TW201132505A - Optical laminate member and method for making same - Google Patents

Optical laminate member and method for making same Download PDF

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Publication number
TW201132505A
TW201132505A TW100100263A TW100100263A TW201132505A TW 201132505 A TW201132505 A TW 201132505A TW 100100263 A TW100100263 A TW 100100263A TW 100100263 A TW100100263 A TW 100100263A TW 201132505 A TW201132505 A TW 201132505A
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Taiwan
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layer
resin
adhesive
plastic sheet
liquid crystal
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TW100100263A
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Chinese (zh)
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TWI526318B (en
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Ryu Takeko
Masashi Fujinaga
Chie Sakaue
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Sumitomo Chemical Co
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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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09J157/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
    • C09J157/10—Homopolymers or copolymers containing elements other than carbon and hydrogen containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • 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
    • B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
    • B32B2329/04—Polyvinylalcohol
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)

Abstract

An adhesive agent layer 2 is formed with an aqueous adhesive agent containing as a major component a polymer (e.g. a polyacrylic acid) which is a monomer having principally a compound having in the molecule an olefinic double bond and a carboxylic group, a glass plate 1 and a plastic sheet 3 is stuck with the adhesive agent layer 2 placed therebetween, to form an optical laminate member 10. The optical laminate member 10 is prepared through the process comprising: (a) the step of forming an adhesive agent composition layer by providing a layer of an aqueous solution on a sticking surface between the glass plate 1 and the plastic sheet 3 or of the plastic sheet 3, the aqueous solution containing the abovesaid polymer, (b) the step of sticking the glass plate 1 and the plastic sheet 3 with the adhesive agent layer placed therebetween, (c) the step of inspecting the stuck articles and removing defective articles from the production line, and (d) the step of curing the stuck articles free of defects. According to the present invention, an optical laminate member which exhibits excellent thin and light feature and durability is provided, and an advantageous method for making such an optical laminate member is provided.

Description

201132505 六、發明說明： 【發明所屬之技術領域】 ^本發明涉及一種適用於液晶顯示裝置的光學積層體， 更詳^而言，涉及—種在以成為液晶顯示裝置的中心部件 的液晶單it基板為典型例的玻璃板上經由黏接劑層層疊以 偏振板為典型例的_片而成的光學積層體。另外，本發 明還涉及有利地製造該光學積層體的方法。 【先前技術】 偏振板作為構成液晶顯示裝置的光學部件是有用的。 作，偏振板’目錢用在由聚乙烯醇系樹脂構㈣偏振膜 ，單=或兩面經由水系黏接劑等層曼包含透明樹脂膜的保 護層這樣的構成的偏振板。作為這樣的透明樹脂膜 ，從光 子透明ϋ、透濕性優異的方面考慮，大多使用三乙酿基纖 維素膜。即使是Ρ、在偏振㈣單面設置保護層的情況下， 在偏振膜的另—面’也大多經由黏接劑（亦稱接著劑）或黏 合劑（亦稱為黏著劑）來層疊具有相位差功能等光學功能的 樹脂膜來兼任保護偏振膜的功能。對於如此構成的偏振 板，可根據需要隔著其它光學功能層，利用黏合劑（也稱為 壓敏黏接劑）貼合在液晶單S基板上，製成液晶面板而組裝 在液晶顯示裝置中。 對於液晶顯示裝置而言，作為液晶電視、液晶監視器、 個人計算機等薄型的顯示晝面，其用途迅速擴大。在這樣 的用途擴大中，要求構成其的部件也更加薄型化。如上所 述，偏振板通常用黏合劑貼合在液晶單元上，這是因為在 4 322672 201132505 貼合後有某些不合適的情況下，可容易地從液晶單元上剝 下並貼q其它的偏振板比較方便。然而，對於黏合劑而 °通吊為了保持適度的黏合力而需要至少20/zm左右的 厚度’在謀求液晶面板或液晶顯示裝置的薄型化方面成為 一個瓶頸。 還有嘗試通過省略偏振膜的液晶單元側保護層、在其 上直接形成黏合劑層、將該黏合劑層貼合在液晶單元上來 謀求薄型化。但是，對於這樣直接用黏合劑層貼合偏振膜 和液晶單疋的狀態，在進行暴露於高溫的耐熱試驗的情況 下’有時僅通過黏合劑層不能充分吸收偏振膜的收縮，會 在偏振膜和黏合劑層之間產生鼓起、剝離、起泡等不良現 象。另外，在進行反復高溫狀態和低溫狀態的熱衝擊試驗 (heat shock試驗）的情況下，仍然存在僅通過黏合劑層而 不能充分吸收偏振膜的伸縮，從而導致偏振膜破裂的情況。 作為謀求偏振板的薄型化的其它的嘗試，例如，日本 JP2004-245924-A中公開了以下技術：在聚乙烯醇系樹脂 上吸附有二色性色棄並使其取向而成的偏振膜的至少一面 上，塗布未硬化的環氧樹脂組成物，然後使該組成物硬化， 由此形成保護膜。然而，在經由黏合劑層將以環氧樹脂組成 物的硬化物作為保護膜的偏振板貼合在液晶單元上的狀態 下，耐久性不充分，例如在進行熱衝擊試驗的情況下，有 時仍然會導致偏振膜破裂。另外，在日本jP2〇〇4_245925—a 公開了以下技術：在聚乙烯醇系樹脂上定向吸附二色性色 素的偏振膜上，經由由以不含芳香環的環氧樹脂為主成分 322672 5 201132505 的組成物構成的黏接劑貼合保護膜，製成偏振板。 另一方面，日本JPH09-159828-A公開了以下技術： 在偏振膜的一面上，形成由光硬化性黏接劑構成黏接層作 成帶黏接層的偏振板，並經由該黏接層將偏振板黏接在液 晶單兀基板上，其中，所述光硬化性黏接劑是相對於乙烯、 丙烯酸酯系或曱基丙烯酸酯系單體、和馬來酸或馬來酸酐 形成的三元共聚物，分別配合規定量的光敏劑和具有丙烯 醯氧基的化合物等不飽和化合物而成的，該文獻還記載有 在偏振膜㈣—面上設置由収光硬化性雜雜成的保 護層的技術。 曰2疋，在該文獻所公開的經由黏接劑將偏振板黏接在 液晶單元基板上的情況下，㈣減驗或熱衝擊試驗中， 雖二在]f尺寸的液晶單元中沒有發現大的問題，但當作 成中里至大型尺寸的液晶單元時，會存在偏振板從液晶單 兀基板表面剝離或偏振膜破裂這樣的問題。另外，對用該 黏，劑將偏振板貼合舰晶單元基板上Μ的光學積層體 一。雖然可以實現薄壁化，但是對於暫時貼合到液晶單 兀上的偏振板而言，無法容易地將錢離。為此，在貼合 的古中&amp;現某些不適合的情況下，如果不經過用特殊 容劑進行處理等步驟，就不能再利用該液晶單元， 故缺乏經濟性。 说娘f日本卿G4-4636~A中公開了經由黏合劑由輥供給 偏振板、直接貼合在液晶單元基板上的技術。 【發明内容】 322672 6 201132505 本發明的目的在於’通過經由特定的黏接劑將以偏振 板為代表例的塑料片和以液晶單元基板為代表例 的玻璃板 貼合，提供一種薄型輕質性且耐久性能優異的光學積層體。 本發明的另一個目的在於，提供可有利地製造這槔的光# 積層體的方法。 本發明包含以下内容。 ^ [1] 一種光學積層體，其是將玻璃板和塑科片，·為分孑 接劑層貼合而成的，所述黏接劑層是由將主要#艨的聚 内具有至少一個烯烴性雙鍵和至少一個羧基的彳b舍物 合物作為主成分的水系黏接劑組成物形成的》 黏换劍 [2] 如[1]所述的光學積層體，其中，所述水系， 組成物還含有矽烷偶合劑。 ^系 [3] 如[1]或[2]所述的光學積層體，其中，户斤述 其中 黏接劑組成物還含有交聯劑。 [4] 如[1]至[3]中任一項所述的光學積層雜， 其中 所述黏接劑層具有5em以下的厚度。 [5] 如[1]至[4]中任一項所述的光學積層錤’ 其中 所述玻璃板為液晶單元基板。 [6] 如[1]至[5]中任一項所述的光學積層#， ^ 所述塑料片是具有在聚乙烯醇系樹脂上吸附有&gt;色f 並使其取向而成的偏振膜的偏振板。 板具横 偏振板具 [7] 如[6]所述的光學積層體，其中，所述偏捩 所述偏振膜和在其至少一個面上形成的透明俤護簷 [8] 如[7]所述的光學積層體，其中，所述 201132505 所述偏振膜和在其至少一個面上所形成的透明保護層，與 所述透明保護層處於相反侧的偏振膜面經由所述點接劑層 直接貼合在所述液晶單元基板上。 [9] 如[7]所述的光學積層體，其中，所述偏振板具備 所述偏振膜、在其一個面上形成的透明保護層、層疊在所 述偏振膜的另一個面上的相位差板，該相位差板侧經由所 述黏接劑層貼合在所述液晶單元基板上。 [10] —種在玻璃板上貼合有塑料片的光學積層體的 製造方法，該方法具備如下步驟： 黏接劑組成物層形成步驟，係在玻璃板和塑料片的各 個貼合面中的至少一個面上設置黏接劑組成物的層，所述 黏接劑組成物的層由包含主要單體為分子内具有至少一個 烯烴性雙鍵和至少一個羧基的聚合物的水溶液所構成. 貼合步驟’係經由該黏接劑組成物層貼合所述坡璃板 和所述塑料片； 檢查步驟，係檢查在所述貼合步驟中得到的貼人口， 將查出有缺陷的貼合品取出至生產線外；以及 硬化步驟，使存在於未經所述檢查步驟查出缺陷的貼 合品中的黏接劑組成物的層硬化。 [11] 如[10]所述的方法，其中，所述玻螭板為液曰單 元基板，所述塑料片是具有在聚乙烯醇系樹脂上吸附=一 色性色素並使其取向而成的偏振膜的偏振板》 一 [12] 如[10]或[11]所述的方法，其具有如下構成，艮 對於在所述檢查步驟查出缺陷的貼合品，將塑料片韌下t 322672 8 201132505 將玻璃板返回到所述黏接劑組成物層形成步驟中。 本發明的光學積層體由於可以經由黏接劑層直接將 塑料片貼合到玻璃板上，因此可以實現薄壁化，而且玻璃 板和塑料片的密合性也良好1別是以液晶單元基板為玻 璃板、、以偏振板為塑料片時，與經由黏合劑層將偏振板貼 合到液晶單元基板上的以往的光學積層體相比，可以降低 厚度，因此可以謀求光學積層體乃至液晶面板的薄型輕質 化，且偏振板和液晶單元基板的密合性也良好。進而，通 過在液晶單元基板和偏振板的接合中使用黏接劑而不是黏 合劑，可以提供還能夠充分耐受裝置組裝時的加熱處理或 震置使用時的環境條件的光學積層體。 另外，根據本發明的方法，可以有利地製造上述光學 積層體。特別是通過在貼合步驟後、硬化步驟前設置檢查 步驟，在查出表面損傷、存在雜質、捲入氣泡、或軸錯位 等缺陷的情況下，由於將查出上述缺陷的貼合品取出到生 產線外’因此可以成品率良好地製造光學積層體。而且， 在貼合以液晶基板為代表例的玻璃板和以偏振板為代表例 的塑料片時’使用了由水溶液組成的黏接劑組成物，只要 是在硬化步驟前就可以容易地將該塑料片從玻璃板上剝 下。因此’對於在上述檢查步驟中查出缺陷而被取到生產 線外的貼合品’將塑料片從其上面剝下後，經過利用水洗 來沖洗黏接劑組成物等簡單步驟，可以返回到所述黏接劑 組成物層形成步驟中，因此可以進一步提高光學積層體的 生產率。 9 322672 201132505 【實施方式】 声二:二’广第1圖的剖面示意圖所示，經由黏接劑 層2將作為典型的液晶單元基板的玻璃板1和作為典型的 偏振板的塑料片3貼合，製成光學積層體1G。黏接劑声2 由以主要單體為分子内具有至少—個烯烴性雙鍵和至^一 =基物的聚合物作為主成分的水系勒接劑組成物 ^成。在本說明書巾，以下，有時將分子h有至少一個 卜和右至少一個縣的化合物稱為、飽和誠化 。物另外，有時將以該不飽和㈣化合物 &quot;含叛基樹脂'首先，對黏接劑組成物及由 料==:行說明’然後’按照一塑 [黏接劑組成物] 〈含羧基樹脂〉 在本發明中，為了黏接玻璃板1和塑料片3，使用以 2基樹脂作為主成分的水系黏接劑組成物。該含叛基樹 γ上所述’為以在分子内具有至少一個稀煙性雙鍵和至 夕個竣基的化合物（即不飽和缓酸化合物）為主要單體， 由其得到的聚合物。用於得到含麟樹脂的聚合可以通過 自由基聚合進行。在讀㈣酸化合物巾所含㈣基可以 形成以鐘鹽、Μ絲料代表躲金屬鹽或銨鹽之類的 鹽的形式’如為分子内具有多倾基的化合物時，也可成 為酸酐的形式L在成為_鹽的形式時，可為和游 離叛基並存的狀態。 322672 10 201132505 作為不飽和羧酸化合物的具體例，除了（曱基）丙烯酸 及其鹽以外’可以舉出：2-(曱基）丙烯醯氧乙基琥珀酸酯、 2-（曱基）丙烯醯氧乙基鄰苯二甲酸酯、2-(甲基）丙烯醯氧 乙基六氫鄰苯二曱酸酯、冷-羧乙基（曱基）丙烯酸酯及ω-敌基-聚己内酯改性（甲基）丙烯酸酯之類的含羧基之（曱基） 丙烯酸系化合物以及其鹽、或富馬酸、馬來酸、衣康酸、 馬來酸酐、鄰苯二甲酸酐、偏苯三酸酐及衣康酸酐之類的 不飽和多元羧酸及其酸酐等。需要說明的是，在本說明書 中，π(曱基）丙烯酸”是指丙烯酸及曱基丙烯酸兩者，另外， 稱為&quot;（曱基）丙烯醯氧基&quot;、&quot;（甲基）丙烯酸酯”等時的&quot;（曱 基）&quot;也是相同的意思。 這些不飽和羧酸化合物可以以各自的均聚合物的形 式作為構成黏接劑組成物的含羧基樹脂來使用，此外，也 可以以使不同的多個化合物共聚的形式作為構成黏接劑組 成物的含羧基樹脂來使用。 在本發明中，根據情況，也可以相對於不飽和羧酸化 合物，使能與其共聚的其它單體適當共聚，製成構成黏接 劑的含羧基樹脂。作為這樣的其它單體，例如可以舉出： 不具有官能基的（甲基）丙烯酸系單體、具有羧基以外的極 性官能基的（甲基）丙稀酸系單體、（甲基）丙烯酸系以外的 具有％酸基的單體、（甲基）丙烯酸系以外的乙烯基系單體、 在分子内具有多個（曱基）丙烯醯基的單體等。 若舉出不具有官能基的（甲基）丙烯酸系單體的例子， 有：（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（曱基）丙烯 322672 11 201132505 酸丙醋、（甲基)丙烯酸正丁醋、（甲基)丙烯酸&quot;氧基乙 酯、曱氧基聚乙二醇（曱基）丙烯酸酯等。 作為具有羧基以外的極性官能基的（甲基）丙烯酸系 單體中的敌基以外的極性官能基’可以舉出：經基、雜環 基、和雜環不同的胺基、磺酸基、氰基、醯胺基等。若舉 出具有羥基的（曱基）丙烯酸系單體的例子，有：（曱基）丙 烯酸2一羥乙酯、（曱基）丙烯酸2-羥丙酯、（曱基）丙烯酸 4羥丁酯、（曱基）丙烯酸2-或3-氣-2-羥丙酯、乙二醇單 (甲基）丙烯酸酯、二乙二醇單（甲基）丙烯酸酯、聚乙二醇 單（曱基）丙烯酸酯等。若舉出具有雜環基的（甲基）丙烯酸 系單體的例子，有：丙烯醯嗎啉、（曱基）丙烯酸四氫糠基 酯、己内酯改性（甲基）丙烯酸四氫糠基酯、3, 4_環氧基環 己基甲基（甲基）丙烯酸酯、（甲基）丙烯酸縮水甘油酯等。 如舉出具有和雜環不同的胺基的（曱基）丙烯酸系單體的例 子有.N，N-一甲基胺基乙基（甲基）丙稀酸酯、N，N-二甲 基胺基丙基（曱基）丙婦酸酯、N，N-二甲基胺基丙基（甲基） 丙烯醯胺等。若舉出具有磺酸基的（甲基）丙烯酸單體的例 子’有：2-(甲基）丙烯醯基乙烷磺酸、2-(甲基）丙烯醢基 丙院續酸、2-(甲基）丙稀醯胺-2-甲基丙烧礦酸等。若舉出 具有氰基的（甲基）丙烯酸系單體的例子，有··（甲基）丙烯 腈等。另外，若舉出具有醯胺基的（甲基）丙烯酸系單體的 例子’有.（甲基）丙稀醢胺、N-取代（甲基）丙烤醯胺等。 如舉出（甲基）丙烯酸系以外的具有磺酸基的單體的例 子，有：乙烯基磺酸、苯乙烯磺酸等。需要說明的是，包 12 322672 201132505 含上述具有磺酸基的（甲基）丙烯酸系單體，單體中的磺酸 基可以為以鋰鹽、鈉鹽及鉀鹽為代表的鹼金屬鹽或銨鹽之 類的鹽的形式。 如舉出（甲基）丙烯酸系以外的乙烯基類單體的例子， 有：如醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己 酸乙烯酯及月桂酸乙烯酯之類的脂肪酸乙烯酯；氯化乙烯 及溴化乙烯之類的齒化乙烯；偏氯乙烯之類的偏函化乙烯； 2-、3-或4-乙烯基吡啶、及N-乙烯基咔唑之類的含氮芳香 族乙烯；丁二烯、異戊二烯、及氣丁二烯之類的共軛二烯 單體；N-乙烯基-2-吡咯烷酮、及N-乙烯基己内醯胺之類 的具有乙烯鍵的環狀醯胺或醚等。 若舉出在分子内具有多個（曱基）丙烯醯基的單體的 例子，有：1，4-丁二醇二（曱基）丙烯酸酯、;[，6_己二醇二（甲 基）丙烯酸酯、1，9-壬二醇二（曱基）丙稀酸酯、乙二醇二（曱 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、聚乙二醇二（曱基）丙烯酸酯、及三丙二醇二 (曱基）丙烯酸酯之類的在分子内具有2個（曱基）丙烯醯基 的單體；三羥甲基丙烷三（曱基）丙烯酸酯之類的在分子内 具有三個（曱基）丙烯醯基的單體等。 在黏接劑組成物中所含的含羧基樹脂宜具有適合的 聚合度，例如，形成5重量％濃度的水溶液時，黏度宜在3 至300raPa.Sec的範圍内，進一步宜在5至1〇〇mPa.sec的 範圍内。 可用於本發明的黏接劑組成物當然可以為包含兩種 322672 13 201132505 以上上述含缓基樹脂的黏接劑組成物。 構成黏接劑層2的含叛基樹脂例如可以利用溶液聚合 法、乳液聚合法、塊狀聚合法、懸浮聚合法等公知的各種 方法進行製造。在該含羧基樹脂的製造中，通常使用聚合 引發劑。聚合引發劑相對於可用於含羧基樹脂的製造中的 全部單體的合計1〇〇重量份，使用0.001至5重量份左右。 作為聚合引發劑’根據賦予聚合時的能量的方法，可 以使用熱聚合引發劑或光聚合引發劑。若舉出光聚合引發 劑的例子，有4-(2-羥基乙氧基）苯基（2_羥基_2_丙基）酮 等。另外，若舉出熱聚合引發劑的例子，有：2, 2，_偶氮雙 異丁腈、2,2，-偶氮雙（2-曱基丁腈）、；[，！，-偶氮雙（環己 烷-卜腈）、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）、二曱基_2, 2，_偶氮雙（2_ 甲基丙酸酯）、2,2，-偶氮雙（2-羥甲基丙腈）、2,2，_偶氮 雙（2-甲基丙脒）鹽酸鹽、及2,2，，氮雙（卜亞胺基如比 嘻咬基1甲基丙幻㈣鹽之_偶氮類化合物；過氧化 ㈣醯、三級丁基過氧化氫、三級丁基過氧化苯甲醯、過 ^化^甲酸三級丁醋、氫過氧化異丙苯、過氧化二碳酸二 過丙S日、過魏二碳酸二丙基自旨、過氧化新癸酸三級丁醋、 過乳化新錢錢了g旨、及（3,5,5_ 物之類的有機過氧化物;過硫酸 基己醯基)過氧化 之類的無機過氧化物等1外，併用=二氧化氣 氧化還原㈣㈣也可作為聚合引發^ 4原劑的 法中 的 在含缓基樹脂的製造中，宜使用以上所示的方 201132505 浴液“法。若舉出合宜的溶液聚合法的具體例 目標早體及水、根據情況進—步混合醇溶劑，〜將 下添加熱聚合引發劑，在40至1〇(rc左右 氛：級境 。〇左右搜拌3至10小時左右的方法 至90 :可:在聚合中連續或間歇地添加翠體及 脂宜在1㈣重量份的範圍内，复中 讀基樹 圍内’進-步宜在心重量“範二 A㈣量份的範圍内。相對於水_重量份，含羧 有黏接性容易降低的傾向， /、濃度過大’有得到的伞與 向。用於該黏接劑組成:的:可== 均二=:發但 鄉财溶液中。 =树μ綠形成轉劑層2_㈣組成物， 合^純接劑層2和麵板1的密合性，宜含有石夕烧偶 =偶合劑可以為在㈣子上鍵合了院氧基之 解性基團的同時還鍵合了具有乙縣、胺基、環氧基、 322672 201132505 鹵烷基、（甲基）丙烯醯基、或巯基之類的反應性官能基的 有機基團的化合物。作為具有乙烯基的矽烷偶合劑的具體 例，包含：乙烯基三曱氧基矽烷、乙烯基三乙氧基矽烷、 乙烯基三（2-甲氧基乙氧基）矽烷等。作為具有胺基的矽烷 偶合劑的具體例’包含：N-(2-胺乙基）-3-胺丙基曱基二曱 氧基矽烷、N-(2-胺乙基）-3__胺丙基三曱氧基矽烷、3_胺丙 基二曱氧基矽烷、3-胺丙基三乙氧基矽烷等。作為具有環 氧基的矽烷偶合劑的具體例，包含：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碎院、3_環氧丙氧基丙基二曱氧基 甲基矽烷、3-環氧丙氧基丙基乙氧基二甲基矽烷、2_(3, 4一 壤氧環己基）乙基三甲氧基㈣等。作為具有㈣基的石夕烧 偶合劑的具體例，包含：3_氣丙基曱基二曱氧基魏、3_ 氣丙基三曱氧基矽烷等。作為具有（曱基）丙烯醯基的矽烷 偶合劑的具體例’包含3_(甲基）丙烯醯氧基丙基三甲氧基 石夕院等。另外，作為具有毓基的矽烷偶合劑的具體例，包 含3-疏基丙基三甲氧基石夕烧等。可以將兩種以上的石夕烧偶 合劑組合使用。其中，如果考慮對水的溶解性或作為黏接 劑的可使用時間（有效時間）’則宜為具有環氧基的矽烷偶 合劑，例如，3-環氧丙氧基丙基三曱氧基石夕院為合宜的石夕 貌偶合劑之一。 矽烷偶合劑可以為有機矽酮低聚物型。當有機矽酮低 聚物以（單體）-(單體）共聚物的形式表示時，例如可以舉出 如下的物質。 16 322672 201132505 3-酼丙基三甲氧基矽烷-四曱氧基矽烷共聚物、3-酼 丙基三曱氧基梦烧-四乙氧基碎烧共聚物、3 -疏丙基三乙氧 基矽烷-四曱氧基矽烷共聚物及3-鲅丙基三乙氧基矽烷-四乙氧基矽烷共聚物之類的含有巯丙基的共聚物； 巯曱基三曱氧基矽烷-四曱氧基矽烷共聚物、巯甲基 三甲氧基矽烷-四乙氧基矽烷共聚物、酼曱基三乙氧基矽烷 -四曱氧基矽烷共聚物及巯甲基三乙氧基矽烷-四乙氧基矽 烷共聚物之類的含酼曱基的共聚物； 3-甲基丙烯醯氧基丙基三曱氧基矽烷-四曱氧基矽烷 共聚物、3-曱基丙烯醯氧基丙基三甲氧基矽烷-四乙氧基矽 烷共聚物、3-甲基丙烯醯氧基丙基三乙氧基矽烷-四曱氧基 矽烷共聚物、3-曱基丙烯醯氧基丙基三乙氧基矽烷-四乙氧 基矽烷共聚物、3-甲基丙烯醯氧基丙基曱基二甲氧基矽烷-四曱氧基矽烷共聚物、3-曱基丙烯醯氧基丙基曱基二甲氧 基矽烷-四乙氧基矽烷共聚物、3-曱基丙烯醯氧基丙基曱基 二乙氧基矽烷-四曱氧基矽烷共聚物及3-曱基丙烯醯氧基 丙基曱基二乙氧基矽烷-四乙氧基矽烷共聚物之類的含曱 基丙烯酿氧基丙基的共聚物； 3 -丙稀酿氧基丙基三甲氧基石夕烧-四甲氧基石夕烧共聚 物、3-丙烯醯氧丙基三曱氧基石夕烧-四乙氧基石夕烧共聚物、 3_丙稀醯氧丙基三乙氧基石夕烧-四曱氧基石夕烧共聚物、3-丙烯醯氧丙基三乙氧基矽烷-四乙氧基矽烷共聚物、3-丙烯 醯氧丙基曱基二甲氧基矽烷-四曱氧基矽烷共聚物、3-丙烯 酿氧丙基曱基二甲氧基破烧-四乙氧基碎烧共聚物、3 -丙稀 17 322672 201132505 醯氧丙基曱基二乙氧基矽烷-四曱氧基矽烷共聚物及3-丙 烯醯氧丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物之類 的含丙烯醯氧丙基的共聚物； 乙烯基三甲氧基矽烷-四曱氧基矽烷共聚物、乙烯基三 甲氧基矽烷-四乙氧基矽烷共聚物、乙烯基三乙氧基矽烷_ 四甲氧基矽烷共聚物、乙烯基三乙氧基矽烷-四乙氧基矽烷 共聚物、乙烯基甲基二曱氧基矽烷-四曱氧基矽烷共聚物、 乙烯基曱基二曱氧基矽烷-四乙氧基矽烷共聚物、乙烯基甲 基二乙氧基矽烷-四曱氧基矽烷共聚物及乙烯基甲基二乙氧 基矽烷-四乙氧基矽烷共聚物之類的含乙烯基的共聚物； 3-胺基丙基三曱氧基矽烷-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-四曱氧基矽烷共聚物、3-胺基丙基三乙氧基 矽烷-四乙氧基矽烷共聚物、3-胺基丙基曱基二曱氧基矽烷 -四曱氧基碎烧共聚物、3 -胺基丙基曱基二曱氧基石夕烧_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 基矽烷共聚物及3-胺基丙基甲基二乙氧基矽烷_四乙氧基 矽烷共聚物之類的含胺基的共聚物等。 由於這些矽烷偶合劑大多情況下為液態，因此可以直 接混合在包含含絲樹脂的切液中^對於黏接劑組成物 中的石夕烧偶合劑的配合4，相對於含緩基樹月旨1〇〇重量 份，通常為0.01至200重量份左右。相對於含叛基樹脂 100重量份的石夕烧偶合劑的配合量，宜$ 15〇重量份以下， 進一步宜為100重量份以下’特別宜為50重量份以下，另 322672 18 201132505 外’宜為0. 03重量份以上。通過相對於含羧基樹脂loo 重量份配合石夕烧偶合劑0. 01重量份以上、特別是〇. 〇3重 量份以上，可以體現黏接劑層2和玻璃板1的密合性提高 的效果。雖然根據含羧基樹脂、矽烷偶合劑的種類等的不 同而不同，但是對於例如即使進行熱衝擊試驗也維持内密 合性的效果而言，通過相對於含羧基樹脂100重量份將石夕 炫偶合劑配合量設為30重量份左右或50重量份左右的$ 法就可以進一步的提高該效果。但是，若矽烷偶合劑的配 合量過多，則矽烷偶合劑有可能會從黏結劑層2中渗出， 宜設為不滲出程度的配合量。 在本發明中用於形成黏接劑層2的黏接劑組成物中 可另含有交聯劑。交聯劑可以配合在不含矽烷偶合劑的人 羧基樹脂的水溶液中，也可以與矽烷偶合劑一起配合在八 叛基樹脂的水溶液中。一般而言，除了石夕烧偶合劑以外 宜含有交聯劑。 交聯劑可以為在分子内至少具有兩個對含羧基樹脂 具有反應性的官能基的化合物。構成交聯劑的官能基包人 異氰酸基（-NCO);環氧基（交聯的;羥基（_〇H)、 基（-CONHNH2)、噁唑啉基（環狀的-CsHAO)等。另外，鎂、 鈣、鐵、鎳、鋅、鋁、鈦、锆之類的二價、三價或四價金 屬的鹽也可為交聯劑。 作為具有異氰酸基的交聯劑（異氰酸酯化合物）的耳 體例，有：曱笨二異氰酸酯、氫化甲苯二異氰酸醋、一〜 甲基丙烧和甲笨二異氰酸酯的加合物、二苯曱烧二異氛妒 322672 19 201132505 酉曰-笨甲烷三異氰酸酯、異佛爾 合物的酮物_嵌段物等。