raised to 80 ° C while introducing nitrogen gas. Next, 0.1 part by mass of 2,2'-azobisisobutyronitrile was added, and polymerization was carried out at 80 ° C for 6 hours under a nitrogen atmosphere. The homopolymer of the obtained monomer was sealed in a simple closed pot. Using a differential scanning calorimeter (DSC), the temperature was raised at 10 ° C/min under a nitrogen stream, and the change in heat was measured, and a graph of "heat absorption" and "temperature" was plotted, and the characteristic inflection point observed at this time was used as a glass transition. Further, the Tg system uses a value obtained by a midpoint method from a DSC curve.

《甲基丙烯酸烷酯(a1)》 "Alkyl methacrylate (a1)"

單體(a1)係均聚物的Tg未滿-10℃且烷基之碳數為8以上的甲基丙烯酸烷酯。前述單體較佳為均聚物的Tg為-80℃以上且未滿-10℃,且烷基之碳數為8以上者,前述單體更佳為Tg為-70至-30℃且烷基之碳數為8以上者,前述單體又更佳為Tg為-70至-30℃且烷基之碳數為10以上者。烷基之碳數的上限例如為18。 The monomer (a1)-based homopolymer has an alkylene methacrylate having a Tg of less than -10 ° C and a carbon number of the alkyl group of 8 or more. Preferably, the monomer has a Tg of -80 ° C or more and less than -10 ° C, and the carbon number of the alkyl group is 8 or more, and the monomer is more preferably a Tg of -70 to -30 ° C and an alkane. When the carbon number of the group is 8 or more, the monomer is more preferably a Tg of -70 to -30 ° C and a carbon number of the alkyl group of 10 or more. The upper limit of the carbon number of the alkyl group is, for example, 18.

藉由單體(a1)共聚所得之共聚物(A),故為具有單體(a1)單元之共聚物(A)之使用,即可得到具有可阻止 水分滲入偏光片之疏水性,並具有適當的水蒸氣透過率之黏著劑。 By using the copolymer (A) obtained by copolymerizing the monomer (a1), the use of the copolymer (A) having a monomer (a1) unit can be obtained to prevent The water penetrates into the polarizer of the polarizer and has an appropriate water vapor transmission rate of the adhesive.

單體(a1)可列舉如:甲基丙烯酸辛酯(-20℃)、甲基丙烯酸異辛酯(-45℃)、甲基丙烯酸異癸酯(-41℃)、甲基丙烯酸月桂酯(-65℃)、甲基丙烯酸十四烷酯(-72℃)、及甲基丙烯酸異硬脂酯(-18℃)。括弧內的數值表示各單體之均聚物的Tg。 The monomer (a1) may, for example, be octyl methacrylate (-20 ° C), isooctyl methacrylate (-45 ° C), isodecyl methacrylate (-41 ° C), lauryl methacrylate ( -65 ° C), tetradecyl methacrylate (-72 ° C), and isostearyl methacrylate (-18 ° C). The numerical values in parentheses indicate the Tg of the homopolymer of each monomer.

若使用含有源自於均聚物之Tg低之甲基丙烯酸烷酯的構成單元的(甲基)丙烯酸系共聚物,則可賦予黏著劑層適當的應力緩和特性。又,若使用甲基丙烯酸烷酯的烷基為長鏈者,則除了應力緩和特性以外也可賦予疏水性。例如藉由使用具有長鏈烷基之單體(a1),而有獲得具有可阻止水分滲入偏光片之疏水性之黏著劑層的傾向。 When a (meth)acrylic copolymer containing a constituent unit derived from an alkyl methacrylate having a low Tg derived from a homopolymer is used, appropriate stress relaxation properties can be imparted to the adhesive layer. Further, when an alkyl group in which an alkyl methacrylate is used is a long chain, hydrophobicity can be imparted in addition to the stress relaxation property. For example, by using the monomer (a1) having a long-chain alkyl group, there is a tendency to obtain an adhesive layer having a hydrophobic property which prevents moisture from penetrating into the polarizer.

單體(a1)可單獨使用1種,也可使用2種以上。 The monomer (a1) may be used alone or in combination of two or more.

共聚物(A)的原料單體之單體成分100質量%中,單體(a1)的使用量為50質量%以上99.5質量%以下,較佳為70至99質量%,更佳為80至98.5質量%。若單體(a1)的使用量在前述範圍,則所得黏著劑層可展現充分疏水功能,故較佳。 In the monomer component of the raw material monomer of the copolymer (A), the amount of the monomer (a1) used is 50% by mass or more and 99.5% by mass or less, preferably 70 to 99% by mass, more preferably 80% by mass. 98.5 mass%. If the amount of the monomer (a1) used is in the above range, the resulting adhesive layer can exhibit a sufficiently hydrophobic function, which is preferable.

《含有交聯性官能基的單體(a2)》 "Complex (a2) containing a crosslinkable functional group"

共聚物(A)的原料單體之單體成分係含有可與交聯劑(B)反應之具有交聯性官能基的單體,亦即含有交聯性官能基的單體(a2),故共聚物(A)係具有單體(a2)單元。 The monomer component of the raw material monomer of the copolymer (A) contains a monomer having a crosslinkable functional group reactive with the crosslinking agent (B), that is, a monomer (a2) having a crosslinkable functional group, Therefore, the copolymer (A) has a monomer (a2) unit.

單體(a2)可列舉如:含有羥基的單體、含有羧基的單 體。 The monomer (a2) may, for example, be a monomer having a hydroxyl group or a single group having a carboxyl group. body.

含有羥基的單體可列舉如:含有羥基的(甲基)丙烯酸酯,具體而言可列舉如:(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯等(甲基)丙烯酸羥基烷酯。(甲基)丙烯酸羥基烷酯的羥基烷基之碳數通常為2至8,較佳為2至6。 The hydroxyl group-containing monomer may, for example, be a hydroxyl group-containing (meth) acrylate, and specific examples thereof include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. A hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate or 8-hydroxyoctyl (meth) acrylate. The hydroxyalkyl group of the hydroxyalkyl (meth) acrylate has a carbon number of usually 2 to 8, preferably 2 to 6.

含有羧基的單體可列舉如:(甲基)丙烯酸β-羧基乙酯、(甲基)丙烯酸5-羧基戊酯、琥珀酸單(甲基)丙烯醯氧基乙酯、ω-羧基聚己內酯單(甲基)丙烯酸酯等含有羧基的(甲基)丙烯酸酯;丙烯酸、甲基丙烯酸、伊康酸、巴豆酸、富馬酸、馬來酸。 Examples of the carboxyl group-containing monomer include β-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, mono(meth)acryloxyethyl succinate, and ω-carboxypoly A carboxyl group-containing (meth) acrylate such as a lactone mono(meth)acrylate; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid.

為了提升黏著劑層的疏水性,上述單體(a2)較佳為具有甲基丙烯酸構造,單體(a2)可單獨使用1種,也可使用2種以上。 In order to improve the hydrophobicity of the adhesive layer, the monomer (a2) preferably has a methacrylic acid structure, and the monomer (a2) may be used singly or in combination of two or more.

共聚物(A)的原料單體之單體成分100質量%中,單體(a2)的使用量為0.5質量%以上且未滿10質量%,較佳為1至8質量%,更佳為2至6質量%。若單體(a2)的使用量未滿前述上限值或為前述上限值以下,則共聚物(A)與交聯劑(B)所形成之交聯密度不會過高,可獲得應力緩和特性優異之黏著劑層。若單體(a2)的使用量為前述下限值以上,則可有效地形成交聯構造,並獲得常溫具有適當強度之黏著劑層。 In 100% by mass of the monomer component of the raw material monomer of the copolymer (A), the amount of the monomer (a2) used is 0.5% by mass or more and less than 10% by mass, preferably 1 to 8% by mass, more preferably 2 to 6 mass%. When the amount of the monomer (a2) used is less than the above upper limit or less than the above upper limit, the crosslinking density of the copolymer (A) and the crosslinking agent (B) is not excessively high, and stress can be obtained. A layer of adhesive that is excellent in easing properties. When the amount of use of the monomer (a2) is at least the above lower limit value, the crosslinked structure can be effectively formed, and an adhesive layer having an appropriate strength at normal temperature can be obtained.

又,單體(a2)的種類及量較佳為設定使共聚 物(A)的酸價(mgKOH/g)為15以下,更佳為13以下,又更佳為12以下。若酸價為前述上限值以下,則可降低共聚物(A)的極性,故可進一步提升疏水性,而獲得水分滲入偏光片的抑制效果高之黏著劑層。 Further, the type and amount of the monomer (a2) are preferably set to copolymerize The acid value (mgKOH/g) of the substance (A) is 15 or less, more preferably 13 or less, still more preferably 12 or less. When the acid value is at most the above upper limit value, the polarity of the copolymer (A) can be lowered, so that the hydrophobicity can be further enhanced, and an adhesive layer having a high effect of inhibiting penetration of moisture into the polarizer can be obtained.

又,共聚物(A)的酸價係根據共聚所使用之含有羧基的單體的分子量、含有羧基的單體的調配量(質量%)而由下述式算出。又,56.1係KOH的分子量。 In addition, the acid value of the copolymer (A) is calculated from the following formula according to the molecular weight of the carboxyl group-containing monomer used for copolymerization and the compounding amount (% by mass) of the carboxyl group-containing monomer. Further, 56.1 is a molecular weight of KOH.

聚合物的酸價 Acid value of polymer

(mgKOH/g)=56.1/X×(Y/100)×1000=561/X×Y。 (mgKOH/g) = 56.1 / X × (Y / 100) × 1000 = 561 / X × Y.

X:含有羧基的單體的分子量。 X: molecular weight of a monomer having a carboxyl group.

Y:含有羧基的單體的調配量。 Y: A compounding amount of a monomer having a carboxyl group.

《其他單體》 Other Monomers

在不損及共聚物(A)的物性之範圍內,共聚物(A)的原料單體之單體成分可使用例如上述單體(a1)以外的(甲基)丙烯酸烷酯、(甲基)丙烯酸烷氧基烷酯、烷氧基聚烷二醇單(甲基)丙烯酸酯、含有脂環式基或芳香環的(甲基)丙烯酸酯、含有羧基的單體以外的含有酸基的單體、含有胺基的單體、含有醯胺基的單體、含有氮系雜環的單體、含有氰基的單體等其他單體。 The monomer component of the raw material monomer of the copolymer (A) can be, for example, an alkyl (meth)acrylate other than the above monomer (a1), (methyl), insofar as the physical properties of the copolymer (A) are not impaired. An alkoxyalkyl acrylate, an alkoxy polyalkylene glycol mono(meth) acrylate, a (meth) acrylate containing an alicyclic group or an aromatic ring, or an acid group containing a carboxyl group-containing monomer Other monomers such as a monomer, an amine group-containing monomer, a guanamine group-containing monomer, a nitrogen-containing heterocyclic ring-containing monomer, and a cyano group-containing monomer.

