TW201623524A - Adhesive composition for polarizing plate and polarizing plate with adhesive layer - Google Patents
Adhesive composition for polarizing plate and polarizing plate with adhesive layer Download PDFInfo
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- TW201623524A TW201623524A TW104135385A TW104135385A TW201623524A TW 201623524 A TW201623524 A TW 201623524A TW 104135385 A TW104135385 A TW 104135385A TW 104135385 A TW104135385 A TW 104135385A TW 201623524 A TW201623524 A TW 201623524A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
Abstract
Description
本發明係關於偏光板用黏著劑組成物及附黏著劑層之偏光板等。 The present invention relates to an adhesive composition for a polarizing plate, a polarizing plate with an adhesive layer, and the like.
液晶單元(liquid crystal cell)係具有液晶層被夾持於2片基板(例如:玻璃板)之間的結構。於構成液晶單元之基板的表面,經由黏著劑層而貼附有偏光板。以往,就偏光板而言,為了提升力學性質及光學耐久性,一般係採用下述結構:於具有偏光功能之偏光片的雙面,積層有三乙酸纖維素膜等偏光片保護膜之結構。 A liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates (for example, a glass plate). A polarizing plate is attached to the surface of the substrate constituting the liquid crystal cell via the adhesive layer. In order to improve the mechanical properties and optical durability, the polarizing plate has a structure in which a polarizer protective film such as a cellulose triacetate film is laminated on both sides of a polarizer having a polarizing function.
近年來,伴隨著液晶單元的薄型化及偏光板的薄型化,高溫高濕熱環境下之液晶單元的翹曲乃成為重大問題。液晶單元之翹曲的原因,係例如可列舉出:以往的黏著劑層係應力緩和特性低,而無法充分地緩和由偏光片的熱收縮(尺寸變化)所導致之應力。 In recent years, with the reduction in thickness of the liquid crystal cell and the reduction in thickness of the polarizing plate, warpage of the liquid crystal cell in a high-temperature, high-humidity heat environment has become a major problem. The reason for the warpage of the liquid crystal cell is, for example, that the conventional adhesive layer has low stress relaxation characteristics, and the stress caused by thermal contraction (size change) of the polarizer cannot be sufficiently alleviated.
另一方面,對於偏光板之薄型化的要求,係有人嘗試省略形成於偏光片的雙面之偏光片保護膜。然而,不具有保護膜之偏光板中,由於黏著劑層直接接觸於 偏光片,故於高溫高濕熱環境下,伴隨著偏光片的熱收縮,使較大的應力施加於黏著劑層,不僅導致液晶單元的翹曲,亦容易產生黏著劑層的斷裂、偏光板的剝離等不良情況。 On the other hand, in order to reduce the thickness of the polarizing plate, attempts have been made to omit the polarizing plate protective film formed on both sides of the polarizing plate. However, in a polarizing plate without a protective film, since the adhesive layer is in direct contact with The polarizer, in the high temperature and high humidity environment, with the thermal contraction of the polarizer, a large stress is applied to the adhesive layer, which not only causes warpage of the liquid crystal cell, but also easily causes breakage of the adhesive layer, and the polarizing plate Defects such as peeling.
專利文獻1中,係記載使由特定的丙烯酸系聚合物與異氰酸酯化合物所構成之黏著劑組成物進行交聯反應,藉此而得到凝膠分率為1%以上50%以下之光學構件用黏著劑。專利文獻1中,記載著藉由前述構成,可緩和由偏光膜的尺寸變化所導致之應力並抑制漏光。然而,關於偏光片保護膜的省略,並未特別提及。 Patent Document 1 describes that an adhesive composition composed of a specific acrylic polymer and an isocyanate compound is subjected to a crosslinking reaction to obtain an adhesive for an optical member having a gel fraction of 1% or more and 50% or less. Agent. According to Patent Document 1, it is described that the above-described configuration can alleviate the stress caused by the dimensional change of the polarizing film and suppress light leakage. However, the omission of the polarizer protective film is not particularly mentioned.
專利文獻2中,係記載一種具有偏光板與設置在該偏光板之黏著劑層的黏著型偏光板,其中,前述偏光板係僅於偏光片的單側具有透明保護膜,前述黏著劑層係被設置在不具有前述透明保護膜之側的偏光片上。然而,關於前述透明保護膜的省略所伴隨之液晶單元的翹曲之問題,並未特別提及。 Patent Document 2 describes an adhesive polarizing plate having 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 It is disposed on a polarizer that does not have the side of the aforementioned transparent protective film. However, the problem of warpage of the liquid crystal cell accompanying the omission of the aforementioned transparent protective film is not particularly mentioned.
專利文獻1:日本特開2004-091500號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-091500
專利文獻2:日本特開2012-247574號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2012-247574
本發明之課題在於提供一種能夠形成下述 黏著劑層之偏光板用黏著劑組成物,該黏著劑層係可適用在省略了通常形成於偏光片的雙面之偏光片保護膜的至少一者之構成,並可抑制液晶單元的翹曲(彎曲)且耐久性優異。 An object of the present invention is to provide a capable of forming the following The adhesive composition for the polarizer of the adhesive layer is applicable to at least one of the polarizer protective films which are usually formed on both sides of the polarizer, and can suppress the warpage of the liquid crystal cell. (bending) and excellent durability.
本發明者們係為了解決上述課題而進行精心探討。結果發現當使用分枝度為特定範圍之(甲基)丙烯酸系共聚物,並使用交聯劑時,就能夠形成可抑制上述液晶單元的翹曲(彎曲)且耐久性優異之黏著劑層。上述專利文獻1至2中,關於分枝度並未特別提及。 The inventors of the present invention have carefully studied in order to solve the above problems. As a result, it has been found that when a (meth)acrylic copolymer having a specific degree of branching is used and a crosslinking agent is used, an adhesive layer capable of suppressing warpage (bending) of the liquid crystal cell and having excellent durability can be formed. In the above Patent Documents 1 to 2, the degree of branching is not particularly mentioned.
亦即,本發明者們係發現到藉由使用具有以下特定構成之偏光板用黏著劑組成物係可解決上述課題,因而完成本發明。 In other words, the present inventors have found that the above problems can be solved by using an adhesive composition system for a polarizing plate having the following specific constitution, and thus the present invention has been completed.
本發明例如為以下之[1]至[8]。 The present invention is, for example, the following [1] to [8].
[1]一種偏光板用黏著劑組成物,係用於形成與偏光片直接接觸之黏著劑層者,該組成物含有(A)(甲基)丙烯酸系共聚物及(B)交聯劑;其中,該(A)(甲基)丙烯酸系共聚物係使含有:烷基的碳數為4至18之(甲基)丙烯酸烷酯,以及含交聯性官能基之單體之單體成分共聚合而得,而該(甲基)丙烯酸系共聚物藉由凝膠滲透層析法/多角度雷射光散射檢測器(GPC-MALS:Gel Permeation Chromatography-Multi Angle Light Scattering)所測得之分枝度為0.55以下。 [1] An adhesive composition for a polarizing plate for forming an adhesive layer in direct contact with a polarizer, the composition comprising (A) a (meth)acrylic copolymer and (B) a crosslinking agent; Here, the (A) (meth)acrylic copolymer is a monomer containing a (meth)acrylic acid alkyl group having 4 to 18 carbon atoms and a monomer having a crosslinkable functional group. Copolymerized, and the (meth)acrylic copolymer is measured by a gel permeation chromatography/Gel Permeation Chromatography-Multi Angle Light Scattering (GPC-MALS: Gel Permeation Chromatography-Multi Angle Light Scattering) The branching degree is 0.55 or less.
[2]如前述[1]所述之偏光板用黏著劑組成物,其中,(甲基)丙烯酸系共聚物(A)係在過氧化物系聚合起始劑的存在下藉由前述共聚合而得到之共聚物。 [2] The adhesive composition for a polarizing plate according to the above [1], wherein the (meth)acrylic copolymer (A) is copolymerized by the foregoing in the presence of a peroxide-based polymerization initiator And the copolymer obtained.
[3]如前述[1]或[2]所述之偏光板用黏著劑組成物,其中,交聯劑(B)係包含選自異氰酸酯化合物(B1)及金屬螯合化合物(B2)之至少1種者。 [3] The adhesive composition for a polarizing plate according to the above [1], wherein the crosslinking agent (B) comprises at least one selected from the group consisting of an isocyanate compound (B1) and a metal chelate compound (B2). 1 species.
[4]如前述[1]至[3]中任一項所述之偏光板用黏著劑組成物,其中,由前述偏光板用黏著劑組成物所形成之黏著劑的凝膠分率係超過50質量%。 [4] The adhesive composition for a polarizing plate according to any one of the above [1], wherein the adhesive component formed by the adhesive composition for a polarizing plate has a gel fraction exceeding 50% by mass.
[5]一種偏光板用黏著劑層,係由如前述[1]至[4]中任一項所述之黏著劑組成物所形成者。 [5] An adhesive layer for a polarizing plate, which is formed by the adhesive composition according to any one of the above [1] to [4].
[6]如前述[5]所述之偏光板用黏著劑層,係於23℃時的儲存彈性模數(storage elastic modulus)為0.1MPa以上,且於85℃時的儲存彈性模數為0.05MPa以下者;並且,當以某溫度T℃時的儲存彈性模數作為G'T,且以T+1℃時的儲存彈性模數作為G'T+1時,在溫度T為23至50℃的範圍中,係一直都滿足G'T/G'T+1<1.07。 [6] The adhesive layer for a polarizing plate according to the above [5], wherein the storage elastic modulus at 23 ° C is 0.1 MPa or more, and the storage elastic modulus at 85 ° C is 0.05. MPa or less; and, when the storage elastic modulus at a certain temperature T ° C is taken as G' T and the storage elastic modulus at T+1 ° C is taken as G' T+1 , the temperature T is 23 to 50. In the range of °C, the system always satisfies G' T /G' T+1 <1.07.
[7]一種偏光板用黏著薄片,係具有如前述[5]或[6]所述之黏著劑層者。 [7] An adhesive sheet for a polarizing plate, comprising the adhesive layer according to the above [5] or [6].
[8]一種附黏著劑層之偏光板,係具有直接積層於偏光片之至少一面之如前述[5]或[6]所述之黏著劑層者。 [8] A polarizing plate with an adhesive layer, which has an adhesive layer as described in the above [5] or [6], which is laminated directly on at least one side of the polarizer.
根據本發明,可提供一種能夠形成下述黏 著劑層之偏光板用黏著劑組成物,該黏著劑層係可適用在省略了通常形成於偏光片的雙面之偏光片保護膜的至少一者之構成,並可抑制液晶單元的翹曲(彎曲)且耐久性優異。此外,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薄片、以及具有前述黏著劑層之附黏著劑層之偏光板。 According to the present invention, it is possible to provide a glue capable of forming the following The adhesive layer of the polarizing plate of the coating layer is applicable to at least one of the polarizer protective films which are usually formed on both sides of the polarizer, and can suppress the warpage of the liquid crystal cell. (bending) and excellent durability. Further, an adhesive layer for a polarizing plate formed of the above composition, an adhesive sheet for a polarizing plate having the above-mentioned adhesive layer, and a polarizing plate having an adhesive layer of the above-mentioned adhesive layer can be provided.
以下係說明本發明之偏光板用黏著劑組成物、偏光板用黏著劑層、偏光板用黏著薄片及附黏著劑層之偏光板。以下,亦將本發明之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薄片,分別稱為「黏著劑組成物」、「黏著劑層」及「黏著薄片」。 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.
本發明之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)與交聯劑(B)。前述組成物,可因應必要而含有選自矽烷偶合劑(C)及抗靜電劑(D)之至少1種,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), and may also contain an organic solvent (E).
(甲基)丙烯酸系共聚物(A),係含有下述單體成分之共聚物,是使該等單體成分進行共聚合而得到者;該單體成 分包含:烷基碳數為4至18之(甲基)丙烯酸烷酯、以及含交聯性官能基之單體。前述共聚物(A)通常具有來自前述(甲基)丙烯酸烷酯的構成單元與來自前述含交聯性官能基之單體的構成單元。 The (meth)acrylic copolymer (A) is a copolymer containing a monomer component obtained by copolymerizing the monomer components; The fraction comprises: an alkyl (meth)acrylate having an alkyl carbon number of 4 to 18, and a monomer having a crosslinkable functional group. The copolymer (A) usually has a constituent unit derived from the above-mentioned (meth)acrylic acid alkyl ester and a constituent unit derived from the above-mentioned crosslinkable functional group-containing monomer.
本說明書中,亦將丙烯酸及甲基丙烯酸總稱而記載為「(甲基)丙烯酸」。此外,亦將聚合物所含有之來自某單體a的構成單元記載為「單體a單元」。 In the present specification, acrylic acid and methacrylic acid are also collectively referred to as "(meth)acrylic acid". Further, the constituent unit derived from a certain monomer a contained in the polymer is also referred to as "monomer a unit".
共聚物(A)之藉由凝膠滲透層析法/多角度雷射光散射檢測器(GPC-MALS)所測得之分枝度為0.55以下,較佳為0.10至0.54,尤佳為0.20至0.53,特佳為0.30至0.53。 The degree of branching of the copolymer (A) measured by gel permeation chromatography/multi-angle laser light scattering detector (GPC-MALS) is 0.55 or less, preferably 0.10 to 0.54, and particularly preferably 0.20 to 0.53, particularly preferably 0.30 to 0.53.