作二些化 劑（環氧化合物）的具體例，有：乙=具=魏基的交聯 二丙=二縮水甘_或丙三醇三縮 水甘㈣、二縮水甘油基苯胺、二縮水; 伸烧基多胺和二_的反應物的聚醯胺多胺與表氯醇^ = = :=::作為具有__ 組成和含縣樹脂一同溶解于水中，形成黏接劑 ，如以下所述，由財溶液巾奸聯劑含量 很夕「可，因此，例如，如果對水具有至少〇 1 的溶;度，則可㈣交侧㈣。當然，騎稱為水；：= 的m對水具有溶解度的化合物更宜料本發明中使用 對於交聯綱配合量，可根據含縣樹脂的種類等適 當，計，相對於含羧基樹脂ΐθθ重量份通常為〇 .丨至6〇 重$份左右，宜為1至5G重量份。通過以該範圍配合交聯 劑，可得到良好的黏接性。交聯劑的配合量過多時，交聯 劑的反應在短時間内進行，黏接劑組成物有在早期凝膠化 的趨勢，其縣，作為黏接劑的可使用時間（有效時間邊 得非常短，不適合用於工業生產。 在黏接劑組成物中，在不妨礙本發明效果的範圍内， 可以配合例如增塑劑、抗靜電劑、微粒等目前公知的適當 322672 20 201132505 的添加劑。 [黏接劑層] 在本發明中’在玻璃板1和塑料片3的貼合面中的至 ’個面上’設置由以上說明的黏接劑組成物、宜配合有 以上的各成分的水溶液構成的黏接劑組成物的層，經由該 點接劑組成物的廣貼合玻璃板1和塑料片3,使該黏接劑= ，物的層硬化，製成黏接劑層2。黏接劑層2的厚度可以嘹 定為5#m以下，通常為0.001至5&quot;111左右宜為〇 二二ΐ ΐ: 〇·05至2&quot;m或0. °5至1&quot;m的範圍。黏接 [坡續_時，可能會導致塑料片3的外觀不良。 使用接劑層2貼合塑料片3的玻璃板卜可以 續板璃的各種玻璃。如上所述，本發明在玻 在液曰I -成液θ曰顯不裝置的液晶單元基板時特別有用。 元，：二基板f另一片基板之間失持液晶構成液晶單 可以由納SI:晶顯示裝置的核心部件。玻續板1 通常所知的各驗财酸錢、無㈣财酸破璃等 [塑料片] 板，液晶單元特別宜使用無驗破璃。 利用St劑層2貼合在玻璃板1上的塑料片3只要是 坡續板it Γ水溶液表現㈣接能力_脂成為貼向 利用含緩基樹就可以沒有限制地使用， 出：包含，讀表現出雜能力賴脂，可以舉 -成纖維素或二醋酸纖維素、乙酸丙酸 322672 21 201132505 乙酸丁酸纖維素等的醋酸纖維素系樹脂；以聚乙稀醇系樹 脂、環烯烴系樹脂、聚丙烯系樹脂為代表的鏈狀稀煙系樹 脂；聚對苯二甲酸伸乙酯系樹脂；丙烯酸系樹脂等。 其中’醋酸纖維素系樹脂或聚乙烯醇系樹脂成為貼向 玻璃板1的貼合面的塑料片經由由含有含羧基樹脂的水溶 液構成的黏接劑，對玻璃板1顯示出高的黏接力。根據需 要，也可以對塑料片3的欲貼合在玻璃板1上的面實施以 皂化處理或電暈放電處理為代表例的易黏接處理後，用於 黏接劑層的形成以及對玻璃板1的貼合。例如，在醋酸、纖 維素系樹脂成為貼向玻璃板1的貼合面時，通過對該面實 施皂化處理，可以進一步提高含羧基樹脂的水溶液的黏接 力。另外’即使在環婦經系樹脂或以聚丙稀系樹脂為代表 的鏈狀烯烴系樹脂成為貼向玻璃板1的貼合面的情況下， 通過對其面實施電暈放電處理之類的易黏接處理，也可表 現出含羧基樹脂的水溶液的高黏接力。 對於塑料片3的厚度’只要是能貼合到玻璃板i上 的狀態’就沒有特別限制，宜在捲成親狀的狀態下用於 對玻璃板1的貼合，因此’還考慮可撓性等時，通常宜 為500/zm以下，進一步宜為300 // m以下、特別宜為 200 am以下。 〈偏振板〉 如上所述，本發明的光學積層體當第1圖中的玻璃板 1為液晶单元基板、塑料片3是具有在聚乙稀醇系樹脂上 吸附有二色性色素並使其取向而成的偏振膜的偏振板時特 322672 22 201132505 別有用。也可以將如上所述的偏振膜本身單獨製成塑料片 3 ’但由於偏振膜単獨使用時易碎，因此，宜使用至少在盆 一面、特別是與貼合在液晶單元基板1上的面相反側的面 上設有透明保護層的偏振板。 第2圖是表示本發明的光學積層體的層構成的一個形 態的剖面示意圖。在該形態中，在偏振膜6的一面設置透 明保護層7作成偏振板5，與設置有透明保護層7的面處 於相反侧的偏振膜6的面經由黏接劑層2直接貼合在液晶 單元基板1上，構成光學積層體11。即，在第2圖的光學 積層體11中，相對於玻璃板1，與黏接劑層2接觸而層疊 偏振膜6，在偏振膜6中的與黏接劑層2處於相反側的面 上層疊透明保護層7。 第3圖是表示本發明的光學積層體的其它的層構成的 剖面示意圖。在該形態中，在偏振膜6的一面設置透明保 護層7 ’在偏振膜6的另一個面設置適當的樹脂層8作成 偏振板5 ’該樹脂層8側經由黏接劑層2貼合在液晶單元 基板1上，構成光學積層體.12。 這樣，偏振板5只要包含偏振膜6,就可以進一步具 有任何的層，但是從在保護偏振膜6的同時薄化光學積層 體乃至液晶面板的觀點考慮，偏振膜6以外的層宜為2層 以下、特別宜為1層或2層。從這樣的觀點考慮，如第2 圖所示的在偏振膜6的一面具有透明保護層7、以與該透 明保護層7處於相反侧的聚乙烯醇系樹脂膜面（偏振膜表 面）經由黏接劑層2直接貼合在液晶單元基板1上的形態為 23 322672 201132505 合宜者之一。在採用如第2圖所示的形態時，也取決於透 明保護層7的種類，但可以將偏振板5的厚度設定在例如 100 /z m 以下。 〈偏振膜〉 構成偏振板5的偏振膜6是在聚乙烯醇系樹脂上吸附 有二色性色素並使其取向而成的。更具體而言，宜使用在 單軸拉伸的聚乙烯醇系樹脂膜上吸附有二色性色素並使其 取向而成的膜。 構成偏振膜的聚乙烯醇系樹脂可以通過將聚乙酸乙 烯酯系樹脂皂化而得到。作為聚乙酸乙烯酯系樹脂，除了 作為乙酸乙烯酯的均聚合物的聚乙酸乙烯酯以外，可以例 示乙酸乙烯酯和能與其共聚的其它單體所形成的共聚物 等。作為可與乙酸乙烯酯共聚的其它單體，例如可以舉出： 不飽和羧酸類、不飽和磺酸類、烯烴類、乙烯基醚類等。 聚乙烯醇系樹脂的皂化度通常為85至100莫耳％左右、宜 為98至100莫耳％。構成偏振膜的聚乙烯醇系樹脂也可以 進一步進行改性，例如，用醛類改性的聚乙烯醇縮曱醛或 聚乙烯醇縮乙醛等也可以作為聚乙烯醇系樹脂使用。構成 偏振膜的聚乙烯醇系樹脂的聚合度通常為1000至10000 左右、宜為1500至10000左右。 這樣的聚乙烯醇系樹脂製成的膜可以用作偏振膜的未 加工膜。將聚乙烯醇系樹脂製成膜的方法沒有特別限定， 可以用公知的方法進行製膜。聚乙烯醇系未加工膜的膜厚 沒有特別限定，例如為10 # m至150 // m左右。 24 322672 201132505 偏振膜通常是經過如下步驟製造而成的：將如 的由聚乙烯醇系樹脂構成的未加工膜進行單軸拉伸的步 驟、將聚乙烯醇系樹脂膜用二色性色素染色並使其吸附該 :色性色素的步驟、將吸附了二色性色素的聚乙烯醇 月曰膜用賴水顧處理的步驟、及在利㈣酸水 後進行水洗的步驟。 — 單軸拉伸可以在利用二色性色素進行染色之前進行， 二色Z染色同時進行’還可以在染色之後進行。在利用 拉伸可以色之^進行單轴拉伸的情況下，該單軸 另外&gt; S&quot;&quot;處理之前崎’也可以在猶處理中進行。 行單在階段進行單軸拉伸。在進 以用熱的親間沿單轴拉伸，也可 乾式拉伸L 伸。另外’可以是在大氣中進行拉仲等 的Mm W是在麟劑使其膨潤的狀態下進行拉伸 愚式拉伸。拉伸倍數通常為3至8倍左右。 mΓ用—色性色素對聚乙烯醇系樹脂膜的染色例如可 〜乙烯醇系樹脂膜浸潰在含有二色性色素的水溶液中 兩仃。作為二色性色素’可使用碘、二色性的有機染料等。 =要說明的是，聚乙烯醇系樹脂膜宜在染色處理之前實施 在水中的浸潰處理。 在使用碟作為二色性色素的情況下，通常利用在含有 :及碘化鉀的水溶液中浸潰聚乙烯醇系樹脂膜的方法進行 ^色。該水溶液中㈣含量相對於水1GG重量份通常為 5重量伤左右’另外，峨化卸的含量相對於水1〇〇 322672 25 201132505 重量份通常為0. 5至10重量份左右。用於染色的水溶液的 溫度通常為20至40°C左右，另外，在該水溶液中的浸潰 時間（染色時間）通常為30至300秒左右。 另一方面，使用二色性的有機染料作為二色性色素的 情況下，通常利用在包含水溶性的二色性有機染料的染料 水溶液中浸潰聚乙烯醇系樹脂膜的方法進行染色。該染料 水溶液中的二色性有機染料的含量相對於水100重量份通 常為lxl(T3至lxl(T2重量份左右。染料水溶液也可以含有 硫酸鈉之類的無機鹽作為染色助劑。染料水溶液的溫度通 常為20至80°C左右，另外，在染料水溶液中的浸潰時間（染 色時間）通常為30至300秒左右。 對於利用二色性色素染色後的硼酸處理，係通過將染 色後的聚乙烯醇系樹脂膜浸潰在含硼酸水溶液中來進行。 含硼酸水溶液中的硼酸含量相對於水100重量份通常為2 至15重量份左右、宜為5至12重量份。在使用碘作為二 色性色素的情況下，含硼酸之水溶液宜還含有碘化鉀。這 種情況下，含硼酸之水溶液中的碘化鉀的含量相對於水 100重量份通常為2至20重量份左右、宜為5至15重量 份。在含硼酸之水溶液中的浸潰時間通常為100至1200 秒左右、宜為150至600秒左右、進一步宜為200至400 秒左右。含硼酸之水溶液的溫度通常為50°C以上、宜為50 至 85X：。 硼酸處理後的聚乙烯醇系樹脂膜通常進行水洗處理。 水洗處理例如通過將硼酸處理過的聚乙烯醇系樹脂膜浸潰 26 322672 201132505 在水中來實施。水洗處理中的水的溫度通常為5至紙卢 -右，浸潰時間為2至120秒左右。水洗後實施乾燥處理;&quot; .得到偏振膜。可以使用熱風乾燥機或遠紅外線加熱器來實 施乾燥處理。乾燥溫度通常為4〇至1〇(rc&amp; 的時間通常為120至_秒左右。 祕里 如上所述，可以製成在單軸拉伸的聚乙烯醇系樹脂膜 上吸附有二色性色素並使其取向而成的偏振獏。得到的偏 振膜的厚度可以設定為5至4〇 Am左右。 〈透明保護層〉 設置在偏振膜6的至少一面的透明保護層7可以由例 如乙酸纖維素系樹脂、環烯烴系樹脂、以聚丙烯系樹脂為 代表的鏈狀烯烴系樹脂、以聚曱基丙烯酸曱酯系樹脂為代 表的丙烯酸系樹脂、聚醯亞胺系樹脂、聚碳酸酯系樹脂、 以聚對苯二曱酸伸乙酯系樹脂為代表的聚酯系樹脂等本 領域中目前廣泛用作保護層的形成材料的適當的熱塑性 樹脂膜構成。另外，透明保護膜7還可以由活性能量線硬 化性樹脂組成物的硬化物構成。從量產性及黏接性的觀點 考慮’宜使用由其中的乙酸纖維素系樹脂、環烯烴系樹 脂、鏈狀烯烴系樹脂、丙烯酸系樹脂或聚酯系樹脂形成的 膜或者活性能量線硬化性樹脂組成物的硬化物作為透明 保護層7。 由熱塑性樹脂膜構成透明保護層7的情況下，其厚度 通常為10至80//m左右，宜製成1〇至50 ym左右的較薄 的層。另一方面，由活性能量線硬化性樹脂組成物的硬化 27 322672 201132505 物構成透明保護層7的情況下，其厚度可以設定為lOym 以下、例如1至1 〇 y m左右。 用作透明保護層7的乙酸纖維素系樹脂膜是由纖維素 的部分或全部的乙酸酯化物構成的膜，例如可以舉出：三 醋酸纖維素膜、二醋酸纖維素膜等。作為這樣的乙酸纖維 素系樹脂膜，可以使用合適的市售品，可以使用例如：由 富士膠片株式會社出售的&quot;FUJITAC TD80&quot;、&quot;FUJITAC TD80UF&quot;及&quot;FUJITACTD80UZ&quot;;由柯尼.卡美能達精密化學株 式會社出售的&quot;KC8UX2M&quot;&amp;MKC8UY&quot;(均為商品名）等。 透明保護層7使用的環稀煙系樹脂是具有由例如降冰 片烯、四環十二烯（別名：二甲橋八氫萘）或其衍生物之類 的環狀烯烴（環烯烴）構成的單體單元的熱塑性樹脂（也稱 為熱塑性稀煙系樹脂）。該環稀經系樹脂可以是上述環稀 烴的開環聚合物的氫化物、或使用2種以上環烯煙的開環 共聚物的氫化物，除此以外，還可以是環烯烴與鏈狀烯烴 及/或具有乙烯基的芳香族化合物等形成的加成共聚物。在 環烯烴系樹脂中可以導入極性基團。 在使用環烯烴與鏈狀烯烴及/或具有乙烯基的芳香族 化合物的加成共聚物構成透明保護層7的情況下，作為鏈 狀稀烴’可以舉出乙缔、丙烯等’另外，作為具有乙稀基 的芳香族化合物，可舉出苯乙稀、基苯乙稀、核^ 取代苯乙料。在it樣的絲财’&amp;料烴構成的單體單 元可以是50莫耳％以下（宜為15 i 5〇莫耳％)。特別是在使 用環烯烴、魏烯烴和具有乙烯基的化合物的三元共 322672 28 201132505 聚物構成透明保護層7的情況下，由環稀烴構成的單體單 π可以δ又疋為如上所述的比較少的量。在這樣的三元 物中，由鏈狀烯烴構成的單體單元和 :眾 族化合物構成的單體單元通常分別為5至別莫耳香 環烯烴系樹脂可以使用合適的市售品，例如：画 ADVANCED _ERS Gmb_製造的由日本的ρ。㈣如⑹ 株式會杜出售的，，T〇PAS&quot;、由〗SR株式會社出售的&quot;腳N&quot;、 由日本ΖΕΟΝ株式會杜出售的&quot;Z_R及&quot;ze〇組、由三井化 学株式会社出售的&quot;舰(均為商品名）等。將這樣的環稀煙 系樹脂製絲時，可適當❹溶·延法，法等公 知的方法。另外’例如’也可以使用由日本聊株式會社 出售的&quot;ZE_R膜&quot;、由通株式會社出售的”娜N膜”等預 先製成獏的市售的環烯烴系樹脂的膜作為透明保護層7。 用於透明保護層7的鏈狀烯烴系樹脂宜為以丙烯為主 要構成單元的聚丙烯系樹脂。聚丙烯系樹脂可以是伸丙基 的均聚合物，除此以外，也可以是使丙烯與以乙婦為代表 例的其它共聚性單體共聚而成的，其它共聚性單 體的聚合 =為10重量％左右、例如丨至1〇重量％左右。聚丙烯系樹 月曰也可以用溶劑流延法、熔融擠出法等公知的方法進行制 膜，製成用於透明保護層7的膜。 用於透明保護層7的丙烯酸系樹脂宜為以曱基丙烯酸 曱酯^主要構成單元的聚曱基丙烯酸甲酯系樹脂。在曱基 丙稀酸曱目旨系樹脂中，有時配合丙烯酸系的橡膠粒子。另 外有時製成具有配合有光擴散劑的聚甲基丙稀酸曱醋系 29 322672 201132505 = 3=:合:光擴散劑的聚曱基丙烯酸甲醋系樹脂 擠出法製成;製Π基丙烯酸甲醋系樹脂通常通過熔融 、、製成多層結構時，可以採用共擠出法。 乙-醢2透月保濩層7的聚酯系樹脂宜為以對苯二曱酸和 ^二t主要構成單元的聚對苯二曱酸伸乙酯系樹脂。聚 法等二酸伸乙㈣樹脂也可以用溶誠延法、熔融擠出 伸二的方法製成膜’將該膜進—步進行單軸或雙軸拉 明㈣Ϊ維持強度的同時提高透明性的薄膜宜使用作為透 0月保5隻摩7。 另一方面，對於用於透明保護層7的活性能量線硬 化性樹脂組成物’可以是例如含有環氧系的活性能量線 硬化性化合物的樹脂組成物，進—步配合氧雜環丁院化 ^物也是有效的。這樣，含有環氧化合物、且還任意地 含有氧雜環T烧化合物時，通常還配合紐陽離子聚合 引發劑。 對於用於透明保護屬7的活性能量線硬化性樹脂組成 物而言’除了環氧化合物及作為任意成分的氧雜環丁烧化 合物以外，含有自由基聚合性化合物、具體為（甲基）丙烯 酸系化合物也是有效的。通過併用（甲基）丙稀I系化合物， 可以製成硬度高、機械強度優異、耐久性能更優異的透明 保護層。進而，能夠更加容易地調節活性能量線硬化性樹 月曰組成物的黏度和硬化速度等。在用於形成透明保護膜7 的活性能量線硬化性樹脂組成物中，以活性能量線硬化性 化合物總量為基準，（曱基）丙烯酸系化合物可以添加至7〇 322672 30 201132505 . 重量％左右。（曱基）丙烯酸系化合物的配合量更宜為35至 • 70重量％、尤其宜為40至60重量％。當（曱基）丙烯酸系化 合物的配合量超過70重量％時，可能會使其與偏振膜的密 , 合性下降。在配合這樣的（曱基）丙烯酸系化合物的情況 下，還可以進一步配合光自由基聚合引發劑。 偏振板5的透明保護膜7也可以在與貼合偏振膜6的 面處於相反侧的面上具有表面處理層，這種表面處理的例 子包括防眩處理、硬塗處理、抗靜電處理、防反射處理等。 另外，也可以在透明保護層7的與偏振膜6貼合的面處於 相反側的面上形成包含液晶性化合物或其高分子量化合物 等的塗層。 在透明保護層7為樹脂膜的情況下，可使用黏接劑貼 合偏振膜6和透明保護層7。作為用於此貼合的黏接劑， 可以舉出：含有活性能量線硬化性化合物的硬化性樹脂組 成物、使黏接劑成分溶解或分散在水中而成的水系黏接劑。 從不需要乾燥步驟、提高生產性的觀點考慮，宜將含 有活性能量線硬化性化合物的硬化性樹脂組成物作為黏接 劑。此時，作為活性能量線硬化性化合物，宜使用環氧系 的陽離子聚合性化合物。另外，除環氧化合物外，配合同 樣為陽離子聚合性的氧雜環丁院化合物也是有效的。這 樣，在含有環氧化合物、且進一步任意含有氧雜環丁燒化 合物時，通常還可配合光致陽離子聚合引發劑。將硬化性 樹脂組成物作為黏接劑時，通常在經由硬化性樹脂組成物 層貼合偏振膜6和透明保護層7後，對該貼合物照射活性 322672 31 201132505 ' 能量線使硬化性樹脂組成物層硬化。 ’ 另一方面，從薄化黏接劑層、薄化整個偏振板5的 觀點考慮，宜為使黏接劑成分溶解或分散在水中而成的 水系黏接劑。作為這種水系黏接劑，可以舉出以聚乙稀 醇系樹脂或聚胺酯樹脂作為主成分的黏接劑組成物。在 使用聚乙稀醇系樹脂作為水系黏接劑的主成分的情況 下’該聚乙烯醇系樹脂除了部分皂化聚乙烯醇、完全皂 化聚乙烯醇以外’還可以是陰離子改性聚乙烯醇系樹 脂、乙醯乙醯基改性聚乙烯醇系樹脂、羥曱基改性聚乙 烯醇樹脂、陽離子改性聚乙烯醇系樹脂等經改性的聚乙 烯醇系樹脂。在使用聚乙烯醇系樹脂作為黏接劑成分的 情況下，該黏接劑通常製成聚乙烯醇系樹脂的水溶液。 黏接劑中的聚乙烯醇系樹脂的濃度相對於水1〇〇重量份 通常為1至10重量份左右、宜為！至5重量份。另外， 併用交聯劑也是有效的。 〈配置在偏振板的液晶單元基板側的樹脂層〉 如第3圖所示的例子，在偏振膜6的液晶單元基板i 侧叹置樹脂層8時，該樹脂層8可以是與設置在偏振膜6 的相反侧的透明保護層7相同或與其不同的透明保護層， 除此之外’還可以是光學功能層。作為光學功能層的例子， 可以舉出為了補償液晶單元導致的相位差或補償視角等而 使用的相位差板。作為相位差板，例如有：由各種樹脂的 拉伸膜構成的雙折射性膜；盤狀液晶或向列液晶取向固定 而成的膜；在膜基材上形成含有上述液晶或無機層狀化合 322672 32 201132505 物等體現相位差物質的塗膜並進行取 此時，作為支撐含有體現相位差物質的=而成的膜等。 使用三醋酸纖維素等乙酸纖維素系樹月^的膜基材，宜 在將由樹餘相構成的雙折射性腺 的情況下，從相位差的體現性或相值^相位差板 考慮，宜將乙酸纖維素系樹脂、環㈣定性等觀點 樹脂等作為構成該相位差板的樹脂材料糸丙稀系 以上作為構成透明保護層7的樹脂 ς树月曰本身與 通過將這麵㈣崎單滅熱㈣^朗的相同。 差、製成相位差板。此φ 可以賦予相位 宜為U至3倍時的拉伸倍率通常為U至5倍、 賦予了相位差的乙酸纖維素系 脂膜在市場上也有販售。例如，作為賦予系樹 :=素系樹脂膜，有由柯尼卡美能達株= 4FR'r或&quot;KC_-T&quot;等，作為賦予了相的 =脂膜’有由積水化料業株式會社出售的煙系 二40”等。另外，以上作為可形成透明 二a或 的例子所列舉的由日本2刪株式會社出售的 _膜”或由JSR(株)出售的&quot;art〇n 差的等級。 ⑯也有賦予相位 在用包含相位差板的樹賴構成樹脂層8時 用與以上在偏振膜6和透明保護層7的貼合中 ^使 劑相同的黏接劑來黏接偏振膜6和樹脂層8。 '龜接 在謀求對偏振板5賦予對因液晶單元導致的相位差、 322672 33 201132505 行補償的功能和補償視㈣魏等時，如第3圖所示的例 子在偏振膜6的個面上形成透明保護層7,在偏振膜6 的另-個面上層疊作為樹脂層8的相位差板製成偏振板 里將ί相位差板側經由以上說明的黏接劑層2貼合到液晶 成Α二板I上的H有效的。這樣，即使在偏振膜6的 =&quot;單元基板1侧的面上層叠相位差板時，也可以將 振板5的厚度設定在以下。另外，只要適當 整個偽:月保遵層7和成為相位差板的樹脂層8 ，也可以將 整個偏振板5的厚度設定在1〇〇㈣下。 [光學積層體的製造方法] 利用供面’對本發明的光學積層體的製造方法進行說明。 ^有以下所示的各步驟的方法，可以有利地製造以 死明的光學積層體。下面，一 邊進行說明。 由邊引用第1圖表示的符成 (a)黏接劑組成物層形成步驟，係在玻璃板丄和塑科 :的各自貼合面中的至少-個面上，設置由包含含羧碁 樹脂的水溶液構成的黏接劑組成物層； ㈣lb)貼合步驟’經由該黏接劑組成物層將玻璃板1和 塑枓片3貼合； (〇檢查步驟，檢查所述貼合步驟中得到的貼合％， f一出有缺陷的貼合品取出到生產線外；及 (d)硬化步驟，使存在於經所述檢查步驟沒有查出缺 陷的貼合品中的黏接劑組成物層硬化。 該製造方法在玻璃板1為液晶單元基板、塑料片3為 34 322672 201132505 以上說明的具有偏振膜的偏振板時特別有用。偏振板可以 是單獨的偏振膜，也可以是如上所述預先層疊有其它層的 偏振膜，如前面參照第2圖及第3圖所說明的那樣，宜具 備形成在偏振膜6的至少一個面上的透明保護層7。這樣， 在將至少層疊有偏振膜6和透明保護層7的偏振板5作為 塑料片1的情況下，以層疊構成偏振板5的各層的狀態製 成塑料片1，將其用於上述黏接劑組成物層形成步驟（a)。 下面，對以上所示的各步驟依次進行說明。 〈黏接劑組成物層形成步驟（a)&gt; 在黏接劑組成物層形成步驟（a)中，在玻璃板1和塑 料片3的各自貼合面中的至少一個面上，設置由包含含羧 基樹脂的水溶液構成的黏接劑組成物之層。在形成黏接劑 層時，可以採用例如在玻璃板1的貼合面及/或塑料片3 的貼合面上塗布上述黏接劑組成物的方法。另外，作為塗 布的一個形態，也可以採用以下方法，即，以在玻璃板1 的表面的一端貼合塑料片3的方式供給，一邊在二者之間 吹入上述黏接劑組成物，一邊在玻璃板1和塑料片3的各 自貼合面上形成黏接劑組成物層，並從塑料片3的外側用 輥進行擠壓，並連續進行接下來的貼合步驟。 在玻璃板1的貼合面及/或塑料片3的貼合面上塗布 黏接劑組成物的方法沒有特別限制，可以利用例如刮刀塗 布、線棒塗布、狹縫塗布、模塗、缺角輪式塗布、凹版塗 布等各種塗布方式。另外，由於各塗布方式有各自最佳的 黏度範圍，因此，通過調節黏接劑組成物中的含羧基樹脂 35 322672 201132505 的濃度等，可以調節黏接劑組成物（水溶液）的黏度。 〈貼合步驟（b)&gt; 在接下來的貼合步驟（b)中，經由前面的黏接劑組成 物層形成步驟（a)中形成的黏接劑組成物層將玻璃板j和 塑料片3貼合。在該步驟中’可有利地採用如下方法：如 前面所說明的那樣，以在玻璃板1的表面的一端經由黏接 劑組成物層貼合塑料片3的方式供給，.一邊從塑料片3的 外側用輥進行擠壓，一邊進行貼合。從抑制氣泡捲入等觀 點考慮’這樣一邊從玻璃板1的表面的一端用親擠壓一邊 與玻璃板1的表面的另一端貼合的方法是有利的。 〈檢查步驟（c)&gt; 在檢查步驟（c)中，檢查前面的貼合步驟（13)中得到的 貼合品’將查出有缺陷的貼合品取出到生產線外。當然， 只要沒有查出缺陷，其貼合品就直接送到接下來的硬化步 驟（d)。在該檢查步驟（c)中，可檢查有無表面損傷、有無 異物、有無氣泡、有無軸錯位等。這種檢查可以用在液晶 面板製造階段通常採用的方法進行。 檢查步驟（c)中查出缺陷的貼合品被取到生產線外。 在該階段中，由於由包含含羧基樹脂的水溶液構成的黏接 劑組成物層還未硬化，因此可以容易地從玻璃板1上剝下 塑料片3。因此，剝下塑料片3後的玻璃板1可以通過水 洗等容易地除去其表面的黏接劑組成物，因此可以在清洗 後返回到黏接劑組成物層形成步驟（a)。將檢查步驟（c)中 查出缺陷的貼合品取出到生產線外，從其上剝下塑料片3 36 322672 201132505 • 並使玻璃板1返回到黏接劑組成物層形成步驟（a)的操作 -相當於重工（rew〇rk)操作，即，在將帶有黏接劑層的偏振 ' 板貼合在液晶單元基板上後，在有任何不適合的情況下， 剝下其偏振板重新貼合。在本發明中，雖然不使用黏合劑 而使㈣接劑將塑料# 3(典型的為偏振板）貼合到玻璃板 1(典型的為液晶單元基板）上，但是由於其黏接劑為水溶 液，因此具有容易進行這樣的重工操作的優點。 〈硬化步驟（d)&gt; 對於在檢查步驟（c)中沒有查出缺陷的合格的貼合品， 在接下來的硬化步驟（d)中，使存在於玻璃板丨和塑料片3 之間的黏接劑組成物層硬化。在硬化步驟中，通過高溫 乾燥、照射活性能量線等使黏接劑組成物層硬化，製成黏 接劑層2。黏接劑組成物層的硬化多採用高溫乾燥。採用高 溫乾燥時，其溫度宜在40至80°C左右的範圍。通過照射活 ^生月b量線使其硬化時，所使用的活性能量線可以是紫外線、 X射線、電子能量線等。另外，還有通過常溫放置使黏接劑 組成物層硬化的方法。在通過高溫乾燥使黏接劑組成物層 硬化的情況下，該處理通常宜在40。(：至80°C下進行1分鐘 至24小時。在通過活性能量線的照射使黏接劑組成物層硬 化的情況下，通常使用紫外線，宜將以照射照度和照射時 間的積表示的累積光量設定為5〇至2〇〇〇mj/cm2。在通過常 溫放置使黏接劑組成物層硬化時，該處理通常宜在2〇&lt;5(：至 30°C、濕度20%至80%的環境下進行〇 5小時至72小時。 [液晶顯示裝置] 322672 37 201132505 本發明的光學積層體10至12在該液晶單元基板1的 與貼合偏振板5的面相反的一側配置另一張液晶單元基板， 將液明爽持在兩者之間，由此可以製成液晶單元或液晶面 板°以該液晶單元或液晶面板為顯示元件，構成液晶顯示 裝置f吊’將在2張液晶單元基板間封入有液晶的狀態 =液曰曰單7L本身作為第i至3圖中的液晶單元基板i，在其 一方或雙方的表面上依照本發明貼合偏振板，製成液晶面 反。本發明的光學制料熱衝擊試驗㈣耐久性優異， 因此如上所述操作而製作的液晶顯示裝置也同樣，對熱 衝擊試驗等的耐久性優異，而且可謀求薄型輕質化。 [實施例] 下面’舉出實施例進一步具體地說明本發明，但本發 :並二子所限定。實施例中，表示含量或用量的 。及f刀/、要沒有特別說明即為重量基準。 [製造例1] 容器=具？冷部官、氮氣導入管、溫度計及攪拌器的反應 =Μ 份及丙軸1GG份，用氮氣置換裝置 、4使其不含氧’使内溫升至80°c。然後，將〇 2份 =:(聚合引發劑)溶解于2〇份水中，將該溶液全部加 ^反應谷II中。進而仙溫79至抓保溫6小時， 力二水’調節使聚丙婦酸濃度為.得到的5 洛液的黏度為52mPa.sec。 歸夂欠 [製造例2] 在具備冷部管、氮氣導入管、溫度計及攪拌器的反應 322672 38 201132505 ' 容器内，加入水870份及丙烯酸100份，用氮氣置換裝置 - 内的空氣使其不含氧，同時使内溫升至80。〇然後，將〇 3 • 份過硫酸鉀（聚合引發劑）溶解于3 0份水中，並將該溶液全 部加入反應容器中。進而在内溫79至81t保溫6小時， 最後加入水，調節使聚丙烯酸濃度為5%。得到的5%聚丙烯 酸水溶液的黏度為41mPa.sec。 [製造例3] 在具備冷卻管、氮氣導入管、溫度計及攪拌器的反應 谷器内，加入水415份、丙烯酸1〇〇份及衣康酸9. 5份， 用氮氣置換裝置内的空氣使其不含氧，同時使内溫升至8〇 °C。然後’將〇. 2份過硫酸鉀（聚合引發劑）溶解於23份水 中並將該溶液全部加入反應容器中。進而在内溫79至81 °C保溫6小時，最後加入水，調節使丙烯酸/衣康酸共聚物 的濃度為5%。得到的丙烯酸/衣康酸共聚物的5%水溶液的 黏度為 27mPa.sec。 [製造例4] 在具備冷卻管、氮氣導入管、溫度計及攪拌器的反應 容器内，加入水400份、丙烯酸1〇〇份及丙烯酸曱酯6. 2 份，用氮氣置換裝置内的空氣使其不含氧，同時使内溫升 至80°C。然後，將〇. 2份過硫酸鉀（聚合引發劑）溶解于23 份水中並將該溶液全部加入反應容器中。進而在内溫79 至81°C保溫6小時，最後加入水，調節使丙烯酸/丙烯酸 曱酯共聚物的濃度為5%。得到的丙烯酸/丙烯酸甲酯共聚 物的5%水溶液的黏度為29mPa • sec ° 39 322672 201132505 、 [實施例1] . 水系黏接劑組成物的製備 . 在製造例1中得到的5%聚丙烯酸水溶液中，將作為矽 ,烧偶口劑的3-環氧丙氧基丙基三曱氧基石夕烧，以聚丙烯 皱·矽烷偶合劑的固形分重量比為1:0.2的方式混合，進 而ス相對於水10 0份聚丙稀酸為5份的方式加入純水進 行稀釋’製備黏接劑組成物。 (b)光學積層體的製作 準備透明玻璃基板（成為液晶單元基板的基板），使用 超音波玻璃清洗機（MICRO技研株式會社製造）清洗該玻璃 基板。另外，準備在聚乙烯醇膜上吸附取向碘的偏振膜的 一面上經由聚乙烯醇系黏接劑貼合有厚度為4〇 Am的由三 醋酸纖維素構成的保護膜的偏振板（住友化學株式會社製 造、商品名“SR0661A-XNSY” 、厚度約70#m)。將該偏振 板切割成lOcmxlO cm的正方形尺寸，分別將在上述（&amp;)製 備的黏接劑組成物在製備後30分鐘内塗布在沒有貼合上 述保護膜的偏振膜面上和上述清洗後的玻璃基板的一個面 上’並將黏接劑面相貼合。將其在常溫下放置24小時後， 在60°C乾燥3分鐘，製成光學積層體。乾燥後的黏接劑層 的厚度約為0. 1 //m。 [實施例2] 將聚丙烯酸：矽烷偶合劑的固形分重量比變更為 1:0.3，其它通過和實施例1(a)同樣的操作製備黏接劑組 成物。而.且，除了使用該黏接劑組成物以外，.以和實施例 322672 40 201132505 1(b)相同的方法製作光學積層體。 [實施例3] 組 將聚丙烯酸：矽烷偶合劑的固形分重量比變更為 1:0. 4 ’其它通過和實施例1 (a)同樣的操作製備點| 成物。