TW201823015A - Optical laminate, liquid display device, adhesive composition and optical film - Google Patents
Optical laminate, liquid display device, adhesive composition and optical film Download PDFInfo
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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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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- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/24—Aluminium
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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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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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
- B32B2551/00—Optical elements
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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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- Nonlinear Science (AREA)
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- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Polarising Elements (AREA)
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- Liquid Crystal (AREA)
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Abstract
Description
本發明係關於構成液晶顯示裝置等的圖像顯示裝置之光學積層體及包含該光學積層體之液晶顯示裝置。 The present invention relates to an optical multilayer body constituting an image display device such as a liquid crystal display device and a liquid crystal display device including the optical multilayer body.
於偏光片的單面或兩面積層貼合透明樹脂膜所成的偏光板為代表的光學膜,被廣泛使用作為構成液晶顯示裝置等的圖像顯示裝置之光學構件。如此的偏光板之光學膜,大多隔著黏著劑層貼合於其他構件(例如液晶顯示裝置之液晶單元等)而被使用[例如參考日本特開2010-229321號公報]。因此,作為光學膜,已知有於其一側的面預先設置黏著劑層之附黏著劑層之光學膜。而且,也已知有為了賦予抗靜電性,於黏著劑層含有離子性化合物者。 An optical film typified by a polarizing plate formed by laminating a transparent resin film on one or both sides of a polarizer is widely used as an optical member constituting an image display device such as a liquid crystal display device. The optical film of such a polarizing plate is often used by being bonded to another member (for example, a liquid crystal cell of a liquid crystal display device) via an adhesive layer [for example, refer to Japanese Patent Application Laid-Open No. 2010-229321]. Therefore, as an optical film, an optical film with an adhesive layer provided with an adhesive layer in advance on one side of the surface is known. It is also known to contain an ionic compound in the adhesive layer in order to impart antistatic properties.
近年,液晶顯示裝置經應用在以智慧型手機、平板型終端、車用導航系統為代表的具有觸控面板功能的移動式機器的用途。於如此的觸控輸入式液晶顯示裝 置中附黏著劑層之光學膜,係其黏著劑層於例如金屬配線所構成的金屬層,例如隔著樹脂層,或直接接觸而配置者。但是,於金屬材料所構成的金屬層及包含離子性化合物的黏著劑層之組合的構成,於高溫高濕環境下,金屬層會腐蝕。腐蝕中之孔蝕,於金屬層的厚度薄的情況或金屬層為金屬配線時其線寬窄的情況,因會貫穿金屬層,特別變成問題。 In recent years, liquid crystal display devices have been used in mobile devices with touch panel functions typified by smart phones, tablet terminals, and car navigation systems. An optical film with an adhesive layer in such a touch input type liquid crystal display device is one in which the adhesive layer is disposed on a metal layer composed of, for example, metal wiring, such as through a resin layer, or by direct contact. However, in a combination of a metal layer made of a metal material and an adhesive layer containing an ionic compound, the metal layer is corroded in a high-temperature and high-humidity environment. Porosity during corrosion is particularly problematic because the thickness of the metal layer is thin or the line width is narrow when the metal layer is metal wiring.
本發明之目的係提供於如金屬配線層的金屬層上積層附黏著劑層之光學膜之光學積層體,其可抑制金屬層的腐蝕之光學積層體及包含該光學積層體之液晶顯示裝置。 An object of the present invention is to provide an optical laminated body in which an optical film with an adhesive layer is laminated on a metal layer such as a metal wiring layer, an optical laminated body capable of suppressing corrosion of a metal layer, and a liquid crystal display device including the optical laminated body.
本發明提供以下所示的光學積層體及包含該光學積層體之液晶顯示裝置;以及黏著劑組成物。 The present invention provides an optical multilayer body and a liquid crystal display device including the optical multilayer body, and an adhesive composition shown below.
[1]光學積層體,其依序包括:光學膜、黏著劑層及金屬層;其中前述黏著劑層係由包含(甲基)丙烯酸系樹脂(A)、異氰酸酯系交聯劑(B)、矽烷化合物(C)及下述式(I)所示的離子性化合物(D)的黏著劑組成物所構成,M+X- (I)(式(I)中,M+表示無機陽離子,X-表示含有氟原子的陰離子);相對於前述(甲基)丙烯酸系樹脂(A)100重量份而言,前述黏著劑組成物含有0.01至2.5重量份的前 述異氰酸酯系交聯劑(B)、0.01至10重量份的前述矽烷化合物(C)及0.2至8重量份的離子性化合物(D)。 [1] An optical laminate, which includes: an optical film, an adhesive layer, and a metal layer in order; wherein the aforementioned adhesive layer is composed of a (meth) acrylic resin (A), an isocyanate-based crosslinking agent (B), Silane compound (C) and the following formula (I) ions compound (D) is shown in the adhesive composition is constituted, M + X - (I) (in the formula (I), M + represents an inorganic cation, X - represents an anion containing a fluorine atom); with respect to the (meth) acrylic resin 100 parts by weight of (a), the aforementioned adhesive composition containing 0.01 to 2.5 parts by weight of the isocyanate-based crosslinking agent (B), 0.01 to 10 parts by weight of the aforementioned silane compound (C) and 0.2 to 8 parts by weight of the ionic compound (D).
[2]如[1]記載之光學積層體,其中前述無機陽離子為鹼金屬陽離子或鹼土金屬陽離子。 [2] The optical laminate according to [1], wherein the inorganic cation is an alkali metal cation or an alkaline earth metal cation.
[3]如[1]或[2]記載之光學積層體,其中前述鹼金屬陽離子為鋰陽離子[Li+]、鉀陽離子[K+]或鈉陽離子[Na+]。 [3] The optical laminate according to [1] or [2], wherein the alkali metal cation is a lithium cation [Li + ], a potassium cation [K + ], or a sodium cation [Na + ].
[4]如[1]或[2]記載之光學積層體,其中前述鹼金屬陽離子為鉀陽離子[K+]。 [4] The optical laminate according to [1] or [2], wherein the alkali metal cation is a potassium cation [K + ].
[5]如[1]至[4]中任一項記載之光學積層體,其中前述含有氟原子的陰離子為下述式(II)所示的含有氟原子的陰離子:[Y(SO2CmF2m+1)n]- (II)(式(II)中,Y表示碳原子或氮原子,Y表示碳原子時n為3,Y表示氮原子時n為2,m表示0至10的整數)。 [5] The optical laminate according to any one of [1] to [4], wherein the fluorine atom-containing anion is a fluorine atom-containing anion represented by the following formula (II): [Y (SO 2 C m F 2m + 1 ) n ] - (II) (In the formula (II), Y represents a carbon atom or a nitrogen atom, Y represents a carbon atom, n is 3, Y represents a nitrogen atom, n is 2, and m represents 0 to 10 Integer).
[6]如[1]至[5]中任一項記載之光學積層體,其中前述含有氟原子的陰離子為雙(氟磺醯基)亞胺陰離子[(FSO2)2N-]或雙(三氟甲烷磺醯基)亞胺陰離子[(CF3SO2)2N-]。 [6] of [1] to [5] The optical laminate of any one of claims, wherein the anion containing a fluorine atom is a bis (fluorosulfonyl acyl) imide anion [(FSO 2) 2 N - ] or bis (trifluoromethane sulfonic acyl) imide anion [(CF 3 SO 2) 2 N -].
[7]如[1]至[5]中任一項記載之光學積層體,其中前述含有氟原子的陰離子為雙(氟磺醯基)亞胺陰離子[(FSO2)2N-]。 [7] of [1] to [5] The optical laminate of any one of claims, wherein the anion containing a fluorine atom is a bis (fluorosulfonyl acyl) imide anion [(FSO 2) 2 N - ].
[8]如[1]至[7]中任一項記載之光學積層體,其中前述(甲基)丙烯酸系樹脂(A)含有來自均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a1)的構成單元以及來自均聚物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a2)的構成單元。 [8] The optical laminate according to any one of [1] to [7], wherein the (meth) acrylic resin (A) contains an alkyl acrylate having a glass transition temperature of less than 0 ° C derived from a homopolymer The structural unit of (a1) and the structural unit of the alkyl acrylate (a2) derived from a homopolymer having a glass transition temperature of 0 ° C or higher.
[9]如[8]記載之光學積層體,其中前述(甲基)丙烯酸系樹脂(A)之前述來自丙烯酸烷酯(a2)的構成單元的含量,在構成(甲基)丙烯酸系樹脂(A)的全部構成單元100重量份中為10重量份以上。 [9] The optical laminate according to [8], wherein the content of the constitutional unit derived from the alkyl acrylate (a2) in the (meth) acrylic resin (A) is the amount of A) It is 10 weight part or more among 100 weight part of all the structural units.
[10]如[8]或[9]記載之光學積層體,其中前述丙烯酸烷酯(a2)包含丙烯酸甲酯。 [10] The optical laminate according to [8] or [9], wherein the alkyl acrylate (a2) contains methyl acrylate.
[11]如[1]至[10]中任一項記載之光學積層體,其中前述(甲基)丙烯酸系樹脂(A)含有來自具有羥基的單體的構成單元。 [11] The optical laminate according to any one of [1] to [10], wherein the (meth) acrylic resin (A) contains a structural unit derived from a monomer having a hydroxyl group.
[12]如[1]至[11]中任一項記載之光學積層體,其中前述(甲基)丙烯酸系樹脂(A)實質上不包含來自具有羧基的單體的構成單元。 [12] The optical laminate according to any one of [1] to [11], wherein the (meth) acrylic resin (A) does not substantially include a structural unit derived from a monomer having a carboxyl group.
[13]如[1]至[12]中任一項記載之光學積層體,其中前述黏著劑組成物實質上不包含選自***系化合物、噻唑系化合物、咪唑系化合物、咪唑啉(Imidazoline)系化合物、喹啉(Quinoline)系化合物、吡啶系化合物、嘧啶系化合物、吲哚系化合物、胺系化合物、尿素系化合物、苯甲酸鈉、苯甲基硫醇系化合物、二-第2丁基硫醚及二苯基亞碸所成群的防鏽劑。 [13] The optical laminate according to any one of [1] to [12], wherein the adhesive composition does not substantially include a member selected from the group consisting of triazole-based compounds, thiazole-based compounds, imidazole-based compounds, and imidazoline. ) Compounds, quinoline compounds, pyridine compounds, pyrimidine compounds, indole compounds, amine compounds, urea compounds, sodium benzoate, benzyl mercaptan compounds, di-2nd butyl A group of rust preventives for thioethers and diphenylsulfinium.
[14]如[1]至[13]中任一項記載之光學積層體,其中前述金屬層包含選自鋁、銅、銀、鐵、錫、鋅、鎳、鉬、鉻、鎢、鉛及包含從該等選擇2種以上的金屬之合金所成群的1種以上。 [14] The optical multilayer body according to any one of [1] to [13], wherein the metal layer includes a member selected from the group consisting of aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and One or more kinds of alloys including alloys of two or more kinds of metals selected from these.
[15]如[1]至[14]中任一項記載之光學積層體,其中前述金屬層包含鋁元素。 [15] The optical multilayer body according to any one of [1] to [14], wherein the metal layer contains an aluminum element.
[16]如[1]至[15]中任一項記載之光學積層體,其中前述金屬層係藉由濺鍍所形成的層。 [16] The optical laminated body according to any one of [1] to [15], wherein the metal layer is a layer formed by sputtering.
[17]如[1]至[16]中任一項記載之光學積層體,其中前述金屬層的厚度為3μm以下。 [17] The optical laminated body according to any one of [1] to [16], wherein the thickness of the metal layer is 3 μm or less.
[18]液晶顯示裝置,其係包括如[1]至[17]中任一項記載之光學積層體。 [18] A liquid crystal display device including the optical multilayer body according to any one of [1] to [17].
[19]黏著劑組成物,其相對於(甲基)丙烯酸系樹脂(A)100重量份而言,係含有0.01至2.5重量份的異氰酸酯系交聯劑(B)、0.01至10重量份的矽烷化合物(C)及0.2至8重量份的下述式(I)所示的離子性化合物(D):M+X- (I)(式(I)中,M+表示無機陽離子,X-表示含有氟原子的陰離子),前述黏著劑組成物係用於在要被積層於金屬層上的黏著劑層的形成者。 [19] An adhesive composition containing 0.01 to 2.5 parts by weight of an isocyanate-based crosslinking agent (B) and 0.01 to 10 parts by weight of 100 parts by weight of the (meth) acrylic resin (A). compound Silane compound (C), and 0.2 to 8 parts by weight of the following formula (I), ionic (D): M + X - () (in the formula (I), M + represents an inorganic cation, X - Represents an anion containing a fluorine atom), and the aforementioned adhesive composition is used for forming an adhesive layer to be laminated on a metal layer.
根據本發明,可提供可抑制金屬層的腐蝕之光學積層體及包含該光學積層體之液晶顯示裝置。 According to the present invention, an optical multilayer body capable of suppressing corrosion of a metal layer and a liquid crystal display device including the optical multilayer body can be provided.
1‧‧‧附黏著劑層之光學膜 1‧‧‧ Optical film with adhesive layer
2‧‧‧偏光片 2‧‧‧ polarizer
3‧‧‧第1樹脂膜 3‧‧‧The first resin film
4‧‧‧第2樹脂膜 4‧‧‧ 2nd resin film
5、6、7‧‧‧光學積層體 5, 6, 7‧‧‧‧ optical laminated body
10‧‧‧光學膜 10‧‧‧ Optical Film
10a、10b‧‧‧偏光板 10a, 10b ‧‧‧ polarizing plate
20‧‧‧黏著劑層 20‧‧‧ Adhesive layer
30‧‧‧金屬層 30‧‧‧ metal layer
40‧‧‧基板 40‧‧‧ substrate
50‧‧‧樹脂層 50‧‧‧ resin layer
第1圖係表示關於本發明的光學積層體之一例的剖面示意圖。 FIG. 1 is a schematic cross-sectional view showing an example of an optical multilayer body according to the present invention.
第2圖係表示偏光板的層構成之一例的剖面示意圖。 Fig. 2 is a schematic cross-sectional view showing an example of a layer configuration of a polarizing plate.
第3圖係表示偏光板的層構成之其他一例的剖面示意圖。 FIG. 3 is a schematic cross-sectional view showing another example of the layer configuration of the polarizing plate.
第4圖係表示光學積層體的層構成之一例的剖面示意圖。 FIG. 4 is a schematic cross-sectional view showing an example of a layer configuration of an optical laminate.
第5圖係表示光學積層體的層構成之其他一例的剖面示意圖。 Fig. 5 is a schematic cross-sectional view showing another example of the layer configuration of the optical laminate.
第6圖係表示光學積層體的層構成之其他一例的剖面示意圖。 Fig. 6 is a schematic cross-sectional view showing another example of the layer configuration of the optical laminate.
第7圖係表示光學積層體的層構成之其他一例的剖面 示意圖。 Fig. 7 is a schematic cross-sectional view showing another example of the layer constitution of the optical laminated body.
第1圖係表示關於本發明的光學積層體之一例的剖面示意圖。如第1圖所示,關於本發明的光學積層體,依序包括光學膜10、黏著劑層20及金屬層30,亦可更包括基板40。該光學積層體,亦可為在形成於基板40上的金屬層30上,將包括光學膜10及積層於其至少一側的面上的黏著劑層20之附黏著劑層之光學膜1,隔著該黏著劑層20貼合而成者。 FIG. 1 is a schematic cross-sectional view showing an example of an optical multilayer body according to the present invention. As shown in FIG. 1, the optical laminate of the present invention includes the optical film 10, the adhesive layer 20, and the metal layer 30 in this order, and may further include a substrate 40. The optical laminated body may also be an optical film 1 with an adhesive layer including an optical film 10 and an adhesive layer 20 laminated on at least one side of the metal layer 30 formed on the substrate 40. It is made by bonding together through this adhesive layer 20.
黏著劑層20,通常直接積層於光學膜10的表面。而且,通常附黏著劑層之光學膜1,係使該黏著劑層20以直接接觸金屬層30之方式積層於金屬層30上。根據本發明,於如此的光學積層體,可有效地抑制金屬層30的腐蝕。以下,可抑制金屬層30的腐蝕之性質,亦稱為「耐金屬腐蝕性」。 The adhesive layer 20 is usually directly laminated on the surface of the optical film 10. Moreover, the optical film 1 with an adhesive layer is usually laminated on the metal layer 30 such that the adhesive layer 20 directly contacts the metal layer 30. According to the present invention, in such an optical laminate, the corrosion of the metal layer 30 can be effectively suppressed. Hereinafter, the property of suppressing the corrosion of the metal layer 30 is also referred to as “metal corrosion resistance”.
光學膜10,可為單層構造的光學膜,亦可為多層構造的光學膜。黏著劑層20係由包含(甲基)丙烯酸系樹脂(A)、異氰酸酯系交聯劑(B)、矽烷化合物(C)及離子性化合物(D)之黏著劑組成物所構成。該黏著劑組成物,可再含有其他成分。於本說明書,所謂「(甲基)丙烯酸」係指選自丙烯酸及甲基丙烯酸所成群的至少一者。關於「(甲基)丙烯酸酯」、「(甲基)丙烯醯基」等,也相同。 The optical film 10 may be an optical film having a single-layer structure or an optical film having a multi-layer structure. The adhesive layer 20 is composed of an adhesive composition containing a (meth) acrylic resin (A), an isocyanate-based crosslinking agent (B), a silane compound (C), and an ionic compound (D). The adhesive composition may further contain other components. In this specification, "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The same applies to "(meth) acrylate", "(meth) acrylfluorenyl", and the like.
關於本發明的光學積層體所具備的光學膜10,係構成附黏著劑層之光學膜1之光學構件,可為可併入液晶顯示裝置等的圖像顯示裝置的各種光學膜(具有光學特性的膜)。光學膜10,可為單層構造的光學膜,亦可為多層構造的光學膜。單層構造的光學膜的具體例,除偏光片外,包括相位差膜、增亮膜、防眩膜、抗反射膜、擴散膜、聚光膜等的光學功能性膜。多層構造的光學膜的具體例,包括偏光板、相位差板。於本說明書,所謂偏光板,係指偏光片的至少一側的面積層樹脂膜或樹脂層者。所謂相位差板,係指相位差膜的至少一側的面積層樹脂膜或樹脂層者。光學膜10,較理想為偏光板、偏光片、相位差板或相位差膜,更理想為偏光板或偏光片。 The optical film 10 included in the optical multilayer body of the present invention is an optical member constituting the optical film 1 with an adhesive layer, and can be various optical films (having optical characteristics) that can be incorporated into an image display device such as a liquid crystal display device. Film). The optical film 10 may be an optical film having a single-layer structure or an optical film having a multi-layer structure. Specific examples of the optical film having a single-layer structure include an optical functional film such as a retardation film, a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, and a light-condensing film, in addition to the polarizer. Specific examples of the optical film having a multilayer structure include a polarizing plate and a retardation plate. In this specification, a polarizing plate refers to a resin film or a resin layer of an area layer on at least one side of a polarizer. The retardation plate refers to an area layer resin film or a resin layer on at least one side of the retardation film. The optical film 10 is preferably a polarizing plate, a polarizing plate, a retardation plate, or a retardation film, and more preferably a polarizing plate or a polarizing plate.
第2圖及第3圖係表示偏光板的層構成的例之剖面示意圖。第2圖所示的偏光板10a,係於偏光片2的一側的面積層貼合第1樹脂膜3之單面保護之偏光板,第3圖所示的偏光板10b,係於偏光片2的另一側的面再積層貼合第2樹脂膜4之兩面保護之偏光板。第1、第2樹脂膜3、4,可隔著未圖示的接著劑層、黏著劑層貼合於偏光片2。偏光板10a、10b,亦可包括第1、第2樹脂膜3、4以外的其他膜、層。 2 and 3 are schematic cross-sectional views showing examples of the layer configuration of a polarizing plate. The polarizing plate 10a shown in FIG. 2 is a polarizing plate in which the area layer on one side of the polarizer 2 is bonded to the single-sided protection of the first resin film 3, and the polarizing plate 10b shown in FIG. 3 is attached to the polarizer. The other side of 2 is further laminated and bonded to the polarizing plates protected on both sides of the second resin film 4. The first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer and an adhesive layer (not shown). The polarizing plates 10a and 10b may include other films and layers other than the first and second resin films 3 and 4.
將第2圖及第3圖所示的偏光板10a、10b,使用作為光學膜時之光學積層體的層構成的例,分別表示於第4圖及第5圖。第4圖所示的光學積層體5,係將第2圖所示的偏光板10a使用作為光學膜時之例,第5圖所示的光學積層體6,係將第3圖所示的偏光板10b使用作為光學膜時之例。 Examples of the layer configuration of the optical laminate when the polarizing plates 10a and 10b shown in FIGS. 2 and 3 are used as an optical film are shown in FIGS. 4 and 5 respectively. The optical laminated body 5 shown in FIG. 4 is an example when the polarizing plate 10 a shown in FIG. 2 is used as an optical film, and the optical laminated body 6 shown in FIG. 5 is a polarized light shown in FIG. 3. An example when the plate 10b is used as an optical film.
偏光片2係具備吸收具有平行其吸收軸的振動面的直線偏光而穿透具有垂直吸收軸(與穿透軸平行)的振動面的直線偏光性質的膜,例如可使用於聚乙烯醇系樹脂膜吸附配向二色性色素的膜。二色性色素可使用碘、二色性有機染料。 The polarizer 2 is a film having a linearly polarizing property that absorbs linearly polarized light having a vibration plane parallel to its absorption axis and penetrates a vibrational plane having a vertical absorption axis (parallel to the transmission axis). For example, it can be used for polyvinyl alcohol resin The film adsorbs a film that aligns a dichroic pigment. As the dichroic pigment, iodine and a dichroic organic dye can be used.
聚乙烯醇系樹脂,可藉由皂化聚乙酸乙烯酯系樹脂而得。作為聚乙酸乙烯酯系樹脂,除乙酸乙烯酯的單獨聚合物之聚乙酸乙烯酯外,可例舉如可與乙酸乙烯酯共聚合之單體與乙酸乙烯酯的共聚物等。作為可與乙酸乙烯酯共聚合之單體,例如不飽和羧酸、烯烴、乙烯醚、不飽和磺酸、具有銨基的(甲基)丙烯醯胺等。 The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. Examples of the polyvinyl acetate-based resin include, in addition to polyvinyl acetate, a separate polymer of vinyl acetate, and copolymers of a monomer copolymerizable with vinyl acetate and vinyl acetate. Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, (meth) acrylamide having an ammonium group, and the like.
聚乙烯醇系樹脂的皂化度,通常為85至100莫耳%,較理想為98莫耳%以上。聚乙烯醇系樹脂可被改質,例如可使用醛類改質的聚乙烯醇縮甲醛或聚乙烯醇縮乙醛等。聚乙烯醇系樹脂的平均聚合度,通常為1000至10000,較理想為1500至5000。聚乙烯醇系樹脂的平均聚合度,可根據JIS K 6726求得。 The saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, and more preferably 98 mol% or more. The polyvinyl alcohol-based resin can be modified. For example, aldehyde-modified polyvinyl formal or polyvinyl acetal can be used. The average degree of polymerization of the polyvinyl alcohol resin is usually 1,000 to 10,000, and more preferably 1500 to 5,000. The average degree of polymerization of the polyvinyl alcohol-based resin can be obtained in accordance with JIS K 6726.