單體(a1)以外的(甲基)丙烯酸烷酯係例如以式:CH2=CR1-COOR2表示。式中,R1為氫或甲基,R2為碳數1至18的烷基。可列舉如:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸 第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、丙烯酸辛酯、丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、丙烯酸異癸酯、(甲基)丙烯酸十一烷酯、丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、丙烯酸異硬脂酯。 The alkyl (meth)acrylate other than the monomer (a1) is represented, for example, by the formula: CH 2 =CR 1 -COOR 2 . In the formula, R 1 is hydrogen or a methyl group, and R 2 is an alkyl group having 1 to 18 carbon atoms. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (methyl) ) isobutyl acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, octyl acrylate, isooctyl acrylate, decyl (meth) acrylate, decyl (meth) acrylate, isodecyl acrylate, undecyl (meth) acrylate, lauryl acrylate, (methyl) Stearyl acrylate, isostearyl acrylate.

(甲基)丙烯酸烷氧基烷酯之例,可列舉如:(甲基)丙烯酸甲氧基甲酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸3-甲氧基丙酯、(甲基)丙烯酸3-乙氧基丙酯、(甲基)丙烯酸4-甲氧基丁酯、(甲基)丙烯酸4-乙氧基丁酯。 Examples of the alkoxyalkyl (meth)acrylate include, for example, methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, and 2-ethoxy(meth)acrylate. Ethyl ethyl ester, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-(meth)acrylate Ethoxybutyl ester.

單(甲基)丙烯酸烷氧基聚烷二醇酯之例,可列舉如:單(甲基)丙烯酸甲氧基二乙二醇酯、單(甲基)丙烯酸甲氧基二丙二醇酯、單(甲基)丙烯酸乙氧基三乙二醇酯、單(甲基)丙烯酸乙氧基二乙二醇酯、單(甲基)丙烯酸甲氧基三乙二醇酯。 Examples of the alkoxy polyalkylene glycol mono(meth)acrylate include, for example, methoxybisethylene glycol mono(meth)acrylate, methoxydipropylene glycol mono(meth)acrylate, and a single Ethoxytriethylene glycol (meth)acrylate, ethoxydiethylene glycol mono(meth)acrylate, methoxytriethylene glycol mono(meth)acrylate.

含有脂環式基或芳香環的(甲基)丙烯酸酯可列舉如:(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯。 Examples of the (meth) acrylate containing an alicyclic group or an aromatic ring include cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, benzyl (meth)acrylate, and (meth)acrylic acid. Phenyl ester.

含有酸基的單體可列舉如:馬來酸酐、伊康酸酐、側鏈具有磷酸基之(甲基)丙烯酸系單體、側鏈具有硫酸基之(甲基)丙烯酸系單體。含有胺基的單體可列舉如:(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯等含有胺基的(甲基)丙烯酸酯。含有醯胺基的單體可列舉如:(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N- 乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺。含有氮系雜環的單體可列舉如:乙烯基吡咯啶酮、丙烯醯基嗎啉、乙烯基己內醯胺。含有氰基的單體之例可列舉如:氰基(甲基)丙烯酸酯、(甲基)丙烯腈。 Examples of the acid group-containing monomer include maleic anhydride, itaconic acid anhydride, a (meth)acrylic monomer having a phosphate group in a side chain, and a (meth)acrylic monomer having a sulfuric acid group in a side chain. The amine group-containing monomer may, for example, be an amino group-containing (meth) acrylate such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate. Examples of the amide group-containing monomer include (meth) acrylamide, N-methyl (meth) acrylamide, and N- Ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-hexyl (meth) acrylamide. Examples of the monomer containing a nitrogen-based hetero ring include vinyl pyrrolidone, acryloyl morpholine, and vinyl caprolactam. Examples of the cyano group-containing monomer include cyano (meth) acrylate and (meth) acrylonitrile.

又,在不損及共聚物(A)的物性之範圍內,其他單體可使用例如苯乙烯系單體、乙酸乙烯酯等共聚性單體。 Moreover, a copolymerizable monomer such as a styrene monomer or a vinyl acetate can be used as the other monomer insofar as the physical properties of the copolymer (A) are not impaired.

苯乙烯系單體可列舉如:苯乙烯;甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、丙基苯乙烯、丁基苯乙烯、己基苯乙烯、庚基苯乙烯、辛基苯乙烯等烷基苯乙烯;氟苯乙烯、氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘化苯乙烯等鹵化苯乙烯;硝基苯乙烯、乙醯基苯乙烯、甲氧基苯乙烯。 Examples of the styrene monomer include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, and octyl group. Alkyl styrene such as styrene; halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene or styrene iodide; nitrostyrene, ethyl styrene styrene, methoxy styrene .

其他單體可單獨使用1種,也可使用2種以上。 The other monomers may be used alone or in combination of two or more.

共聚物(A)的原料單體之單體成分100質量%中,以上其他單體(例:上述單體(a1)以外的(甲基)丙烯酸烷酯、共聚性單體)的總使用量較佳為0至45質量%,更佳為0至25質量%。 The total amount of the above other monomer (for example, alkyl (meth)acrylate or copolymerizable monomer other than the above monomer (a1)) in 100% by mass of the monomer component of the raw material monomer of the copolymer (A) It is preferably from 0 to 45% by mass, more preferably from 0 to 25% by mass.

《(甲基)丙烯酸系共聚物(A)的製造條件》 <<Production Conditions of (Meth)Acrylic Copolymer (A)>>

(甲基)丙烯酸系共聚物(A)的製造條件係沒有特別限定,例如能夠使用溶液聚合法來製造。具體而言,係在反應容器內添加聚合溶劑及單體成分,在氮氣等惰性氣體環境下添加聚合起始劑,而且反應起始溫度通常設為40至100℃,較佳為50至80℃,且反應系統通常維持在50至 90℃,較佳為70至90℃的溫度並且反應4至20小時。 The production conditions of the (meth)acrylic copolymer (A) are not particularly limited, and can be produced, for example, by a solution polymerization method. Specifically, a polymerization solvent and a monomer component are added to the reaction vessel, and a polymerization initiator is added in an inert gas atmosphere such as nitrogen, and the reaction initiation temperature is usually 40 to 100 ° C, preferably 50 to 80 ° C. And the reaction system is usually maintained at 50 to The temperature is 90 ° C, preferably 70 to 90 ° C and the reaction is 4 to 20 hours.

共聚物(A)係例如將含有上述單體(a1)、(a2)之單體成分共聚所得,但可為無規共聚物或嵌段共聚物。該等中較佳為無規共聚物。 The copolymer (A) is obtained by, for example, copolymerizing a monomer component containing the above monomers (a1) and (a2), but may be a random copolymer or a block copolymer. Preferred among these are random copolymers.

溶液聚合中使用之聚合溶劑之例,可列舉如:苯、甲苯、二甲苯等芳香族烴類;正戊烷、正己烷、正庚烷、正辛烷等脂肪族烴類;環戊烷、環己烷、環庚烷、環辛烷等脂環烴類;二乙基醚、二異丙基醚、1,2-二甲氧基乙烷、二丁基醚、四氫呋喃、二噁烷、苯甲醚、苯基乙基醚、二苯基醚等醚類;氯仿、四氯化碳、1,2-二氯乙烷、氯苯等鹵烴類;乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸甲酯等酯類;丙酮、甲基乙基酮、二乙基酮、甲基異丁基酮、環己酮等酮類;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等醯胺類;乙腈、苯甲腈等腈類;二甲基亞碸、環丁碸等亞碸類等。此類聚合溶劑可單獨使用1種,亦可使用2種以上。 Examples of the polymerization solvent used in the solution polymerization include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; and cyclopentane; An alicyclic hydrocarbon such as cyclohexane, cycloheptane or cyclooctane; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, An ether such as anisole, phenylethyl ether or diphenyl ether; a halogenated hydrocarbon such as chloroform, carbon tetrachloride, 1,2-dichloroethane or chlorobenzene; ethyl acetate, propyl acetate, acetic acid Esters such as butyl ester and methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone; N, N-dimethylformamide, N , amides such as N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; and fluorenes such as dimethyl hydrazine and cyclobutyl hydrazine. These polymerization solvents may be used alone or in combination of two or more.

溶液聚合所使用之聚合起始劑可列舉如:偶氮系起始劑、過氧化物系起始劑。具體而言可列舉如:2,2’-偶氮雙異丁腈等偶氮化合物;過氧化苯甲醯、過氧化月桂醯等過氧化物。該等中較佳為偶氮化合物。偶氮化合物可列舉如:2,2’-偶氮雙異丁腈、2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮雙(2-環丙基丙腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷-1-腈)、2-(胺甲醯基偶氮)異丁腈、2- 苯基偶氮-4-甲氧基-2,4-二甲基戊腈、2,2'-偶氮雙(2-甲脒基丙烷)二鹽酸鹽、2,2'-偶氮雙(N,N'-二亞甲基異丁基脒)、2,2'-偶氮雙(異丁基醯胺基)二水合物、4,4'-偶氮雙(4-氰基戊酸)、2,2'-偶氮雙(2-氰基丙醇)、二甲基-2,2'-偶氮雙(2-甲基丙酸酯)、2,2'-偶氮雙[2-甲基-N-(2-羥基乙基)丙醯胺]。該等的聚合起始劑可單獨使用1種,也可使用2種以上。 The polymerization initiator used in the solution polymerization may, for example, be an azo initiator or a peroxide initiator. Specific examples thereof include azo compounds such as 2,2'-azobisisobutyronitrile; peroxides such as benzamidine peroxide and lauric acid peroxide. Among these, an azo compound is preferred. The azo compound may, for example, be 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'- Azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(aminomethylmercaptoazo)isobutyronitrile, 2- Phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis(2-methylamidinopropane) dihydrochloride, 2,2'-azo double (N,N'-Dimethyleneisobutylphosphonium), 2,2'-azobis(isobutylguanidino)dihydrate, 4,4'-azobis(4-cyanopentane) Acid), 2,2'-azobis(2-cyanopropanol), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azo double [2-Methyl-N-(2-hydroxyethyl)propanamide]. These polymerization initiators may be used alone or in combination of two or more.

相對於(甲基)丙烯酸系共聚物(A)的原料單體之單體成分100質量份,聚合起始劑通常使用0.01至5質量份,較佳為0.01至3質量份的範圍內的量。又,上述聚合反應中可適當地補充添加聚合起始劑、鏈轉移劑、單體成分、聚合溶媒。 The polymerization initiator is usually used in an amount of from 0.01 to 5 parts by mass, preferably from 0.01 to 3 parts by mass, per 100 parts by mass of the monomer component of the raw material monomer of the (meth)acrylic copolymer (A). . Further, a polymerization initiator, a chain transfer agent, a monomer component, and a polymerization solvent may be appropriately added to the polymerization reaction.

《(甲基)丙烯酸系共聚物(A)的物性及含量》 "Physical properties and content of (meth)acrylic copolymer (A)"

(甲基)丙烯酸系共聚物(A)藉由膠體滲透層析(GPC)法所測定之重量平均分子量(Mw)以聚苯乙烯換算值通常為40萬至300萬,較佳為60萬至250萬,更佳為80萬至200萬,又更佳為80萬至130萬。藉由使用Mw在前述範圍且具有上述單體單元之共聚物(A),而可展現可阻止水分滲入偏光片之疏水性。進一步易獲得黏著力的平衡,可為適於塗布之黏度的黏著劑組成物。 The weight average molecular weight (Mw) of the (meth)acrylic copolymer (A) measured by a colloidal permeation chromatography (GPC) method is usually 400,000 to 3,000,000, preferably 600,000 to 200,000. 2.5 million, more preferably 800,000 to 2 million, and even better 800,000 to 1.3 million. By using the copolymer (A) having the above-mentioned range of Mw and having the above monomer unit, it is possible to exhibit hydrophobicity which can prevent moisture from penetrating into the polarizer. Further, it is easy to obtain a balance of adhesion, which may be an adhesive composition suitable for the viscosity of the coating.