而且，除了使用該黏接劑組成物以外， 1(b)相同的方法製作光學積層體。 [實施例4] 使用在製造例2中得到的5%聚丙烯酸水溶液， 丙烯酸：矽烷偶合劑的固形分重量比為1: i 以和實施例 以該聚 的方式進行 混合，除此以外，通過和實施例1(a)同樣的操作製備黏Z 劑組成物。而且，除了使用該黏接劑組成物以外，以和實 施例1(b)相同的方法製作光學積層體。 [實施例5] 使用在製造例3中得到的丙烯酸/衣康酸共聚物的5% 水溶液，以該共聚物：矽烷偶合劑的固形分重量比為 1:0.2的方式進行混合，除此以外，通過和實施例1(a)同 樣的操作製備黏接劑組成物。而且，除了使用該黏接劑組 成物以外，以和實施例1(b)相同的方法製作光學積層體。 [實施例6] 將共聚物：矽烷偶合劑的固形分重量比變更為1:0. 3 , 其它通過和實施例5前半部分同樣的操作製備黏接劑組成 物。而且，除了使用該黏接劑組成物以外，以和實施例丨（b) 相同的方法製作光學積層體。 [實施例7] 322672 201132505 t - 使用在製造例4中得到的丙烯酸/丙烯酸甲酯共聚物 - 的5%水溶液，以該共聚物：矽烷偶合劑的固形分重量比為 * 1: 〇 _ 3的方式進行混合’除此以外，通過和實施例1 (a)同 ‘ 樣的操作製備黏接劑組成物。而且，除了使用該黏接劑組 成物以外，以和實施例1(b)相同的方法製作光學積層體。 [比較例1 ] 在聚乙烯吡咯烷酮的20°/。水溶液（日本觸媒株式會社 製造、商品名“K-85W”）中，將作為矽烷偶合劑的3〜環氧 丙氧基丙基三曱氧基矽烷以聚乙烯吡咯烷酮··矽烷偶合劑 的固形分重量比為1:0. 1的方式進行混合，進而，以相對 於水100份之聚乙烯吡咯烷酮為2份的方式加入純水進行 稀釋’製備黏接劑組成物。使用該黏接劑組成物，以和實 施例1(b)相同的方法製作光學積層體。 [比較例2] 代替由聚丙烯酸水溶液構成的黏接劑組成物，使用厚 度為25//m的丙烯酸系黏合劑，經由該丙烯酸系黏合劑， 在透明玻璃基板的一個面上與在實施例1中使用的相同的 沒有貼合偏振板保護膜的偏振膜面貼合。然後，在5〇。〇的 高壓爸中’在壓力5kg/cm2(約0. 5MPa)下處理20分鐘，製 作光學積層體。 [比較例3] 代替由聚丙烯酸水溶液構成的黏接劑組成物，使用純 水’除此以外’以和實施例1(b)相同的方法製作光學積層 42 322672 201132505 [評價試驗] (a) 耐久試驗 用以下方法評價上述實施例及比較例製作的光學積 層體的财久性。 對於進行在溫度8〇。(：的乾燥下保管1〇〇小時的耐熱試 驗的情況；進行在溫度6(rc、相對濕度9〇%下保管1〇〇小 時的耐濕熱試驗的情況；以及進行將從加熱到7(rc的狀態 降溫到-35°C、然後再升溫到7(TC的過程作為一個循環（2 小時）並將該循環反復6〇次的耐熱衝擊試驗（在表中記為” 耐HS試驗π)的情況，分別以目測觀察試驗後的光學積層 體。按以下標準將結果進行分類，匯總在表1中。 (耐熱、耐濕熱及耐熱衝擊試驗的評價標準） ◎:完全看不到鼓起、剝離、偏振膜龜裂等的外觀變化。 〇：幾乎看不到鼓起、剝離、偏振膜龜裂等的外觀變化。 △:鼓起、剝離、偏振膜龜裂等的外觀變化稍明顯。 X :可明顯看到鼓起、剥離、偏振膜龜裂等的外觀變化。 (b) 重工性評價 在玻璃基板上貼合偏振板，3小時後（在實施例1至7 及比較例1和3中，在常溫下放置24小時的過程中的第3 小時，另外在比較例2中，在高壓爸處理結束後第3小時）， 為了觀察偏振板是否能從玻璃基板剝離，以300mm/分鐘的 速度沿180方向（反折沿著玻璃基板面的方向）從貼合試 驗片剝下偏振板，進行剝離試驗。按以下標準將結果進行 分類，匯總在表1中。 43 322672 201132505 % 、 （重工性評價標準） 〇：可以剝離。 .X:偏振板斷裂’不能剝離。 表 1 _____________ * -一~—和偏振板間$偏振板+i 对熱耐濕熱耐HS重J1 例No. 黏接劑木 接劑的厚度 試驗試驗 試驗 試驗 實施例1 PAA基體 實施例2 PAA基體 實施例3 PAA基體 實施例4 PAA基體 實施例5 AIC基體 實施例6 AIC基體 實施例7 AMAC基體 PVP 基 i 比較例2 黏合劑 比較例3 系屯# . //Μ y.//¾.仁 ooooooo 7 7 7 7 7 7 7 //¾.¾ 0 5 0 7 9 7 ◎◎◎◎◎◎◎ 〇〇〇〇〇〇〇 〇〇〇〇〇〇〇 〇△ 〇〇 0X0 木PAA :聚丙烯酸 AIC:丙烯酸/衣康酸共聚物 AMAC :丙烯酸/丙烯酸甲酯共聚物 PVP:聚乙烯基吡咯烷酮 實施例1至7的光學積層體較薄，而且耐久性和重工 性都優異。另一方面，使用聚乙烯基吡咯烷酮水溶液作為 黏接劑組成物的比較例1的光學積層體在耐久性試驗中產 生不良情況。另外，將丙烯酸系黏合劑用於玻璃和偏振板 的黏接的比較例2的光學積層體在财熱衝擊性和重工性方 面不良。進而’將純水用於黏接劑的比較例3的光學積層 體在耐熱性和财熱衝擊性方面不良。 【圖式簡單說明】 第1圖是表示本發明的光學積層體的基本層構成的剖 面示意圖。 44 322672 201132505 . 第2圖是表示本發明的光學積層體的層構成的一個形 - 態的剖面示意圖。 . 第3圖是表示本發明的光學積層體的另一個層構成的 剖面示意圖。 【主要元件符號說明】 1 玻璃板（液晶早元基板） 2 黏接劑層 3 塑料片 5 偏振板 6 偏振膜 7 透明保護層 8 樹脂層 10、11、12 光學積層體 45 322672201132505 VI. Description of the Invention: [Technical Field] The present invention relates to an optical layered body suitable for use in a liquid crystal display device, and more particularly, relates to a liquid crystal single it in order to become a central component of a liquid crystal display device The substrate is an optical laminate in which a glass plate of a typical example is laminated with a polarizing plate as a typical example via an adhesive layer. Further, the present invention relates to a method of advantageously manufacturing the optical laminate. [Prior Art] A polarizing plate is useful as an optical component constituting a liquid crystal display device. The polarizing plate is a polarizing plate having a structure in which a protective film of a transparent resin film is laminated on a single layer or a double layer via a water-based adhesive, such as a polarizing film made of a polyvinyl alcohol-based resin. As such a transparent resin film, a triethyl styrene cellulose film is often used from the viewpoint of excellent phototransparency and excellent moisture permeability. Even in the case where the protective layer is provided on one side of the polarizing (four), the other side of the polarizing film is mostly laminated via an adhesive (also called an adhesive) or a binder (also called an adhesive). A resin film having an optical function such as a poor function functions as a protective polarizing film. The polarizing plate having such a configuration can be bonded to a liquid crystal single S substrate by a binder (also referred to as a pressure sensitive adhesive) via a different optical function layer as needed, and a liquid crystal panel can be formed and assembled in a liquid crystal display device. . The liquid crystal display device is rapidly expanding its use as a thin display surface such as a liquid crystal television, a liquid crystal monitor, or a personal computer. In such an expansion of use, it is required that the components constituting the same are also made thinner. As described above, the polarizing plate is usually attached to the liquid crystal cell with an adhesive because it can be easily peeled off from the liquid crystal cell and attached to the other after some improper conditions after the bonding of 4 322 672 201132505. The polarizing plate is convenient. However, in order to maintain an appropriate adhesive force, a thickness of at least about 20/zm is required for the adhesive to be a bottleneck in the reduction in thickness of a liquid crystal panel or a liquid crystal display device. Further, it has been attempted to reduce the thickness by omitting the liquid crystal cell side protective layer of the polarizing film, directly forming a binder layer thereon, and bonding the adhesive layer to the liquid crystal cell. However, in the case where the polarizing film and the liquid crystal cell are bonded directly to the adhesive layer in this manner, in the case of performing a heat resistance test exposed to a high temperature, the shrinkage of the polarizing film may not be sufficiently absorbed by the adhesive layer alone, and polarization may occur. Difficulties such as bulging, peeling, and foaming occur between the film and the adhesive layer. Further, in the case of performing a thermal shock test (heat shock test) in a repeated high temperature state and a low temperature state, there is still a case where the polarizing film is not sufficiently absorbed by the adhesive layer, and the polarizing film is broken. In another attempt to reduce the thickness of the polarizing plate, for example, Japanese Patent Publication No. 2004-245924-A discloses a polarizing film in which a dichroic color is adsorbed and oriented on a polyvinyl alcohol-based resin. On at least one side, an uncured epoxy resin composition is applied, and then the composition is cured to form a protective film. However, in a state in which a polarizing plate having a cured product of an epoxy resin composition as a protective film is bonded to a liquid crystal cell via a binder layer, durability is insufficient, for example, in the case of performing a thermal shock test, sometimes It still causes the polarizing film to rupture. In addition, Japanese Patent Publication No. 4-245925-a discloses a technique in which a polarizing film which adsorbs a dichroic dye on a polyvinyl alcohol-based resin is passed through an epoxy resin containing no aromatic ring as a main component 322672 5 201132505 The adhesive composed of the composition is bonded to the protective film to form a polarizing plate. On the other hand, Japanese JPH 09-159828-A discloses the following technique: On one side of a polarizing film, a polarizing plate formed of a photocurable adhesive to form an adhesive layer is formed, and a bonding layer is formed through the adhesive layer The polarizing plate is adhered to the liquid crystal single-layer substrate, wherein the photo-curable adhesive is a ternary formed with respect to ethylene, an acrylate-based or methacrylate-based monomer, and maleic acid or maleic anhydride. The copolymer is prepared by blending a predetermined amount of a photosensitizer and an unsaturated compound such as a compound having a propylene fluorenyloxy group, and a protective layer containing a light-curing heterojunction on the surface of the polarizing film (4) is also described. Technology.曰2疋, in the case where the polarizing plate is bonded to the liquid crystal cell substrate via the adhesive disclosed in the document, (4) in the reduction test or the thermal shock test, although no large difference is found in the liquid crystal cell of the f-size However, when it is used as a liquid crystal cell of a medium to large size, there is a problem that the polarizing plate is peeled off from the surface of the liquid crystal single-sided substrate or the polarizing film is broken. Further, the optical layered body of the crucible unit substrate is bonded to the polarizing plate by the adhesive. Although it is possible to achieve thinning, it is not easy to separate the money for the polarizing plate temporarily attached to the liquid crystal cell. For this reason, in the case where the past and the past are not suitable, the liquid crystal cell can no longer be used without undergoing the treatment with a special container, and thus it is economical. A technique in which a polarizing plate is supplied from a roller via an adhesive and directly bonded to a liquid crystal cell substrate is disclosed in Japanese Patent Publication No. G4-4636-A. SUMMARY OF THE INVENTION 322672 6 201132505 An object of the present invention is to provide a thin and lightweight fabric by bonding a plastic sheet represented by a polarizing plate to a glass plate represented by a liquid crystal cell substrate via a specific adhesive. An optical laminate having excellent durability. Another object of the present invention is to provide a method of advantageously manufacturing such a light-emitting layer. The present invention includes the following. ^ [1] An optical laminate which is formed by laminating a glass plate and a plastic sheet, which are at least one of a plurality of inner layers. An optical layered body according to the above [1], wherein the water system is formed by the olefinic double bond and the at least one carboxyl group of the ruthenium b. The composition also contains a decane coupling agent. [3] The optical laminate according to [1] or [2], wherein the adhesive composition further contains a crosslinking agent. [4] The optical laminate according to any one of [1] to [3] wherein the adhesive layer has a thickness of 5 em or less. [5] The optical laminate 錤' according to any one of [1] to [4] wherein the glass plate is a liquid crystal cell substrate. [6] The optical laminate #1 according to any one of [1] to [5], wherein the plastic sheet has a polarization in which a color f is adsorbed on a polyvinyl alcohol-based resin and oriented. The polarizing plate of the film. The optical layered body according to [6], wherein the polarizing film and the transparent enamel formed on at least one surface thereof are [8] as in [7]. The optical layered body, wherein the polarizing film of the 201132505 and a transparent protective layer formed on at least one surface thereof, and a polarizing film surface on a side opposite to the transparent protective layer pass through the point layer Directly attached to the liquid crystal cell substrate. [9] The optical layered body according to [7], wherein the polarizing plate is provided with the polarizing film, a transparent protective layer formed on one surface thereof, and a phase laminated on the other surface of the polarizing film The difference plate is bonded to the liquid crystal cell substrate via the adhesive layer. [10] A method for producing an optical laminate in which a plastic sheet is bonded to a glass sheet, the method comprising the steps of: forming a binder composition layer in each of the bonding surfaces of the glass sheet and the plastic sheet Providing a layer of an adhesive composition on at least one side, the layer of the adhesive composition being composed of an aqueous solution comprising a main monomer having a polymer having at least one olefinic double bond and at least one carboxyl group in the molecule.  