通常將聚乙烯醇系樹脂製成膜者,係使用 作為偏光片2的原料膜。聚乙烯醇系樹脂,可用習知的方法製膜。原料膜的厚度,通常為1至150μm,考慮延伸的容易性等,較理想為10μm以上。 In general, a film made of a polyvinyl alcohol resin is used as a raw material film of the polarizer 2. The polyvinyl alcohol resin can be formed into a film by a conventional method. The thickness of the raw material film is usually 1 to 150 μm, and considering the ease of stretching, etc., it is preferably 10 μm or more.
偏光片2係例如對原料膜實施一軸延伸的步驟、用二色性色素將膜染色使吸附該二色性色素的步驟、用硼酸水溶液處理膜的步驟以及水洗膜的步驟,最後使其乾燥而製造。偏光片2的厚度,通常為1至30μm,從附黏著劑層之光學膜1的薄膜化的觀點,較理想為20μm以下,更理想為15μm以下,更加理想為10μm以下。 The polarizer 2 is, for example, a step of uniaxially stretching the raw film, a step of dyeing the film with a dichroic pigment to adsorb the dichroic pigment, a step of treating the film with a boric acid aqueous solution, and a step of washing the film, and finally drying and Manufacturing. The thickness of the polarizer 2 is usually 1 to 30 μm. From the viewpoint of thinning the optical film 1 with an adhesive layer, the thickness is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less.
二色性色素吸附配向於聚乙烯醇系樹脂膜所成的偏光片2,係藉由1)使用聚乙烯醇系樹脂膜的單獨膜作為原料膜,對該膜實施一軸延伸處理及二色性色素的染色處理之方法以及,2)塗佈含有聚乙烯醇系樹脂的塗佈液(水溶液等)於基材膜,使其乾燥,得到具有聚乙烯醇系樹脂層的基材膜後,將其與基材膜一起進行一軸延伸,對延伸後的聚乙烯醇系樹脂層進行二色性色素的染色處理,然後剝離除去基材膜的方法而可得到。作為基材膜,可使用後述與可構成第1、第2樹脂膜3、4之熱塑性樹脂相同的熱塑性樹脂所構成的膜,較理想為聚對苯二甲酸乙二酯等的聚酯系樹脂、聚碳酸酯系樹脂、三乙醯基纖維素等的纖維素系樹脂、降莰烯系樹脂等的環狀聚烯烴系樹脂、聚苯乙烯系樹脂等所構成的膜。根據上述2)的方法,薄膜的偏光片2的製作變容易,可容易地製作例如厚度7μm以下的偏光片2。 The polarizer 2 formed of a dichroic pigment adsorbed and aligned on a polyvinyl alcohol-based resin film uses 1) a single film of a polyvinyl alcohol-based resin film as a raw material film, and the film is subjected to uniaxial stretching and dichroism. A method for dyeing a pigment and 2) applying a coating solution (aqueous solution, etc.) containing a polyvinyl alcohol resin to a substrate film and drying the substrate film to obtain a substrate film having a polyvinyl alcohol resin layer, and then It can be obtained by performing uniaxial stretching together with the base film, applying a dichroic dye to the stretched polyvinyl alcohol resin layer, and then peeling and removing the base film. As the base film, a film made of the same thermoplastic resin as the thermoplastic resin constituting the first and second resin films 3 and 4 described below can be used, and a polyester resin such as polyethylene terephthalate is more preferable. , A polycarbonate resin, a cellulose resin such as triethylfluorenyl cellulose, a cyclic polyolefin resin such as norbornene resin, a polystyrene resin, and the like. According to the method 2), the production of the thin film polarizer 2 is easy, and the polarizer 2 having a thickness of, for example, 7 μm or less can be easily produced.
第1、第2樹脂膜3、4,分別獨立地具有透光性,較理想為光學上透明的熱塑性樹脂,例如鏈狀聚烯烴系樹脂(聚乙烯系樹脂、聚丙烯系樹脂等)、環狀聚烯烴系樹脂(降莰烯系樹脂等)之聚烯烴系樹脂;纖維素系樹脂(纖維素酯系樹脂等);聚酯系樹脂(聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯等);聚碳酸酯系樹脂;(甲基)丙烯酸系樹脂;聚苯乙烯系樹脂;聚醚醚酮系樹脂;聚碸系樹脂;或該等的混合物、共聚物等所構成的膜。其中,第1、第2樹脂膜3、4,分別為選自環狀聚烯烴系樹脂、聚碳酸酯系樹脂、纖維素系樹脂、聚酯系樹脂及(甲基)丙烯酸系樹脂所成群的樹脂所構成者較理想,更理想為選自纖維素系樹脂及環狀聚烯烴系樹脂所成群的樹脂所構成者。 The first and second resin films 3 and 4 each have a light-transmitting property independently, and are preferably optically transparent thermoplastic resins, such as a chain polyolefin resin (polyethylene resin, polypropylene resin, etc.), and a ring. Polyolefin resins (such as norbornene resins); cellulose resins (cellulose ester resins, etc.); polyester resins (polyethylene terephthalate, polyethylene naphthalate) (Ethylene glycol, polybutylene terephthalate, etc.); polycarbonate resins; (meth) acrylic resins; polystyrene resins; polyetheretherketone resins; polyfluorene resins; or such Films made of mixtures, copolymers, etc. Among them, the first and second resin films 3 and 4 are each a group selected from the group consisting of a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, and a (meth) acrylic resin. The resin composition is preferably composed of a resin selected from the group consisting of a cellulose resin and a cyclic polyolefin resin.
作為鏈狀聚烯烴系樹脂,除聚乙烯系樹脂、聚丙烯系樹脂等的鏈狀烯烴的均聚物外,可例舉如2種以上鏈狀烯烴所構成的共聚物。 As the chain polyolefin resin, in addition to a homopolymer of a chain olefin such as a polyethylene resin and a polypropylene resin, a copolymer composed of two or more types of chain olefins may be mentioned.
環狀聚烯烴系樹脂為包含降莰烯、四環十二烯(別名:二甲橋八氫萘)或該等的衍生物為代表例的環狀烯烴作為聚合單元的樹脂的總稱。舉環狀聚烯烴系樹脂的具體例時,有環狀烯烴的開環(共)聚合物及其氫化物、環狀烯烴的加成聚合物、環狀烯烴與如乙烯、丙烯的鏈狀烯烴或具有乙烯基的芳香族化合物的共聚物以及該等以不飽和羧酸或其衍生物改質的改質(共)聚合物等。其中,作為環狀烯烴,以使用降莰烯或多環降莰烯系單體等的降莰 烯系單體之降莰烯系樹脂較理想。 The cyclic polyolefin resin is a general term for a resin including norbornene, tetracyclododecene (alias: dimethyl bridge octahydronaphthalene), or a cyclic olefin as a representative example thereof as a polymerization unit. Specific examples of cyclic polyolefin resins include ring-opened (co) polymers of cyclic olefins and their hydrides, addition polymers of cyclic olefins, cyclic olefins, and chain olefins such as ethylene and propylene. Or copolymers of aromatic compounds having a vinyl group, and such modified (co) polymers modified with an unsaturated carboxylic acid or a derivative thereof. Among them, as the cyclic olefin, a norbornene-based resin using a norbornene-based monomer such as norbornene or a polycyclic norbornene-based monomer is preferred.
纖維素系樹脂,較理想為纖維素酯系樹脂,亦即纖維素的部分或完全酯化物等,例如纖維素的乙酸酯、丙酸酯、丁酸酯、該等的混合酯等。其中,使用三乙醯基纖維素、二乙醯基纖維素、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等較理想。 The cellulose-based resin is preferably a cellulose ester-based resin, that is, a partial or complete esterification of cellulose, such as cellulose acetate, propionate, butyrate, and mixed esters thereof. Among them, triethyl cellulose, diethyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, etc. are preferably used.
聚酯系樹脂為具有酯鍵結之上述纖維素酯系樹脂以外的樹脂,一般為多元羧酸或其衍生物與多元醇的縮聚物所構成。聚酯系樹脂的具體例,包括聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、聚對苯二甲酸丙二酯、聚萘二甲酸丙二酯、聚對苯二甲酸環己烷二甲酯、聚萘二甲酸環己烷二甲酯。 The polyester resin is a resin other than the above-mentioned cellulose ester resin having an ester bond, and is generally composed of a polycondensate of a polycarboxylic acid or a derivative thereof and a polyhydric alcohol. Specific examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polytrimethylene terephthalate. Ester, polynaphthalate, polycyclohexane dimethyl terephthalate, cyclohexane dimethyl polynaphthalate.
聚碳酸酯系樹脂,係由碳酸與二醇或雙酚所形成的聚酯。其中,從耐熱性、耐候性及耐酸性的觀點以使用分子鏈具有二苯基烷的芳香族碳酸酯較理想。作為聚碳酸酯,例如由如2,2-雙(4-羥基苯基)丙烷(別名:雙酚A)、2,2-雙(4-羥基苯基)丁烷、1,1-雙(4-羥基苯基)環己烷、1,1-雙(4-羥基苯基)異丁烷、1,1-雙(4-羥基苯基)乙烷等雙酚衍生的聚碳酸酯。 Polycarbonate resins are polyesters made of carbonic acid and diols or bisphenols. Among them, it is preferable to use an aromatic carbonate having a diphenylalkane in the molecular chain from the viewpoints of heat resistance, weather resistance, and acid resistance. As the polycarbonate, for example, 2,2-bis (4-hydroxyphenyl) propane (alias: bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis ( Polycarbonates derived from bisphenols such as 4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) isobutane, and 1,1-bis (4-hydroxyphenyl) ethane.
可構成第1、第2樹脂膜3、4之(甲基)丙烯酸系樹脂,可為以來自甲基丙烯酸酯的構成單元為主體(例如包含50重量%以上)的聚合物,較理想為其與其他共聚成分共聚合的共聚物。(甲基)丙烯酸系樹脂,包含2種以 上的來自甲基丙烯酸酯的構成單元。作為甲基丙烯酸酯,例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯等的甲基丙烯酸酯的C1至C4烷酯。 The (meth) acrylic resin that can constitute the first and second resin films 3 and 4 can be a polymer mainly composed of a methacrylate-derived unit (for example, containing 50% by weight or more), and is more preferably Copolymer copolymerized with other copolymerization components. The (meth) acrylic resin contains two or more kinds of constituent units derived from a methacrylate. Examples of the methacrylate include C 1 to C 4 alkyl esters of methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
作為可與甲基丙烯酸酯共聚合的共聚合成分,可例舉如丙烯酸酯。丙烯酸酯,較理想為丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等的丙烯酸C1至C8烷酯。其他共聚合成分的具體例為例如(甲基)丙烯酸等的不飽和酸類;苯乙烯、鹵化苯乙烯、α-甲基苯乙烯、乙烯基甲苯等的芳香族乙烯基化合物;(甲基)丙烯腈等的乙烯基氰化物;順丁烯二酸酐、甲基順丁烯二酸酐等的不飽和酸酐;苯基馬來醯亞胺、環己基馬來醯亞胺等的不飽和醯亞胺類等的分子內具有1個聚合性碳-碳雙鍵的丙烯酸酯以外的化合物。也可使用分子內具有2個以上聚合性碳-碳雙鍵的化合物作為共聚合成分。共聚合成分,可使用單獨1種,亦可併用2種以上。 As a copolymerization component copolymerizable with a methacrylate, an acrylate is mentioned, for example. The acrylate is preferably a C 1 to C 8 alkyl acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate. Specific examples of other copolymerization components are, for example, unsaturated acids such as (meth) acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene, and vinyl toluene; (meth) propylene Vinyl cyanide, such as nitrile; Unsaturated anhydride, such as maleic anhydride, methyl maleic anhydride; Unsaturated hydrazone, such as phenylmaleimide, cyclohexylmaleimide, etc. Compounds other than acrylate having one polymerizable carbon-carbon double bond in the molecule. A compound having two or more polymerizable carbon-carbon double bonds in the molecule may be used as a copolymerization component. A copolymerization component may be used individually by 1 type, and may use 2 or more types together.
(甲基)丙烯酸樹脂,在可提高膜的耐久性之點,於高分子主鏈可具有環構造。環構造,較理想為環狀酸酐構造、環狀醯亞胺構造、內酯環構造等的雜環構造。作為環狀酸酐構造的具體例,例如戊二酸酐構造、琥珀酸酐構造,作為環狀醯亞胺構造的具體例,例如戊二醯亞胺構造、琥珀醯亞胺構造,作為內酯環構造,例如丁內酯環構造、戊內酯環構造。 The (meth) acrylic resin may have a ring structure in the polymer main chain in order to improve the durability of the film. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic amidine structure, and a lactone ring structure. As specific examples of the cyclic anhydride structure, for example, glutaric anhydride structure and succinic anhydride structure, and as specific examples of the cyclic amidine structure, for example, glutarimide structure, succinimide structure, and lactone ring structure, For example, a butyrolactone ring structure and a valerolactone ring structure.
(甲基)丙烯酸系樹脂,從對膜的製膜性及膜的耐衝擊性等的觀點,可含有丙烯酸系橡膠粒子。所謂丙 烯酸系橡膠粒子,係指以丙烯酸酯為主體的彈性聚合物為必須成分的粒子,例如實質上只由該彈性聚合物所構成的單層構造者、或以該彈性聚合物為1層的多層構造者。作為彈性聚合物的例,例如以丙烯酸烷酯為主成分,與可與其共聚合的其他乙烯基單體及交聯性單體共聚合的交聯彈性共聚物。作為成為彈性聚合物的主成分的丙烯酸烷酯,可例舉如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等的丙烯酸的C1至C8烷酯。烷基的碳數,較理想為4以上。 The (meth) acrylic resin may contain acrylic rubber particles from the viewpoints of film forming properties and impact resistance of the film. The acrylic rubber particles refer to particles having an elastic polymer mainly composed of acrylate as an essential component. For example, a single-layer structure consisting essentially of the elastic polymer or one layer of the elastic polymer is used. Multi-layer constructor. Examples of the elastic polymer include, for example, a crosslinked elastic copolymer containing an alkyl acrylate as a main component and copolymerized with other vinyl monomers and crosslinkable monomers copolymerizable therewith. Examples of the alkyl acrylate to be the main component of the elastic polymer include C 1 to C 8 alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. The carbon number of the alkyl group is preferably 4 or more.
作為可與丙烯酸烷酯共聚合的其他乙烯基單體,可例舉如分子內具有1個聚合性碳-碳雙鍵的化合物,更具體地例如甲基丙烯酸甲酯的甲基丙烯酸酯、如苯乙烯的芳香族乙烯基化合物、如(甲基)丙烯腈的乙烯基氰化物等。作為交聯性單體,可例舉如分子內具有2個以上的聚合性碳-碳雙鍵的交聯性化合物,更具體地例如乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯等的多元醇的(甲基)丙烯酸酯、(甲基)丙烯酸烯丙酯等的(甲基)丙烯酸的烯酯、二乙烯基苯等。 Examples of other vinyl monomers that can be copolymerized with alkyl acrylates include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methyl methacrylate, such as Aromatic vinyl compounds of styrene, vinyl cyanides such as (meth) acrylonitrile, and the like. Examples of the crosslinkable monomer include a crosslinkable compound having two or more polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate and butanediol di (Meth) acrylates of polyhydric alcohols such as (meth) acrylates, (meth) acrylic alkenes such as allyl (meth) acrylate, divinylbenzene, and the like.
丙烯酸系橡膠粒子的含量,對(甲基)丙烯酸系樹脂100重量份而言,較理想為5重量份以上,更理想為10重量份以上。丙烯酸系橡膠粒子的含量太多時,膜的表面硬度低,而且對膜實施表面處理時,對表面處理劑中的有機溶劑之耐溶劑性低。所以,丙烯酸系橡膠粒子的含量,對(甲基)丙烯酸系樹脂100重量份而言,通常為80重 量份以下,較理想為60重量份以下。 The content of the acrylic rubber particles is preferably 5 parts by weight or more, and more preferably 10 parts by weight or more, based on 100 parts by weight of the (meth) acrylic resin. When the content of the acrylic rubber particles is too large, the surface hardness of the film is low, and when the film is subjected to a surface treatment, the solvent resistance to the organic solvent in the surface treatment agent is low. Therefore, the content of the acrylic rubber particles is usually 80 parts by weight or less, and more preferably 60 parts by weight or less, based on 100 parts by weight of the (meth) acrylic resin.
第1、第2樹脂膜3、4,可含有本發明的技術領域之通常的添加劑。添加劑的具體例,例如包括紫外線吸收劑、紅外線吸收劑、有機系染料、顏料、無機系色素、抗氧化劑、抗靜電劑、界面活性劑、潤滑劑、分散劑、熱安定劑等。 The first and second resin films 3 and 4 may contain ordinary additives in the technical field of the present invention. Specific examples of the additives include, for example, ultraviolet absorbers, infrared absorbers, organic dyes, pigments, inorganic pigments, antioxidants, antistatic agents, surfactants, lubricants, dispersants, and thermal stabilizers.
作為紫外線吸收劑,例如水楊酸酯系化合物、二苯基甲酮系化合物、苯並***系化合物、三(triazine)化合物、氰基(甲基)丙烯酸酯化合物、鎳錯鹽等。 Examples of the ultraviolet absorber include a salicylate-based compound, a diphenyl ketone-based compound, a benzotriazole-based compound, and (triazine) compounds, cyano (meth) acrylate compounds, nickel salts, and the like.
第1、第2樹脂膜3、4,分別可為無延伸的膜,或者可為一軸或二軸延伸的膜。二軸延伸,可為2個延伸方向同時延伸的同時二軸延伸,亦可為在指定的方向延伸後延伸另一方向之逐次二軸延伸。第1樹脂膜3及/或第2樹脂膜4,可為擔負保護偏光片2任務之保護膜,可合併具有如後述的相位差膜的光學功能的保護膜。相位差膜為顯示光學異向性的光學膜。例如將上述熱塑性樹脂所構成的膜延伸(一軸延伸或二軸延伸等),或藉由於該熱塑性樹脂膜上形成液晶層等,可成為被賦予任意相位差值之相位差膜。 The first and second resin films 3 and 4 may be non-stretched films, or may be uniaxially or biaxially stretched films. Biaxial extension can be simultaneous biaxial extension in two extension directions, or successive biaxial extension in the other direction after extending in the specified direction. The first resin film 3 and / or the second resin film 4 may be a protective film that is responsible for protecting the polarizer 2 and may be a protective film having an optical function of a retardation film as described later. The retardation film is an optical film showing optical anisotropy. For example, a film made of the thermoplastic resin (e.g., uniaxial or biaxial stretching) or a liquid crystal layer formed on the thermoplastic resin film can be used to form a retardation film having an arbitrary retardation value.
第1樹脂膜3及第2樹脂膜4,可為相同的熱塑性樹脂所構成的膜,亦可為相異的熱塑性樹脂所構成的膜。第1樹脂膜3及第2樹脂膜4,於厚度、添加劑的有無及種類、相位差特性等,可為相同,亦可為不同。 The first resin film 3 and the second resin film 4 may be films made of the same thermoplastic resin or films made of different thermoplastic resins. The first resin film 3 and the second resin film 4 may be the same as or different from each other in thickness, presence or absence and type of additives, retardation characteristics, and the like.
第1樹脂膜3及/或第2樹脂膜4,可於其 外面(與偏光片2相反側的表面)具備硬塗層、防眩層、抗反射層、光擴散層、抗靜電層、防污層、導電層等的表面處理層(塗覆層)。 The first resin film 3 and / or the second resin film 4 may be provided with a hard coat layer, an anti-glare layer, an anti-reflection layer, a light diffusion layer, an anti-static layer, and an anti-glare layer on the outer surface (the surface opposite to the polarizer 2). Surface treatment layer (coating layer) such as a stain layer, a conductive layer, and the like.
第1樹脂膜3及第2樹脂膜4的厚度,分別通常為1至150μm,較理想為5至100μm,更理想為5至60μm。該厚度為50μm以下,又可為30μm以下。第1、第2樹脂膜3、4的厚度小,有利於附黏著劑層之光學膜1及光學積層體的薄膜化,進而有利於包含附黏著劑層之光學膜1或光學積層體之液晶顯示裝置的薄膜化。 The thickness of the first resin film 3 and the second resin film 4 are usually 1 to 150 μm, more preferably 5 to 100 μm, and even more preferably 5 to 60 μm. The thickness is 50 μm or less, and may be 30 μm or less. The small thickness of the first and second resin films 3 and 4 is beneficial to the thinning of the optical film 1 and the optical laminated body with the adhesive layer, and further facilitates the optical film 1 or the liquid crystal of the optical laminated body including the adhesive layer. Thinning the display device.
特別是對於稱為智慧型手機、平板型終端的中小型的偏光板,由於薄膜化的要求,作為第1樹脂膜3及/或第2樹脂膜4,大多使用厚度30μm以下薄的膜,如此的偏光板,抑制偏光片2的收縮力弱,耐久性容易變不足。根據本發明,即使於使用如此的偏光板作為光學膜10的情況,亦可提供具有良好的耐久性之附黏著劑層之光學膜1及光學積層體。所謂附黏著劑層之光學膜1及光學積層體的耐久性,係指例如高溫環境下、高溫高濕環境下、高溫與低溫反覆的環境下等,可抑制黏著劑層20與鄰接其之光學構件的界面的浮起、剝離、黏著劑層20的起泡等缺陷之性質。 In particular, for small and medium-sized polarizers called smart phones and tablet terminals, thin films with a thickness of 30 μm or less are often used as the first resin film 3 and / or the second resin film 4 due to thin film requirements. The polarizing plate has a weak contraction force for suppressing the polarizer 2 and is liable to become insufficient in durability. According to the present invention, even when such a polarizing plate is used as the optical film 10, it is possible to provide an optical film 1 with an adhesive layer and an optical laminate having excellent durability. The durability of the optical film 1 with the adhesive layer and the optical laminated body refers to, for example, a high-temperature environment, a high-temperature and high-humidity environment, and a high-temperature and low-temperature environment where the adhesive layer 20 and the optical adjacent to it can be suppressed. Defects such as floating, peeling of the interface of the member, and blistering of the adhesive layer 20.
而且,從偏光板的薄膜化的觀點,如第2圖所示的偏光板10a,以只於偏光片2的單面,配置樹脂膜之構成為有利。於該情況,通常於偏光片2的另一側的面,直接貼合黏著劑層20,成為附黏著劑層之光學膜1(參 考第4圖)。於如此的構成的偏光板的情況,由於黏著劑層20所含有的離子性化合物,於高溫高濕環境下偏光板的光學性能降低的問題變得特別顯著。根據本發明,即使於使用如此的偏光板作為光學膜10的情況,亦可提供具有良好的光學耐久性(可抑制光學特性的劣化之性質)之附黏著劑層之光學膜1及光學積層體。 From the viewpoint of thinning the polarizing plate, the polarizing plate 10 a shown in FIG. 2 is advantageous in that a resin film is arranged on only one side of the polarizing plate 2. In this case, the adhesive layer 20 is usually directly adhered to the other surface of the polarizer 2 to form an optical film 1 with an adhesive layer (see FIG. 4). In the case of a polarizing plate having such a configuration, the problem of a reduction in the optical performance of the polarizing plate in a high-temperature and high-humidity environment becomes particularly significant due to the ionic compound contained in the adhesive layer 20. According to the present invention, even in the case where such a polarizing plate is used as the optical film 10, it is possible to provide an optical film 1 with an adhesive layer and an optical laminate having excellent optical durability (property capable of suppressing deterioration of optical characteristics). .
