TW201702063A - Optical laminate and liquid crystal display device - Google Patents
Optical laminate and liquid crystal display device Download PDFInfo
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- TW201702063A TW201702063A TW105109824A TW105109824A TW201702063A TW 201702063 A TW201702063 A TW 201702063A TW 105109824 A TW105109824 A TW 105109824A TW 105109824 A TW105109824 A TW 105109824A TW 201702063 A TW201702063 A TW 201702063A
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- B32B15/00—Layered products comprising a layer of metal
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- 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
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
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- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- 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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- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/28—Metal sheet
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- 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
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- G—PHYSICS
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- 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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- 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
- G02F1/133528—Polarisers
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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
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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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- 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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Abstract
Description
本發明係關於一種構成液晶顯示裝置等圖像顯示裝置之光學積層體、及包含光學積層體之液晶顯示裝置。 The present invention relates to an optical layered body constituting an image display device such as a liquid crystal display device, and a liquid crystal display device including the optical layered body.
於偏光片之單面或雙面積層貼合透明樹脂膜而成之偏光板為代表之光學膜,係被廣泛使用來作為構成液晶顯示裝置等圖像顯示裝置之光學構件。如偏光板之光學膜係多為透過黏著劑層而貼合於其他構件(例如液晶顯示裝置中之液晶單元等)而使用(例如參照日本特開2010-229321號公報)。因此,就光學膜而言,已知於其一面預先設有黏著劑層之附黏著劑層之光學膜。又,為賦予抗靜電性,亦已知於黏著劑層含有離子性化合物者。 An optical film represented by a polarizing plate in which a transparent resin film is bonded to a single surface or a double-area layer of a polarizing plate is widely used as an optical member constituting an image display device such as a liquid crystal display device. The optical film of the polarizing plate is often used by being bonded to another member (for example, a liquid crystal cell in a liquid crystal display device) through an adhesive layer (for example, see JP-A-2010-229321). Therefore, in the case of an optical film, an optical film in which an adhesive layer of an adhesive layer is provided in advance is known. Further, in order to impart antistatic properties, it is also known that the adhesive layer contains an ionic compound.
近年,液晶顯示裝置係已被拓展至智慧型手機或桌上型終端、車載用導航系統為代表之具有觸控面板機能的攜帶型機器用途。在如此之觸控輸入式液晶顯示裝置中附黏著劑層之光學膜,亦有於例如由金屬配線所構 成之金屬層以透過例如樹脂層或直接接觸之方式配置該黏著劑層。然而,在將由金屬材料所構成之金屬層及含有離子性化合物之黏著劑層組合而成之構成中,亦有在高溫高濕環境下金屬層腐蝕之情況。腐蝕之中,孔蝕係金屬層之厚度為較薄之情形,或金屬層為金屬配線時其線寬較窄之情形,由於金屬層會完全貫通,故特別成為問題。 In recent years, liquid crystal display devices have been extended to portable mobile phones with touch panel functions represented by smart phones or desktop terminals and car navigation systems. The optical film with an adhesive layer in such a touch input type liquid crystal display device is also constructed, for example, by metal wiring. The metal layer is disposed such that the adhesive layer is disposed through, for example, a resin layer or in direct contact. However, in the configuration in which a metal layer composed of a metal material and an adhesive layer containing an ionic compound are combined, the metal layer may be corroded in a high-temperature and high-humidity environment. In the case of corrosion, when the thickness of the pitting metal layer is thin, or when the metal layer is metal wiring, the line width is narrow, and the metal layer is completely penetrated, which is particularly problematic.
本發明之目的在於提供一種光學積層體及包含該光學積層體之液晶顯示裝置,該光學積層體於如金屬配線層之金屬層上積層附黏著劑層之光學膜,並可抑制金屬層之腐蝕的光學積層體。 An object of the present invention is to provide an optical layered body and a liquid crystal display device comprising the same, which can deposit an optical film with an adhesive layer on a metal layer such as a metal wiring layer, and can suppress corrosion of the metal layer. Optical laminate.
本發明係提供如下所示之光學積層體、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 layered body as shown below, a liquid crystal display device including the optical layered body, and an adhesive composition.
[1]一種光學積層體,其係依序含有光學膜、黏著劑層及金屬層, 前述黏著劑層係含有對於60℃之水100g的溶解度為6g以下之離子性化合物。 [1] An optical laminate comprising an optical film, an adhesive layer and a metal layer in sequence. The pressure-sensitive adhesive layer contains an ionic compound having a solubility of 100 g or less per 100 g of water at 60 ° C.
[2]如[1]項所述之光學積層體,其中,前述離子性化合物之陰離子為含氟原子之亞胺(imide)陰離子。 [2] The optical layered product according to [1], wherein the anion of the ionic compound is an imide anion of a fluorine atom.
[3]如[1]項所述之光學積層體,其中,前述離子性化合物之陰離子為雙(氟磺醯基)亞胺陰離子或雙(三氟甲烷磺醯基)亞胺陰離子。 [3] The optical layered product according to [1], wherein the anion of the ionic compound is a bis(fluorosulfonyl)imide anion or a bis(trifluoromethanesulfonyl)imide anion.
[4]如[1]項所述之光學積層體,其中,前述離子性化合物之陰離子為雙(氟磺醯基)亞胺陰離子。 [4] The optical layered product according to [1], wherein the anion of the ionic compound is a bis(fluorosulfonyl)imide anion.
[5]一種光學積層體,其係依序含有光學
膜、黏著劑層及金屬層,
前述黏著劑層係包含下述式(I)所示之離子性化合物:
(式中,R1及R2分別獨立地表示氫原子、或可含有雜原子之碳數1至16之烴基,R3表示可含有雜原子之碳數4至20之烴基,X-表示含有氟原子之亞胺陰離子)。 (wherein R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms which may contain a hetero atom, and R 3 represents a hydrocarbon group having 4 to 20 carbon atoms which may contain a hetero atom, and X - represents An imine anion of a fluorine atom).
[6]如[5]項所述之光學積層體,其中,前述式(I)之R3係碳數為4或5。 [6] The optical layered product according to [5], wherein the R 3 series carbon number of the above formula (I) is 4 or 5.
[7]一種光學積層體,其係依序含有光學膜、黏著劑層及金屬層,
前述黏著劑層係含有下述式(II)所示之離子性化合物:
(式中,R4係表示碳數3至16之直鏈或分枝構造之烷基,R5至R9係分別獨立地表示氫原子、可具有取代基之烷基、可具有取代基之烯基、可具有取代基之炔基、可具有取代基之芳基、可具有取代基之雜環基、羥基、醚基、羧基、羰基、或鹵素原子,相鄰之取代基彼此可形成環,X-係表示與前述相同之意義)。 (wherein R 4 represents an alkyl group having a linear or branched structure of 3 to 16 carbon atoms, and R 5 to R 9 each independently represent a hydrogen atom, an alkyl group which may have a substituent, and may have a substituent. An alkenyl group, an alkynyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a hydroxyl group, an ether group, a carboxyl group, a carbonyl group, or a halogen atom, and adjacent substituents may form a ring with each other , X - means the same meaning as described above).
[8]如[7]項所述之光學積層體,其中,前 述式(II)之R5至R9係分別獨立地表示氫原子、或碳數1至16之直鏈或分枝構造的烷基。 [8] The optical layered product according to [7], wherein R 5 to R 9 of the above formula (II) each independently represent a hydrogen atom or a linear or branched structure having a carbon number of 1 to 16. alkyl.
[9]如[5]至[8]項中任一項所述之光學積層體,其中,前述X-係雙(氟磺醯基)亞胺陰離子或雙(三氟甲烷磺醯基)亞胺陰離子。 The optical layered body according to any one of the above aspects, wherein the X - based bis(fluorosulfonyl)imide anion or bis(trifluoromethanesulfonyl) Amine anion.
[10]如[5]至[8]項中任一項所述之光學積層體,其中,前述X-係雙(氟磺醯基)亞胺陰離子。 [10] The optical layered product according to any one of [5] to [8] wherein the X - based bis(fluorosulfonyl)imide anion.
[11]如[1]至[10]項中任一項所述之光學積層體,其中,前述黏著劑層另含有(甲基)丙烯酸系樹脂, 前述(甲基)丙烯酸系樹脂係含有源自均聚物之玻璃轉移溫度未達0℃之丙烯酸烷酯(a1)之構成單元、及源自均聚物之玻璃轉移溫度為0℃以上之丙烯酸烷酯(a2)之構成單元。 [11] The optical layered product according to any one of [1], wherein the adhesive layer further contains a (meth)acrylic resin. The (meth)acrylic resin contains a constituent unit derived from an alkyl acrylate (a1) having a glass transition temperature of less than 0 ° C derived from a homopolymer, and an acrylic acid having a glass transition temperature of 0 ° C or higher derived from a homopolymer. a constituent unit of the alkyl ester (a2).
[12]如[11]項所述之光學積層體,其中,前述(甲基)丙烯酸系樹脂係前述源自丙烯酸烷酯(a2)之構成單元的含量在構成前述(甲基)丙烯酸系樹脂之全構成單元100重量份中為10重量份以上。 The optical layered product according to the above-mentioned (meth)acrylic resin, wherein the content of the constituent unit derived from the alkyl acrylate (a2) is constituting the (meth)acrylic resin. 10 parts by weight or more of 100 parts by weight of the total constituent unit.
[13]如[11]或[12]項所述之光學積層體,其中,前述丙烯酸烷酯(a2)係包含丙烯酸甲酯。 [13] The optical layered product according to [11] or [12] wherein the alkyl acrylate (a2) comprises methyl acrylate.
[14]如[1]至[13]項中任一項所述之光學積層體,其中,前述金屬層含有選自由鋁、銅、銀、鐵、錫、鋅、鎳、鉬、鉻、鎢、鉛及含有選自此等之2種以上的金屬之合金所構成之群的1種以上。 [14] The optical layered body according to any one of [1] to [13] wherein the metal layer contains aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten One or more of the group consisting of lead and an alloy containing two or more kinds of metals selected from these.
[15]如[1]至[14]項中任一項所述之光學 積層體,其中,前述金屬層含有鋁元素。 [15] The optical according to any one of [1] to [14] A laminate in which the aforementioned metal layer contains an aluminum element.
[16]如[1]至[15]項中任一項所述之光學積層體,其中,前述金屬層係藉濺鍍所形成之層。 [16] The optical layered body according to any one of [1] to [15] wherein the metal layer is a layer formed by sputtering.
[17]如[1]至[16]項中任一項所述之光學積層體,其中,前述金屬層之厚度為3μm以下。 The optical layered body according to any one of the aspects of the present invention, wherein the metal layer has a thickness of 3 μm or less.
[18]一種液晶顯示裝置,係含有[1]至[17]項中任一項所述之光學積層體。 [18] A liquid crystal display device comprising the optical layered body according to any one of [1] to [17].
[19]一種黏著劑組成物,係含有(甲基)丙烯酸系樹脂及離子性化合物,且使用於要被積層在金屬層上之黏著劑層的形成。 [19] An adhesive composition comprising a (meth)acrylic resin and an ionic compound and used for forming an adhesive layer to be laminated on a metal layer.
前述離子性化合物係對於60℃之水100g的溶解度為6g以下者。 The ionic compound is one in which the solubility in 100 g of water at 60 ° C is 6 g or less.
[20]一種黏著劑組成物,係含有(甲基)丙烯酸系樹脂及離子性化合物,且使用於要被積層在金屬層上之黏著劑層的形成。 [20] An adhesive composition comprising a (meth)acrylic resin and an ionic compound and used for forming an adhesive layer to be laminated on a metal layer.
前述離子性化合物係下述式(I)所示之離子性化合物:
(式中,R1及R2係分別獨立地表示氫原子、或可含有雜原子之碳數1至16的烴基,R3係表示可含有雜原子之碳數4至20的烴基,X-表示含有氟原子之亞胺陰離子)。 (wherein R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms which may contain a hetero atom, and R 3 represents a hydrocarbon group having 4 to 20 carbon atoms which may contain a hetero atom, X - Indicates an imine anion containing a fluorine atom).
[21]一種黏著劑組成物,係含有(甲基)丙烯酸系樹脂及離子性化合物,且使用於要被積層在金屬層上之黏著劑層的形成。 [21] An adhesive composition comprising a (meth)acrylic resin and an ionic compound and used for forming an adhesive layer to be laminated on a metal layer.
前述離子性化合物係下述式(II)所示之離子性化合物:
(式中,R4係表示碳數3至16之直鏈或分枝構造的烷基,R5至R9係分別獨立地表示氫原子、可具有取代基之烷基、可具有取代基之烯基、可具有取代基之炔基、可具有取代基之芳基、可具有取代基之雜環基、羥基、醚基、羧基、羰基、或鹵素原子,相鄰之取代基彼此可形成環;X-係表示與前述相同之意義)。 (wherein R 4 represents an alkyl group having a linear or branched structure of 3 to 16 carbon atoms, and R 5 to R 9 each independently represent a hydrogen atom, an alkyl group which may have a substituent, and may have a substituent. An alkenyl group, an alkynyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a hydroxyl group, an ether group, a carboxyl group, a carbonyl group, or a halogen atom, and adjacent substituents may form a ring with each other The X - line means the same meaning as described above).
若依據本發明,可提供一種可抑制金屬層之腐蝕的光學積層體、及包含該光學積層體之液晶顯示裝置。 According to the present invention, an optical layered body capable of suppressing corrosion of a metal layer and a liquid crystal display device including the optical layered 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‧‧‧1st resin film
4‧‧‧第2樹脂膜 4‧‧‧2nd resin film
5、6、7‧‧‧光學積層體 5, 6, 7‧‧‧ Optical laminates
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圖係表示本發明之光學積層體的一例之概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing an example of an optical layered body of the present invention.
第2圖係表示偏光板之層構成的一例之概略剖面圖。 Fig. 2 is a schematic cross-sectional view showing an example of a layer configuration of a polarizing plate.
第3圖係表示偏光板之層構成的另一例的概略剖面 圖。 Fig. 3 is a schematic cross-sectional view showing another example of the layer configuration of the polarizing plate Figure.
第4圖係表示光學積層體之層構成的一例之概略剖面圖。 Fig. 4 is a schematic cross-sectional view showing an example of a layer configuration of an optical layered body.
第5圖係表示光學積層體之層構成的另一例之概略剖面圖。 Fig. 5 is a schematic cross-sectional view showing another example of the layer configuration of the optical layered body.
第6圖係表示光學積層體之層構成的另一例之概略剖面圖。 Fig. 6 is a schematic cross-sectional view showing another example of the layer configuration of the optical layered body.
第7圖係表示光學積層體之層構成的另一例之概略剖面圖。 Fig. 7 is a schematic cross-sectional view showing another example of the layer constitution of the optical layered body.
第1圖係表示本發明之光學積層體的一例之概略剖面圖。如第1圖所示,本發明之光學積層體係依序包含光學膜10、黏著劑層20、及金屬層30,可更包含基板。該光學積層體係可使附黏著劑層之光學膜1透過該黏著劑層20貼合於基板40上所形成之金屬層30上而成者,該附黏著劑層之光學膜1係包含光學膜10、及積層於其至少一面上之黏著劑層20。 Fig. 1 is a schematic cross-sectional view showing an example of an optical layered body of the present invention. As shown in Fig. 1, the optical layering system of the present invention sequentially includes the optical film 10, the adhesive layer 20, and the metal layer 30, and may further include a substrate. The optical layering system can be formed by adhering the optical film 1 with an adhesive layer to the metal layer 30 formed on the substrate 40 through the adhesive layer 20, and the optical film 1 of the adhesive layer comprises an optical film. 10. An adhesive layer 20 laminated on at least one side thereof.
黏著劑層20係通常直接積層於光學膜10之表面。又,通常,附黏著劑層之光學膜1係以該黏著劑層20直接接觸金屬層30之方式積層於金屬層30上。若依據本發明,在如此之光學積層體中,可有效地抑制金屬層30之腐蝕。以下,亦將可抑制金屬層30腐蝕的性質稱為 「耐金屬腐蝕性」。 The adhesive layer 20 is usually laminated directly on the surface of the optical film 10. Further, in general, the optical film 1 with the adhesive layer is 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 layered body, corrosion of the metal layer 30 can be effectively suppressed. Hereinafter, the property of suppressing corrosion of the metal layer 30 is also referred to as "Corrosion resistance to metals".
光學膜10係可為單層構造之光學膜,亦可為多層構造之光學膜。黏著劑層20係由包含規定之離子性化合物(D)之黏著劑組成物所構成。該黏著劑組成物通常更包含(甲基)丙烯酸系樹脂(A),亦可更含有異氰酸酯系交聯劑(B)及/或矽烷化合物(C)。該黏著劑組成物係亦可更包含其他成分。本說明書中,「(甲基)丙烯醯基」係意指選自由丙烯酸系及甲基丙烯酸系所構成之群中的至少一者。有關「(甲基)丙烯酸酯」或「(甲基)丙烯醯基」等亦同樣。 The optical film 10 may be an optical film of a single layer structure or an optical film of a multilayer structure. The adhesive layer 20 is composed of an adhesive composition containing a predetermined ionic compound (D). The adhesive composition usually further contains a (meth)acrylic resin (A), and may further contain an isocyanate crosslinking agent (B) and/or a decane compound (C). The adhesive composition may further comprise other ingredients. In the present specification, "(meth)acrylonitrile" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The same applies to "(meth) acrylate" or "(meth) acryl thiol".
[1]光學膜 [1] optical film
本發明之光學積層體具備之光學膜10係構成附黏著劑層之光學膜1的光學構件,可為組入於液晶顯示裝置等圖像顯示裝置之各種光學膜(具有光學特性之膜)。光學膜10係可為單層構造之光學膜,亦可為多層構造之光學膜。單層構造之光學膜的具體例係除偏光片之外,包含相位差膜、增亮膜、防眩膜、抗反射膜、擴散膜、聚光膜等光學機能性膜。多層構造之光學膜的具體例係包含偏光板、相位差板。本說明書中所謂偏光板係指於偏光片之至少一面積層樹脂膜或樹脂層者。相位差板係指於相位差膜之至少一面積層樹脂膜或樹脂層者。光學膜10較佳係偏光板、偏光片、相位差板或相位差膜,更佳係偏光板或偏光片。 The optical film 10 of the optical layered product of the present invention constitutes an optical member of the optical film 1 with an adhesive layer, and can be various optical films (films having optical characteristics) incorporated in an image display device such as a liquid crystal display device. The optical film 10 may be an optical film of a single layer structure or an optical film of a multilayer 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-concentrating film, in addition to the polarizer. Specific examples of the multilayer optical film include a polarizing plate and a phase difference plate. The polarizing plate in the present specification refers to a resin film or a resin layer of at least one area of the polarizing plate. The phase difference plate refers to a resin film or a resin layer of at least one area of the retardation film. The optical film 10 is preferably a polarizing plate, a polarizing plate, a phase difference plate or a retardation film, and more preferably a polarizing plate or a polarizing plate.
[1-1]偏光板 [1-1] Polarizer
第2圖及第3圖係表示偏光板之層構成的例之概略剖面圖。第2圖所示之偏光板10a係於偏光片2之一面積層貼合第1樹脂膜3之單面保護偏光板,第3圖所示之偏光板10b係於偏光片2之另一面更積層貼合第2樹脂膜4之雙面保護偏光板。第1、第2樹脂膜3、4係可透過未圖示之接著劑層或黏著劑層而貼合於偏光片2。偏光板10a,10b係亦可包含第1,第2樹脂膜3,4以外之其他膜或層。 2 and 3 are schematic cross-sectional views showing an example of a layer configuration of a polarizing plate. The polarizing plate 10a shown in Fig. 2 is a single-sided protective polarizing plate in which the first resin film 3 is bonded to one area of the polarizing plate 2, and the polarizing plate 10b shown in Fig. 3 is laminated on the other side of the polarizing plate 2. The double-sided protective polarizing plate to which the second resin film 4 is bonded is bonded. The first and second resin films 3 and 4 are bonded to the polarizer 2 through an adhesive layer or an adhesive layer (not shown). The polarizing plates 10a and 10b may include other films or layers other than the first and second resin films 3 and 4.
使用第2圖及第3圖所示之偏光板10a,10b作為光學膜10時之光學積層體的層構成之例分別表示於第4圖及第5圖。第4圖所示之光學積層體5係使用第2圖所示之偏光板10a作為光學膜10之例,第5圖所示之光學積層體6係使用第3圖所示之偏光板10b作為光學膜10之例。 Examples of the layer configuration of the optical layered body when the polarizing plates 10a and 10b shown in Figs. 2 and 3 are used as the optical film 10 are shown in Figs. 4 and 5, respectively. The optical layered body 5 shown in Fig. 4 is an example in which the polarizing plate 10a shown in Fig. 2 is used as the optical film 10. The optical layered body 6 shown in Fig. 5 is formed by using the polarizing plate 10b shown in Fig. 3 as the optical layered body 10b. An example of the optical film 10.
偏光片2係具有如下性質之膜:吸收具有平行於其吸收軸之振動面的直線偏光,透過具有正交於吸收軸之(與透過軸平行之)振動面的直線偏光;例如,可使用於聚乙烯醇系樹脂膜吸附配向二色性色素之膜。二色性色素係可使用碘或二色性有機染料。 The polarizer 2 is a film having a linear polarized light having a vibration plane parallel to the absorption axis thereof, and a linearly polarized light having a vibration plane orthogonal to the absorption axis (parallel to the transmission axis); for example, it can be used for The polyvinyl alcohol-based resin film adsorbs a film of a dichroic dye. As the dichroic dye system, iodine or a dichroic organic dye can be used.
聚乙烯醇系樹脂係可藉由使聚乙酸乙烯酯系樹脂皂化而獲得。聚乙酸乙烯酯系樹脂係除了乙酸乙烯酯之同元聚合物的聚乙酸乙烯酯之外,可舉例如可與乙酸乙烯酯共聚合之單體與乙酸乙烯酯之共聚物等。可與乙酸乙烯酯共聚合之單體係可舉例如不飽和羧酸、烯烴、乙烯基醚、不飽和磺酸、具有銨基之(甲基)丙烯醯胺等。 The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. The polyvinyl acetate-based resin may be, for example, a polyvinyl acetate which is a homopolymer of vinyl acetate, and may, for example, be a copolymer of a monomer copolymerizable with vinyl acetate and vinyl acetate. The single system which can be copolymerized with vinyl acetate may, for example, be an unsaturated carboxylic acid, an olefin, a vinyl ether, an unsaturated sulfonic acid, a (meth) acrylamide having an ammonium group, or the like.
聚乙烯醇系樹脂之皂化度通常為85至100莫耳%,較佳係98莫耳%以上。聚乙烯醇系樹脂係可被改質,例如亦可使用被醛類改質之聚乙烯基甲醛或聚乙烯基乙醛等。聚乙烯醇系樹脂之平均聚合度通常為1000至10000,較佳為1500至5000。聚乙烯醇系樹脂之平均聚合度係可依據JIS K6726而求取。 The degree of saponification of the polyvinyl alcohol-based resin is usually from 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formaldehyde or polyvinyl acetaldehyde modified with an aldehyde may be used. The average degree of polymerization of the polyvinyl alcohol-based resin is usually from 1,000 to 10,000, preferably from 1,500 to 5,000. The average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K6726.
通常,使用將聚乙烯醇系樹脂製膜而成者作為偏光片2之胚膜。聚乙烯醇系樹脂係可以公知之方法製膜。胚膜之厚度通常為1至150μm,若考量延伸之容易性等,較佳係10μm以上。 Usually, a film made of a polyvinyl alcohol-based resin is used as the embryonic film of the polarizer 2. The polyvinyl alcohol-based resin can be formed into a film by a known method. The thickness of the germ film is usually from 1 to 150 μm, and is preferably 10 μm or more in consideration of ease of stretching and the like.
偏光片2係實施如下步驟,最後加以乾燥而製造:例如對胚膜進行一軸延伸之步驟、以二色性色素將膜染色而吸附該二色性色素之步驟、以硼酸水溶液處理膜之步驟、及水洗膜之步驟。偏光片2之厚度通常為1至30μm,從附黏著劑層之光學膜1的薄膜化觀點,較佳係20μm以下,更佳係15μm以下,再更佳係10μm以下。 The polarizer 2 is subjected to the following steps, and is finally dried and produced: for example, a step of axially stretching the embryonic membrane, a step of dyeing the membrane with a dichroic dye to adsorb the dichroic dye, a step of treating the membrane with an aqueous solution of boric acid, And the step of washing the film. The thickness of the polarizer 2 is usually 1 to 30 μm, and is preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less from the viewpoint of thin film formation of the optical film 1 with an adhesive layer.