所謂分枝度,係意指將使用GPC-MALS所測得之旋轉半徑(nm)及分子量(g/mol),點繪於以旋轉半徑作為縱軸且以分子量作為橫軸之雙對數圖表中而得到之直線(以下亦稱為「旋轉半徑及分子量的雙對數直線」)的斜率。理論上,直鏈分子係前述直線的斜率為1者,斜率愈小,即分枝的程度愈高。 The degree of branching means the radius of gyration (nm) and molecular weight (g/mol) measured by GPC-MALS, plotted in a double logarithmic chart with the radius of rotation as the vertical axis and the molecular weight as the horizontal axis. The slope of the obtained straight line (hereinafter also referred to as "double logarithmic straight line of radius of rotation and molecular weight"). Theoretically, the straight line molecular system has a slope of one of the aforementioned straight lines, and the smaller the slope, that is, the higher the degree of branching.
分枝度之測定條件的詳細內容係如實施例所記載。 The details of the measurement conditions of the branching degree are as described in the examples.
分枝度係為指標,當其為0.55以下時即顯示是分枝狀聚合物,當其超過0.55時即顯示是直鏈狀聚合物。此外,分枝狀聚合物中,當分枝度之值較小時,即表示聚合物分子的分枝多且具有高分枝鏈,當分枝度之值較大時,即表示聚合物分子的分枝少且具有低分枝鏈。 The degree of branching is an index, and when it is 0.55 or less, it shows a branched polymer, and when it exceeds 0.55, it shows a linear polymer. In addition, in the branched polymer, when the value of the branching degree is small, it means that the polymer molecule has many branches and has a high branching chain, and when the value of the branching degree is large, it means a polymer molecule. It has few branches and has a low branching chain.
分枝度為上述範圍內之共聚物(A),有下述 兩種情形:(1)於室溫程度下,多量地產生由聚合物分子彼此的分枝鏈所造成之交纏,結果得到維持聚合物的凝聚性、黏著特性、鑿穿黏著劑層等之加工性、黏著劑層的變形及滲出少等保管性優異之黏著劑層;(2)於高溫(例如:60℃)下,由於聚合物分子彼此的前述交纏被部分性地鬆緩,所以黏著劑層顯示出優異的柔軟性,對於偏光片的熱收縮所伴隨之被黏著體的翹曲(彎曲)之抑制性優異,且因部分性地殘存之前述交纏,而使黏著劑層顯示出優異的耐久性(例如:耐熱性、耐濕熱性)。 The copolymer (A) having a branching degree within the above range has the following In two cases: (1) at a room temperature, a large amount of entanglement caused by the branched chains of the polymer molecules is generated, and as a result, the cohesiveness, adhesive properties, and the adhesive layer of the polymer are maintained. (2) At a high temperature (for example, 60 ° C), the entanglement of the polymer molecules is partially relaxed at a high temperature (for example, 60 ° C), so that the workability, the deformation of the adhesive layer, and the bleed out are small, the entanglement of the polymer molecules is partially relaxed. The adhesive layer exhibits excellent flexibility, and is excellent in suppressing warpage (bending) of the adherend accompanying heat shrinkage of the polarizer, and exhibiting the adhesive layer due to the partial entanglement remaining. Excellent durability (for example, heat resistance and moist heat resistance).
關於抑制被黏著體的翹曲之特點,可推測是由如下理由所致。例如在偏光片/黏著劑層/被黏著體之構成中,以使用玻璃板作為被黏著體者為例來說明。偏光片及玻璃板之熱收縮率係彼此不同,與玻璃板相比,偏光片之熱收縮率(尺寸變化)通常較大。當黏著劑層欠缺於高溫高濕熱環境下之柔軟性時,黏著劑層無法跟上偏光片的尺寸變化,結果無法以黏著劑層緩和應力,使應力集中於玻璃板,因而導致玻璃板的翹曲。另一方面,使用本發明之黏著劑組成物所形成之黏著劑層係含有高分枝鏈聚合物,於高溫高濕熱環境下會使上述交纏被部分性地鬆緩,故黏著劑層可跟上偏光片的尺寸變化,因此不會產生應力,且應力不會集中於玻璃板。此外,偏光片不會產生異向性而能夠均一地熱收縮,不會引發偏光片的雙折射。 The characteristics of suppressing the warpage of the adherend are presumed to be due to the following reasons. For example, in the configuration of the polarizer/adhesive layer/adhered body, a case where a glass plate is used as an adherend will be described as an example. The heat shrinkage ratios of the polarizer and the glass plate are different from each other, and the heat shrinkage ratio (size change) of the polarizer is generally larger than that of the glass plate. When the adhesive layer is lacking in the softness under high temperature and high humidity, the adhesive layer cannot keep up with the size change of the polarizer, and as a result, the stress can not be relieved by the adhesive layer, and the stress is concentrated on the glass plate, thereby causing the glass plate to be warped. song. On the other hand, the adhesive layer formed by using the adhesive composition of the present invention contains a high-branched chain polymer, and the entanglement is partially relaxed in a high-temperature and high-humidity heat environment, so that the adhesive layer can be Keeping up with the dimensional change of the polarizer, no stress is generated and the stress is not concentrated on the glass plate. Further, the polarizer does not cause anisotropy and can be uniformly heat-shrinked without causing birefringence of the polarizer.
如上述般,本發明中,可推測是黏著劑層可緩和偏光片尺寸變化所伴隨之應力,因此不會對玻璃板 施加過度的應力(負荷),而有利於抑制玻璃板的翹曲。 As described above, in the present invention, it is presumed that the adhesive layer can alleviate the stress accompanying the change in the size of the polarizer, and therefore does not affect the glass plate. Excessive stress (load) is applied to suppress the warpage of the glass sheet.
本發明之黏著劑組成物係由於具有以上特性,故適合用於構成液晶單元之基板與偏光片之貼合的用途。尤其是即使在構成經薄型化後之液晶單元之玻璃板的厚度小至1mm以下之程度時,亦適合用於該基板與偏光片之貼合的用途。 Since the adhesive composition of the present invention has the above characteristics, it is suitable for use in bonding a substrate constituting a liquid crystal cell and a polarizer. In particular, even when the thickness of the glass plate constituting the thinned liquid crystal cell is as small as 1 mm or less, it is suitable for use in bonding the substrate to the polarizer.
(甲基)丙烯酸烷酯係使用烷基碳數為4至18之(甲基)丙烯酸烷酯(CH2=CR1-COOR2;R1為氫原子或甲基,R2為碳數4至18的烷基),在此,前述烷基碳數尤佳為4至12。 The alkyl (meth)acrylate is an alkyl (meth)acrylate having an alkyl carbon number of 4 to 18 (CH 2 =CR 1 -COOR 2 ; R 1 is a hydrogen atom or a methyl group, and R 2 is a carbon number 4 Here, the alkyl group has a carbon number of from 4 to 12, particularly preferably from 4 to 12.
烷基碳數為4至18之(甲基)丙烯酸烷酯,例如可列舉出(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(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、(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)丙烯酸十一烷酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯。此等係可單獨使用1種,亦可使用2種以上。 The alkyl (meth)acrylate having 4 to 18 carbon atoms may, for example, be n-butyl (meth)acrylate, isobutyl (meth)acrylate or tertiary butyl (meth)acrylate, ( Amyl methacrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate Ester, decyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylate Isostearyl ester. These may be used alone or in combination of two or more.
形成共聚物(A)之單體成分100質量%中,烷基碳數為4至18之(甲基)丙烯酸烷酯的用量,從顯現良好的黏著力及耐久性之觀點來看,較佳為99.8至20質量%,尤佳為99.5至30質量%,更佳為99至50質量%。 In the case of forming 100% by mass of the monomer component of the copolymer (A), the amount of the alkyl (meth)acrylate having an alkyl group of 4 to 18 is preferably from the viewpoint of exhibiting good adhesion and durability. It is from 99.8 to 20% by mass, particularly preferably from 99.5 to 30% by mass, more preferably from 99 to 50% by mass.
形成共聚物(A)之單體成分,亦可進一步使 用烷基碳數為1至3之(甲基)丙烯酸烷酯(CH2=CR3-COOR4;R3為氫原子或甲基,R4為碳數1至3的烷基)。 The monomer component of the copolymer (A) is formed, and an alkyl (meth)acrylate having an alkyl group having 1 to 3 carbon atoms (CH 2 =CR 3 -COOR 4 ; R 3 is a hydrogen atom or a methyl group) may be further used. R 4 is an alkyl group having 1 to 3 carbon atoms).
烷基碳數為1至3之(甲基)丙烯酸烷酯,例如可列舉出(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。此等係可單獨使用1種,亦可使用2種以上。 The alkyl (meth)acrylate having an alkyl carbon number of 1 to 3 may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate or n-propyl (meth)acrylate, or (methyl). Isopropyl acrylate. These may be used alone or in combination of two or more.
形成共聚物(A)之單體成分100質量%中,烷基碳數為1至3之(甲基)丙烯酸烷酯的用量,從應力緩和之觀點來看,較佳為60質量%以下,尤佳為50質量%以下,更佳為40質量%以下。 The amount of the (meth)acrylic acid alkyl ester having an alkyl group having 1 to 3 alkyl groups in the amount of 100% by mass of the monomer component of the copolymer (A) is preferably 60% by mass or less from the viewpoint of stress relaxation. It is preferably 50% by mass or less, more preferably 40% by mass or less.
形成共聚物(A)之單體成分,更包含:具有可與交聯劑(B)反應之交聯性官能基之單體,亦即,含交聯性官能基之單體。 The monomer component forming the copolymer (A) further comprises a monomer having a crosslinkable functional group reactive with the crosslinking agent (B), that is, a monomer having a crosslinkable functional group.
含交聯性官能基之單體,例如可列舉出含羥基之單體、含酸基之單體、含胺基之單體、含醯胺基之單體、含氮系雜環之單體、含氰基之單體。本說明書中,酸基係例如可列舉出羧基、酸酐基、磷酸基、硫酸基。 Examples of the monomer having a crosslinkable functional group include a hydroxyl group-containing monomer, an acid group-containing monomer, an amine group-containing monomer, a mercapto group-containing monomer, and a nitrogen-containing heterocyclic monomer. , a monomer containing a cyano group. In the present specification, examples of the acid group include a carboxyl group, an acid anhydride group, a phosphoric acid group, and a sulfuric acid group.
含羥基之單體,例如可列舉出含羥基之(甲基)丙烯酸酯,具體可列舉出(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯等(甲基)丙烯酸羥烷酯。(甲基)丙烯酸羥烷酯中之羥烷基的碳數,通常為2至 8,較佳為2至6。 Examples of the hydroxyl group-containing monomer include a hydroxyl group-containing (meth) acrylate, and specific examples thereof include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (methyl). A hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth)acrylate or 8-hydroxyoctyl (meth)acrylate. The carbon number of the hydroxyalkyl group in the hydroxyalkyl (meth) acrylate, usually 2 to 8, preferably 2 to 6.
含羧基之單體,例如可列舉出:(甲基)丙烯酸β-羧乙酯、(甲基)丙烯酸5-羧戊酯、琥珀酸單(甲基)丙烯醯氧基乙酯、ω-羧基聚己內酯單(甲基)丙烯酸酯等含羧基之(甲基)丙烯酸酯;丙烯酸、甲基丙烯酸、伊康酸、巴豆酸、反丁烯二酸、順丁烯二酸等。含酸酐基之單體,例如可列舉出順丁烯二酸酐、伊康酸酐。含磷酸基之單體係例如可列舉出側鏈具有磷酸基之(甲基)丙烯酸系單體,含硫酸基之單體係例如可列舉出側鏈具有硫酸基之(甲基)丙烯酸系單體。 Examples of the carboxyl group-containing monomer include β-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, mono(meth)acryloxyethyl succinate, and ω-carboxyl groups. A carboxyl group-containing (meth) acrylate such as polycaprolactone mono(meth)acrylate; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or the like. Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride. The mono-system containing a phosphate group may, for example, be a (meth)acrylic monomer having a phosphate group in a side chain, and the mono-system containing a sulfate group may, for example, be a (meth)acrylic acid having a sulfate group in a side chain. body.
含胺基之單體,例如可列舉出(甲基)丙烯酸二甲基胺乙酯、(甲基)丙烯酸二乙基胺乙酯等含胺基之(甲基)丙烯酸酯。含醯胺基之單體,例如可列舉出(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。含氮系雜環之單體,例如可列舉出乙烯基吡咯啶酮、丙烯醯基嗎啉、乙烯基己內醯胺。含氰基之單體,例如可列舉出氰基(甲基)丙烯酸酯、(甲基)丙烯腈。 The amine group-containing monomer may, for example, be an amino group-containing (meth) acrylate such as dimethylaminoethyl (meth)acrylate or diethylamine ethyl (meth)acrylate. Examples of the mercapto group-containing monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-propyl (A). Base) acrylamide, N-hexyl (meth) acrylamide. Examples of the monomer containing a nitrogen-containing hetero ring include vinyl pyrrolidone, acryloyl morpholine, and vinyl caprolactam. Examples of the cyano group-containing monomer include cyano (meth) acrylate and (meth) acrylonitrile.
含交聯性官能基之單體係可單獨使用1種,亦可使用2種以上。 The single system containing a crosslinkable functional group may be used alone or in combination of two or more.