第1、第2樹脂膜3、4,可隔著接著劑層、黏著劑層,貼合於偏光片2。作為形成接著劑層的接著劑,可使用水系接著劑或活性能量線硬化性接著劑。 The first and second resin films 3 and 4 can be bonded to the polarizer 2 through an adhesive layer and an adhesive layer. As the adhesive for forming the adhesive layer, a water-based adhesive or an active energy ray-curable adhesive can be used.
作為水系接著劑,例如聚乙烯醇系樹脂水溶液所構成的接著劑、水系二液型胺酯系乳化接著劑等。其中,適合使用聚乙烯醇系樹脂水溶液所構成的水系接著劑。作為聚乙烯醇系樹脂,除可使用將乙酸乙烯酯均聚物之聚乙酸乙烯酯進行皂化處理所得之乙烯醇均聚物外,亦可使用將乙酸乙烯酯及可與其共聚合的其他單體的共聚物進行皂化處理所得之聚乙烯醇系共聚物、或該等的羥基部分改質的改質聚乙烯醇系聚合物等。水系接著劑,可包含醛化合物、環氧化合物、三聚氰胺系化合物、羥甲基化合物、異氰酸酯化合物、胺化合物、多價金屬鹽等的交聯劑。 Examples of the water-based adhesive include an adhesive composed of a polyvinyl alcohol-based resin aqueous solution, and a water-based two-liquid amine ester-based emulsification adhesive. Among these, a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution is suitably used. As the polyvinyl alcohol resin, in addition to a vinyl alcohol homopolymer obtained by saponifying a polyvinyl acetate homopolymer of polyvinyl acetate, vinyl acetate and other monomers copolymerizable therewith may also be used. The polyvinyl alcohol-based copolymer obtained by saponifying the copolymer, or the modified polyvinyl alcohol-based polymer in which the hydroxyl group is partially modified. The water-based adhesive may include a crosslinking agent such as an aldehyde compound, an epoxy compound, a melamine-based compound, a methylol compound, an isocyanate compound, an amine compound, or a polyvalent metal salt.
於使用水系接著劑的情況,偏光片2與第1、第2樹脂膜3、4貼合後,為了除去包含於水系接著劑中的水,實施乾燥步驟較理想。乾燥步驟後,亦可設置例如於20至45℃左右熟成的熟成步驟。 In the case of using a water-based adhesive, it is preferable to perform a drying step in order to remove the water contained in the water-based adhesive after the polarizer 2 is bonded to the first and second resin films 3 and 4. After the drying step, a ripening step such as ripening at about 20 to 45 ° C. may be provided.
上述所謂活性能量線硬化性接著劑,係指 藉由照射如紫外線、電子線等的活性能量線而硬化的接著劑,例如包含聚合性化合物及光聚合引發劑的硬化性組成物、包含光反應性樹脂的硬化性組成物、包含黏結劑樹脂及光反應***聯劑的硬化性組成物等。較理想為紫外線硬化性接著劑。作為聚合性化合物,例如光硬化性環氧系單體、光硬化性(甲基)丙烯酸系單體、光硬化性胺酯系單體的光聚合性單體、來自光聚合性單體的寡聚物。作為光聚合引發劑,例如包含藉由活性能量線的照射而產生中性自由基、陰離子自由基、陽離子自由基等活性物種的物質者。作為包含聚合性化合物及光聚合引發劑的活性能量線硬化性接著劑,以使用包含光硬化性環氧系單體及光陽離子聚合引發劑的硬化性組成物、包含光硬化性(甲基)丙烯酸系單體及光自由基聚合引發劑的硬化性組成物、或該等的硬化性組成物的混合物較理想。 The above-mentioned active energy ray-curable adhesive refers to an adhesive that is cured by irradiating active energy rays such as ultraviolet rays and electron rays, and includes, for example, a curable composition containing a polymerizable compound and a photopolymerization initiator, and a photoreaction A curable composition of a flexible resin, a curable composition containing a binder resin and a photoreactive cross-linking agent, and the like. A UV-curable adhesive is more preferable. Examples of the polymerizable compound include a photocurable epoxy-based monomer, a photocurable (meth) acrylic monomer, a photocurable monomer of a photocurable amine ester monomer, and an oligo derived from the photopolymerizable monomer. Polymer. The photopolymerization initiator includes, for example, a substance that generates active species such as neutral radicals, anionic radicals, and cationic radicals upon irradiation with active energy rays. As the active energy ray-curable adhesive containing a polymerizable compound and a photopolymerization initiator, a photocurable (meth) -containing curable composition containing a photocurable epoxy-based monomer and a photocationic polymerization initiator is used. A curable composition of an acrylic monomer and a photoradical polymerization initiator, or a mixture of such curable compositions is preferred.
於使用活性能量線硬化性接著劑的情況,偏光片2與第1、第2樹脂膜3、4貼合後,依需要進行乾燥步驟,然後進行藉由照射活性能量線使活性能量線硬化性接著劑硬化的硬化步驟。活性能量線的光源,無特別限制,具有波長400nm以下的發光分佈的紫外線較理想,具體地可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、金屬鹵化物燈等。 In the case of using an active energy ray-curable adhesive, after the polarizer 2 is bonded to the first and second resin films 3 and 4, a drying step is performed as required, and then the active energy ray is hardened by irradiating the active energy ray. A hardening step followed by hardening of the agent. There is no particular limitation on the source of the active energy ray. Ultraviolet rays with a light emission distribution below 400 nm are ideal. Specifically, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black lights, microwave-excited mercury lamps, Metal halide lamps, etc.
偏光片2與第1、第2樹脂膜3、4貼合時,於該等至少一者的貼合面,可實施皂化處理、電暈處理、 電漿處理等的表面活性化處理。於偏光片2的兩面貼合樹脂膜的情況,貼合該等樹脂膜用的接著劑,可為相同種的接著劑,亦可為不同種的接著劑。 When the polarizer 2 and the first and second resin films 3 and 4 are bonded, a surface activation treatment such as saponification treatment, corona treatment, or plasma treatment may be performed on the bonding surface of at least one of these. When a resin film is bonded to both sides of the polarizer 2, the adhesive for bonding these resin films may be the same kind of adhesive or different kinds of adhesives.
偏光板10a、10b,可再包含其他膜或層。其具體例,除後述的相位差膜外,有增亮膜、防眩膜、抗反射膜、擴散膜、聚光膜、黏著劑層20以外的黏著劑層、塗覆層、保護膜等。保護膜係以保護偏光板等的光學膜10的表面不受傷、污染為目的所使用的膜,在附黏著劑層之光學膜1貼合於例如金屬層30上後,通常被剝離除去。 The polarizing plates 10a and 10b may further include other films or layers. Specific examples thereof include a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, a light-condensing film, and an adhesive layer, a coating layer, a protective film, and the like other than the retardation film described later. The protective film is a film used for the purpose of protecting the surface of the optical film 10 such as a polarizing plate from being damaged or contaminated. After the optical film 1 with an adhesive layer is attached to, for example, the metal layer 30, it is usually peeled and removed.
保護膜,通常係由基材膜及積層於其上的黏著劑層所構成。基材膜可由熱塑性樹脂,例如聚乙烯系樹脂、聚丙烯系樹脂等的聚烯烴系樹脂;聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等的聚酯系樹脂;聚碳酸酯系樹脂;(甲基)丙烯酸系樹脂等所構成。 The protective film is usually composed of a base film and an adhesive layer laminated on the base film. The base film can be made of thermoplastic resins such as polyolefin resins such as polyethylene resins and polypropylene resins; polyester resins such as polyethylene terephthalate, polyethylene naphthalate; polycarbonate Based resin; (meth) acrylic based resin.
包含於相位差板的相位差膜,如上述為顯示光學異向性的光學膜,除可使用於第1、第2樹脂膜3、4之上述例示的熱塑性樹脂外,例如聚乙烯醇系樹脂、聚芳酯系樹脂、聚醯亞胺系樹脂、聚醚碸系樹脂、聚偏氟乙烯/聚甲基丙烯酸甲酯系樹脂、液晶聚酯系樹脂、乙烯-乙酸乙烯酯共聚物皂化物、聚氯乙烯系樹脂等所構成的樹脂膜,藉由延伸1.01至6倍左右所得之延伸膜。其中,以將聚碳酸酯系樹脂膜、環狀烯烴系樹脂膜、(甲基)丙烯酸系樹脂膜或纖維素系樹 脂膜一軸延伸或二軸延伸的延伸膜較理想。而且,於本說明書,零遲滯膜也包含於相位差膜(但是零延遲膜也可作為保護膜)。此外,稱為一軸性相位差膜、廣視角相位差膜、低光彈性率相位差膜等的膜,也可能應用作為相位差膜。 The retardation film included in the retardation plate is an optical film exhibiting optical anisotropy as described above. In addition to the thermoplastic resins exemplified above for the first and second resin films 3 and 4, for example, polyvinyl alcohol resins , Polyarylate resin, polyimide resin, polyether fluorene resin, polyvinylidene fluoride / polymethyl methacrylate resin, liquid crystal polyester resin, ethylene-vinyl acetate copolymer saponification, A resin film made of a polyvinyl chloride resin or the like is a stretched film obtained by stretching about 1.01 to 6 times. Among these, a polycarbonate resin film, a cyclic olefin resin film, a (meth) acrylic resin film, or a cellulose resin film is preferably an uniaxially or biaxially stretched stretched film. Moreover, in this specification, a zero retardation film is also included in a retardation film (however, a zero retardation film can also be used as a protective film). In addition, a film called a uniaxial retardation film, a wide viewing angle retardation film, a low photoelasticity retardation film, or the like may also be applied as the retardation film.
所謂零遲滯膜,係指面內相位差值Re及厚度方向相位差值Rth皆為-15至15nm的膜。該相位差膜,適合使用於IPS(面內切換)模式液晶顯示裝置。面內相位差值Re及厚度方向相位差值Rth,較理想為-10至10nm,更理想為-5至5nm。此處所謂面內相位差值Re及厚度方向相位差值Rth,係指波長590nm的值。 The zero-hysteresis film refers to a film in which both the in-plane retardation value R e and the thickness direction retardation value R th are -15 to 15 nm. This retardation film is suitable for use in an IPS (In-Plane Switching) mode liquid crystal display device. The in-plane retardation value R e and the thickness direction retardation value R th are preferably -10 to 10 nm, and more preferably -5 to 5 nm. Here, the in-plane retardation value R e and the thickness direction retardation value R th are values having a wavelength of 590 nm.
面內相位差值Re及厚度方向相位差值Rth,分別以下述式定義:Re=(nx-ny)×d The in-plane phase difference value R e and the thickness direction phase difference value R th are respectively defined by the following formulas: R e = (n x -n y ) × d
Rth=[(nx+ny)/2-nz]×d。式中,nx為膜面內的慢軸方向(x軸方向)的折射率,ny為膜面內的前快軸方向(在面內與x軸垂直的y軸方向)的折射率,nz為膜的厚度方向(垂直膜面的z軸方向)的折射率,d為膜的厚度。 R th = [(n x + n y ) / 2-n z ] × d. In the formula, n x is the refractive index in the slow axis direction (x-axis direction) in the film plane, and n y is the refractive index in the front fast axis direction (y-axis direction perpendicular to the x-axis in the plane) in the film plane. n z is the refractive index in the thickness direction of the film (the z-axis direction perpendicular to the film surface), and d is the thickness of the film.
於零遲滯膜,例如可使用如纖維素系樹脂、鏈狀聚烯烴系樹脂及環狀聚烯烴系樹脂的聚烯烴系樹脂、聚對苯二甲酸乙二酯或(甲基)丙烯酸系樹脂所構成的樹脂膜。特別是由於相位差值的控制容易、取得容易,以使用纖維素系樹脂、聚烯烴系樹脂或(甲基)丙烯酸系樹脂較理想。 For a zero-lag film, for example, a polyolefin resin such as a cellulose resin, a chain polyolefin resin, and a cyclic polyolefin resin, a polyethylene terephthalate, or a (meth) acrylic resin can be used. Composition of the resin film. In particular, it is preferable to use a cellulose-based resin, a polyolefin-based resin, or a (meth) acrylic resin because the phase difference value is easy to control and obtain.
而且,藉由液晶性化合物的塗佈/配向而表現光學異向性的膜或藉由無機層狀化合物的塗佈而表現光學異向性的膜,也可使用作為相位差膜。於如此的相位差膜,有稱為溫度補償型相位差膜者、由JX日礦日石能源(股)以「NH FILM」的商品名販售的棒狀液晶為經傾斜配向的膜、由富士薄膜(股)以「WV FILM」的商品名販售的圓盤狀液晶為經傾斜配向的膜、由住友化學(股)以「VAC FILM」的商品名販售的完全二軸配向型的膜、同樣由住友化學(股)以「new VAC FILM」的商品名販售的二軸配向型的膜等。 Further, a film that exhibits optical anisotropy by coating / alignment of a liquid crystalline compound or a film that exhibits optical anisotropy by application of an inorganic layered compound can also be used as a retardation film. For such retardation films, there are those known as temperature-compensated retardation films, and rod-shaped liquid crystals sold by JX Nippon Steel and Nissho Energy Co., Ltd. under the trade name of "NH FILM" are obliquely aligned films. The disc-shaped liquid crystals sold under the brand name of “WV FILM” by Fujifilm (stock) are obliquely aligned films. The fully biaxially-aligned type is sold by Sumitomo Chemical (stock) under the brand name of “VAC FILM” Membranes, biaxially oriented membranes, etc. that are also sold under the brand name "new VAC FILM" by Sumitomo Chemical Co., Ltd.
積層於相位差膜的至少一側的面之樹脂膜,例如可為上述的保護膜。 The resin film laminated on at least one surface of the retardation film may be, for example, the above-mentioned protective film.
配置於光學膜10與金屬層30之間的黏著劑層20,係由包含(甲基)丙烯酸系樹脂(A)、異氰酸酯系交聯劑(B)、矽烷化合物(C)及離子性化合物(D)之黏著劑組成物所構成。於該黏著劑組成物中之離子性化合物(D)係下述式(I):M+X- (I)所示的離子性化合物。式(I)中,M+表示無機陽離子,X-表示含有氟原子的陰離子。 The adhesive layer 20 disposed between the optical film 10 and the metal layer 30 is composed of a (meth) acrylic resin (A), an isocyanate-based crosslinking agent (B), a silane compound (C), and an ionic compound ( D) An adhesive composition. In the adhesive compositions in an ionic compound (D) based the following formula (I): M + X - ionic compound (I) shown below. In formula (I), M + represents an inorganic cation, and X − represents an anion containing a fluorine atom.
對(甲基)丙烯酸系樹脂(A)100重量份而言,上述黏著劑組成物含有0.01至2.5重量份的異氰酸酯系交聯劑(B)、0.01至10重量份的矽烷化合物(C)及0.2至8重量份的離子性化合物(D)。 For 100 parts by weight of the (meth) acrylic resin (A), the above-mentioned adhesive composition contains 0.01 to 2.5 parts by weight of an isocyanate-based crosslinking agent (B), 0.01 to 10 parts by weight of a silane compound (C), and 0.2 to 8 parts by weight of the ionic compound (D).
根據上述黏著劑組成物所構成的黏著劑層20,於包含黏著劑層20及金屬層30構成之光學積層體,可抑制金屬層30的腐蝕,而且,可提高附黏著劑層之光學膜1及光學積層體的耐久性。再者,根據上述黏著劑組成物所構成的黏著劑層20,附黏著劑層之光學膜1及光學積層體即使係黏著劑層20直接貼合於偏光片2而構成,也可顯示良好的光學耐久性。 According to the adhesive layer 20 composed of the above-mentioned adhesive composition, in the optical laminated body including the adhesive layer 20 and the metal layer 30, the corrosion of the metal layer 30 can be suppressed, and the optical film 1 with the adhesive layer can be improved. And the durability of optical laminates. In addition, according to the adhesive layer 20 composed of the above-mentioned adhesive composition, the optical film 1 and the optical laminate with the adhesive layer formed thereon can be displayed well even if the adhesive layer 20 is directly bonded to the polarizer 2. Optical durability.
黏著劑層20的厚度,通常為2至40μm,從附黏著劑層之光學膜1及光學積層體的耐久性、附黏著劑層之光學膜1的重工性等的觀點,較理想為5至30μm,更理想為10至25μm。而且,黏著劑層20的厚度為10μm以上時,黏著劑層20對光學膜10的尺寸變化之追隨性變好,25μm以下時,重工性變好。 The thickness of the adhesive layer 20 is usually 2 to 40 μm. From the viewpoints of the durability of the optical film 1 and the optical laminate with the adhesive layer, and the reworkability of the optical film 1 with the adhesive layer, it is more preferably 5 to 30 μm, more preferably 10 to 25 μm. In addition, when the thickness of the adhesive layer 20 is 10 μm or more, the followability of the adhesive layer 20 to the dimensional change of the optical film 10 is improved, and when it is 25 μm or less, reworkability is improved.
黏著劑層20,以於23至80℃的溫度範圍顯示0.1至5MPa的儲存彈性模數者較理想。藉此,可更有效地提高附黏著劑層之光學膜1及光學積層體的耐久性。所謂「於23至80℃的溫度範圍顯示0.1至5MPa的儲存彈性模數」,係指於該範圍的任一溫度,儲存彈性模數為上述範圍內的值。儲存彈性模數,通常伴隨溫度上升而漸減,23℃及80℃的儲存彈性模數為上述範圍內的話,於該溫度範圍,可顯示上述範圍內的儲存彈性模數。黏著劑層20的儲存彈性模數,可使用市售的黏彈性測定裝置,例如REOMETERIC公司製的黏彈性測定裝置「DYNAMIC ANALYZER RDA II」測定。 The adhesive layer 20 preferably exhibits a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80 ° C. Thereby, the durability of the optical film 1 and an optical laminated body with an adhesive layer can be improved more effectively. The so-called "displaying a storage elastic modulus in a temperature range of 23 to 80 ° C from 0.1 to 5 MPa" means any temperature in this range, and the storage elastic modulus is a value within the above range. The storage elastic modulus generally decreases with increasing temperature. If the storage elastic modulus at 23 ° C and 80 ° C is within the above range, the storage elastic modulus within the above range can be displayed in this temperature range. The storage elastic modulus of the adhesive layer 20 can be measured using a commercially available viscoelasticity measuring device, for example, a viscoelasticity measuring device "DYNAMIC ANALYZER RDA II" manufactured by REOMETERIC.
(甲基)丙烯酸系樹脂(A)係以來自(甲基)丙烯酸系單體的構成單元為主成分(較理想為包含50重量%以上)之聚合物或共聚物。(甲基)丙烯酸系單體,例如包括具有(甲基)丙烯醯基的單體,較理想為包括(甲基)丙烯酸烷酯。(甲基)丙烯酸烷酯所具有的烷基,其碳數較理想為1至14,更理想為1至12,更加理想為1至8,可為直鏈狀、分支狀或環狀。作為(甲基)丙烯酸烷酯,也可使用如後述於烷基導入取代基之含有取代基的丙烯酸烷酯之含有取代基之(甲基)丙烯酸烷酯。(甲基)丙烯酸烷酯,可只使用1種,亦可併用2種以上。 The (meth) acrylic resin (A) is a polymer or copolymer having a structural unit derived from a (meth) acrylic monomer as a main component (preferably containing 50% by weight or more). The (meth) acrylic monomer includes, for example, a monomer having a (meth) acrylfluorene group, and preferably includes an alkyl (meth) acrylate. The alkyl group of the alkyl (meth) acrylate preferably has a carbon number of 1 to 14, more preferably 1 to 12, and even more preferably 1 to 8, and may be linear, branched, or cyclic. As the alkyl (meth) acrylate, a substituent-containing alkyl (meth) acrylate containing a substituent-containing alkyl acrylate introduced into a substituent as described later can also be used. The alkyl (meth) acrylate may be used alone or in combination of two or more.
(甲基)丙烯酸烷酯的具體例,包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正-及異-丙酯、(甲基)丙烯酸正-、異-及第三-丁酯、(甲基)丙烯酸正-及異-戊酯、(甲基)丙烯酸正-及異-己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸正-及異-庚酯、(甲基)丙烯酸正-及異-辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正-及異-壬酯、(甲基)丙烯酸正-及異-癸酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸正-及異-十二烷酯、(甲基)丙烯酸硬脂酯等。 Specific examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, n- and iso-propyl (meth) acrylate, n-, (meth) acrylate, and iso -And third-butyl ester, n- and iso-pentyl (meth) acrylate, n- and iso-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n- (meth) acrylate- And iso-heptyl, n- and iso-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n- and iso-nonyl (meth) acrylate, and n- (meth) acrylate -And iso-decyl, isobornyl (meth) acrylate, n- and iso-dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like.
(甲基)丙烯酸系樹脂(A),以含有來自均聚物的玻璃轉移溫度Tg未達0℃之丙烯酸烷酯(a1)的構成單元及均聚物的Tg為0℃以上之丙烯酸烷酯(a2)的構成單元 較理想。如此有利於提高附黏著劑層之光學膜1及光學積層體的耐金屬腐蝕性及耐久性。丙烯酸烷酯的均聚物的Tg,例如可採用聚合物手冊(Polymer Handbook,Wiley-Interscience)等的文獻值。 The (meth) acrylic resin (A) contains a structural unit containing an alkyl acrylate (a1) having a glass transition temperature Tg of less than 0 ° C derived from the homopolymer and an alkyl acrylate having a Tg of the homopolymer of 0 ° C or higher The constituent unit of (a2) is preferable. This is beneficial to improve the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer. The Tg of the homopolymer of the alkyl acrylate can be, for example, a literature value such as the Polymer Handbook (Wiley-Interscience).