(甲基)丙烯酸系共聚物(A)以GPC法測定之分子量分布(Mw/Mn)通常為15以下,較佳為2至15,更佳為4至13。 The molecular weight distribution (Mw/Mn) of the (meth)acrylic copolymer (A) measured by the GPC method is usually 15 or less, preferably 2 to 15, more preferably 4 to 13.

(甲基)丙烯酸系共聚物(A)之玻璃轉移溫度(Tg),係例如可由構成該共聚物之單體單元及其含有比例 而藉由Fox式計算。例如可合成(甲基)丙烯酸系共聚物(A)使以Fox式所求之玻璃轉移溫度(Tg)通常為-80至-10℃,較佳為-80至-20℃,更佳為-70至-30℃。藉由使用具有如此玻璃轉移溫度(Tg)之(甲基)丙烯酸系共聚物(A),而可獲得應力緩和特性及耐久性優異、且常溫下之黏著性優異之黏著劑組成物。 The glass transition temperature (Tg) of the (meth)acrylic copolymer (A) is, for example, a monomer unit constituting the copolymer and a ratio thereof And by the Fox type calculation. For example, the (meth)acrylic copolymer (A) can be synthesized so that the glass transition temperature (Tg) obtained by the Fox formula is usually -80 to -10 ° C, preferably -80 to -20 ° C, more preferably - 70 to -30 ° C. By using the (meth)acrylic copolymer (A) having such a glass transition temperature (Tg), an adhesive composition which is excellent in stress relaxation property and durability and excellent in adhesion at normal temperature can be obtained.

Fox的式:1/Tg=(W1/Tg1)+(W2/Tg2)+…+(Wm/Tgm)。 Fox's formula: 1/Tg = (W 1 /Tg 1 ) + (W 2 /Tg 2 )+...+(W m /T gm ).

W1+W2+…+Wm=1。 W 1 + W 2 +...+W m =1.

式中,Tg為(甲基)丙烯酸系共聚物(A)之玻璃轉移溫度,Tg1、Tg2、…、Tgm係各單體所構成之均聚物之玻璃轉移溫度,W1、W2、…、Wm係源自於各單體之構成單元在前述共聚物(A)中的重量分率。源自各單體之構成單元之重量分率,係可使用共聚物合成時各單體相對於全單體之添加比例。 In the formula, Tg is the glass transition temperature of the (meth)acrylic copolymer (A), and the glass transition temperature of the homopolymer composed of Tg 1 , Tg 2 , ..., Tg m monomers, W 1 , W 2 , ..., W m is a weight fraction derived from the constituent unit of each monomer in the copolymer (A). The weight fraction of the constituent units derived from each monomer can be a ratio of addition of each monomer to the total monomer when the copolymer is synthesized.

前述Fox式中各單體所構成之均聚物的玻璃轉移溫度例如可使用Polymer Handbook Fourth Edition(Wiley-Interscience 2003)記載的值。又,上述文獻未記載Tg之單體,係例如以上述條件測定以上述條件合成之均聚物的Tg。 The glass transition temperature of the homopolymer composed of each monomer in the above Fox formula can be, for example, a value described in Polymer Handbook Fourth Edition (Wiley-Interscience 2003). Further, the above document does not describe a monomer of Tg, and for example, the Tg of the homopolymer synthesized under the above conditions is measured under the above conditions.

本發明的黏著劑組成物中,在除了組成物中的有機溶媒之固形分100質量%中,(甲基)丙烯酸系共聚物(A)的含量通常為60至99.99質量%,較佳為70至99.95質量%,特佳為80至99.90質量%。若(甲基)丙烯酸系共聚物(A)的含量在前述範圍,則作為黏著劑的性能平衡,且黏 著特性優異。 In the adhesive composition of the present invention, the content of the (meth)acrylic copolymer (A) is usually 60 to 99.99% by mass, preferably 70, in addition to 100% by mass of the solid content of the organic solvent in the composition. It is up to 99.95 mass%, particularly preferably 80 to 99.90 mass%. When the content of the (meth)acrylic copolymer (A) is in the above range, the performance as an adhesive is balanced and sticky. Excellent characteristics.

[交聯劑(B)] [Crosslinking agent (B)]

本發明的黏著劑組成物係進一步含有交聯劑(B)。 The adhesive composition of the present invention further contains a crosslinking agent (B).

交聯劑(B)只要是可與(甲基)丙烯酸系共聚物(A)所具有之源自含有交聯性官能基的單體(a2)的交聯性官能基產生交聯反應之成分,則無特別限定,可列舉如:異氰酸酯化合物(B1)、金屬螯合物化合物(B2)、環氧化合物(B3)。 The crosslinking agent (B) is a component which can form a crosslinking reaction with a crosslinkable functional group derived from the crosslinking functional group-containing monomer (a2) which the (meth)acrylic copolymer (A) has. Further, it is not particularly limited, and examples thereof include an isocyanate compound (B1), a metal chelate compound (B2), and an epoxy compound (B3).

交聯劑(B)可單獨使用1種,也可使用2種以上。 The crosslinking agent (B) may be used alone or in combination of two or more.

本發明的黏著劑組成物中,相對於(甲基)丙烯酸系共聚物(A)100質量份,交聯劑(B)的含量通常為0.01至5質量份,較佳為0.05至2.5質量份,又更佳為0.1至1質量份。若該含量在前述範圍,則以容易使耐久性與應力緩和特性平衡此點而言係較佳。 In the adhesive composition of the present invention, the content of the crosslinking agent (B) is usually 0.01 to 5 parts by mass, preferably 0.05 to 2.5 parts by mass, per 100 parts by mass of the (meth)acrylic copolymer (A). More preferably, it is 0.1 to 1 part by mass. When the content is in the above range, it is preferable in that the durability and the stress relaxation property are easily balanced.

《異氰酸酯化合物(B1)》 Isocyanate Compound (B1)

作為異氰酸酯化合物(B1),通常使用1分子中的異氰酸酯基數為2以上之異氰酸酯化合物。藉由異氰酸酯化合物(B1)使(甲基)丙烯酸系共聚物(A)交聯,能夠形成交聯體(網狀聚合物)。 As the isocyanate compound (B1), an isocyanate compound having an isocyanate group number of 2 or more in one molecule is usually used. By crosslinking the (meth)acryl-based copolymer (A) with the isocyanate compound (B1), a crosslinked body (network polymer) can be formed.

異氰酸酯化合物(B1)的異氰酸酯基數,通常為2以上,以2至8為佳,以3至6更佳。異氰酸酯基數在前述範圍時,以(甲基)丙烯酸系共聚物(A)與異氰酸酯化合物(B1)的交聯反應效率之點、及保持黏著劑層的柔軟性之點方面較佳。 The isocyanate compound (B1) has an isocyanate group number of usually 2 or more, preferably 2 to 8 and more preferably 3 to 6. When the number of isocyanate groups is in the above range, the point of the crosslinking reaction efficiency of the (meth)acrylic copolymer (A) and the isocyanate compound (B1) and the viewpoint of maintaining the flexibility of the pressure-sensitive adhesive layer are preferable.

1分子中的異氰酸酯基數為2之二異氰酸酯 化合物之例,可列舉如:脂肪族二異氰酸酯、脂環族二異氰酸酯、芳香族二異氰酸酯。脂肪族二異氰酸酯之例,可列舉如:二異氰酸伸乙酯、四亞甲基二異氰酸酯、五亞甲基二異氰酸酯、六亞甲基二異氰酸酯、2-甲基-1,5-戊烷二異氰酸酯、3-甲基-1,5-戊烷二異氰酸酯、2,2,4-三甲基-1,6-六亞甲基二異氰酸酯等碳數4至30的脂肪族二異氰酸酯。脂環族二異氰酸酯之例,可列舉如:異佛爾酮二異氰酸酯、環戊基二異氰酸酯、環己基二異氰酸酯、氫化二甲苯二異氰酸酯、氫化甲苯二異氰酸酯、氫化二苯基甲烷二異氰酸酯、氫化四甲基二甲苯二異氰酸酯等碳數7至30的脂環族二異氰酸酯。芳香族二異氰酸酯之例,可列舉如:伸苯二異氰酸酯、甲苯二異氰酸酯、二甲苯二異氰酸酯、伸萘二異氰酸酯、二苯基醚二異氰酸酯、二苯基甲烷二異氰酸酯、二苯基丙烷二異氰酸酯等碳數8至30的芳香族二異氰酸酯。 The number of isocyanate groups in one molecule is 2 isocyanate Examples of the compound include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate. Examples of the aliphatic diisocyanate include, for example, ethyl diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentyl An aliphatic diisocyanate having 4 to 30 carbon atoms such as an alkyl diisocyanate, 3-methyl-1,5-pentane diisocyanate or 2,2,4-trimethyl-1,6-hexamethylene diisocyanate. Examples of the alicyclic diisocyanate include isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenation. An alicyclic diisocyanate having 7 to 30 carbon atoms such as tetramethylxylene diisocyanate. Examples of the aromatic diisocyanate include, for example, phenylene diisocyanate, toluene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, diphenylpropane diisocyanate. An aromatic diisocyanate having a carbon number of 8 to 30.

作為1分子中的異氰酸酯基數為3以上的異氰酸酯化合物之例,可列舉如:芳香族聚異氰酸酯、脂肪族聚異氰酸酯、脂環族聚異氰酸酯。具體而言,可列舉如:2,4,6-三異氰酸酯甲苯、1,3,5-三異氰酸酯苯、4,4’,4’’-三苯基甲烷三異氰酸酯。 Examples of the isocyanate compound having 3 or more isocyanate groups in one molecule include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Specific examples thereof include 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, and 4,4',4''-triphenylmethane triisocyanate.

同時,異氰酸酯化合物(B1)之例,可列舉如:異氰酸酯基數為2或3以上之上述異氰酸酯化合物的多聚物(例如:2聚物或3聚物、縮二脲體、異三聚氰酸酯體)、衍生物(例如:多元醇與2分子以上的二異氰酸酯化合物之 加成反應生成物)、聚合物。前述衍生物中之多元醇,可列舉如:低分子量多元醇,例如:三羥甲基丙烷、丙三醇、新戊四醇等3價以上之醇;高分子量多元醇,例如:聚醚多元醇、聚酯多元醇、丙烯酸多元醇、聚丁二烯多元醇、聚異戊二烯多元醇。 Meanwhile, examples of the isocyanate compound (B1) include a polymer of the above isocyanate compound having an isocyanate group number of 2 or more (for example, a 2-mer or a 3-mer, a biuret, or an isocyanuric acid). Ester), a derivative (for example, a polyol and two or more molecules of a diisocyanate compound) Addition reaction product), polymer. The polyhydric alcohol in the above derivative may, for example, be a low molecular weight polyol such as trivalent or higher alcohol such as trimethylolpropane, glycerol or neopentyl alcohol; or a high molecular weight polyol such as polyether plural. Alcohol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol.