The bonding step 'adheres the slab and the plastic sheet through the adhesive composition layer; the inspection step checks the posted population obtained in the bonding step, and detects the defective sticker The product is taken out of the production line; and a hardening step is performed to harden the layer of the adhesive composition present in the laminate that has not been found to have defects in the inspection step. [11] The method according to [10], wherein the glass plate is a liquid helium unit substrate, and the plastic sheet has a structure of adsorbing and aligning a coloring pigment on a polyvinyl alcohol resin. The polarizing plate of the polarizing film is a method according to [10] or [11], which has the following constitution, and the plastic sheet is toughened for the fitting which is defective in the inspection step, t 322672 8 201132505 Return the glass sheet to the adhesive composition layer forming step. Since the optical laminate of the present invention can directly bond the plastic sheet to the glass plate via the adhesive layer, the thickness can be reduced, and the adhesion between the glass plate and the plastic sheet is also good. When the glass plate and the polarizing plate are made of a plastic sheet, the thickness can be reduced as compared with the conventional optical layered body in which the polarizing plate is bonded to the liquid crystal cell substrate via the adhesive layer, so that the optical layered body or the liquid crystal panel can be obtained. The thickness is thin and light, and the adhesion between the polarizing plate and the liquid crystal cell substrate is also good. Further, by using an adhesive instead of a binder in the joining of the liquid crystal cell substrate and the polarizing plate, it is possible to provide an optical layered body which can sufficiently withstand the environmental conditions at the time of heat treatment or the use of the device during assembly. Further, according to the method of the present invention, the above optical laminate can be advantageously produced. In particular, by providing an inspection step after the bonding step and before the hardening step, in the case of detecting defects such as surface damage, presence of impurities, entrapment of air bubbles, or axial misalignment, the laminate in which the above defects are detected is taken out Out of the production line 'Therefore, the optical laminate can be manufactured with good yield. Further, in the case of bonding a glass plate represented by a liquid crystal substrate and a plastic sheet represented by a polarizing plate, an adhesive composition composed of an aqueous solution is used, as long as it is before the hardening step. The plastic sheet is peeled off from the glass plate. Therefore, 'the product which has been taken out of the production line in the above-mentioned inspection step and peeled off from the production line', after being peeled off from the plastic sheet, can be returned to the station by a simple step of washing the adhesive composition by washing with water. In the binder composition layer forming step, the productivity of the optical layered body can be further improved. 9 322672 201132505 [Embodiment] As shown in the cross-sectional view of Fig. 1 and Fig. 1, a glass plate 1 as a typical liquid crystal cell substrate and a plastic sheet 3 as a typical polarizing plate are attached via an adhesive layer 2. The optical laminate 1G was produced. The adhesive sound 2 is composed of a water-based catalyst composition in which a main monomer is a polymer having at least one olefinic double bond and a polymer in the molecule as a main component. In the specification sheet, in the following, a compound having at least one molecule h and at least one county in the right is sometimes referred to as saturated and sincere. In addition, sometimes the unsaturated (four) compound &quot;containing a base resin' first, the adhesive composition and the material ==: line description 'and then' according to a plastic [adhesive composition] Carboxyl Resin In the present invention, in order to bond the glass plate 1 and the plastic sheet 3, a water-based adhesive composition containing a 2-base resin as a main component is used. The above-mentioned "restricted base tree γ" is a polymer obtained by using a compound having at least one dilute smoky double bond and a sulfhydryl group in the molecule (i.e., an unsaturated acid-lowering compound) as a main monomer. The polymerization for obtaining the lining resin can be carried out by radical polymerization. The (4) group contained in the reading (tetra) acid compound towel may be formed in the form of a salt such as a bell salt or a silk material, which is a metal salt or an ammonium salt, and may also be in the form of an acid anhydride when it is a compound having a polydip group in the molecule. When L is in the form of _salt, it can be in a state of coexistence with free rebel. 322672 10 201132505 Specific examples of the unsaturated carboxylic acid compound include, in addition to (fluorenyl)acrylic acid and a salt thereof, 2-(indenyl)acryloyloxyethyl succinate and 2-(indenyl)propene. Ethoxyethyl phthalate, 2-(methyl) propylene oxiranyl hexahydrophthalate, cold-carboxyethyl (decyl) acrylate and ω-enyl-poly a carboxyl group-containing (fluorenyl) acrylic compound such as a lactone-modified (meth) acrylate, and a salt thereof, or fumaric acid, maleic acid, itaconic acid, maleic anhydride, phthalic anhydride, An unsaturated polycarboxylic acid such as trimellitic anhydride or itaconic anhydride or an acid anhydride thereof. In the present specification, π(fluorenyl)acrylic acid means both acrylic acid and mercaptoacrylic acid, and is also called &quot;(fluorenyl)acryloxyloxy&quot;, &quot;(methyl) "Acrylate" isochronous "(曱基)&quot; is the same meaning. These unsaturated carboxylic acid compounds may be used as a carboxyl group-containing resin constituting the binder composition in the form of a respective homopolymer, or may be used as a binder composition in a form in which a plurality of different compounds are copolymerized. The carboxyl group-containing resin is used. In the present invention, depending on the case, other monomers copolymerizable with the unsaturated carboxylic acid compound may be appropriately copolymerized to form a carboxyl group-containing resin constituting the binder. Examples of such other monomers include a (meth)acrylic monomer having no functional group, a (meth)acrylic monomer having a polar functional group other than a carboxyl group, and (meth)acrylic acid. A monomer having a % acid group other than the system, a vinyl monomer other than the (meth)acrylic acid, and a monomer having a plurality of (fluorenyl) acrylonitrile groups in the molecule. Examples of the (meth)acrylic monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, and (mercapto)propylene 322672 11 201132505 acid propyl vinegar, Methyl acrylate n-butyl vinegar, (meth) acrylic acid &quot; oxyethyl ester, decyloxy polyethylene glycol (fluorenyl) acrylate, and the like. Examples of the polar functional group other than the ester group in the (meth)acrylic monomer having a polar functional group other than a carboxyl group include an amino group and a sulfonic acid group which are different from a hetero group, a heterocyclic group, and a heterocyclic ring. Cyano group, guanamine group and the like. Examples of the (fluorenyl) acrylic monomer having a hydroxyl group are: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , (mercapto)acrylic acid 2- or 3-gas-2-hydroxypropyl ester, ethylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (indenyl) ) Acrylate and the like. Examples of the (meth)acrylic monomer having a heterocyclic group include propylene morpholine, tetrahydrofurfuryl (meth) acrylate, and caprolactone modified tetrahydro hydrazine (meth) acrylate. A base ester, 3, 4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate or the like. An example of a (fluorenyl) acrylic monomer having an amine group different from a heterocyclic ring is given. N,N-monomethylaminoethyl (meth) acrylate, N,N-dimethylaminopropyl (decyl) propionate, N,N-dimethylaminopropyl Base (methyl) acrylamide and the like. An example of a (meth)acrylic monomer having a sulfonic acid group is as follows: 2-(methyl)propenylethanesulfonic acid, 2-(methyl)acrylonitrile-propionic acid, 2- (Methyl) acrylamide-2-methylpropanol ore and the like. Examples of the (meth)acrylic monomer having a cyano group include (meth)acrylonitrile and the like. Further, an example of a (meth)acrylic monomer having a guanamine group is given. (Methyl) acrylamide, N-substituted (meth) propanamide, and the like. Examples of the monomer having a sulfonic acid group other than the (meth)acrylic acid include vinylsulfonic acid and styrenesulfonic acid. It should be noted that the package 12 322672 201132505 contains the above (meth)acrylic monomer having a sulfonic acid group, and the sulfonic acid group in the monomer may be an alkali metal salt represented by a lithium salt, a sodium salt and a potassium salt or A form of a salt such as an ammonium salt. Examples of the vinyl monomer other than the (meth)acrylic acid include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate. Fatty acid vinyl esters; dentate ethylene such as ethylene chloride and ethylene bromide; partially functionalized ethylene such as vinylidene chloride; 2-, 3- or 4-vinylpyridine, and N-vinylcarbazole Nitrogen-containing aromatic vinyl such as conjugated diene monomer such as butadiene, isoprene, and aerodene; N-vinyl-2-pyrrolidone, and N-vinyl caprolactone A cyclic guanamine or ether having a vinyl bond such as an amine. Examples of the monomer having a plurality of (fluorenyl) acrylonitrile groups in the molecule are: 1,4-butanediol bis(indenyl) acrylate; [6-hexanediol bis(A) Acrylate, 1,9-nonanediol bis(indenyl) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol a monomer having two (indenyl) acrylonitrile groups in the molecule such as (meth) acrylate, polyethylene glycol bis(indenyl) acrylate, and tripropylene glycol bis(indenyl) acrylate; A monomer having three (fluorenyl) acrylonitrile groups in the molecule, such as hydroxymethylpropane tri(indenyl) acrylate. The carboxyl group-containing resin contained in the adhesive composition preferably has a suitable degree of polymerization. For example, when a 5% by weight aqueous solution is formed, the viscosity is preferably from 3 to 300 raPa. Within the scope of Sec, it is further suitable to be 5 to 1 〇〇 mPa. Within the scope of sec. The adhesive composition which can be used in the present invention may of course be an adhesive composition comprising the above-mentioned slow-resin-containing resin of 322672 13 201132505 or more. The ruthenium-containing resin constituting the adhesive layer 2 can be produced, for example, by various known methods such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, or a suspension polymerization method. In the production of the carboxyl group-containing resin, a polymerization initiator is usually used. The polymerization initiator is used in an amount of 1 part by weight based on the total of all monomers usable in the production of the carboxyl group-containing resin. 001 to 5 parts by weight or so. As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used depending on the method of imparting energy at the time of polymerization. Examples of the photopolymerization initiator include 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone and the like. Further, examples of the thermal polymerization initiator include: 2, 2, azobisisobutyronitrile, 2,2,-azobis(2-mercaptobutyronitrile); [,! ,-azobis(cyclohexane-b-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2,-azobis(2,4-dimethyl —4-methoxyvaleronitrile, dimercapto-2, 2,-azobis(2-methylpropionate), 2,2,-azobis(2-hydroxymethylpropionitrile), 2 , 2, _ azobis(2-methylpropionamidine) hydrochloride, and 2,2,, nitrogen bis(i-imide group, such as 嘻 嘻 1 1 甲基 甲基 甲基 甲基 甲基 1 1 1 1 Peroxidation (tetra) hydrazine, tertiary butyl hydroperoxide, tertiary butyl benzoyl peroxide, tertiary carboxylic acid, tertiary butyl vinegar, cumene hydroperoxide, diperoxydicarbonate , Dipropyl propylene dicarboxylate, peroxidic neodecanoic acid tertiary vinegar, over-emulsified new money, and organic peroxides such as 3,5,5_; persulfate In the production of a slow-reacting resin, it is preferable to use the above-mentioned inorganic peroxides such as peroxidation, etc., in addition to oxidation-reduction (4) (4), which can also be used as a polymerization initiator. The method of the 201132505 bath "method. If the appropriate solution polymerization method is specified, the target body and water, root According to the situation, the alcohol solvent is mixed, and the thermal polymerization initiator is added under 40 to 1 〇 (circle of rc: level. Mix about 3 to 10 hours to 90: to: in the polymerization Continuous or intermittent addition of the green body and the fat should be in the range of 1 (four) parts by weight, in the range of the reading of the base tree within the range of the weight of the heart, the range of the weight of the two parts. There is a tendency that the adhesion is easy to decrease, /, the concentration is too large, and the obtained umbrella and the direction are used. For the composition of the adhesive:: == average =: hair but in the middle of the wealth solution. The composition of the transfer agent layer 2_(4), the adhesion between the pure solder layer 2 and the panel 1, preferably containing the Shixi burning couple = coupling agent may be bonded to the (4) sub-group of the decomposing group of the oxy group A compound having an organic group having a reactive functional group such as a phenyl group, an amine group, an epoxy group, a 322672 201132505 haloalkyl group, a (meth) acryl fluorenyl group, or a fluorenyl group is bonded as a decane having a vinyl group. Specific examples of the coupling agent include: vinyl trimethoxy decane, vinyl triethoxy decane, vinyl (2-methoxyethoxy) decane, etc. Specific examples of the decane coupling agent having an amine group include: N-(2-aminoethyl)-3-aminopropyl decyl decyloxydecane, N-(2-Aminoethyl)-3_-aminopropyltrimethoxy decane, 3-aminopropyldimethoxy decane, 3-aminopropyltriethoxydecane, etc. as an epoxy group Specific examples of the decane coupling agent include: 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropylmethyldi Methoxy cleavage, 3_glycidoxypropyl decyloxymethyl decane, 3-glycidoxypropyl ethoxy dimethyl decane, 2_(3, 4 oxalocyclohexyl) Ethyltrimethoxy (tetra) and the like. Specific examples of the Shihua burning coupling agent having a (tetra) group include: 3-propyl fluorenyldimethoxyne, 3-cyclopropyltrimethoxy decane, and the like. Specific examples of the decane coupling agent having a (fluorenyl) acrylonitrile group include 3-(meth)acryloxypropyltrimethoxy-steryl or the like. Further, as a specific example of the decane coupling agent having a mercapto group, 3-sulfopropyltrimethoxysulfanium or the like is contained. It is possible to use two or more kinds of Shixia coupling agents in combination. Among them, if considering the solubility in water or the usable time (effective time) as an adhesive, it is preferably a decane coupling agent having an epoxy group, for example, 3-glycidoxypropyltrimethoxylate. Xiyuan is one of the appropriate Shixi appearance coupling agents. The decane coupling agent may be an organic fluorenone oligomer type. When the organic fluorenone oligomer is represented by a (monomer)-(monomer) copolymer, for example, the following may be mentioned. 16 322672 201132505 3-Mercaptopropyltrimethoxydecane-tetradecyloxydecane copolymer, 3-mercaptopropyltrimethoxyoxymethanol-tetraethoxycalcined copolymer, 3-isopropylpropyltriethoxy a fluorenyl-containing copolymer such as a decyl-tetradecyloxydecane copolymer and a 3-mercaptopropyltriethoxydecane-tetraethoxydecane copolymer; decyltrimethoxy decane-four a decyloxydecane copolymer, a fluorenylmethyltrimethoxydecane-tetraethoxydecane copolymer, a decyltriethoxydecane-tetradecyloxydecane copolymer, and a fluorenylmethyltriethoxydecane-four a mercapto group-containing copolymer such as an ethoxylated decane copolymer; a 3-methacryloxypropyltrimethoxy decane-tetradecyloxydecane copolymer; 3-mercaptopropene methoxypropane Trimethoxy decane-tetraethoxy decane copolymer, 3-methacryloxypropyltriethoxy decane-tetradecyloxydecane copolymer, 3-mercaptopropenyloxypropyltriethyl Oxydecane-tetraethoxydecane copolymer, 3-methylpropenyloxypropyl-decyldimethoxydecane-tetradecyloxydecane copolymer, 3-mercaptopropenyloxypropyl Dimethoxy decane-tetraethoxy decane copolymer, 3-mercapto propylene methoxy propyl fluorenyl diethoxy decane-tetradecyl decane copolymer and 3-mercapto propylene methoxy propylene Copolymer containing fluorenyl propylene oxypropyl group such as fluorenyl diethoxy decane-tetraethoxy decane copolymer; 3- propyleneoxy methoxy propyl trimethoxy sulphur - tetramethoxy Base stone smelting copolymer, 3-propenyl oxypropyltrimethoxy oxy-stone-sinter-tetraethoxy sulphuric acid copolymer, 3_ propylene sulfoxypropyl triethoxy sulphide-tetradecyl oxy-stone Copolymer, 3-propenyl methoxypropyltriethoxydecane-tetraethoxydecane copolymer, 3-propenyl methoxypropyl decyl dimethoxy decane-tetradecyl decane copolymer, 3-propene Brewed oxypropyl decyl dimethoxy-degraded-tetraethoxy pulverized copolymer, 3-propylene propylene 17 322672 201132505 oxiranyl decyl diethoxy decane-tetradecyl decane copolymer and 3 -Acetyloxypropyl-containing copolymer such as propylene oxypropylmethyldiethoxy decane-tetraethoxydecane copolymer; vinyl trimethoxy decane-tetradecyl decane copolymer , vinyl trimethoxy decane-tetraethoxy decane copolymer, vinyl triethoxy decane _ tetramethoxy decane copolymer, vinyl triethoxy decane - tetraethoxy decane copolymer, vinyl Methyl dimethoxy decane-tetradecyl decane copolymer, vinyl decyl decyl decane-tetraethoxy decane copolymer, vinyl methyl diethoxy decane - tetradecyl decane copolymer And a vinyl group-containing copolymer such as a vinyl methyldiethoxydecane-tetraethoxydecane copolymer; a 3-aminopropyltrimethoxy decane-tetramethoxydecane copolymer, 3 -Aminopropyltrimethoxydecane-tetraethoxydecane copolymer, 3-aminopropyltriethoxydecane-tetradecyloxydecane copolymer, 3-aminopropyltriethoxydecane- Tetraethoxy decane copolymer, 3-aminopropyl decyl decyloxy decane-tetradecyloxycalcined copolymer, 3-aminopropyl decyl bisoxy oxy sulphide _ tetraethoxy Decane copolymer, 3-aminopropylmethyldiethoxydecane-tetramethoxydecane copolymer and 3-aminopropylmethyldiethoxydecane-tetraethoxydecane An amine group-containing copolymer or the like such as a copolymer. Since these decane coupling agents are mostly liquid, they can be directly mixed in the cutting liquid containing the silk-containing resin, and the compound 4 of the stagnation coupling agent in the adhesive composition is compared with the slow-based tree. 〇〇 by weight, usually 0. 01 to 200 parts by weight or so. The amount of the sulphur coupling agent to be used in an amount of preferably 100 parts by weight or less, more preferably 100 parts by weight or less, particularly preferably 50 parts by weight or less, and 322,672, 18, Is 0.  03 parts by weight or more. By using a weight ratio of the carboxyl group-containing resin loo to match the stone smelting coupling agent.  01 parts by weight or more, especially 〇.  When the amount is more than 3 parts by weight, the effect of improving the adhesion between the adhesive layer 2 and the glass sheet 1 can be exhibited. Though it differs depending on the kind of the carboxyl group-containing resin and the decane coupling agent, for example, for the effect of maintaining the internal adhesion even in the thermal shock test, the Shi Xi Xuan coupling agent is used with respect to 100 parts by weight of the carboxyl group-containing resin. This effect can be further improved by setting the amount to be about 30 parts by weight or about 50 parts by weight. However, if the amount of the decane coupling agent is too large, the decane coupling agent may bleed out from the binder layer 2, and it is preferable to set it as a non-bleeding amount. The binder composition for forming the adhesive layer 2 in the present invention may further contain a crosslinking agent. The crosslinking agent may be blended in an aqueous solution of a human carboxy resin containing no decane coupling agent, or may be blended with an oxane coupling agent in an aqueous solution of an octacycline resin. In general, it is preferred to include a crosslinking agent in addition to the sulphur coupling agent. The crosslinking agent may be a compound having at least two functional groups reactive with a carboxyl group-containing resin in the molecule. The functional group constituting the crosslinking agent is coated with human isocyanato group (-NCO); epoxy group (crosslinked; hydroxyl group (_〇H), group (-CONHNH2), oxazoline group (cyclic-CsHAO) In addition, a salt of a divalent, trivalent or tetravalent metal such as magnesium, calcium, iron, nickel, zinc, aluminum, titanium or zirconium may also be a crosslinking agent. As a crosslinking agent having an isocyanate group Examples of the ear (isocyanate compound) include: anthraquinone diisocyanate, hydrogenated toluene diisocyanate, monomethyl propylene oxide and methyl benzene diisocyanate adduct, diphenyl hydrazine diene 妒 322672 19 201132505酉曰-methane methane triisocyanate, ketones of isophora _ block, etc. Specific examples of two chemicals (epoxy compounds) are: B = crosslinked dipropyl = = = Wei Di-glycidyl- or glycerol tri-glycidyl (tetra), diglycidylaniline, di-condensed; polyamine-polyamine and epichlorohydrin of the reaction of polyalkylene and di-dioxide ^ = = :=:: As a __ composition and a resin containing a county dissolved in water to form an adhesive, as described below, the content of the agent is very good, so, for example, such as If the water has a solubility of at least 〇1, then (4) the side (4). Of course, riding a compound called water; := m has solubility in water, and it is more suitable to use the amount of cross-linking in the present invention. The amount of ΐθθ of the carboxyl group-containing resin is usually 〇 depending on the type of the resin contained in the county, and the like. 丨 to 6 〇 Weighing about 0 parts, preferably 1 to 5G parts by weight. By blending the crosslinking agent in this range, good adhesion can be obtained. When the amount of the crosslinking agent is too large, the reaction of the crosslinking agent proceeds in a short time, and the composition of the adhesive has a tendency to gel at an early stage, and the county can be used as an adhesive (the effective time is obtained). It is very short and is not suitable for industrial production. In the adhesive composition, an additive of 322672 20 201132505, which is currently known, such as a plasticizer, an antistatic agent, or a fine particle, may be blended in a range which does not impair the effects of the present invention. [Adhesive Layer] In the present invention, the above-described adhesive composition is preferably provided on the 'surfaces' of the bonding surfaces of the glass sheet 1 and the plastic sheet 3, and the above components are preferably blended. The layer of the adhesive composition composed of the aqueous solution is bonded to the glass sheet 1 and the plastic sheet 3 through the joint composition, and the layer of the adhesive is cured to form the adhesive layer 2. The thickness of the adhesive layer 2 can be determined to be 5#m or less, usually 0. 001 to 5&quot;111 or so should be 〇二二ΐ ΐ: 〇·05 to 2&quot;m or 0.  Range of °5 to 1&quot;m. Bonding [Slope _ may cause poor appearance of the plastic sheet 3. The glass plate of the plastic sheet 3 is bonded to the glass sheet of the plastic sheet 3 by using the adhesive layer 2. As described above, the present invention is particularly useful in the case of a liquid crystal cell substrate in which a liquid crystal is formed. Element: two substrates f are held between another substrate, and the liquid crystal is formed to constitute a liquid crystal unit. The core component of the nano SI: crystal display device can be used. Glass slab 1 is generally known for all kinds of money, such as money, no (four) acid acid broken glass, etc. [Plastic sheet] board, liquid crystal unit is particularly suitable for use without inspection. The plastic sheet 3 bonded to the glass sheet 1 by the St layer 2 is used as long as it is a slab of water. (4) The ability to connect _ grease becomes a paste to use a slow-base tree, and can be used without limitation. The ability to produce impurities is exemplified by cellulose acetate or cellulose diacetate, cellulose acetate propionate 322672 21 201132505 cellulose acetate butyrate resin, etc.; polyethylene glycol resin, cycloolefin resin, A chain-like flue-cured resin represented by a polypropylene resin; a polyethylene terephthalate ethyl ester resin; an acrylic resin. Among them, the cellulose acetate-based resin or the polyvinyl alcohol-based resin is a plastic sheet attached to the bonding surface of the glass sheet 1 and exhibits high adhesion to the glass sheet 1 via an adhesive composed of an aqueous solution containing a carboxyl group-containing resin. . If necessary, the surface of the plastic sheet 3 to be bonded to the glass sheet 1 may be subjected to an easy adhesion treatment by a saponification treatment or a corona discharge treatment, and may be used for the formation of the adhesive layer and the glass. The bonding of the board 1. For example, when the acetic acid or cellulose-based resin is applied to the bonding surface of the glass sheet 1, the saponification treatment is applied to the surface to further improve the adhesion of the aqueous solution of the carboxyl group-containing