形成共聚物(A)之單體成分100質量%中,含交聯性官能基之單體的用量較佳為0.01至15質量%,尤佳為0.05至10質量%,更佳為0.1至5質量%。含交聯性官能基之單體的用量為前述上限值以下時,由共聚物(A) 與交聯劑(B)所形成之交聯密度不會過高,可得到應力緩和特性優異之黏著劑層。含交聯性官能基之單體的用量為前述下限值以上時,可有效地形成交聯結構,而得到常溫下具有適當強度之黏著劑層。 The monomer containing the crosslinkable functional group is preferably used in an amount of from 0.01 to 15% by mass, particularly preferably from 0.05 to 10% by mass, more preferably from 0.1 to 5, per 100% by mass of the monomer component of the copolymer (A). quality%. When the amount of the monomer having a crosslinkable functional group is less than or equal to the above upper limit, the copolymer (A) The crosslinking density formed by the crosslinking agent (B) is not excessively high, and an adhesive layer excellent in stress relaxation characteristics can be obtained. When the amount of the monomer having a crosslinkable functional group is at least the above lower limit value, the bonded structure can be effectively formed to obtain an adhesive layer having an appropriate strength at normal temperature.
形成共聚物(A)之單體成分,在不損及共聚物(A)的物性之範圍內,例如可包含(甲基)丙烯酸烷氧基烷酯、單(甲基)丙烯酸烷氧基聚烷二醇酯、含脂環型基或芳香環之(甲基)丙烯酸酯等其他(甲基)丙烯酸酯。亦即,前述共聚物(A)可更具有來自前述其他(甲基)丙烯酸酯的構成單元。 The monomer component forming the copolymer (A) may contain, for example, an alkoxyalkyl (meth)acrylate or an alkoxy poly(meth)acrylate, within a range not impairing the physical properties of the copolymer (A). Other (meth) acrylates such as alkylene glycol esters, alicyclic groups or aromatic ring-containing (meth) acrylates. That is, the copolymer (A) may further have a constituent unit derived from the other (meth) acrylate described above.
(甲基)丙烯酸烷氧基烷酯,例如可列舉出(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 methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, and 2-ethoxyethyl (meth)acrylate. Ester, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxy (meth)acrylate Butyl ester.
單(甲基)丙烯酸烷氧基聚烷二醇酯,例如可列舉出單(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 mono(meth)acrylic alkoxypolyalkylene glycol esters include methoxybisethylene glycol mono(meth)acrylate, methoxydipropylene glycol mono(meth)acrylate, and mono(A). Ethylene ethoxylated triethylene glycol acrylate, ethoxylated diethylene glycol mono(meth)acrylate, methoxytriethylene glycol mono(meth)acrylate.
含脂環型基或芳香環之(甲基)丙烯酸酯,例如可列舉出(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯。藉由使用含芳香環之(甲基)丙烯酸酯,可 提升黏著劑層的耐漏光性能。 Examples of the (meth) acrylate containing an alicyclic group or an aromatic ring include cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and phenyl (meth)acrylate. By using an aromatic ring-containing (meth) acrylate, Improve the light leakage resistance of the adhesive layer.
形成共聚物(A)之單體成分100質量%中,上述其他(甲基)丙烯酸酯的全部用量較佳為60質量%以下,尤佳為40質量%以下。 In 100% by mass of the monomer component of the copolymer (A), the total amount of the other (meth) acrylate is preferably 60% by mass or less, and particularly preferably 40% by mass or less.
此外,形成共聚物(A)之單體成分,在不損及共聚物(A)的物性之範圍內,例如可包含苯乙烯系單體、乙酸乙烯酯等共聚合性單體。亦即,前述共聚物(A)可更具有來自前述共聚合性單體的構成單元。 Further, the monomer component forming the copolymer (A) may contain, for example, a copolymerizable monomer such as a styrene monomer or vinyl acetate, within a range not impairing the physical properties of the copolymer (A). That is, the copolymer (A) may further have a constituent unit derived from the above-mentioned copolymerizable monomer.
苯乙烯系單體,例如可列舉出: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、甲氧基苯乙烯等。 Examples of the styrene monomer include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, propyl styrene, butyl styrene, hexyl styrene, and heptyl styrene. Alkyl styrene such as octyl styrene; halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodine styrene; nitrostyrene, ethyl styrene styrene, methoxy benzene Ethylene and the like.
形成共聚物(A)之單體成分100質量%中,上述共聚合性單體的全部用量較佳為40質量%以下,尤佳為20質量%以下。 In 100% by mass of the monomer component of the copolymer (A), the total amount of the above-mentioned copolymerizable monomer is preferably 40% by mass or less, and particularly preferably 20% by mass or less.
其他單體係可單獨使用1種,亦可使用2種以上。 The other single system may be used alone or in combination of two or more.
(甲基)丙烯酸系共聚物(A),較佳係在過氧化物系聚合起始劑的存在下藉由前述共聚合而得到之共聚物。亦即,藉由使用過氧化物系聚合起始劑作為聚合起始劑,乃具有 會得到分枝度位於上述範圍之共聚物之傾向。 The (meth)acrylic copolymer (A) is preferably a copolymer obtained by the above copolymerization in the presence of a peroxide polymerization initiator. That is, by using a peroxide-based polymerization initiator as a polymerization initiator, There is a tendency to obtain a copolymer having a branching degree within the above range.
(甲基)丙烯酸系共聚物(A),例如可藉由溶液聚合法、整體聚合法(bulk polymerization)、乳化聚合法、懸浮聚合法等以往一般所知的聚合方法來製造。此等當中,較佳為溶液聚合法。具體而言,係將聚合溶劑及單體成分裝入反應容器內,於氮氣等惰性氣體環境下添加聚合起始劑,將反應起始溫度設定在通常為40至100℃,較佳為50至80℃,並將反應系統維持在通常為50至90℃,較佳為70至90℃的溫度,進行4至20小時的反應。此外,上述聚合反應中,可適當地追加添加聚合起始劑、鏈轉移劑、單體成分、聚合溶劑。 The (meth)acrylic copolymer (A) can be produced, for example, by a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, or a suspension polymerization method. Among these, a solution polymerization method is preferred. Specifically, the polymerization solvent and the monomer component are charged into a reaction vessel, and a polymerization initiator is added under an inert gas atmosphere such as nitrogen to set the reaction initiation temperature to usually 40 to 100 ° C, preferably 50 to The reaction system is maintained at a temperature of usually 50 to 90 ° C, preferably 70 to 90 ° C, at 80 ° C for 4 to 20 hours. Further, in the above polymerization reaction, a polymerization initiator, a chain transfer agent, a monomer component, and a polymerization solvent may be appropriately added.
過氧化物系聚合起始劑,例如可列舉出:二(2-二-三級丁基過氧化異丙基)苯、過氧化二(異丙苯基)、2,5-二甲基-2,5-二(三級丁基過氧化)己烷、過氧化三級丁基異丙苯基、過氧化二(三級己基)、過氧化二(三級丁基)等過氧化二烷基類(例如:以R-O-O-R表示之化合物,式中的R分別獨立地為烷基或經芳基取代之烷基;以R-O-O-A-O-O-R表示之化合物,式中的R分別獨立地為烷基或經芳基取代之烷基,A為2價烴基);過氧化二(異丁醯基)、過氧化二(3,5,5-三甲基己醯基)、過氧化二(月桂醯基)、過氧化二(苯甲醯基)、過氧化苯甲醯基(3-甲基苯甲醯基)、過氧化二(3-甲基苯甲醯基)、過氧化二(4-甲基苯甲醯基)等過氧化二醯基類(例如:以R-COO-OCO-R表示之化合物,式中的R分別獨立地為烷基 或芳基);過氧化二碳酸二正丙酯、過氧化二碳酸二異丙酯、過氧化二碳酸二(4-三級丁基環己基)酯、過氧化二碳酸二(2-乙基己基)酯、過氧化二碳酸二(二級丁基)酯等過氧化二碳酸酯(例如:以R-OCO-O-O-COO-R表示之化合物,式中的R分別獨立地為烷基或環烷基);過氧化新癸酸異丙苯酯、過氧化新癸酸1,1,3,3-四甲基丁酯、過氧化新癸酸三級己酯、過氧化新癸酸三級丁酯、過氧化新庚酸三級丁酯、過氧化新戊酸三級己酯、過氧化新戊酸三級丁酯、過氧化-2-乙基己酸1,1,3,3-四甲基丁酯、2,5-二甲基-2,5-二(2-乙基己醯基過氧化)己烷、過氧化-2-乙基己酸三級己酯、過氧化-2-乙基己酸三級丁酯、過氧化-3,5,5-三甲基己酸三級丁酯、過氧化月桂酸三級丁酯、過氧化苄酸三級己酯、2,5-二甲基-2,5-二(苯甲醯基過氧化)己烷、過氧化乙酸三級丁酯、過氧化-3-甲基苄酸三級丁酯、過氧化苄酸三級丁酯等過氧化酯類(例如:以R1-O-O-CO-R2表示之化合物,式中的R1為烷基或經芳基取代之烷基,R2為烷基、芳基或經芳基取代之烷基;以R-CO-O-O-A-O-O-CO-R表示之化合物,式中的R分別獨立地為烷基或芳基,A為2價烴基);單碳酸三級己酯過氧化異丙酯、單碳酸三級丁酯過氧化異丙酯、單碳酸三級丁酯過氧化-2-乙基己酯等單碳酸過氧化酯類(例如:以R-O-O-COO-R表示之化合物,式中的R分別獨立地為烷基)。 Examples of the peroxide-based polymerization initiator include bis(2-di-tert-butylperoxyisopropyl)benzene, bis(isopropylphenyl) peroxide, and 2,5-dimethyl- 2,5-di (tertiary butyl peroxy) hexane, tributyl cumyl peroxide, di(tertiary hexyl peroxide), di(tertiary butyl) peroxide, dioxane a base (for example, a compound represented by ROOR, wherein R is independently an alkyl group or an alkyl group substituted with an aryl group; a compound represented by ROOAOOR, wherein R in each case is independently an alkyl group or an aryl group; Substituted alkyl group, A is a divalent hydrocarbon group); bis(isobutyl decyl) peroxide, bis(3,5,5-trimethylhexyl) peroxide, bis(laurel), peroxide (benzhydryl), benzhydryl peroxide (3-methylbenzhydryl), bis(3-methylbenzhydryl) peroxide, bis(4-methylbenzhydryl) peroxide a perylene dihydrazyl group (for example, a compound represented by R-COO-OCO-R, wherein R in the formula is independently an alkyl group or an aryl group); di-n-propyl peroxydicarbonate, peroxidized Diisopropyl carbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, peroxygen a peroxydicarbonate such as di(2-ethylhexyl) dicarbonate or di(tertiary butyl) peroxydicarbonate (for example, a compound represented by R-OCO-OO-COO-R, R is independently alkyl or cycloalkyl); cumene peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, tertiary neodecanoate Ester, tertiary butyl peroxy neodecanoate, tertiary butyl peroxy neoheptanoate, tertiary hexyl peroxypivalate, tertiary butyl peroxypivalate, peroxy-2-ethyl 1,1,3,3-tetramethylbutyl acid, 2,5-dimethyl-2,5-di(2-ethylhexylperoxy)hexane, peroxy-2-ethyl Tert-butyl hexanoate, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl laurate, peroxidation Tert-Benzyl Benzate, 2,5-Dimethyl-2,5-bis(benzhydrylperoxy)hexane, tertiary butyl peroxyacetate, 3-methyl peroxy-3-benzylate Peroxy esters such as butyl ester and butyl peroxybenzylate (for example, a compound represented by R 1 -OO-CO-R 2 wherein R 1 is an alkyl group or an alkyl group substituted with an aryl group, R 2 is an alkyl group, an aryl group or an alkyl group substituted with an aryl group; a compound represented by R-CO-OOAOO-CO-R, wherein R is independently an alkyl group or an aryl group, and A is a divalent hydrocarbon group) ; mono-carbonic acid peroxyesters such as dimethyl peroxyacetate monoisopropylate, butyl peroxycarbonate isopropyl perester, monobutyl butyl carbonate, peroxy-2-ethylhexyl ester (eg: A compound represented by ROO-COO-R wherein R in the formula is independently an alkyl group).
過氧化物系聚合起始劑中,從得到高分枝鏈的(甲基)丙烯酸系共聚物來看,較佳為過氧化酯類,尤佳為以下述式(1)表示之過氧化物系聚合起始劑。 In the peroxide-based polymerization initiator, a peroxy ester is preferred from the viewpoint of obtaining a (meth)acrylic copolymer having a high branched chain, and a peroxide represented by the following formula (1) is particularly preferable. It is a polymerization initiator.
式(1)中,RA至RF分別獨立地為氫原子、烷基或芳基,從得到高分枝鏈的共聚物之觀點來看,較佳為碳數1至10的烷基、苯基,尤佳為碳數1至8的烷基,更佳為碳數1至4的烷基,特佳為碳數1至2的烷基。 In the formula (1), R A to R F are each independently a hydrogen atom, an alkyl group or an aryl group, and from the viewpoint of obtaining a copolymer of a highly branched chain, an alkyl group having 1 to 10 carbon atoms is preferable. The phenyl group is particularly preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 to 2 carbon atoms.