於聚乙烯醇系樹脂膜使二色性色素吸附配向而成之偏光片2可依據1)使用聚乙烯醇系樹脂膜之單獨膜作為胚膜,對該膜施予一軸延伸處理及二色性色素之染色處理的方法,2)於基材膜塗布含有聚乙烯醇系樹脂之塗佈液(水溶液等),並使其乾燥而獲得具有聚乙烯醇系樹脂層之基材膜後,將此基材膜整體進行一軸延伸,對於延伸後之聚乙烯醇系樹脂層施予二色性色素之染色處理,然後,藉由剝離除去基材膜之方法製得。基材膜係可使用與 可構成後述之第1、第2樹脂膜3、4之熱塑性樹脂同樣之熱塑性樹脂所構成之膜,較佳係由聚對苯二甲酸乙二酯等聚酯系樹脂、聚碳酸酯系樹脂、三乙醯基纖維素等纖維素系樹脂、降茨烯系樹脂等環狀聚烯烴系樹脂、聚苯乙烯系樹脂等所構成之膜。若依據上述2)之方法,容易製作薄膜之偏光片2,亦容易製作例如厚度7μm以下之偏光片2。 The polarizer 2 in which the dichroic dye is adsorbed and aligned in the polyvinyl alcohol-based resin film can be subjected to a single-axis stretching treatment and dichroism according to 1) using a separate film of a polyvinyl alcohol-based resin film as a germ film. (2) a method of dyeing a dye, 2) applying a coating liquid (aqueous solution or the like) containing a polyvinyl alcohol-based resin to a substrate film, and drying the substrate to obtain a base film having a polyvinyl alcohol-based resin layer. The entire base film is stretched by one axis, and the dyed process of the dichroic dye is applied to the stretched polyvinyl alcohol-based resin layer, and then the substrate film is removed by peeling off. Substrate film system can be used with A film composed of a thermoplastic resin similar to the thermoplastic resin of the first and second resin films 3 and 4 to be described later is preferably a polyester resin such as polyethylene terephthalate or a polycarbonate resin. A film composed of a cellulose resin such as triethylenesulfonyl cellulose, a cyclic polyolefin resin such as a decylene-based resin, or a polystyrene resin. According to the method of the above 2), it is easy to produce the polarizer 2 of the film, and it is also easy to produce the polarizer 2 having a thickness of, for example, 7 μm or less.
第1,第2樹脂膜3,4係可分別獨立為具有透光性者,其較佳係由光學性透明之熱塑性樹脂,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(降茨烯系樹脂等)類之聚烯烴系樹脂;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、或此等之混合物、共聚物等所構成之膜。其中,第1,第2樹脂膜3,4係分別以由環狀聚烯烴系樹脂、聚碳酸酯系樹脂、纖維素系樹脂、聚酯系樹脂、及(甲基)丙烯酸系樹脂所組成之群選出的樹脂所組成者為較佳,以由纖維素系樹脂及環狀聚烯烴系樹脂所組成之群中選出的樹脂所構成者為更佳。 Each of the first and second resin films 3 and 4 may be independently light transmissive, and is preferably an optically transparent thermoplastic resin such as a chain polyolefin resin (polyethylene resin or polypropylene resin). Or a polyolefin resin such as a cyclic polyolefin resin (such as a decene-based resin); a cellulose resin (such as a cellulose ester resin); and a polyester resin (polyethylene terephthalate) , polyethylene naphthalate, polybutylene terephthalate, etc.; polycarbonate resin; (meth)acrylic resin; polystyrene resin; polyether ether ketone resin; polyfluorene A resin, or a mixture of such a mixture, a copolymer, or the like. In addition, each of the first and second resin films 3 and 4 is composed of a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, and a (meth)acrylic resin. It is preferable that the resin selected from the group is composed of a resin selected from the group consisting of a cellulose resin and a cyclic polyolefin resin.
鏈狀聚烯烴系樹脂係除了聚乙烯樹脂、聚丙烯樹脂等鏈狀烯烴之均聚物之外,可舉例如由2種以上之鏈狀烯烴所構成之共聚物。 The chain-like polyolefin resin is a copolymer of two or more kinds of chain olefins, in addition to a homopolymer of a chain olefin such as a polyethylene resin or a polypropylene resin.
環狀聚烯烴系樹脂係含有以降茨烯或四環十二烯(別名:二甲橋萘(dimethanonaphthalene))或其等之衍 生物為代表例之環狀烯烴作為聚合單元之樹脂的總稱。若列舉環狀聚烯烴系樹脂之具體例,可為環狀烯烴之開環(共)聚合物及其氫化物、環狀烯烴之加成聚合物、環狀烯烴與乙烯、丙烯類鏈狀烯烴或具有乙烯基之芳香族化合物之共聚物、以及使此等以不飽和羧酸或其衍生物改質而成之改質(共)聚合物等。其中,以使用降茨烯或多環降茨烯系單體等降茨烯系單體作為環狀烯烴之降茨烯系樹脂為較佳。 The cyclic polyolefin resin contains deuterated or tetracyclododecene (alias: dimethanonaphthalene) or the like A generic term for a resin in which a cyclic olefin is a polymerized unit. Specific examples of the cyclic polyolefin-based resin include a ring-opened (co)polymer of a cyclic olefin, a hydrogenated product thereof, an addition polymer of a cyclic olefin, a cyclic olefin, and an ethylene or propylene chain olefin. Or a copolymer having an aromatic compound of a vinyl group, and a modified (co)polymer obtained by modifying such an unsaturated carboxylic acid or a derivative thereof. Among them, a decylene-based resin having a nordene-based monomer such as a norbornene or a polycyclic nordzene-based monomer as a cyclic olefin is preferred.
纖維素系樹脂較佳係纖維素酯系樹脂,亦即纖維素之部分或完全酯化物等,可舉例如纖維素之乙酸酯、丙酸酯、丁酸酯、其等之混合酯等。其中,以三乙醯基纖維素、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為較宜使用。 The cellulose resin is preferably a cellulose ester resin, that is, a partial or complete esterified product of cellulose, and examples thereof include cellulose acetate, propionate, butyrate, and a mixed ester thereof. Among them, triethyl fluorenyl cellulose, diethyl hydrazine cellulose, cellulose acetate propionate, cellulose acetate butyrate or the like is preferably used.
聚酯系樹脂係具有酯鍵之上述纖維素酯系樹脂以外之樹脂,多元羧酸或其衍生物及多元醇之聚縮聚合體所構成者。聚酯系樹脂之具體例係包含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、聚環己烷二甲基對苯二甲酸酯、聚環己烷萘酸二甲酯。 The polyester resin is a resin other than the cellulose ester resin having an ester bond, a polyvalent carboxylic acid or a derivative thereof, and a polycondensation polymer of a polyhydric alcohol. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polytrimethylene terephthalate. Ester, propylene naphthalate, polycyclohexane dimethyl terephthalate, dimethyl polycyclohexane naphthate.
聚碳酸酯系樹脂係由碳酸及甘醇或雙酚所形成之聚酯。其中,從耐熱性、耐候性及耐酸性之觀點而言,較佳係使用於分子鏈具有二苯基烷之芳香族聚碳酸酯。聚碳酸酯可例示2,2-雙(4-羥苯基)丙烷(別名雙酚A)、2,2-雙(4-羥苯基)丁烷、1,1-雙(4-羥苯基)環己烷、1,1-雙(4-羥苯基)異丁烷、1,1-雙(4-羥苯基)乙烷類由雙酚所衍生之 聚碳酸酯。 The polycarbonate resin is a polyester formed of carbonic acid and glycol or bisphenol. Among them, from the viewpoint of heat resistance, weather resistance, and acid resistance, it is preferably used in an aromatic polycarbonate having a diphenyl alkane in a molecular chain. The polycarbonate can be exemplified by 2,2-bis(4-hydroxyphenyl)propane (alias bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxybenzene). Cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutane, 1,1-bis(4-hydroxyphenyl)ethane derived from bisphenol Polycarbonate.
可構成第1,第2樹脂膜3,4之(甲基)丙烯酸系樹脂係可為以源自甲基丙烯酸酯之構成單元作為主體(例如包含此50重量%以上)之聚合物,以使其再與其他共聚合成分共聚合之共聚物為較佳。(甲基)丙烯酸系樹脂係可含有源自甲基丙烯酸酯之構成單元2種以上。甲基丙烯酸酯係可舉例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯等甲基丙烯酸之C1至C4烷基酯。 The (meth)acrylic resin which can constitute the first and second resin films 3 and 4 can be a polymer mainly composed of a constituent unit derived from methacrylate (for example, containing 50% by weight or more), so that Copolymers which are further copolymerized with other copolymerization components are preferred. The (meth)acrylic resin may contain two or more kinds of constituent units derived from methacrylate. The methacrylate type may, for example, be a C 1 to C 4 alkyl methacrylate such as methyl methacrylate, ethyl methacrylate or butyl methacrylate.
可與甲基丙烯酸酯共聚合之共聚合成分係可舉例如丙烯酸酯。丙烯酸酯較佳係丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己基酯等丙烯酸之C1至C8烷基酯。其他之共聚合成分之具體例係可舉例如(甲基)丙烯酸等之不飽和酸類;苯乙烯、鹵化苯乙烯、α-甲基苯乙烯、乙烯基甲苯等芳香族乙烯化合物;(甲基)丙烯腈等乙烯基氰化合物;馬來酸酐、依康酸酐等不飽和酸酐;苯基馬來醯亞胺、環己基馬來醯亞胺等不飽和醯亞胺等之於分子內具有1個聚合性碳-碳雙鍵的丙烯酸酯以外之化合物。亦可使用於分子內具有2個以上之聚合性碳-碳雙鍵的化合物作為共聚合成分。共聚合成分係可僅使用1種,亦可併用2種以上。 The copolymerizable component copolymerizable with the methacrylate may, for example, be an acrylate. 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 the other copolymerization component include unsaturated acids such as (meth)acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene, and vinyltoluene; a vinyl cyanide compound such as acrylonitrile; an unsaturated acid anhydride such as maleic anhydride or isocanic anhydride; an unsaturated quinone imine such as phenyl maleimide or cyclohexylmaleimine; A compound other than an acrylate of a carbon-carbon double bond. A compound having two or more polymerizable carbon-carbon double bonds in the molecule may also be used as the copolymerization component. The copolymerization component may be used alone or in combination of two or more.
就可提高膜之耐久性之點,(甲基)丙烯酸樹脂亦可於高分子主鏈具有環構造。環構造係以環狀酸酐構造、環狀醯亞胺構造、內酯環構造等雜環構造為佳。環狀酸酐構造之具體例係可舉例如戊二酸酐構造、琥珀酸酐構 造,環狀醯亞胺構造之具體例係可舉例如戊二醯亞胺構造、琥珀醯亞胺構造,內酯環構造之具體例係可舉例如丁內酯環構造、戊內酯環構造。 In order to improve the durability of the film, the (meth)acrylic resin may have a ring structure in the polymer main chain. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic quinone imine structure, or a lactone ring structure. Specific examples of the cyclic acid anhydride structure include, for example, glutaric anhydride structure and succinic anhydride structure. Specific examples of the structure of the cyclic quinone imine structure include a glutarylene imine structure and an amber quinone structure. Specific examples of the lactone ring structure include, for example, a butyrolactone ring structure and a valerolactone ring structure. .
從對膜之製膜性或膜之耐衝撃性等觀點而言,(甲基)丙烯酸系樹脂亦可含有丙烯酸系橡膠粒子。所謂丙烯酸系橡膠粒子係以丙烯酸酯作為主體之彈性聚合物作為必要成分之粒子,實質上可舉例如僅由此彈性聚合物所構成之單層構造者、或使彈性聚合物為1層之多層構造者。彈性聚合物之例可舉例如以丙烯酸烷酯作為主成分,使可與其共聚合之其他乙烯基單體及交聯性單體共聚合而成之交聯彈性共聚物。成為彈性聚合物之主成分的丙烯酸烷酯係可舉例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己基酯等丙烯酸之C1至C8烷基酯。烷基之碳數較佳係4以上。 The (meth)acrylic resin may contain acrylic rubber particles from the viewpoints of film forming properties of the film, impact resistance of the film, and the like. The acrylic rubber particles are particles in which an elastic polymer mainly composed of acrylate is used as an essential component, and may be, for example, a single layer structure composed of only the elastic polymer or a multilayer having one layer of the elastic polymer. Constructor. Examples of the elastic polymer include a crosslinked elastic copolymer obtained by copolymerizing an alkyl acrylate as a main component and a copolymerizable other vinyl monomer and a crosslinkable monomer. The alkyl acrylate which is a main component of the elastic polymer may, for example, be a C 1 to C 8 alkyl acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate. The number of carbon atoms of the alkyl group is preferably 4 or more.
可與丙烯酸烷酯共聚合之其他乙烯基單體係可舉例如於分子內具有1個聚合性碳-碳雙鍵之化合物,更具體而言係可舉例如甲基丙烯酸甲酯之甲基丙烯酸酯、苯乙烯之芳香族乙烯化合物、(甲基)丙烯腈之乙烯基氰化合物等。交聯性單體係可舉例如於分子內至少具有2個聚合性碳-碳雙鍵之交聯性化合物,更具體而言係可舉例如乙二醇二(甲基)丙烯酸酯、丁烷二醇二(甲基)丙烯酸酯等多元醇的(甲基)丙烯酸酯、烯丙基(甲基)丙烯酸酯等(甲基)丙烯酸之烯基酯、二乙烯基苯等。 Other vinyl single-systems copolymerizable with an alkyl acrylate may, for example, be a compound having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid such as methyl methacrylate An aromatic vinyl compound of an ester or styrene, a vinyl cyanide compound of (meth)acrylonitrile, or the like. The crosslinkable single system may, for example, be a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, for example, ethylene glycol di(meth)acrylate or butane a (meth) acrylate of a polyhydric alcohol such as diol di(meth)acrylate, an alkenyl ester of (meth)acrylic acid such as allyl (meth) acrylate, or divinylbenzene.
丙烯酸系橡膠粒子之含量係相對於(甲基) 丙烯酸系樹脂100重量份,較佳係5重量份以上,更佳係10重量份以上。若丙烯酸系橡膠粒子之含量太多,膜之表面硬度會降低,又,對膜實施表面處理之時,對表面處理劑中之有機溶劑的耐溶劑性會降低。因此,丙烯酸系橡膠粒子之含量相對於(甲基)丙烯酸系樹脂100重量份,通常為80重量份以下,較佳係60重量份以下。 The content of acrylic rubber particles is relative to (methyl) The acrylic resin is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, based on 100 parts by weight of the acrylic resin. If the content of the acrylic rubber particles is too large, the surface hardness of the film is lowered, and when the film is subjected to surface treatment, the solvent resistance to the organic solvent in the surface treatment agent is lowered. Therefore, the content of the acrylic rubber particles is usually 80 parts by weight or less, 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係可含有本發明之技術領域中之一般添加劑。添加劑之具體例係含有例如紫外線吸收劑、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、滑劑、分散劑、熱安定劑等。 The first and second resin films 3 and 4 may contain general additives in the technical field of the present invention. Specific examples of the additive include, for example, an ultraviolet absorber, an infrared absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a slip agent, a dispersant, a heat stabilizer, and the like.
紫外線吸收劑係可舉例如水楊酸酯化合物、二苯甲酮化合物、苯並三唑化合物、三化合物、氰基(甲基)丙烯酸酯化合物、鎳錯鹽等。 The ultraviolet absorber may, for example, be a salicylate compound, a benzophenone compound, a benzotriazole compound, or the like. A compound, a cyano (meth) acrylate compound, a nickel salt or the like.
第1,第2樹脂膜3,4係分別可為未被延伸之膜、或經一軸或二軸延伸之膜的任一者。二軸延伸係可朝2個延伸方向同時進行延伸之同時二軸延伸,亦可朝預定方向延伸之後朝其他方向進行延伸之逐次二軸延伸。第1樹脂膜3及/或第2樹脂膜4亦可為擔任保護偏光片2之任務之保護膜,亦可為一併具有後述之相位差膜之光學機能的保護膜。相位差膜係顯示光學異方性之光學膜。例如可使由上述熱塑性樹脂所構成之膜進行延伸(一軸延伸或二軸延伸等),於該熱塑性樹脂膜上形成液晶層等,藉此,形成賦予任意之相位差值的相位差膜。 Each of the first and second resin films 3 and 4 may be either a film that is not stretched or a film that extends through one or two axes. The two-axis extension system can simultaneously extend in two extending directions while extending the two-axis, and can also extend in a predetermined direction and then extend in two directions. The first resin film 3 and/or the second resin film 4 may be a protective film for protecting the polarizing film 2, or may be a protective film having an optical function of a retardation film to be described later. The retardation film shows an optical film of optical anisotropy. For example, a film made of the thermoplastic resin may be stretched (one-axis stretching or biaxial stretching), and a liquid crystal layer or the like may be formed on the thermoplastic resin film to form a retardation film which imparts an arbitrary retardation value.
第1樹脂膜3及第2樹脂膜4係可為以由相同之熱塑性樹脂所構成之膜,亦可為由互異之熱塑性樹脂所構成的膜。第1樹脂膜3及第2樹脂膜4係可在厚度、添加劑之有無或種類、相位差特性等為相同,或相異。 The first resin film 3 and the second resin film 4 may be films made of the same thermoplastic resin, or may be formed of mutually different thermoplastic resins. The first resin film 3 and the second resin film 4 may be the same or different in thickness, presence or absence of additives, phase difference characteristics, and the like.
第1樹脂膜3及/或第2樹脂膜4係可於其外面(與偏光片2為相反側之表面)具備硬塗層、防眩層、抗反射層、光擴散層、抗靜電層、防污層、導電層等表面處理層(塗佈層)。 The first resin film 3 and/or the second resin film 4 may have a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, an antistatic layer, and the like on the outer surface (the surface opposite to the polarizer 2). A surface treatment layer (coating layer) such as an antifouling layer or a conductive layer.
第1樹脂膜3及第2樹脂膜4之厚度係分別通常為1至150μm,較佳係5至100μm,更佳係5至60μm。該厚度係50μm以下,更可為30μm以下。減少第1,第2樹脂膜3,4之厚度係對附黏著劑層之光學膜1及光學積層體之薄膜化、甚至含有附黏著劑層之光學膜1或光學積層體的液晶顯示裝置之薄膜化為有利。 The thicknesses of the first resin film 3 and the second resin film 4 are usually from 1 to 150 μm, preferably from 5 to 100 μm, more preferably from 5 to 60 μm. The thickness is 50 μm or less, and more preferably 30 μm or less. The thickness of the first and second resin films 3 and 4 is reduced to the thickness of the optical film 1 and the optical layered body to which the adhesive layer is applied, and even to the liquid crystal display device including the optical film 1 or the optical layered body with the adhesive layer. Thin film formation is advantageous.
特別如智慧型手機或桌上型終端之以中小型為對象之偏光板係從薄膜化之要求,就第1樹脂膜3及/或第2樹脂膜4而言,常使用厚度為30μm以下之較薄者,但如此之偏光板係抑制偏光片2之收縮力的力量較弱,耐久性易不足。若依據本發明,即使使用如此之偏光板作為光學膜10時,亦可提供具有良好耐久性之附黏著劑層之光學膜1及光學積層體。附黏著劑層之光學膜1及光學積層體之耐久性係謂在例如高溫環境下、高溫高濕環境下、反覆高溫及低溫之環境下等之中,可抑制黏著劑層20與鄰接於黏著劑層20之光學構件之界面的浮起或剝離、黏著劑層 20之發泡等不佳情形的性質。 In particular, in the case of a small-sized and medium-sized polarizing plate for a smart phone or a desktop terminal, the thickness of the first resin film 3 and/or the second resin film 4 is usually 30 μm or less. The thinner one, but such a polarizing plate suppresses the contraction force of the polarizer 2, and the durability is insufficient. According to the present invention, even when such a polarizing plate is used as the optical film 10, the optical film 1 and the optical layered body with the adhesive layer having good durability can be provided. The durability of the optical film 1 and the optical laminate with the adhesive layer is such that, in a high-temperature environment, a high-temperature high-humidity environment, a high-temperature and low-temperature environment, etc., the adhesive layer 20 and the adjacent adhesive layer can be suppressed. Float or peeling of the interface of the optical member of the agent layer 20, adhesive layer The nature of the poor condition such as foaming of 20.
第1,第2樹脂膜3,4係可透過接著劑層或黏著劑層而貼合於偏光片2。形成接著劑層之接著劑係可使用水性接著劑或活性能量線硬化性接著劑。 The first and second resin films 3 and 4 are bonded to the polarizer 2 through the adhesive layer or the adhesive layer. The adhesive forming the adhesive layer may be an aqueous adhesive or an active energy ray-curable adhesive.
水性接著劑係可舉例如由聚乙烯醇系樹脂水溶液所構成之接著劑、水性二液型胺基甲酸酯系乳化液接著劑等。其中,適宜使用由聚乙烯醇系樹脂水溶液所構成之水性接著劑。聚乙烯醇系樹脂係除了將乙酸乙烯酯之均聚物的聚乙酸乙烯酯進行皂化處理而製得之乙烯醇均聚物之外,可使用將乙酸乙烯酯及可與其共聚合之其他單體之共聚物進行皂化處理而獲得之聚乙烯醇系共聚物、或將其等之羥基經部分改質而成之改質聚乙烯醇系聚合物等。水性接著劑係可含有醛化合物、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、多價金屬鹽等之交聯劑。 The aqueous adhesive agent may, for example, be an adhesive composed of a polyvinyl alcohol-based resin aqueous solution or an aqueous two-component urethane-based emulsion adhesive. Among them, an aqueous adhesive composed of a polyvinyl alcohol-based resin aqueous solution is suitably used. In the polyvinyl alcohol-based resin, vinyl acetate and other monomers copolymerizable therewith may be used in addition to the vinyl alcohol homopolymer obtained by subjecting polyvinyl acetate of a homopolymer of vinyl acetate to saponification. The polyvinyl alcohol-based copolymer obtained by subjecting the copolymer to saponification or a modified polyvinyl alcohol-based polymer obtained by partially modifying the hydroxyl group of the copolymer or the like. The aqueous binder may contain a crosslinking agent such as an aldehyde compound, an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, an amine compound, or a polyvalent metal salt.
使用水性接著劑之時,較佳係貼合偏光片2與第1,第2樹脂膜3,4之後,實施除去水性接著劑中所含之水,使其乾燥之步驟。乾燥步驟後,亦可設置例如20至45℃左右之溫度進行熟成之熟成步驟。 When an aqueous adhesive is used, it is preferred to adhere the polarizer 2 and the first and second resin films 3 and 4, and then remove the water contained in the aqueous adhesive and dry it. After the drying step, a ripening step of, for example, a temperature of about 20 to 45 ° C may be provided.
上述活性能量線硬化性接著劑係指照射紫外線或電子線等活性能量線使硬化之接著劑,可舉例如含有聚合性化合物及光聚合起始劑之硬化性組成物、含有光反應性樹脂之硬化性組成物、含有黏結劑樹脂及光反應性交聯劑之硬化性組成物等。較佳係紫外線硬化性接著劑。 聚合性化合物係可舉例如光硬化性環氧系單體、光硬化性(甲基)丙烯酸系單體、光硬化性胺基甲酸酯系單體等光聚合性單體、或源自光聚合性單體之寡聚物。光聚合起始劑係可舉例如含有藉活性能量線之照射產生中性自由基、陰離子自由基、陽離子自由基等活性種之物質者。含有聚合性化合物及光聚合起始劑之活性能量線硬化性接著劑較宜使用:含有光硬化性環氧系單體及光陽離子聚合起始劑之硬化性組成物、或含有光硬化性(甲基)丙烯酸系單體及光自由基聚合起始劑之硬化性組成物、或此等硬化性組成物的混合物。 The active energy ray-curable adhesive agent is an adhesive which is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam, and is, for example, a curable composition containing a polymerizable compound and a photopolymerization initiator, and a photoreactive resin. A curable composition, a curable composition containing a binder resin and a photoreactive crosslinking agent, and the like. It is preferably an ultraviolet curable adhesive. The polymerizable compound may, for example, be a photocurable epoxy monomer, a photocurable (meth)acrylic monomer, or a photocurable urethane monomer, or may be derived from light. An oligomer of a polymerizable monomer. The photopolymerization initiator may, for example, be one containing an active species such as a neutral radical, an anionic radical, or a cationic radical by irradiation with an active energy ray. An active energy ray-curable adhesive containing a polymerizable compound and a photopolymerization initiator is preferably used: a curable composition containing a photocurable epoxy-based monomer and a photocationic polymerization initiator, or photocurability ( A curable composition of a methyl)acrylic monomer and a photoradical polymerization initiator, or a mixture of such curable compositions.
使用活性能量線硬化性接著劑時,係貼合偏光片2與第1,第2樹脂膜3,4之後,依需要而進行乾燥步驟,然後,藉由照射活性能量線,而進行使活性能量線硬化性接著劑硬化之硬化步驟。活性能量線之光源係無特別限定,但以於波長400nm以下具有發光分布之紫外線為佳,具體而言,係可使用低壓水銀燈、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、金屬鹵素燈等。 When the active energy ray-curable adhesive is used, after the polarizer 2 and the first and second resin films 3 and 4 are bonded, a drying step is performed as needed, and then the active energy is irradiated to the active energy. A hardening step of hardening the wire hardener. The light source of the active energy ray is not particularly limited, but is preferably an ultraviolet ray having a light-emitting distribution at a wavelength of 400 nm or less. Specifically, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a black lamp can be used. Microwave-excited mercury lamps, metal halide lamps, and the like.