resin. In addition, even when the chain olefin-based resin represented by the silicone resin or the chain-like olefin resin represented by the polypropylene resin is applied to the bonding surface of the glass plate 1, it is easy to perform corona discharge treatment on the surface thereof. The adhesion treatment can also exhibit high adhesion of an aqueous solution containing a carboxyl resin. The thickness ' of the plastic sheet 3' is not particularly limited as long as it can be attached to the glass sheet i, and it is preferable to apply it to the glass sheet 1 in a state of being rolled into a parent shape, so that flexibility is also considered. The isochronous amount is usually preferably 500/zm or less, more preferably 300 // m or less, and particularly preferably 200 or less. <Polarizing Plate> As described above, the optical layered body of the present invention is a liquid crystal cell substrate in the first embodiment, and the plastic sheet 3 has a dichroic dye adsorbed on the polyethylene resin. The polarizing plate of the polarizing film oriented is particularly useful for 322672 22 201132505. It is also possible to separately form the polarizing film itself as the plastic sheet 3', but since the polarizing film is fragile when used alone, it is preferable to use at least one side of the bowl, particularly the surface to be bonded to the liquid crystal cell substrate 1. A polarizing plate having a transparent protective layer is provided on the opposite side. Fig. 2 is a schematic cross-sectional view showing one state of a layer configuration of an optical layered body of the present invention. In this embodiment, a transparent protective layer 7 is provided on one surface of the polarizing film 6 to form the polarizing plate 5, and the surface of the polarizing film 6 on the opposite side to the surface on which the transparent protective layer 7 is provided is directly bonded to the liquid crystal via the adhesive layer 2. The optical laminate 11 is formed on the unit substrate 1. In other words, in the optical layered body 11 of Fig. 2, the polarizing film 6 is laminated on the glass sheet 1 in contact with the adhesive layer 2, and the surface of the polarizing film 6 on the opposite side to the adhesive layer 2 is formed. The transparent protective layer 7 is laminated. Fig. 3 is a schematic cross-sectional view showing another layer configuration of the optical layered body of the present invention. In this embodiment, a transparent protective layer 7' is provided on one surface of the polarizing film 6, and an appropriate resin layer 8 is provided on the other surface of the polarizing film 6 to form a polarizing plate 5'. The resin layer 8 side is bonded via the adhesive layer 2 On the liquid crystal cell substrate 1, an optical laminate is formed. 12. In this way, the polarizing plate 5 may further have any layer as long as it includes the polarizing film 6. However, from the viewpoint of thinning the optical layered body or the liquid crystal panel while protecting the polarizing film 6, the layer other than the polarizing film 6 is preferably two layers. Hereinafter, it is particularly preferable to be one layer or two layers. From such a viewpoint, as shown in FIG. 2, the transparent protective layer 7 is provided on one surface of the polarizing film 6, and the polyvinyl alcohol-based resin film surface (polarizing film surface) on the opposite side to the transparent protective layer 7 is adhered. The form in which the adhesive layer 2 is directly bonded to the liquid crystal cell substrate 1 is one of 23 322672 201132505. When the form as shown in Fig. 2 is employed, it depends on the type of the transparent protective layer 7, but the thickness of the polarizing plate 5 can be set to, for example, 100 / z m or less. <Polarizing film> The polarizing film 6 constituting the polarizing plate 5 is obtained by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin. More specifically, a film obtained by adsorbing and orienting a dichroic dye on a uniaxially stretched polyvinyl alcohol resin film is preferably used. The polyvinyl alcohol-based resin constituting the polarizing film can be obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith can be exemplified. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, and vinyl ethers. The degree of saponification of the polyvinyl alcohol-based resin is usually from about 85 to 100 mol%, preferably from 98 to 100 mol%. The polyvinyl alcohol-based resin constituting the polarizing film may be further modified. For example, polyvinyl acetal or polyvinyl acetal modified with an aldehyde may be used as the polyvinyl alcohol-based resin. The degree of polymerization of the polyvinyl alcohol-based resin constituting the polarizing film is usually from about 1,000 to 10,000, preferably from about 1,500 to 10,000. A film made of such a polyvinyl alcohol-based resin can be used as an unprocessed film of a polarizing film. The method of forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film formation can be carried out by a known method. The film thickness of the polyvinyl alcohol-based unprocessed film is not particularly limited and is, for example, about 10 #m to 150 // m. 24 322672 201132505 The polarizing film is usually produced by the steps of uniaxially stretching a raw film made of a polyvinyl alcohol-based resin, and dyeing the polyvinyl alcohol-based resin film with a dichroic dye. Further, the step of adsorbing the coloring dye, the step of treating the polyvinyl alcohol meniscus film to which the dichroic dye is adsorbed, and the step of washing with water after the acid water are carried out. — Uniaxial stretching can be carried out before dyeing with a dichroic dye, and simultaneous dyeing with two-color Z can also be carried out after dyeing. In the case of uniaxial stretching by stretching, the uniaxial addition &gt;S&quot;&quot; before treatment can also be carried out in the treatment. The line is uniaxially stretched at the stage. The uniaxial stretching is carried out with the hot parent, and the L stretching is also possible. Further, Mm W which may be pulled in the atmosphere or the like may be stretched and stretched in a state in which the stalk is swollen. The draw ratio is usually about 3 to 8 times. For the dyeing of the polyvinyl alcohol-based resin film, for example, the vinyl alcohol-based resin film may be impregnated into an aqueous solution containing a dichroic dye. As the dichroic dye, an organic dye such as iodine or a dichroic dye can be used. = It is to be noted that the polyvinyl alcohol-based resin film is preferably subjected to an impregnation treatment in water before the dyeing treatment. When a dish is used as the dichroic dye, it is usually subjected to a method of impregnating a polyvinyl alcohol-based resin film in an aqueous solution containing: and potassium iodide. The content of (iv) in the aqueous solution is usually about 5 weights of damage relative to 1 GG by weight of water. In addition, the content of hydrazine unloading is usually 0% with respect to water 1 〇〇 322672 25 201132505 parts by weight.  5 to 10 parts by weight or so. The temperature of the aqueous solution used for dyeing is usually about 20 to 40 ° C, and the dipping time (dyeing time) in the aqueous solution is usually about 30 to 300 seconds. On the other hand, when a dichroic organic dye is used as the dichroic dye, the dyeing is usually carried out by a method of impregnating the polyvinyl alcohol-based resin film in an aqueous dye solution containing a water-soluble dichroic organic dye. The content of the dichroic organic dye in the aqueous dye solution is usually 1 x 1 (T3 to lx1 (about 2 parts by weight) per 100 parts by weight of water. The aqueous dye solution may also contain an inorganic salt such as sodium sulfate as a dyeing assistant. The temperature is usually about 20 to 80 ° C, and the dipping time (dyeing time) in the dye aqueous solution is usually about 30 to 300 seconds. The boric acid treatment after dyeing with the dichroic dye is carried out by dyeing. The polyvinyl alcohol-based resin film is impregnated in a boric acid-containing aqueous solution. The boric acid content in the boric acid-containing aqueous solution is usually from 2 to 15 parts by weight, preferably from 5 to 12 parts by weight, based on 100 parts by weight of water. In the case of a dichroic dye, the aqueous solution containing boric acid preferably further contains potassium iodide. In this case, the content of potassium iodide in the aqueous solution containing boric acid is usually about 2 to 20 parts by weight, preferably 5, based on 100 parts by weight of water. To 15 parts by weight, the impregnation time in the aqueous solution containing boric acid is usually about 100 to 1200 seconds, preferably about 150 to 600 seconds, more preferably about 200 to 400 seconds. The temperature of the aqueous solution is usually 50 ° C or higher, preferably 50 to 85 X. The polyvinyl alcohol resin film after the boric acid treatment is usually subjected to a water washing treatment. The water washing treatment is, for example, by impregnating a boric acid treated polyvinyl alcohol resin film. 26 322672 201132505 It is implemented in water. The temperature of the water in the water washing treatment is usually 5 to 5%-right, and the immersion time is about 2 to 120 seconds. After washing, it is dried; &quot; . A polarizing film was obtained. Drying can be carried out using a hot air dryer or a far infrared heater. The drying temperature is usually from 4 Torr to 1 Torr (the time of rc & usually is about 120 to _ second. As described above, the secret can be made to adsorb a dichroic dye on a uniaxially stretched polyvinyl alcohol resin film. The polarizing enthalpy obtained by orienting it may be set to a thickness of about 5 to 4 Å. <Transparent protective layer> The transparent protective layer 7 provided on at least one side of the polarizing film 6 may be, for example, cellulose acetate. A resin, a cycloolefin resin, a chain olefin resin represented by a polypropylene resin, an acrylic resin typified by a polydecyl acrylate resin, a polyimide resin, or a polycarbonate resin. A polyester-based resin typified by a polyethylene terephthalate-based ethylenic resin, or the like, which is widely used as a material for forming a protective layer in the art. Further, the transparent protective film 7 can also be composed of The cured structure of the active energy ray-curable resin composition. From the viewpoint of mass productivity and adhesion, it is preferable to use a cellulose acetate resin, a cycloolefin resin, a chain olefin resin, or the like. A film formed of an olefinic resin or a polyester resin or a cured product of an active energy ray-curable resin composition is used as the transparent protective layer 7. When the transparent protective layer 7 is composed of a thermoplastic resin film, the thickness is usually 10 to 80. It is preferable to form a thin layer of about 1 to 50 ym on the other hand. On the other hand, in the case where the active energy ray-curable resin composition is cured, 27 322672 201132505 constitutes the transparent protective layer 7, the thickness thereof is The cellulose acetate-based resin film used as the transparent protective layer 7 is a film composed of a part or all of the cellulose acetate of the transparent protective layer 7, and examples thereof include, for example, three. A cellulose acetate film, a cellulose diacetate film, etc. As such a cellulose acetate-based resin film, a commercially available product can be used, and for example, "FUJITAC TD80&quot;, &quot;FUJITAC sold by Fujifilm Co., Ltd. can be used. TD80UF&quot; and &quot;FUJITACTD80UZ&quot;; by Kony. &quot;KC8UX2M&quot;&amp;MKC8UY&quot; (all are trade names) sold by Kamengda Precision Chemical Co., Ltd. The ring-type flue-cured resin used for the transparent protective layer 7 is composed of a cyclic olefin (cycloolefin) such as norbornene or tetracyclododecene (alias: dimethicone) or a derivative thereof. A thermoplastic resin of a monomer unit (also referred to as a thermoplastic thin-smoke resin). The ring-thin resin may be a hydrogenated product of a ring-opening polymer of the above-mentioned ring-dilute hydrocarbon or a hydrogenated product of a ring-opening copolymer of two or more kinds of cycloolefins, and may be a cyclic olefin or a chain. An addition copolymer formed of an olefin and/or an aromatic compound having a vinyl group or the like. A