丙烯酸烷酯(a1)的具體例,包括丙烯酸乙酯、丙烯酸正-及異-丙酯、丙烯酸正-及異-丁酯、丙烯酸正-戊酯、丙烯酸正-及異-己酯、丙烯酸正-庚酯、丙烯酸正-及異-辛酯、丙烯酸2-乙基己酯、丙烯酸正-及異-壬酯、丙烯酸正-及異-癸酯、丙烯酸正-十二烷酯等烷基的碳數為2至12左右的丙烯酸烷酯。作為丙烯酸烷酯(a1)的其他具體例,可為例如烷基的碳數為2至12左右的丙烯酸烷酯中之烷基導入取代基之含有取代基的丙烯酸烷酯。含有取代基的丙烯酸烷酯的取代基,可為取代烷基的氫原子之基,其具體例包括苯基、烷氧基、苯氧基。作為含有取代基的丙烯酸烷酯,具體地例如丙烯酸2-甲氧基乙酯、丙烯酸乙氧基甲酯、丙烯酸苯氧基乙酯、苯氧基二乙二醇丙烯酸酯等。丙烯酸烷酯(a1)的烷基,可為具有脂環式構造,較理想為直鏈狀或分支狀的烷基。 Specific examples of the alkyl acrylate (a1) include ethyl acrylate, n- and iso-propyl acrylate, n- and iso-butyl acrylate, n-pentyl acrylate, n- and iso-hexyl acrylate, and n-acrylate -Heptyl, n- and iso-octyl acrylate, 2-ethylhexyl acrylate, n- and iso-nonyl acrylate, n- and iso-decyl acrylate, and n-dodecyl acrylate Alkyl acrylate having a carbon number of about 2 to 12. As another specific example of the alkyl acrylate (a1), for example, an alkyl acrylate containing a substituent may be used as the alkyl group-inducing substituent in the alkyl acrylate having an alkyl group having about 2 to 12 carbon atoms. The substituent of the alkyl acrylate containing a substituent may be a group substituted for a hydrogen atom of an alkyl group, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group. Specific examples of the alkyl acrylate containing a substituent include 2-methoxyethyl acrylate, ethoxymethyl acrylate, phenoxyethyl acrylate, and phenoxydiethylene glycol acrylate. The alkyl group of the alkyl acrylate (a1) may have an alicyclic structure, and is preferably a linear or branched alkyl group.
丙烯酸烷酯(a1),可只使用1種,亦可併用2種以上。其中,丙烯酸烷酯(a1)以包含選自丙烯酸乙酯、丙烯酸正-丁酯、丙烯酸2-乙基己酯之1種或2種以上較理想。從附黏著劑層之光學膜1所具有的黏著劑層20對光學膜10的追隨性、重工性的觀點,丙烯酸烷酯(a1)以包含丙烯酸正-丁酯較理想。 The alkyl acrylate (a1) may be used alone or in combination of two or more. Among them, the alkyl acrylate (a1) preferably contains one or two or more selected from the group consisting of ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. From the viewpoint of the followability and reworkability of the adhesive layer 20 of the optical film 1 with the adhesive layer to the optical film 10, it is preferable that the alkyl acrylate (a1) contains n-butyl acrylate.
丙烯酸烷酯(a2),係丙烯酸烷酯(a1)以外的丙烯酸烷酯。丙烯酸烷酯(a2)的具體例,包括丙烯酸甲酯、丙烯酸環己酯、丙烯酸異冰片酯、丙烯酸硬脂酯、丙烯酸第三丁酯等。 The alkyl acrylate (a2) is an alkyl acrylate other than the alkyl acrylate (a1). Specific examples of the alkyl acrylate (a2) include methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, stearyl acrylate, and tert-butyl acrylate.
丙烯酸烷酯(a2),可只使用1種,亦可併用2種以上。其中,從耐金屬腐蝕性及耐久性的觀點,丙烯酸烷酯(a2)包括丙烯酸甲酯、丙烯酸環己酯、丙烯酸異冰片酯等較理想,包括丙烯酸甲酯更理想。 The alkyl acrylate (a2) may be used alone or in combination of two or more. Among them, from the viewpoint of resistance to metal corrosion and durability, alkyl acrylate (a2) is preferably including methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, and the like, and methyl acrylate is more preferable.
(甲基)丙烯酸系樹脂(A)中來自丙烯酸烷酯(a2)的構成單元的含量,從附黏著劑層之光學膜1及光學積層體的耐金屬腐蝕性及耐久性的觀點,在構成(甲基)丙烯酸系樹脂(A)的全部構成單元100重量份中,較理想為10重量份以上,更理想為15重量份以上,更加理想為20重量份以上,特別理想為25重量份以上。而且,從黏著劑層20對光學膜10的追隨性及重工性的觀點,來自丙烯酸烷酯(a2)的構成單元的含量,較理想為70重量份以下,更理想為60重量份以下,更加理想為50重量份以下。 The content of the structural unit derived from the alkyl acrylate (a2) in the (meth) acrylic resin (A) is in terms of the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer Out of 100 parts by weight of all the constituent units of the (meth) acrylic resin (A), it is more preferably 10 parts by weight or more, more preferably 15 parts by weight or more, still more preferably 20 parts by weight or more, and even more preferably 25 parts by weight or more. . From the viewpoint of the followability and reworkability of the adhesive layer 20 to the optical film 10, the content of the constituent units derived from the alkyl acrylate (a2) is preferably 70 parts by weight or less, more preferably 60 parts by weight or less, and more preferably It is preferably 50 parts by weight or less.
(甲基)丙烯酸系樹脂(A),可含有來自丙烯酸烷酯(a1)及(a2)以外的其他單體的構成單元。(甲基)丙烯酸系樹脂(A),可只包含1種來自其他單體的構成單元,亦可包含2種以上。其他單體的具體例,表示如下。 The (meth) acrylic resin (A) may contain a structural unit derived from a monomer other than the alkyl acrylates (a1) and (a2). The (meth) acrylic resin (A) may contain only one kind of structural unit derived from another monomer, and may contain two or more kinds. Specific examples of other monomers are shown below.
作為具有極性官能基的單體,例如具有羥基、羧基、 取代或無取代胺基、環氧基等的雜環基等的取代基之(甲基)丙烯酸酯。具體地,例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-(2-羥基乙氧基)乙酯、(甲基)丙烯酸2-氯-2-羥基丙酯、(甲基)丙烯酸3-氯-2-羥基丙酯、二乙二醇單(甲基)丙烯酸酯等的具有羥基的單體;丙烯醯基嗎啉、乙烯基己內醯胺、N-乙烯基-2-吡咯啶酮、乙烯基吡啶、(甲基)丙烯酸四氫呋喃甲酯、己內酯改質丙烯酸四氫呋喃甲酯、(甲基)丙烯酸3,4-環氧基環己基甲酯、(甲基)丙烯酸環氧丙酯、2,5-二氫呋喃等的具有雜環基的單體;(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸二甲基胺基丙酯等的具有取代或無取代胺基的單體;(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯等的具有羧基的單體。其中,具有羥基的單體較理想,就(甲基)丙烯酸系樹脂(A)與交聯劑的反應性之點,具有羥基的(甲基)丙烯酸酯更理想。 Examples of the monomer having a polar functional group include (meth) acrylates having a substituent such as a hydroxyl group, a carboxyl group, a substituted or unsubstituted heterocyclic group such as an amine group, and an epoxy group. Specifically, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (2-hydroxyethoxy) (meth) acrylate (Hydroxy) ethyl ester, 2-chloro-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, etc. Monomers; allyl morpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, tetrahydrofuran methyl (meth) acrylate, tetrahydrofuran methyl acrylate modified Monomers having a heterocyclic group such as 3,4-epoxycyclohexyl methyl (meth) acrylate, propylene oxide (meth) acrylate, 2,5-dihydrofuran; (meth) acrylic acid Monomers with substituted or unsubstituted amino groups, such as aminoethyl esters, N, N-dimethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate; (methyl ) A monomer having a carboxyl group such as acrylic acid or carboxyethyl (meth) acrylate. Among these, a monomer having a hydroxyl group is preferable, and a (meth) acrylic acid ester having a hydroxyl group is more preferable in terms of the reactivity of the (meth) acrylic resin (A) and the crosslinking agent.
亦可與具有羥基的(甲基)丙烯酸酯一起含有具有上述其他極性官能基的單體,從防止可積層於黏著劑層20的外面之離型膜的剝離力亢進的觀點,以實質上不包含具有胺基的單體較理想。而且,從提高對ITO之耐腐蝕性的觀點,以實質上不包含具有羧基的單體較理想。此處所謂實質上不包含,係指構成(甲基)丙烯酸系樹脂(A)的全部構成單元100重量份中為0.1重量份以下。 The monomer having the above-mentioned other polar functional group may be contained together with the (meth) acrylate having a hydroxyl group. From the viewpoint of preventing the release force of the release film that can be laminated on the outer surface of the adhesive layer 20 from being excessively increased, It is desirable to include a monomer having an amine group. Further, from the viewpoint of improving the corrosion resistance to ITO, it is preferable to substantially not contain a monomer having a carboxyl group. The term "substantially not included" herein means that the total weight of all constituent units constituting the (meth) acrylic resin (A) is 0.1 part by weight or less.
例如N-羥甲基丙烯醯胺、N-(2-羥基乙基)丙烯醯胺、N-(3-羥基丙基)丙烯醯胺、N-(4-羥基丁基)丙烯醯胺、N-(5-羥基戊基)丙烯醯胺、N-(6-羥基己基)丙烯醯胺、N,N-二甲基丙烯醯胺、N,N-二乙基丙烯醯胺、N-異丙基丙烯醯胺、N-(3-二甲基胺基丙基)丙烯醯胺、N-(1,1-二甲基-3-側氧基丁基)丙烯醯胺、N-[2-(2-側氧基-1-咪唑啶基)乙基]丙烯醯胺、2-丙烯醯基胺基-2-甲基-1-丙烷磺酸、N-(甲氧基甲基)丙烯醯胺、N-(乙氧基甲基)丙烯醯胺、N-(丙氧基甲基)丙烯醯胺、N-(1-甲基乙氧基甲基)丙烯醯胺、N-(1-甲基丙氧基甲基)丙烯醯胺、N-(2-甲基丙氧基甲基)丙烯醯胺[別名:N-(異丁氧基甲基)丙烯醯胺]、N-(丁氧基甲基)丙烯醯胺、N-(1,1-二甲基乙氧基甲基)丙烯醯胺、N-(2-甲氧基乙基)丙烯醯胺、N-(2-乙氧基乙基)丙烯醯胺、N-(2-丙氧基乙基)丙烯醯胺、N-[2-(1-甲基乙氧基)乙基]丙烯醯胺、N-[2-(1-甲基丙氧基)乙基]丙烯醯胺、N-[2-(2-甲基丙氧基)乙基]丙烯醯胺[別名:N-(異丁氧基乙基)丙烯醯胺]、N-(2-丁氧基乙基)丙烯醯胺、N-[2-(1,1-二甲基乙氧基)乙基]丙烯醯胺等。其中,使用N-(甲氧基甲基)丙烯醯胺、N-(乙氧基甲基)丙烯醯胺、N-(丙氧基甲基)丙烯醯胺、N-(丁氧基甲基)丙烯醯胺、N-(2-甲基丙氧基甲基)丙烯醯胺較理想。 For example, N-hydroxymethyl acrylamide, N- (2-hydroxyethyl) acrylamide, N- (3-hydroxypropyl) acrylamide, N- (4-hydroxybutyl) acrylamide, N -(5-hydroxypentyl) acrylamide, N- (6-hydroxyhexyl) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropyl Acrylamide, N- (3-dimethylaminopropyl) acrylamide, N- (1,1-dimethyl-3-butoxybutyl) acrylamide, N- [2- (2-Pentoxy-1-imidazolidinyl) ethyl] acrylamidonium, 2-propenylaminoamino-2-methyl-1-propanesulfonic acid, N- (methoxymethyl) propenehydrazone Amine, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (1-methylethoxymethyl) acrylamide, N- (1- Methylpropoxymethyl) acrylamide, N- (2-methylpropoxymethyl) acrylamide [alias: N- (isobutoxymethyl) acrylamide], N- (butyl Oxymethyl) acrylamide, N- (1,1-dimethylethoxymethyl) acrylamide, N- (2-methoxyethyl) acrylamide, N- (2-ethyl (Oxyethyl) acrylamide, N- (2-propoxyethyl) acrylamide, N- [2- (1-methylethoxy) ethyl] acrylamide, N- [2- (1-methylpropane (Yl) ethyl] acrylamide, N- [2- (2-methylpropoxy) ethyl] acrylamide [alias: N- (isobutoxyethyl) acrylamide], N- ( 2-butoxyethyl) acrylamide, N- [2- (1,1-dimethylethoxy) ethyl] acrylamide, and the like. Among them, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) ) Acrylamide and N- (2-methylpropoxymethyl) acrylamide are preferred.
例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲基丙烯酸正辛酯、甲基丙烯 酸月桂酯等的甲基丙烯酸的直鏈狀烷酯;甲基丙烯酸異丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸異辛酯等的甲基丙烯酸的分支狀烷酯;甲基丙烯酸異冰片酯、甲基丙烯酸環己酯、甲基丙烯酸二環戊酯、甲基丙烯酸環十二烷酯、甲基丙烯酸甲基環己酯、甲基丙烯酸三甲基環己酯、甲基丙烯酸第三丁基環己酯、甲基丙烯酸環己基苯酯等的甲基丙烯酸的脂環式烷酯;甲基丙烯酸2-甲氧基乙酯、甲基丙烯酸乙氧基甲酯等的甲基丙烯酸的烷氧基烷酯;甲基丙烯酸苯甲酯等的甲基丙烯酸的芳烷酯;甲基丙烯酸2-羥基乙酯、甲基丙烯酸3-羥基丙酯、甲基丙烯酸4-羥基丁酯、甲基丙烯酸2-(2-羥基乙氧基)乙酯、甲基丙烯酸2-氯-2-羥基丙酯、甲基丙烯酸3-氯-2-羥基丙酯、二乙二醇單甲基丙烯酸酯等的具有羥基的甲基丙烯酸的烷酯;甲基丙烯酸胺基乙酯、甲基丙烯酸N,N-二甲基胺基乙酯、甲基丙烯酸二甲基胺基丙酯等的具有取代或無取代胺基的甲基丙烯酸的烷酯;甲基丙烯酸2-苯氧基乙酯、甲基丙烯酸2-(2-苯氧基乙氧基)乙酯、(甲基)丙烯酸的環氧乙烷改質壬基苯酚酯、甲基丙烯酸2-(鄰-苯基苯氧基)乙酯等的具有苯氧基乙基的甲基丙烯酸的酯等。 For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, lauryl methacrylate and the like are linear alkyl methacrylates; Branched alkyl methacrylates such as isobutyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate; isobornyl methacrylate, cyclohexyl methacrylate, methyl Dicyclopentyl acrylate, cyclododecyl methacrylate, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, third butyl cyclohexyl methacrylate, cyclohexyl methacrylate Alicyclic alkyl esters of methacrylic acid such as phenyl esters; alkoxyalkyl esters of methacrylic acid such as 2-methoxyethyl methacrylate and ethoxymethyl methacrylate; benzoyl methacrylate Aryl methacrylates such as esters; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2- (2-hydroxyethoxy methacrylate) ) Ethyl ester, 2-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxy methacrylate Alkyl esters of methacrylic acid having a hydroxyl group such as esters, diethylene glycol monomethacrylate; aminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, dimethacrylate Alkyl esters of methacrylic acid having substituted or unsubstituted amine groups such as methylaminopropyl ester; 2-phenoxyethyl methacrylate, 2- (2-phenoxyethoxy) ethyl methacrylate Esters, ethylene oxide modified nonylphenol esters of (meth) acrylic acid, esters of methacrylic acid having phenoxyethyl groups such as 2- (o-phenylphenoxy) ethyl methacrylate, etc. .
例如對應上述1)記載的丙烯醯胺系單體之甲基丙烯醯胺系單體。 For example, a methacrylamide-based monomer corresponding to the acrylamide-based monomer described in 1) above.
例如苯乙烯;如甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、三乙基苯乙烯、丙基苯乙烯、丁基苯乙烯、己基苯乙烯、庚基苯乙烯、辛基苯乙烯等的烷基苯乙烯;如氟苯乙烯、氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯等的鹵化苯乙烯;硝基苯乙烯;乙醯基苯乙烯;甲氧基苯乙烯;二乙烯基苯等。 For example, styrene; such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexyl Alkylstyrenes such as styrene, heptylstyrene, octylstyrene, etc .; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene, etc .; nitrostyrene ; Ethyl styrene; methoxystyrene; divinylbenzene and the like.
例如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯等的脂肪酸乙烯酯;氯化乙烯、溴化乙烯等的鹵化乙烯;氯化亞乙烯的鹵化亞乙烯;乙烯基吡啶、乙烯基吡咯啶酮、乙烯基咔唑等的含氮芳香族乙烯;如丁二烯、異戊二烯、氯丁二烯等的共軛二烯單體;丙烯腈、甲基丙烯腈等的不飽和腈等。 For example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, and other fatty acid vinyl esters; vinyl chloride, vinyl bromide, and other halogenated ethylene; vinyl chloride Halogenated vinylidene; nitrogen-containing aromatic vinyl such as vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc .; conjugated diene monomers such as butadiene, isoprene, chloroprene, etc .; Unsaturated nitriles such as acrylonitrile and methacrylonitrile.
例如1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等的分子內具有2個(甲基)丙烯醯基的單體;三羥甲基丙烷三(甲基)丙烯酸酯等的分子內具有3個(甲基)丙烯醯基的單體等。 For example 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, ethylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, etc. have two (methyl) ) Monomers of acryl fluorenyl group; monomers having three (meth) acryl fluorenyl groups in the molecule such as trimethylolpropane tri (meth) acrylate and the like.
如上述,(甲基)丙烯酸系樹脂(A),從附黏 著劑層之光學膜1及光學積層體的耐久性及耐金屬腐蝕性的觀點,除了來自(甲基)丙烯酸烷酯的構成單元外,以包含來自具有極性官能基的單體之構成單元較理想。具有極性官能基的單體,較理想為具有極性官能基的(甲基)丙烯酸酯系單體,更理想為具有羥基的單體。來自具有極性官能基的單體之構成單元的含量,在構成(甲基)丙烯酸系樹脂(A)的全部構成單元100重量份中,較理想為0.1至10重量份,更理想為0.25至5重量份,更加理想為0.5至5重量份。 As described above, the (meth) acrylic resin (A), from the viewpoint of the durability and metal corrosion resistance of the optical film 1 and the optical laminated body with the adhesive layer, is the constituent unit derived from the alkyl (meth) acrylate In addition, it is preferable to include a structural unit derived from a monomer having a polar functional group. The monomer having a polar functional group is more preferably a (meth) acrylate-based monomer having a polar functional group, and more preferably a monomer having a hydroxyl group. The content of the constituent unit derived from the monomer having a polar functional group is preferably from 0.1 to 10 parts by weight and more preferably from 0.25 to 5 out of 100 parts by weight of all the constituent units constituting the (meth) acrylic resin (A). It is more preferably 0.5 to 5 parts by weight.
而且,從附黏著劑層之光學膜1的重工性的觀點,(甲基)丙烯酸系樹脂(A)以來自甲基丙烯酸酯(甲基丙烯酸的酯)、甲基丙烯醯胺系單體等的甲基丙烯酸系單體之構成單元的含量少較理想,具體地該構成單元的含量,在構成(甲基)丙烯酸系樹脂(A)的全部構成單元100重量份中,較理想為10重量份以下,更理想為5重量份以下,更加理想為實質上不含有該構成單元(0.1重量份以下)。 Further, from the viewpoint of reworkability of the optical film 1 with the adhesive layer, the (meth) acrylic resin (A) is derived from a methacrylate (methacrylic acid ester), a methacrylamide-based monomer, or the like The content of the constituent units of the methacrylic monomer is preferably less. Specifically, the content of the constituent units is preferably 10 parts by weight based on 100 parts by weight of all constituent units constituting the (meth) acrylic resin (A). 5 parts by weight or less, more preferably 5 parts by weight or less, and more preferably, the constituent unit is not substantially contained (0.1 parts by weight or less).
(甲基)丙烯酸系樹脂(A),於凝膠滲透層析儀(GPC)之排出曲線上的重量平均分子量Mw1000至250萬的範圍,具有單一波峰較理想,於Mw1000至250萬的範圍具有單一波峰且含有來自丙烯酸烷酯(a1)及(a2)的構成單元更理想。以此種(甲基)丙烯酸系樹脂(A)為基質聚合物之黏著劑層20,在提高附黏著劑層之光學膜1及光學積層體的耐久性有利。於上述Mw的範圍之波峰數為2以上的情況,有無法得到充分耐久性的傾向。 The (meth) acrylic resin (A) has a weight average molecular weight on the discharge curve of a gel permeation chromatograph (GPC) in the range of Mw 10 to 2.5 million, and preferably has a single peak, and in the range of Mw 1000 to 2.5 million It is more preferable that it has a single peak and contains a structural unit derived from the alkyl acrylates (a1) and (a2). The adhesive layer 20 using such a (meth) acrylic resin (A) as a matrix polymer is advantageous in improving the durability of the optical film 1 and the optical laminate with the adhesive layer. In the case where the number of peaks in the above-mentioned range of Mw is 2 or more, there is a tendency that sufficient durability cannot be obtained.
求出Mw1000至250萬的範圍之GPC排出曲線的波峰數,係根據實施例的項目記載的GPC測定條件,取得排出曲線。於所得之排出曲線的上述範圍,所謂「具有單一波峰」,係指於Mw1000至250萬的範圍只具有1個極大值。於本說明書,於GPC排出曲線,將S/N比為30以上者定義為波峰。 The number of peaks of the GPC discharge curve in the range of Mw1000 to 2.5 million was determined, and the discharge curve was obtained according to the GPC measurement conditions described in the item of the example. In the above range of the obtained discharge curve, the so-called "having a single peak" means that the range of Mw1000 to 2.5 million has only one maximum value. In this specification, a peak is defined as a G / C discharge curve with an S / N ratio of 30 or more.
(甲基)丙烯酸系樹脂(A),其根據GPC的換算標準聚苯乙烯的Mw以50萬至250萬的範圍較理想,60萬至200萬的範圍更理想。Mw為50萬以上時,有利於提高附黏著劑層之光學膜1及光學積層體的耐金屬腐蝕性及耐久性,也有提高附黏著劑層之光學膜1的重工性之傾向。而且,Mw為250萬以下時,黏著劑層20對光學膜10的尺寸變化之追隨性變好。以重量平均分子量Mw與數量平均分子量Mn的比Mw/Mn表示之分子量分佈,通常為2至10。(甲基)丙烯酸系樹脂(A)的Mw及Mn,可根據實施例的項目記載的GPC測定條件求得。 According to the (meth) acrylic resin (A), the Mw of polystyrene according to the GPC conversion standard is preferably in the range of 500,000 to 2.5 million, and more preferably in the range of 600,000 to 2 million. When Mw is 500,000 or more, it is beneficial to improve the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer, and it also tends to improve the reworkability of the optical film 1 with the adhesive layer. When Mw is 2.5 million or less, the followability of the adhesive layer 20 to the dimensional change of the optical film 10 is improved. The molecular weight distribution represented by the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is usually 2 to 10. Mw and Mn of the (meth) acrylic resin (A) can be determined according to the GPC measurement conditions described in the items of the examples.