當貼合偏光片2與第1,第2樹脂膜3,4時,係可對此等之至少任一者的貼合面實施皂化處理、電暈處理、電漿處理等表面活性化處理。於偏光片2之雙面貼合樹脂膜時,用以貼合此等樹脂膜的接著劑係可為同種之接著劑,亦可為異種之接著劑。 When the polarizer 2 and the first and second resin films 3 and 4 are bonded together, the bonding surface of at least one of these may be subjected to surface activation treatment such as saponification treatment, corona treatment, or plasma treatment. When the resin film is bonded to both surfaces of the polarizer 2, the adhesive agent for bonding these resin films may be the same kind of adhesive or may be a different type of adhesive.
偏光板10a,10b係可更含有其他之膜或 層。其具體例係後述之相位差膜之外,為增亮膜、防眩膜、抗反射膜、擴散膜、集光膜、黏著劑層20以外之黏著劑層、塗佈層、保護膜等。保護膜係就保護偏光板等光學膜10之表面免受刮傷或污染之目的所使用的膜,以附黏著劑層之光學膜1貼合於例如金屬層30上之後,剝離除去者為通例。 The polarizing plates 10a, 10b may further contain other films or Floor. Specific examples thereof include a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, a light-concentrating film, and an adhesive layer other than the adhesive layer 20, a coating layer, a protective film, and the like, in addition to the retardation film to be 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 scratching or contamination. After the optical film 1 with the adhesive layer is attached to, for example, the metal layer 30, the peeling and removing is a general case. .
保護膜通常係以基材膜、及積層於其上之黏著劑層構成。基材膜係可以熱塑性樹脂例如聚乙烯系樹脂、聚丙烯系樹脂等聚烯烴系樹脂;聚對苯二甲酸乙二酯或聚萘二甲酸乙二酯等聚酯系樹脂;聚碳酸酯系樹脂;(甲基)丙烯酸系樹脂等構成。 The protective film is usually composed of a base film and an adhesive layer laminated thereon. The base film may be a thermoplastic resin such as a polyolefin resin such as a polyethylene resin or a polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; and a polycarbonate resin. (meth)acrylic resin or the like.
[1-2]相位差板 [1-2] phase difference plate
於相位差板所含之相位差膜如上述係顯示光學異方性之光學膜,可使用於第1,第2樹脂膜3,4者,係於上文所例示之熱塑性樹脂之外,可為例如將聚乙烯醇系樹脂、聚芳酸酯系樹脂、聚醯亞胺系樹脂、聚醚碸系樹脂、聚偏二氟乙烯/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之樹脂膜延伸至1.01至6倍左右所得之延伸膜。其中,將聚碳酸酯系樹脂膜或環狀烯烴系樹脂膜、(甲基)丙烯酸系樹脂膜或纖維素系樹脂膜經一軸延伸或二軸延伸之延伸膜為較佳。又,本說明書中零延遲性膜亦包含於相位差膜(但,亦可使用為保護膜)。其他,被稱為一軸性相位 差膜、廣視角相位差膜、低光彈性率相位差膜等之膜亦可適用作為相位差膜。 The retardation film contained in the retardation film is an optical film exhibiting optical anisotropy as described above, and the first and second resin films 3 and 4 can be used in addition to the thermoplastic resin exemplified above. For example, a polyvinyl alcohol-based resin, a polyarylate-based resin, a polyimide-based resin, a polyether oxime resin, a polyvinylidene fluoride/polymethyl methacrylate resin, a liquid crystal polyester resin, A stretched film obtained by stretching a resin film composed of an ethylene-vinyl acetate copolymer saponified product or a polyvinyl chloride-based resin to about 1.01 to 6 times. Among them, a stretched film in which a polycarbonate resin film, a cyclic olefin resin film, a (meth)acrylic resin film, or a cellulose resin film is stretched by one axis or biaxially is preferable. Further, the zero retardation film in the present specification is also included in the retardation film (however, it may be used as a protective film). One-axis phase A film such as a poor film, a wide viewing angle retardation film, or a low photoelastic retardation film can also be suitably used as the retardation film.
所謂零延遲性膜係面內相位差值Re及厚度方向相位差值Rth皆為-15至15nm之膜。此相位差膜係可適宜使用於IPS模式之液晶顯示裝置。面內相位差值Re及厚度方向相位差值Rth較佳係均為-10至10nm,更佳係均為-5至5nm。此處所謂之面內相位差值Re及厚度方向相位差值Rth係波長590nm之值。 A so-called zero retardation value based retardation film face R e and R th retardation value in the thickness direction of the film are all 15nm to -15. This retardation film can be suitably used for an IPS mode liquid crystal display device. The in-plane retardation value R e and the thickness direction retardation value R th are preferably from -10 to 10 nm, more preferably from -5 to 5 nm. Here, the in-plane phase difference value R e and the thickness direction phase difference value R th are values of a wavelength of 590 nm.
面內相位差值Re及厚度方向相位差值Rth係分別以下述式定義:Re=(nx-ny)×d Rth=[(nx+ny)/2-nz]×d。式中,nx係膜面內之慢軸方向(x軸方向)之折射率,ny係膜面內之快軸方向(在面內與x軸正交之y軸方向)之折射率,nz係膜厚度方向(與膜面垂直之z軸方向)之折射率,d係膜之厚度。 The in-plane phase difference value R e and the thickness direction phase difference value R th are respectively defined by the following equation: R e =(n x -n y )×d R th =[(n x +n y )/2-n z ] × d. In the formula, the refractive index of the slow axis direction (x-axis direction) in the plane of the n x film, and the refractive index of the fast axis direction (the y-axis direction orthogonal to the x axis) in the plane of the n y film, n z is the refractive index of the film thickness direction (z-axis direction perpendicular to the film surface), and the thickness of the d-type film.
零延遲性膜係可使用例如由纖維素系樹脂、鏈狀聚烯烴系樹脂及環狀聚烯烴系樹脂等聚烯烴系樹脂、聚對苯二甲酸乙二酯系樹脂或(甲基)丙烯酸系樹脂所構成之樹脂膜。特別,就相位差值容易控制,且容易取得之點,較宜使用纖維素系樹脂、聚烯烴系樹脂或(甲基)丙烯酸系樹脂。 For the zero-delay film, for example, a polyolefin resin such as a cellulose resin, a chain polyolefin resin, or a cyclic polyolefin resin, a polyethylene terephthalate resin, or a (meth)acrylic resin can be used. A resin film composed of a resin. In particular, a cellulose resin, a polyolefin resin, or a (meth)acrylic resin is preferably used because the phase difference value is easily controlled and easily obtained.
又,亦可使用藉液晶性化合物之塗布/配向而顯現光學異方性之膜、或藉由無機層狀化合物之塗布而 顯現光學異方性之膜作為相位差膜。如此之相位差膜係有:被稱為溫度補償型相位差膜者,又,由JX日礦日石能量(股)以「NH膜」之商品名販售之棒狀液晶經傾斜配向而成之膜、由富士Film(股)以「WV膜」之商品名販售之圓盤狀液晶經傾斜配向而成之膜、由住友化學(股)以「VAC膜」之商品名販售之完全二軸配向型之膜、相同地由住友化學(股)「new VAC膜」之商品名販售之二軸配向型之膜等。 Further, it is also possible to use a film which exhibits optical anisotropy by coating/alignment of a liquid crystal compound or a coating of an inorganic layered compound. A film exhibiting optical anisotropy is used as a retardation film. Such a retardation film is a type of a temperature-compensated retardation film, and a rod-shaped liquid crystal sold under the trade name "NH film" by JX Nippon Mining & Energy Co., Ltd. is obliquely aligned. The membrane, the disc-shaped liquid crystal sold by Fuji Film Co., Ltd. under the trade name "WV film", which is slanted and aligned, is sold by Sumitomo Chemical Co., Ltd. under the trade name "VAC film". A two-axis alignment type film, and a two-axis alignment type film which is sold under the trade name of "new VAC film" by Sumitomo Chemical Co., Ltd.
積層於相位差膜之至少一面的樹脂膜係可為例如上述之保護膜。 The resin film laminated on at least one surface of the retardation film may be, for example, the above-mentioned protective film.
[2]黏著劑層 [2] adhesive layer
配置於光學膜10與金屬層30之間的黏著劑層20係由含有特定之離子性化合物(D)之黏著劑組成物所構成。該黏著劑組成物係一般更含有(甲基)丙烯酸系樹脂(A),亦可更含有異氰酸酯系交聯劑(B)及/或矽烷化合物(C)。 The adhesive layer 20 disposed between the optical film 10 and the metal layer 30 is composed of an adhesive composition containing a specific ionic compound (D). The adhesive composition generally further contains a (meth)acrylic resin (A), and may further contain an isocyanate crosslinking agent (B) and/or a decane compound (C).
藉由以上述之黏著劑組成物所構成之黏著劑層20,在含有黏著劑層20及金屬層30之構成的光學積層體中,可抑制金屬層30之腐蝕,又,可提高附黏著劑層之光學膜1及光學積層體之耐久性。更且,藉由以上述之黏著劑組成物所構成之黏著劑層20,附黏著劑層之光學膜1及光學積層體可顯示良好之光學耐久性(可抑制光學特性之劣化性質)。 By the adhesive layer 20 composed of the above-described adhesive composition, in the optical laminate including the adhesive layer 20 and the metal layer 30, corrosion of the metal layer 30 can be suppressed, and the adhesive can be improved. The durability of the optical film 1 and the optical laminate of the layer. Further, the optical film 1 and the optical laminate having the adhesive layer can exhibit good optical durability (deterioration of deterioration of optical characteristics) by the adhesive layer 20 composed of the above-described adhesive composition.
黏著劑層20之厚度通常為2至40μm,從附黏著劑層之光學膜1及光學積層體之耐久性或附黏著劑 層之光學膜1的重工性等觀點而言,較佳係5至30μm,更佳係10至25μm。又,若黏著劑層20之厚度為10μm以上,則黏著劑層20對光學膜10之尺寸變化之追隨性為良好,若為25μm以下,重工性變良好。 The thickness of the adhesive layer 20 is usually 2 to 40 μm, and the durability or adhesion of the optical film 1 and the optical laminate from the adhesive layer. The viewpoint of the workability of the optical film 1 of the layer is 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 adhesion of the adhesive layer 20 to the dimensional change of the optical film 10 is good, and when it is 25 μm or less, the workability is improved.
黏著劑層20係在23至80℃之溫度範圍中顯示0.1至5MPa之貯存彈性率者為較佳。藉此,可更有效地提高附黏著劑層之光學膜1及光學積層體之耐久性。「在23至80℃之溫度範圍中顯示0.1至5MPa之貯存彈性率」係意指在此範圍之任一溫度中,貯存彈性率為上述範圍內之值。貯存彈性率通常隨溫度上昇而漸減,故若在23℃及80℃中之貯存彈性率任一者均落入上述範圍,在此範圍之溫度中,可看到顯示上述範圍內之貯存彈性率。黏著劑層20之貯存彈性率係可使用市售之黏彈性測定裝置例如REOMETRIC公司製之黏彈性測定裝置「DYNAMIC ANALYZER RDA II」而測定。 The adhesive layer 20 is preferably one having a storage 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 the optical layered body with the adhesive layer can be more effectively improved. "Displaying a storage modulus of 0.1 to 5 MPa in a temperature range of 23 to 80 ° C" means that the storage modulus is a value within the above range at any of the temperatures. The storage modulus usually decreases with increasing temperature. Therefore, if either of the storage elastic ratios at 23 ° C and 80 ° C falls within the above range, the storage elastic modulus in the above range can be seen in the temperature of this range. . The storage modulus of the adhesive layer 20 can be measured using a commercially available viscoelasticity measuring device such as a viscoelasticity measuring device "DYNAMIC ANALYZER RDA II" manufactured by REOMETRIC.
[2-1](甲基)丙烯酸系樹脂(A) [2-1] (Meth)acrylic resin (A)
(甲基)丙烯酸系樹脂(A)係以源自(甲基)丙烯酸系單體之構成單元作為主成分(較佳係含有50重量%以上)之聚合物或共聚物。(甲基)丙烯酸系單體係例如含有具有(甲基)丙烯醯基之單體,較佳係含有(甲基)丙烯酸烷酯。(甲基)丙烯酸烷酯具有之烷基係碳數較佳為1至14,更佳為1至12,再更佳為1至8,並可為直鏈狀、分枝狀或環狀構造。就(甲基)丙烯酸烷酯而言,亦可使用後述之於烷基導入取 代基而成之含有取代基的丙烯酸烷酯類之含有取代基的(甲基)丙烯酸烷酯。(甲基)丙烯酸烷酯係可只使用1種,亦可併用2種以上。 The (meth)acrylic resin (A) is a polymer or copolymer containing a constituent unit derived from a (meth)acrylic monomer as a main component (preferably containing 50% by weight or more). The (meth)acrylic single system contains, for example, a monomer having a (meth)acrylonitrile group, and preferably contains an alkyl (meth)acrylate. The alkyl (meth)acrylate has an alkyl group having a carbon number of preferably 1 to 14, more preferably 1 to 12, still more preferably 1 to 8, and may be a linear, branched or cyclic structure. . For the (meth)acrylic acid alkyl ester, the alkyl group introduction described later can also be used. A substituent-containing (meth)acrylic acid alkyl ester of a substituted alkyl acrylate having a substituent. The alkyl (meth)acrylate may be used alone or in combination of two or more.
(甲基)丙烯酸烷酯之具體例係包括(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、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-十二碳基酯、(甲基)丙烯酸硬脂基酯等。 Specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n- and iso-propyl (meth)acrylate, and (meth)acrylic acid. - and third-butyl ester, n- and iso-amyl acrylate, n- and iso-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n- and iso-heptyl (meth) acrylate Ester, n- and iso-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n- and iso-decyl (meth)acrylate, n- and iso-(meth)acrylate An oxime ester, isobornyl (meth)acrylate, n- and iso-dodecyl (meth)acrylate, stearyl (meth)acrylate, and the like.
(甲基)丙烯酸系樹脂(A)較佳係含有源自均聚物之玻璃轉移溫度Tg為未達0℃之丙烯酸烷酯(a1)之構成單元、及源自均聚物之Tg為0℃以上的丙烯酸烷酯(a2)之構成單元。此事係就提高附黏著劑層之光學膜1及光學積層體之耐金屬腐蝕性及耐久性上為有利。丙烯酸烷酯之均聚物之Tg係可採用例如Polymer Handbook(Wiley-Interscience)等之文獻值。 The (meth)acrylic resin (A) preferably contains a constituent unit derived from a homopolymer of a glass transition temperature Tg of an alkyl acrylate (a1) of less than 0 ° C, and a Tg derived from a homopolymer of 0. The constituent unit of the alkyl acrylate (a2) above °C. This is advantageous in improving the metal corrosion resistance and durability of the optical film 1 and the optical laminate having the adhesive layer. The Tg of the homopolymer of the alkyl acrylate may be, for example, a literature value of a Polymer Handbook (Wiley-Interscience) or the like.
丙烯酸烷酯(a1)之具體例係包含:丙烯酸乙酯、丙烯酸正-及異-丙基酯、丙烯酸正-及異-丁基酯、丙烯酸正-戊基酯、丙烯酸正-及異-己基酯、丙烯酸正-庚基酯、丙烯酸正-及異-辛基酯、丙烯酸2-乙基己基酯、丙烯酸正-及異-壬基酯、正-及異-癸基丙烯酸酯、丙烯酸正-十二碳基酯等烷基之碳數為2至12左右之丙烯酸烷酯。丙烯酸烷酯 (a1)之其他具體例可舉例如於烷基之碳數為2至12左右之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。含有取代基之丙烯酸烷酯之取代基係取代烷基之氫原子的基,其具體例係包含苯基、烷氧基、苯氧基。含有取代基之丙烯酸烷酯具體而言係可舉例如丙烯酸2-甲氧基乙基酯、丙烯酸乙氧基甲基酯、丙烯酸苯氧基乙基酯、苯氧基二乙二醇丙烯酸酯等。丙烯酸烷酯(a1)之烷基係可具有脂環式構造,但較佳係直鏈狀或分枝構造之烷基。 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. Ester, n-heptyl acrylate, n- and iso-octyl acrylate, 2-ethylhexyl acrylate, n- and iso-decyl acrylate, n- and iso-decyl acrylate, acrylic acid - An alkyl acrylate having an alkyl group such as a dodecyl ester of from 2 to 12 carbon atoms. Alkyl acrylate Other specific examples of (a1) include, for example, an alkyl acrylate containing a substituent in an alkyl group-introduced substituent of an alkyl acrylate having an alkyl group number of from 2 to 12. The substituent of the alkyl acrylate containing a substituent is a group of a hydrogen atom of the substituted 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, phenoxy diethylene glycol acrylate, and the like. . The alkyl group of the alkyl acrylate (a1) may have an alicyclic structure, but is preferably an alkyl group having a linear or branched structure.
丙烯酸烷酯(a1)係可僅使用1種,亦可併用2種以上。其中,丙烯酸烷酯(a1)係以含有選自丙烯酸乙酯、丙烯酸正-丁基酯、丙烯酸2-乙基己基酯之1種或2種以上為較佳。從附黏著劑層之光學膜1具有之黏著劑層20對光學膜10之追從性、重工性之觀點而言,丙烯酸烷酯(a1)係以含有丙烯酸正-丁基酯為較佳。 The alkyl acrylate (a1) may be used alone or in combination of two or more. In particular, the alkyl acrylate (a1) is preferably one 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 an adhesive layer to the optical film 10, the alkyl acrylate (a1) is preferably a n-butyl acrylate.
丙烯酸烷酯(a2)係丙烯酸烷酯(a1)以外之丙烯酸烷酯。丙烯酸烷酯(a2)之具體例係包含丙烯酸甲酯、丙烯酸環己基酯、丙烯酸異冰片酯、丙烯酸硬脂基酯、丙烯酸第三-丁基酯等。 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 tributyl acrylate.
丙烯酸烷酯(a2)係可僅使用1種,亦可併用2種以上。其中,從耐金屬腐蝕性及耐久性之觀點而言,丙烯酸烷酯(a2)係以含有丙烯酸甲酯、丙烯酸環己基酯、丙烯酸異冰片酯等為較佳,以含有丙烯酸甲酯為更佳。 The alkyl acrylate (a2) may be used alone or in combination of two or more. Among them, from the viewpoint of metal corrosion resistance and durability, the alkyl acrylate (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isobornyl acrylate or the like, and preferably contains methyl acrylate. .
(甲基)丙烯酸系樹脂(A)中之源自丙烯酸烷酯(a2)之構成單元之含量,從附黏著劑層之光學膜1及光 學積層體之耐金屬腐蝕性及耐久性之觀點而言,於構成(甲基)丙烯酸系樹脂(A)之全構成單元100重量份中,較佳係10重量份以上,更佳係15重量份以上,再更佳係20重量份以上,特別佳係25重量份以上。又,黏著劑層20對光學膜10之追從性及重工性之觀點而言,源自丙烯酸烷酯(a2)之構成單元之含量較佳係70重量份以下,更佳係60重量份以下,再更佳係50重量份以下。 The content of the constituent unit derived from the alkyl acrylate (a2) in the (meth)acrylic resin (A), the optical film 1 and the light from the adhesive layer From the viewpoint of the metal corrosion resistance and the durability of the laminated body, it is preferably 10 parts by weight or more, more preferably 15 parts by weight based on 100 parts by weight of the total constituent unit of the (meth)acrylic resin (A). More preferably, it is more preferably 20 parts by weight or more, and particularly preferably 25 parts by weight or more. Further, from the viewpoint of the followability and reworkability of the optical film 10, the content of the constituent unit derived from the alkyl acrylate (a2) is preferably 70 parts by weight or less, more preferably 60 parts by weight or less. More preferably, it is 50 parts by weight or less.
(甲基)丙烯酸系樹脂(A)係可含有源自丙烯酸烷酯(a1)及(a2)以外之其他單體之構成單元。(甲基)丙烯酸系樹脂(A)係可含有1種源自該其他單體之構成單元,亦可含有2種以上。將其他之單體之具體例表示於以下。 The (meth)acrylic resin (A) may contain constituent units derived from monomers other than the alkyl acrylates (a1) and (a2). The (meth)acrylic resin (A) may contain one type of constituent unit derived from the other monomer, and may contain two or more kinds. Specific examples of other monomers are shown below.
1)具有極性官能基之單體。 1) A monomer having a polar functional group.
具有極性官能基之單體係可舉例如具有羥基、羧基、取代或無取代胺基、環氧基等雜環基等之取代基的(甲基)丙烯酸酯。具體而言係可舉例如(甲基)丙烯酸2-羥乙基酯、(甲基)丙烯酸3-羥丙基酯、(甲基)丙烯酸4-羥丁基酯、(甲基)丙烯酸2-(2-羥乙氧基)乙基酯、(甲基)丙烯酸2-氯-2-羥丙基酯、(甲基)丙烯酸3-氯-2-羥丙基酯、二乙二醇單(甲基)丙烯酸酯等具有羥基之單體;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)丙烯酸四氫呋喃甲基酯、己內酯改質丙烯酸四氫呋喃甲基酯、(甲基)丙烯酸3,4-環氧基環己基甲基酯、(甲基)丙烯酸縮水甘油基酯、2,5-二氫呋喃等具有雜環基之單體;(甲基)丙烯 酸胺基乙基酯、(甲基)丙烯酸N,N-二甲基胺基乙基酯、(甲基)丙烯酸二甲基胺基丙基酯等具有取代或無取代胺基之單體;(甲基)丙烯酸、(甲基)丙烯酸羧基乙基酯等具有羧基之單體。其中,以具有羥基之單體為較佳,就(甲基)丙烯酸系樹脂(A)與交聯劑之反應性之點,以具有羥基之(甲基)丙烯酸酯為更佳。 The single system having a polar functional group may, for example, be a (meth) acrylate having a substituent such as a hydroxyl group, a carboxyl group, a substituted or unsubstituted amino group or a heterocyclic group such as an epoxy group. Specific examples thereof include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-(meth)acrylate. (2-hydroxyethoxy)ethyl ester, 2-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, diethylene glycol mono ( a monomer having a hydroxyl group such as methyl acrylate; acryloyl morpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, tetrahydrofuran methyl (meth) acrylate, Caprolactone modified with tetrahydrofuran methyl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, 2,5-dihydrofuran, etc. Monomer; (meth) propylene a monomer having a substituted or unsubstituted amine group such as an acid aminoethyl ester, N,N-dimethylaminoethyl (meth)acrylate, or dimethylaminopropyl (meth)acrylate; A monomer having a carboxyl group such as (meth)acrylic acid or carboxyethyl (meth)acrylate. Among them, a monomer having a hydroxyl group is preferred, and a point of reactivity of the (meth)acrylic resin (A) with a crosslinking agent is more preferably a (meth) acrylate having a hydroxyl group.
亦可含有具有羥基之(甲基)丙烯酸酯與上述具有其他極性官能基之單體,但從可防止積層於黏著劑層20之外面的分離膜之剝離力亢進的觀點,以實質上不含有具有胺基之單體為較佳。又,從提高對於ITO之耐腐蝕性的觀點而言,以實質上不含有具有羧基之單體為較佳。此處實質上不含有係指於構成(甲基)丙烯酸系樹脂(A)之全構成單元100重量份中,為0.1重量份以下。 Further, the (meth) acrylate having a hydroxyl group and the above-mentioned monomer having another polar functional group may be contained, but from the viewpoint of preventing peeling force of the separation film laminated on the outer surface of the adhesive layer 20, substantially no A monomer having an amine group is preferred. Further, from the viewpoint of improving the corrosion resistance to ITO, it is preferred that the monomer having a carboxyl group is not substantially contained. The content of the total constituent unit of the (meth)acrylic resin (A) is not more than 0.1 part by weight.
2)丙烯醯胺系單體。 2) A acrylamide monomer.