此類異氰酸酯化合物之例,可列舉如:二苯基甲烷二異氰酸酯之3聚物、聚亞甲基聚苯基聚異氰酸酯、六亞甲基二異氰酸酯或甲苯二異氰酸酯之縮二脲體或異三聚氰酸酯體、三羥甲基丙烷與甲苯二異氰酸酯或二甲苯二異氰酸酯之反應生成物(例如:甲苯二異氰酸酯或二甲苯二異氰酸酯之3分子加成化合物)、三羥甲基丙烷與六亞甲基二異氰酸酯之反應生成物(例如:六亞甲基二異氰酸酯之3分子加成物)、聚醚聚異氰酸酯、聚酯聚異氰酸酯。 Examples of such an isocyanate compound include, for example, a trimer of diphenylmethane diisocyanate, a polymethylene polyphenyl polyisocyanate, a hexamethylene diisocyanate or a toluene diisocyanate biuret or a different three. a reaction product of a polycyanate body, trimethylolpropane and toluene diisocyanate or xylene diisocyanate (for example, a 3-molecular addition compound of toluene diisocyanate or xylene diisocyanate), trimethylolpropane and six A reaction product of methylene diisocyanate (for example, a 3-molecular adduct of hexamethylene diisocyanate), a polyether polyisocyanate, or a polyester polyisocyanate.

異氰酸酯化合物(B1)中,以可提升老化性之觀點而言,較佳為三羥甲基丙烷與甲苯二異氰酸酯或二甲苯二異氰酸酯之反應生成物(綜研化學股份有限公司製L-45、綜研化學股份有限公司製TD-75等)、六亞甲基二異氰酸酯或甲苯二異氰酸酯之異三聚氰酸酯體(旭化成股份有限公司製TSE-100、日本Polyurethane工業股份有限公司製2050等)。 In the isocyanate compound (B1), a reaction product of trimethylolpropane and toluene diisocyanate or xylene diisocyanate is preferred from the viewpoint of improving aging property (L-45, manufactured by Soken Chemical Co., Ltd.) Chemical Co., Ltd., TD-75, etc.), hexamethylene diisocyanate or toluene diisocyanate, isomeric isocyanate (TSE-100, manufactured by Asahi Kasei Co., Ltd., 2050, manufactured by Japan Polyurethane Industrial Co., Ltd.).

異氰酸酯化合物(B1)可單獨使用1種,也可使用2種以上。 The isocyanate compound (B1) may be used alone or in combination of two or more.

《金屬螯合化合物(B2)》 Metal Chelate Compound (B2)

作為金屬螯合化合物(B2)之例,可列舉如:烷氧化物、 乙醯丙酮、乙醯乙酸乙酯等配位在鋁、鐵、銅、鋅、錫、鈦、鎳、銻、鎂、釩、鉻、鋯等多價金屬之化合物。 As an example of the metal chelate compound (B2), for example, an alkoxide, Ethylacetone, ethyl acetate and the like are compounds which are coordinated to polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, ruthenium, magnesium, vanadium, chromium, zirconium and the like.

該等中特佳為鋁螯合物化合物(綜研化學股份有限公司製M-12AT等)。具體而言可列舉如:異丙醇鋁、第二丁酸鋁鹽、乙基乙醯乙酸鋁鹽/二異丙醇、三乙基乙醯乙酸鋁鹽、三乙醯丙酮鋁。 Among these, it is an aluminum chelate compound (M-12AT manufactured by Soken Chemical Co., Ltd.). Specific examples thereof include aluminum isopropoxide, aluminum salt of second butyrate, aluminum salt of ethyl acetoacetate/diisopropyl alcohol, aluminum salt of triethylacetonitrileacetate, and aluminum triacetate.

金屬螯合物化合物(B2)可單獨使用1種,也可使用2種以上。 The metal chelate compound (B2) may be used alone or in combination of two or more.

金屬螯合化合物(B2)係藉由配位鍵使(甲基)丙烯酸系共聚物(A)交聯(虛擬交聯)。使用金屬螯合化合物(B2)作為交聯劑(B)時,相對於在室溫時,維持前述交聯且使聚合物發揮凝聚性,在高溫時,一部分前述交聯被解除而使黏著劑層顯示較優異的柔軟性。 The metal chelate compound (B2) crosslinks (virtual crosslinks) the (meth)acrylic copolymer (A) by a coordinate bond. When the metal chelate compound (B2) is used as the crosslinking agent (B), the crosslinking is maintained and the polymer is cohesive at room temperature, and at a high temperature, a part of the crosslinking is released to cause the adhesive. The layer shows superior softness.

《環氧化合物(B3)》 Epoxy Compound (B3)

環氧化合物(B3)通常使用1分子中的環氧基數為2以上的環氧化合物。可列舉如:乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、甘油二環氧丙基醚、甘油三環氧丙基醚、1,3-雙(N,N-二環氧丙基胺基甲基)環己烷、N,N,N’,N’-四環氧丙基-間二甲苯基二胺、N,N,N’,N’-四環氧丙基胺基苯基甲烷、異三聚氰酸三環氧丙酯、間-N,N-二環氧丙基胺基苯基環氧丙基醚、N,N-二環氧丙基甲苯胺、N,N-二環氧丙基苯胺。 As the epoxy compound (B3), an epoxy compound having 2 or more epoxy groups in one molecule is usually used. For example, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, 1,3-double (N, N -diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-m-xylyldiamine, N,N,N',N'-tetracyclic Oxypropyl propyl phenylmethane, triglycidyl isocyanate, m-N,N-diepoxypropylaminophenyl epoxidized propyl ether, N,N-diepoxypropyl Toluidine, N,N-diepoxypropyl aniline.

[矽烷偶合劑(C)] [decane coupling agent (C)]

本發明的黏著劑組成物,較佳為進一步含有矽烷偶合 劑(C)。矽烷偶合劑(C)係使黏著劑層堅固地接著於玻璃板等被黏著物,而有助於防止在高濕熱環境下的剝落。 The adhesive composition of the present invention preferably further contains a decane coupling Agent (C). The decane coupling agent (C) helps the adhesive layer to be adhered to a glass plate or the like firmly, thereby helping to prevent flaking in a high moist heat environment.

矽烷耦合劑(C)之例可列舉如:乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、甲基丙烯醯氧基丙基三甲氧基矽烷等含有聚合性不飽和基之矽烷耦合劑;3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等含有環氧基之矽烷耦合劑;3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷等含有胺基之矽烷耦合劑;3-氯丙基三甲氧基矽烷等含有鹵素之矽烷耦合劑;3-側氧基丁酸-3-(三甲氧基矽基)丙酯、及寡聚物型矽烷耦合劑等。其中,以濕熱環境下不易發生剝落此點而言,矽烷耦合劑較佳為具有與(甲基)丙烯酸系共聚物(A)中所含官能基反應而形成共價鍵的官能基、或可與(甲基)丙烯酸系共聚物(A)藉由相互作用形成鍵結之官能基。 Examples of the decane coupling agent (C) include a decane coupling agent containing a polymerizable unsaturated group such as vinyl trimethoxy decane, vinyl triethoxy decane, or methacryloxypropyl trimethoxy decane. 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-ring Epoxy-containing decane coupling agent such as oxypropoxypropylmethyldiethoxydecane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-aminopropyltrimethoxy Baseline, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, etc. a decane coupling agent containing an amine group; a halogen-containing decane coupling agent such as 3-chloropropyltrimethoxydecane; 3-tert-oxybutyric acid-3-(trimethoxyindolyl)propyl ester, and an oligomer type A decane coupling agent, etc. In particular, the decane coupling agent preferably has a functional group which reacts with a functional group contained in the (meth)acrylic copolymer (A) to form a covalent bond, or may be a non-peeling agent in a hot and humid environment. A functional group which forms a bond by interaction with the (meth)acrylic copolymer (A).

在本發明的黏著劑組成物,相對於(甲基)丙烯酸系共聚物(A)100質量份,矽烷偶合劑(C)的含量通常為1質量份以下,較佳為0.01至1質量份,更佳為0.05至0.5質量份。含量為前述範圍時,有防止偏光板在高濕熱環境下剝落、矽烷偶合劑(C)在高溫環境下滲出之傾向。 In the adhesive composition of the present invention, the content of the decane coupling agent (C) is usually 1 part by mass or less, preferably 0.01 to 1 part by mass, based on 100 parts by mass of the (meth)acrylic copolymer (A). More preferably, it is 0.05 to 0.5 part by mass. When the content is in the above range, there is a tendency to prevent the polarizing plate from peeling off in a high-humidity heat environment and the decane coupling agent (C) to ooze out in a high-temperature environment.

[抗靜電劑(D)] [Antistatic agent (D)]

抗靜電劑(D),例如可使用於為了降低由本發明的黏著 劑組成物所形成的黏著劑層之表面電阻。作為抗靜電劑(D)之例如可列舉如:界面活性劑、離子性化合物、導電性聚合物。 The antistatic agent (D) can be used, for example, in order to reduce adhesion by the present invention. The surface resistance of the adhesive layer formed by the composition of the agent. Examples of the antistatic agent (D) include a surfactant, an ionic compound, and a conductive polymer.

界面活性劑之例,可列舉如:四級銨鹽類、醯胺四級銨鹽類、吡啶鹽類、一級至三級胺基等含陽離子性基的陽離子性界面活性劑;具有磺酸鹽基、硫酸酯鹽基、磷酸酯鹽基等陰離子性基的陰離子性界面活性劑;烷基甜菜鹼類、烷基咪唑啉鎓甜菜鹼類、烷基胺氧化物類、胺基酸硫酸酯類等兩性界面活性劑;丙三醇脂酸酯類、山梨醇酐脂肪酸酯類、聚氧乙烯烷基胺類、聚氧乙烯烷基胺脂肪酸酯類、N-羥基乙基-N-2-羥基烷基胺類、烷基二乙醇醯胺類等非離子性界面活性劑。 Examples of the surfactant include cationic amine-containing cationic surfactants such as quaternary ammonium salts, guanamine quaternary ammonium salts, pyridinium salts, and primary to tertiary amine groups; Anionic surfactants such as an anionic group such as a sulfonate group or a phosphate group; alkylbetaines, alkylimidazolinium betaines, alkylamine oxides, and amino acid sulfates Amphoteric surfactants; glycerol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2-hydroxyl Nonionic surfactants such as alkylamines and alkyldiethanolamines.

又,界面活性劑亦可列舉具有聚合性基之反應型乳化劑,亦可使用將含有上述界面活性劑或反應性乳化劑之單體成分高分子量化的聚合物系界面活性劑。 Further, the surfactant may be a reactive emulsifier having a polymerizable group, or a polymer-based surfactant which is obtained by polymerizing a monomer component containing the above surfactant or reactive emulsifier.

離子性化合物係由陽離子部與陰離子部所構成,在室溫下(23℃/50%RH)可為固體狀或液體狀。 The ionic compound is composed of a cationic portion and an anionic portion, and may be solid or liquid at room temperature (23 ° C / 50% RH).