以式(1)表示之過氧化物系聚合起始劑中,較佳為過氧化新戊酸三級丁酯、過氧化新戊酸三級己酯、過氧化新癸酸三級丁酯、過氧化新庚酸三級丁酯、過氧化-2-乙基己酸三級丁酯、過氧化新癸酸異丙苯酯,從得到高分枝鏈的共聚物之觀點來看,特佳為過氧化新戊酸三級丁酯、過氧化新戊酸三級己酯、過氧化新癸酸三級丁酯、過氧化新庚酸三級丁酯、過氧化-2-乙基己酸三級丁酯。 Among the peroxide-based polymerization initiators represented by the formula (1), preferred are tertiary butyl peroxypivalate, tertiary hexyl peroxypivalate, and tertiary butyl peroxy neodecanoate. Peroxidic neoheptanoic acid tert-butyl acrylate, peroxy-2-ethylhexanoate tert-butyl acrylate, peroxyphenyl phthalate, from the viewpoint of obtaining a highly branched chain copolymer, Is peroxidized tertiary butyl pivalate, tertiary hexyl peroxypivalate, tertiary butyl peroxy neodecanoate, tertiary butyl peroxy neoheptate, peroxy-2-ethylhexanoate Tertiary butyl ester.
過氧化物系聚合起始劑係可單獨使用1種,亦可使用2種以上。此外,於聚合中,亦不受限制地可添加複數次過氧化物系聚合起始劑。 The peroxide polymerization initiator may be used singly or in combination of two or more. Further, in the polymerization, a plurality of peroxide-based polymerization initiators may be added without limitation.
聚合起始劑只要分枝度為上述範圍內,則亦可與過氧化物系起始劑一起使用偶氮系起始劑。偶氮系 起始劑係例如可列舉出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-甲腈)、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、二氫氯化-2,2'-偶氮雙(2-甲脒基丙烷)、2,2'-偶氮雙(N,N'-二亞甲基異丁基甲脒基)、2,2'-偶氮雙[2-甲基-N-(2-羥基乙基)-丙醯胺]、二水合化-2,2'-偶氮雙(異丁醯胺)、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)等偶氮化合物。此等聚合起始劑係可單獨使用1種,亦可使用2種以上。 As the polymerization initiator, an azo-based initiator may be used together with the peroxide-based initiator as long as the degree of branching is within the above range. Azo system The initiator 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-(aminomercaptoazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4 - dimethyl valeronitrile, dihydrochloride-2,2'-azobis(2-carboxynylpropane), 2,2'-azobis(N,N'-dimethylene isobutylformamidine , 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propanamide], dihydrated-2,2'-azobis(isobutylamine) , 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-cyanopropanol), dimethyl-2,2'-azobis(2- An azo compound such as methyl propionate). These polymerization initiators may be used alone or in combination of two or more.
相對於形成(甲基)丙烯酸系共聚物(A)之單體成分100質量份,過氧化物系聚合起始劑通常是以0.001至5質量份,較佳是以於0.005至3質量份之範圍內的量來使用。此外,以不使用偶氮系起始劑為較佳,其用量相對於過氧化物系聚合起始劑100質量份,較佳為0.5質量份以下,尤佳為0.2質量份以下,更佳為0質量份。惟於反應後半以減少殘存單體為目的來使用時,並不受限。 The peroxide-based polymerization initiator is usually 0.001 to 5 parts by mass, preferably 0.005 to 3 parts by mass, per 100 parts by mass of the monomer component forming the (meth)acryl-based copolymer (A). The amount within the range is used. Further, the azo-based initiator is preferably used, and the amount thereof is preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less, more preferably 0.2 parts by mass or less, more preferably 100 parts by mass or less based on the peroxide-based polymerization initiator. 0 parts by mass. However, it is not limited to use in the latter half of the reaction for the purpose of reducing residual monomers.
聚合溶劑係例如可列舉出: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、環辛烷等脂環型烴類;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、苯乙醚、二苯基醚等醚類;氯仿、四氯化碳、1,2-二氯乙烷、氯苯等鹵化烴類; 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,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。此等聚合溶劑係可單獨使用1種,亦可使用2種以上。 Examples of the polymerization solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; and cyclopentane, cyclohexane, and cycloheptane. An alicyclic hydrocarbon such as an alkane or a cyclooctane; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, benzene An ether such as diethyl ether or diphenyl ether; a halogenated hydrocarbon such as chloroform, carbon tetrachloride, 1,2-dichloroethane or chlorobenzene; Ethyl acetate, propyl acetate, butyl acetate, methyl propionate and other esters; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; N, N - guanamines such as dimethylformamide, N,N-dimethylacetamide, N,N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; dimethyl hydrazine and cycline碸 and other Aachen. These polymerization solvents may be used alone or in combination of two or more.
(甲基)丙烯酸系共聚物(A)之藉由GPC法所測得之重量平均分子量(Mw),以聚苯乙烯換算值計,通常為20萬至150萬,較佳為40萬至130萬,尤佳為50萬至110萬。共聚物(A)係由於為高分枝聚合物,所以共聚物(A)鏈彼此可相互適度地交纏,黏著劑層的加工性不會惡化。尤其當Mw為40萬以上時,可得到凝聚性高之黏著劑層。 The weight average molecular weight (Mw) of the (meth)acrylic copolymer (A) measured by the GPC method is usually 200,000 to 1,500,000, preferably 400,000 to 130, in terms of polystyrene. 10,000, especially good for 500,000 to 1.1 million. Since the copolymer (A) is a highly branched polymer, the copolymer (A) chains can be appropriately intertwined with each other, and the workability of the adhesive layer does not deteriorate. In particular, when the Mw is 400,000 or more, an adhesive layer having high cohesiveness can be obtained.
(甲基)丙烯酸系共聚物(A)之藉由GPC法所測得之分子量分布(Mw/Mn)通常為50以下,較佳為10至40,尤佳為10至30。 The molecular weight distribution (Mw/Mn) of the (meth)acrylic copolymer (A) measured by the GPC method is usually 50 or less, preferably 10 to 40, and particularly preferably 10 to 30.
(甲基)丙烯酸系共聚物(A)的玻璃轉移溫度(Tg),例如可從構成該共聚物之單體單元及其含有比率中,依據Fox的算式來算出。例如,能夠以使依據Fox的算式所求取之玻璃轉移溫度(Tg)通常成為-70至0℃,較佳係成為-60至-30℃之方式,來合成(甲基)丙烯酸系共聚物(A)。藉由使用具有如此之玻璃轉移溫度(Tg)之(甲基)丙烯酸系共聚物(A),可得到常溫下黏著性優異之黏著劑組成 物。 The glass transition temperature (Tg) of the (meth)acrylic copolymer (A) can be calculated, for example, from the monomer unit constituting the copolymer and the content ratio thereof according to the formula of Fox. For example, the (meth)acrylic copolymer can be synthesized in such a manner that the glass transition temperature (Tg) obtained by the calculation formula according to Fox is usually -70 to 0 ° C, preferably -60 to -30 ° C. (A). By using a (meth)acrylic copolymer (A) having such a glass transition temperature (Tg), an adhesive composition excellent in adhesion at normal temperature can be obtained. Things.
Fox的算式:1/Tg=(W1/Tg1)+(W2/Tg2)+‧‧‧+(Wm/Tgm) W1+W2+‧‧‧+Wm=1 Fox's formula: 1/Tg=(W 1 /Tg 1 )+(W 2 /Tg 2 )+‧‧‧+(W m /Tg m ) W 1 +W 2 +‧‧‧+W m =1
式中,Tg為(甲基)丙烯酸系共聚物(A)的玻璃轉移溫度(單位:K),Tg1、Tg2、‧‧‧、Tgm為由各單體所構成之均聚物的玻璃轉移溫度(單位:K),W1、W2、‧‧‧、Wm為來自各單體之構成單元於前述共聚物(A)中的重量分率。來自各單體之構成單元的重量分率,可使用於共聚物合成時之各單體相對於全部單體之裝入比率。 In the formula, Tg is a glass transition temperature (unit: K) of the (meth)acrylic copolymer (A), and Tg 1 , Tg 2 , ‧ ‧ and Tg m are homopolymers composed of each monomer The glass transition temperature (unit: K), W 1 , W 2 , ‧ ‧ , W m is the weight fraction of the constituent unit derived from each monomer in the copolymer (A). The weight fraction of the constituent units derived from the respective monomers can be used for the ratio of the loading of each monomer to the total monomers when the copolymer is synthesized.
前述Fox的算式中,由各單體所構成之均聚物的玻璃轉移溫度,例如可採用Polymer Handbook Fourth Edition(Wiley-Interscience 2003)所記載之值。 In the above formula of Fox, the glass transition temperature of the homopolymer composed of each monomer can be, for example, a value described in Polymer Handbook Fourth Edition (Wiley-Interscience 2003).
本發明之黏著劑組成物中,(甲基)丙烯酸系共聚物(A)的含量,於該組成物中之扣除有機溶劑(E)之固體成分100質量%中,通常為50至99.99質量%,尤佳為60至99.95質量%,特佳為80至99.90質量%。當(甲基)丙烯酸系共聚物(A)的含量位於前述範圍時,可取得作為黏著劑之性能之均衡,黏著特性優異。 In the adhesive composition of the present invention, the content of the (meth)acrylic copolymer (A) is usually from 50 to 99.99% by mass based on 100% by mass of the solid content of the organic solvent (E) in the composition. More preferably, it is 60 to 99.95 mass%, and particularly preferably 80 to 99.90 mass%. When the content of the (meth)acrylic copolymer (A) is in the above range, a balance of properties as an adhesive can be obtained, and the adhesive property is excellent.
本發明之黏著劑組成物更含有交聯劑(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)所具有之來自含交聯性官能基之單體的交聯性官 能基引起交聯反應之成分即可,並無特別限定,例如可列舉出異氰酸酯化合物(B1)、金屬螯合化合物(B2)、環氧化合物(B3)。 The crosslinking agent (B) is a crosslinkable member which can be derived from a monomer having a crosslinkable functional group which is compatible with the (meth)acrylic copolymer (A). The component capable of causing a crosslinking reaction 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)係可單獨使用1種,亦可使用2種以上。 The crosslinking agent (B) may be used alone or in combination of two or more.
交聯劑(B)中,較佳係使用選自異氰酸酯化合物(B1)及金屬螯合化合物(B2)之至少1種,尤佳係併用異氰酸酯化合物(B1)及金屬螯合化合物(B2)。 In the crosslinking agent (B), at least one selected from the group consisting of an isocyanate compound (B1) and a metal chelate compound (B2) is preferably used, and an isocyanate compound (B1) and a metal chelate compound (B2) are preferably used in combination.
相對於(甲基)丙烯酸系共聚物(A),較佳係形成下述交聯:由依據異氰酸酯化合物(B1)之共價鍵所形成的交聯、及/或由依據金屬螯合化合物(B2)之配位鍵所形成的虛擬交聯。 With respect to the (meth)acrylic copolymer (A), crosslinking is preferably carried out by crosslinking formed by a covalent bond of the isocyanate compound (B1), and/or by a metal chelate compound ( The virtual crosslink formed by the coordination key of B2).
本發明之黏著劑組成物中,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,尤佳為0.05至2.5質量份,更佳為0.1至1質量份。該含量位於前述範圍時,從容易取得耐久性與應力緩和特性的均衡之觀點來看為佳。 In the adhesive composition of the present invention, the content of the crosslinking agent (B) is usually 0.01 to 5 parts by mass, particularly 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 from the viewpoint of easily obtaining a balance between durability and stress relaxation characteristics.
異氰酸酯化合物(B1),通常是使用1分子中的異氰酸酯基數為2以上之異氰酸酯化合物。藉由以異氰酸酯化合物(B1)將(甲基)丙烯酸系共聚物(A)交聯,可形成交聯體(網狀聚合物)。 The isocyanate compound (B1) is usually an isocyanate compound having an isocyanate group number of 2 or more in one molecule. By crosslinking the (meth)acrylic copolymer (A) with the isocyanate compound (B1), a crosslinked body (mesh 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,較佳為2至8,尤佳為3至6。當異氰酸酯基數位於前述範圍時,從(甲基)丙烯酸系共聚物(A)與異氰酸酯化合物(B1)之交聯反應效率之觀點、以及保持黏著劑層的柔軟性之觀點來看為佳。 The isocyanate group number of the isocyanate compound (B1) is usually It is 2 or more, preferably 2 to 8, and particularly preferably 3 to 6. When the number of isocyanate groups is in the above range, it is preferable from the viewpoint of the crosslinking reaction efficiency of the (meth)acrylic copolymer (A) and the isocyanate compound (B1) and the flexibility of the adhesive layer.
1分子中的異氰酸酯基數為2之異氰酸酯化合物,例如可列舉出脂肪族二異氰酸酯、脂環族二異氰酸酯、芳香族二異氰酸酯。脂肪族二異氰酸酯,可列舉出伸乙基二異氰酸酯、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,可列舉出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,例如可列舉出伸苯二異氰酸酯、甲苯二異氰酸酯、二甲苯二異氰酸酯、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 isocyanate compound having an isocyanate group number of 2 in one molecule may, for example, be an aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate. Examples of the aliphatic diisocyanate include ethyl diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, and 3 An aliphatic diisocyanate having 4 to 30 carbon atoms such as 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 hydrogen tetramethylate. An alicyclic diisocyanate having 7 to 30 carbon atoms such as xylene diisocyanate. Examples of the aromatic diisocyanate include carbon number such as phenylene diisocyanate, toluene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate. 8 to 30 aromatic diisocyanates.