(甲基)丙烯酸系樹脂(A),溶解於乙酸乙酯作為濃度20重量%的溶液時,以25℃之黏度為20Pa‧s以下較理想,0.1至7Pa‧s更理想。如此的範圍之黏度,有利於附黏著劑層之光學膜1及光學積層體的耐久性之提高、附黏著劑層之光學膜1的重工性。上述黏度,可藉由布氏(Brookfield)黏度計測定。 When the (meth) acrylic resin (A) is dissolved in ethyl acetate as a solution having a concentration of 20% by weight, a viscosity at 25 ° C. of 20 Pa · s or less is preferable, and 0.1 to 7 Pa · s is more preferable. A viscosity in such a range is advantageous for improving the durability of the optical film 1 and the optical laminate with the adhesive layer, and the reworkability of the optical film 1 with the adhesive layer. The above viscosity can be measured by a Brookfield viscometer.
(甲基)丙烯酸系樹脂(A),藉由示差掃描熱量計(DSC)測定之玻璃轉移溫度Tg為-60至-10℃較理想, -55至-15℃更理想。如此的範圍之Tg,有利於附黏著劑層之光學膜1及光學積層體的耐金屬腐蝕性及耐久性之提高。 The (meth) acrylic resin (A) has a glass transition temperature Tg measured by a differential scanning calorimeter (DSC) of preferably -60 to -10 ° C, and more preferably -55 to -15 ° C. A Tg in this range is advantageous for improving the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer.
黏著劑組成物,可含有2種以上屬於(甲基)丙烯酸系樹脂(A)之(甲基)丙烯酸系樹脂。而且,黏著劑組成物,亦可含有不同於(甲基)丙烯酸系樹脂(A)之其他(甲基)丙烯酸系樹脂。但是,從附黏著劑層之光學膜1及光學積層體的耐金屬腐蝕性及耐久性的觀點,(甲基)丙烯酸系樹脂(A)的含量,在全部的(甲基)丙烯酸系樹脂的合計中,較理想為70重量%以上,更理想為80重量%以上,更加理想為90重量%以上,黏著劑組成物以只含有(甲基)丙烯酸系樹脂(A)作為基質聚合物者特別理想。 The adhesive composition may contain two or more types of (meth) acrylic resins that belong to the (meth) acrylic resin (A). Moreover, the adhesive composition may contain other (meth) acrylic resin other than (meth) acrylic resin (A). However, from the viewpoint of the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer, the content of the (meth) acrylic resin (A) is the same as that of the entire (meth) acrylic resin. In the total, it is more preferably 70% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more. The adhesive composition is particularly one containing only (meth) acrylic resin (A) as a matrix polymer. ideal.
(甲基)丙烯酸系樹脂(A)或依需要可併用的其他(甲基)丙烯酸系樹脂,可藉由例如溶液聚合法、總體聚合法、懸浮聚合法、乳化聚合法等習知的方法而製造。於(甲基)丙烯酸系樹脂的製造,通常使用聚合引發劑。聚合引發劑,對(甲基)丙烯酸系樹脂的製造所使用的全部單體的合計100重量份而言,使用0.001至5重量份左右。而且,(甲基)丙烯酸系樹脂,例如亦可藉由紫外線等活性能量線使其進行聚合的方法製造。 The (meth) acrylic resin (A) or other (meth) acrylic resin that can be used in combination as required can be obtained by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method. Manufacturing. For the production of (meth) acrylic resins, a polymerization initiator is usually used. The polymerization initiator is used in an amount of about 0.001 to 5 parts by weight based on 100 parts by weight of the total of all the monomers used in the production of the (meth) acrylic resin. The (meth) acrylic resin can also be produced by, for example, a method of polymerizing an active energy ray such as ultraviolet rays.
作為聚合引發劑,可使用熱聚合引發劑、光聚合引發劑等。作為光聚合引發劑,例如4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮等。作為熱聚合引發劑,例如2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮 雙(環己烷-1-甲腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基-2,2’-偶氮雙(2-甲基丙酸酯)、2,2’-偶氮雙(2-羥基甲基丙腈)之偶氮系化合物;如過氧化月桂基、過氧化第三丁基、過氧化苯甲醯、過氧化苯甲酸第三丁酯、過氧化氫異丙苯、過氧化二碳酸二異丙酯、過氧化二碳酸二丙酯、過氧化新癸酸第三丁酯、過氧化新戊酸第三丁酯、過氧化(3,5,5-三甲基己醯基)之有機過氧化物;如過硫酸鉀、過硫酸銨、過氧化氫之無機過氧化物等。而且,過氧化物與還原劑併用的氧化還原系引發劑等,也可使用作為聚合引發劑。 As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like can be used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone. As the thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1) -Nitrile), 2,2'-Azobis (2,4-dimethylvaleronitrile), 2,2'-Azobis (2,4-dimethyl-4-methoxyvaleronitrile) Azo compounds such as dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-hydroxymethylpropionitrile); such as laurel peroxide Base, third butyl peroxide, benzoylperoxide, third butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, peroxidation Tertiary butyl neodecanoate, tertiary butyl peroxypivalate, organic peroxides (3,5,5-trimethylhexyl) peroxide; such as potassium persulfate, ammonium persulfate, persulfate Inorganic peroxides such as hydrogen oxide. Further, a redox-based initiator used in combination with a peroxide and a reducing agent can also be used as a polymerization initiator.
作為(甲基)丙烯酸系樹脂的製造方法,上述所示的方法中,較理想為溶液聚合法。溶液聚合法的一例,係將所使用的單體與有機溶劑混合,在氮氣環境下添加熱聚合引發劑,於40至90℃左右,較理想為50至80℃左右攪拌3至15小時左右。為了控制反應,聚合中可連續地或間歇地添加單體、熱聚合引發劑,亦可在溶解於有機溶劑的狀態添加。作為有機溶劑,例如可使用如甲苯、二甲苯的芳香族烴類;如乙酸乙酯、乙酸丁酯的酯類;如丙醇、異丙醇等的脂肪族醇類;如丙酮、甲基乙基酮、甲基異丁基酮等的酮類等。 As a method for producing a (meth) acrylic resin, among the methods described above, a solution polymerization method is preferred. An example of the solution polymerization method is to mix the monomers used with an organic solvent, add a thermal polymerization initiator under a nitrogen atmosphere, and stir at about 40 to 90 ° C, preferably about 50 to 80 ° C, for about 3 to 15 hours. In order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization, or may be added in a state of being dissolved in an organic solvent. As the organic solvent, for example, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropyl alcohol; such as acetone and methyl ethyl Ketones such as methyl ketone and methyl isobutyl ketone.
黏著劑組成物含有異氰酸酯系交聯劑(B)。藉由使用異氰酸酯系交聯劑(B)作為交聯劑,可提高附黏著劑層之光學 膜1及光學積層體的耐金屬腐蝕性及耐久性。異氰酸酯系交聯劑(B),可使用單獨1種,亦可併用2種以上。 The adhesive composition contains an isocyanate-based crosslinking agent (B). By using the isocyanate-based crosslinking agent (B) as the crosslinking agent, it is possible to improve the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer. The isocyanate-based crosslinking agent (B) may be used singly or in combination of two or more kinds.
異氰酸酯系交聯劑(B),係分子內具有至少2個異氰酸酯基(-NCO)的化合物,具體地,例如伸甲苯基二異氰酸酯、六亞甲基二異氰酸酯、異佛酮二異氰酸酯、伸二甲苯基二異氰酸酯、氫化伸二甲苯基二異氰酸酯、二苯基甲烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、伸萘基二異氰酸酯、三苯基甲烷三異氰酸酯等。而且,異氰酸酯系交聯劑(B),亦可為該等異氰酸酯化合物的多元醇化合物加成物(例如丙三醇、三羥甲基丙烷的加成物)、異氰脲酸酯化合物、縮二脲(biuret)型化合物、再者與聚醚聚醇、聚酯聚醇、丙烯酸聚醇、聚丁二烯聚醇、聚異戊二烯聚醇等的加成反應的胺酯預聚物型異氰酸酯化合物等的衍生物。上述之中,特別是伸甲苯基二異氰酸酯、六亞甲基二異氰酸酯、伸二甲苯基二異氰酸酯或該等異氰酸酯化合物的多元醇化合物加成物較理想,從附黏著劑層之光學膜1及光學積層體的耐久性的觀點,以伸二甲苯基二異氰酸酯或其多元醇化合物加成物更理想。 Isocyanate-based crosslinking agent (B) is a compound having at least two isocyanate groups (-NCO) in the molecule, and specifically, for example, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene Diisocyanate, hydrogenated xylyl diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthyl diisocyanate, triphenylmethane triisocyanate, and the like. The isocyanate-based crosslinking agent (B) may be an adduct of a polyol compound of the isocyanate compound (for example, an adduct of glycerol or trimethylolpropane), an isocyanurate compound, or a polycondensate. Biuret type compounds, and amine ester prepolymers with addition reactions such as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. Derivatives such as isocyanate compounds. Among the above, in particular, xylylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, or polyol compound adducts of these isocyanate compounds are preferable. From the optical film 1 and the From the viewpoint of the durability of the laminated body, a xylylene diisocyanate or an adduct of a polyol compound thereof is more preferable.
異氰酸酯系交聯劑(B)的含量,對(甲基)丙烯酸系樹脂(A)100重量份而言,較理想為0.01至2.5重量份,更理想為0.1至2重量份(例如1重量份以下)。異氰酸酯系交聯劑(B)的含量為該範圍時,在附黏著劑層之光學膜1及光學積層體兼具耐金屬腐蝕性及耐久性有利。 The content of the isocyanate-based crosslinking agent (B) is preferably 0.01 to 2.5 parts by weight, and more preferably 0.1 to 2 parts by weight (for example, 1 part by weight) for 100 parts by weight of the (meth) acrylic resin (A). the following). When the content of the isocyanate-based cross-linking agent (B) is within this range, the optical film 1 and the optical laminated body with the adhesive layer are both excellent in metal corrosion resistance and durability.
黏著劑組成物,與異氰酸酯系交聯劑(B)一 起,可併用其以外的交聯劑,係例如環氧化合物、氮丙啶(aziridine)化合物、金屬鉗合物化合物、過氧化物等,從附黏著劑層之光學膜1及光學積層體的耐金屬腐蝕性及耐久性的觀點,黏著劑組成物以只含有異氰酸酯系交聯劑(B),特別是實質上不包含過氧化物者較理想。此處所謂實質上不包含,係指對(甲基)丙烯酸系樹脂(A)100重量份而言,含量為0.01重量份以下。 The adhesive composition may be used together with the isocyanate-based crosslinking agent (B), and other crosslinking agents such as epoxy compounds, aziridine compounds, metal clamp compounds, peroxides, etc. From the standpoint of the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer, the adhesive composition contains only an isocyanate-based crosslinking agent (B), and particularly does not substantially contain a peroxide. More ideal. The term "substantially not included" means that the content of the (meth) acrylic resin (A) is 0.01 parts by weight or less.
黏著劑組成物含有矽烷化合物(C)。藉此,可提高黏著劑層20與金屬層30、玻璃基板等的密著性。亦可使用2種以上的矽烷化合物(C)。 The adhesive composition contains a silane compound (C). Thereby, the adhesiveness of the adhesive layer 20, the metal layer 30, a glass substrate, etc. can be improved. Two or more kinds of silane compounds (C) may be used.
作為矽烷化合物(C),例如乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基乙氧基二甲基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等。 Examples of the silane compound (C) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylium Oxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.
矽烷化合物(C)係亦可包含聚矽氧寡聚物型者。聚矽氧寡聚物以單體彼此組合的形式表示時,如以下所示者。 The silane compound (C) may include a polysiloxane oligomer type. When the polysiloxane oligomer is expressed as a combination of monomers, it is as shown below.
3-巰基丙基三甲氧基矽烷-四甲氧基矽烷寡聚物、3-巰基丙基三甲氧基矽烷-四乙氧基矽烷寡聚物、3-巰基丙基三乙氧基矽烷-四甲氧基矽烷寡聚物、3-巰基丙基三乙氧基矽烷-四乙氧基矽烷寡聚物等的含有巰基丙基的寡聚物;巰基甲基三甲氧基矽烷-四甲氧基矽烷寡聚物、巰基甲基三甲氧基矽烷-四乙氧基矽烷寡聚物、巰基甲基三乙氧基矽烷-四甲氧基矽烷寡聚物、巰基甲基三乙氧基矽烷-四乙氧基矽烷寡聚物等的含有巰基甲基的寡聚物;3-環氧丙氧基丙基三甲氧基矽烷-四甲氧基矽烷寡聚物、3-環氧丙氧基丙基三甲氧基矽烷-四乙氧基矽烷寡聚物、3-環氧丙氧基丙基三乙氧基矽烷-四甲氧基矽烷寡聚物、3-環氧丙氧基丙基三乙氧基矽烷-四乙氧基矽烷寡聚物、3-環氧丙氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷寡聚物、3-環氧丙氧基丙基甲基二甲氧基矽烷-四乙氧基矽烷寡聚物、3-環氧丙氧基丙基甲基二乙氧基矽烷-四甲氧基矽烷寡聚物、 3-環氧丙氧基丙基甲基二乙氧基矽烷-四乙氧基矽烷寡聚物等的含有3-環氧丙氧基丙基的寡聚物;3-甲基丙烯醯氧基丙基三甲氧基矽烷-四甲氧基矽烷寡聚物、3-甲基丙烯醯氧基丙基三甲氧基矽烷-四乙氧基矽烷寡聚物、3-甲基丙烯醯氧基丙基三乙氧基矽烷-四甲氧基矽烷寡聚物、3-甲基丙烯醯氧基丙基三乙氧基矽烷-四乙氧基矽烷寡聚物、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷寡聚物、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷-四乙氧基矽烷寡聚物、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷-四甲氧基矽烷寡聚物、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷-四乙氧基矽烷寡聚物等的含有甲基丙烯醯氧基丙基的寡聚物;3-丙烯醯氧基丙基三甲氧基矽烷-四甲氧基矽烷寡聚物、3-丙烯醯氧基丙基三甲氧基矽烷-四乙氧基矽烷寡聚物、3-丙烯醯氧基丙基三乙氧基矽烷-四甲氧基矽烷寡聚物、 3-丙烯醯氧基丙基三乙氧基矽烷-四乙氧基矽烷寡聚物、3-丙烯醯氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷寡聚物、3-丙烯醯氧基丙基甲基二甲氧基矽烷-四乙氧基矽烷寡聚物、3-丙烯醯氧基丙基甲基二乙氧基矽烷-四甲氧基矽烷寡聚物、3-丙烯醯氧基丙基甲基二乙氧基矽烷-四乙氧基矽烷寡聚物等的含有丙烯醯氧基丙基的寡聚物;乙烯基三甲氧基矽烷-四甲氧基矽烷寡聚物、乙烯基三甲氧基矽烷-四乙氧基矽烷寡聚物、乙烯基三乙氧基矽烷-四甲氧基矽烷寡聚物、乙烯基三乙氧基矽烷-四乙氧基矽烷寡聚物、乙烯基甲基二甲氧基矽烷-四甲氧基矽烷寡聚物、乙烯基甲基二甲氧基矽烷-四乙氧基矽烷寡聚物、乙烯基甲基二乙甲氧基矽烷-四甲氧基矽烷寡聚物、乙烯基甲基二乙氧基矽烷-四乙氧基矽烷寡聚物等的含有乙烯基的寡聚物;3-胺基丙基三甲氧基矽烷-四甲氧基矽烷寡聚物、3-胺基丙基三甲氧基矽烷-四乙氧基矽烷寡聚物、3-胺基丙基三乙氧基矽烷-四甲氧基矽烷寡聚物、3-胺基丙基三乙氧基矽烷-四乙氧基矽烷寡聚物、3-胺基丙基甲基二甲氧基矽烷-四甲氧基矽烷寡聚物、 3-胺基丙基甲基二甲氧基矽烷-四乙氧基矽烷寡聚物、3-胺基丙基甲基二乙氧基矽烷-四甲氧基矽烷寡聚物、3-胺基丙基甲基二乙氧基矽烷-四乙氧基矽烷寡聚物等的含有胺基的寡聚物等。 3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane Mercaptopropyl-containing oligomers such as methoxysilane oligomers, 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomers; mercaptomethyltrimethoxysilane-tetramethoxy Silane oligomer, mercaptomethyltrimethoxysilane-tetraethoxysilane oligomer, mercaptomethyltriethoxysilane-tetramethoxysilane oligomer, mercaptomethyltriethoxysilane-tetraol Mercaptomethyl-containing oligomers such as ethoxysilane oligomers; 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane oligomers, 3-glycidoxypropyl Trimethoxysilane-tetraethoxysilane oligomer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropyltriethoxy Silane-tetraethoxysilane oligomer, 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropylmethyldi Methoxysilane-tetraethoxysilane Oligomer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropylmethyldiethoxysilane-tetraethoxy 3-glycidyloxypropyl-containing oligomers such as silane oligomers; 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane oligomers, 3-methyl Acrylic methoxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-methacrylic acid propyltriethoxysilane-tetramethoxysilane oligomer, 3-methylpropene Methoxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-methyl Propylene alkoxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer Oligomers including methacryloxypropyl, 3, 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomers; Trimethoxysilane-tetramethoxysilane oligomer, 3-propenefluorene Propyltrimethoxysilane-tetraethoxysilane oligomer, 3-propenyloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropyltriethyl Oxysilane-tetraethoxysilane oligomer, 3-propenyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldimethyl Oxysilane-tetraethoxysilane oligomer, 3-propenyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldiethyl Propylene methoxypropyl group-containing oligomers such as oxysilane-tetraethoxysilane oligomer; vinyltrimethoxysilane-tetramethoxysilane oligomer, vinyltrimethoxysilane-tetrayl Ethoxysilane oligomer, vinyltriethoxysilane-tetramethoxysilane oligomer, vinyltriethoxysilane-tetraethoxysilane oligomer, vinylmethyldimethoxy Silane-tetramethoxysilane oligomer, vinylmethyldimethoxysilane-tetraethoxysilane oligomer, vinylmethyldiethoxysilane-tetramethoxysilane oligomer, Vinyl armor Vinyl-containing oligomers such as didiethoxysilane-tetraethoxysilane oligomer; 3-aminopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-aminopropyl Trimethoxysilane-tetraethoxysilane oligomer, 3-aminopropyltriethoxysilane-tetramethoxysilane oligomer, 3-aminopropyltriethoxysilane-tetraethyl Oxysilane oligomer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane oligomer Polymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane oligomer, etc. Amine-containing oligomers and the like.
黏著劑組成物中,矽烷化合物(C)的含量,對(甲基)丙烯酸系樹脂(A)100重量份而言為0.01至10重量份,較理想為0.03至5重量份,更理想為0.05至2重量份,更加理想為0.1至1重量份。矽烷化合物(C)的量為0.01重量份以上時,容易得到黏著劑層20與金屬層30、玻璃基板等的密著性的提高效果。含量為10重量份以下時,可抑制矽烷化合物(C)從黏著劑層20的滲出。 The content of the silane compound (C) in the adhesive composition is 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, and more preferably 0.05 for 100 parts by weight of the (meth) acrylic resin (A). To 2 parts by weight, more preferably 0.1 to 1 part by weight. When the amount of the silane compound (C) is 0.01 parts by weight or more, the effect of improving the adhesion of the adhesive layer 20, the metal layer 30, a glass substrate, and the like is easily obtained. When the content is 10 parts by weight or less, bleeding of the silane compound (C) from the adhesive layer 20 can be suppressed.
黏著劑組成物含有離子性化合物(D)。離子性化合物(D),係下述式(I):M+X- (I)(式(I)中,M+表示無機陽離子,X-表示含有氟原子的陰離子)所示的離子性化合物。藉由使用離子性化合物(D),不僅可賦予黏著劑層20良好的抗靜電功能,又可賦予良好的耐金屬腐蝕性及光學耐久性。黏著劑組成物可含有1種或2種以上的離子性化合物(D)。 The adhesive composition contains an ionic compound (D). Ionic compound (D), based the following formula (I): M + X - (I) ( in the formula (I), M + represents an inorganic cation, X - represents an anion containing fluorine atoms) represented by ionic compound . By using the ionic compound (D), not only the antistatic function of the adhesive layer 20 can be provided, but also good metal corrosion resistance and optical durability can be provided. The adhesive composition may contain one or two or more ionic compounds (D).
上述式(I)中,M+表示無機陽離子。無機陽離子的具體例,包括鋰陽離子[Li+]、鈉陽離子[Na+]、鉀陽離子[K+]、銫陽離子[Cs+]等的鹼金屬離子;鈹陽離子 [Be2+]、鎂陽離子[Mg2+]、鈣陽離子[Ca2+]等的鹼土金屬離子等。其中,從附黏著劑層之光學膜1及光學積層體的耐金屬腐蝕性的觀點,以使用鋰陽離子[Li+]、鈉陽離子[Na+]、鉀陽離子[K+]較理想,從附黏著劑層之光學膜1及光學積層體的耐久性的觀點,使用鉀陽離子[K+]更理想。 In the formula (I), M + represents an inorganic cation. Specific examples of the inorganic cation include alkali metal ions such as lithium cation [Li + ], sodium cation [Na + ], potassium cation [K + ], cesium cation [Cs + ]; beryllium cation [Be 2+ ], and magnesium cation Alkaline earth metal ions such as [Mg 2+ ], calcium cation [Ca 2+ ], and the like. Among them, it is preferable to use lithium cation [Li + ], sodium cation [Na + ], and potassium cation [K + ] from the viewpoint of the metal corrosion resistance of the optical film 1 with the adhesive layer and the optical laminate. From the viewpoint of durability of the optical film 1 and the optical laminate of the adhesive layer, it is more preferable to use potassium cation [K + ].
上述式(I)中,X-表示含有氟原子的陰離子。含有氟原子的陰離子,有容易賦予抗靜電功能佳的離子性化合物(D)之傾向。含有氟原子的陰離子,可使用無機陰離子及有機陰離子的任一者。可構成離子性化合物(D)的無機陰離子的具體例,包括四氟硼酸根陰離子[BF4 -]、六氟磷酸根陰離子[PF6 -]、六氟砷酸根陰離子[AsF6 -]、六氟銻酸根陰離子[SbF6 -]、六氟鈮酸根陰離子[NbF6 -]、六氟鉭酸根陰離子[TaF6 -]、雙(氟磺醯基)亞胺陰離子[(FSO2)2N-]、(聚)氟化氫氟化物陰離子[F(HF)n -](n為1至3左右)等。 In the above formula (I), X - represents an anion containing a fluorine atom. The anion containing a fluorine atom tends to easily impart an ionic compound (D) having an excellent antistatic function. As the anion containing a fluorine atom, either an inorganic anion or an organic anion can be used. Specific examples of inorganic anions can form ionic compound (D), comprising tetrafluoroborate anion [BF 4 -], hexafluorophosphate anions [PF 6 -], hexafluoroarsenate anion [AsF 6 -], six hexafluoroarsenate anion [SbF 6 -], niobium hexafluorophosphate anion [NbF 6 -], six tantalum fluoride anion [TaF 6 -], bis (sulfo-fluoro-acyl) imide anion [(FSO 2) 2 N - ], (poly) fluoride anion fluoride [F (HF) n -] (n is about 1 to 3) and the like.