可適宜使用例如N-羥甲基丙烯醯胺、N-(2-羥乙基)丙烯醯胺、N-(3-羥丙基)丙烯醯胺、N-(4-羥丁基)丙烯醯胺、N-(5-羥戊基)丙烯醯胺、N-(6-羥己基)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-(2-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,較佳使用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。 For example, N-methylol acrylamide, N-(2-hydroxyethyl) acrylamide, N-(3-hydroxypropyl) acrylamide, N-(4-hydroxybutyl) propylene oxime can be suitably used. Amine, N-(5-hydroxypentyl) acrylamide, N-(6-hydroxyhexyl) acrylamide, N,N-dimethyl decylamine, N,N-diethyl acrylamide, N -isopropyl acrylamide, N-(3-dimethylaminopropyl) acrylamide, N-(1,1-dimethyl-3-oxobutyl) decylamine, N- [2-(2-Sideoxy-1-imidazolidinyl)ethyl]propenylamine, 2-propenylamino-2-methyl-1-propanesulfonic acid, N-(methoxymethyl) Acrylamide, N-(ethoxymethyl)propenylamine, N-(propoxymethyl)propenylamine, N-(1-methylethoxymethyl)propenylamine, N- (1-methylpropoxy Methyl) acrylamide, N-(2-methylpropoxymethyl) acrylamide [alias: N-(isobutoxymethyl) acrylamide], N-(butoxymethyl) Acrylamide, N-(1,1-dimethylethoxymethyl)propenylamine, N-(2-methoxyethyl)propenylamine, N-(2-ethoxyethyl) Acrylamide, N-(2-propoxyethyl)propenylamine, N-[2-(1-methylethoxy)ethyl]propenylamine, N-[2-(1-methyl) Propoxy)ethyl]propenylamine, N-[2-(2-methylpropoxy)ethyl]propenylamine [alias: N-(2-isobutoxyethyl) acrylamide] N-(2-butoxyethyl) acrylamide, N-[2-(1,1-dimethylethoxy)ethyl]acrylamide or the like. Among them, N-(methoxymethyl)propenylamine, N-(ethoxymethyl)propenylamine, N-(propoxymethyl)propenylamine, N-(butoxy group) are preferably used. Methyl) acrylamide, N-(2-methylpropoxymethyl) acrylamide.
3)甲基丙烯酸酯、亦即甲基丙烯酸之酯。 3) Methacrylate, that is, an ester of methacrylic acid.
例如甲基丙烯酸甲基酯、甲基丙烯酸乙基酯、甲基丙烯酸丙基酯、甲基丙烯酸正-丁基酯、甲基丙烯酸正-辛基酯、甲基丙烯酸月桂基酯等甲基丙烯酸之直鏈狀烷基酯;甲基丙烯酸異丁基酯、甲基丙烯酸2-乙基己基酯、甲基丙烯酸異-辛基酯等甲基丙烯酸之分枝狀烷基酯;甲基丙烯酸異冰片基酯、甲基丙烯酸環己基酯、甲基丙烯酸二環戊基酯、甲基丙烯酸環十二碳基酯、甲基丙烯酸甲基環己基酯、甲基丙烯酸三甲基環己基酯、甲基丙烯酸第三-丁基環己基酯、甲基丙烯酸環己基苯基酯等甲基丙烯酸之脂環式烷基酯;甲基丙烯酸2-甲氧基乙基酯、甲基丙烯酸乙氧基甲基酯等甲基丙烯酸之烷氧基烷基酯;甲基丙烯酸苯甲基酯等 甲基丙烯酸芳烷基酯;甲基丙烯酸2-羥乙基酯、甲基丙烯酸3-羥丙基酯、甲基丙烯酸4-羥丁基酯、甲基丙烯酸2-(2-羥乙氧基)乙基酯、甲基丙烯酸2-氯-2-羥丙基酯、甲基丙烯酸3-氯-2-羥丙基酯、二乙二醇單甲基丙烯酸酯等具有羥基之甲基丙烯酸之烷基酯;甲基丙烯酸胺基乙基酯、甲基丙烯酸N,N-二甲基胺基乙基酯、甲基丙烯酸二甲基胺基丙基酯等具有取代或無取代胺基之甲基丙烯酸之烷基酯;甲基丙烯酸2-苯氧基乙基酯、甲基丙烯酸2-(2-苯氧基乙氧基)乙基酯、(甲基)丙烯酸之環氧乙烷改質壬基酚酯(nonylphenol)、甲基丙烯酸2-(鄰-苯基苯氧基)乙基酯等具有苯氧基乙基之甲基丙烯酸之酯等。 For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, lauryl methacrylate, etc. a linear alkyl ester; a branched alkyl ester of methacrylic acid such as isobutyl methacrylate, 2-ethylhexyl methacrylate or iso-octyl methacrylate; Borneol base ester, cyclohexyl methacrylate, dicyclopentyl methacrylate, cyclododecanyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, A Alicyclic alkyl ester of methacrylic acid such as tri-butylcyclohexyl acrylate or cyclohexyl phenyl methacrylate; 2-methoxyethyl methacrylate, ethoxy methacrylate Alkoxyalkyl ester of methacrylic acid such as ester; benzyl methacrylate Aralkyl methacrylate; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-(2-hydroxyethoxy) methacrylate Ethyl ester, 2-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monomethacrylate, etc. Alkyl ester; Aminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, etc. A substituted or unsubstituted amine group Alkyl acrylates; 2-phenoxyethyl methacrylate, 2-(2-phenoxyethoxy)ethyl methacrylate, ethylene oxide modification of (meth)acrylic acid An ester of methacrylic acid having a phenoxyethyl group such as nonylphenol or 2-(o-phenylphenoxy)ethyl methacrylate.
4)甲基丙烯醯胺系單體。 4) A methacrylamide amide monomer.
例如對應於上述1)記載之丙烯醯胺系單體的甲基丙烯醯胺系單體。 For example, the methacrylamide-based monomer corresponding to the acrylamide-based monomer described in the above 1).
5)苯乙烯系單體。 5) Styrene monomer.
例如苯乙烯;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、辛基苯乙烯等之烷基苯乙烯;氟苯乙烯、氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯等之鹵化苯乙烯;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; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl benzene Alkyl styrene such as ethylene, heptyl styrene or octyl styrene; halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene or iodine; nitrostyrene; Mercaptostyrene; methoxystyrene; divinylbenzene and the like.
6)乙烯系單體。 6) A vinyl monomer.
例如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己烷酸乙烯酯、月桂酸乙烯酯等脂肪酸乙烯酯;氯乙烯、溴乙烯等鹵化乙烯;偏氯乙烯等偏鹵化乙烯;乙烯基吡啶、乙烯基吡咯啶酮、乙烯基咔唑等含氮芳香族乙烯;丁二烯、異戊二烯、氯丁二烯等共軛二烯單體;丙烯腈、甲基丙烯腈等不飽和腈等。 For example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, etc.; vinyl halide such as vinyl chloride or vinyl bromide; vinylidene halide such as vinylidene chloride a nitrogen-containing aromatic vinyl such as vinyl pyridine, vinyl pyrrolidone or vinyl carbazole; a conjugated diene monomer such as butadiene, isoprene or chloroprene; acrylonitrile or methacrylonitrile Such as unsaturated nitrile and the like.
7)於分子內具有複數之(甲基)丙烯醯基之單體。 7) A monomer having a plurality of (meth) acrylonitrile groups in the molecule.
例如1,4-丁烷二醇二(甲基)丙烯酸酯、1,6-己烷二醇二(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)丙烯酸酯等於分子內具有2個(甲基)丙烯醯基之單體;三羥甲基丙烷三(甲基)丙烯酸酯等於分子內具有3個(甲基)丙烯醯基之單體等。 For example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene Alcohol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate is equal to two in the molecule (A) A monomer of an acrylonitrile group; a trimethylolpropane tri(meth) acrylate is equal to a monomer having three (meth) acrylonitrile groups in the molecule.
如上述,從附黏著劑層之光學膜1及光學積層體之耐久性及耐金屬腐蝕性之觀點而言,(甲基)丙烯酸系樹脂(A)係除了源自(甲基)丙烯酸烷酯之構成單元,以包含源自具有極性官能基之單體的構成單元為較佳。具有極性官能基之單體係以具有極性官能基之(甲基)丙烯酸酯系單體為較佳,具有羥基之單體為更佳。源自具有極性官能基之單體的構成單元之含量係在構成(甲基)丙烯酸系樹脂(A)之全構成單元100重量份中,較佳係0.1至10重量份,更佳係0.25至5重量份,再更佳係0.5至5重量份。 As described above, the (meth)acrylic resin (A) is derived from the alkyl (meth)acrylate from the viewpoints of durability and metal corrosion resistance of the optical film 1 and the optical laminate having the adhesive layer. The constituent unit is preferably a constituent unit containing a monomer derived from a polar functional group. The single system having a polar functional group is preferably a (meth) acrylate 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 0.1 to 10 parts by weight, more preferably 0.25 to 100 parts by weight of the total constituent unit constituting the (meth)acrylic resin (A). 5 parts by weight, more preferably 0.5 to 5 parts by weight.
又,從附黏著劑層之光學膜1之重工性之觀點而言,(甲基)丙烯酸系樹脂(A)較佳係甲基丙烯酸酯(甲基丙烯酸之酯)、甲基丙烯醯胺系單體等源自甲基丙烯酸系單體之構成單元之含量小,具體而言,該構成單元之含量係在構成(甲基)丙烯酸系樹脂(A)之全構成單元100重量份中,較佳係10重量份以下,更佳係5重量份以下,以實質上不含有該構成單元(0.1重量份以下)為再更佳。 Further, from the viewpoint of the reworkability of the optical film 1 to which the adhesive layer is attached, the (meth)acrylic resin (A) is preferably a methacrylate (ester of methacrylic acid) or a methacrylamide. The content of the constituent unit derived from the methacrylic monomer such as a monomer is small, and specifically, the content of the constituent unit is 100 parts by weight of the total constituent unit constituting the (meth)acrylic resin (A). It is more preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and substantially no such structural unit (0.1 part by weight or less).
(甲基)丙烯酸系樹脂(A)較佳係凝膠滲透色層分析(GPC)中之排出曲線上之重量平均分子量Mw1000至250萬之範圍中具有單一波峰,更佳係Mw1000至250萬之範圍中具有單一波峰,且含有源自丙烯酸烷酯(a1)及(a2)之構成單元為更佳。以如此之(甲基)丙烯酸系樹脂(A)作為基質聚合物之黏著劑層20就提高附黏著劑層之光學膜1及光學積層體之耐久性方面為有利。在上述Mw之範圍之波峰數為2以上時,有無法獲得充分耐久性之傾向。 The (meth)acrylic resin (A) preferably has a single peak in the range of the weight average molecular weight Mw of 1,000 to 2.5 million on the discharge curve in the gel permeation chromatography (GPC), and more preferably Mw 1000 to 2.5 million. It is more preferable to have a single peak in the range and to contain constituent units derived from the alkyl acrylates (a1) and (a2). The adhesive layer 20 having such a (meth)acrylic resin (A) as a matrix polymer is advantageous in terms of improving the durability of the optical film 1 and the optical laminate of the adhesive layer. When the number of peaks in the range of the above Mw is 2 or more, sufficient durability may not be obtained.
當求出在Mw1000至250萬之範圍中之GPC排出曲線之波峰數時,係依據實施例之項記載之GPC測定條件而取得排出曲線。所得到之排出曲線之上述範圍中「具有單一波峰」係意指在Mw1000至250萬之範圍中只具有1個極大值。本說明書中係在GPC排出曲線中,將S/N比為30以上者定義為波峰。 When the number of peaks of the GPC discharge curve in the range of Mw 1000 to 2.5 million was obtained, the discharge curve was obtained according to the GPC measurement conditions described in the examples. The "having a single peak" in the above range of the obtained discharge curve means that there is only one maximum value in the range of Mw 1000 to 2.5 million. In the present specification, in the GPC discharge curve, a band having an S/N ratio of 30 or more is defined as a peak.
(甲基)丙烯酸系樹脂(A)較佳係以GPC所得之標準聚苯乙烯換算之Mw為50萬至250萬之範圍,更佳為60萬至200萬之範圍。若Mw為50萬以上,對附黏著 劑層之光學膜1及光學積層體之耐金屬腐蝕性及耐久性之提昇有利,亦有提升附黏著劑層之光學膜1之重工性的傾向。又,若Mw為250萬以下,黏著劑層20對光學膜10之尺寸變化之追随性良好。以重量平均分子量Mw及數平均分子量Mn之比Mw/Mn所示之分子量分布通常為2至10。(甲基)丙烯酸系樹脂(A)之Mw及Mn係依照實施例之項記載之GPC測定條件而求出。 The (meth)acrylic resin (A) is preferably in the range of 500,000 to 2.5 million in terms of standard polystyrene obtained by GPC, more preferably in the range of 600,000 to 2,000,000. If the Mw is more than 500,000, it is attached. The improvement of the metal corrosion resistance and durability of the optical film 1 and the optical laminate of the agent layer is advantageous, and there is a tendency to improve the reworkability of the optical film 1 with the adhesive layer. Further, when the Mw is 2.5 million or less, the adhesion of the adhesive layer 20 to the dimensional change of the optical film 10 is good. The molecular weight distribution represented by the ratio Mw/Mn of the weight average molecular weight Mw and the number average molecular weight Mn is usually 2 to 10. The Mw and Mn of the (meth)acrylic resin (A) were determined according to the GPC measurement conditions described in the examples.
(甲基)丙烯酸系樹脂(A)係以溶解於乙酸乙酯而成為濃度20重量%之溶液時,在25℃中之黏度為20Pa‧s以下較佳,以0.1至7Pa‧s為更佳。如此之範圍之黏度係對附黏著劑層之光學膜1及光學積層體之耐久性之提昇、或附黏著劑層之光學膜1之重工性為有利。上述黏度係藉由Brookfield黏度計而測定。 When the (meth)acrylic resin (A) is a solution having a concentration of 20% by weight dissolved in ethyl acetate, the viscosity at 25 ° C is preferably 20 Pa ‧ or less, more preferably 0.1 to 7 Pa ‧ s. . The viscosity in such a range is advantageous in that the durability of the optical film 1 and the optical layered body with the adhesive layer is improved, or the reworkability of the optical film 1 to which the adhesive layer is attached. The above viscosity is determined by a Brookfield viscometer.
(甲基)丙烯酸系樹脂(A)較佳係以示差掃描熱量計(DSC)所測定之玻璃轉移溫度Tg為-60至-10℃,以-55至-15℃為更佳。如此之範圍之Tg係對附黏著劑層之光學膜1及光學積層體之耐金屬腐蝕性及耐久性之提昇為有利。 The (meth)acrylic resin (A) is preferably a glass transition temperature Tg of from -60 to -10 ° C as measured by a differential scanning calorimeter (DSC), more preferably from -55 to -15 ° C. The Tg in such a range is advantageous in improving the metal corrosion resistance and durability of the optical film 1 and the optical laminate having the adhesive layer.
黏著劑組成物係亦可含有2種以上之屬於(甲基)丙烯酸系樹脂(A)的(甲基)丙烯酸系樹脂。又,黏著劑組成物係亦可含有與(甲基)丙烯酸系樹脂(A)相異之其他之(甲基)丙烯酸系樹脂。但,從附黏著劑層之光學膜1及光學積層體之耐金屬腐蝕性及耐久性之觀點而言,(甲基)丙烯酸系樹脂(A)之含量在全部之(甲基)丙烯酸系樹脂之 合計中,較佳係70重量%以上,更佳係80重量%以上,再更佳係90重量%以上,黏著劑組成物以只含有(甲基)丙烯酸系樹脂(A)作為基質聚合物為特別佳。 The adhesive composition may contain two or more (meth)acrylic resins belonging to the (meth)acrylic resin (A). Further, the adhesive composition may contain another (meth)acrylic resin different from the (meth)acrylic resin (A). However, from the viewpoint of metal corrosion resistance and durability of the optical film 1 and the optical laminate having the adhesive layer, the content of the (meth)acrylic resin (A) is all (meth)acrylic resin. It In general, it is preferably 70% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and the adhesive composition contains only the (meth)acrylic resin (A) as a matrix polymer. Especially good.
(甲基)丙烯酸系樹脂(A)或可依需要而併用之其他之(甲基)丙烯酸系樹脂係可藉由例如溶液聚合法、塊狀聚合法、懸濁聚合法、乳化聚合法等公知之方法來製造。(甲基)丙烯酸系樹脂之製造中通常可使用聚合起始劑。聚合起始劑係相對於可使用於(甲基)丙烯酸系樹脂之製造的全部單體之合計100重量份,使用0.001至5重量份左右。又,(甲基)丙烯酸系樹脂係例如亦可利用藉由紫外線等活性能量線而進行聚合之方法來製造。 The (meth)acrylic resin (A) or other (meth)acrylic resin which can be used in combination as needed can be known by, for example, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, or the like. The method to manufacture. A polymerization initiator can be usually used in the production of a (meth)acrylic resin. 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 monomers which can be used for the production of the (meth)acrylic resin. Further, the (meth)acrylic resin can be produced, for example, by a method in which polymerization is carried out by an active energy ray such as ultraviolet rays.
聚合起始劑係可使用熱聚合起始劑或光聚合起始劑等。光聚合起始劑可舉例如4-(2-羥乙氧基)苯基(2-羥基-2-丙基)酮等。熱聚合起始劑可舉例如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-羥甲基丙腈)之偶氮系化合物;月桂基過氧化物、第三-丁基氫過氧化物、過氧化苯甲醯、第三-丁基過氧化苯甲酸酯、異丙苯氫過氧化物、二異丙基過氧化二碳酸酯、二丙基過氧化二碳酸酯、第三-丁基過氧化新癸酸酯、第三-丁基過氧化三甲基乙酸酯、(3,5,5-三甲基己醯基)過氧化物之有機過氧化物;過硫酸鉀、過硫酸銨、過氧化氫之無機過氧化物等。又,併用過氧化物 與還原劑之氧化還原系起始劑等亦可使用作為聚合起始劑。 As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like can be used. The photopolymerization initiator may, for example, be 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl) ketone or the like. The thermal polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane- 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile , an azo compound of dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile); Oxide, tri-butyl hydroperoxide, benzammonium peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, Propyl peroxydicarbonate, tri-butyl peroxy neodecanoate, tert-butylperoxytrimethyl acetate, (3,5,5-trimethylhexyl) peroxidation Organic peroxides; potassium persulfate, ammonium persulfate, inorganic peroxides of hydrogen peroxide, and the like. Again, using peroxide A redox initiator such as a reducing agent can also be used as a polymerization initiator.
(甲基)丙烯酸系樹脂之製造方法係在上面所示之方法中,亦以溶液聚合法為較佳。溶液聚合法之一例,係混合所使用之單體及有機溶劑,在氮環境下,添加熱聚合起始劑,以40至90℃左右,較佳係50至80℃左右,攪拌3至15小時左右。為控制反應,於聚合中連續或間歇性添加單體或熱聚合起始劑,或以溶解於有機溶劑之狀態添加。有機溶係可使用例如甲苯、二甲苯之芳香族烴類;乙酸乙酯、乙酸丁基酯等酯類;丙醇、異丙醇等脂肪族醇類;丙酮、甲乙酮、甲基異丁基酮等酮類等。 The method for producing the (meth)acrylic resin is preferably the solution polymerization method as described above. An example of the solution polymerization method is a monomer and an organic solvent used for mixing, and a thermal polymerization initiator is added under a nitrogen atmosphere at a temperature of about 40 to 90 ° C, preferably about 50 to 80 ° C, and stirred for 3 to 15 hours. about. In order to control the reaction, a monomer or a thermal polymerization initiator is continuously or intermittently added in the polymerization, or is added in a state of being dissolved in an organic solvent. As the organic solvent, for example, an aromatic hydrocarbon such as toluene or xylene; an ester such as ethyl acetate or butyl acetate; an aliphatic alcohol such as propanol or isopropanol; acetone, methyl ethyl ketone or methyl isobutyl ketone; Ketones, etc.
[2-4]異氰酸酯系交聯劑(B) [2-4] Isocyanate crosslinking agent (B)
黏著劑組成物係以含有異氰酸酯系交聯劑(B)為較佳。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及光學積層體之耐金屬腐蝕性及耐久性。異氰酸酯系交聯劑(B)係可僅單獨使用1種,亦可併用2種以上。 The adhesive composition preferably contains an isocyanate crosslinking agent (B). By using the isocyanate crosslinking agent (B) as a crosslinking agent, the metal corrosion resistance and durability of the optical film 1 and the optical laminate of the pressure-sensitive adhesive layer can be improved. The isocyanate-based crosslinking agent (B) may be used alone or in combination of two or more.
異氰酸酯系交聯劑(B)係於分子內具有至少2個異氰酸基(-NCO)之化合物,具體上係可舉例如甲苯二異氰酸酯、六亞甲基二異氰酸酯、異佛酮二異氰酸酯、二甲苯二異氰酸酯、氫化二甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、萘二異氰酸酯、三苯基甲烷三異氰酸酯等。又,異氰酸酯系交聯劑(D)係可 為此等異氰酸酯化合物之多元醇化合物加成物(例如甘油或三羥甲基丙烷之加成物)、三聚異氰酸酯化合物、縮二脲型化合物,更且可為與聚醚多元醇或聚酯多元醇、丙烯醯基多元醇、聚丁二烯多元醇、聚異戊二烯多元醇等進行加成反應而得之胺基甲酸酯預聚物型之異氰酸酯化合物等衍生物。上述之中,特別佳係甲苯二異氰酸酯、六亞甲基二異氰酸酯、二甲苯二異氰酸酯或此等異氰酸酯化合物的多元醇化合物加成物,從附黏著劑層之光學膜1及光學積層體之耐久性觀點而言,以二甲苯二異氰酸酯或其多元醇化合物加成物為更佳。 The isocyanate crosslinking agent (B) is a compound having at least two isocyanato groups (-NCO) in the molecule, and specific examples thereof include toluene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Xylene diisocyanate, hydrogenated xylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like. Further, the isocyanate crosslinking agent (D) is acceptable A polyol compound adduct of such an isocyanate compound (for example, an adduct of glycerin or trimethylolpropane), a trimer isocyanate compound, a biuret type compound, and more preferably a polyether polyol or polyester. A derivative such as a urethane prepolymer type isocyanate compound obtained by an addition reaction such as a polyhydric alcohol, an acrylonitrile-based polyhydric alcohol, a polybutadiene polyol, or a polyisoprene polyol. Among the above, particularly preferred are toluene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate or a polyol compound adduct of such an isocyanate compound, which is durable from the optical film 1 and the optical laminate of the adhesive layer. From the viewpoint of the above, xylene diisocyanate or a polyol compound adduct thereof is more preferable.
異氰酸酯系交聯劑(B)之含量相對於(甲基)丙烯酸系樹脂(A)100重量份,較佳係0.08至2.5重量份,更佳係0.1至2重量份(例如1重量份以下)。異氰酸酯系交聯劑(B)之含量在此範圍時,在附黏著劑層之光學膜1及光學積層體之耐金屬腐蝕性及耐久性兼俱上為有利。 The content of the isocyanate crosslinking agent (B) is preferably 0.08 to 2.5 parts by weight, more preferably 0.1 to 2 parts by weight (for example, 1 part by weight or less) based on 100 parts by weight of the (meth)acrylic resin (A). . When the content of the isocyanate crosslinking agent (B) is within this range, it is advantageous in both the metal film corrosion resistance and the durability of the optical film 1 and the optical laminate of the pressure-sensitive adhesive layer.
黏著劑組成物係可併用異氰酸酯系交聯劑(B)以及此以外之交聯劑,例如環氧化合物、氮丙啶化合物、金屬螯合物化合物、過氧化物等,但從附黏著劑層之光學膜1及光學積層體之耐金屬腐蝕性及耐久性觀點而言,黏著劑組成物以只含有異氰酸酯系交聯劑(B)作為交聯劑,特別是實質上不含過氧化物為較佳。此處,實質上不含係指相對於(甲基)丙烯酸系樹脂(A)100重量份之含量為0.01重量份以下。 The adhesive composition may be used in combination with an isocyanate crosslinking agent (B) and a crosslinking agent other than the crosslinking agent such as an epoxy compound, an aziridine compound, a metal chelate compound, a peroxide, etc., but from an adhesive layer. From the viewpoint of metal corrosion resistance and durability of the optical film 1 and the optical laminate, the adhesive composition contains only the isocyanate crosslinking agent (B) as a crosslinking agent, and particularly contains no peroxide. Preferably. Here, the content of the (meth)acrylic resin (A) is substantially 0.01 part by weight or less based on 100 parts by weight of the (meth)acrylic resin (A).
[2-3]矽烷化合物(C) [2-3] decane compound (C)
黏著劑組成物係可含有矽烷化合物(C)。藉此,可提高黏著劑層20與金屬層30或玻璃基板等之密著性。亦可使用2種以上之矽烷化合物(C)。 The adhesive composition may contain a decane compound (C). Thereby, the adhesion of the adhesive layer 20 to the metal layer 30, the glass substrate, etc. can be improved. Two or more kinds of decane compounds (C) can also be used.
矽烷化合物(C)係可舉例如乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(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-氫硫基丙基三甲氧基矽烷等。 The decane compound (C) may, for example, be vinyltrimethoxydecane, vinyltriethoxydecane, vinylstilbene (2-methoxyethoxy)decane, 3-glycidoxypropyltrimethoxy Baseline, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylethoxymethyl Decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropene醯oxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane, and the like.