1分子中的異氰酸酯基數為3以上之異氰酸酯化合物,例如可列舉出芳香族聚異氰酸酯、脂肪族聚異氰酸酯、脂環族聚異氰酸酯。具體可列舉出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。 The isocyanate compound having 3 or more isocyanate groups in one molecule may, for example, be an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate. Specific examples thereof include 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, and 4,4',4"-triphenylmethane triisocyanate.
此外,異氰酸酯化合物(B1),例如可列舉出異氰酸酯基數為2或3以上之上述異氰酸酯化合物的多聚物(例如二聚物或三聚物、縮二脲體、三聚異氰酸體)、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)、聚合物等。關於前述衍生物中的多元醇,低分子量多元醇係例如可列舉出三羥甲基丙烷、甘油、新戊四醇等3元以上的醇,高分子量多元醇係例如可列舉出聚醚多元醇、聚酯多元醇、丙烯酸系多元醇、聚丁二烯多元醇、聚異戊二烯多元醇。 Further, examples of the isocyanate compound (B1) include a polymer (for example, a dimer or a trimer, a biuret or a trimeric isocyanate) of the above isocyanate compound having an isocyanate group number of 2 or more, A derivative (for example, an addition reaction product of a polyhydric alcohol and two or more molecules of a diisocyanate compound), a polymer, or the like. Examples of the polyhydric alcohol in the above-mentioned derivative include a trihydric or higher alcohol such as trimethylolpropane, glycerin or neopentyl alcohol, and examples of the high molecular weight polyhydric alcohol include polyether polyol. Polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol.
如此之異氰酸酯化合物,例如可列舉出二苯基甲烷二異氰酸酯的三聚物、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的縮二脲體或三聚異氰酸酯體、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三分子加成物)、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三分子加成物)、聚醚聚異氰酸酯、聚酯聚異氰酸酯。 Examples of such an isocyanate compound include a trimer of diphenylmethane diisocyanate, a polymethylene polyphenyl polyisocyanate, a hexamethylene diisocyanate or a toluene diisocyanate or a trimeric isocyanate. a reaction product of trimethylolpropane with toluene diisocyanate or xylene diisocyanate (for example, a three-molecule adduct of toluene diisocyanate or xylene diisocyanate), trimethylolpropane and hexamethylene diisocyanate. A reaction product (for example, a three-molecular adduct of hexamethylene diisocyanate), a polyether polyisocyanate, or a polyester polyisocyanate.
異氰酸酯化合物(B1)中,從可提升熟化性之觀點來看,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的異三聚氰酸酯體(旭化成股份有限公司製TSE-100、Nippon Polyurethane Industry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 the ripening property (L-45, manufactured by Soken Chemical Co., Ltd.) Isocyanate of hexamethylene diisocyanate or toluene diisocyanate (TSE-100 manufactured by Asahi Kasei Co., Ltd., 2050 manufactured by Nippon Polyurethane Industry Co., Ltd., etc.).
異氰酸酯化合物(B1)係可單獨使用1種,亦可使用2種以上。 The isocyanate compound (B1) may be used alone or in combination of two or more.
本發明之黏著劑組成物中,相對於(甲基)丙烯酸系共聚物(A)100質量份,異氰酸酯化合物(B1)的含量較佳為5質量份以下,尤佳為2.5質量份以下,更佳為1質量份以下,特佳為0.5質量份以下。該含量位於前述範圍時,從容易取得耐久性與應力緩和特性的均衡之觀點來看為佳。使用前述(B1)時,其下限值係例如為0.001質量份,較佳為0.01質量份。 In the adhesive composition of the present invention, the content of the isocyanate compound (B1) is preferably 5 parts by mass or less, more preferably 2.5 parts by mass or less, based on 100 parts by mass of the (meth)acryl-based copolymer (A). It is preferably 1 part by mass or less, and particularly preferably 0.5 part by mass or less. When the content is in the above range, it is preferable from the viewpoint of easily obtaining a balance between durability and stress relaxation characteristics. When the above (B1) is used, the lower limit thereof is, for example, 0.001 part by mass, preferably 0.01 part by mass.
金屬螯合化合物(B2),例如可列舉出使烷氧化物、乙醯丙酮、乙醯乙酸乙酯配位於鋁、鐵、銅、鋅、錫、鈦、鎳、銻、鎂、釩、鉻及鋯等多價金屬而成之化合物等。 The metal chelate compound (B2) may, for example, be alkoxide, acetamidineacetone or ethyl acetoacetate in aluminum, iron, copper, zinc, tin, titanium, nickel, bismuth, magnesium, vanadium, chromium and A compound obtained by a polyvalent metal such as zirconium or the like.
此等當中,特佳為鋁螯合化合物(綜研化學股份有限公司製M-12AT等)。具體可列舉出異丙醇鋁、二級丁醇鋁、乙醯乙酸乙酯-二異丙醇鋁、三乙醯乙酸乙酯鋁(aluminum tris(ethyl acetoacetate))、三乙醯丙酮鋁(a1uminum tris(acetylacetonate))。 Among these, it is particularly preferred to be an aluminum chelate compound (M-12AT manufactured by Soken Chemical Co., Ltd.). Specific examples thereof include aluminum isopropoxide, aluminum secondary aluminoxide, ethyl acetate-diisopropyl aluminum, aluminum tris (ethyl acetoacetate), and aluminum triacetate (a1uminum). Tris (acetylacetonate)).
金屬螯合化合物(B2),係可單獨使用1種,亦可使用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)係藉由配位鍵而將(甲基)丙烯酸系共聚物(A)予以交聯(虛擬交聯)。當使用金屬螯合化合物(B2)作為交聯劑(B)時,於室溫時會維持前述交聯 並使聚合物發揮凝聚性,相對於此,於高溫時前述交聯會被部分性地解開,而使黏著劑層顯示出更優異的柔軟性。 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 cross-linking agent (B), the aforementioned cross-linking is maintained at room temperature In contrast, the polymer is partially cohesive at a high temperature, and the adhesive layer exhibits more excellent flexibility.
本發明之黏著劑組成物中,相對於(甲基)丙烯酸系共聚物(A)100質量份,金屬螯合化合物(B2)的含量較佳為5質量份以下,尤佳為2.5質量份以下,更佳為1質量份以下,特佳為0.5質量份以下。該含量位於前述範圍時,從容易取得耐久性與應力緩和特性的均衡之觀點來看為佳。使用前述(B2)時,其下限值係例如為0.001質量份,較佳為0.01質量份。 In the adhesive composition of the present invention, the content of the metal chelate compound (B2) is preferably 5 parts by mass or less, and particularly preferably 2.5 parts by mass or less based on 100 parts by mass of the (meth)acryl-based copolymer (A). More preferably, it is 1 part by mass or less, and particularly preferably 0.5 part by mass or less. When the content is in the above range, it is preferable from the viewpoint of easily obtaining a balance between durability and stress relaxation characteristics. When the above (B2) is used, the lower limit thereof is, for example, 0.001 part by mass, preferably 0.01 part by mass.
本發明之黏著劑組成物中,當使用異氰酸酯化合物(B1)與金屬螯合化合物(B2)作為交聯劑(B)時,相對於前述(B1)100質量份,前述(B2)的含量通常係超過0質量份且為1000質量份以下,尤佳為超過0質量份且為600質量份以下,更佳為超過0質量份且為400質量份以下。該含量位於前述範圍時,從抑制彎曲、及提升偏光片與黏著劑層之密合性之觀點來看為佳。 In the adhesive composition of the present invention, when the isocyanate compound (B1) and the metal chelate compound (B2) are used as the crosslinking agent (B), the content of the above (B2) is usually 100 parts by mass based on the above (B1). It is more than 0 parts by mass and is 1000 parts by mass or less, more preferably more than 0 parts by mass and 600 parts by mass or less, more preferably more than 0 parts by mass and 400 parts by mass or less. When the content is in the above range, it is preferable from the viewpoint of suppressing the bending and improving the adhesion between the polarizer and the adhesive layer.
環氧化合物(B3)通常係使用1分子中的環氧基數為2個以上之環氧化合物。例如可列舉出乙二醇二環氧丙基醚(ethylene glycol diglycidyl ether)、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-間二甲苯二胺、N,N,N',N'-四環氧丙基胺基苯基甲烷、三聚異氰酸環 氧丙基酯、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。 The epoxy compound (B3) is usually an epoxy compound having two or more epoxy groups in one molecule. For example, ethylene glycol diglycidyl ether, polyethylene glycol diepoxypropyl ether, glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, 1, 3 -Bis(N,N'-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-m-xylenediamine, N,N,N' , N'-tetraepoxypropylaminophenylmethane, trimeric isocyanate ring Oxypropyl propyl ester, m-N,N-diepoxypropylaminophenyl epoxypropyl ether, N,N-diepoxypropyl toluidine, N,N-diepoxypropyl aniline.
本發明之黏著劑組成物中,相對於(甲基)丙烯酸系共聚物(A)100質量份,環氧化合物(B3)的含量較佳為2質量份以下,尤佳為1質量份以下,更佳為0.5質量份以下。使用前述(B3)時,其下限值係例如為0.001質量份,較佳為0.01質量份。 In the adhesive composition of the present invention, the content of the epoxy compound (B3) is preferably 2 parts by mass or less, and particularly preferably 1 part by mass or less based on 100 parts by mass of the (meth)acryl-based copolymer (A). More preferably, it is 0.5 mass part or less. When the above (B3) is used, the lower limit thereof is, for example, 0.001 part by mass, preferably 0.01 part by mass.
本發明之黏著劑組成物,較佳係更含有矽烷偶合劑(C)。矽烷偶合劑(C)係對於將黏著劑層堅固地接著於玻璃板等被接著體,有助於防止高濕熱環境下的剝離。 The adhesive composition of the present invention preferably further contains a decane coupling agent (C). The decane coupling agent (C) contributes to prevention of peeling in a high-humidity heat environment by adhering the adhesive layer firmly to a adherend such as a glass plate.
矽烷偶合劑(C),例如可列舉出: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聚合性不飽和基之矽烷偶合劑;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環氧基之矽烷偶合劑;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胺基之矽烷偶合劑;3-氯丙基三甲氧基矽烷等含鹵素之矽烷偶合劑。 Examples of the decane coupling agent (C) include a polymerizable unsaturated group-containing decane coupling agent such as vinyltrimethoxydecane, vinyltriethoxysilane or methacryloxypropyltrimethoxydecane. 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-ring An epoxy group-containing decane coupling agent such as oxypropoxypropylmethyldiethoxy decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-aminopropyltrimethoxy Baseline, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, etc. A halogen-containing decane coupling agent such as an amine group-containing decane coupling agent; 3-chloropropyltrimethoxy decane.
本發明之黏著劑組成物中,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,尤佳為0.05至0.5質量份。當其含量位於前述範圍時,乃具有可防止高濕熱環境下之偏光板的剝離、或是高溫環境下之矽烷偶合劑(C)的滲出之傾向。 In the adhesive composition of the present invention, the content of the decane coupling agent (C) is usually 100 parts by mass based on the (meth)acrylic copolymer (A). It is 1 part by mass or less, preferably 0.01 to 1 part by mass, particularly preferably 0.05 to 0.5 part by mass. When the content is in the above range, it tends to prevent peeling of the polarizing plate in a high-humidity heat environment or bleed out of the decane coupling agent (C) in a high-temperature environment.
抗靜電劑(D)係例如可用於降低由本發明之黏著劑組成物所形成之黏著劑層的表面電阻值。抗靜電劑(D)係例如可列舉出界面活性劑、離子性化合物、導電性聚合物。 The antistatic agent (D) can be used, for example, to lower the surface resistance value of the adhesive layer formed of the adhesive composition of the present invention. Examples of the antistatic agent (D) include a surfactant, an ionic compound, and a conductive polymer.
界面活性劑係例如可列舉出:4級銨鹽類、醯胺4級銨鹽類、吡啶鎓鹽、具有1級至3級胺基等陽離子性基之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之陰離子性界面活性劑;烷基甜菜鹼類、烷基咪唑鎓甜菜鹼類、氧化烷基胺類、胺基酸硫酸酯類等雙性界面活性劑、甘油脂肪酸酯類、山梨醇脂肪酸酯類、聚氧伸乙基烷基胺類、聚氧伸乙基烷基胺脂肪酸酯類、N-羥乙基-N-2-羥烷基胺類、烷基二乙醇胺類等非離子性界面活性劑。 Examples of the surfactant include a 4-stage ammonium salt, a guanamine 4-grade ammonium salt, a pyridinium salt, and a cationic surfactant having a cationic group such as a 1st to a third amine group; Anionic surfactants such as an anionic group such as a sulfonate group or a phosphate group; an alkylbetaine, an alkylimidazolium betaine, an alkylamine oxide, an amino acid sulfate, etc. Sexual surfactants, glycerol fatty acid esters, sorbitan fatty acid esters, polyoxyethylidene amines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2-hydroxyalkane A nonionic surfactant such as a base amine or an alkyl diethanolamine.
此外,就界面活性劑而言,亦可列舉出具有聚合性基之反應性乳化劑,並且亦可使用使含有上述界面活性劑或反應性乳化劑之單體成分進行高分子量化而成之聚合物系界面活性劑。 Further, as the surfactant, a reactive emulsifier having a polymerizable group may be used, and a polymerization of a monomer component containing the above surfactant or reactive emulsifier may be used. System surfactant.