可構成離子性化合物(D)的有機陰離子的具體例,包括三氟乙酸根陰離子[CF3COO-]、三氟甲烷磺酸根陰離子[CF3SO3 -]、雙(三氟甲烷磺醯基)亞胺陰離子[(CF3SO2)2N-]、三(三氟甲烷磺醯基)甲基(methanide)陰離子[(CF3SO2)3C-]、全氟丁烷磺酸根陰離子[C4F9SO3 -]、雙(五氟乙烷磺醯基)亞胺陰離子[(C2F5SO2)2N-]、全氟丁酸根陰離子[C3F7COO-]、(三氟甲烷磺醯基)(三氟甲烷羰基)亞胺陰離子[(CF3SO2)(CF3CO)N-]、全氟丙烷-1,3-二磺酸根陰離子[-O3S(CF2)3SO3 -]、四芳基硼酸根陰離子(例如四(五氟苯基) 硼酸根陰離子等)、二氰亞胺陰離子[(CN)2N-]及下述式(III):
含有氟原子的陰離子,從附黏著劑層之光學膜1及光學積層體的抗靜電功能、耐金屬腐蝕性及耐久性的觀點,較理想為下述式(II):[Y(SO2CmF2m+1)n]- (II)(式(II)中,Y表示碳原子或氮原子,Y表示碳原子時n為3,Y表示氮原子時n為2,m表示0至10的整數)所示的含有氟原子的陰離子。式(II)所示的含有氟原子的陰離子的具體例,包括雙(氟磺醯基)亞胺陰離子、雙(三氟甲烷磺醯基)亞胺陰離子、三(三氟甲烷磺醯基)甲基陰離子、雙(五氟乙烷磺醯基)亞胺陰離子等。其中,使用雙(氟磺醯基)亞胺陰離子[FSI-]或雙(三氟甲烷磺醯基)亞胺陰離子[TFSI-]之離子性化合物(D),特別有利於提高附黏著劑層之光學膜1及光學積層體的抗靜電功能、耐金屬腐蝕性及耐久性。Y為氮原子較理想,m為0至4的整數較理想,更理想為0至1的整數,特別理想為0。 The fluorine atom-containing anion is preferably from the viewpoint of the antistatic function, the metal corrosion resistance, and the durability of the optical film 1 with the adhesive layer and the optical laminate, and the following formula (II): [Y (SO 2 C m F 2m + 1 ) n ] - (II) (In the formula (II), Y represents a carbon atom or a nitrogen atom, Y represents a carbon atom, n is 3, Y represents a nitrogen atom, n is 2, and m represents 0 to 10 An anion represented by). Specific examples of the fluorine atom-containing anion represented by the formula (II) include a bis (fluorosulfonyl) imide anion, a bis (trifluoromethanesulfonyl) imide anion, and tris (trifluoromethanesulfonyl) Methyl anion, bis (pentafluoroethanesulfonyl) imide anion, etc. Wherein, using bis (fluorosulfonyl acyl) imide anion [FSI -] or bis (trifluoromethane sulfonic acyl) imide anion [TFSI -] of the ionic compound (D), in particular, help to improve the adhesive attachment layer The optical film 1 and the optical laminated body have antistatic function, metal corrosion resistance and durability. Y is preferably a nitrogen atom, m is an integer of 0 to 4 is more desirable, an integer of 0 to 1 is more desirable, and 0 is particularly desirable.
舉上述式(I)所示的離子性化合物(D)之較 佳例,係如以下。 Preferable examples of the ionic compound (D) represented by the formula (I) are as follows.
雙(氟磺醯基)亞胺 鋰 Bis (fluorosulfonyl) imide lithium
雙(三氟甲烷磺醯基)亞胺 鋰 Bis (trifluoromethanesulfonyl) imide lithium
雙(五氟乙烷磺醯基)亞胺 鋰 Bis (pentafluoroethanesulfonyl) imide lithium
三(三氟甲烷磺醯基)甲基 鋰 Tris (trifluoromethanesulfonyl) methyl lithium
雙(氟磺醯基)亞胺 鈉 Bis (fluorosulfonyl) imide sodium
雙(三氟甲烷磺醯基)亞胺 鈉 Bis (trifluoromethanesulfonyl) imide sodium
雙(五氟乙烷磺醯基)亞胺 鈉 Bis (pentafluoroethanesulfonyl) imide sodium
三(三氟甲烷磺醯基)甲基 鈉 Tris (trifluoromethanesulfonyl) methyl sodium
雙(氟磺醯基)亞胺 鉀 Bis (fluorosulfonyl) imide potassium
雙(三氟甲烷磺醯基)亞胺 鉀 Bis (trifluoromethanesulfonyl) imide potassium
雙(五氟乙烷磺醯基)亞胺 鉀 Bis (pentafluoroethanesulfonyl) imide potassium
三(三氟甲烷磺醯基)甲基 鉀 Tris (trifluoromethanesulfonyl) methyl potassium
黏著劑組成物中離子性化合物(D)的含量,對(甲基)丙烯酸系樹脂(A)100重量份而言為0.2至8重量份較理想,0.2至7重量份更理想,0.3至5重量份更加理想,0.5至3重量份特別理想。離子性化合物(D)的含量為0.2重量份以上,有利於提高抗靜電功能,8重量份以下時有利於附黏著劑層之光學膜1及光學積層體的耐金屬腐蝕性及耐久性。 The content of the ionic compound (D) in the adhesive composition is preferably 0.2 to 8 parts by weight, more preferably 0.2 to 7 parts by weight, and 0.3 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic resin (A). Part by weight is more preferable, and 0.5 to 3 parts by weight is particularly preferable. The content of the ionic compound (D) is 0.2 parts by weight or more, which is helpful to improve the antistatic function. When the content is 8 parts by weight or less, it is beneficial to the resistance to metal corrosion and durability of the optical film 1 and the optical laminate with the adhesive layer.
黏著劑組成物,可與上述式(I)所示的離子性化合物(D)一起,併用其以外的抗靜電劑,從附黏著劑層之光學膜1及光學積層體的耐金屬腐蝕性等的觀點,黏著 劑組成物以只含有上述式(I)所示的離子性化合物(D)作為抗靜電劑較理想。 The adhesive composition can be used together with the ionic compound (D) represented by the above formula (I) and an antistatic agent other than the metal film 1 of the optical film 1 with an adhesive layer and the optical multilayer body, etc. From the viewpoint, it is preferable that the adhesive composition contains only the ionic compound (D) represented by the formula (I) as an antistatic agent.
黏著劑組成物,可含有1種或2種以上的溶劑、交聯觸媒、紫外線吸收劑、耐候安定劑、增黏劑、可塑劑、軟化劑、染料、顏料、無機填充劑、光散射性微粒子等的添加劑。此外,於黏著劑組成物調配紫外線硬化性化合物,形成黏著劑層後,照射紫外線使其硬化,有用於成為更硬的黏著劑層。作為交聯觸媒,例如六亞甲基二胺、伸乙基二胺、聚伸乙基亞胺、六亞甲基四胺、二伸乙基三胺、三伸乙基四胺、異佛酮二胺、三亞甲基二胺、聚胺基樹脂及三聚氰胺樹脂等的胺系化合物。 Adhesive composition, which may contain one or more solvents, cross-linking catalysts, ultraviolet absorbers, weather stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, light scattering properties Additives such as micro particles. In addition, an ultraviolet curable compound is blended in the adhesive composition to form an adhesive layer, and then is irradiated with ultraviolet rays to harden it. This is useful for making a harder adhesive layer. Examples of cross-linking catalysts include hexamethylene diamine, ethylene diamine, polyethylenimine, hexamethylene tetramine, diethylene triamine, triethylene tetramine, isophor Amine compounds such as ketodiamine, trimethylenediamine, polyamine resin, and melamine resin.
黏著劑組成物,可含有可提高附黏著劑層之光學膜1及光學積層體的耐金屬腐蝕性之防鏽劑。作為防鏽劑,例如苯並***系化合物、其他***系化合物等的***系化合物;苯並噻唑系化合物、其他噻唑系化合物等的噻唑系化合物;苯甲基咪唑系化合物、其他咪唑系化合物等的咪唑系化合物;咪唑啉系化合物;喹啉系化合物;吡啶系化合物;嘧啶系化合物;吲哚系化合物;胺系化合物;尿素系化合物;苯甲酸鈉;苯甲基硫醇系化合物;二-第二丁基硫醚;及二苯基亞碸。 The adhesive composition may contain a rust preventive agent that can improve the metal corrosion resistance of the optical film 1 with the adhesive layer and the optical laminate. Examples of rust inhibitors include triazole compounds such as benzotriazole compounds and other triazole compounds; thiazoly compounds such as benzothiazole compounds and other thiazole compounds; benzimidazole compounds and other imidazoles Imidazole compounds; imidazoline compounds; quinoline compounds; pyridine compounds; pyrimidine compounds; indole compounds; amine compounds; urea compounds; sodium benzoate; benzyl mercaptan compounds; Di-second butyl sulfide; and diphenylsulfinium.
但是,根據本發明,即使不含有防鏽劑,也可得到充分的耐金屬腐蝕性,因而防鏽劑的含量盡可能 的小較理想,特別是,黏著劑組成物以實質上不包含作為防鏽劑的***系化合物較理想,實質上不包含選自上述化合物群的防鏽劑更理想。此處所謂實質上不包含,係指對(甲基)丙烯酸系樹脂(A)100重量份而言為0.01重量份以下。 However, according to the present invention, sufficient corrosion resistance can be obtained even if no rust inhibitor is contained. Therefore, the content of the rust inhibitor is preferably as small as possible. In particular, the adhesive composition is substantially not contained as an antirust agent. A triazole-based compound of a rusting agent is preferable, and a rust preventive agent not substantially selected from the above-mentioned compound group is more preferable. The term "substantially not included" means that the content of the (meth) acrylic resin (A) is 0.01 parts by weight or less.
金屬層30,例如可為包含選自鋁、銅、銀、金、鐵、錫、鋅、鎳、鉬、鉻、鎢、鉛及包含從該等選擇2種以上的金屬之合金所成群的1種以上的層,從導電性的觀點,較理想為包含選自鋁、銅、銀及金所成群的金屬元素的層,從導電性及成本的觀點,更理想為包含鋁元素的層,更加理想為包含鋁元素作為主成分的層。所謂作為主成分而包含,係指構成金屬層30的金屬成分為全部金屬成分的30重量%以上,又50重量%以上。 The metal layer 30 may be, for example, a group consisting of an alloy selected from the group consisting of aluminum, copper, silver, gold, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and two or more metals selected from these. One or more layers are more preferably a layer containing a metal element selected from the group consisting of aluminum, copper, silver, and gold from the viewpoint of conductivity, and more preferably a layer containing an aluminum element from the viewpoint of conductivity and cost. More preferably, it is a layer containing an aluminum element as a main component. Including as a main component means that the metal component constituting the metal layer 30 is 30% by weight or more and 50% by weight or more of the total metal component.
金屬層30,可為例如ITO等的金屬氧化物層,關於本發明的附黏著劑層之光學膜,由於特別對金屬單體、合金的耐腐蝕性良好,金屬層30以包含上述金屬元素所構成的金屬單體及/或含有上述金屬元素的2種以上的合金較理想。但是光學積層體,可與如此的金屬層30一起,具有ITO等的金屬氧化物所構成的透明電極層。 The metal layer 30 may be, for example, a metal oxide layer such as ITO. As for the optical film with an adhesive layer of the present invention, the metal layer 30 contains the above-mentioned metal element because of its excellent corrosion resistance to metal monomers and alloys. The constituent metal monomer and / or two or more alloys containing the above-mentioned metal element are preferred. However, the optical laminate may include a transparent electrode layer made of a metal oxide such as ITO together with such a metal layer 30.
金屬層30的形態(例如厚度等)、調製方法,無特別限制,除可為金屬箔外,亦可藉由真空蒸鍍法、濺鍍法、離子鍍法、噴墨印刷法、凹版印刷法形成,較理想 為藉由濺鍍法、噴墨印刷法、凹版印刷法形成的金屬層,更理想為濺鍍法形成的金屬層。濺鍍所形成的金屬層與金屬箔,前者有耐腐蝕性差的傾向,惟根據關於本發明的光學積層體,即使對濺鍍所形成的金屬層,亦具有良好的耐金屬腐蝕性。金屬層30的厚度,通常為3μm以下,較理想為1μm以下,更理想為0.8μm以下。而且,金屬層30的厚度,通常為0.01μm以上。再者,金屬層30為金屬配線層的情況,該金屬配線層所具有的金屬配線的線寬,通常為10μm以下,較理想為5μm以下,更理想為3μm以下。而且,金屬配線的線寬,通常為0.01μm以上,較理想為0.1μm以上,更加理想為0.5μm以上。即使對如此的薄膜的金屬層30、細線的金屬配線所構成的金屬層30,本發明的光學積層體仍顯示良好的耐金屬腐蝕性。特別是金屬配線例如為厚度3μm以下、線寬10μm以下的情況,或者厚度3μm以下、線寬10μm以下、且係藉由濺鍍形成的情況,亦可抑制其腐蝕,特別是孔蝕。 The form (for example, thickness, etc.) and the method of preparing the metal layer 30 are not particularly limited. In addition to being a metal foil, a vacuum evaporation method, a sputtering method, an ion plating method, an inkjet printing method, or a gravure printing method may be used. The formation is preferably a metal layer formed by a sputtering method, an inkjet printing method, or a gravure printing method, and more preferably a metal layer formed by a sputtering method. The metal layer and the metal foil formed by sputtering tend to have poor corrosion resistance. However, according to the optical multilayer body of the present invention, the metal layer formed by sputtering has good metal corrosion resistance. The thickness of the metal layer 30 is usually 3 μm or less, more preferably 1 μm or less, and even more preferably 0.8 μm or less. The thickness of the metal layer 30 is usually 0.01 μm or more. When the metal layer 30 is a metal wiring layer, the line width of the metal wiring included in the metal wiring layer is usually 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The line width of the metal wiring is usually 0.01 μm or more, more preferably 0.1 μm or more, and even more preferably 0.5 μm or more. The optical layered body of the present invention exhibits good resistance to metal corrosion even with such a thin-film metal layer 30 and a thin-wire metal wiring. In particular, when the metal wiring has a thickness of 3 μm or less and a line width of 10 μm or less or a thickness of 3 μm or less and a line width of 10 μm or less is formed by sputtering, corrosion, especially pitting, can be suppressed.
金屬層30,可為例如觸控輸入式液晶顯示裝置所具有的觸控輸入元件的金屬配線層(亦即電極層)。於該情況,金屬層30通常圖形化為指定的形狀。於圖形化的金屬層30上,積層黏著劑層20的情況,黏著劑層20可具有不接觸金屬層30的部分。金屬層30,可為包含上述金屬或合金的連續膜。 The metal layer 30 may be, for example, a metal wiring layer (ie, an electrode layer) of a touch input element included in a touch input liquid crystal display device. In this case, the metal layer 30 is usually patterned into a predetermined shape. When the adhesive layer 20 is laminated on the patterned metal layer 30, the adhesive layer 20 may have a portion that does not contact the metal layer 30. The metal layer 30 may be a continuous film including the above-mentioned metal or alloy.
而且,金屬層30可為單層構造,亦可為2層或3層以上的多層構造。作為多層構造的金屬層,例如鉬/鋁/鉬 所示的3層構造的含有金屬的層(金屬網等)。 In addition, the metal layer 30 may have a single-layer structure or a multi-layer structure of two or more layers. Examples of the metal layer having a multilayer structure include a metal-containing layer (metal mesh, etc.) having a three-layer structure shown by molybdenum / aluminum / molybdenum.
如第1圖所示,例如金屬配線層的金屬層30,通常形成於基板40上,於該情況,關於本發明的光學積層體包括該基板40。對基板40上的金屬層30的形成,可藉由例如濺鍍進行。基板40,可為構成包含觸控輸入元件的液晶單元之透明基板。基板40,較理想為玻璃基板。作為玻璃基板的材料,例如鈉鈣玻璃、低鹼玻璃、無鹼玻璃等。金屬層30,可形成於基板40的全部表面,亦可形成於其一部分。於基板40上形成圖形化的金屬層30的情況等,於基板40的表面的一部分形成金屬層30的情況,黏著劑層20的一部分,例如成為與玻璃所構成的基板40直接接觸,由於本發明的光學積層體之黏著劑層20與玻璃的密著性佳,光學積層體及具備該光學積層體之液晶顯示裝置係於此情況之耐久性也佳。 As shown in FIG. 1, a metal layer 30 such as a metal wiring layer is usually formed on a substrate 40. In this case, the optical laminate of the present invention includes the substrate 40. The metal layer 30 on the substrate 40 can be formed by, for example, sputtering. The substrate 40 may be a transparent substrate constituting a liquid crystal cell including a touch input element. The substrate 40 is preferably a glass substrate. Examples of the material of the glass substrate include soda-lime glass, low-alkali glass, and alkali-free glass. The metal layer 30 may be formed on the entire surface of the substrate 40 or may be formed on a part thereof. When the patterned metal layer 30 is formed on the substrate 40, and when the metal layer 30 is formed on a part of the surface of the substrate 40, a part of the adhesive layer 20, for example, comes into direct contact with the substrate 40 made of glass. The adhesive layer 20 of the optical laminated body of the invention has good adhesion to glass, and the optical laminated body and the liquid crystal display device provided with the optical laminated body are also excellent in durability in this case.
於一實施態樣,關於本發明的光學積層體,如第4圖及第5圖所示,包括附黏著劑層之光學膜1、積層於其黏著劑層20的金屬層30。於如第4圖及第5圖所示的光學積層體5、6,附黏著劑層之光學膜1係其黏著劑層20以直接接觸金屬層30的方式積層於金屬層30上。根據本發明,即使於如此的黏著劑層20直接接觸金屬層30的構成之光學積層體,亦可有效地抑制金屬層30的腐蝕。 In an embodiment, as shown in FIG. 4 and FIG. 5, the optical laminated body of the present invention includes an optical film 1 with an adhesive layer 1 and a metal layer 30 laminated on the adhesive layer 20. In the optical laminates 5 and 6 shown in FIGS. 4 and 5, the optical film 1 with the adhesive layer is laminated on the metal layer 30 so that the adhesive layer 20 directly contacts the metal layer 30. According to the present invention, even if the optical laminated body having such a configuration that the adhesive layer 20 directly contacts the metal layer 30 can effectively suppress the corrosion of the metal layer 30.
第6圖係表示本發明光學積層體的層構成 之其他一例的剖面示意圖。於其他實施態樣,關於本發明的光學積層體,如第6圖所示的光學積層體7,附黏著劑層之光學膜1的黏著劑層20係隔著樹脂層50積層於金屬層30。黏著劑層20係直接接觸樹脂層50。即使於如此的光學積層體7,亦可有效地抑制金屬層30的腐蝕。配置於黏著劑層20與金屬層30之間的樹脂層50,例如可為硬化性樹脂的硬化物層。作為可形成樹脂層50的硬化性樹脂,可使用習知者,例如日本特開2009-217037號公報記載者。 Fig. 6 is a schematic cross-sectional view showing another example of the layer constitution of the optical laminated body of the present invention. In other embodiments, as for the optical laminate of the present invention, as shown in FIG. 6, the adhesive layer 20 of the optical film 1 with the adhesive layer is laminated on the metal layer 30 via the resin layer 50. . The adhesive layer 20 is in direct contact with the resin layer 50. Even in such an optical multilayer body 7, the corrosion of the metal layer 30 can be effectively suppressed. The resin layer 50 disposed between the adhesive layer 20 and the metal layer 30 may be, for example, a cured product layer of a curable resin. As the curable resin capable of forming the resin layer 50, a known person can be used, for example, the one described in Japanese Patent Application Laid-Open No. 2009-217037.
如上述金屬層30,可為金屬配線層。金屬層30為金屬配線層的情況之一例表示於第7圖。於第7圖所示的光學積層體,可省略樹脂層50。 As described above, the metal layer 30 may be a metal wiring layer. An example of a case where the metal layer 30 is a metal wiring layer is shown in FIG. 7. In the optical laminated body shown in FIG. 7, the resin layer 50 may be omitted.
光學積層體,例如在形成於基板40上的金屬層30上,將包括光學膜10及積層於其至少一側的面上之黏著劑層20的附黏著劑層之光學膜1,隔著其黏著劑層20加以貼合而製作。 The optical laminated body is, for example, an optical film 1 with an adhesive layer including an optical film 10 and an adhesive layer 20 laminated on at least one side of the metal layer 30 formed on the substrate 40 with the optical film 1 interposed therebetween. The adhesive layer 20 is bonded and manufactured.
如上述附黏著劑層之光學膜1係包括光學膜10及積層於其至少一側的面上之黏著劑層20(第1圖)。可於光學膜10的兩面積層黏著劑層20。通常黏著劑層20係直接積層於光學膜10的表面。將黏著劑層20設置於光學膜10的表面之時,於光學膜10的貼合面及/或黏著劑層20的貼合面形成底塗層、表面活性化處理,例如實施電漿處理、電暈處理等較理想,實施電暈處理更理想。 As described above, the optical film 1 with an adhesive layer includes an optical film 10 and an adhesive layer 20 (FIG. 1) laminated on at least one side of the optical film 10. An adhesive layer 20 may be layered on two areas of the optical film 10. Generally, the adhesive layer 20 is directly laminated on the surface of the optical film 10. When the adhesive layer 20 is provided on the surface of the optical film 10, an undercoat layer is formed on the bonding surface of the optical film 10 and / or the bonding surface of the adhesive layer 20, and a surface activation treatment is performed, for example, plasma treatment, Corona treatment is ideal, and corona treatment is more ideal.
光學膜10為如第2圖所示的單面保護的偏光板的情況,黏著劑層20通常較理想係直接積層於偏光片 面,亦即與偏光片2的第1樹脂膜3相反側的面。光學膜10為如第3圖所示的兩面保護的偏光板的情況,黏著劑層20可積層於第1、第2樹脂膜3、4之任一者的外面,亦可積層於兩者的外面。 In the case where the optical film 10 is a single-sided protected polarizing plate as shown in FIG. 2, the adhesive layer 20 is usually ideally laminated directly on the surface of the polarizer, that is, the surface opposite to the first resin film 3 of the polarizer 2 . In the case where the optical film 10 is a polarizing plate protected on both sides as shown in FIG. 3, the adhesive layer 20 may be laminated on either of the first and second resin films 3 and 4 or may be laminated on both of them. outside.
光學膜10與黏著劑層20之間亦可另外設置抗靜電層,本發明的黏著劑層20因單獨黏著劑層即可賦予良好的抗靜電性,在光學積層體的薄膜化、積層體製作步驟的簡化方面,以光學膜10與黏著劑層20之間不具有抗靜電層較理想。 An antistatic layer can also be provided between the optical film 10 and the adhesive layer 20. The adhesive layer 20 of the present invention can provide good antistatic properties because of the separate adhesive layer. In terms of simplification, it is preferable that there is no antistatic layer between the optical film 10 and the adhesive layer 20.