polar group can be introduced into the cycloolefin resin. When the transparent protective layer 7 is formed by using an addition copolymer of a cyclic olefin and a chain olefin and/or an aromatic compound having a vinyl group, the chain-like hydrocarbons may be exemplified by ethylene, propylene, etc. Examples of the aromatic compound having a vinyl group include styrene, styrene, and phenol. The monomer unit composed of the like-like silk &apos; hydrocarbon may be 50 mol% or less (preferably 15 i 5 mol%). Particularly in the case of using a ternary 322672 28 201132505 polymer of a cycloolefin, a olefin, and a compound having a vinyl group to form the transparent protective layer 7, the monomer π composed of a cycloaliphatic hydrocarbon can be δ as described above. Said a relatively small amount. In such a ternary substance, a monomer unit composed of a chain olefin and a monomer unit composed of a group compound are usually 5 to a monomole ring olefin-based resin, and a suitable commercial product can be used, for example: Draw the ADVANCED _ERS Gmb_ manufactured by Japanese ρ. (4) If (6) is sold by the company, T〇PAS&quot;, &quot;Foot N&quot; sold by 〖SR Co., Ltd., &quot;Z_R &&quot;ze〇 group sold by Japanese ΖΕΟΝ 式 杜 Du, by Mitsui Chemicals &quot;ships (all trade names) sold by the club. When such a ring-thin-type resin is produced, a known method such as dissolution, extension, or the like can be suitably employed. In addition, as for example, a film of a commercially available cycloolefin-based resin which has been previously prepared by using a "ZE_R film" sold by Nippon Co., Ltd., or a "N-N film" sold by Nippon Co., Ltd., may be used as a transparent protection. Layer 7. The chain olefin-based resin used for the transparent protective layer 7 is preferably a polypropylene-based resin mainly composed of propylene. The polypropylene-based resin may be a homopolymer of a propyl group, or may be a copolymer of propylene and another copolymerizable monomer represented by a berry. The polymerization of other copolymerizable monomers is About 10% by weight, for example, 丨 to about 1% by weight. Polypropylene tree The cerium can also be formed into a film for the transparent protective layer 7 by a known method such as a solvent casting method or a melt extrusion method. The acrylic resin used for the transparent protective layer 7 is preferably a polymethyl methacrylate-based resin which is a main constituent unit of decyl acrylate. In the mercaptopropionate-based resin, acrylic rubber particles may be blended. In addition, it is sometimes made into a polymethyl acrylate vinegar system with a light diffusing agent, 29 322672 201132505 = 3 =: a light diffusing agent, a poly(methacrylic acid) acetal resin extrusion method; When the methacrylic resin is usually melted to form a multilayer structure, a coextrusion method can be employed. The polyester-based resin of the acetaminophen 7 is preferably a polyethylene terephthalate ethyl ester resin having a main constituent unit of terephthalic acid and bis. The di-acid (E) resin such as poly-method can also be formed into a film by the method of melt-casting and melt-extrusion, and the film can be uniaxially or biaxially drawn (4) to maintain the strength while improving the transparency. The film should be used as a through-the-money 5 for 5 months. On the other hand, the active energy ray-curable resin composition for the transparent protective layer 7 may be, for example, a resin composition containing an epoxy-based active energy ray-curable compound, and further blended with an oxetane. ^The object is also effective. When the epoxy compound is contained in this manner and the oxygen ring-containing T-sinter compound is optionally contained, a neocation polymerization initiator is usually blended. The active energy ray-curable resin composition for the transparent protective genus 7 contains a radical polymerizable compound, specifically (meth)acrylic acid, in addition to the epoxy compound and the oxetane compound as an optional component. The compounds are also effective. By using a (meth)acrylic I compound in combination, a transparent protective layer having high hardness, excellent mechanical strength, and excellent durability can be obtained. Further, the viscosity, the curing rate, and the like of the active energy ray-curable tree sap composition can be adjusted more easily. In the active energy ray-curable resin composition for forming the transparent protective film 7, the (fluorenyl) acrylic compound can be added to 7 〇 322672 30 201132505 based on the total amount of the active energy ray-curable compound.  About weight%. The compounding amount of the (fluorenyl) acrylic compound is more preferably from 35 to 70% by weight, particularly preferably from 40 to 60% by weight. When the compounding amount of the (fluorenyl)acrylic compound exceeds 70% by weight, the adhesion to the polarizing film may be lowered. In the case of blending such a (fluorenyl) acrylic compound, a photoradical polymerization initiator may be further blended. The transparent protective film 7 of the polarizing plate 5 may have a surface treatment layer on the surface opposite to the surface on which the polarizing film 6 is bonded. Examples of such surface treatment include anti-glare treatment, hard coating treatment, antistatic treatment, and prevention. Reflection processing, etc. Further, a coating layer containing a liquid crystal compound or a high molecular weight compound or the like may be formed on the surface of the transparent protective layer 7 on the opposite side to the surface to which the polarizing film 6 is bonded. In the case where the transparent protective layer 7 is a resin film, the polarizing film 6 and the transparent protective layer 7 can be bonded together using an adhesive. Examples of the adhesive to be used for the bonding include a curable resin composition containing an active energy ray-curable compound, and a water-based adhesive obtained by dissolving or dispersing the binder component in water. From the viewpoint of not requiring a drying step and improving productivity, it is preferred to use a curable resin composition containing an active energy ray-curable compound as a binder. In this case, as the active energy ray-curable compound, an epoxy-based cationically polymerizable compound is preferably used. Further, in addition to the epoxy compound, it is also effective to carry out a cationically polymerizable oxetane compound. Thus, when an epoxy compound is contained and the oxetane compound is further optionally contained, a photocationic polymerization initiator can usually be blended. When the curable resin composition is used as a binder, the polarizing film 6 and the transparent protective layer 7 are usually bonded to each other via the curable resin composition layer, and then the composition is irradiated with activity 322672 31 201132505 ' Energy line to make the curable resin The composition layer is hardened. On the other hand, from the viewpoint of thinning the adhesive layer and thinning the entire polarizing plate 5, it is preferable to use a water-based adhesive in which the binder component is dissolved or dispersed in water. As such a water-based adhesive, a binder composition containing a polyethylene resin or a polyurethane resin as a main component can be mentioned. When a polyvinyl alcohol-based resin is used as a main component of a water-based adhesive, the polyvinyl alcohol-based resin may be an anion-modified polyvinyl alcohol system other than a partially saponified polyvinyl alcohol or a fully saponified polyvinyl alcohol. A modified polyvinyl alcohol-based resin such as a resin, an ethylene glycol-modified polyvinyl alcohol-based resin, a hydroxyindole-modified polyvinyl alcohol resin, or a cationically modified polyvinyl alcohol-based resin. In the case where a polyvinyl alcohol-based resin is used as the binder component, the binder is usually made into an aqueous solution of a polyvinyl alcohol-based resin. The concentration of the polyvinyl alcohol-based resin in the adhesive is usually about 1 to 10 parts by weight based on 1 part by weight of water, preferably! Up to 5 parts by weight. In addition, it is also effective to use a crosslinking agent in combination. <Resin layer disposed on the liquid crystal cell substrate side of the polarizing plate> As in the example shown in Fig. 3, when the resin layer 8 is slanted on the liquid crystal cell substrate i side of the polarizing film 6, the resin layer 8 may be disposed and polarized. The transparent protective layer 7 on the opposite side of the film 6 is the same or different from the transparent protective layer, and may be an optical functional layer. As an example of the optical functional layer, a phase difference plate used to compensate for a phase difference caused by a liquid crystal cell or to compensate a viewing angle or the like can be cited. Examples of the retardation film include a birefringent film composed of a stretched film of various resins, a film in which a discotic liquid crystal or a nematic liquid crystal is aligned, and a liquid crystal or inorganic layered compound formed on the film substrate. 322672 32 201132505 A coating film containing a phase difference material is used as a film to support a phase difference substance. It is preferable to use a cellulose substrate of cellulose acetate, such as cellulose triacetate, in the case of a birefringent gland composed of a residual phase of the tree, and it is preferable to consider the phase difference of the phase difference or the phase difference. A resin such as a cellulose acetate-based resin or a ring (four) is used as a resin material constituting the retardation film, and the resin constituting the transparent protective layer 7 as a resin constituting the transparent protective layer 7 itself and by heating the surface (four) (4) The same as ^lang. Poor, made of phase difference plate. This φ can be imparted to a U to 3 times in the case where the phase is preferably U to 3 times, and a cellulose acetate film which imparts a phase difference is also commercially available. For example, as a system for imparting a tether: = a resin film, there is a Konica Minolta strain = 4FR'r or &quot;KC_-T&quot;, etc. In the case of the company, the company is sold as a "film" sold by Japan's 2nd Co., Ltd., or a product sold by JSR Co., Ltd. The level. 16 also has a phase imparting adhesion to the polarizing film 6 and the resin by using the same adhesive as the above bonding film of the polarizing film 6 and the transparent protective layer 7 when the resin layer 8 is formed by the tree containing the phase difference plate. Layer 8. In the case where the turtle is attached to the polarizing plate 5 to give a phase difference due to the liquid crystal cell, a function of compensating the 322672 33 201132505 line, and a compensation view (four) Wei, the example shown in FIG. 3 is on the surface of the polarizing film 6. The transparent protective layer 7 is formed, and a phase difference plate as a resin layer 8 is laminated on the other surface of the polarizing film 6 to form a polarizing plate, and the phase difference plate side is bonded to the liquid crystal via the adhesive layer 2 described above. The H on the second board I is valid. Thus, even when the retardation film is laminated on the surface of the polarizing film 6 on the unit substrate 1 side, the thickness of the vibration plate 5 can be set to be lower. Further, the thickness of the entire polarizing plate 5 may be set to 1 〇〇 (4) as long as the entire dummy is properly applied: the layer 7 and the resin layer 8 serving as the phase difference plate. [Method for Producing Optical Laminate] A method for producing the optical layered body of the present invention will be described using a supply surface. ^The method of each step shown below can advantageously produce an optical laminate which is dead. Below, the description will be made. The step of forming the (a) adhesive composition layer formed by referring to FIG. 1 is carried out on at least one of the respective bonding faces of the glass plate and the plastics: a layer of an adhesive composition composed of an aqueous solution of a resin; (4) lb) a bonding step 'adhering the glass sheet 1 and the plastic sheet 3 through the layer of the adhesive composition; (〇 inspection step, checking the bonding step The obtained bonding %, f is taken out of the production line with the defective bonding