離子性化合物係由陽離子部與陰離子部所構成,於室溫下(23℃/50%RH)可為固體狀及液體狀中的任 一種。 The ionic compound is composed of a cationic portion and an anionic portion, and can be either solid or liquid at room temperature (23 ° C / 50% RH). One.
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者或兩者。無機系陽離子較佳為鹼金屬離子及鹼土金屬離子,尤佳為抗靜電性優異之Li+、Na+及K+。有機系陽離子係例如可列舉出吡啶鎓陽離子、哌啶鎓陽離子、吡咯啶鎓陽離子、二氫吡咯陽離子、吡咯陽離子、咪唑鎓陽離子、四氫嘧啶鎓陽離子、二氫嘧啶鎓陽離子、吡唑鎓陽離子、吡唑啉鎓陽離子、四烷基銨陽離子、三烷基鋶陽離子、四烷基鏻陽離子及此等之衍生物。 The cation 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 particularly preferably Li + , Na + and K + having excellent antistatic properties. Examples of the organic cation system include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a dihydropyrrole cation, a pyrrole cation, an imidazolium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, and a pyrazolium cation. And pyrazolinium cations, tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations and derivatives thereof.
構成離子性化合物之陰離子部,只要是可與陽離子部進行離子鍵結而形成離子性化合物者即可,並無特別限制。具體可列舉出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-、C4H9SO3 -、(C2F5SO2)2N-、C3F7COO-及(CF3SO2)(CF3CO)N-。此等當中,含有氟原子之陰離子係因可賦予低熔點的離子性化合物,故為較佳,特佳為(F2SO2)2N-及(CF3SO2)2N-。 The anion portion constituting the ionic compound is not particularly limited as long as it can be ionically 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 H 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 containing a fluorine atom is preferred because it can impart an ionic compound having a low melting point, and particularly preferably (F 2 SO 2 ) 2 N - and (CF 3 SO 2 ) 2 N - .
離子性化合物較佳為雙(三氟甲烷磺醯基)醯亞胺鋰、雙(二氟磺醯基)醯亞胺鋰、三(三氟甲烷磺醯基)甲烷鋰、雙(三氟甲烷磺醯基)醯亞胺鉀、雙(二氟磺醯基)醯亞胺鉀、六氟磷酸1-乙基吡啶鎓鹽、六氟磷酸1-丁基吡啶鎓鹽、六氟磷酸1-己基-4-甲基吡啶鎓鹽、六氟磷酸1- 辛基-4-甲基吡啶鎓鹽、雙(氟磺醯基)醯亞胺1-辛基-4-甲基吡啶鎓鹽、雙(三氟甲烷磺醯基)醯亞胺1-辛基-4-甲基吡啶鎓鹽、四氟硼酸(N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨、雙(三氟甲烷磺醯基)醯亞胺N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨、醯亞胺1-辛基吡啶鎓氟鋶、1-辛基-3-甲基吡啶鎓、醯亞胺三氟鋶。 The ionic compound is preferably lithium bis(trifluoromethanesulfonyl) phthalimide, lithium bis(difluorosulfonyl) ruthenium, lithium tris(trifluoromethanesulfonyl)methane, bis(trifluoromethane) Sulfonyl) sulfinium imide, potassium bis(difluorosulfonyl) sulfinium imide, 1-ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-hexyl hexafluorophosphate -4-methylpyridinium salt, hexafluorophosphate 1- Octyl-4-methylpyridinium salt, bis(fluorosulfonyl) quinone imine 1-octyl-4-methylpyridinium salt, bis(trifluoromethanesulfonyl) quinone imine 1-octyl -4-methylpyridinium salt, tetrafluoroboric acid (N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium, bis(trifluoromethanesulfonyl)pyrene Amine N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium, quinone imine 1-octylpyridinium fluoranthene, 1-octyl-3-methylpyridinium , quinone imine trifluorohydrazine.
導電性聚合物係例如可列舉出聚噻吩、聚苯胺、聚吡咯及此等之衍生物。 Examples of the conductive polymer include polythiophene, polyaniline, polypyrrole, and derivatives thereof.
本發明之黏著劑組成物中,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,尤佳為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.
本發明之黏著劑組成物中,為了調整其塗布性,較佳係含有有機溶劑(E)。有機溶劑係可列舉出(甲基)丙烯酸系共聚物(A)的欄中所說明之聚合溶劑。例如,可將上述共聚合所得之含有(甲基)丙烯酸系共聚物(A)及聚合溶劑之聚合物溶液、與交聯劑(B)混合,而調製出黏著劑組成物。本發明之黏著劑組成物中,有機溶劑(E)的含量通常為50至90質量%,較佳為60至85質量%。 In order to adjust the coatability, the adhesive composition of the present invention preferably contains an organic solvent (E). The organic solvent is 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.
本說明書中,所謂「固體成分」係意指黏著劑組成物的含有成分中之扣除上述有機溶劑(E)後的全部成分,所謂「固體成分濃度」係意指前述固體成分相對 於黏著劑組成物100質量%之比率。 In the present specification, the term "solid content" means all components after the organic solvent (E) is deducted from the components of the adhesive composition, and the "solid content concentration" means that the solid components are relatively The ratio of the adhesive composition to 100% by mass.
本發明之黏著劑組成物中,除了上述成分之外,在不損及本發明的效果之範圍內,可含有選自抗氧化劑、光穩定劑、抗金屬腐蝕劑、黏著賦予劑、可塑劑、交聯促進劑、前述(A)以外的(甲基)丙烯酸系聚合物及重加工劑之1種或2種以上。 The adhesive composition of the present invention may contain, in addition to the above components, an antioxidant, a light stabilizer, a metal corrosion inhibitor, an adhesion promoter, a plasticizer, and the like, within a range not impairing 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 (A).
本發明之黏著劑組成物,可藉由以往所知的一般方法,混合(甲基)丙烯酸系共聚物(A)與交聯劑(B)以及因應必要之其他成分而調製出。例如可列舉出:將交聯劑(B)以及因應必要之其他成分,調配於合成(甲基)丙烯酸系共聚物(A)時所得之包含該聚合物之聚合溶液中。 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 conventional method known in the art. For example, a crosslinking agent (B) and other components as necessary may be blended in a polymerization solution containing the polymer obtained by synthesizing the (meth)acryl-based copolymer (A).
由本發明之黏著劑組成物所形成之黏著劑的凝膠分率,較佳係超過50質量%,尤佳係超過50質量%且為80質量%以下,更佳為60至75質量%。凝膠分率係例如為對依實施例所記載之條件所採集之黏著劑進行測定所得之值。 The gel fraction of the adhesive formed of the adhesive composition of the present invention is preferably more than 50% by mass, more preferably more than 50% by mass and more preferably 80% by mass or less, still more preferably 60% by mass to 75% by mass. The gel fraction is, for example, a value obtained by measuring the adhesive collected under the conditions described in the examples.
本發明之偏光板用黏著劑層係由上述黏著劑組成物所形成。藉由使用本發明之黏著劑組成物,可形成具有以 下之儲存彈性模數特性之黏著劑層。 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, it can be formed to have The adhesive layer that stores the elastic modulus characteristics.
本發明之黏著劑層,於23℃時的儲存彈性模數(G'1)較佳為0.1MPa以上,尤佳為0.1至0.2MPa,特佳為0.1至0.15MPa;於85℃時的儲存彈性模數(G'2)較佳為0.05MPa以下,尤佳為0.05至0.02MPa,特佳為0.05至0.03MPa。 The storage elastic layer of the present invention preferably has a storage elastic modulus (G'1) at 23 ° C of 0.1 MPa or more, particularly preferably 0.1 to 0.2 MPa, particularly preferably 0.1 to 0.15 MPa; and storage at 85 ° C The modulus of elasticity (G'2) is preferably 0.05 MPa or less, more preferably 0.05 to 0.02 MPa, particularly preferably 0.05 to 0.03 MPa.
本發明之黏著劑層,當以某溫度T℃時的儲存彈性模數作為G'T,且以T+1℃時的儲存彈性模數作為G'T+1時,在溫度T為23至50℃的範圍中,較佳係一直都滿足G'T/G'T+1<1.07,尤佳係一直都滿足1≦G'T/G'T+1≦1.05。 The adhesive layer of the present invention has a storage elastic modulus at a certain temperature T ° C as G' T and a storage elastic modulus at T+1 ° C as G' T+1 at a temperature T of 23 In the range of 50 ° C, the preferred system always satisfies G' T /G' T+1 <1.07, and the better system always satisfies 1≦G' T /G' T+1 ≦1.05.
上述儲存彈性模數,係例如將上述黏著劑層彼此貼合複數次,製作出厚度約1.0mm的積層體,並從對該積層體所測得之動態黏彈性圖譜中所算出之值。 The storage elastic modulus is, for example, a result of laminating the pressure-sensitive adhesive layers to each other to form a laminate having a thickness of about 1.0 mm and calculating the dynamic viscoelasticity spectrum measured from the laminate.
藉由使於23℃時的儲存彈性模數(G'1)位於上述範圍,而使本發明之黏著劑層於常溫下的硬質性優異並提升加工性。例如於裁切黏著劑層時,可防止黏著劑附著於裁切刃或是黏著劑層的拉絲等。 When the storage elastic modulus (G'1) at 23 ° C is in the above range, the adhesive layer of the present invention is excellent in hardness at normal temperature and improves workability. For example, when the adhesive layer is cut, it is possible to prevent the adhesive from adhering to the cutting edge or the drawing of the adhesive layer.
藉由使於85℃時的儲存彈性模數(G'2)位於上述範圍,而使本發明之黏著劑層在高溫環境下具有充分的柔軟性,所以可充分地緩和由偏光片的熱收縮(尺寸變化)所造成之應力。因此,即使暴露在高溫環境下,亦可降低被黏著體的翹曲,且不易產生黏著劑層的斷裂或是黏著劑層從偏光片之剝離。 By setting the storage elastic modulus (G'2) at 85 ° C to the above range, the adhesive layer of the present invention has sufficient flexibility in a high temperature environment, so that heat shrinkage by the polarizer can be sufficiently alleviated. The stress caused by (dimension change). Therefore, even when exposed to a high temperature environment, the warpage of the adherend can be lowered, and the breakage of the adhesive layer or the peeling of the adhesive layer from the polarizer is less likely to occur.
所謂在23至50℃的範圍中一直都滿足 G'T/G'T+1<1.07,係意指在此溫度範圍中的彈性模數之變化小,可抑制黏著劑層的變形及滲出。 It is said that G' T /G' T+1 <1.07 is always satisfied in the range of 23 to 50 ° C, which means that the change in the elastic modulus in this temperature range is small, and deformation and bleeding of the adhesive layer can be suppressed.
由本發明之黏著劑組成物所形成之黏著劑層,從偏光板的應變抑制、凝聚力、接著力、再剝離性之觀點來看,凝膠分率較佳係超過50質量%,尤佳係超過50質量%且為80質量%以下,更佳為60至75質量%。當凝膠分率位於前述範圍時,黏著劑層可顯示出優異的耐久性。此外,即使凝膠分率位於前述範圍,由於高溫下(甲基)丙烯酸系共聚物(A)的分枝鏈彼此係部分性地鬆緩,所以黏著劑層可顯示出優異的應力緩和特性。 The adhesive layer formed of the adhesive composition of the present invention preferably has a gel fraction of more than 50% by mass from the viewpoint of strain suppression, cohesive force, adhesion, and removability of the polarizing plate, and more preferably exceeds 50% by mass and 80% by mass or less, more preferably 60 to 75% by mass. When the gel fraction is in the above range, the adhesive layer can exhibit excellent durability. Further, even if the gel fraction is in the above range, since the branching chains of the (meth)acrylic copolymer (A) are partially relaxed at a high temperature, the adhesive layer can exhibit excellent stress relaxation properties.
本發明之黏著劑層,係例如藉由進行上述黏著劑組成物中的交聯反應,具體而言,藉由以交聯劑(B)將(甲基)丙烯酸系共聚物(A)交聯而得到。 The adhesive layer of the present invention is crosslinked by, for example, performing the crosslinking reaction in the above adhesive composition, specifically, by crosslinking the (meth)acrylic copolymer (A) with the crosslinking agent (B). And get it.
黏著劑層的形成條件係例如為以下所述者。將本發明之黏著劑組成物塗布於支撐體上,雖因溶劑的種類而不同,但通常於50至150℃,較佳於60至100℃,通常乾燥1至10分鐘,較佳乾燥2至7分鐘來去除溶劑,以形成塗膜。乾燥塗膜的膜厚通常為5至75μm,較佳為10至50μm。 The conditions for forming the adhesive layer are, for example, those described below. The adhesive composition of the present invention is applied to a support, although it varies depending on the kind of the solvent, but is usually 50 to 150 ° C, preferably 60 to 100 ° C, usually dried for 1 to 10 minutes, preferably 2 to dry. The solvent was removed in 7 minutes to form a coating film. The film thickness of the dried coating film is usually from 5 to 75 μm, preferably from 10 to 50 μm.