作為構成離子性化合物之陽離子部,可為無機系陽離子或有機系陽離子中的任一種或二者。作為無機系陽離子,較佳為鹼金屬離子及鹼土類金屬離子,更佳為抗靜電性優異之Li+、Na+及K+。作為有機系陽離子之例可列舉如:吡啶陽離子、哌啶陽離子、吡咯啶陽離子、吡咯啉(pyrroline)陽離子、吡咯陽離子、咪唑陽離子、四氫嘧啶陽離子、二氫嘧啶陽離子、吡唑陽離子、吡唑啉陽離子、 四烷基銨陽離子、三烷基鋶陽離子、四烷基鏻陽離子及該等衍生物。 The cationic portion constituting the ionic compound may be either or both of an inorganic cation or an organic cation. The inorganic cation is preferably an alkali metal ion or an alkaline earth metal ion, and more preferably Li+, Na+, and K+ having excellent antistatic properties. Examples of the organic cation include a pyridinium cation, a piperidine cation, a pyrrolidine cation, a pyrroline cation, a pyrrole cation, an imidazolium cation, a tetrahydropyrimidine cation, a dihydropyrimidinium cation, a pyrazole cation, and a pyrazole. Porphyrin cation, a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and the like.

構成離子性化合物之陰離子部只要可與陽離子部進行離子鍵結而形成離子性化合物者,則無特別限制。具體而言可列舉如:F-、Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、SCN-、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、(F2SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-及(CF3SO2)(CF3CO)N-。該等中,含氟原子之陰離子可賦予低熔點的離子性化合物,故較佳,更佳為(F2SO2)2N-及(CF3SO2)2N-,以偏光片不易產生劣化此點而言,特佳為(CF3SO2)2N-The anion portion constituting the ionic compound is not particularly limited as long as it can be ion-bonded to the cation portion to form an ionic compound. Specific examples thereof include F - , Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF 6 - , SCN - , ClO 4 - , NO 3 - , CH 3 COO - , CF 3 COO - , CH 3 SO 3 - , CF 3 SO 3 - , (CF 3 SO 2 ) 2 N - , (F 2 SO 2 ) 2 N - , (CF 3 SO 2 ) 3 C - , AsF 6 - , SbF 6 - , NbF 6 - , TaF 6 - , F(HF) n - , (CN) 2 N - , C 4 F 9 SO 3 - , (C 2 F 5 SO 2 ) 2 N - , C 3 F 7 COO - and (CF 3 SO 2 )(CF 3 CO)N - . Among these, an anion of a fluorine atom can impart an ionic compound having a low melting point, and therefore, more preferably, it is (F 2 SO 2 ) 2 N - and (CF 3 SO 2 ) 2 N - , which is less likely to be produced by a polarizer. In terms of deterioration, it is particularly preferably (CF 3 SO 2 ) 2 N - .

離子性化合物較佳為鋰雙(三氟甲烷磺醯基)亞胺、鋰雙(二氟磺醯基)亞胺、鋰三(三氟甲烷磺醯基)甲烷、鉀雙(三氟甲烷磺醯基)亞胺、鉀雙(二氟磺醯基)亞胺、1-乙基吡啶鎓六氟磷酸鹽、1-丁基吡啶鎓六氟磷酸鹽、1-己基-4-甲基吡啶鎓六氟磷酸鹽、1-辛基-4-甲基吡啶鎓六氟磷酸鹽、1-辛基-4-甲基吡啶鎓雙(氟磺醯基)亞胺、1-辛基-4-甲基吡啶鎓雙(三氟甲烷磺醯基)亞胺、三丁基甲基銨雙(氟磺醯基)亞胺、三丁基甲基銨雙(三氟甲烷磺醯基)亞胺、(N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨四氟硼酸鹽、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(三氟甲烷磺醯基)亞胺、1-辛基吡啶鎓氟磺醯醯亞胺、1-辛基-3-甲基吡啶鎓三氟鋶亞胺。 The ionic compound is preferably lithium bis(trifluoromethanesulfonyl)imide, lithium bis(difluorosulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methane, potassium bis(trifluoromethanesulfonate) Mercapto)imide, potassium bis(difluorosulfonyl)imide, 1-ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-hexyl-4-methylpyridinium Hexafluorophosphate, 1-octyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1-octyl-4-methyl Pyridinium bis(trifluoromethanesulfonyl)imide, tributylmethylammonium bis(fluorosulfonyl)imide, tributylmethylammonium bis(trifluoromethanesulfonyl)imide, (N,N- Diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-diethyl-N-methyl-N-(2-methoxyethyl) Ammonium bis(trifluoromethanesulfonyl)imide, 1-octylpyridinium fluorosulfonimide, 1-octyl-3-methylpyridinium trifluoroimide.

導電性聚合物可列舉如:聚噻吩、聚苯胺、聚吡咯及該等之衍生物。 Examples of the conductive polymer include polythiophene, polyaniline, polypyrrole, and derivatives thereof.

在本發明的黏著劑組成物,相對於(甲基)丙烯酸系共聚物(A)100質量份,抗靜電劑(D)的含量通常為3質量份以下,較佳為0.01至3質量份,更佳為0.05至2.5質量份。 In the adhesive composition of the present invention, the content of the antistatic agent (D) is usually 3 parts by mass or less, preferably 0.01 to 3 parts by mass, per 100 parts by mass of the (meth)acrylic copolymer (A). More preferably, it is 0.05 to 2.5 parts by mass.

[有機溶媒(E)] [Organic Solvent (E)]

本發明之黏著劑組成物係為了調整其塗布性,較佳為含有有機溶媒(E)。有機溶媒可列舉如:(甲基)丙烯酸系共聚物(A)之欄所說明之聚合溶媒。例如可將上述共聚所得之含有(甲基)丙烯酸系共聚物(A)及聚合溶媒之聚合物溶液與交聯劑(B)混合,而調製黏著劑組成物。本發明的黏著劑組成物中,有機溶媒(E)的含量通常為50至90質量%,較佳為60至85質量%。 The adhesive composition of the present invention preferably contains an organic solvent (E) in order to adjust the coatability. The organic solvent may, for example, be a polymerization solvent described in the column of the (meth)acrylic copolymer (A). For example, the polymer solution containing the (meth)acrylic copolymer (A) and the polymerization solvent obtained by the above copolymerization may be mixed with the crosslinking agent (B) to prepare an adhesive composition. In the adhesive composition of the present invention, the content of the organic solvent (E) is usually from 50 to 90% by mass, preferably from 60 to 85% by mass.

再者,本說明書中之「固形物」,係指黏著劑組成物所含成分之中除去上述有機溶劑(E)以外之全部成分,「固形物濃度」,係指相對於黏著劑組成物100質量%之前述固形物的比例。 In the present specification, the term "solid matter" means all components other than the organic solvent (E) among the components contained in the adhesive composition, and "solid content" means the composition 100 with respect to the adhesive. % by mass of the aforementioned solids.

[添加劑] [additive]

本發明之黏著劑組成物,除了上述成分之外,在不損及本發明效果之範圍下,亦可再含選自:抗氧化劑、光安定劑、金屬防蝕劑、賦黏著劑、塑化劑、促交聯劑、前述(A)以外之(甲基)丙烯酸系聚合物及再加工劑的1種或2種以上。 The adhesive composition of the present invention may further contain, in addition to the above components, an antioxidant, a light stabilizer, a metal corrosion inhibitor, an adhesive, and a plasticizer, without departing from the effects of the present invention. One or two or more kinds of the (meth)acrylic polymer and the rework agent other than the above-mentioned (A).

[偏光板用黏著劑組成物的調製] [Modulation of Adhesive Composition for Polarizing Plate]

本發明的黏著劑組成物,係能夠藉由使用先前眾所周知的方法將(甲基)丙烯酸系共聚物(A)、交聯劑(B)及按照必要之其他成分進行混合而調製。可列舉例如:於合成(甲基)丙烯酸系共聚物(A)時所得之含有該聚合物之聚合物溶液中,調配交聯劑(B)及按照必要之其他成分。 The adhesive composition of the present invention can be prepared by mixing a (meth)acrylic copolymer (A), a crosslinking agent (B), and other components as necessary, by a conventionally known method. For example, in the polymer solution containing the polymer obtained by synthesizing the (meth)acrylic copolymer (A), a crosslinking agent (B) and other components as necessary may be blended.

本發明的黏著劑組成物,係適合於構成液晶單元之基板與偏光片的貼合用途。特別是即便以薄型化的液晶單元構成之玻璃板的厚度為0.05至1.0mm左右較小之情形,亦適合使用於該基板與偏光片的貼合用途。 The adhesive composition of the present invention is suitable for the bonding of a substrate constituting a liquid crystal cell and a polarizer. In particular, even when the thickness of the glass plate composed of the thinned liquid crystal cell is as small as about 0.05 to 1.0 mm, it is suitable for use in bonding the substrate to the polarizer.

本發明的黏著劑組成物所形成之黏著劑的凝膠分率較佳為40質量%以上,更佳為40至95質量%,又更佳為45至90質量%。前述凝膠分率係例如以實施例之記載條件所採集黏著劑所測定的值。 The gel fraction of the adhesive formed by the adhesive composition of the present invention is preferably 40% by mass or more, more preferably 40 to 95% by mass, still more preferably 45 to 90% by mass. The gel fraction is, for example, a value measured by the adhesive collected under the conditions described in the examples.

〔偏光板用黏著劑層〕 [Adhesive layer for polarizing plate]

本發明的偏光板用黏著劑層係由上述黏著劑組成物所形成。藉由使用本發明的黏著劑組成物,而可形成具有以下水蒸氣透過率之黏著劑層。 The adhesive layer for a polarizing plate of the present invention is formed of the above-described adhesive composition. By using the adhesive composition of the present invention, an adhesive layer having the following water vapor transmission rate can be formed.

本發明的黏著劑層之水蒸氣透過率較佳為800g/m2.day以下,更佳為600g/m2.day以下,又更佳為400g/m2.day以下。 The water vapor transmission rate of the adhesive layer of the present invention is preferably 800 g/m 2 . Below day, more preferably 600g/m 2 . Below day, it is more preferably 400g/m 2 . Below day.

上述水蒸氣透過率的測定方法係於下述實施例之欄詳細說明。 The method for measuring the water vapor transmission rate is described in detail in the following examples.

藉由使水蒸氣透過率在上述範圍,本發明的 黏著劑層在高濕熱環境下中也可防止偏光片之收縮,且防止裂痕等的產生。又,亦可抑制偏光片所含碘錯合物的劣化,故可減少耐久性試驗前後之光學特性的變化。 By making the water vapor transmission rate within the above range, the present invention The adhesive layer also prevents shrinkage of the polarizer in a high-humidity heat environment, and prevents generation of cracks and the like. Further, deterioration of the iodine complex contained in the polarizer can be suppressed, so that changes in optical characteristics before and after the durability test can be reduced.

從抑制偏光板之變形、凝集力、接著力、再剝離性之觀點而言,本發明之黏著劑組成物所形成之黏著劑層的凝膠分率較佳為40質量%以上,更佳為40至95質量%,又更佳為45至90質量%。若凝膠分率在前述範圍,則黏著劑層顯示優異耐久性。 The gel fraction of the adhesive layer formed of the adhesive composition of the present invention is preferably 40% by mass or more, more preferably from the viewpoint of suppressing deformation, cohesive force, adhesion, and removability of the polarizing plate. 40 to 95% by mass, and more preferably 45 to 90% by mass. When the gel fraction is in the above range, the adhesive layer exhibits excellent durability.