附黏著劑層之光學膜1,亦可包含積層於黏著劑層20外面的離型膜(剝離膜)。該離型膜,通常於黏著劑層20使用時(例如於金屬層30上積層時)剝離除去。剝離膜,例如可於聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚碳酸酯、聚芳酯等的各種樹脂所構成的膜,形成黏著劑層20的面實施聚矽氧處理等的離型處理者。 The optical film 1 with the adhesive layer may also include a release film (release film) laminated on the outside of the adhesive layer 20. This release film is usually peeled and removed when the adhesive layer 20 is used (for example, when it is laminated on the metal layer 30). The release film can be, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, and the like. Polysilicon can be formed on the surface forming the adhesive layer 20. Release processors such as oxygen treatment.
附黏著劑層之光學膜1,可將構成上述黏著劑組成物的各成分溶解或分散於溶劑,作為含有溶劑的黏著劑組成物,然後將其塗佈於光學膜10的表面並使其乾燥,形成黏著劑層20而得。又,附黏著劑層之光學膜1,亦可於離型膜的離型處理面,與上述同樣地形成黏著劑層20,並將該黏著劑層20積層(轉印)於光學膜10的表面而得。 The optical film 1 with an adhesive layer can dissolve or disperse the components constituting the above-mentioned adhesive composition in a solvent, and then apply the solvent-containing adhesive composition to the surface of the optical film 10 and dry it. , Obtained by forming the adhesive layer 20. The optical film 1 with an adhesive layer may be formed on the release-treated surface of the release film in the same manner as described above, and the adhesive layer 20 may be laminated (transferred) on the optical film 10. From the surface.
藉由將附黏著劑層之光學膜1隔著其黏著劑層20貼合於金屬層30(或上述樹脂層)上,可得到光學積 層體。附黏著劑層之光學膜1與金屬層30黏接,製作光學積層體後,於有任何缺陷的情況,有從金屬層30將附黏著劑層之光學膜1剝離,重新將其他附黏著劑層之光學膜1貼合於金屬層30,而有所謂重工作業之必要。關於本發明的光學積層體,從金屬層30剝離附黏著劑層之光學膜1後的金屬層30的表面不易發生混濁、殘膠等,重工性佳。根據本發明的光學積層體,貼合黏著劑層20的表面不是金屬層30而是玻璃基板、ITO層時,也可顯示良好的重工性。 By bonding the optical film 1 with an adhesive layer to the metal layer 30 (or the above-mentioned resin layer) via the adhesive layer 20, an optical laminate can be obtained. The optical film 1 with the adhesive layer is adhered to the metal layer 30. After making the optical laminate, if there is any defect, the optical film 1 with the adhesive layer is peeled off from the metal layer 30, and other adhesives are re-attached. The layer of the optical film 1 is adhered to the metal layer 30, and so-called heavy work is necessary. With regard to the optical multilayer body of the present invention, the surface of the metal layer 30 after peeling off the optical film 1 with the adhesive layer from the metal layer 30 is less prone to turbidity, adhesive residue, and the like, and has excellent reworkability. According to the optical multilayer body of the present invention, when the surface of the adhesive layer 20 is bonded to the glass substrate or the ITO layer instead of the metal layer 30, good reworkability can be exhibited.
關於本發明的液晶顯示裝置,係包含上述本發明的光學積層體。關於本發明的液晶顯示裝置,可抑制金屬層30的腐蝕,而且顯示良好的耐久性。 The liquid crystal display device of the present invention includes the optical laminate of the present invention. The liquid crystal display device of the present invention can suppress corrosion of the metal layer 30 and exhibit good durability.
關於本發明的液晶顯示裝置,較理想為具有觸控面板功能的觸控輸入式液晶顯示裝置。觸控輸入式液晶顯示裝置,具備包含液晶單元的觸控輸入元件及背光。觸控面板的構成,可為外單元(Out-cell)型、單元上(on-cell)型、內單元(in-cell)型等習知的任一方式,而且觸控面板的動作方式,可為電阻膜方式、電容方式(表面型電容方式、投影型電容方式)等的傳統習知的任一方式。關於本發明的光學積層體,可配置於觸控輸入元件(液晶單元)的觀賞側,亦可配置於背光側,亦可配置於兩者。液晶單元的驅動方式,可為TN方式、VA方式、IPS方式、多區域方式、OCB方式等傳統習知的任一方式。於關於本發明 的液晶顯示裝置,光學積層體所具有的基板40,可為包含於上述液晶單元的基板(典型地玻璃基板)。 The liquid crystal display device of the present invention is preferably a touch input type liquid crystal display device having a touch panel function. A touch input type liquid crystal display device includes a touch input element including a liquid crystal cell and a backlight. The structure of the touch panel can be any of the conventional methods such as Out-cell type, on-cell type, and in-cell type, and the operation mode of the touch panel, It may be any conventionally known method such as a resistive film method, a capacitive method (surface type capacitive method, projection type capacitive method) and the like. The optical laminated body of the present invention may be arranged on the viewing side of a touch input element (liquid crystal unit), on the backlight side, or on both. The driving method of the liquid crystal cell may be any of conventionally known methods such as a TN method, a VA method, an IPS method, a multi-region method, and an OCB method. In the liquid crystal display device of the present invention, the substrate 40 included in the optical laminate may be a substrate (typically a glass substrate) included in the liquid crystal cell.
以下,顯示實施例及比較例,更具體地說明本發明,但本發明不限於該等例。以下,表示使用量、含量的份及%,在無另外註明下為重量基準。 Hereinafter, the present invention will be described more specifically by showing examples and comparative examples, but the present invention is not limited to these examples. In the following, the usage amount, content, and% are indicated, and the weight basis is used unless otherwise specified.
於具備冷卻管、氮氣導入管、溫度計及攪拌機的反應容器,放入表1所示的組成(表1的數值為重量份)的單體與乙酸乙酯81.8份混合而得之溶液。以氮氣取代反應容器內的空氣後,將內溫升溫至60℃。然後,添加偶氮雙異丁腈0.12份溶解於乙酸乙酯10份的溶液。在相同溫度保持1小時後,一邊保持內溫為54至56℃,一邊以添加速度17.3份/小時朝反應容器內連續添加乙酸乙酯,使聚合物的濃度成為約35%。從添加乙酸乙酯開始到經過12小時為止保持54至56℃後,添加乙酸乙酯,調整使聚合物的濃度成為20%,得到(甲基)丙烯酸系樹脂(A-1)的乙酸乙酯溶液。(甲基)丙烯酸系樹脂(A-1)的重量平均分子量Mw為139萬,重量平均分子量Mw與數量平均分子量Mn的比Mw/Mn為5.32。於凝膠滲透層析(GPC)之排出曲線,Mw139萬的成分顯示單一波峰,於Mw1000至250萬的範圍,沒有其他波峰。 In a reaction vessel provided with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, a solution obtained by mixing a monomer having a composition shown in Table 1 (the numerical value in Table 1 is parts by weight) with 81.8 parts of ethyl acetate was placed. After replacing the air in the reaction vessel with nitrogen, the internal temperature was raised to 60 ° C. Then, a solution in which 0.12 parts of azobisisobutyronitrile was dissolved in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, while maintaining the internal temperature at 54 to 56 ° C., ethyl acetate was continuously added into the reaction container at an addition rate of 17.3 parts / hour, so that the concentration of the polymer became approximately 35%. After maintaining the temperature at 54 to 56 ° C. for 12 hours from the start of the addition of ethyl acetate, the concentration of the polymer was adjusted to 20% to obtain ethyl acetate of the (meth) acrylic resin (A-1). Solution. The weight average molecular weight Mw of the (meth) acrylic resin (A-1) was 1.39 million, and the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn was 5.32. In the gel permeation chromatography (GPC) discharge curve, the composition of Mw 1.39 million showed a single peak. In the range of Mw 1000 to 2.5 million, there were no other peaks.
除單體的組成如表1所示以外,與製造例1同樣地,得到(甲基)丙烯酸系樹脂(A-2)的乙酸乙酯溶液(樹脂濃度:20%)。(甲基)丙烯酸系樹脂(A-2)的重量平均分子量Mw為141萬,Mw/Mn為4.71。於GPC之排出曲線,Mw139萬的成分顯示單一波峰,於Mw1000至250萬的範圍,沒有其他波峰。 An ethyl acetate solution (resin concentration: 20%) of a (meth) acrylic resin (A-2) was obtained in the same manner as in Production Example 1 except that the monomer composition was shown in Table 1. The weight average molecular weight Mw of the (meth) acrylic resin (A-2) was 1.41 million, and Mw / Mn was 4.71. In the discharge curve of GPC, the composition of Mw 1.39 million shows a single peak. In the range of Mw 1000 to 2.5 million, there are no other peaks.
於上述製造例,重量平均分子量Mw及數量平均分子量Mn,係於GPC裝置,以Tosoh(股)製的「TSKgel XL」4根及昭和電工(股)製的昭光通商(股)販售的「Shodex GPC KF-802」1根的共5根配置成串列作為管柱,使用四氫呋喃作為洗提液,樣品濃度為5mg/mL,樣品導入量為100μL,於溫度40℃,流速1mL/分的條件下,藉由換算標準聚苯乙烯測定。得到GPC之排出曲線時的條件也與其相同。 In the above manufacturing examples, the weight average molecular weight Mw and the number average molecular weight Mn are based on GPC equipment and are sold as 4 "TSKgel XL" made by Tosoh Co., Ltd. and "Shokotsu Corporation" made by Showa Denko Corporation. A total of 5 Shodex GPC KF-802 "s were arranged in series as a column, and tetrahydrofuran was used as the eluent. The sample concentration was 5 mg / mL, and the sample introduction amount was 100 μL. The temperature was 40 ° C and the flow rate was 1 mL / min. Under the conditions, it is measured by converting standard polystyrene. The conditions under which the GPC discharge curve is obtained are also the same.
玻璃轉移溫度Tg係使用SII奈米科技公司製的示差掃描熱量計(DSC)「EXSTAR DSC600」,在氮氣環境下,測定溫度範圍為-80至50℃、升溫溫度10℃/分的條件下測定。 The glass transition temperature Tg is measured using a differential scanning calorimeter (DSC) "EXSTAR DSC600" manufactured by SII Nano Technology Co., Ltd., under a nitrogen environment, the measurement temperature range is -80 to 50 ° C, and the temperature rise temperature is 10 ° C / min. .
各製造例之單體的組成(表1的數值為重量份)及GPC的排出曲線上的Mw1000至250萬的範圍之波峰數(於表1表示為「GPC波峰數」)彙整於表1。 The composition of the monomers in each manufacturing example (the numerical values in Table 1 are parts by weight) and the number of peaks in the range of Mw1000 to 2.5 million (expressed as "GPC peak number" in Table 1) on the GPC discharge curve are summarized in Table 1.
表1的「單體組成」的欄之簡稱,係指以下的單體。 The abbreviations in the column of "monomer composition" in Table 1 refer to the following monomers.
BA:丙烯酸丁酯(均聚物的玻璃轉移溫度:-54℃) BA: butyl acrylate (glass transition temperature of homopolymer: -54 ° C)
MA:丙烯酸甲酯(均聚物的玻璃轉移溫度:10℃) MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C)
HEA:丙烯酸2-羥基乙酯 HEA: 2-hydroxyethyl acrylate
上述製造例所得之(甲基)丙烯酸系樹脂的乙酸乙酯溶液(樹脂濃度:20%),對該溶液的固體成分100份,依表2所示的量(重量份)混合表2所示的異氰酸酯系交聯劑(B)、矽烷化合物(C)及離子性化合物(D),再添加乙酸乙酯,使固體成分濃度為14%,得到黏著劑組成物。表2所示的各調配成分的調配量,於使用的商品包含溶劑等的情況,為包含於其中的有效成分的重量份數。 In the ethyl acetate solution (resin concentration: 20%) of the (meth) acrylic resin obtained in the above-mentioned production example, 100 parts of the solid content of the solution was mixed as shown in Table 2 (parts by weight). The isocyanate-based cross-linking agent (B), the silane compound (C), and the ionic compound (D) were added to ethyl acetate to make the solid content concentration 14% to obtain an adhesive composition. The blending amount of each blending ingredient shown in Table 2 is the weight part of the active ingredient contained in the case where the product used includes a solvent or the like.
於表2以簡稱所示的各調配成分的詳細,係如以下。 The details of each of the compounding components shown by abbreviations in Table 2 are as follows.
B-1:伸二甲苯基二異氰酸酯的三羥甲基丙烷加成物的乙酸乙酯溶液(固體成分濃度75%)、從三井化學(股)公司取得的商品名「TAKENATE D-110N」 B-1: Ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate (solid content concentration 75%), trade name "TAKENATE D-110N" obtained from Mitsui Chemicals Co., Ltd.
C-1:3-環氧丙氧基丙基三甲氧基矽烷、從信越化學工業(股)公司取得的商品名「KBM403」。 C-1: 3-glycidoxypropyltrimethoxysilane, trade name "KBM403" obtained from Shin-Etsu Chemical Industry Co., Ltd.
D-1:雙(氟磺醯基)亞胺 鉀 D-1: Bis (fluorosulfonyl) imide potassium
D-2:雙(三氟甲烷磺醯基)亞胺 鋰 D-2: Bis (trifluoromethanesulfonyl) imide lithium
D-3:N-辛基-4-甲基吡啶鎓 六氟磷酸鹽 D-3: N-octyl-4-methylpyridinium hexafluorophosphate
將上述(1)調製的各黏著劑組成物,使用塗敷器(applicator),塗佈於經施予離型處理的聚對苯二甲酸乙二酯所構成的離型膜[LINTEC公司取得之「PLR-382051」]的離型處理面,使乾燥後的厚度成為20μm,於100℃下乾燥1分鐘,製作黏著劑層(黏著劑片)。 Each adhesive composition prepared in the above (1) was applied to a release film made of polyethylene terephthalate subjected to a release treatment using an applicator [available from LINTEC Corporation] "PLR-382051"], releasing the treated surface to a thickness of 20 μm after drying, and drying at 100 ° C. for 1 minute to prepare an adhesive layer (adhesive sheet).
將平均聚合度約2400、皂化度99.9莫耳%、厚度60μm的聚乙烯醇膜[可樂麗(Kuraray)公司製的商品名「Kuraray Vinylon VF-PE#6000」]浸漬於37℃之純水後,在30℃浸漬於包含碘及碘化鉀的水溶液(碘/碘化鉀/水(重量比)=0.04/1.5/100)。然後,在56.5℃浸漬於包含碘化鉀及硼酸的水溶液(碘化鉀/硼酸/水(重量比)=12/3.6/100)。將膜以10℃的純水洗淨後,於85℃乾燥,得到碘吸附配向於聚乙烯醇的厚度約23μm的偏光片。延伸,主要在碘染色及硼酸處理的步驟進行,全部的延伸倍率為5.3倍。 A polyvinyl alcohol film with an average degree of polymerization of about 2400, a degree of saponification of 99.9 mol%, and a thickness of 60 μm [Kuraray Vinylon VF-PE # 6000 manufactured by Kuraray Co., Ltd.] was immersed in pure water at 37 ° C. , And immersed in an aqueous solution containing iodine and potassium iodide (iodine / potassium iodide / water (weight ratio) = 0.04 / 1.5 / 100) at 30 ° C. Then, it was immersed in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100) at 56.5 ° C. The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizer having a thickness of about 23 μm that is iodine-adsorbed and aligned with polyvinyl alcohol. Stretching is mainly performed in the steps of iodine staining and boric acid treatment, and the total stretching ratio is 5.3 times.
於所得之偏光片的單面,隔著聚乙烯醇系樹脂的水溶液所構成的接著劑,貼合厚度25μm的三乙醯基纖維素膜所構成的透明保護膜[柯尼卡美能達光學(股)製的商品名「KC2UA」]。然後,於與上述偏光片之三乙醯基纖維素膜相反側的面,隔著聚乙烯醇系樹脂的水溶液所構成的接著劑,貼合厚度23μm的環狀聚烯烴系樹脂所 構成的零相位差膜[日本ZEON(股)製的商品名「ZEONOR」],製作偏光板。然後,於零相位差膜之與偏光片接觸的面的相反側的面,實施為了提高密著性的電暈放電處理後,藉由積層機貼合上述(2)製作的黏著劑層的離型膜相反側的面(黏著劑層面)後,在溫度23℃、相對濕度65%的條件下熟成7天,得到附黏著劑層之光學膜(P-1)。 On one side of the obtained polarizer, a transparent protective film composed of a triethylfluorene-based cellulose film having a thickness of 25 μm was bonded through an adhesive made of an aqueous solution of a polyvinyl alcohol resin [Konica Minolta Optics ( "KC2UA"). Then, on the surface opposite to the triacetamyl cellulose film of the above-mentioned polarizer, an adhesive made of an aqueous solution of a polyvinyl alcohol-based resin was laminated to a zero-thickness of a cyclic polyolefin resin having a thickness of 23 μm. A retardation film [trade name "ZEONOR" manufactured by ZEON (Japan)] was used to produce a polarizing plate. Then, a corona discharge treatment is performed on the surface of the zero-phase retardation film opposite to the surface in contact with the polarizer to improve adhesion, and then the lamination machine is used to bond the release layer of the adhesive layer prepared in (2) above. After the surface (adhesive layer) on the opposite side of the mold film was aged at a temperature of 23 ° C. and a relative humidity of 65% for 7 days, an optical film (P-1) with an adhesive layer was obtained.
將平均聚合度約2400、皂化度99.9莫耳%、厚度30μm的聚乙烯醇膜[可樂麗(Kuraray)公司製的商品名「Kuraray Vinylon VF-PE#3000」]浸漬於37℃之純水後,在30℃浸漬於包含碘及碘化鉀的水溶液(碘/碘化鉀/水(重量比)=0.04/1.5/100)。然後,在56.5℃浸漬於包含碘化鉀及硼酸的水溶液(碘化鉀/硼酸/水(重量比)=12/3.6/100)。將膜以10℃的純水洗淨後,於85℃乾燥,得到碘吸附配向於聚乙烯醇的厚度約12μm的偏光片。延伸,主要在碘染色及硼酸處理的步驟進行,全部的延伸倍率為5.3倍。 A polyvinyl alcohol film with an average degree of polymerization of about 2400, a degree of saponification of 99.9 mol%, and a thickness of 30 μm [Kuraray Vinylon VF-PE # 3000 manufactured by Kuraray Co., Ltd.] was immersed in pure water at 37 ° C. , And immersed in an aqueous solution containing iodine and potassium iodide (iodine / potassium iodide / water (weight ratio) = 0.04 / 1.5 / 100) at 30 ° C. Then, it was immersed in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100) at 56.5 ° C. The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizer having a thickness of about 12 μm that is iodine-adsorbed and aligned with polyvinyl alcohol. Stretching is mainly performed in the steps of iodine staining and boric acid treatment, and the total stretching ratio is 5.3 times.
於所得之偏光片的單面,隔著聚乙烯醇系樹脂的水溶液所構成的接著劑,貼合厚度25μm的三乙醯基纖維素膜所構成的透明保護膜[柯尼卡美能達光學(股)製的商品名「KC2UA」],製作偏光板。然後,於與偏光片的保護膜的貼合面相反的面,藉由積層機貼合上述(2)製作的黏著劑層的離型膜相反側的面(黏著劑層面)後,在溫度23℃、相對濕度65%的條件下熟成7天,得到附黏著 劑層之光學膜(P-2)。 On one side of the obtained polarizer, a transparent protective film composed of a triethylfluorene-based cellulose film having a thickness of 25 μm was bonded through an adhesive made of an aqueous solution of a polyvinyl alcohol resin [Konica Minolta Optics ( Under the trade name "KC2UA"] to make a polarizing plate. Then, the opposite surface (adhesive layer) of the release film of the adhesive layer prepared in the above (2) was bonded to the surface opposite to the bonding surface of the protective film of the polarizer by a laminator, and the temperature was 23 at a temperature of 23 The film was aged for 7 days at a temperature of 65 ° C and a relative humidity of 65% to obtain an optical film (P-2) with an adhesive layer.
將上述(3)製作的附黏著劑層之光學膜(P-1),裁切為20mm×50mm大小的測試片,隔著黏著劑層,貼附於附金屬層的玻璃基板的金屬層側。附金屬層的玻璃基板係使用於無鹼玻璃表面藉由濺鍍積層厚度約500nm的金屬鋁層之玻璃基板(GEOMATEC公司製)。所得之光學積層體於溫度60℃、相對濕度90%的烤箱中保管500小時後,附黏著劑層之光學膜所貼附的部分之金屬層的狀態,從玻璃基板的背面對著光,從偏光板表面通過放大鏡觀察,關於孔蝕(直徑0.1mm以上,可穿透光的孔之發生),用以下的基準評價。結果表示於表3。 The optical film (P-1) with an adhesive layer prepared in the above (3) was cut into a test piece having a size of 20 mm × 50 mm, and the metal layer was attached to the metal layer side of the glass substrate with a metal layer through the adhesive layer. . The glass substrate with a metal layer is a glass substrate (manufactured by GEOMATEC) used on the surface of an alkali-free glass by sputtering a metal aluminum layer having a thickness of about 500 nm. After the obtained optical laminated body was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 500 hours, the state of the metal layer of the portion to which the optical film with the adhesive layer was attached was directed from the back of the glass substrate to the light, The surface of the polarizing plate was observed with a magnifying glass, and the pitting corrosion (the occurrence of holes having a diameter of 0.1 mm or more that can penetrate light) was evaluated by the following criteria. The results are shown in Table 3.
4:發生於金屬層表面的孔蝕的數目為2個以下、3:發生於金屬層表面的孔蝕的數目為3個至5個、2:發生於金屬層表面的孔蝕的數目為6個以上、1:金屬層表面的全部表面發生多數孔蝕且發生白濁。 4: The number of pitting corrosion occurring on the surface of the metal layer is 2 or less, 3: the number of pitting corrosion occurring on the surface of the metal layer is 3 to 5, and 2: the number of pitting corrosion occurring on the surface of the metal layer is 6 More than one, 1: The entire surface of the metal layer surface has a large number of pitting corrosions and white turbidity.
將上述(3)製作的附黏著劑層之光學膜(P-1),以使偏光板的延伸軸方向成為長邊地裁切為200mm×150mm大小,剝離離型膜,將露出的黏著劑層面貼合於玻璃基板。將所得之玻璃基板貼附的測試片(玻璃基板貼附的附黏著 劑層之光學膜),在高壓釜中,溫度50℃、壓力5kg/cm2(490.3kPa)加壓20分鐘。玻璃基板係使用康寧公司製的無鹼玻璃、商品名「Eagle XG」。對所得之光學積層體,實施以下的3種耐久性測試。 The optical film (P-1) with an adhesive layer prepared in the above (3) was cut to a length of 200 mm × 150 mm so that the extension axis direction of the polarizing plate became a long side, and the release film was peeled off to expose the exposed adhesive layer. Laminated on a glass substrate. The obtained test piece (the optical film with an adhesive layer attached to the glass substrate) to which the obtained glass substrate was attached was pressurized in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. As the glass substrate, alkali-free glass manufactured by Corning Corporation and trade name "Eagle XG" was used. The obtained optical laminated body was subjected to the following three types of durability tests.