矽烷化合物(C)係可含有聚矽氧寡聚物型者。若將聚矽氧寡聚物之具體例以單體彼此間之組合的形式表記,如下。 The decane compound (C) may contain a polyoxyxene oligomer type. Specific examples of the polyoxyxene oligomer are expressed as a combination of monomers, as follows.
3-氫硫基丙基三甲氧基矽烷-四甲氧基矽烷寡聚物、3-氫硫基丙基三甲氧基矽烷-四乙氧基矽烷寡聚物、3-氫硫基丙基三乙氧基矽烷-四甲氧基矽烷寡聚物、3-氫硫基丙基三乙氧基矽烷-四乙氧基矽烷寡聚物等含有氫硫基丙基之寡聚物;氫硫基甲基三甲氧基矽烷-四甲氧基矽烷寡聚物、氫硫基甲基三甲氧基矽烷-四乙氧基矽烷寡聚物、氫硫基甲基三乙氧基矽烷-四甲氧基矽烷寡聚物、 氫硫基甲基三乙氧基矽烷-四乙氧基矽烷寡聚物等含有氫硫基甲基之寡聚物;3-環氧丙氧基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、3-環氧丙氧基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、3-環氧丙氧基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、3-環氧丙氧基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、3-環氧丙氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、3-環氧丙氧基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、3-環氧丙氧基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、3-環氧丙氧基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物等含有3-環氧丙氧基丙基之共聚物;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含有甲基丙烯醯氧基丙基之寡聚物;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含有丙烯醯氧基丙基之寡聚物;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含有乙烯基之寡聚物;3-胺基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、3-胺基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、3-胺基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、3-胺基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、3-胺基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、3-胺基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、3-胺基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、3-胺基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物等含有胺基之共聚物等。 3-Hydroxythiopropyltrimethoxydecane-tetramethoxydecane oligomer, 3-hydrothiopropyltrimethoxydecane-tetraethoxydecane oligomer, 3-hydrothiopropyltri An oligomer containing a thiopropyl group such as an ethoxy decane-tetramethoxy decane oligomer or a 3-hydrothiopropyltriethoxy decane-tetraethoxy decane oligomer; a thiol group; Methyltrimethoxydecane-tetramethoxydecane oligomer, thiolmethyltrimethoxydecane-tetraethoxydecane oligomer, thiomethylmethyltriethoxydecane-tetramethoxy Decane oligomer, Oxythiomethyl-containing oligomer such as thiomethylmethyltriethoxydecane-tetraethoxydecane oligomer; 3-glycidoxypropyltrimethoxydecane-tetramethoxydecane Copolymer, 3-glycidoxypropyltrimethoxydecane-tetraethoxydecane copolymer, 3-glycidoxypropyltriethoxydecane-tetramethoxydecane copolymer, 3- Glycidoxypropyltriethoxydecane-tetraethoxydecane copolymer, 3-glycidoxypropylmethyldimethoxydecane-tetramethoxydecane copolymer, 3-epoxy Propyloxypropylmethyldimethoxydecane-tetraethoxydecane copolymer, 3-glycidoxypropylmethyldiethoxydecane-tetramethoxydecane copolymer, 3-epoxy a copolymer containing 3-glycidoxypropyl group, such as a propoxypropylmethyldiethoxydecane-tetraethoxydecane copolymer; 3-methylpropenyloxypropyltrimethoxydecane- Tetramethoxydecane oligomer, 3-methacryloxypropyltrimethoxydecane-tetraethoxydecane oligomer, 3-methylpropenyloxypropyltriethoxydecane-four Methoxy decane oligomer, 3-methyl propylene oxime Propyltriethoxysilane Silane - tetraethyl orthosilicate oligomers, methyl propyl methyl dimethoxy Bing Xixi Silane - Silane tetramethoxysilane oligomer, 3-methylpropenyloxypropylmethyldimethoxydecane-tetraethoxydecane oligomer, 3-methylpropenyloxypropylmethyldiethoxydecane-tetramethoxydecane Oligomer, 3-methacryloxypropylmethyldiethoxydecane-tetraethoxydecane oligomer, etc. oligomer containing methacryloxypropyl group; 3-propene oxide Propyltrimethoxydecane-tetramethoxydecane oligomer, 3-propenyloxypropyltrimethoxydecane-tetraethoxydecane oligomer, 3-propenyloxypropyltriethoxy Cyclodecane-tetramethoxydecane oligomer, 3-propenylmethoxypropyltriethoxydecane-tetraethoxydecane oligomer, 3-propenyloxypropylmethyldimethoxydecane -tetramethoxydecane oligomer, 3-propenylmethoxypropylmethyldimethoxydecane-tetraethoxydecane oligomer, 3-propenyloxypropylmethyldiethoxydecane - oligomers containing propylene methoxy propyl groups such as tetramethoxy decane oligomer, 3-propenyl methoxymethyl methyl diethoxy decane-tetraethoxy decane oligomer; vinyl trimethyl Oxydecane-tetramethoxynonane oligomer, Vinyl trimethoxy decane-tetraethoxy decane oligomer, vinyl triethoxy decane-tetramethoxy decane oligomer, vinyl triethoxy decane-tetraethoxy decane oligomer, Vinylmethyldimethoxydecane-tetramethoxydecane oligomer, vinylmethyldimethoxydecane-tetraethoxydecane oligomer, vinylmethyldiethoxydecane-tetramethyl a vinyl-containing oligomer such as a oxydecane oligomer, a vinylmethyldiethoxydecane-tetraethoxydecane oligomer, or the like; 3-aminopropyltrimethoxydecane-tetramethoxydecane Copolymer, 3-aminopropyltrimethoxydecane-tetraethoxydecane copolymer, 3-aminopropyltriethoxydecane-tetramethoxydecane copolymer, 3-aminopropyltriethyl Oxydecane-tetraethoxydecane copolymer, 3-aminopropylmethyldimethoxydecane-tetramethoxydecane copolymer, 3-aminopropylmethyldimethoxydecane-tetraethyl Oxydecane copolymer, 3-aminopropylmethyldiethoxydecane-tetramethoxydecane copolymer, 3-aminopropylmethyldiethoxydecane-tetraethoxydecane copolymer, etc. A copolymer containing an amine group or the like.
黏著劑組成物中之矽烷化合物(C)之含量係相對於(甲基)丙烯酸系樹脂(A)100重量份,通常為0.01至10重量份,較佳係0.03至5重量份,更佳係0.05至2重量份,再更佳係0.1至1重量份。若矽烷化合物(B)之含量為0.01重量份以上,容易獲得黏著劑層20與金屬層30或玻璃基板等之密著性提昇效果。又若含量為10重量份以下,可抑制來自黏著劑層20之矽烷化合物(B)之滲出。 The content of the decane compound (C) in the adhesive composition is usually 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, based on 100 parts by weight of the (meth)acrylic resin (A), more preferably It is 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight. When the content of the decane compound (B) is 0.01 parts by weight or more, the adhesion improving effect of the adhesive layer 20, the metal layer 30, or the glass substrate can be easily obtained. Further, when the content is 10 parts by weight or less, the bleed out of the decane compound (B) from the adhesive layer 20 can be suppressed.
[2-4]離子性化合物(D) [2-4] Ionic compound (D)
黏著劑組成物係含有離子性化合物(D)。在1個實施形 態(第1實施形態)中離子性化合物(D)係對於60℃之水100g的溶解度為6g以下。離子性化合物(D)之溶解度較佳係3g以下,更佳係1g以下,再更佳係0.4g以下。藉由使用對於60℃之水100g的溶解度為6g以下之離子性化合物(D),不僅可對黏著劑層20賦予良好之抗靜電性能,亦可賦予優異之耐金屬腐蝕性及光學耐久性。黏著劑組成物係可含有對於60℃之水100g的溶解度為6g以下之離子性化合物(D)1種或2種以上。 The adhesive composition contains an ionic compound (D). In one implementation form In the first embodiment, the ionic compound (D) has a solubility of 100 g or less per 100 g of water at 60 ° C. The solubility of the ionic compound (D) is preferably 3 g or less, more preferably 1 g or less, still more preferably 0.4 g or less. By using an ionic compound (D) having a solubility of 100 g or less per 100 g of water at 60 ° C, it is possible to impart not only excellent antistatic properties to the adhesive layer 20 but also excellent metal corrosion resistance and optical durability. The adhesive composition may contain one or two or more kinds of ionic compounds (D) having a solubility of 100 g or less per 100 g of water at 60 ° C.
對於60℃之水100g之離子性化合物的溶解度可如下方式測定。亦即,混合經精秤之離子性化合物100mg及純水2mL之後,在攪拌下於溫度60℃保管24小時。然後,取樣水層之一部分(精秤量),將此以使用於下述液體色層分析之移動相或構成此之液體介質稀釋後,將溶解於所得之測定試樣之離子性化合物的重量濃度定量,從此定量值求出溶解度。該定量通常係使用液體色層分析法。具體之測定條件可依據後述之實施例之項目的記載。但,難予以液體色層分析法定量時,可使用離子色層分析法(IC)、元素分析法、ICP發光法、電泳法等。 The solubility of 100 g of the ionic compound in water at 60 ° C can be measured in the following manner. That is, 100 mg of the ionic compound of the fine scale and 2 mL of pure water were mixed, and then stored under stirring at a temperature of 60 ° C for 24 hours. Then, a part of the water layer (fine weighing amount) is sampled, and the weight concentration of the ionic compound dissolved in the obtained measurement sample is diluted with the mobile phase used for the liquid chromatography analysis described below or diluted with the liquid medium constituting the liquid crystal layer. Quantitative, and the solubility is determined from the quantitative value. This quantification is usually done using liquid chromatography. The specific measurement conditions can be based on the description of the items of the examples to be described later. However, when it is difficult to quantify by the liquid chromatography method, an ion chromatography method (IC), an elemental analysis method, an ICP luminescence method, an electrophoresis method, or the like can be used.
從上述溶解度之觀點,離子性化合物(D)之陽離子係以有機陽離子為佳。有機陽離子之具體例係包含吡啶鎓陽離子、咪唑鎓陽離子、哌啶鎓陽離子、吡咯啶鎓陽離子、四氫吡啶鎓陽離子、二氫吡啶鎓陽離子、四氫嘧啶鎓陽離子、二氫嘧啶鎓陽離子、吡唑鎓陽離子、吡唑啉鎓陽離子、銨陽離子、鋶陽離子、鏻陽離子等。有機陽離 子較好具有取代基。例如藉由調整取代基之碳數,可控制離子性化合物(D)之上述溶解度。取代基例如為可含有雜原子之碳數1至20的烴基,較佳係可含有雜原子之碳數1至16的烴基。烴基例如為直鏈、分枝或環狀構造之烷基,較佳係直鏈或分枝構造之烷基。 From the viewpoint of the above solubility, the cation of the ionic compound (D) is preferably an organic cation. Specific examples of the organic cation include a pyridinium cation, an imidazolium cation, a piperidinium cation, a pyrrolidinium cation, a tetrahydropyridinium cation, a dihydropyridinium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, and a pyridinium. An oxazolium cation, a pyrazolinium cation, an ammonium cation, a phosphonium cation, a phosphonium cation, or the like. Organic cation The subunit preferably has a substituent. For example, by adjusting the carbon number of the substituent, the above solubility of the ionic compound (D) can be controlled. The substituent is, for example, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, and preferably a hydrocarbon group having 1 to 16 carbon atoms which may contain a hetero atom. The hydrocarbon group is, for example, an alkyl group in a linear, branched or cyclic configuration, preferably an alkyl group in a linear or branched configuration.
第1實施形態之離子性化合物(D)所具有之陰離子係可為無機陰離子、有機陰離子之任一者。無機陰離子之具體例包含氯陰離子[Cl-]、溴陰離子[Br-]、碘陰離子[I-]、四氯化鋁陰離子[AlCl4 -]、七氯化二鋁陰離子[Al2Cl7 -]、四氟化硼陰離子[BF4 -]、六氟化磷陰離子[PF6 -]、過氯酸陰離子[ClO4 -]、硝酸根陰離子[NO3 -]、六氟化砷陰離子[AsF6 -]、六氟化銻陰離子[SbF6 -]、六氟化鈮陰離子[NbF6 -]、六氟化鉭陰離子[TaF6 -]、雙(氟磺醯基)亞胺陰離子[(FSO2)2N-]、(聚)氫氟化氟化物陰離子[F(HF)n -](n係1至3左右)等。 The anion of the ionic compound (D) of the first embodiment may be either an inorganic anion or an organic anion. Specific examples of the inorganic anion include a chloride anion [Cl - ], a bromine anion [Br - ], an iodine anion [I - ], an aluminum tetrachloride anion [AlCl 4 - ], an aluminum hexachloride anion [Al 2 Cl 7 - ], boron tetrafluoride anion [BF 4 - ], phosphorus hexafluoride anion [PF 6 - ], perchlorate anion [ClO 4 - ], nitrate anion [NO 3 - ], arsenic hexafluoride anion [AsF] 6 - ], antimony hexafluoride anion [SbF 6 - ], antimony hexafluoride anion [NbF 6 - ], antimony hexafluoride anion [TaF 6 - ], bis(fluorosulfonyl) imine anion [(FSO 2 ) 2 N - ], (poly) hydrofluorinated fluoride anion [F(HF) n - ] (n is about 1 to 3) and the like.
有機陰離子的具體例係包含乙酸根陰離子[CH3COO-]、三氟乙酸根陰離子[CF3COO-]、甲烷磺酸根陰離子[CH3SO3 -]、三氟甲烷磺酸根陰離子[CF3SO3 -]、對-甲苯磺酸根陰離子[p-CH3C6H4SO3 -]、雙(三氟甲烷磺醯基)亞胺陰離子[(CF3SO2)2N-]、參(三氟甲烷磺醯基)甲基陰離子[(CF3SO2)3C-]、二甲基膦酸根陰離子[(CH3)2POO-]、硫氰陰離子[SCN-]、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 -]、碳酸根陰離子[CO3 2-]、四芳基硼酸根陰離子(例如肆(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)所示之亞胺陰離子等:
此外,在其他之實施形態(第2實施形態)中離子性化合物(D)係下述式(I)所示之離子性化合物:
藉由使用上述式(I)所示之離子性化合物(D),對黏著劑層20不僅可賦予良好之抗靜電性能,亦可賦予優異之耐金屬腐蝕性及光學耐久性。黏著劑組成物係可含有上述式(I)所示之離子性化合物(D)1種或2種以上。上述式(I)所示之離子性化合物(D)從耐金屬腐蝕性及光學耐久性等之觀點,較佳為對於60℃之水100g的溶解度為6g以下。上述式(I)所示之離子性化合物(D)的溶解度更佳為3g以下,再更佳為1g以下,特佳為0.4g以下。 By using the ionic compound (D) represented by the above formula (I), the adhesive layer 20 can impart not only excellent antistatic properties but also excellent metal corrosion resistance and optical durability. The adhesive composition may contain one or two or more kinds of the ionic compound (D) represented by the above formula (I). The ionic compound (D) represented by the above formula (I) preferably has a solubility of 100 g or less per 100 g of water at 60 ° C from the viewpoint of metal corrosion resistance and optical durability. The solubility of the ionic compound (D) represented by the above formula (I) is more preferably 3 g or less, still more preferably 1 g or less, and particularly preferably 0.4 g or less.
R1及R2較佳係分別獨立地為氫原子、或可含有雜原子之碳數1至16的直鏈、分枝或環狀構造之烷基。R3較佳係可含有雜原子之碳數4至20的直鏈或分枝構造之烷基。R3之碳數較佳係4至10,更佳係4至8,再更佳為4或5。 R 1 and R 2 are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having a carbon number of 1 to 16 which may contain a hetero atom. R 3 is preferably an alkyl group which may have a linear or branched configuration of 4 to 20 carbon atoms of a hetero atom. The carbon number of R 3 is preferably 4 to 10, more preferably 4 to 8, still more preferably 4 or 5.
上述式(I)所示之離子性化合物(D)的陽離子之具體例係包含哌啶鎓陽離子、吡咯啶鎓陽離子、四氫吡啶鎓陽離子、二氫吡啶鎓陽離子、四氫嘧啶鎓陽離子、二氫嘧啶鎓陽離子、吡唑鎓陽離子、吡唑啉鎓陽離子等。此等陽離子可具有取代基。取代基例如為可含有雜原子之碳 數1至20之烴基,較佳係碳數1至16之烴基。烴基例如為直鏈、分枝或環狀構造之烷基,較佳係直鏈或分枝構造之烷基。 Specific examples of the cation of the ionic compound (D) represented by the above formula (I) include piperidinium cation, pyrrolidinium cation, tetrahydropyridinium cation, dihydropyridinium cation, tetrahydropyrimidinium cation, and Hydropyrimidine cation, pyrazolium cation, pyrazolinium cation, and the like. These cations may have a substituent. The substituent is, for example, a carbon which may contain a hetero atom The hydrocarbon group of 1 to 20 is preferably a hydrocarbon group having 1 to 16 carbon atoms. The hydrocarbon group is, for example, an alkyl group in a linear, branched or cyclic configuration, preferably an alkyl group in a linear or branched configuration.
從偏光板之薄膜化的觀點而言,如第2圖所示之偏光板10a,以只於偏光子2之單面配置樹脂膜之構成為有利。此時,通常於偏光子2之另一面直接貼合黏著劑層20而成為附黏著劑層之光學膜1(參照第4圖)。為此種構成的偏光板時,由於黏著劑層20所含有之離子性化合物而在高溫高濕環境下使偏光板之光學性能降低之問題特別顯著,但若藉由含有上述式(I)所示之離子性化合物(D)的黏著劑組成物(例如具有吡咯啶鎓陽離子之離子性化合物(D)的黏著劑組成物),則即使為使用此種偏光板作為光學膜10時,亦可提供具有良好之光學耐久性(可抑制光學特性劣化之性質)的附黏著劑層之光學膜1及光學積層體。 From the viewpoint of thinning of the polarizing plate, the polarizing plate 10a shown in Fig. 2 is advantageous in that the resin film is disposed only on one side of the polarizer 2. At this time, the adhesive layer 20 is directly bonded 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 the polarizing plate of this type, the problem of lowering the optical performance of the polarizing plate in a high-temperature and high-humidity environment due to the ionic compound contained in the adhesive layer 20 is particularly remarkable, but by including the above formula (I) When an adhesive composition of the ionic compound (D) (for example, an adhesive composition of an ionic compound (D) having a pyrrolizinium cation) is used, even when such a polarizing plate is used as the optical film 10, An optical film 1 and an optical layered body having an adhesive layer having good optical durability (a property of suppressing deterioration of optical characteristics) are provided.
進一步,在其他之實施形態(第3實施形態)中離子性化合物(D)係下述式(II)所示之離子性化合物:
上述式(II)中,R4係表示碳數3至16之直鏈或分枝構造之烷基,R5至R9係分別獨立地表示氫原子、可具有取代基之烷基、可具有取代基之烯基、可具有取代基之炔基、可具有取代基之芳基、可具有取代基之雜環基、羥基、醚基、羧基、羰基或鹵素原子,相隣之取代基亦可合併形成環。X-係表示與上述式(I)中之X-相同意義。上述式(II)所示之離子性化合物(D)係亦可成為對於60℃之水100g的溶解度為6g以下之離子性化合物之適當例。 In the above formula (II), R 4 represents an alkyl group having a linear or branched structure of 3 to 16 carbon atoms, and R 5 to R 9 each independently represent a hydrogen atom, an alkyl group which may have a substituent, and may have An alkenyl group of a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a hydroxyl group, an ether group, a carboxyl group, a carbonyl group or a halogen atom, and adjacent substituents may also be used. Combine to form a ring. X - represents a system of the above formula (I) the X - have the same meaning. The ionic compound (D) represented by the above formula (II) may be a suitable example of an ionic compound having a solubility of 100 g or less per 100 g of water at 60 ° C.
可具有取代基之烷基係碳數1至30之烷基為較佳,其具體例係包含例如甲基、乙基、丙基、丁基、己基、辛基、癸基、十二碳基、十八碳基、異丙基、異丁基、第二-丁基、第三-丁基、1-乙基戊基、環戊基、環己基、三氟甲基、2-乙基己基、苯甲醯甲基、1-萘甲醯基甲基、2-萘甲醯基甲基、4-甲基硫基苯甲醯甲基、4-苯基硫基苯甲醯甲基、4-二甲基胺基苯甲醯甲基、4-氰基苯甲醯甲基4-甲基苯甲醯甲基、2-甲基苯甲醯甲基、3-氟苯甲醯甲基、3-三氟甲基苯甲醯甲基、3-硝基苯甲醯甲基。 The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. , octadecyl, isopropyl, isobutyl, second-butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl , benzamidine methyl, 1-naphthylmethylmethyl, 2-naphthylmethylmethyl, 4-methylthiobenzimidylmethyl, 4-phenylthiobenzimidylmethyl, 4 - dimethylaminobenzimidylmethyl, 4-cyanobenzhydrylmethyl 4-methylbenzhydrylmethyl, 2-methylbenzhydrylmethyl, 3-fluorobenzhydrylmethyl, 3-Trifluoromethylbenzimidylmethyl, 3-nitrobenzimidylmethyl.
可具有取代基之烯基係以碳數2至10之烯基為較佳,其具體例係例如包含乙烯基、烯丙基、苯乙烯 基。可具有取代基之炔基係以碳數2至10之炔基為較佳,其具體例係包含例如乙炔基、丙炔基、炔丙基。 The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and specific examples thereof include, for example, a vinyl group, an allyl group, and a styrene group. base. The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and specific examples thereof include, for example, an ethynyl group, a propynyl group, and a propargyl group.
可具有取代基之芳基係以碳數6至30的芳基為較佳,其具體例係包含例如苯基、聯苯基、1-萘基、2-萘基、9-蒽基、9-菲基、1-芘基、5-稠四苯基、1-茚基、2-薁基(azulenyl)、9-茀基、聯三苯基、聯四苯基、鄰-、間-、及對-甲苯基、二甲苯基、鄰-、間-、及對-異丙苯基、均三甲苯基、並環戊二烯基、聯萘基、聯三萘基、聯四萘基、並環庚三烯基、伸聯苯基、二環戊二烯並苯基、螢蒽基、苊基、苯並苊基、丙烯合萘基(Phenalenyl)、茀基、蒽基、聯蒽基、聯三蒽基、聯四蒽基、蒽醌基、菲基、伸三苯基、芘基、苯並菲基、伸四苯基、七曜烯基、苉基、苝基、五苯基、稠五苯基、四伸苯基、六苯基、稠六苯基、茹基、蔻基(coromenyl)、聯伸三萘基、七苯基、稠七苯基、芘蒽基、莪基。 The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include, for example, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, and 9 -phenanthryl, 1-indenyl, 5-thick tetraphenyl, 1-indenyl, azulenyl, 9-fluorenyl, triphenyl, biphenyl, o-, m-, And p-tolyl, xylyl, o-, m-, and p-cumyl, mesityl, cyclopentadienyl, binaphthyl, dinaphthyl, dinaphthyl, And cycloheptatrienyl, biphenyl, dicyclopentadienylphenyl, fluorenyl, fluorenyl, benzofluorenyl, phenylnaphthyl, fluorenyl, fluorenyl, fluorenyl , hydrazine, hydrazinyl, fluorenyl, phenanthryl, triphenyl, fluorenyl, benzophenanyl, tetraphenyl, heptaenyl, decyl, decyl, pentaphenyl, thick Pentaphenyl, tetraphenylene, hexaphenyl, hexaphenyl, ruthenyl, coromenyl, extended trinaphthyl, heptaphenyl, hexaphenyl, fluorenyl, fluorenyl.
可具有取代基之雜環基係以含有氮原子、氧原子、硫原子、磷原子之芳香族或脂肪族之雜環為佳,其具體例係例如噻吩基、苯並[b]噻吩基、萘並[2,3-b]噻吩基、噻蒽基、呋喃基、吡喃基、異苯並呋喃基、苯並哌喃基、呫噸基(xanthenyl)、啡噻基、2H-吡咯基、吡咯基、咪唑基、吡唑基、吡啶基、吡基、嘧啶基、嗒基、中氮茚基(indolizinyl)、異吲哚基、3H-吲哚基、吲哚基、1H-吲唑基、嘌呤基、4H-喹基、異喹啉基、喹啉基、酞基、萘啶基(Naphthyridinyl)、喹啉基、喹唑啉基、辛啉基 (Cinnolinyl)、喋啶基、4aH-咔唑基、咔唑基、β-咔啉基、啡啶基、吖啶基、呸啶基、啡啉基、啡基、啡噻基、異噻唑基、啡噻基、異唑基、呋吖基、啡基、異香豆素基、香豆素基、吡咯啶基、吡咯啉基、咪唑啶基、咪唑啉基、吡唑啶基、吡唑基、哌啶基、哌基、吲哚啉基、異吲哚啉基、奎寧啶基、嗎啉基、噻噸酮基。 The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and specific examples thereof are, for example, a thienyl group, a benzo[b]thienyl group, Naphtho[2,3-b]thienyl, thioxyl, furyl, pyranyl, isobenzofuranyl, benzopyranyl, xanthenyl, brown Thio group, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyridyl Base, pyrimidinyl, oxime , indolizinyl, isodecyl, 3H-fluorenyl, fluorenyl, 1H-carbazolyl, fluorenyl, 4H-quin Base, isoquinolyl, quinolyl, anthracene Naphthyridinyl, quinine Lolinyl, quinazolinyl, cinnolinyl, acridinyl, 4aH-carbazolyl, oxazolyl, β-carbolinyl, phenanthryl, acridinyl, acridinyl, morpholinyl, brown Thiophene Base, isothiazolyl, thiophene Basis Azyl, furazolyl, brown Base, isocoumarin, coumarin, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolyl, piperidinyl, piperidin Base, porphyrinyl, isoindolyl, quinuclidinyl, morpholinyl, thioxanthone.