本發明的黏著劑層,係例如藉由上述黏著劑組成物中進行交聯反應,具體而言,係藉由交聯劑(B)使(甲基)丙烯酸系共聚物(A)交聯而得到。 The adhesive layer of the present invention is subjected to a crosslinking reaction by, for example, the above-mentioned adhesive composition, specifically, crosslinking of the (meth)acrylic copolymer (A) by a crosslinking agent (B). get.

黏著劑層之形成條件之例係如下述。將本發明之黏著劑組成物塗布於支撐體上,視溶劑之種類而不同,通常在50至150℃,更好在60至100℃下,再乾燥通常1至10分鐘,更好2至7分鐘以去除溶劑,即可形成塗膜。乾燥塗膜之膜厚,通常為5至75μm,而以10至50μm為佳。 Examples of the conditions for forming the adhesive layer are as follows. The adhesive composition of the present invention is applied to a support, depending on the kind of the solvent, usually at 50 to 150 ° C, more preferably at 60 to 100 ° C, and then dried for usually 1 to 10 minutes, more preferably 2 to 7 In minutes, the solvent is removed to form a coating film. The film thickness of the dried coating film is usually 5 to 75 μm, preferably 10 to 50 μm.

黏著劑層,係在以下之條件下形成為佳。將本發明之黏著劑組成物塗布在支撐體上,再於上述條件所形成之塗膜上黏貼覆蓋膜後,通常以3日以上,更好以7至10日,在通常為5至60℃,更好為15至40℃,及通常為30至70% RH,更好為40至70% RH之環境下固化。再於如上述之熟成條件下進行交聯,即可有效地形成交聯體(網狀聚合物)。 The adhesive layer is preferably formed under the following conditions. Applying the adhesive composition of the present invention to a support, and then adhering the cover film to the coating film formed under the above conditions, usually for 3 days or longer, more preferably 7 to 10 days, and usually 5 to 60 ° C. More preferably, it is cured in an environment of 15 to 40 ° C, and usually 30 to 70% RH, more preferably 40 to 70% RH. Further, crosslinking is carried out under the above-mentioned ripening conditions, and the crosslinked body (mesh polymer) can be effectively formed.

黏著劑組成物的塗布方法方面,可使用一般已知之方法,例如:旋塗法、刮刀塗布法、輥塗法、棒塗法、刮板塗布法、模塗布法、凹版塗布法等,進行塗布/乾燥成為預定之厚度的方法操作。 The coating method of the adhesive composition can be applied by a generally known method such as a spin coating method, a knife coating method, a roll coating method, a bar coating method, a blade coating method, a die coating method, a gravure coating method, or the like. / Drying is performed to a predetermined thickness.

支撐體及覆蓋膜之例,可列舉如:聚對苯二甲酸乙二酯(PET)等聚酯膜;聚乙烯、聚丙烯、乙烯-乙酸乙烯酯共聚物等聚烯烴膜等之塑膠膜。 Examples of the support and the cover film include a polyester film such as polyethylene terephthalate (PET); and a plastic film such as a polyolefin film such as polyethylene, polypropylene or an ethylene-vinyl acetate copolymer.

[偏光板用黏著片] [Adhesive sheet for polarizing plate]

本發明的偏光板用黏著片,係具有由上述的黏著劑組成物所形之黏著劑層。作為黏著片,可列舉例如:只具有上述黏著劑層之兩面黏著片;具有基材、及形成於基材兩面的上述黏著劑層之兩面黏著片;具有基材、及形成在基材的一面的上述黏著劑層之單面黏著片;以及在該等黏著片的黏著劑層之未與基材接觸的面,貼附經剝離處理的覆蓋膜而成之黏著片。 The adhesive sheet for a polarizing plate of the present invention has an adhesive layer formed of the above-described adhesive composition. Examples of the adhesive sheet include a double-sided adhesive sheet having only the above-mentioned adhesive layer, a double-sided adhesive sheet having a base material and the above-mentioned adhesive layer formed on both surfaces of the base material, a base material, and one side formed on the base material. The one-side adhesive sheet of the above adhesive layer; and the adhesive sheet formed by attaching the peeled cover film to the surface of the adhesive layer of the adhesive sheet which is not in contact with the substrate.

基材及保護膜之例可列舉如:聚對苯二甲酸乙二酯(PET)等聚酯膜;聚乙烯、聚丙烯、乙烯/乙酸乙烯酯共聚物等聚烯烴膜等的塑膠膜。 Examples of the substrate and the protective film include a polyester film such as polyethylene terephthalate (PET); a plastic film such as a polyolefin film such as polyethylene, polypropylene or an ethylene/vinyl acetate copolymer.

黏著劑層的形成條件係與〔偏光板用黏著劑層〕之欄所記載條件相同。 The conditions for forming the adhesive layer are the same as those described in the column of [Adhesive Layer for Polarizing Plate].

從維持黏著性能的觀點而言,黏著劑層的膜厚係通常為5至75μm,較佳為10至50μm。基材及覆蓋膜的膜厚係沒有特別限定,通常為10至125μm,較佳為25至75μm。 The film thickness of the adhesive layer is usually from 5 to 75 μm, preferably from 10 to 50 μm, from the viewpoint of maintaining adhesive properties. The film thickness of the substrate and the cover film is not particularly limited, but is usually 10 to 125 μm, preferably 25 to 75 μm.

[附黏著劑層之偏光板] [Polarizer with Adhesive Layer]

本發明的附黏著劑層之偏光板,係具有直接積層於偏光片的至少一面之由本發明的黏著劑組成物所形成之黏著劑層。又,在本說明書,「偏光板」係包含「偏光膜」之意思而使用。 The polarizing plate with an adhesive layer of the present invention has an adhesive layer formed of the adhesive composition of the present invention directly laminated on at least one side of the polarizing plate. In addition, in the present specification, the "polarizing plate" is used in the sense of including a "polarizing film".

作為偏光板,係能夠使用先前眾所周知的偏光膜。可列舉例如:偏光片本身,以及具有偏光片及配置在偏光片上的偏光片保護膜之多層膜。在本發明,由於將上述黏著劑層直接相接於偏光片而配置,故可列舉:僅於偏光片的一面配置偏光片保護膜之構成,以及於偏光片的兩面均未配置偏光片保護膜之構成。 As the polarizing plate, a previously known polarizing film can be used. For example, a polarizer itself, and a multilayer film having a polarizer and a polarizer protective film disposed on the polarizer can be cited. In the present invention, since the adhesive layer is directly placed in contact with the polarizer, a configuration in which the polarizer protective film is disposed only on one surface of the polarizer, and a polarizer protective film is not disposed on both surfaces of the polarizer The composition.

作為偏光片,可列舉例如:使由聚乙烯醇系樹脂所構成之膜含有偏光成分且藉由延伸而得之延伸膜。作為聚乙烯醇系樹脂,可列舉例如:聚乙烯醇、聚乙烯基甲醛、聚乙烯基縮醛、乙烯-乙酸乙烯酯共聚物的皂化物。作為偏光成分,可列舉例如:碘或二色性染料。 The polarizing film may, for example, be a stretched film obtained by stretching a film made of a polyvinyl alcohol-based resin and containing a polarizing component. Examples of the polyvinyl alcohol-based resin include saponified products of polyvinyl alcohol, polyvinyl formaldehyde, polyvinyl acetal, and ethylene-vinyl acetate copolymer. Examples of the polarizing component include iodine or a dichroic dye.

作為偏光片保護膜,可列舉例如:由熱可塑性樹脂所構成之膜。作為熱可塑性樹脂,可列舉例如:三乙酸纖維素等的纖維素樹脂、聚酯樹脂、聚醚碸樹脂、聚碸樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚烯烴樹脂、(甲基)丙烯酸樹脂、環狀聚烯烴樹脂(降莰烯系樹脂)、聚芳香酯(polyarylate)樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂、及選自該等樹脂之2種以上的混合物。 The polarizer protective film may, for example, be a film composed of a thermoplastic resin. Examples of the thermoplastic resin include a cellulose resin such as cellulose triacetate, a polyester resin, a polyether oxime resin, a polyfluorene resin, a polycarbonate resin, a polyamide resin, a polyimide resin, and a polyolefin. Resin, (meth)acrylic resin, cyclic polyolefin resin (northene-based resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and two or more kinds selected from the resins mixture.

偏光板的厚度通常為10至200μm,較佳為 30至100μm。本發明中可省略形成於偏光片上之偏光片保護膜,故可使偏光板薄型化。 The thickness of the polarizing plate is usually 10 to 200 μm, preferably 30 to 100 μm. In the present invention, the polarizer protective film formed on the polarizer can be omitted, so that the polarizing plate can be made thinner.

在本發明,上述黏著劑層係直接相接於偏光片而形成。作為本發明的附黏著劑層之偏光板,例如依序積層偏光片保護膜、偏光片及上述黏著劑層之構成;依序積層上述黏著劑層、偏光片保護膜、偏光片及上述黏著劑層之構成;及依序積層上述黏著劑層、偏光片及上述黏著劑層之構成。在該等構成,亦可在黏著劑層上配置上述覆蓋膜作為最外層。 In the present invention, the adhesive layer is formed by directly contacting the polarizer. The polarizing plate with an adhesive layer of the present invention is, for example, a laminated polarizer protective film, a polarizer, and the above-mentioned adhesive layer; the adhesive layer, the polarizer protective film, the polarizer, and the above adhesive are sequentially laminated. The composition of the layers; and the formation of the above-mentioned adhesive layer, polarizer and the above-mentioned adhesive layer. In such a configuration, the cover film may be disposed on the adhesive layer as the outermost layer.

在偏光片表面形成黏著劑層之方法係沒有特別限制,可列舉如:直接使用桿塗佈器等將上述黏著劑組成物塗佈在偏光片表面且使其乾燥及熟成之方法;及將本發明的偏光板用黏著片所具有之黏著劑層轉印至偏光片表面且使其熟成之方法。乾燥及熟成的條件、凝膠分率範圍等係與在[偏光板用黏著劑層]的欄所記載之條件相同。 The method of forming the adhesive layer on the surface of the polarizer is not particularly limited, and examples thereof include a method in which the above-mentioned adhesive composition is directly applied to a surface of a polarizer by a bar coater, and dried and cooked; and The polarizing plate of the invention is a method in which an adhesive layer of an adhesive sheet is transferred to a surface of a polarizer and is made mature. The conditions for drying and aging, the gel fraction range, and the like are the same as those described in the column of [Adhesive Layer for Polarizing Plate].

黏著劑層之厚度以乾燥膜厚而言通常為5至75μm,較佳為10至50μm。又,黏著劑層只要以偏光片至少一面上與偏光片相接而形成即可,可列舉如:僅在偏光片單面形成黏著劑層之態樣、及在偏光片兩面形成黏著劑層之態樣。 The thickness of the adhesive layer is usually from 5 to 75 μm, preferably from 10 to 50 μm in terms of dry film thickness. Further, the adhesive layer may be formed by contacting at least one surface of the polarizer with the polarizer, and examples thereof include forming an adhesive layer on only one side of the polarizer and forming an adhesive layer on both sides of the polarizer. Aspect.

又,上述偏光板可積層例如保護層、防眩層、相位差層、視角提升層等具有其他功能的層。 Further, the polarizing plate may have a layer having other functions such as a protective layer, an antiglare layer, a retardation layer, and a viewing angle lifting layer.