黏著劑層較佳係藉由以下條件來形成。將本發明之黏著劑組成物塗布於支撐體上,將覆蓋膜(cover film)貼附於以上述條件所形成之塗膜上後,通常於3天以上,較佳於7至10天,且通常於5至60℃,較佳於15至40℃,通常於30至70%RH,較佳於40至70%RH的環境下 進行熟化。以上述熟化條件來進行交聯時,可有效率地形成交聯體(網狀聚合物)。 The adhesive layer is preferably formed by the following conditions. Applying the adhesive composition of the present invention to a support, and attaching a cover film to the coating film formed under the above conditions, usually for 3 days or longer, preferably 7 to 10 days, and Usually at 5 to 60 ° C, preferably 15 to 40 ° C, usually 30 to 70% RH, preferably 40 to 70% RH Maturation. When cross-linking is carried out under the above-mentioned ripening conditions, the cross-linking (network polymer) can be efficiently formed.
黏著劑組成物的塗布方法,可使用一般所知的方法,例如藉由旋轉塗布法、刮刀塗布法(knife coating)、輥塗布法、棒塗布法、刮板塗布法(blade coating)、模具塗布法、凹版塗布法等,以成為既定厚度之方式進行塗布及乾燥之方法。 The coating method of the adhesive composition can be a generally known method, for example, by a spin coating method, a knife coating method, a roll coating method, a bar coating method, a blade coating method, or a die coating method. A method of applying and drying a method such as a method or a gravure coating method to have a predetermined thickness.
支撐體及覆蓋膜,例如可列舉出: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.
本發明之偏光板用黏著薄片係具有由上述黏著劑組成物所形成之黏著劑層。黏著薄片係例如可列舉出:僅具有上述黏著劑層之雙面黏著薄片;具有基材與形成於基材的雙面的上述黏著劑層之雙面黏著薄片;具有基材與形成於基材的一面的上述黏著劑層之單面黏著薄片;以及在此等黏著薄片的黏著劑層之未與基材接觸的面上貼合有經施行剝離處理後的覆蓋膜之黏著薄片。 The adhesive sheet for a polarizing plate of the present invention has an adhesive layer formed of the above-mentioned adhesive composition. The adhesive sheet may, for example, be a double-sided adhesive sheet having only the above adhesive layer; a double-sided adhesive sheet having a substrate and the above-mentioned adhesive layer formed on both sides of the substrate; and a substrate and a substrate; One side of the adhesive layer on one side of the adhesive sheet; and an adhesive sheet on which the cover film after the release treatment is applied is adhered to the surface of the adhesive layer of the adhesive sheet which is not in contact with the substrate.
基材及覆蓋膜,例如可列舉出: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塑膠膜。 Examples of the substrate 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.
黏著劑層的形成條件,係與[偏光板用黏著劑層]的欄所記載之條件相同。 The conditions for forming the adhesive layer are the same as those described in the column of [Adhesive Layer for Polarizing Plate].
黏著劑層的膜厚,從維持黏著性能之觀點來看,通常為5至75μm,較佳為10至50μm。基材及覆蓋膜的膜厚並無特別限定,通常為10至125μm,較佳為25至75μm。 The film thickness of the adhesive layer is usually 5 to 75 μm, preferably 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.
本發明之附黏著劑層之偏光板係具有:直接積層於偏光片之至少一面且由本發明之黏著劑組成物所形成之黏著劑層。本說明書中,「偏光板」係以包含「偏光膜」之涵義來使用。 The polarizing plate with an adhesive layer of the present invention has an adhesive layer formed directly on at least one side of the polarizer and formed of the adhesive composition of the present invention. In the present specification, the "polarizing plate" is used in the sense of including a "polarizing film".
偏光板係可使用以往所知的偏光膜。例如可列舉出:偏光片本身、以及具有偏光片與配置在偏光片上之偏光片保護膜的多層膜。本發明中,由於上述黏著劑層是直接接觸於偏光片而配置,故列舉出僅於偏光片的單面配置有偏光片保護膜之構成、以及於偏光片的雙面未配置偏光片保護膜之構成。 As the polarizing plate, a conventionally known polarizing film can be used. For example, the polarizer itself and a multilayer film having a polarizer and a polarizer protective film disposed on the polarizer can be exemplified. In the present invention, since the adhesive layer is disposed in direct 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.
偏光片,係例如可列舉出使偏光成分含有於由聚乙烯醇系樹脂所構成之膜中並進行延伸而得之延伸膜。聚乙烯醇系樹脂,例如可列舉出聚乙烯醇、聚乙烯基甲醛(polyvinyl formal)、聚乙烯基縮醛(polyvinyl acetal)、乙烯-乙酸乙烯酯共聚物的皂化物。偏光成分,例如可列舉出碘或雙色性染料。 The polarizing film is, for example, a stretched film obtained by including a polarizing component in a film made of a polyvinyl alcohol-based resin and extending it. Examples of the polyvinyl alcohol-based resin include saponified products of polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, and ethylene-vinyl acetate copolymer. Examples of the polarizing component include iodine or a dichroic dye.
偏光片保護膜,例如可列舉出由熱塑性樹脂所構成之膜。熱塑性樹脂,例如可列舉出:三乙酸纖維 素等纖維素樹脂、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)丙烯酸系樹脂、環狀聚烯烴樹脂(降莰烯系樹脂)、聚芳酯樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂、及選自此等樹脂之2種以上的混合物。 The polarizer protective film may, for example, be a film made of a thermoplastic resin. The thermoplastic resin may, for example, be a triacetate fiber. Cellulose resin, polyester resin, polyether oxime resin, polyfluorene resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth)acrylic resin, cyclic polymerization An olefin resin (northene-based resin), a polyarylate resin, a polystyrene resin, a polyvinyl alcohol resin, and a mixture of two or more kinds selected from the above resins.
偏光板的厚度通常為10至200μm,較佳為50至100μm。本發明中,由於可省略形成於偏光片上之偏光片保護膜,所以可達到偏光板的薄型化。 The thickness of the polarizing plate is usually from 10 to 200 μm, preferably from 50 to 100 μm. In the present invention, since the polarizer protective film formed on the polarizer can be omitted, the thickness of the polarizing plate can be reduced.
本發明中,上述黏著劑層係直接接觸於偏光片而形成。本發明之附黏著劑層之偏光板,例如可列舉出下述構成:依序積層偏光片保護膜與偏光片與上述黏著劑層之構成;依序積層上述黏著劑層與偏光片保護膜與偏光片與上述黏著劑層之構成;依序積層上述黏著劑層與偏光片與上述黏著劑層之構成。此等構成中,於黏著劑層上,可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 includes, for example, a structure in which a polarizer protective film and a polarizer and the adhesive layer are sequentially laminated; the adhesive layer and the polarizer protective film are sequentially laminated; The polarizer and the adhesive layer are formed; the adhesive layer and the polarizer and the adhesive layer are laminated in this order. In such a configuration, the cover film may be disposed as the outermost layer on the adhesive layer.
將黏著劑層形成於偏光片表面之方法並無特別限定,可列舉出下述方法:使用棒塗布機等將上述黏著劑組成物直接塗布於偏光片表面,然後進行乾燥及熟化之方法;以及將本發明之偏光板用黏著薄片所具有之黏著劑層轉印至偏光片表面並進行熟化之方法。乾燥及熟化的條件和凝膠分率的範圍等,係與[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 a method of directly applying the above-described adhesive composition to the surface of the polarizer using a bar coater or the like, followed by drying and aging; The method of transferring the adhesive layer of the polarizing plate of the present invention to the surface of the polarizer and aging it is carried out. The conditions for drying and aging, the range of the gel fraction, and the like are the same as those described in the column of [Adhesive Layer for Polarizing Plate].
黏著劑層的厚度,以乾燥膜厚計,通常為5至75μm,較佳為10至50μm。此外,黏著劑層只要是在 偏光片之至少一面上與偏光片接觸而形成即可,可列舉出:僅於偏光片的單面形成有黏著劑層之樣態、以及於偏光片的雙面形成有黏著劑層之樣態。 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. In addition, the adhesive layer is only The polarizer may be formed by contacting the polarizer on at least one side thereof, and examples thereof include an adhesive layer formed on only one side of the polarizer and an adhesive layer formed on both surfaces of the polarizer. .
此外,於上述偏光板上,例如可積層保護層、防眩層、相位差層、視角提升層等具有其他功能之層。 Further, on the above polarizing plate, for example, a protective layer, an antiglare layer, a phase difference layer, a viewing angle lifting layer, or the like having other functions may be laminated.
藉由將如上述方式所得之本發明之附黏著劑層之偏光板設置在液晶單元的基板表面,而製造出液晶元件。在此,液晶單元係具有液晶層被夾持於2片基板之間之結構。 A liquid crystal element was produced by disposing a polarizing plate of the adhesive layer of the present invention obtained as described above on the surface of a substrate of a liquid crystal cell. Here, the liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates.
液晶單元所具有之基板,例如可列舉出玻璃板。基板的厚度,通常為0.05至3mm,較佳為0.2至1mm。本發明中,藉由使用上述黏著劑層,即使將黏著劑層直接積層於偏光片上,亦可抑制偏光板及基板的翹曲。因此,即使在基板厚度較小時(例如:1mm以下,較佳為0.2至1mm),上述黏著劑組成物亦可較佳地使用在偏光板與基板之貼合。 The substrate of the liquid crystal cell is, for example, 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-mentioned adhesive layer, warpage of the polarizing plate and the substrate can be suppressed even if 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 preferably used for bonding the polarizing plate to the substrate.
以下係根據實施例來更具體說明本發明,但本發明並不限定於此等實施例。以下之實施例等的記載中,在未特別言明時,「份」表示「質量份」。 The present invention will be more specifically described below based on 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.
對於(甲基)丙烯酸系共聚物,係藉由凝膠滲透層析法(GPC法)以下述條件而求出重量平均分子量(Mw)及數量平 均分子量(Mn),並且藉由凝膠滲透層析法/多角度雷射光散射檢測器(GPC-MALS)以下述條件而算出旋轉半徑及分子量的雙對數直線的斜率並求取分枝度。 For the (meth)acrylic copolymer, the weight average molecular weight (Mw) and the amount are determined by gel permeation chromatography (GPC method) under the following conditions. The average molecular weight (Mn) was calculated by a gel permeation chromatography/multi-angle laser light scattering detector (GPC-MALS) under the following conditions to calculate the slope of the double logarithmic straight line of the radius of gyration and the molecular weight, and to obtain the branching degree.
‧測定裝置:HLC-8320GPC(Tosoh股份有限公司製) ‧Measurement device: HLC-8320GPC (manufactured by Tosoh Co., Ltd.)
‧GPC管柱構成:以下4串聯管柱(均為Tosoh股份有限公司製) ‧GPC column structure: The following 4 series column (both made by Tosoh Co., Ltd.)
(1)TSKgel HxL-H(防護管柱,即guard column) (1) TSKgel HxL-H (guard column, guard column)
(2)TSKgel GMHxL (2) TSKgel GMHxL
(3)TSKgel GMHxL (3) TSKgel GMHxL
(4)TSKgel G2500HxL (4)TSKgel G2500HxL
‧流速:1.0ml/分鐘 ‧Flow rate: 1.0ml/min
‧管柱溫度:40℃ ‧column temperature: 40 ° C
‧樣本濃度:1.5%(w/v)(以四氫呋喃稀釋) ‧ Sample concentration: 1.5% (w / v) (diluted with tetrahydrofuran)
‧移動相溶劑:四氫呋喃 ‧Mobile phase solvent: tetrahydrofuran
‧檢測器:DAWN HELEOS(MALS檢測器)+OptiLab rEE(RI檢測器) ‧Detector: DAWN HELEOS (MALS detector) + OptiLab rEE (RI detector)
‧標準聚苯乙烯換算(測定Mw及Mn時) ‧Standard polystyrene conversion (when measuring Mw and Mn)
將丙烯酸正丁酯76.8份、丙烯酸苄酯20份、丙烯酸3份、丙烯酸2-羥乙酯0.2份及乙酸乙酯溶劑100份,裝入具備攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,一邊導入氮氣一邊升溫至80℃。接著加入過氧化新戊酸三級丁酯0.1份,於氮氣環境下,於80℃進行6小時的聚合反應。反應結束後,藉由乙酸乙酯來稀釋而調製出 固體成分濃度30質量%的聚合物溶液。所得之(甲基)丙烯酸系共聚物A1的重量平均分子量(Mw)為67萬,分子量分布(Mw/Mn)為13,分枝度為0.48。 76.8 parts of n-butyl acrylate, 20 parts of benzyl acrylate, 3 parts of acrylic acid, 0.2 parts of 2-hydroxyethyl acrylate and 100 parts of ethyl acetate solvent were placed in a reaction equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube. In the apparatus, the temperature was raised to 80 ° C while introducing nitrogen gas. Next, 0.1 part of butyl peroxypivalate was added, and polymerization was carried out at 80 ° C for 6 hours under a nitrogen atmosphere. After the reaction is completed, it is prepared by diluting with ethyl acetate. 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 670,000, a molecular weight distribution (Mw/Mn) of 13, and a branching degree of 0.48.
除了將聚合反應所使用之單體成分及聚合起始劑變更如第1表所記載者之外,其他與合成例1同樣地進行,而調製出固體成分濃度30質量%的聚合物溶液。結果如第1表所示。 A polymer solution having a solid concentration of 30% by mass was prepared in the same manner as in Synthesis Example 1 except that the monomer component and the polymerization initiator used in the polymerization reaction were changed as described in Table 1. The results are shown in Table 1.