上述可具有取代基之烷基、可具有取代基之烯基、可具有取代基之炔基、可具有取代基之芳基、及可將可具有取代基之雜環基的氫原子取代之取代基的具體例係包含例如氟原子、氯原子、溴原子、碘原子等鹵素原子;甲氧基、乙氧基、第三-丁氧基等烷氧基;苯氧基、對-甲苯氧基等芳基氧基、甲氧基羰基、丁氧基羰基、苯氧基羰基、乙烯基氧羰基、芳基氧羰基等烷氧基羰基;乙醯氧基、丙醯氧基、苯甲醯基氧基等醯氧基;乙醯基、苯甲醯基、異丁醯基、丙烯醯基、甲基丙烯醯基、甲氧草醯基等醯基;甲基硫基、第三-丁基硫基等烷基硫基;苯基硫基、對甲苯基硫基等芳基硫基;甲基胺基、環己基胺基等之烷基胺基;二甲基胺基、二乙基胺基、N-嗎啉基、N-哌啶基等二烷基胺基;苯基胺基、對甲苯基胺基等芳基胺基;甲基、乙基、第三-丁基、十二碳基等烷基;苯基、對甲苯基、二甲苯基、異丙苯基、萘基、蒽基、菲基等芳基;羥基、羧基、碸醯胺基、甲醯基、氫硫基、磺基、均三甲苯基、對甲苯磺醯基、胺基、硝基、亞硝基、氰基、三氟甲基、三氯甲基、三甲基矽基、膦酸亞基、磷醯基、烷基磺醯基、 芳基磺醯基、三烷基銨基、二甲基鋶基、三苯基苯甲醯甲基鏻基。 The above-mentioned alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, and a substitution of a hydrogen atom which may have a heterocyclic group which may have a substituent Specific examples of the group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group or a tris-butoxy group; a phenoxy group or a p-tolyloxy group; Alkoxycarbonyl group such as an aryloxy group, a methoxycarbonyl group, a butoxycarbonyl group, a phenoxycarbonyl group, a vinyloxycarbonyl group or an aryloxycarbonyl group; an ethoxy group, a propenyloxy group, a benzamidine group An oxo group such as an oxy group; an oxime group such as an ethyl fluorenyl group, a benzhydryl group, an isobutyl fluorenyl group, an acryl fluorenyl group, a methacryl fluorenyl group, or a methoxycyanyl group; a methylthio group and a tert-butylthio group; An alkylthio group; an arylthio group such as a phenylthio group or a p-tolylthio group; an alkylamino group such as a methylamino group or a cyclohexylamino group; a dimethylamino group, a diethylamino group, a dialkylamino group such as N-morpholinyl or N-piperidinyl; an arylamine group such as a phenylamino group or a p-tolylamino group; a methyl group, an ethyl group, a tert-butyl group or a dodecyl group; An alkyl group; an aryl group such as a phenyl group, a p-tolyl group, a xylyl group, a cumyl group, a naphthyl group, an anthranyl group or a phenanthryl group; a hydroxyl group, a carboxyl group, a decylamino group, a decyl group, a thiol group, a sulfo group , mesityl, p-toluenesulfonyl, amine, nitro, nitroso, cyano, trifluoromethyl, trichloromethyl, trimethylsulfonyl, phosphonic acid subunit, phosphonium, Alkylsulfonyl, Arylsulfonyl, trialkylammonium, dimethylindenyl, triphenylbenzylidenemethylhydrazine.
在上述式(II)所示之離子性化合物(D)具有之N-取代吡啶鎓陽離子中R4為碳數3至16之直鏈或分枝構造之烷基。R5至R9係分別獨立地較佳為氫原子、碳數1至20之直鏈、分枝或環狀構造之烷基、羥基、或鹵素原子,更佳為氫原子或碳數1至20之直鏈或分枝構造之烷基,再更佳為氫原子或碳數1至16之直鏈或分枝構造之烷基。 In the N-substituted pyridinium cation of the ionic compound (D) represented by the above formula (II), R 4 is a linear or branched alkyl group having a carbon number of 3 to 16. R 5 to R 9 are each independently preferably a hydrogen atom, an alkyl group having a carbon number of 1 to 20, a branched or cyclic structure, a hydroxyl group, or a halogen atom, more preferably a hydrogen atom or a carbon number of 1 to The alkyl group of a linear or branched structure of 20 is more preferably a hydrogen atom or an alkyl group having a linear or branched structure of from 1 to 16.
在上述式(I)及(II)中之X-表示含氟原子之亞胺陰離子。使用陰離子為含氟原子之亞胺陰離子的離子性化合物(D)係於附黏著劑層之光學膜1及光學積層體之抗靜電性能、耐金屬腐蝕性及光學耐久性之提升上為有利。其中,較佳係雙(三氟甲烷磺醯基)亞胺陰離子、雙(氟磺醯基)亞胺陰離子、上述式(III)所示之亞胺陰離子等含氟原子之亞胺陰離子,以雙(三氟甲烷磺醯基)亞胺陰離子、雙(氟磺醯基)亞胺陰離子為更佳,以雙(氟磺醯基)亞胺陰離子為再更佳。 X - in the above formulae (I) and (II) represents an imine anion of a fluorine atom. The use of the ionic compound (D) having an anion of a fluorine atom-containing anion anion is advantageous in improving the antistatic property, metal corrosion resistance and optical durability of the optical film 1 and the optical laminate having the adhesive layer. Among them, a bis(trifluoromethanesulfonyl)imide anion, a bis(fluorosulfonyl)imide anion, and an imine anion such as an imide anion represented by the above formula (III) are preferably used. The bis(trifluoromethanesulfonyl)imide anion, bis(fluorosulfonyl)imide anion is more preferred, and the bis(fluorosulfonyl)imide anion is more preferably.
若舉出上述式(I)或(II)所示之離子性化合物(D)的較佳例,係下述式(IV)所示之離子性化合物:
黏著劑組成物中之離子性化合物(D)的含量係相對於(甲基)丙烯酸系樹脂(A)100重量份,較佳係0.1至10重量份,更佳係0.2至8重量份,再更佳係0.3至5重量份,特別較佳係0.5至3重量份。離子性化合物(D)之含量為0.1重量份以上係對於抗靜電性能之提昇上有利,為10重量份以下係對於附黏著劑層之光學膜1及光學積層體之耐金屬腐蝕性及耐久性上有利。 The content of the ionic compound (D) in the adhesive composition is preferably from 0.1 to 10 parts by weight, more preferably from 0.2 to 8 parts by weight, based on 100 parts by weight of the (meth)acrylic resin (A). More preferably, it is 0.3 to 5 parts by weight, particularly preferably 0.5 to 3 parts by weight. The content of the ionic compound (D) of 0.1 part by weight or more is advantageous for the improvement of the antistatic property, and the metal corrosion resistance and durability of the optical film 1 and the optical laminate of the adhesive layer are 10 parts by weight or less. It is beneficial.
黏著劑組成物係可併用第1、第2及/或第3實施形態之離子性化合物(D)以及此等以外之抗靜電劑,但從附黏著劑層之光學膜1及光學積層體之耐金屬腐蝕性等觀點,黏著劑組成物較佳係僅含有第1、第2及/或第3實施形態之離子性化合物(D)作為抗靜電劑。 In the adhesive composition, the ionic compound (D) of the first, second, and/or third embodiments and the antistatic agent other than the above may be used in combination, but the optical film 1 and the optical laminate of the adhesive layer are used. From the viewpoint of metal corrosion resistance and the like, the adhesive composition preferably contains only the ionic compound (D) of the first, second, and/or third embodiments as an antistatic agent.
[2-5]其他之成分 [2-5] Other ingredients
黏著劑組成物係可含有溶劑、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、光散射性微粒子等添加劑1種或2種以上。其他,亦可於黏著劑組成物中調配紫外線硬化性化合物,形成黏著劑層之後照射紫外線使其硬化,有用於形成更硬之黏著劑層。交聯觸媒係可舉例如六亞甲基二胺、乙二胺、 聚乙烯亞胺、六亞甲基四胺、二乙三胺、三乙四胺、異佛酮二胺、三亞甲基二胺、聚胺基樹脂及三聚氰胺樹脂等胺系化合物。 The adhesive composition may contain one or two additives such as a solvent, a crosslinking catalyst, a UV absorber, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, and a light-scattering fine particle. More than one species. Alternatively, an ultraviolet curable compound may be blended in the adhesive composition to form an adhesive layer, which is cured by irradiation with ultraviolet rays, and is used to form a harder adhesive layer. The cross-linking catalyst system may, for example, be hexamethylenediamine or ethylenediamine. An amine compound such as polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamine resin, and melamine resin.
黏著劑組成物係可含有用以提高附黏著劑層之光學膜1及光學積層體之耐金屬腐蝕性的防鏽劑。防錆劑係苯並三唑系化合物、其他之三唑系化合物等三唑系化合物;苯並噻唑系化合物、其他之噻唑系化合物等噻唑系化合物;苯甲基咪唑系化合物、其他之咪唑系化合物等咪唑系化合物;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;脲系化合物;苯甲酸鈉;苯甲基氫硫基系化合物;二-第二-丁基硫醚;及二苯基亞碸。 The adhesive composition may contain a rust preventive for improving the metal corrosion resistance of the optical film 1 and the optical laminate of the adhesive layer. The anti-caries agent is a triazole compound such as a benzotriazole-based compound or another triazole-based compound; a thiazole-based compound such as a benzothiazole-based compound or another thiazole-based compound; a benzylimidazole-based compound or another imidazole-based compound; Imidazole compound such as compound; imidazoline compound; quinoline compound; pyridine compound; pyrimidine compound; anthraquinone compound; amine compound; urea compound; sodium benzoate; - second-butyl sulfide; and diphenylarylene.
但,若依據本發明,即使不含有防鏽劑,亦可獲得充分之耐金屬腐蝕性,故防鏽劑之含量係儘可能地小為較佳。特別,黏著劑組成物係以實質上不含有作為防鏽劑之三唑系化合物為較佳,以實質上不含有選自上述化合物群之防鏽劑為更佳。此處實質上不含係謂相對於(甲基)丙烯酸系樹脂(A)100重量份之含量為0.01重量份以下。 However, according to the present invention, even if the rust preventive agent is not contained, sufficient metal corrosion resistance can be obtained, so that the content of the rust preventive agent is as small as possible. In particular, the adhesive composition is preferably a triazole-based compound which does not substantially contain a rust preventive agent, and is preferably more preferably contains no rust inhibitor selected from the above compound group. The content of the (meth)acrylic resin (A) is preferably 0.01 parts by weight or less based on 100 parts by weight of the (meth)acrylic resin (A).
[3]金屬層及基板 [3] Metal layer and substrate
金屬層30係可為包含例如選自由鋁、銅、銀、金、鐵、錫、鋅、鎳、鉬、鉻、鎢、鉛及含有選自此等之2種以上金屬的合金所組成之群的1種以上之層,從導電性之觀點而言,較佳係包含選自由鋁、銅、銀及金所組成之群的金 屬元素之層,從導電性及成本之觀點而言,更佳係包含鋁元素之層,再更佳係包含鋁元素作為主成分之層。含有作為主成分係謂構成金屬層30之金屬成分為全金屬成分之30重量%以上,更且係50重量%以上。 The metal layer 30 may be, for example, a group selected from the group consisting of aluminum, copper, silver, gold, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and an alloy containing two or more metals selected from the group consisting of The one or more layers preferably contain gold selected from the group consisting of aluminum, copper, silver, and gold from the viewpoint of conductivity. The layer of the genus element is more preferably a layer containing an aluminum element from the viewpoint of conductivity and cost, and more preferably a layer containing an aluminum element as a main component. The metal component containing the metal layer 30 as a main component is 30% by weight or more of the total metal component, and more preferably 50% by weight or more.
金屬層30係可為例如ITO等金屬氧化物層,但本發明之附黏著劑層之光學膜1係特別對於金屬單體或合金之耐腐蝕性為良好,故金屬層30係以包含由上述金屬元素所構成之金屬單體及/或含有上述金屬元素2種以上之合金為較佳。但,光學積層體係亦可具有如此之金屬層30以及由ITO等金屬氧化物所構成之透明電極層。 The metal layer 30 may be a metal oxide layer such as ITO. However, the optical film 1 of the adhesive layer of the present invention is particularly resistant to metal monomers or alloys, so the metal layer 30 is comprised by the above. A metal monomer composed of a metal element and/or an alloy containing two or more kinds of the above metal elements is preferable. However, the optical layering system may have such a metal layer 30 and a transparent electrode layer composed of a metal oxide such as ITO.
金屬層30之形態(例如厚度等)或調製方法係無特別限定,可為金屬箔之外,亦可為藉由真空蒸鍍法、濺鍍法、離子鍍法、噴墨印刷法、凹版印刷法所形成者,但較佳係以濺鍍法、噴墨印刷法、凹版印刷法所形成之金屬層,更佳係以濺鍍所形成之金屬層。以濺鍍所形成之金屬層及金屬箔係前者有耐腐蝕性較差之傾向,但若依據本發明之光學積層體,即使對於以濺鍍所形成之金屬層,亦具有良好之耐金屬腐蝕性。金屬層30之厚度通常為3μm以下,較佳係1μm以下,更佳係0.8μm以下。又,金屬層30之厚度通常為0.01μm以上。更且,金屬層30為金屬配線層之時,其金屬配線層具有之金屬配線的線寬通常為10μm以下,較佳係5μm以下,再更佳係3μm以下。又,金屬配線之線寬通常為0.01μm以上,較佳係0.1μm以上,再更佳係0.5μm以上。對於如此薄膜的金屬層30 或細線之金屬配線所構成之金屬層30,本發明之光學積層體亦顯示良好之耐金屬腐蝕性。特別,金屬配線例如為厚度3μm以下,線寬為10μm以下時,或厚度為3μm以下且線寬為10μm以下,即使以濺鍍法所形成時,亦可抑制其腐蝕特別是孔蝕。 The form (for example, thickness) or the preparation method of the metal layer 30 is not particularly limited, and may be a metal foil, or may be a vacuum deposition method, a sputtering method, an ion plating method, an inkjet printing method, or gravure printing. The method is formed by a method, but 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 sputtering. The metal layer formed by sputtering and the metal foil have a tendency to have poor corrosion resistance. However, according to the optical laminate of the present invention, metal corrosion resistance is good even for a metal layer formed by sputtering. . The thickness of the metal layer 30 is usually 3 μm or less, preferably 1 μm or less, and more preferably 0.8 μm or less. Further, the thickness of the metal layer 30 is usually 0.01 μm or more. Further, when the metal layer 30 is a metal wiring layer, the metal wiring layer has a metal wiring having a line width of usually 10 μm or less, preferably 5 μm or less, and more preferably 3 μm or less. Further, the line width of the metal wiring is usually 0.01 μm or more, preferably 0.1 μm or more, and more preferably 0.5 μm or more. For the metal layer 30 of such a film Or the metal layer 30 composed of the metal wires of the thin wires, the optical laminate of the present invention also exhibits good metal corrosion resistance. In particular, when the metal wiring has a thickness of 3 μm or less, 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, corrosion, particularly pitting corrosion, can be suppressed even when formed by a sputtering method.
金屬層30係例如可為觸控輸入式液晶顯示裝置具有之觸控輸入元件的金屬配線層(亦即電極層)。此時,金屬層30一般係圖型化為預定之形狀。於被圖型化之金屬層30上積層黏著劑層20時,黏著劑20係可具有未接觸金屬層30之部分。金屬層30係可為包含上述金屬或合金之連續膜。 The metal layer 30 is, for example, a metal wiring layer (ie, an electrode layer) of a touch input element of the touch input type liquid crystal display device. At this time, the metal layer 30 is generally patterned into a predetermined shape. When the adhesive layer 20 is laminated on the patterned metal layer 30, the adhesive 20 may have a portion that is not in contact with the metal layer 30. The metal layer 30 may be a continuous film comprising the above metal or alloy.
又,金屬層30係可為單層構造,亦可為2層或3層以上之多層構造。多層構造之金屬層係可舉例如以鉬/鋁/鉬表示之3層構造的含有金屬的層(金屬網目等)。 Further, the metal layer 30 may have a single layer structure or a multilayer structure of two or more layers. The metal layer of the multilayer structure may, for example, be a metal-containing layer (metal mesh or the like) having a three-layer structure represented by molybdenum/aluminum/molybdenum.
如第1圖所示,例如為金屬配線層之金屬層30通常形成於基板40上,此時,本發明之光學積層體係包含此基板40。於基板40上之金屬層30的形成係可藉由例如濺鍍來進行。基板40係可為構成觸控輸入元件中所含之液晶單元的透明基板。基板40較佳係玻璃基板。玻璃基板之材料可舉例如鈉鈣玻璃、低鹼玻璃、無鹼玻璃等。金屬層30係可形成於基板40全面,亦可形成於其一部分。基板40上形成被圖型化之金屬層30時等、於基板40之表面的一部份形成金屬層30時,係黏著劑層20之一部分例如與玻璃所構成之基板40直接接觸,但本發明之光學積層 體中之黏著劑層20係與玻璃之密著性亦優異,故光學積層體、及具備該光學積層體之液晶顯示裝置係在此情況的耐久性亦優異。 As shown in Fig. 1, a metal layer 30 such as a metal wiring layer is usually formed on the substrate 40. In this case, the optical layering system of the present invention comprises the substrate 40. The formation of the metal layer 30 on the substrate 40 can be performed by, for example, sputtering. The substrate 40 may be a transparent substrate constituting a liquid crystal cell included in the 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 substrate 40 or formed on a part thereof. When the metal layer 30 is formed on the surface of the substrate 40 when the patterned metal layer 30 is formed on the substrate 40, a portion of the adhesive layer 20 is directly in contact with the substrate 40 formed of glass, for example, but Optical laminate of the invention Since the adhesive layer 20 in the body is also excellent in adhesion to glass, the optical layered body and the liquid crystal display device including the optical layered body are excellent in durability.
[4]光學積層體之構成及製造方法 [4] Composition and manufacturing method of optical laminate
在1個實施形態中,本發明之光學積層體係如第4圖及第5圖所示,包含附黏著劑層之光學膜1、及積層於其黏著劑層20側之金屬層30。於第4圖及第5圖所示之光學積層體5,6中,附黏著劑層之光學膜1係以其黏著劑層20直接接觸金屬層30之方式積層於金屬層30上。若依據本發明,如此地,即使以黏著劑層20直接接觸金屬層30之方式構成的光學積層體中,亦可有效地抑制金屬層30之腐蝕。 In one embodiment, as shown in Figs. 4 and 5, the optical layering system of the present invention comprises an optical film 1 with an adhesive layer and a metal layer 30 laminated on the side of the adhesive layer 20. In the optical laminates 5, 6 shown in Figs. 4 and 5, the optical film 1 with the adhesive layer is laminated on the metal layer 30 such that the adhesive layer 20 directly contacts the metal layer 30. According to the present invention, even in the optical layered body in which the adhesive layer 20 directly contacts the metal layer 30, the corrosion of the metal layer 30 can be effectively suppressed.
第6圖係表示本發明之光學積層體的層構成之其他一例的概略剖面圖。其他之實施形態中,本發明之光學積層體係如第6圖所示之光學積層體7,附黏著劑層之光學膜1之黏著劑層20係透過樹脂層50而積層於金屬層30。黏著劑層20係直接接觸樹脂層50。即使在如此之光學積層體7中,亦可有效地抑制金屬層30之腐蝕。配置於黏著劑層20及金屬層30之間的樹脂層50係例如可為硬化性樹脂之硬化物層。可形成樹脂層50之硬化性樹脂係可使用公知者,可舉例如日本特開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 layered body of the present invention. In the other embodiment, the optical layered body 7 of the present invention has the optical layered body 7 shown in Fig. 6, and the adhesive layer 20 of the optical film 1 with the adhesive layer is laminated on the metal layer 30 through the resin layer 50. The adhesive layer 20 is in direct contact with the resin layer 50. Even in such an optical layered body 7, 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 layer of a curable resin. A curable resin which can form the resin layer 50 can be used, and it is known, for example, as described in JP-A-2009-217037.
如上述,金屬層30係可為金屬配線層。將 金屬層30為金屬配線層時之一例表示於第7圖。第7圖所示之光學積層體中,樹脂層50係亦可被省略。 As described above, the metal layer 30 may be a metal wiring layer. will An example of the case where the metal layer 30 is a metal wiring layer is shown in FIG. In the optical laminate shown in Fig. 7, the resin layer 50 may be omitted.
光學積層體係例如在形成於基板40上之金屬層30上,將包含光學膜10及積層於其至少一面上之黏著劑層20的附黏著劑層之光學膜1透過其黏著劑層20貼合即可製作。 The optical layering system is bonded to the optical layer 1 including the optical film 10 and the adhesive layer 20 of the adhesive layer 20 laminated on at least one surface thereof through the adhesive layer 20, for example, on the metal layer 30 formed on the substrate 40. You can make it.
如上述,附黏著劑層之光學膜1係包含光學膜10及積層於其至少一面之黏著劑層20(第1圖)。亦可於光學膜10之雙面積層黏著劑層20。通常,黏著劑層20係直接積層於光學膜10之表面。將黏著劑層20設於光學膜10之表面時,較佳係於光學膜10之貼合面及/或黏著劑層20之貼合面形成底塗層、或施予表面活性化處理例如電漿處理、電暈處理等,以實施電暈處理為更佳。 As described above, the optical film 1 with the adhesive layer includes the optical film 10 and the adhesive layer 20 laminated on at least one side thereof (Fig. 1). The double layer adhesive layer 20 of the optical film 10 can also be used. 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, it is preferable to form an undercoat layer on the bonding surface of the optical film 10 and/or the bonding surface of the adhesive layer 20, or to apply a surface activation treatment such as electricity. Pulp treatment, corona treatment, etc., to perform corona treatment is more preferable.
光學膜10為如第2圖所示之單面保護偏光板時,通常在與偏光片面、亦即與偏光片2中之第1樹脂膜3為相反側之面,較佳係直接積層黏著劑層20。光學膜10為如第3圖所示之雙面保護偏光板時,可在第1,第2樹脂膜3,4之任一外面積層黏著劑層20,亦可於兩方之外面積層黏著劑層20。 When the optical film 10 is a single-sided protective polarizing plate as shown in Fig. 2, it is usually a surface on the opposite side of the polarizing plate surface, that is, the first resin film 3 in the polarizing plate 2, and it is preferable to directly deposit an adhesive. Layer 20. When the optical film 10 is a double-sided protective polarizing plate as shown in FIG. 3, the adhesive layer 20 may be applied to any of the first and second resin films 3 and 4, or may be applied to the outer layer of the two layers. Layer 20.
於光學膜10及黏著劑層20之間係可另外地設置抗靜電層,但由於本發明之黏著劑層20以黏著劑層單獨即可賦予優異之抗靜電性,故以光學積層體之薄膜化或積層體製作步驟之簡單化之點,以於光學膜10及黏著劑層20之間不具有抗靜電層為較佳。 An antistatic layer may be additionally provided between the optical film 10 and the adhesive layer 20. However, since the adhesive layer 20 of the present invention can provide excellent antistatic property by the adhesive layer alone, the film of the optical laminate is used. The simplification of the step of fabricating or laminating the film is preferably such that the anti-static layer is not provided between the optical film 10 and the adhesive layer 20.
附黏著劑層之光學膜1係亦可含有積層於黏著劑層20之外面的分離膜(剝離膜)。此分離膜通常於黏著劑層20之使用時(例如於金屬層30上之積層時)被剝離除去。分離膜係例如可對由聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚碳酸酯、聚芳酸酯等各種樹脂所構成之膜形成黏著劑層20之面,施予聚矽氧處理等離型處理者。 The optical film 1 to which the adhesive layer is attached may also contain a separation film (release film) laminated on the outer surface of the adhesive layer 20. This separation film is usually removed by peeling off when the adhesive layer 20 is used (for example, when laminated on the metal layer 30). The separation membrane system can form a coating on the surface of the adhesive layer 20, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate. Oxygen treatment isolating processor.