藉由在液晶單元的基板表面設置如上述方式所得之本發明的附黏著劑層之偏光板,而製造液晶元件。 在此,液晶單元係具有在2片基板間夾住液晶層之構造。 A liquid crystal element is produced by providing a polarizing plate of the present invention with an adhesive layer obtained as described above on the surface of the substrate of the liquid crystal cell. Here, the liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates.

作為液晶單元所具有的基板,可列舉例如:玻璃板。作為基板的厚度,通常為0.05至3mm,較佳為0.2至1mm。在本發明,藉由使用上述黏著劑組成物,即便將黏著劑層直接積層於偏光片上時,亦能夠抑制偏光板及基板之翹曲。因此,即便基板的厚度較小時(例如:1mm以下,較佳為0.2至1mm),上述黏著劑組成物亦能夠適合使用於偏光板與基板的貼合。 Examples of the substrate of the liquid crystal cell include a glass plate. The thickness of the substrate is usually from 0.05 to 3 mm, preferably from 0.2 to 1 mm. In the present invention, by using the above-described adhesive composition, warpage of the polarizing plate and the substrate can be suppressed even when the adhesive layer is directly laminated on the polarizer. Therefore, even when the thickness of the substrate is small (for example, 1 mm or less, preferably 0.2 to 1 mm), the above-mentioned adhesive composition can be suitably used for bonding a polarizing plate and a substrate.

(實施例) (Example)

以下,本發明再以實施例更具體地說明,惟本發明並不限定於該等實施例。以下之實施例等之記載中,除非特別說明,「份」係表示「質量份」。 Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the examples. In the following description of the examples and the like, "parts" means "parts by mass" unless otherwise specified.

〔GPC〕 [GPC]

將(甲基)丙烯酸系共聚物以膠體滲透層析法(GPC法)用下述條件求取重量平均分子量(Mw)及數目平均分子量(Mn)。 The (meth)acrylic copolymer was subjected to colloidal permeation chromatography (GPC method) to obtain a weight average molecular weight (Mw) and a number average molecular weight (Mn) under the following conditions.

.測定裝置:HLC-8320GPC(TOSOH股份有限公司製)。 . Measuring device: HLC-8320GPC (manufactured by TOSOH Co., Ltd.).

.GPC管柱構成:以下4連管柱(皆為TOSOH股份有限公司製)。 . GPC column structure: The following four columns (all manufactured by TOSOH Co., Ltd.).

(1)TSKgel HxL-H(保護管柱)。 (1) TSKgel HxL-H (protective column).

(2)TSKgel GMHxL。 (2) TSKgel GMHxL.

(3)TSKgel GMHxL。 (3) TSKgel GMHxL.

(4)TSKgel G2500HxL。 (4) TSKgel G2500HxL.

.流速:1.0mL/min。 . Flow rate: 1.0 mL/min.

.管柱溫度:40℃。 . Column temperature: 40 ° C.

.樣品濃度:1.5%(w/v)(以四氫呋喃稀釋)。 . Sample concentration: 1.5% (w/v) (diluted with tetrahydrofuran).

.移動相溶媒:四氫呋喃。 . Mobile phase solvent: tetrahydrofuran.

.標準聚苯乙烯換算。 . Standard polystyrene conversion.

[合成例1] [Synthesis Example 1]

在具有攪拌機、迴流冷卻器、溫度計及氮導入管之反應裝置加入甲基丙烯酸月桂酯98.3份、丙烯酸1.5份、丙烯酸2-羥基乙酯0.2份及乙酸乙酯溶媒100份,一邊導入氮氣一邊升溫至80℃。接著加入2,2'-偶氮雙異丁腈0.1份,在氮氣環境下以80℃進行6小時聚合反應。反應結束後以乙酸乙酯稀釋,調製固形分濃度30質量%之聚合物溶液。所得(甲基)丙烯酸系共聚物A1之重量平均分子量(Mw)為80萬,分子量分布(Mw/Mn)為8,酸價為11.7mgKOH/g。 In a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 98.3 parts of lauryl methacrylate, 1.5 parts of acrylic acid, 0.2 parts of 2-hydroxyethyl acrylate, and 100 parts of an ethyl acetate solvent were added, and the temperature was raised while introducing nitrogen gas. To 80 ° C. Next, 0.1 part of 2,2'-azobisisobutyronitrile was added, and polymerization was carried out at 80 ° C for 6 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was diluted with ethyl acetate to prepare a polymer solution having a solid concentration of 30% by mass. The obtained (meth)acrylic copolymer A1 had a weight average molecular weight (Mw) of 800,000, a molecular weight distribution (Mw/Mn) of 8, and an acid value of 11.7 mgKOH/g.

[合成例2至8] [Synthesis Examples 2 to 8]

除了2,2’-偶氮雙異丁腈的使用量為0.05質量份且聚合反應所使用之單體成分變更為表1所記載以外,以與合成例1相同方式進行,而調製固形分濃度30質量%之聚合物溶液。結果示於表1。 The solid content concentration was adjusted in the same manner as in Synthesis Example 1 except that the amount of the 2,2'-azobisisobutyronitrile used was 0.05 parts by mass and the monomer components used in the polymerization reaction were changed as shown in Table 1. 30% by mass of the polymer solution. The results are shown in Table 1.

[實施例1] [Example 1]

(1)調製黏著劑組成物 (1) Modifying the adhesive composition

將合成例1所得之聚合物溶液(固形分濃度30質量%)、相對於該溶液所含(甲基)丙烯酸系共聚物A1 100份(固形分量)之作為異氰酸酯化合物之綜研化學股份有限公司製「L-45」(固形分45質量%、乙酸乙酯溶液)0.15份(固形 分量)、作為矽烷耦合劑之綜研化學股份有限公司製「A-50」(固形分50質量%、甲苯溶液)0.2份(固形分量)、作為抗靜電劑之三丁基甲基銨雙(三氟甲烷磺醯基)亞胺0.8份混合,而獲得黏著劑組成物。 The polymer solution obtained in Synthesis Example 1 (solid content concentration: 30% by mass) and 100 parts (solid content) of the (meth)acrylic copolymer A1 contained in the solution were used as isocyanate compounds. "L-45" (solid content: 45 mass%, ethyl acetate solution) 0.15 parts (solid form) "A-50" (solid content 50% by mass, toluene solution) 0.2 parts (solid content), and tributylmethylammonium bis(trifluoromethane) as an antistatic agent, as a decane coupling agent The sulfonyl)imine was mixed in 0.8 parts to obtain an adhesive composition.

(2)黏著片的製造 (2) Manufacture of adhesive sheets

將上述(1)所得之黏著劑組成物消泡後,使用刮刀塗佈器塗佈於經剝離處理的聚對酞酸乙二酯膜(PET膜),於90℃乾燥3分鐘而形成乾燥膜厚20μm的塗膜。在塗膜之與前述PET膜的貼附面為相反之面,進一步貼合經剝離處理的PET膜,而且在23℃/50%RH環境下靜置7天使其熟成,而得到具有在2片PET膜夾有厚度20μm的黏著劑層之黏著片。 The adhesive composition obtained in the above (1) was defoamed, and then applied to a release-treated polyethylene terephthalate film (PET film) using a knife coater, and dried at 90 ° C for 3 minutes to form a dried film. A coating film having a thickness of 20 μm. The peeled PET film was further bonded to the surface of the coating film opposite to the adhesion surface of the PET film, and the glaze was allowed to stand at 23 ° C / 50% RH for 7 angels to obtain 2 tablets. The PET film was sandwiched with an adhesive sheet of an adhesive layer having a thickness of 20 μm.

(3)附黏著劑層之偏光板的製造 (3) Manufacture of polarizing plate with adhesive layer

將上述(1)所得到的黏著劑組成物消泡後,使用刮刀塗佈器塗佈於經剝離處理的聚對酞酸乙二酯膜(PET膜)上,於90℃乾燥3分鐘而得到具有乾燥膜厚20μm的塗膜之片。將該片的塗膜面,以與由偏光片之聚乙烯醇膜及偏光片保護膜之三乙酸纖維素膜所構成之2層構成(厚度60μm)的偏光板的聚乙烯醇膜面接觸之方式貼合,而且在23℃/50%RH的條件下靜置7天使其熟成,而得到具有PET膜、厚度20μm的黏著劑層、偏光片及偏光片保護膜之附黏著劑層之偏光板。 The adhesive composition obtained in the above (1) was defoamed, and then applied onto a release-treated polyethylene terephthalate film (PET film) using a knife coater, followed by drying at 90 ° C for 3 minutes. A sheet having a coating film having a dried film thickness of 20 μm. The coating film surface of the sheet was in contact with the polyvinyl alcohol film of a polarizing plate composed of two layers (thickness: 60 μm) composed of a polyvinyl alcohol film of a polarizing plate and a cellulose triacetate film of a polarizer. The film was laminated, and it was allowed to stand at 23 ° C / 50% RH for 7 days to obtain a polarizing plate having a PET film, an adhesive layer having a thickness of 20 μm, a polarizer, and an adhesive layer of a polarizer protective film. .

[實施例2至7,比較例1、2] [Examples 2 to 7, Comparative Examples 1, 2]

實施例1中,除了將聚合物溶液變更為合成例2至8 所得之聚合物溶液,且將調配組成變更為表2所記載者之外,以與實施例1相同方式而獲得黏著劑組成物、黏著片及附黏著劑層的偏光板。又,TD-75係異氰酸酯化合物(綜研化學股份有限公司製),另一種抗靜電劑係1-辛基-4-甲基吡啶鎓雙(氟磺醯基)亞胺。 In Example 1, except that the polymer solution was changed to Synthesis Examples 2 to 8. The obtained polymer solution was changed to the composition shown in Table 2, and the adhesive composition, the adhesive sheet, and the polarizing plate with the adhesive layer were obtained in the same manner as in Example 1. Further, a TD-75 isocyanate compound (manufactured by Soken Chemical Co., Ltd.), and another antistatic agent is 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide.

[評量] [rating]

[凝膠分率] [Gel fraction]

先由實施例/比較例中所得之黏著片,將黏著劑約0.1g採集於樣品瓶中,再加入乙酸乙酯30mL並振盪4小時之後,將該樣品瓶中的內容物以200網目之不銹鋼製金屬網過濾,然後將金屬網上之殘留物於100℃中乾燥2小時再測定乾燥重量。之後以下式,求出黏著劑的凝膠分率。 First, from the adhesive sheet obtained in the example/comparative example, about 0.1 g of the adhesive was collected in a sample bottle, and after adding 30 mL of ethyl acetate and shaking for 4 hours, the contents of the sample bottle were made of 200 mesh stainless steel. The metal mesh was filtered, and the residue on the metal mesh was dried at 100 ° C for 2 hours and then the dry weight was measured. Then, the gel fraction of the adhesive was determined by the following formula.