將合成例1所得之聚合物溶液(固體成分濃度30質量%),與相對於該溶液所含有之(甲基)丙烯酸系共聚物A1 100份(固體成分量)而作為交聯劑之綜研化學股份有限公司製的「TD-75」(固體成分75質量%、乙酸乙酯溶液)0.07份(固體成分量)及「M-12AT」0.2份(固體成分量)、及作為矽烷偶合劑之信越化學工業股份有限公司製的「KBM-403」(固體成分100質量%)0.2份混合,而得到黏著劑組成物。 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 a crosslinking agent. "TD-75" (solid content: 75 mass%, ethyl acetate solution), 0.07 parts (solid content), "M-12AT" 0.2 parts (solid content), and Shin-Etsu as a decane coupling agent 0.2 parts of "KBM-403" (solid content: 100% by mass) manufactured by Chemical Industry Co., Ltd. was mixed to obtain an adhesive composition.
將上述(1)所得之黏著劑組成物,經過脫泡後,使用刮板塗布機塗布於經剝離處理後之聚對苯二甲酸乙二酯膜(PET膜)上,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膜的貼合面為相反之面上,更進一步貼合經剝離處理後之PET膜,於23℃/50%RH的環境下靜置7天以進行熟化,而得到具有被夾持於2片PET膜中之厚度20μm的黏著劑層之黏著薄片。 The adhesive composition obtained in the above (1) was subjected to defoaming, and then applied to a polyethylene terephthalate film (PET film) subjected to release treatment using a blade coater, and dried at 90 ° C for 3 minutes. On the other hand, a coating film having a dry film thickness of 20 μm was formed. The PET film after the release treatment was further bonded to the surface of the coating film opposite to the bonding surface of the PET film, and allowed to stand in an environment of 23° C./50% RH for 7 days to be aged. An adhesive sheet having an adhesive layer having a thickness of 20 μm held in two PET films.
將上述(1)所得之黏著劑組成物,經過脫泡後,使用刮板塗布機塗布於經剝離處理後之聚對苯二甲酸乙二酯膜(PET膜),於90℃乾燥3分鐘,而得到具有乾燥膜厚20μm的塗膜之薄片。以使該薄片的塗膜面、與由作為偏光片的聚乙烯醇膜及作為偏光片保護膜的三乙酸纖維素膜所構 成之雙層構成(厚度60μm)之偏光板的聚乙烯醇膜面接觸之方式來貼合,於23℃/50%RH的環境下靜置7天以進行熟化,而得到具有PET膜與厚度20μm的黏著劑層與偏光片與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 subjected to defoaming, and then applied to a polyethylene terephthalate film (PET film) which had been subjected to release treatment using a blade coater, and dried at 90 ° C for 3 minutes. Thus, a sheet having a coating film having a dry film thickness of 20 μm was obtained. The coating film surface of the sheet, the polyvinyl alcohol film as a polarizer, and the cellulose triacetate film as a polarizer protective film The polyvinyl alcohol film of the polarizing plate having a two-layer structure (thickness: 60 μm) was brought into contact with each other, and was allowed to stand in an environment of 23° C./50% RH for 7 days for aging, thereby obtaining a PET film and a thickness. A 20 μm adhesive layer and a polarizer of the polarizer and the adhesive layer of the polarizer protective film.
實施例1中,將聚合物溶液變更為合成例2至5中所得之聚合物溶液、及/或將調配組成變更如第2表所記載者,除此之外,其他與實施例1同樣地進行,而得到黏著劑組成物、黏著薄片及附黏著劑層之偏光板。 In the same manner as in Example 1, except that the polymer solution was changed to the polymer solution obtained in Synthesis Examples 2 to 5, and/or the composition of the formulation was changed as described in Table 2, in the same manner as in Example 1. The adhesive composition, the adhesive sheet, and the polarizing plate with the adhesive layer are obtained.
從實施例、比較例所得之黏著薄片中,將黏著劑採集約0.1g至樣本瓶,加入乙酸乙酯30mL並振動4小時後,以200網目的不鏽鋼製金網過濾該樣本瓶的內容物,並於100℃將金網上的殘留物乾燥2小時,測定乾燥重量。藉由下述式來求取黏著劑的凝膠分率。 From the adhesive sheets obtained in the examples and the comparative examples, about 0.1 g of the adhesive was collected into the sample bottle, and 30 mL of ethyl acetate was added and shaken for 4 hours, and then the contents of the sample bottle were filtered with a stainless steel gold mesh of 200 mesh, and The residue on the gold mesh was dried at 100 ° C for 2 hours, and the dry weight was measured. 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 (%)
在實施例、比較例所得之黏著薄片中,於23℃/50%RH的環境下將厚度20μm的黏著劑層彼此貼合複數次,並於50℃/5atm的高壓釜中處理20分鐘,而製作出厚度1.0mm的黏著劑層。使用Anton Paar公司製的「Physica MCR300」, 依據以JIS K7244為基準之動態黏彈性測定法(溫度範圍-40至160℃、升溫速度3.67℃/分鐘、頻率1Hz的條件),對該厚度1.0mm的黏著劑層測定黏彈性圖譜,決定在溫度23℃及85℃時的儲存彈性模數、以及在23至50℃的範圍中之G'T/G'T+1的最大值。 In the adhesive sheets obtained in the examples and the comparative examples, the adhesive layers having a thickness of 20 μm were adhered to each other in an environment of 23° C./50% RH for several times, and were treated in an autoclave at 50° C./5 atm for 20 minutes. An adhesive layer having a thickness of 1.0 mm was produced. "Physica MCR300" manufactured by Anton Paar Co., Ltd., according to the dynamic viscoelasticity measurement method based on JIS K7244 (temperature range -40 to 160 ° C, temperature rising rate 3.67 ° C / min, frequency 1 Hz), the thickness is 1.0 mm. The adhesive layer was measured for the viscoelastic spectrum, and the storage elastic modulus at temperatures of 23 ° C and 85 ° C and the maximum value of G' T /G' T+1 in the range of 23 to 50 ° C were determined.
將實施例、比較例所得之附黏著劑層之偏光板(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70mm×25mm的大小,而製作出試驗片。從試驗片中剝離PET膜,並使用壓合輥,以使黏著劑層與玻璃板接觸之方式,將由黏著劑層/偏光片/偏光片保護膜所構成之積層體貼著於厚度2mm之玻璃板的單面。將所得之積層體保持在調整為50℃/5大氣壓之高壓釜中20分鐘。接著於23℃/50%RH的環境下放置1小時後,以300mm/分鐘的速度,將偏光板的端部往相對於玻璃板呈90°的方向拉離,並測定黏著力(剝離強度)。 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 70 mm×25 mm to prepare a test. sheet. The PET film was peeled off from the test piece, and a laminate of the adhesive layer/polarizer/polarizer protective film was applied to the glass plate having a thickness of 2 mm by using a pressure roller so that the adhesive layer was in contact with the glass plate. One side. The obtained laminate was kept in an autoclave adjusted to 50 ° C / 5 atm for 20 minutes. Then, after standing for 1 hour in an environment of 23 ° C / 50% RH, the end portion of the polarizing plate was pulled at a rate of 90° with respect to the glass plate at a speed of 300 mm/min, and the adhesion (peel strength) was measured. .
將實施例、比較例所得之附黏著劑層之偏光板(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的大小,而製作出試驗片。從試驗片中剝離PET膜,並使用壓合輥,以使黏著劑層與玻璃板接觸之方式,將由黏著劑層/偏光片/偏光片保護膜所構成之積 層體貼著於厚度0.5mm之玻璃板的單面。將所得之積層體保持在調整為50℃/5大氣壓之高壓釜中20分鐘,而製作出試驗板。製作2片同樣的試驗板。將前述試驗板,於溫度80℃的條件下(耐熱性)或溫度60℃/濕度90%RH的條件下(耐濕熱性)放置500小時,並藉由以下基準來觀察發泡、浮起、剝離的產生,以進行評估。 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. sheet. The PET film is peeled from the test piece, and a product of the adhesive layer/polarizer/polarizer protective film is formed by using a pressure roller to bring the adhesive layer into contact with the glass plate. The layer is attached to one side of a glass plate having a thickness of 0.5 mm. The obtained laminate was held in an autoclave adjusted to 50 ° C / 5 atm for 20 minutes to prepare a test plate. Make two identical test panels. The test plate was placed under conditions of a temperature of 80 ° C (heat resistance) or a temperature of 60 ° C / humidity of 90% RH (moisture resistance) for 500 hours, and foaming, floating, and the like were observed by the following criteria. The production of peeling is performed for evaluation.
‧AA:未觀察到發泡、浮起、剝離等外觀不良 ‧AA: No appearance defects such as foaming, floating, peeling, etc. were observed
‧BB:僅觀察到些許發泡、浮起、剝離等外觀不良 ‧BB: Only a few appearances such as foaming, floating, peeling, etc. were observed.
‧CC:觀察到明顯的發泡、浮起、剝離等外觀不良 ‧CC: Observed obvious appearance such as foaming, floating, peeling, etc.
將實施例、比較例所得之2片附黏著劑層之偏光板(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310mm×385mm的大小,而製作出試驗片。從試驗片中剝離PET膜,並使用壓合輥,以使偏光軸相互正交且黏著劑層與玻璃板接觸之方式,將由黏著劑層/偏光片/偏光片保護膜所構成之積層體貼著於厚度0.5mm之玻璃板的兩側。將所得之積層體保持在調整為50℃/5大氣壓之高壓釜中20分鐘,而製作出試驗板。將該試驗板於溫度80℃的條件下放置500小時,並藉由以下基準來進行漏光的觀察。 The polarizing plate (the laminated body composed of the PET film/adhesive layer/polarizer/polarizer protective film) obtained by the two examples of the adhesive layer obtained in the examples and the comparative examples was cut into a size of 310 mm × 385 mm, and was produced. Test strips. The PET film was peeled off from the test piece, and a laminating body composed of an adhesive layer/polarizer/polarizer protective film was attached to the test piece so that the polarizing axes were orthogonal to each other and the adhesive layer was in contact with the glass plate. On both sides of a glass plate with a thickness of 0.5 mm. The obtained laminate was held in an autoclave adjusted to 50 ° C / 5 atm for 20 minutes to prepare a test plate. The test plate was allowed to stand at a temperature of 80 ° C for 500 hours, and observation of light leakage was performed by the following reference.
AA:未觀察到漏光 AA: No light leakage was observed
BB:僅觀察到些許漏光 BB: Only a few light leaks were observed
CC:觀察到明顯的漏光 CC: Observed significant light leakage
將實施例、比較例所得之附黏著劑層之偏光板(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35mm×400mm的大小,而製作出試驗片。從試驗片中剝離PET膜,並使用壓合輥,以使黏著劑層與玻璃板接觸之方式,將由黏著劑層/偏光片/偏光片保護膜所構成之積層體貼著於厚度0.7mm、40mm×410mm之玻璃板的單面。將所得之積層體放置在23℃/50%RH的環境下24小時後,於60℃的烤爐中保持72小時。將單方的末端固定在相對於地面呈垂直之壁面上,並以尺來測定相反側末端的浮起量。 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 35 mm×400 mm to prepare a test. sheet. The PET film was peeled off from the test piece, and a laminate body composed of an adhesive layer/polarizer/polarizer protective film was attached to a thickness of 0.7 mm and 40 mm by using a pressure roller so that the adhesive layer was in contact with the glass plate. One side of a glass plate of ×410 mm. The obtained laminate was placed in an environment of 23 ° C / 50% RH for 24 hours, and then kept in an oven at 60 ° C for 72 hours. The end of the single side was fixed to a wall surface perpendicular to the ground, and the amount of floating at the opposite end was measured by a ruler.
藉由以下基準來進行翹曲(彎曲)的觀察。 The observation of warpage (bending) was performed by the following criteria.
AA:末端的浮起為3mm以下 AA: The floating of the end is 3mm or less
BB:末端的浮起超過3mm且未達5mm BB: The end floats more than 3mm and is less than 5mm
CC:末端的浮起為5mm以上 CC: The floating at the end is 5mm or more
使用湯姆森鑿穿機,以50mm×50mm的湯姆森刃將實施例、比較例所得之黏著薄片切割出30片。在剛裁切完後,立即觀察端部的形狀,於30片中,連一處均未觀察到糊狀物滲出或端部潰裂、黏著劑層缺損者係判定為AA,有觀察到者則判定為CC。 The adhesive sheets obtained in the examples and the comparative examples were cut out into 30 pieces using a Thomson cutting machine using a Thomson cutting machine of 50 mm × 50 mm. Immediately after the cutting, the shape of the end portion was observed. In 30 pieces, no oozing or end cracking was observed in one place, and the defect of the adhesive layer was judged as AA, and there was observed. Then it is judged as CC.
將實施例、比較例所得之附黏著劑層之偏光板裁切為 100mm×100mm者予以積層10片,從上方施加1kg的荷重並放置24小時,藉由以下基準並以目視來觀察黏著劑層的滲出。 The polarizing plates of the adhesive layer obtained in the examples and the comparative examples were cut into Ten sheets of 100 mm × 100 mm were laminated, and a load of 1 kg was applied from above and left for 24 hours, and the bleeding of the adhesive layer was visually observed by the following criteria.
AA:未觀察到黏著劑層的滲出 AA: No seepage of the adhesive layer was observed
BB:僅觀察到些許黏著劑層的滲出 BB: Only a few oozing layers of the adhesive layer were observed.
CC:觀察到明顯的黏著劑層的滲出 CC: Obvious bleed out of the adhesive layer was observed
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