‧溫度85℃的乾燥條件下保持750小時的耐熱測試;‧溫度60℃、相對濕度90%的環境下保持750小時的耐濕熱測試;‧以溫度85℃的乾燥條件下保持30分鐘,然後-40℃的乾燥條件下保持30分鐘為1循環,重複400循環的耐熱衝擊(HS)測試。 ‧Heat resistance test for 750 hours under dry conditions at a temperature of 85 ℃; ‧Heat resistance test for 750 hours under an environment with a temperature of 60 ℃ and a relative humidity of 90%; It was maintained at 40 ° C. for 30 minutes as one cycle, and the heat shock (HS) test was repeated for 400 cycles.
目視觀察各測試後的光學積層體,以目視觀察黏著劑層的浮起、剝離、起泡等的外觀變化的有無,根據下述的評價基準,評價耐久性。結果表示於表3。 The optical laminate after each test was visually observed, the presence or absence of appearance changes such as floating, peeling, and foaming of the adhesive layer was visually observed, and durability was evaluated according to the following evaluation criteria. The results are shown in Table 3.
4:完全無法認知浮起、剝離、起泡等的外觀變化 4: It is impossible to recognize appearance changes such as floating, peeling, and foaming
3:幾乎無法認知浮起、剝離、起泡等的外觀變化 3: It is almost impossible to recognize appearance changes such as floating, peeling, and foaming
2:稍微看到浮起、剝離、起泡等的外觀變化 2: Slight changes in appearance such as floating, peeling, and foaming
1:顯著地確認浮起、剝離、起泡等的外觀變化 1: Significantly confirm appearance changes such as floating, peeling, and foaming
將上述(3)製作的附黏著劑層之光學膜(P-1),裁切為25mm×150mm的測試片。從該測試片剝離離型膜後,將 其黏著劑層面貼附於玻璃基板。將所得之貼附玻璃基板的測試片(貼附玻璃基板的附黏著劑層之光學膜),於高壓釜中,於溫度50℃、壓力5kg/cm2(490.3kPa)下加壓20分鐘。然後,於溫度50℃的烘箱中保持48小時後,再於溫度23℃、相對濕度50%的環境中,從測試片將光學膜連黏著劑層一起以300mm/分的速度於180。方向剝離。觀察剝離後的玻璃基板表面的狀態,用以下的評價基準進行評價。結果表示於表3。 The optical film (P-1) with an adhesive layer prepared in the above (3) was cut into a test piece of 25 mm × 150 mm. After releasing the release film from the test piece, the adhesive layer was attached to a glass substrate. The obtained glass substrate-attached test piece (the optical film with an adhesive layer attached to the glass substrate) was pressed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Then, after keeping it in an oven at a temperature of 50 ° C. for 48 hours, the optical film was bonded to the adhesive layer at a speed of 300 mm / min from the test piece at 180 ° C. in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Direction peeling. The state of the surface of the glass substrate after peeling was observed, and it evaluated using the following evaluation criteria. The results are shown in Table 3.
4:玻璃基板的表面完全無法確認混濁、3:玻璃基板的表面幾乎無法確認混濁、2:玻璃基板的表面可確認有混濁、1:玻璃基板的表面確認黏著劑層的殘留 4: Cloudiness cannot be confirmed on the surface of the glass substrate at all, 3: Cloudiness can not be confirmed on the surface of the glass substrate at all, 2: Cloudiness can be confirmed on the surface of the glass substrate, 1: Residue of the adhesive layer can be confirmed on the surface of the glass substrate
將上述(4)製作的附黏著劑層之光學膜(P-2),裁切為30mm×30mm大小,剝離離型膜,將露出的黏著劑層面貼合於玻璃基板。玻璃基板係使用康寧公司製的無鹼玻璃、商品名「Eagle XG」。對所得之光學積層體,使用附積分球的分光光度計[日本分光(股)製的製品名「V7100」],測定波長380至780nm的範圍之MD穿透率及TD穿透率,算出各波長之單體穿透率、偏光度,再藉由JIS Z8701:1999「顏色顯示方法-XYZ表色系及X10Y10Z10表色系」之2度視野(C光源),進行視感度校正,求得耐久測試前的視 感度校正單體穿透率(Ty)及視感度校正偏光度(Py)。再者,光學積層體,係以偏光板的三乙醯基纖維素膜側為偵測器側,以從玻璃基板側射入光的方式設置於附積分球的分光光度計。 The optical film (P-2) with an adhesive layer prepared in the above (4) was cut into a size of 30 mm × 30 mm, the release film was peeled off, and the exposed adhesive layer was bonded to a glass substrate. As the glass substrate, alkali-free glass manufactured by Corning Corporation and trade name "Eagle XG" was used. For the obtained optical multilayer body, using a spectrophotometer with a integrating sphere [product name "V7100" manufactured by JASCO Corporation), the MD transmittance and TD transmittance in the range of 380 to 780 nm were measured, and each was calculated. The single-wavelength transmittance and polarization degree of the wavelength, and then the visual sensitivity of the 2-degree field of view (C light source) according to JIS Z8701: 1999 "Color display method-XYZ color system and X 10 Y 10 Z 10 color system" Correction: Obtain the visual sensitivity correction unit transmittance (Ty) and visual sensitivity correction polarization (Py) before the endurance test. In addition, the optical laminated body is a spectrophotometer with an integrating sphere, with the triethyl cellulose film side of the polarizing plate as the detector side, and the light entering from the glass substrate side.
單體穿透率及偏光度,係分別以下述式定義:單體穿透率(λ)=0.5×(Tp(λ)+Tc(λ)) The cell transmittance and polarization are defined by the following formulas: cell transmittance (λ) = 0.5 × (Tp (λ) + Tc (λ))
偏光度(λ)=100×((Tp(λ)-Tc(λ))/(Tp(λ)+Tc(λ)))。Tp(λ)係以入射的波長λ(nm)的直線偏光與平行尼科爾(Parallel Nicol)的關係測定的光學積層體的穿透率(%),Tc(λ)係以入射的波長λ(nm)的直線偏光與交叉尼科爾(Cross Nicol)的關係測定的光學積層體的穿透率(%)。 Polarization (λ) = 100 × ((Tp (λ) -Tc (λ)) / (Tp (λ) + Tc (λ))). Tp (λ) is the transmittance (%) of the optical multilayer as measured by the relationship between the linearly polarized light at the incident wavelength λ (nm) and Parallel Nicol, and Tc (λ) is the incident wavelength λ (nm) The transmittance (%) of the optical laminate as measured by the relationship between linear polarized light and Cross Nicol.
然後,該光學積層體於溫度80℃、相對濕度90%的濕熱環境下放置24小時,再於溫度23℃、相對濕度60%的環境下放置24小時後,藉由與耐久測試前相同的方法,求得耐久測試後的Ty及Py。然後,從測試後的Py及Ty,分別減去測試前的Py及Ty,算出耐久測試前後的變化量,求得偏光度變化量(△Py)及單體穿透率變化量(△Ty)。△Py表示於表3。 Then, the optical laminated body was left for 24 hours in a hot and humid environment at a temperature of 80 ° C and a relative humidity of 90%, and then left for 24 hours in an environment of a temperature of 23 ° C and a relative humidity of 60% by the same method as before the endurance test. , Find the Ty and Py after the endurance test. Then, subtract the Py and Ty before the test from the Py and Ty after the test to calculate the change before and after the endurance test, and obtain the change in polarization (△ Py) and the change in monomer transmittance (△ Ty). . ΔPy is shown in Table 3.
於具備冷卻管、氮氣導入管、溫度計及攪拌機的反應容器,放入表4所示的組成(表4的數值為重量份)的單體與乙酸乙酯81.8份混合而得之溶液。以氮氣取代反應容器內的空氣後,將內溫升溫至60℃。然後,添加偶氮雙異丁腈0.12份溶解於乙酸乙酯10份的溶液。在相同溫度保持1小時後,一邊保持內溫為54至56℃,一邊以添加速度17.3份/小時連續朝反應容器內添加乙酸乙酯,使聚合物的濃度成為約35%。從添加乙酸乙酯開始到經過12小時為止保持54至56℃後,添加乙酸乙酯,調整使聚合物的濃度成為20%,得到(甲基)丙烯酸系樹脂(A-1)的乙酸乙酯溶液。(甲基)丙烯酸系樹脂(A-1)的重量平均分子量Mw為139萬,重量平均分子量Mw與數量平均分子量Mn的比Mw/Mn為5.32。於凝膠滲透層析(GPC)之排出曲線,Mw139萬的成分顯示單一波峰,於Mw1000至250萬的範圍,未見到其他波峰。 In a reaction vessel including a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, a solution obtained by mixing a monomer having a composition shown in Table 4 (the numerical value in Table 4 is parts by weight) with 81.8 parts of ethyl acetate was placed. After replacing the air in the reaction vessel with nitrogen, the internal temperature was raised to 60 ° C. Then, a solution in which 0.12 parts of azobisisobutyronitrile was dissolved in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, while maintaining the internal temperature at 54 to 56 ° C., ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts / hour, so that the polymer concentration became approximately 35%. After maintaining the temperature at 54 to 56 ° C. for 12 hours from the start of the addition of ethyl acetate, the concentration of the polymer was adjusted to 20% to obtain ethyl acetate of the (meth) acrylic resin (A-1). Solution. The weight average molecular weight Mw of the (meth) acrylic resin (A-1) was 1.39 million, and the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn was 5.32. In the discharge curve of gel permeation chromatography (GPC), the composition of Mw 1.39 million showed a single peak. In the range of Mw 1000 to 2.5 million, no other peak was seen.
於上述製造例,重量平均分子量Mw及數量平均分子量Mn,於GPC裝置,以Tosoh(股)製的「TSKgel XL」4根及昭和電工(股)製的昭光通商(股)販售的「Shodex GPC KF-802」1根的共5根配置成串列作為管柱,使用四氫呋喃作為洗提液,樣品濃度為5mg/mL,樣品導入量為100μL,於溫度40℃,流速1mL/分的條件下,藉由換算標準聚苯乙烯測定。得到GPC之排出曲線時的條件也與其相同。 In the above manufacturing example, the weight average molecular weight Mw and the number average molecular weight Mn were sold in a GPC device with 4 "TSKgel XL" manufactured by Tosoh Corporation, and "Shodex" sold by Showa Denki Co., Ltd. A total of 5 GPC KF-802 "s were arranged in series as a column, using tetrahydrofuran as an eluent, a sample concentration of 5 mg / mL, a sample introduction amount of 100 μL, and a temperature of 40 ° C and a flow rate of 1 mL / min. In the following, it is measured by converting standard polystyrene. The conditions under which the GPC discharge curve is obtained are also the same.
玻璃轉移溫度Tg係使用SII奈米科技公司製的示差掃描熱量計(DSC)「EXSTAR DSC600」,在氮氣環境下,測定溫度範圍為-80至50℃、升溫溫度10℃/分的條件下測定。 The glass transition temperature Tg is measured using a differential scanning calorimeter (DSC) "EXSTAR DSC600" manufactured by SII Nano Technology Co., Ltd., under a nitrogen environment, the measurement temperature range is -80 to 50 ° C, and the temperature rise temperature is 10 ° C / min. .
各製造例之單體的組成(表4的數值為重量份)及GPC的排出曲線上的Mw1000至250萬的範圍之波峰數(於表4表示為「GPC波峰數」)彙整於表4。 The composition of the monomers in each manufacturing example (the numerical values in Table 4 are parts by weight) and the number of peaks in the range of Mw1000 to 2.5 million (expressed as "GPC peak number" in Table 4) on the GPC discharge curve are summarized in Table 4.
表4的「單體組成」的欄之簡稱,係指以下的單體。 The abbreviations in the column of "monomer composition" in Table 4 refer to the following monomers.
BA:丙烯酸丁酯(均聚物的玻璃轉移溫度:-54℃) BA: butyl acrylate (glass transition temperature of homopolymer: -54 ° C)
MA:丙烯酸甲酯(均聚物的玻璃轉移溫度:10℃) MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C)
HEA:丙烯酸2-羥基乙酯 HEA: 2-hydroxyethyl acrylate
於上述製造例所得之(甲基)丙烯酸系樹脂的乙酸乙酯溶液(樹脂濃度:20%),對該溶液的固體成分100份,分別依表5所示的量(重量份)混合表5所示的異氰酸酯系交聯劑(B)、矽烷化合物(C)及離子性化合物(D),再添加乙酸乙酯,使固體成分濃度為14%,得到黏著劑組成物。表5所示的各調配成分的調配量,於使用的商品包含溶劑等的情況,為包含於其中的有效成分的重量份數。 In the ethyl acetate solution (resin concentration: 20%) of the (meth) acrylic resin obtained in the above production example, 100 parts of the solid content of the solution were mixed in the amounts (parts by weight) shown in Table 5 respectively. Table 5 The isocyanate-based cross-linking agent (B), the silane compound (C), and the ionic compound (D) were added, and ethyl acetate was added to a solid content concentration of 14% to obtain an adhesive composition. The formulation amount of each formulation component shown in Table 5 is a weight part of the active ingredient contained in the case where the product used contains a solvent etc.
於表5,簡稱所示的各調配成分的詳細,係如以下。 In Table 5, the details of each compounding component shown by the abbreviation are as follows.
B-1:伸二甲苯基二異氰酸酯的三羥甲基丙烷加成物的乙酸乙酯溶液(固體成分濃度75%)、從三井化學(股)公司取得的商品名「TAKENATE D-110N」 B-1: Ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate (solid content concentration 75%), trade name "TAKENATE D-110N" obtained from Mitsui Chemicals Co., Ltd.
C-1:3-環氧丙氧基丙基三甲氧基矽烷、從信越化學工業(股)公司取得的商品名「KBM403」。 C-1: 3-glycidoxypropyltrimethoxysilane, trade name "KBM403" obtained from Shin-Etsu Chemical Industry Co., Ltd.
D-1:雙(氟磺醯基)亞胺 鉀 D-1: Bis (fluorosulfonyl) imide potassium
D-2:雙(三氟甲烷磺醯基)亞胺 鋰 D-2: Bis (trifluoromethanesulfonyl) imide lithium
D-3:N-辛基-4-甲基吡啶鎓 六氟磷酸鹽 D-3: N-octyl-4-methylpyridinium hexafluorophosphate
D-4:碘化鋰 D-4: lithium iodide
將上述(1)調製的各黏著劑組成物,使用塗敷器,塗佈於施以離型處理的聚對苯二甲酸乙二酯所構成的離型膜[LINTEC公司取得之「PLR-382051」]的離型處理面,使乾燥後的厚度成為20μm,於100℃下乾燥1分鐘,製作黏著劑層(黏著劑片)。 Each of the adhesive compositions prepared in the above (1) was applied to a release film made of polyethylene terephthalate subjected to a release treatment using an applicator [PLR-382051 obtained by LINTEC Corporation]. "] The release-treated surface was adjusted to a thickness of 20 µm after drying, and dried at 100 ° C for 1 minute to prepare an adhesive layer (adhesive sheet).
平均聚合度約2400、皂化度99.9莫耳%、厚度60μm的聚乙烯醇膜[可樂麗(Kuraray)公司製的商品名「Kuraray Vinylon VF-PE#6000」]浸漬於37℃的純水後,在30℃下浸漬於包含碘及碘化鉀的水溶液(碘/碘化鉀/水(重量比)=0.04/1.5/100)。然後,在56.5℃下浸漬於包含碘化鉀及硼酸的水溶液(碘化鉀/硼酸/水(重量比)=12/3.6/100)。將膜以10℃的純水洗淨後,於85℃乾燥,得到碘吸附配向於聚乙烯醇的厚度約23μm的偏光片。延伸,主要在碘染色及硼酸處理的步驟進行,全部的延伸倍率為5.3倍。 A polyvinyl alcohol film with an average degree of polymerization of about 2400, a degree of saponification of 99.9 mol%, and a thickness of 60 μm [Kuraray Vinylon VF-PE # 6000 manufactured by Kuraray Co., Ltd.] was immersed in pure water at 37 ° C. An aqueous solution (iodine / potassium iodide / water (weight ratio) = 0.04 / 1.5 / 100) containing iodine and potassium iodide was immersed at 30 ° C. Then, it was immersed in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100) at 56.5 ° C. The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizer having a thickness of about 23 μm that is iodine-adsorbed and aligned with polyvinyl alcohol. Stretching is mainly performed in the steps of iodine staining and boric acid treatment, and the total stretching ratio is 5.3 times.
於所得之偏光片的單面,隔著聚乙烯醇系樹脂的水溶液所構成的接著劑,貼合厚度25μm的三乙醯基纖維素膜所構成的透明保護膜[柯尼卡美能達光學(股)製的商品名「KC2UA」]。然後,於與上述偏光片之三乙醯基纖維素膜相反側的面,隔著聚乙烯醇系樹脂的水溶液所構成的接著劑,貼合厚度23μm的環狀聚烯烴系樹脂所構成的零相位差膜[日本ZEON(股)製的商品名「ZEONOR」],製作偏光板。然後,於零相位差膜之與偏光片接觸的面的相反側的面,實施為了提高密著性的電暈放電處理後,藉由積層機貼合上述(2)製作的黏著劑層的離型膜相反側的面(黏著劑層面)後,在溫度23℃、相對濕度65%的條件下熟成7天,得到附黏著劑層之光學膜(P-1)。 On one side of the obtained polarizer, a transparent protective film composed of a triethylfluorene-based cellulose film having a thickness of 25 μm was bonded through an adhesive made of an aqueous solution of a polyvinyl alcohol resin [Konica Minolta Optics ( "KC2UA"). Then, on the surface opposite to the triacetamyl cellulose film of the above-mentioned polarizer, an adhesive made of an aqueous solution of a polyvinyl alcohol-based resin was laminated to a zero-thickness of a cyclic polyolefin resin having a thickness of 23 μm. A retardation film [trade name "ZEONOR" manufactured by ZEON (Japan)] was used to produce a polarizing plate. Then, a corona discharge treatment is performed on the surface of the zero-phase retardation film opposite to the surface in contact with the polarizer to improve adhesion, and then the lamination machine is used to bond the release layer of the adhesive layer prepared in (2) above. After the surface (adhesive layer) on the opposite side of the mold film was aged at a temperature of 23 ° C. and a relative humidity of 65% for 7 days, an optical film (P-1) with an adhesive layer was obtained.
將上述(3)製作的附黏著劑層之光學膜(P-1),裁切為20mm×50mm大小的測試片,隔著黏著劑層,貼附於附金屬層的玻璃基板的金屬層側。附金屬層的玻璃基板係使用於無鹼玻璃表面藉由濺鍍積層厚度約500nm的金屬鋁層之玻璃基板(GEOMATEC公司製)。所得之光學積層體於溫度60℃、相對濕度90%的烤箱中保管500小時後,附黏著劑層之光學膜所貼附的部分之金屬層的狀態,從玻璃基板的背面對著光,從偏光板表面通過放大鏡觀察,關於孔蝕(直徑0.1mm以上,可穿透光的孔之發生),用以下的基準評價。結果表示於表6。 The optical film (P-1) with an adhesive layer prepared in the above (3) was cut into a test piece having a size of 20 mm × 50 mm, and the metal layer was attached to the metal layer side of the glass substrate with a metal layer through the adhesive layer. . The glass substrate with a metal layer is a glass substrate (manufactured by GEOMATEC) used on the surface of an alkali-free glass by sputtering a metal aluminum layer having a thickness of about 500 nm. After the obtained optical laminated body was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 500 hours, the state of the metal layer of the portion to which the optical film with the adhesive layer was attached was directed from the back of the glass substrate to the light, The surface of the polarizing plate was observed with a magnifying glass, and the pitting corrosion (the occurrence of holes having a diameter of 0.1 mm or more that can penetrate light) was evaluated by the following criteria. The results are shown in Table 6.
將上述(3)製作的附黏著劑層之光學膜(P-1),裁切為20mm×50mm大小的測試片,隔著黏著劑層,貼附於附金屬層的玻璃基板的金屬層側。附金屬層的玻璃基板係使用藉由濺鍍積層厚度約500nm的銀合金(包含銀為主成分、鈀及銅的合金、APC)層於無鹼玻璃表面之玻璃基板。所得之光學積層體於溫度60℃、相對濕度90%的烤箱中保管500小時後,附黏著劑層之光學膜所貼附的部分之金屬層的狀態,從玻璃基板的背面對著光,從偏光板表面通過放大鏡觀察,關於孔蝕(直徑0.1mm以上,可穿透光的孔之發生),用以下的基準評價。結果表示於表6。 The optical film (P-1) with an adhesive layer prepared in the above (3) was cut into a test piece having a size of 20 mm × 50 mm, and the metal layer was attached to the metal layer side of the glass substrate with the adhesive layer therebetween. . The glass substrate with a metal layer is a glass substrate using a silver alloy (containing silver as the main component, an alloy of palladium and copper, and APC) with a thickness of about 500 nm on the surface of an alkali-free glass by sputtering. After the obtained optical laminated body was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 500 hours, the state of the metal layer of the portion to which the optical film with the adhesive layer was attached was directed from the back of the glass substrate to the light, The surface of the polarizing plate was observed with a magnifying glass, and the pitting corrosion (the occurrence of holes having a diameter of 0.1 mm or more that can penetrate light) was evaluated by the following criteria. The results are shown in Table 6.
4:發生於金屬層表面的孔蝕的數目為2個以下、3:發生於金屬層表面的孔蝕的數目為3個至5個、 2:發生於金屬層表面的孔蝕的數目為6個以上、1:金屬層表面的全部表面發生多數孔蝕且發生白濁。 4: The number of pitting corrosion occurring on the surface of the metal layer is 2 or less, 3: the number of pitting corrosion occurring on the surface of the metal layer is 3 to 5, and the number of pitting corrosion occurring on the surface of the metal layer is 6 More than one, 1: The entire surface of the metal layer surface has a large number of pitting corrosions and white turbidity.
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2016
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- 2016-03-29 TW TW107108451A patent/TW201823015A/en unknown
- 2016-03-29 CN CN201610184576.7A patent/CN106019447B/en active Active
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2017
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2018
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI822773B (en) * | 2018-09-27 | 2023-11-21 | 日商藤森工業股份有限公司 | Adhesive composition, adhesive film, surface-protective film, surface-protective film for polarizing plate and optical film with an adhesive layer |
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TW201741130A (en) | 2017-12-01 |
KR101858405B1 (en) | 2018-05-15 |
TWI621525B (en) | 2018-04-21 |
JP2016193603A (en) | 2016-11-17 |
KR102568075B1 (en) | 2023-08-17 |
KR20160117282A (en) | 2016-10-10 |
KR20230126683A (en) | 2023-08-30 |
JP2017186566A (en) | 2017-10-12 |
KR102513209B1 (en) | 2023-03-22 |
TW201702345A (en) | 2017-01-16 |
KR20170117907A (en) | 2017-10-24 |
TWI597340B (en) | 2017-09-01 |
KR20180053604A (en) | 2018-05-23 |
CN110308509B (en) | 2022-04-15 |
CN106019447A (en) | 2016-10-12 |
KR102665602B1 (en) | 2024-05-14 |
CN110308509A (en) | 2019-10-08 |
JP6753813B2 (en) | 2020-09-09 |
KR101785198B1 (en) | 2017-10-12 |
KR20220020294A (en) | 2022-02-18 |
CN106019447B (en) | 2019-08-02 |
JP6170202B2 (en) | 2017-07-26 |
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