.凝膠分率(%)=(乾燥重量/黏著劑採集重量)×100(%) . Gel fraction (%) = (dry weight / adhesive collection weight) × 100 (%)

〔黏著力之測定〕 [Measurement of adhesion]

將實施例、比較例所得之附黏著劑層的偏光板(PET膜/黏著劑層/偏光片/偏光片保護膜所構成之積層體)裁切為70mm×25mm的尺寸,而製作試驗片。從試驗片剝離PET膜,使用2kg的輥,將黏著劑層/偏光片/偏光片保護膜所構成之積層體以黏著劑層與玻璃板相接之方式貼黏於厚度2mm之玻璃板的一面。將所得積層體放置於23℃/50%RH環境下2小時後,對於玻璃板面在90°方向以300mm/min的速度拉伸偏光板端部,並測定黏著力(剝離強度)。 The polarizing plate (PET film/adhesive layer/layer of polarizer/polarizer protective film) with the adhesive layer obtained in the examples and the comparative examples was cut into a size of 70 mm × 25 mm to prepare a test piece. The PET film was peeled off from the test piece, and the laminate composed of the adhesive layer/polarizer/polarizer protective film was adhered to one side of the glass plate having a thickness of 2 mm by bonding the adhesive layer to the glass plate using a 2 kg roller. . After the obtained laminate was placed in an environment of 23° C./50% RH for 2 hours, the end of the polarizing plate was stretched at a speed of 300 mm/min in the direction of 90° on the glass plate surface, and the adhesion (peeling strength) was measured.

〔水蒸氣透過率〕 [Water vapor transmission rate]

水蒸氣透過率係根據JIS Z0208而用以下方式測定。 以與「(2)黏著片之製作」之欄所記載方法相同之方式而製作具有厚度50μm的黏著劑層之黏著片。從該黏著片剝離PET膜,在黏著劑層兩面貼合不織布(所得積層體稱為「片A」),並配合透濕杯的直徑裁切。在透濕杯(內徑60mm)加入氯化鈣10g,裝設經裁切之片A、橡膠墊、保護環並以螺栓固定。於40℃/90%RH的恒溫恒濕條件下投入裝設片A等之透濕杯,24小時後取出透濕杯,秤量透濕杯的重量(初期重量)。使經秤量之透濕杯回到40℃/90%RH條件下,每24小時秤量重量。在每24小時的質量增加為5%以內之範圍之時間點,由最後的質量變化量、測定間隔而使用下述式而算出水蒸氣透過率。 The water vapor transmission rate was measured in the following manner in accordance with JIS Z0208. An adhesive sheet having an adhesive layer having a thickness of 50 μm was produced in the same manner as in the method of "(2) Preparation of an adhesive sheet". The PET film was peeled off from the adhesive sheet, and a non-woven fabric was bonded to both surfaces of the adhesive layer (the resulting laminated body was referred to as "sheet A"), and cut to fit the diameter of the moisture-permeable cup. 10 g of calcium chloride was added to the moisture permeable cup (inner diameter 60 mm), and the cut piece A, the rubber pad, the protective ring were attached and fixed by bolts. The moisture permeable cup in which the sheet A or the like was placed was placed under constant temperature and humidity conditions of 40 ° C / 90% RH, and after 24 hours, the moisture permeable cup was taken out, and the weight (initial weight) of the moisture permeable cup was weighed. The weighed cup that has been weighed is returned to 40 ° C / 90% RH, and the weight is weighed every 24 hours. The water vapor transmission rate was calculated from the last mass change amount and the measurement interval using the following formula at a time point when the mass increase per 24 hours was within 5%.

水蒸氣透過率[g/m2.day]=240×M/T.S。 Water vapor transmission rate [g/m 2 . Day]=240×M/T. S.

M:進行試驗之最後二個秤量間隔的增加質量(mg)。 M: The mass (mg) of the last two weighing intervals of the test.

T:進行試驗之最後二個秤量間隔的時間(小時)。 T: Time (hours) of the last two weighing intervals for the test.

S:透過面積(cm2)。 S: transmission area (cm 2 ).

又,g/m2.day係表示g/m2/day。 Also, g/m 2 . Day means g/m 2 /day.

〔耐久性試驗(耐熱性、耐濕熱性試驗)〕 [Durability test (heat resistance, heat and humidity resistance test)]

將實施例、比較例所得之附黏著劑層的偏光板(PET膜/黏著劑層/偏光片/偏光片保護膜所構成之積層體)裁切為150mm×250mm之尺寸,而製作試驗片。由試驗片剝離PET膜,使用層合輥,將黏著劑層/偏光片/偏光片保護膜所構成之積層體,以黏著劑層與玻璃板相接之方式貼黏於厚度0.5mm之玻璃板單面。將所得之積層體於調整至50℃/5大氣壓之高壓釜中保持20分鐘,而製作試驗板。製作相同之 試驗板2片。將前述試驗板於溫度80℃/乾燥之條件下(耐濕性)、或溫度60℃/濕度90%RH的條件下(耐濕熱性)放置500小時,用以下基準觀察發泡、浮起、剝落的產生並評價。 The polarizing plate (PET film/adhesive layer/layer of polarizer/polarizer protective film) with the adhesive layer obtained in the examples and the comparative examples was cut into a size of 150 mm × 250 mm to prepare a test piece. The PET film is peeled off from the test piece, and the laminated body composed of the adhesive layer/polarizer/polarizer protective film is adhered to the glass plate having a thickness of 0.5 mm by bonding the adhesive layer to the glass plate by using a laminating roll. Single side. The obtained laminate was held in an autoclave adjusted to 50 ° C / 5 atm for 20 minutes to prepare a test plate. Make the same Two test plates. The test plate was allowed to stand under the conditions of a temperature of 80 ° C / dry (moisture resistance) or a temperature of 60 ° C / humidity of 90% RH (moisture resistance) for 500 hours, and foaming and floating were observed by the following criteria. The emergence and evaluation of spalling.

AA:未觀察到發泡、浮起、剝落等的外觀不良。 AA: No appearance defects such as foaming, floating, peeling, and the like were observed.

BB:稍微觀察到發泡、浮起、剝落等的外觀不良。 BB: The appearance of foaming, floating, peeling, and the like was slightly observed.

CC:明顯觀察到發泡、浮起、剝落等的外觀不良。 CC: Obviously, the appearance of foaming, floating, peeling, and the like was poor.

〔光學性試驗(耐熱光學特性、耐濕熱光學特性試驗)〕 [Optical test (heat-resistant optical properties, moisture-resistant thermal properties test)]

將實施例、比較例所得之附黏著劑層的偏光板(由PET膜/黏著劑層/偏光片/偏光片保護膜所構成之積層體)裁切為150mm×250mm之尺寸,而製作試驗片。由試驗片剝離PET膜,使用層合輥,將黏著劑層/偏光片/偏光片保護膜所構成之積層體,以厚度0.5mm之玻璃板兩側互相之偏光軸正交且黏著劑層與玻璃板相接之方式貼黏。將所得之積層體於調整至50℃/5大氣壓之高壓釜中保持20分鐘,而製作試驗板。製作相同之試驗板2片,將前述試驗板以溫度80℃/乾燥之條件下(耐熱性)、或溫度60℃/濕度90%RH之條件下(耐濕熱性)放置500小時,使用霧度計(HM-150型:村上色彩技術研究所股份有限公司製)測定全光線透過率。又,耐久性試驗前的前述試驗板的全光線透過率為0%。 The polarizing plate with the adhesive layer obtained in the examples and the comparative examples (the laminated body composed of the PET film/adhesive layer/polarizing sheet/polarizing sheet protective film) was cut into a size of 150 mm×250 mm to prepare a test piece. . The PET film was peeled off from the test piece, and the laminated body composed of the adhesive layer/polarizer/polarizer protective film was laminated using a laminating roll, and the polarizing axes of the two sides of the glass plate having a thickness of 0.5 mm were orthogonal to each other and the adhesive layer was The glass plates are attached to each other in a sticky manner. The obtained laminate was held in an autoclave adjusted to 50 ° C / 5 atm for 20 minutes to prepare a test plate. Two sheets of the same test plate were prepared, and the test plate was placed under conditions of a temperature of 80 ° C / dry (heat resistance) or a temperature of 60 ° C / humidity of 90% RH (heat and humidity resistance) for 500 hours, using haze The total light transmittance was measured by HM-150 (manufactured by Murakami Color Technology Research Co., Ltd.). Further, the total light transmittance of the test plate before the durability test was 0%.

作為形成(甲基)丙烯酸系共聚物之單體,(1)如實施例所示,以上述特定比例使用單體(a1)與單體(a2)的例中,水蒸氣透過率低(疏水性高)且耐久性、光學特性優異,(2)如比較例1所示之不使用甲基丙烯酸烷酯而使用丙烯酸烷酯的例中、以及(3)如比較例2所示之未以上述特定比例使用單體(a1)與單體(a2)的例中,結果係水蒸氣透過率高(疏水性低)且黏著片的耐久性、及光學特性差。 As a monomer for forming a (meth)acrylic copolymer, (1) as shown in the examples, in the case where the monomer (a1) and the monomer (a2) are used in the above specific ratio, the water vapor transmission rate is low (hydrophobic High in durability and excellent in optical properties, (2) in the case of using an alkyl acrylate without using an alkyl methacrylate as shown in Comparative Example 1, and (3) as shown in Comparative Example 2 In the examples in which the monomer (a1) and the monomer (a2) are used in the above specific ratio, the water vapor transmission rate is high (hydrophobicity is low), and the durability and optical properties of the pressure-sensitive adhesive sheet are inferior.

Claims (5)

一種偏光板用黏著劑組成物,係用以形成與偏光片直接相接之黏著劑層,並含有:(A)(甲基)丙烯酸系共聚物,係單體成分共聚所得,該單體成分含有均聚物的玻璃轉移溫度(Tg)未滿-10℃且烷基之碳數為8以上的甲基丙烯酸烷酯(a1)50質量%以上99.5質量%以下、及含有交聯性官能基的單體(a2)0.5質量%以上且未滿10質量%的量;以及(B)交聯劑。 An adhesive composition for a polarizing plate for forming an adhesive layer directly in contact with a polarizer, and comprising: (A) a (meth)acrylic copolymer obtained by copolymerizing a monomer component, the monomer component The alkyl methacrylate (a1) having a glass transition temperature (Tg) of less than -10 ° C and having a carbon number of 8 or more and containing 50% by mass or more and 99.5% by mass or less of a crosslinkable functional group The amount of the monomer (a2) of 0.5% by mass or more and less than 10% by mass; and (B) the crosslinking agent. 一種偏光板用黏著劑層,係由申請專利範圍第1項所記載的黏著劑組成物所形成。 An adhesive layer for a polarizing plate is formed by the adhesive composition described in claim 1 of the patent application. 如申請專利範圍第2項所記載的偏光板用黏著劑層,其中水蒸氣透過率為800g/m2.day以下。 The adhesive layer for a polarizing plate according to the second aspect of the invention, wherein the water vapor transmission rate is 800 g/m 2 . Below day. 一種偏光板用黏著片,係具有申請專利範圍第2或3項所記載的黏著劑層。 An adhesive sheet for a polarizing plate, which has the adhesive layer described in claim 2 or 3. 一種附黏著劑層之偏光板,係具有直接積層於偏光片的至少一面之申請專利範圍第2或3項所記載的黏著劑層。 A polarizing plate with an adhesive layer is an adhesive layer as described in claim 2 or 3 of the patent application of the polarizer.
TW105118350A 2015-06-15 2016-06-13 Adhesive composition for polarizing plate, adhesive layer and adhesive sheet, and adhesive layer attached polarizing plate TW201702344A (en)

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