附黏著劑層之光學膜1係將構成上述黏著劑組成物之各成分溶解或分散於溶劑而形成含有溶劑之黏著劑組成物,然後,將其塗布於光學膜10之表面並乾燥而形成黏著劑層20即可製得。又,附黏著劑層之光學膜1係可藉由於分離膜之離型處理面與上述同樣地形成黏著劑層20,使該黏著劑層20積層(轉印)於光學膜10之表面而製得。 The optical film 1 with an adhesive layer is formed by dissolving or dispersing the components constituting the above-mentioned adhesive composition in a solvent to form a solvent-containing adhesive composition, and then applying it to the surface of the optical film 10 to dry and form an adhesive. The agent layer 20 can be obtained. Further, the optical film 1 with an adhesive layer can be formed by laminating (transferring) the adhesive layer 20 on the surface of the optical film 10 by forming the adhesive layer 20 in the same manner as described above. Got it.
可藉由於金屬層30(或上述樹脂層)上將附黏著劑層之光學膜1透過其黏著劑層20貼合,以獲得光學積層體。貼合附黏著劑層之光學膜1及金屬層30而製作光學積層體後,有任何不佳情形時,有時必須將附黏著劑層之光學膜1從金屬層30剝離,再將另外之附黏著劑層之光學膜1重新貼合於金屬層30,而有所謂重工作業。本發明之光學積層體係於將附黏著劑層之光學膜1從金屬層30剝離之後的金屬層30之表面不易產生霧化或殘糊等,且重工性優異。若依據本發明之光學積層體,貼合黏著劑層20之表面並非金屬層30,而為玻璃基板或ITO層之時亦可顯示良好的重工性。 The optical layer 1 of the adhesive layer may be bonded through the adhesive layer 20 on the metal layer 30 (or the above resin layer) to obtain an optical laminate. When the optical film 1 and the metal layer 30 with the adhesive layer are bonded to each other to form an optical laminate, if any of the optical layers are not preferable, the optical film 1 with the adhesive layer may be peeled off from the metal layer 30, and then the other may be peeled off. The optical film 1 with the adhesive layer is reattached to the metal layer 30, and there is a so-called heavy work. In the optical layering system of the present invention, the surface of the metal layer 30 after the optical film 1 with the adhesive layer is peeled off from the metal layer 30 is less likely to cause fogging or residue, and is excellent in reworkability. According to the optical layered body of the present invention, the surface of the adhesive layer 20 is not the metal layer 30, and the glass substrate or the ITO layer can exhibit good reworkability.
本發明之液晶顯示裝置係含有上述本發明之光學積層體者。本發明之液晶顯示裝置係可抑制金屬層30之腐蝕,又,顯示良好的耐久性。 The liquid crystal display device of the present invention contains the above-described 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.
本發明之液晶顯示裝置較佳係具有觸控面板機能之觸控輸入式液晶顯示裝置。觸控輸入式液晶顯示裝置係具備含有液晶單元之觸控輸入元件及背光。觸控面板之構成係可為外掛式(out cell)型、內掛式(on cell)型、內嵌式(in cell)型等以往公知之任一方式,又,觸控面板之動作方式係可為電阻膜方式、靜電容量方式(表面型靜電容量方式、投影型靜電容量方式)等以往公知之任一方式。本發明之光學積層體係可配置於觸控輸入元件(液晶單元)之辨視側,可配置於背光側,亦可配置於兩方。液晶單元之驅動方式係可為TN方式、VA方式、IPS方式、多域方式、OCB方式等以往公知之任一方式。本發明之液晶顯示裝置中,光學積層體具有之基板40係可為上述液晶單元所含之基板(典型為玻璃基板)。 The liquid crystal display device of the present invention is preferably a touch input type liquid crystal display device having a touch panel function. The touch input type liquid crystal display device includes a touch input element including a liquid crystal cell and a backlight. The configuration of the touch panel may be any one of the conventional methods such as an out cell type, an on cell type, and an in cell type, and the operation mode of the touch panel is Any of the conventionally known methods such as a resistive film method and an electrostatic capacitance method (surface type electrostatic capacitance method or projection type electrostatic capacitance method) may be used. The optical layering system of the present invention can be disposed on the viewing side of the touch input element (liquid crystal cell), can be disposed on the backlight side, or can be disposed on both sides. The driving method of the liquid crystal cell may be any one of conventionally known methods such as a TN method, a VA method, an IPS method, a multi-domain method, and an OCB method. In the liquid crystal display device of the present invention, the substrate 40 included in the optical layered body 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而更具體地說明本發明,但本發明係不限定於此等之例。以下,表示使用量、含量之份及%係只要無特別聲明,為重量基準。 Hereinafter, the present invention will be more specifically described by showing examples and comparative examples, but the present invention is not limited thereto. Hereinafter, the amount of use, the amount of the content, and the % are based on the weight unless otherwise stated.
於具備冷卻管、氮氣導入管、溫度計及攪拌機之反應容器中,加入表1所示之組成(表1之數值為重量份)之單體與乙酸乙酯81.8份混合而得到之溶液。將反應容器內之空氣以氮氣取代後,使內溫為60℃。其後,添加將偶氮雙異丁腈0.12份溶解於乙酸乙酯10份而得之溶液。以相同溫度保持1小時後,將內溫保持於54至56℃,並以添加速度17.3份/Hr將乙酸乙酯以聚合物之濃度成為約35%之方式連續加入於反應容器內。從乙酸乙酯之添加開始經過12小時為止將內溫保持於54至56℃之後,加入乙酸乙酯以使聚合物之濃度成為20%之方式進行調整,製得(甲基)丙烯酸系樹脂(A-1)之乙酸乙酯溶液。(甲基)丙烯酸系樹脂(A-1)之重量平均分子量Mw係139萬,重量平均分子量Mw及數量平均分子量Mn之比Mw/Mn為5.32。凝膠滲透色層分析(GPC)之排出曲線中,Mw139萬之成分係表示單一之波峰,Mw1000至250萬之範圍中看不出其他之波峰。 Into a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirrer, a solution obtained by mixing a monomer having a composition shown in Table 1 (amount in Table 1 in parts by weight) and 81.8 parts of ethyl acetate was added. After the air in the reaction vessel was replaced with nitrogen, the internal temperature was made 60 °C. Thereafter, a solution obtained by dissolving 0.12 parts of azobisisobutyronitrile in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, the internal temperature was maintained at 54 to 56 ° C, and ethyl acetate was continuously added to the reaction vessel at a rate of addition of 17.3 parts/Hr to a concentration of the polymer of about 35%. The internal temperature was maintained at 54 to 56 ° C after 12 hours from the addition of ethyl acetate, and ethyl acetate was added to adjust the concentration of the polymer to 20% to obtain a (meth)acrylic resin ( A-1) ethyl acetate 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 and the number average molecular weight Mn was 5.32. In the gel permeation chromatography (GPC) discharge curve, the composition of Mw 1.39 million represents a single peak, and no other peaks are seen in the range of Mw 1000 to 2.5 million.
除了使單體之組成成為如表1所示以外,係與製造例1同樣做法,製得(甲基)丙烯酸系樹脂(A-2)之乙酸乙酯溶液(樹脂濃度:20%)。(甲基)丙烯酸系樹脂(A-2)之重量平均分子量Mw為141萬,Mw/Mn為4.71。GPC之排出曲線中,Mw141萬之成分係顯示單一之波峰,Mw1000至250萬之 範圍中,看不出其他之波峰。 An ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin (A-2) was obtained in the same manner as in Production Example 1 except that the composition of the monomer was as shown in Table 1. The (meth)acrylic resin (A-2) had a weight average molecular weight Mw of 1.41 million and Mw/Mn of 4.71. In the GPC discharge curve, the composition of Mw 1.4 million shows a single peak, Mw 1000 to 2.5 million No other peaks are visible in the range.
除了使單體之組成為如表1所示以外,其餘係與製造例1同樣做法,獲得(甲基)丙烯酸系樹脂(A-3)之乙酸乙酯溶液(樹脂濃度:20%)。(甲基)丙烯酸系樹脂(A-3)之重量平均分子量Mw為75萬、Mw/Mn為5.02。在GPC之排出曲線中,Mw75萬之成分顯示單一之波峰,Mw1000至250萬之範圍中看不出其他之波峰。 The ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin (A-3) was obtained in the same manner as in Production Example 1 except that the composition of the monomer was as shown in Table 1. The (meth)acrylic resin (A-3) had a weight average molecular weight Mw of 750,000 and an Mw/Mn of 5.02. In the GPC discharge curve, the composition of Mw75 million shows a single peak, and no other peaks are seen in the range of Mw1000 to 2.5 million.
上述之製造例中,重量平均分子量Mw及數量平均分子量Mn係於GPC裝置將東曹(股)製之「TSKgel XL」4根、及昭和電工(股)製之「Shodex GPC KF-802」1根之共計5根串聯連接配置作為管柱,使用四氫呋喃作為溶離液,以試料濃度5mg/mL、試料導入量100μL、溫度40℃、流速1mL/分之條件,藉標準聚苯乙烯換算來測定。製得GPC之排出曲線時之條件亦與此相同。 In the above-mentioned production example, the weight average molecular weight Mw and the number average molecular weight Mn are four "TSKgel XL" manufactured by Tosoh Corporation and "Shodex GPC KF-802" manufactured by Showa Denko Co., Ltd. in the GPC apparatus. A total of five roots were connected in series as a column, and tetrahydrofuran was used as the elution solution, and the sample concentration was 5 mg/mL, the sample introduction amount was 100 μL, the temperature was 40 ° C, and the flow rate was 1 mL/min, and the measurement was carried out by standard polystyrene conversion. The conditions for producing the GPC discharge curve are also the same.
玻璃轉移溫度Tg係使用SII Nanotechnology(股)公司製之示差掃描熱量計(DSC)「EXSTAR DSC6000」,在氮氣環境下、以測定溫度範圍-80至50℃、昇溫速度10℃/分之條件測定。 The glass transition temperature Tg was measured using a differential scanning calorimeter (DSC) "EXSTAR DSC6000" manufactured by SII Nanotechnology Co., Ltd. under a nitrogen atmosphere at a measurement temperature range of -80 to 50 ° C and a temperature increase rate of 10 ° C /min. .
各製造例中之單體之組成(表1之數值為重量份)、及GPC之排出曲線上之Mw1000至250萬之範圍中之波峰數(表1中表記為「GPC波峰數」)彙整於表1中。 The composition of the monomers in each of the production examples (the values in Table 1 are parts by weight), and the number of peaks in the range of Mw 1000 to 2.5 million on the GPC discharge curve (in Table 1, the number of "GPC peaks" is summarized) in FIG. 1.
於表1之「單體組成」之欄中的簡稱係意指如下之單體。 The abbreviation in the column of "monomer composition" in Table 1 means the following monomers.
BA:丙烯酸丁酯(均聚物之玻璃轉移溫度:-54℃)、MA:丙烯酸甲酯(均聚物之玻璃轉移溫度:10℃)、2EHA:丙烯酸2-乙基己酯(均聚物之玻璃轉移溫度:-50℃)、HEA:丙烯酸2-羥乙基酯。 BA: butyl acrylate (glass transition temperature of homopolymer: -54 ° C), MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C), 2EHA: 2-ethylhexyl acrylate (homopolymer) Glass transition temperature: -50 ° C), HEA: 2-hydroxyethyl acrylate.
AM:丙烯醯胺、M-90G:甲氧基聚乙二醇# 400甲基丙烯酸酯(EO 9mol),取自新中村化學工業(股)之商品名「M-90G」。 AM: acrylamide, M-90G: methoxypolyethylene glycol #400 methacrylate (EO 9 mol), taken from the brand name "M-90G" of Shin-Nakamura Chemical Industry Co., Ltd.
(1)黏著劑組成物之調製 (1) Modulation of adhesive composition
於上述製造例所得到之(甲基)丙烯酸系樹脂之乙酸乙酯溶液(樹脂濃度:20%)中,相對於該溶液之固形分100份,將表2所示之異氰酸酯系交聯劑(B)、矽烷化合物(C)、 及離子性化合物(D)分別以表2所示之量(重量份)混合,更且以固形分濃度成為14%之方式添加乙酸乙酯而製得黏著劑組成物。當所使用之商品含有溶劑等之時,表2所示之各配合成分之配合量係其中所含之作為有效成分之重量份數。 In the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above production example, the isocyanate crosslinking agent shown in Table 2 was added to 100 parts of the solid content of the solution ( B), decane compound (C), The ionic compound (D) was mixed in an amount (parts by weight) shown in Table 2, and ethyl acetate was added so that the solid content concentration became 14% to obtain an adhesive composition. When the product to be used contains a solvent or the like, the compounding amount of each component shown in Table 2 is a part by weight as an active ingredient contained therein.
表2中以簡稱表示之各配合成分之內容係如下。 The contents of the respective components indicated by the abbreviation in Table 2 are as follows.
(異氰酸酯系交聯劑) (isocyanate crosslinking agent)
B-1:二甲苯二異氰酸酯之三羥甲基丙烷加成物之乙酸乙酯溶液(固形分濃度75%)、取自三井化學(股)之商品名「Takenate D-110N」。 B-1: an ethyl acetate solution of a trimethylolpropane adduct of xylene diisocyanate (solid content concentration: 75%), and a trade name "Takenate D-110N" from Mitsui Chemicals Co., Ltd.
(矽烷化合物) (decane compound)
C-1:3-環氧丙氧基丙基三甲氧基矽烷,由信越化學工業(股)取得之商品名「K BM403」。 C-1: 3-glycidoxypropyltrimethoxydecane, trade name "K BM403" obtained from Shin-Etsu Chemical Co., Ltd.
(離子性化合物) (ionic compound)
D-1:N-丙基吡啶鎓 雙(氟磺醯基)亞胺、D-2:N-辛基吡啶鎓 雙(氟磺醯基)亞胺、D-3:N-癸基吡啶鎓 雙(氟磺醯基)亞胺、D-4:N-十二碳基吡啶鎓 雙(氟磺醯基)亞胺。D-5:N-十六碳基吡啶鎓 雙(氟磺醯基)亞胺、D-6:1-乙基-1-甲基吡咯啶鎓 雙(三氟甲烷磺醯基)亞胺、D-7:N-甲基吡啶鎓 雙(氟磺醯基)亞胺。 D-1: N-propylpyridinium bis(fluorosulfonyl)imide, D-2: N-octylpyridinium bis(fluorosulfonyl)imide, D-3: N-decylpyridinium Bis(fluorosulfonyl)imide, D-4: N-dodecylpyridinium bis(fluorosulfonyl)imide. D-5: N-hexadecylpyridinium bis(fluorosulfonyl)imide, D-6: 1-ethyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, D-7: N-methylpyridinium bis(fluorosulfonyl)imide.
表2中之「溶解度」係對於60℃之水100g的離子性化合物(D)之溶解度(g)。該溶解度係依據如下之順序求出。首先,混合經精秤之離子性化合物100mg與純水2mL之後,於攪拌下以溫度60℃保管24小時。取得之離子性化合物含有溶劑時,係可藉減壓蒸餾除去溶劑而獲得乾固之離子性化合物,再精秤。然後,取樣水層之一部分(精秤量),將此以乙腈適度地稀釋後,將溶解於所得之測定試樣之離子性化合物的重量濃度藉由液體色層質量分析法(LC/MS)之絶對檢量線法來定量。LC/MS之測定條件如下。依據定量結果,求出離子性化合物(D)之溶解度。 The "solubility" in Table 2 is the solubility (g) of the ionic compound (D) of 100 g of water at 60 °C. The solubility was determined in the following order. First, 100 mg of the ionic compound of the fine scale and 2 mL of pure water were mixed, and then stored under stirring at a temperature of 60 ° C for 24 hours. When the obtained ionic compound contains a solvent, the solvent can be distilled off under reduced pressure to obtain a dry solid ionic compound, which is then weighed. Then, a part of the water layer (fine weighing amount) is sampled, and after appropriately diluted with acetonitrile, the weight concentration of the ionic compound dissolved in the obtained measurement sample is determined by liquid chromatography (LC/MS). Absolute calibrated line method to quantify. The measurement conditions of LC/MS are as follows. The solubility of the ionic compound (D) was determined based on the quantitative results.
分析裝置:Agilent Technologies LC/MS裝置1260型/6130型 Analytical device: Agilent Technologies LC/MS device type 1260/6130
分離管柱:Kinetex 2.6u C18 100A(3.0×100mm,2.7μm) Separation column: Kinetex 2.6u C18 100A (3.0×100mm, 2.7μm)
移動相:添加0.05% TFA之水/乙腈之混合溶劑的梯度法 Mobile phase: gradient method of adding 0.05% TFA water/acetonitrile mixed solvent
移動相之流量:0.5mL/min. Mobile phase flow: 0.5mL/min.
試樣注入量:2.5μL Sample injection amount: 2.5 μL
烘箱溫度:40℃ Oven temperature: 40 ° C
UV檢測波長:254nm UV detection wavelength: 254nm
MS檢測條件:電子噴射離子化(ESI)法Positive。 MS detection conditions: Electrospray ionization (ESI) method Positive.
又,對於離子性化合物D-1至D-5及D-7係UV檢測器(波長254nm)、離子性化合物D-6係藉由MS檢測器之選擇離子檢測(SIM)模式而進行定量(偵測質量m/z=114)。 Further, for the ionic compounds D-1 to D-5 and the D-7 system UV detector (wavelength 254 nm), the ionic compound D-6 was quantified by the selective ion detection (SIM) mode of the MS detector ( Detection quality m/z = 114).
(2)黏著劑層之作製 (2) The layer of adhesive layer
於被施予離型處理之聚對苯二甲酸乙二酯膜所構成之分離膜[取自Lintec(股)之商品名「PLR-382051」]之離型處理面,使用薄塗器(applicator)以乾燥後之厚度成為20μm之方式塗布上述(1)所調製之各黏著劑組成物,以100℃乾燥1分鐘而製作黏著劑層(黏著劑片)。 A thin coater (applicator) is used for the release film of the separation film composed of the polyethylene terephthalate film subjected to the release treatment [taken from the brand name "PLR-382051" of Lintec Co., Ltd.]. The adhesive composition prepared in the above (1) was applied so as to have a thickness of 20 μm after drying, and dried at 100 ° C for 1 minute to prepare an adhesive layer (adhesive sheet).
(3)附黏著劑層之光學膜(P-1)之製作 (3) Production of optical film (P-1) with adhesive layer
將平均聚合度約2400、皂化度99.9莫耳%、厚度60μm之聚乙烯醇膜[(股)Kuraray製之商品名「Kuraray Vinylon VF-PE#6000」]浸漬於37℃之純水後,以30℃浸漬於含有碘及碘化鉀之水溶液(碘/碘化鉀/水(重量比)=0.04/1.5/100)。其後,以56.5℃浸漬於含有碘化鉀及硼酸之水溶液(碘化鉀/硼酸/水(重量比)=12/3.6/100)。將膜以10℃之純水洗浄後,以85℃乾燥,獲得於聚乙烯醇吸附配向有碘之厚度約23μm之偏光片。延伸主要係於碘染色及硼酸處理之步驟進行,整體之延伸倍率為5.3倍。 A polyvinyl alcohol film having an average polymerization degree of about 2,400, a saponification degree of 99.9 mol%, and a thickness of 60 μm [Kuraray Vinylon, manufactured by Kuraray Co., Ltd. VF-PE #6000"] was immersed in pure water at 37 ° C, and then immersed in an aqueous solution containing iodine and potassium iodide (iodine / potassium iodide / water (weight ratio) = 0.44 / 1.5 / 100) at 30 ° C. Thereafter, 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 in the form of iodine adsorbed on polyvinyl alcohol. The extension is mainly carried out in the steps of iodine dyeing and boric acid treatment, and the overall stretching ratio is 5.3 times.
於所得到之偏光片之單面透過聚乙烯醇系樹脂之水溶液所構成之接著劑而貼合厚度25μm之三乙醯基纖維素膜所構成之透明保護膜[Konica Minolta Opto(股)製之商品名「KC2UA」]。然後,於與上述偏光片之三乙醯基纖維素膜為相反側之面,透過聚乙烯醇系樹脂之水溶液所構成之接著劑而貼合厚度23μm之環狀聚烯烴系樹脂所構成之零相位差膜[日本Zeon(股)製之商品名「ZEONOR」],製作偏光板。然後,於零相位差膜之與偏光片接觸之面為相反側之面,在施予用以提升密著性之電暈放電處理後,以積層機貼合與上述(2)製作之黏著劑層的分離膜為相反側之面(黏著劑層面)後,以溫度23℃、相對濕度65%之條件熟成7日,製得附黏著劑層之光學膜(P-1)。 A transparent protective film made of a triethylenesulfonated cellulose film having a thickness of 25 μm is applied to a single surface of the obtained polarizer through an adhesive composed of an aqueous solution of a polyvinyl alcohol resin [Konica Minolta Opto Co., Ltd. Product name "KC2UA"]. Then, on the opposite side of the triacetyl cellulose film of the polarizer, a layer of a cyclic polyolefin resin having a thickness of 23 μm is bonded by an adhesive composed of an aqueous solution of a polyvinyl alcohol resin. A retardation film [trade name "ZEONOR" manufactured by Zeon, Japan) was used to produce a polarizing plate. Then, on the opposite side of the surface of the zero retardation film that is in contact with the polarizer, after applying the corona discharge treatment for improving the adhesion, the adhesive prepared by the above (2) is bonded by a laminator. After the separation membrane of the layer was on the opposite side (adhesive layer), it was aged at a temperature of 23 ° C and a relative humidity of 65% for 7 days to obtain an optical film (P-1) with an adhesive layer.
(4)附黏著劑層之光學膜(P-2)之製作 (4) Production of optical film (P-2) with adhesive layer
將平均聚合度約2400、皂化度99.9莫耳%、厚度30μm之聚乙烯醇膜[(股)Kuraray製之商品名「Kuraray Vinylon VF-PE#3000」]浸漬於37℃之純水後,以30℃浸漬於含有 碘及碘化鉀之水溶液(碘/碘化鉀/水(重量比)=0.04/1.5/100)。其後,以56.5℃浸漬於含有碘化鉀及硼酸之水溶液(碘化鉀/硼酸/水(重量比)=12/3.6/100)。將膜以10℃之純水洗浄後,以85℃乾燥,獲得於聚乙烯醇吸附配向有碘之厚度約12μm之偏光片。延伸主要係於碘染色及硼酸處理之步驟進行,整體之延伸倍率為5.3倍。 A polyvinyl alcohol film having an average polymerization degree of about 2400, a saponification degree of 99.9 mol%, and a thickness of 30 μm was immersed in pure water at 37 ° C under the trade name "Kuraray Vinylon VF-PE #3000" (manufactured by Kuraray Co., Ltd.). 30 ° C immersion in containing An aqueous solution of iodine and potassium iodide (iodine/potassium iodide/water (weight ratio) = 0.04/1.5/100). Thereafter, 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 in the form of iodine adsorbed on polyvinyl alcohol. The extension is mainly carried out in the steps of iodine dyeing and boric acid treatment, and the overall stretching ratio is 5.3 times.
於所得到之偏光片之單面透過聚乙烯醇系樹脂之水溶液所構成之接著劑而貼合厚度25μm之三乙醯基纖維素膜所構成之透明保護膜[Konica Minolta Opto(股)製之商品名「KC2UA」]而製作偏光板。然後,於偏光片之與貼合有保護膜之面為相反之面,以積層機貼合與上述(2)所製作之黏著劑層的分離膜為相反側之面(黏著劑層面)後,以溫度23℃、相對濕度65%之條件熟成7日,製得附黏著劑層之光學膜(P-2)。 A transparent protective film made of a triethylenesulfonated cellulose film having a thickness of 25 μm is applied to a single surface of the obtained polarizer through an adhesive composed of an aqueous solution of a polyvinyl alcohol resin [Konica Minolta Opto Co., Ltd. The product name "KC2UA"] was used to make a polarizing plate. Then, on the opposite side of the surface of the polarizer to which the protective film is bonded, and the surface of the adhesive layer of the adhesive layer prepared in the above (2) is bonded to the surface (adhesive layer) by a laminator. The film was aged for 7 days under the conditions of a temperature of 23 ° C and a relative humidity of 65% to obtain an optical film (P-2) with an adhesive layer.
(5)附黏著劑層之光學膜之耐金屬腐蝕性評價 (5) Evaluation of metal corrosion resistance of optical film with adhesive layer
將上述(3)所製作之附黏著劑層之光學膜(P-1)裁切為20mm×50mm大小的試驗片,透過黏著劑層而貼附於附金屬層之玻璃基板的金屬層側。附金屬層之玻璃基板係使用於無鹼玻璃表面藉由濺鍍而積層厚度約500nm之金屬鋁層的玻璃基板(Geomatec公司製)。將所得到之光學積層體於溫度60℃、相對濕度90%之烘箱中保管500小時後,將貼黏於附黏著劑層之光學膜的部分之金屬層之狀態從玻璃基板之背面照射光線而從偏光板表面經由放大鏡觀察,對於孔 蝕(直徑0.1mm以上,可透過光之孔的發生)以如下之基準評價。結果表示於表3中。 The optical film (P-1) with the adhesive layer prepared in the above (3) was cut into a test piece having a size of 20 mm × 50 mm, and adhered to the metal layer side of the glass substrate with the metal layer through the adhesive layer. The glass substrate with a metal layer is a glass substrate (manufactured by Geomatec Co., Ltd.) in which a metal aluminum layer having a thickness of about 500 nm is deposited by sputtering on the surface of the alkali-free glass. After the obtained optical laminate 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 adhered to the portion of the optical film to which the adhesive layer was attached was irradiated with light from the back surface of the glass substrate. Observed from the surface of the polarizer via a magnifying glass The etch (the diameter of 0.1 mm or more and the permeable light hole) was evaluated on the basis of the following. The results are shown in Table 3.
4:產生於金屬層表面之孔蝕之數量為2個以下、3:產生於金屬層表面之孔蝕之數量為3個至5個、2:產生於金屬層表面之孔蝕之數量為6個以上、1:於金屬層表面之全面產生許多數量之孔蝕,且亦產生白濁。 4: the number of pitting corrosion generated on the surface of the metal layer is 2 or less, 3: the number of pitting corrosion generated on the surface of the metal layer is 3 to 5, 2: the number of pitting corrosion generated on the surface of the metal layer is 6 More than one, 1: a large number of pittings are generated on the surface of the metal layer, and white turbidity is also generated.
(6)附黏著劑層之光學膜之耐久性評價 (6) Durability evaluation of optical film with adhesive layer
將上述(3)所製作之附黏著劑層之光學膜(P-1)以偏光板之延伸軸方向成為長邊之方式裁切成200mm×150mm之大小並剝離分離膜,將所露出之黏著劑層面貼合於玻璃基板。將所得到之貼黏有玻璃基板之試驗片(貼黏有玻璃基板之附黏著劑層的光學膜)於高壓釜中以溫度50℃、壓力5kg/cm2(490.3kPa)加壓20分鐘。玻璃基板係使用康寧公司製之無鹼玻璃 商品名「Eagle XG」。對於所得到之光學積層體,實施下列之3種耐久性試驗。 The optical film (P-1) with the adhesive layer produced in the above (3) is cut into a size of 200 mm × 150 mm so that the direction of the extension axis of the polarizing plate becomes a long side, and the separation film is peeled off to adhere the exposed film. The agent layer is attached to the glass substrate. The obtained test piece to which a glass substrate was adhered (an optical film to which an adhesive layer of a glass substrate was adhered) 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. For the glass substrate, the alkali-free glass product name "Eagle XG" manufactured by Corning Incorporated was used. For the obtained optical laminate, the following three durability tests were carried out.
‧溫度85℃之乾燥條件下保持750小時之耐熱試驗、‧溫度60℃、相對濕度90%之環境下保持750小時之耐濕熱試驗、‧以在溫度85℃之乾燥條件下保持30分鐘,然後,在溫 度-40℃之乾燥條件下保持30分鐘之操作作為1循環,將此重複400循環之耐熱衝擊(HS)試驗。 ‧ 750 hours of heat resistance test under dry conditions at 85 ° C, 750 hours of humidity resistance at 60 ° C, relative humidity of 90%, ‧ for 30 minutes at a temperature of 85 ° C, then At temperature The operation was maintained for 30 minutes under a dry condition of -40 ° C as 1 cycle, and this was repeated for 400 cycles of a thermal shock (HS) test.
目視觀察試驗後之各光學積層體,以目視觀察黏著劑層之浮起、剝離、發泡等外觀變化之有無,依據下述之評價基準而評估耐久性。將結果表示於表3中。 The optical laminates after the test were visually observed, and the appearance changes such as floating, peeling, and foaming of the pressure-sensitive adhesive layer were visually observed, and the durability was evaluated in accordance with the following evaluation criteria. The results are shown in Table 3.
4:完全看不出浮起、剝離、發泡等外觀變化、3:幾乎看不出浮起、剝離、發泡等外觀變化、2:浮起、剝離、發泡等外觀變化略醒目、1:明顯看出浮起、剝離、發泡等外觀變化。 4: No change in appearance such as lifting, peeling, foaming, etc., 3: almost no appearance change such as floating, peeling, foaming, etc., 2: appearance change such as floating, peeling, foaming, etc., slightly conspicuous, 1 : Apparent changes in appearance such as lifting, peeling, and foaming are apparent.
(7)附黏著劑層之光學膜之重工性評價 (7) Evaluation of the reworkability of the optical film with the adhesive layer
將上述(3)所製作之附黏著劑層之光學膜(P-1)裁切成25mm×150mm之大小的試驗片。從試驗片剝離分離膜,將其黏著劑面貼於玻璃基板。將所得到之貼附有玻璃基板之試驗片(貼附有玻璃基板之附黏著劑層的光學膜)於高壓釜中以溫度50℃、壓力5kg/cm2(490.3kPa)加壓20分鐘。然後,於50℃之烘箱中保管48小時,更且,在溫度23℃、相對濕度50%之環境中,從試驗片將光學膜與黏著劑層一起以300mm/分之速度朝180°方向剝離。觀察剝離後之玻璃基板表面之狀態,以下列之基準評價。結果表示於表3中。 The optical film (P-1) with the adhesive layer prepared in the above (3) was cut into a test piece having a size of 25 mm × 150 mm. The separation membrane was peeled off from the test piece, and the adhesive surface was attached to the glass substrate. The obtained test piece to which the glass substrate was attached (the optical film with the adhesive layer attached to the glass substrate) 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. Then, it was stored in an oven at 50 ° C for 48 hours, and further, in an environment of a temperature of 23 ° C and a relative humidity of 50%, the optical film and the adhesive layer were peeled off from the test piece at a speed of 300 mm/min toward the 180° direction. . The state of the surface of the glass substrate after peeling was observed, and it evaluated on the following basis. The results are shown in Table 3.
4:於玻璃基板之表面完全看不出霧化等、3:於玻璃基板之表面幾乎看不出霧化等、 2:於玻璃基板之表面可看到霧化等、1:於玻璃基板之表面可看到黏著劑層之殘留。 4: No atomization or the like is observed on the surface of the glass substrate, and 3: no fogging is observed on the surface of the glass substrate. 2: Atomization or the like can be seen on the surface of the glass substrate. 1: The residue of the adhesive layer can be seen on the surface of the glass substrate.
於具備冷卻管、氮氣導入管、溫度計及攪拌機之反應容器中,加入由表4所示之組成(表4之數值為重量份)之單體與乙酸乙酯81.8份混合所得到之溶液。將反應容器內之空氣以氮氣取代後,使內溫為60℃。其後,添加將偶氮雙異丁腈0.12份溶解於乙酸乙酯10份而得之溶液。以相同溫度保持1小時後,將內溫保持於54至56℃,同時並以使添加速度17.3份/Hr將乙酸乙酯以使聚合物之濃度成 為約35%之方式連續加入於反應容器內。從乙酸乙酯之添加開始經過12小時為止將內溫保持於54至56℃之後,加入乙酸乙酯以使聚合物之濃度成為20%之方式進行調整,製得(甲基)丙烯酸系樹脂(A-1)之乙酸乙酯溶液。(甲基)丙烯酸系樹脂(A-1)之重量平均分子量Mw係139萬,重量平均分子量Mw及數量平均分子量Mn之比Mw/Mn為5.32。凝膠滲透色層分析(GPC)之排出曲線中,Mw139萬之成分係顯示單一之波峰,Mw1000至250萬之範圍中看不出其他之波峰。 To a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirrer, a solution obtained by mixing a monomer having a composition shown in Table 4 (amount in Table 4 in parts by weight) and 81.8 parts of ethyl acetate was added. After the air in the reaction vessel was replaced with nitrogen, the internal temperature was made 60 °C. Thereafter, a solution obtained by dissolving 0.12 parts of azobisisobutyronitrile in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, the internal temperature was maintained at 54 to 56 ° C while the ethyl acetate was added to make the concentration of the polymer at an addition rate of 17.3 parts/Hr. It was continuously added to the reaction vessel in a manner of about 35%. The internal temperature was maintained at 54 to 56 ° C after 12 hours from the addition of ethyl acetate, and ethyl acetate was added to adjust the concentration of the polymer to 20% to obtain a (meth)acrylic resin ( A-1) ethyl acetate 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 and the number average molecular weight Mn was 5.32. In the gel permeation chromatography (GPC) discharge curve, the composition of Mw 1.39 million shows a single peak, and no other peaks are seen in the range of Mw 1000 to 2.5 million.
上述之製造例中,重量平均分子量Mw及數量平均分子量Mn係於GPC裝置將東曹(股)製之「TSKgel XL」4根、及昭和電工(股)製之「Shodex GPC KF-802」1根之共計5根串聯連接配置作為管柱,使用四氫呋喃作為溶離液,以試料濃度5mg/mL、試料導入量100μL、溫度40℃、流速1mL/分之條件,藉標準聚苯乙烯換算來測定。製得GPC之排出曲線時之條件亦與此相同。 In the above-mentioned production example, the weight average molecular weight Mw and the number average molecular weight Mn are four "TSKgel XL" manufactured by Tosoh Corporation and "Shodex GPC KF-802" manufactured by Showa Denko Co., Ltd. in the GPC apparatus. A total of five roots were connected in series as a column, and tetrahydrofuran was used as the elution solution, and the sample concentration was 5 mg/mL, the sample introduction amount was 100 μL, the temperature was 40 ° C, and the flow rate was 1 mL/min, and the measurement was carried out by standard polystyrene conversion. The conditions for producing the GPC discharge curve are also the same.
玻璃轉移溫度Tg係使用SII Nanotechnology股式公司製之示差掃描熱量計(DSC)「EXSTAR DSC6000」,在氮氣環境下、以測定溫度範圍-80至50℃、昇溫速度10℃/分之條件測定。 The glass transition temperature Tg was measured using a differential scanning calorimeter (DSC) "EXSTAR DSC6000" manufactured by SII Nanotechnology Co., Ltd. under a nitrogen atmosphere at a measurement temperature range of -80 to 50 ° C and a temperature increase rate of 10 ° C /min.
製造例4中之單體之組成(表4之數值為重量份)、及GPC之排出曲線上之Mw1000至250萬之範圍中之波峰數(表4中表記為「GPC波峰數」)彙整於表4中。 The composition of the monomer in Production Example 4 (the value in Table 4 is part by weight), and the number of peaks in the range of Mw of 1,000 to 2.5 million on the discharge curve of GPC (in Table 4, the number of "GPC peaks" is summarized) In Table 4.
表4之「單體組成」的欄之簡稱係意指如下之單體。 The abbreviation of the column of "monomer composition" in Table 4 means the following monomers.
BA:丙烯酸丁酯(均聚物之玻璃轉移溫度:-54℃)、MA:丙烯酸甲酯(均聚物之玻璃轉移溫度:10℃)、HEA:丙烯酸2-羥乙基酯。 BA: butyl acrylate (glass transition temperature of homopolymer: -54 ° C), MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C), HEA: 2-hydroxyethyl acrylate.
(1)黏著劑組成物之調製 (1) Modulation of adhesive composition
於製造例4所得到之(甲基)丙烯酸系樹脂之乙酸乙酯溶液(樹脂濃度:20%)中,相對於該溶液之固形分100份,將表5所示之異氰酸酯系交聯劑(B)、矽烷化合物(C)、離子性化合物(D)分別以表5所示之量(重量份)混合,更且以使固形分濃度為14%之方式添加乙酸乙酯而製得黏著劑組成物。當所使用之商品含有溶劑等之時,表5所示之各配合成分之配合量係其中所含之有效成分之重量份數。 In the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in Production Example 4, the isocyanate crosslinking agent shown in Table 5 was added to 100 parts of the solid content of the solution ( B), the decane compound (C) and the ionic compound (D) were each mixed in an amount (parts by weight) shown in Table 5, and an ethyl acetate was added so that the solid content concentration was 14% to prepare an adhesive. Composition. When the product to be used contains a solvent or the like, the compounding amount of each component shown in Table 5 is the parts by weight of the active ingredient contained therein.
在表5中以簡稱所示之各調配成分的內容如下。 The contents of the respective compounding ingredients shown by the abbreviation in Table 5 are as follows.
(異氰酸酯系交聯劑) (isocyanate crosslinking agent)
B-1:二甲苯二異氰酸酯之三羥甲基丙烷加成物的乙酸乙酯溶液(固形分濃度75%)、取自三井化學(股)之商品名「Takenate D-110N」。 B-1: an ethyl acetate solution of a trimethylolpropane adduct of xylene diisocyanate (solid content concentration: 75%), and a trade name "Takenate D-110N" from Mitsui Chemicals Co., Ltd.
(矽烷化合物) (decane compound)
C-1:3-環氧丙氧基丙基三甲氧基矽烷、取自信越化學工業(股)之商品名「K BM403」。 C-1: 3-glycidoxypropyltrimethoxydecane, and the trade name "K BM403" of the chemical industry (share).
(離子性化合物) (ionic compound)
D-1:N-丙基吡啶鎓 雙(氟磺醯基)亞胺、D-3:N-癸基吡啶鎓 雙(氟磺醯基)亞胺、D-6:1-乙基-1-甲基吡咯啶鎓 雙(三氟甲烷磺醯基) 亞胺、D-7:N-甲基吡啶鎓 雙(氟磺醯基)亞胺。 D-1: N-propylpyridinium bis(fluorosulfonyl)imide, D-3: N-decylpyridinium bis(fluorosulfonyl)imide, D-6: 1-ethyl-1 -methylpyrrolidinium bis(trifluoromethanesulfonyl) Imine, D-7: N-methylpyridinium bis(fluorosulfonyl)imide.
表5中之「溶解度」係對於60℃之水100g的離子性化合物(D)之溶解度(g)。該溶解度係依據如下之順序求出。首先,混合經精秤之離子性化合物100mg與純水2mL之後,於攪拌下以溫度60℃保管24小時。取得之離子性化合物含有溶劑時,可藉減壓蒸餾除去溶劑而獲得乾固之離子性化合物,再精秤。然後,取樣水層之一部分(精秤量),將此以乙腈適度地稀釋後,將溶解於所得之測定試樣之離子性化合物的重量濃度藉由液體色層質量分析法(LC/MS)之絶對檢量線法來定量。LC/MS之測定條件如下。依據定量結果,求出離子性化合物(D)之溶解度。 The "solubility" in Table 5 is the solubility (g) of the ionic compound (D) of 100 g of water at 60 °C. The solubility was determined in the following order. First, 100 mg of the ionic compound of the fine scale and 2 mL of pure water were mixed, and then stored under stirring at a temperature of 60 ° C for 24 hours. When the obtained ionic compound contains a solvent, the solvent can be distilled off under reduced pressure to obtain a dry solid ionic compound, which is then weighed. Then, a part of the water layer (fine weighing amount) is sampled, and after appropriately diluted with acetonitrile, the weight concentration of the ionic compound dissolved in the obtained measurement sample is determined by liquid chromatography (LC/MS). Absolute calibrated line method to quantify. The measurement conditions of LC/MS are as follows. The solubility of the ionic compound (D) was determined based on the quantitative results.
分析裝置:Agilent Technologies LC/MS裝置1260型/6130型 Analytical device: Agilent Technologies LC/MS device type 1260/6130
分離管柱:Kinetex 2.6u C18 100A(3.0×100mm,2.7μm) Separation column: Kinetex 2.6u C18 100A (3.0×100mm, 2.7μm)
移動相:添加0.05% TFA之水/乙腈之混合溶劑的梯度法 Mobile phase: gradient method of adding 0.05% TFA water/acetonitrile mixed solvent
移動相之流量:0.5mL/min. Mobile phase flow: 0.5mL/min.
試樣注入量:2.5μL Sample injection amount: 2.5 μL
烘箱溫度:40℃ Oven temperature: 40 ° C
UV檢測波長:254nm UV detection wavelength: 254nm
MS檢測條件:電子噴射離子化(ESI)法Positive。 MS detection conditions: Electrospray ionization (ESI) method Positive.
又,對於離子性化合物D-1、D-3及D-7係藉由UV檢測器(波長254nm)、離子性化合物D-6係藉由MS檢測器之選擇離子檢測(SIM)模式而進行定量(偵測質量 m/z=114)。 Further, the ionic compounds D-1, D-3 and D-7 were carried out by a UV detector (wavelength 254 nm) and an ionic compound D-6 by a selective ion detection (SIM) mode of an MS detector. Quantitative m/z = 114).
(2)黏著劑層之製作 (2) Production of adhesive layer
於被施予離型處理之聚對苯二甲酸乙二酯膜所構成之分離膜[取自Lintec(股)之商品名「PLR-382051」]之離型處理面,使用薄塗器以使乾燥後之厚度成為20μm之方式塗布上述(1)所調製之各黏著劑組成物,以100℃乾燥1分鐘而製作黏著劑層(黏著劑片)。 Using a thin coater to form a separation membrane composed of a polyethylene terephthalate film subjected to release treatment [taken from the trade name "PLR-382051" of Lintec Co., Ltd.] The adhesive composition prepared in the above (1) was applied so as to have a thickness of 20 μm after drying, and dried at 100 ° C for 1 minute to prepare an adhesive layer (adhesive sheet).
(3)附黏著劑層之光學膜(P-1)之製作 (3) Production of optical film (P-1) with adhesive layer
將平均聚合度約2400、皂化度99.9莫耳%、厚度60μm之聚乙烯醇膜[(股)Kuraray製之商品名「Kuraray Vinylon VF-PE#6000」]浸漬於37℃之純水後,以30℃浸漬於含有碘及碘化鉀之水溶液(碘/碘化鉀/水(重量比)=0.04/1.5/100)。其後,以56.5℃浸漬於含有碘化鉀及硼酸之水溶液(碘化鉀/硼酸/水(重量比)=12/3.6/100)。將膜以10℃之純水洗浄後,以85℃乾燥,獲得於聚乙烯醇吸附配向有碘之厚度約23μm之偏光片。延伸主要係於碘染色及硼酸處理之步驟進行,整體之延伸倍率為5.3倍。 A polyvinyl alcohol film having an average polymerization degree of about 2400, a degree of saponification of 99.9 mol%, and a thickness of 60 μm, which is a product of Kuraray Vinylon VF-PE #6000, manufactured by Kuraray, was immersed in pure water at 37 ° C, and then Immersed in an aqueous solution containing iodine and potassium iodide at 30 ° C (iodine / potassium iodide / water (weight ratio) = 0.04 / 1.5 / 100). Thereafter, 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 in the form of iodine adsorbed on polyvinyl alcohol. The extension is mainly carried out in the steps of iodine dyeing and boric acid treatment, and the overall stretching ratio is 5.3 times.
於所得到之偏光片之單面透過聚乙烯醇系樹脂之水溶液所構成之接著劑貼合厚度25μm之三乙醯基纖維素膜所構成之透明保護膜[Konica Minolta Opto(股)製之商品名「KC2UA」]。然後,於與上述偏光片中之三乙醯基纖維素膜為相反側之面,透過聚乙烯醇系樹脂之水溶液 所構成之接著劑貼合厚度23μm之環狀聚烯烴系樹脂所構成之零相位差膜[日本Zeon(股)製之商品名「ZEONOR」],製作偏光板。然後,於與零相位差膜中之偏光片接觸之面為相反側之面,施予用以提升密著性之電暈放電處理後,藉由積層機貼合與上述(2)製作之黏著劑層的分離膜為相反側之面(黏著劑層面)後,以溫度23℃、相對濕度65%之條件熟成7日,製得附黏著劑層之光學膜(P-1)。 A transparent protective film made of a triethylenesulfonated cellulose film having a thickness of 25 μm is adhered to an adhesive made of an aqueous solution of a polyvinyl alcohol resin on one side of the obtained polarizer [Konica Minolta Opto Co., Ltd. Name "KC2UA"]. Then, an aqueous solution of a polyvinyl alcohol-based resin is passed through the surface opposite to the triacetyl cellulose film in the polarizer. A polarizing film made of a cyclic polyolefin resin having a thickness of 23 μm (trade name "ZEONOR" manufactured by Zeon Co., Ltd.) was bonded to the adhesive to form a polarizing plate. Then, on the opposite side to the surface in contact with the polarizer in the zero retardation film, after applying a corona discharge treatment for improving adhesion, the adhesive is bonded to the above (2) by a laminator. After the separation film of the agent layer was on the opposite side (adhesive layer), it was aged at a temperature of 23 ° C and a relative humidity of 65% for 7 days to obtain an optical film (P-1) with an adhesive layer.
(4)附黏著劑層之光學膜的耐金屬腐蝕性評價 (4) Evaluation of metal corrosion resistance of optical film with adhesive layer
(4-1)實施例10至11、比較例2之情形 (4-1) Cases of Examples 10 to 11 and Comparative Example 2
將上述(3)所製作之附黏著劑層之光學膜(P-1)裁切成20mm×50mm之試驗片,透過黏著劑層而貼附於附金屬層之玻璃基板的金屬層側。附金屬層之玻璃基板係使用於無鹼玻璃表面藉由濺鍍而積層厚度約500nm之金屬銅層的玻璃基板(Geomatec公司製)。將所得到之光學積層體於溫度60℃、相對濕度90%之烘箱中保管120小時後,將附黏著劑層之光學膜的黏貼部分之金屬層之狀態從玻璃基板之背面照射光線而從偏光板表面經由放大鏡觀察,對於孔蝕(直徑0.1mm以上,可透過光之孔的發生)以如下之基準評價。將結果表示於表6中。 The optical film (P-1) with the adhesive layer prepared in the above (3) was cut into a test piece of 20 mm × 50 mm, and attached to the metal layer side of the glass substrate with the metal layer through the adhesive layer. The glass substrate with a metal layer is a glass substrate (manufactured by Geomatec Co., Ltd.) in which a metal copper layer having a thickness of about 500 nm is deposited by sputtering on the surface of the alkali-free glass. After the obtained optical laminate was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 120 hours, the state of the metal layer of the adhesive portion of the optical film with the adhesive layer was irradiated with light from the back surface of the glass substrate to be polarized. The surface of the plate was observed through a magnifying glass, and pitting corrosion (the occurrence of a hole having a diameter of 0.1 mm or more and permeable to light) was evaluated on the following basis. The results are shown in Table 6.
(4-2)實施例12至14之情形 (4-2) Cases of Embodiments 12 to 14
將上述(3)所製作之附黏著劑層之光學膜(P-1)裁切成20mm×50mm之試驗片,透過黏著劑層而貼附於附金屬層之 玻璃基板的金屬層側。附金屬層之玻璃基板係使用於無鹼玻璃表面藉由濺鍍而積層厚度約500nm之銀合金(以銀為主成分,且含有鈀及銅之合金、APC)層之玻璃基板(Geomatec公司製)。將所得到之光學積層體於溫度60℃、相對濕度90%之烘箱中保管500小時後,將附黏著劑層之光學膜的貼黏部分之金屬層之狀態從玻璃基板之背面照射光線而從偏光板表面經由放大鏡觀察,對於孔蝕(直徑0.1mm以上,可透過光之孔的發生)以如下之基準評價。將結果表示於表6中。 The optical film (P-1) with the adhesive layer prepared in the above (3) was cut into a test piece of 20 mm × 50 mm, and attached to the metal layer through the adhesive layer. The metal layer side of the glass substrate. A glass substrate with a metal layer is a glass substrate (manufactured by Geomatec Co., Ltd.) which is a layer of a silver alloy (a component containing silver and containing an alloy of Palladium and copper, APC) having a thickness of about 500 nm by sputtering on the surface of an alkali-free glass. ). After the obtained optical laminate 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 adhesive portion of the optical film with the adhesive layer was irradiated with light from the back surface of the glass substrate. The surface of the polarizing plate was observed through a magnifying glass, and pitting corrosion (the occurrence of a hole having a diameter of 0.1 mm or more and permeable to light) was evaluated on the following basis. The results are shown in Table 6.
4:產生於金屬層表面之孔蝕之數量為2個以下、3:產生於金屬層表面之孔蝕之數量為3個至5個、2:產生於金屬層表面之孔蝕之數量為6個以上、1:於金屬層表面之全面產生許多數量之孔蝕,且亦產生白濁。 4: the number of pitting corrosion generated on the surface of the metal layer is 2 or less, 3: the number of pitting corrosion generated on the surface of the metal layer is 3 to 5, 2: the number of pitting corrosion generated on the surface of the metal layer is 6 More than one, 1: a large number of pittings are generated on the surface of the metal layer, and white turbidity is also generated.
1‧‧‧附黏著劑層之光學膜 1‧‧‧Optical film with adhesive layer
10‧‧‧光學膜 10‧‧‧Optical film
20‧‧‧黏著劑層 20‧‧‧Adhesive layer
30‧‧‧金屬層 30‧‧‧metal layer
40‧‧‧基板 40‧‧‧Substrate
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