product; and (d) the hardening step, so that the adhesive composition existing in the bonding product which has not detected the defect by the inspection step This method is particularly useful when the glass plate 1 is a liquid crystal cell substrate and the plastic plate 3 is a polarizing plate having a polarizing film described above, and the polarizing plate may be a separate polarizing film, or may be as described above. The polarizing film in which another layer is laminated in advance, as described above with reference to Figs. 2 and 3, preferably includes a transparent protective layer 7 formed on at least one surface of the polarizing film 6. Thus, at least a polarization layer is laminated. Polarization of film 6 and transparent protective layer 7 In the case of the plastic sheet 1, the plastic sheet 1 is formed in a state in which the respective layers constituting the polarizing plate 5 are laminated, and this is used for the above-described adhesive composition layer forming step (a). <Step of Forming Adhesive Composition Layer (a)&gt; In the adhesive composition layer forming step (a), at least one of the respective bonding faces of the glass plate 1 and the plastic sheet 3 On the surface, a layer of an adhesive composition comprising an aqueous solution containing a carboxyl group-containing resin is provided. When the adhesive layer is formed, for example, a bonding surface of the glass plate 1 and/or a bonding surface of the plastic sheet 3 can be used. A method of applying the above-mentioned adhesive composition. Alternatively, as one form of coating, a method in which the plastic sheet 3 is bonded to one end of the surface of the glass sheet 1 may be used. The adhesive composition is blown into the adhesive composition layer, and the adhesive composition layer is formed on the respective bonding faces of the glass plate 1 and the plastic sheet 3, and is pressed from the outside of the plastic sheet 3 by a roller, and continuously connected. The fitting step down. The sticker on the glass plate 1 The method of applying the adhesive composition on the surface of the surface and/or the plastic sheet 3 is not particularly limited, and for example, doctor blade coating, wire bar coating, slit coating, die coating, notch wheel coating, gravure coating, etc. may be used. Various coating methods. In addition, since each coating method has an optimum viscosity range, the adhesive composition (aqueous solution) can be adjusted by adjusting the concentration of the carboxyl group-containing resin 35 322672 201132505 in the adhesive composition. [Adhesion step (b)&gt; In the subsequent bonding step (b), the adhesive composition layer formed in the step (a) is formed via the front adhesive composition layer to the glass plate j It is bonded to the plastic sheet 3. In this step, it is advantageous to employ a method of feeding the plastic sheet 3 at one end of the surface of the glass sheet 1 via the adhesive composition layer as described above. , The film is bonded while being pressed from the outside of the plastic sheet 3 by a roll. From the viewpoint of suppressing the entrapment of the bubble, etc., it is advantageous to adhere to the other end of the surface of the glass sheet 1 from the one end of the surface of the glass sheet 1 while being pressed. <Inspection Step (c)&gt; In the inspection step (c), the laminate obtained in the previous bonding step (13) is inspected to take out the defective laminate and take it out of the production line. Of course, as long as no defects are detected, the fittings are sent directly to the subsequent hardening step (d). In the inspection step (c), it is possible to check for surface damage, presence or absence of foreign matter, presence or absence of bubbles, presence or absence of axial misalignment, and the like. This inspection can be carried out by the usual method used in the manufacturing stage of the liquid crystal panel. The inspection product in which the defect is found in the inspection step (c) is taken out of the production line. At this stage, since the layer of the adhesive composition composed of the aqueous solution containing the carboxyl group-containing resin is not yet hardened, the plastic sheet 3 can be easily peeled off from the glass sheet 1. Therefore, the glass sheet 1 from which the plastic sheet 3 is peeled off can be easily removed by water washing or the like, so that it can be returned to the adhesive composition layer forming step (a) after washing. Remove the defective defect in the inspection step (c) out of the production line, and peel off the plastic sheet from it. 3 36 322672 201132505 • Return the glass sheet 1 to the adhesive composition layer forming step (a) Operation - equivalent to rew〇rk operation, that is, after bonding the polarizing plate with the adhesive layer to the liquid crystal cell substrate, peeling off the polarizing plate and re-applying it if there is any unsuitability Hehe. In the present invention, although the adhesive (4) is used to bond the plastic #3 (typically a polarizing plate) to the glass plate 1 (typically a liquid crystal cell substrate), the adhesive is an aqueous solution. Therefore, there is an advantage that it is easy to perform such a rework operation. <hardening step (d)&gt; For a qualified laminate in which no defect is detected in the inspection step (c), in the subsequent hardening step (d), it is present between the glass sheet and the plastic sheet 3. The adhesive composition layer hardens. In the hardening step, the adhesive composition layer is cured by high-temperature drying, irradiation with an active energy ray, or the like to form the adhesive layer 2. The hardening of the composition layer of the adhesive is mostly carried out by high temperature drying. When drying at a high temperature, the temperature is preferably in the range of about 40 to 80 °C. The active energy ray used may be ultraviolet rays, X-rays, electron energy rays or the like when it is hardened by irradiation. Further, there is a method of hardening the adhesive composition layer by standing at a normal temperature. In the case where the adhesive composition layer is hardened by high-temperature drying, the treatment is usually preferably 40. (: 1 minute to 24 hours at 80 ° C. In the case where the adhesive composition layer is hardened by irradiation with an active energy ray, ultraviolet rays are usually used, and accumulation in terms of product of irradiation illuminance and irradiation time is preferable. The amount of light is set to 5 〇 to 2 〇〇〇 mj/cm 2. When the layer of the adhesive composition is hardened by standing at room temperature, the treatment is usually preferably 2 〇. &lt;5 (: to 30 ° C, humidity of 20% to 80%, 〇 5 hours to 72 hours. [Liquid Crystal Display Device] 322672 37 201132505 The optical laminates 10 to 12 of the present invention are on the liquid crystal cell substrate 1 The other liquid crystal cell substrate is disposed on the side opposite to the surface on which the polarizing plate 5 is bonded, and the liquid crystal cell or the liquid crystal panel is formed as the liquid crystal cell or the liquid crystal panel. In the liquid crystal display device f, the liquid crystal display device f is mounted in a state in which liquid crystal is sealed between two liquid crystal cell substrates. The liquid crystal cell 7L itself is used as the liquid crystal cell substrate i in the first to third figures, and one or both of them are provided. The polarizing plate is bonded to the surface according to the present invention to form a liquid crystal surface. The optical material thermal shock test (4) of the present invention is excellent in durability, and therefore, the liquid crystal display device produced as described above is also subjected to a thermal shock test or the like. It is excellent in durability and can be made thinner and lighter. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is defined by the second embodiment. In the examples, the contents or amounts are indicated. Knife/, Unless otherwise specified, it is a weight basis. [Manufacturing Example 1] Container = reaction with a cold portion, a nitrogen gas introduction tube, a thermometer, and a stirrer = 1 part of a propylene portion and a polypropylene shaft, and the device was replaced with a nitrogen gas, and 4 was not contained. Oxygen' raises the internal temperature to 80 ° C. Then, 〇 2 parts =: (polymerization initiator) is dissolved in 2 parts of water, and the solution is added to the reaction valley II. Then, the temperature is 79 to the holding temperature 6 In the hour, the force of the water is adjusted to make the concentration of the polyglycolic acid acid. The viscosity of the obtained liquid is 52 mPa·sec. 夂 夂 [Production Example 2] Reaction with a cold tube, a nitrogen inlet tube, a thermometer, and a stirrer 322672 38 201132505 'In the container, add 870 parts of water and 100 parts of acrylic acid, replace the device with nitrogen to make it free of oxygen, and raise the internal temperature to 80. Then, 〇3 • part of potassium persulfate ( The polymerization initiator was dissolved in 30 parts of water, and the solution was all added to the reaction vessel, and further incubated at an internal temperature of 79 to 81 t for 6 hours, and finally water was added to adjust the concentration of the polyacrylic acid to 5%. The viscosity of the aqueous acrylic acid solution was 41 mPa·sec. [Production Example 3] With cooling 415 parts of water, 1 part of acrylic acid and 9.5 parts of itaconic acid were added to the reaction vessel of the tube, the nitrogen inlet tube, the thermometer and the stirrer, and the air in the device was replaced with nitrogen to make it free of oxygen, and at the same time The internal temperature is raised to 8 ° C. Then, 2 parts of potassium persulfate (polymerization initiator) is dissolved in 23 parts of water and the solution is completely added to the reaction vessel, and then the internal temperature is maintained at 79 to 81 ° C. After the hour, water was finally added, and the concentration of the acrylic acid/itaconic acid copolymer was adjusted to 5%. The obtained 5% aqueous solution of the acrylic acid/itaconic acid copolymer had a viscosity of 27 mPa·sec. [Production Example 4] 400 parts of water, 1 part of acrylic acid, and 6.2 parts of decyl acrylate were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirrer, and the air in the apparatus was replaced with nitrogen. It does not contain oxygen and raises the internal temperature to 80 °C. Then, 2 parts of potassium persulfate (polymerization initiator) was dissolved in 23 parts of water and the solution was entirely added to the reaction vessel. Further, the temperature was maintained at an internal temperature of 79 to 81 ° C for 6 hours, and finally water was added to adjust the concentration of the acrylic acid/acrylic acid acrylate copolymer to 5%. The viscosity of the obtained 5% aqueous solution of the acrylic acid/methyl acrylate copolymer was 29 mPa • sec ° 39 322672 201132505, [Example 1] . Preparation of water-based adhesive composition. 5% polyacrylic acid obtained in Production Example 1. In the aqueous solution, 3-glycidoxypropyltrimethoxy oxycarbazide as a oxime and a bubbling agent is mixed, and the solid weight ratio of the polypropylene crepe coupling agent is 1:0.2, and further The hydrazine was prepared by adding pure water to the mixture of 10 parts of water and 10 parts of polyacrylic acid to prepare an adhesive composition. (b) Preparation of optical laminate A transparent glass substrate (a substrate to be a liquid crystal cell substrate) was prepared, and the glass substrate was washed using an ultrasonic glass cleaner (manufactured by MICROTECH., Ltd.). In addition, a polarizing plate made of a protective film made of cellulose triacetate having a thickness of 4 〇 Am adhered to one surface of a polarizing film in which iodine is adsorbed on a polyvinyl alcohol film is attached to a polyvinyl alcohol-based adhesive (Sumitomo Chemical Co., Ltd.) Manufactured by the company, trade name "SR0661A-XNSY", thickness: about 70#m). The polarizing plate was cut into a square size of 10 cm×10 cm, and the adhesive composition prepared in the above (&amp;) was applied to the polarizing film surface not attached to the protective film and after the cleaning, within 30 minutes after preparation. One side of the glass substrate' and the adhesive surface is attached. This was allowed to stand at room temperature for 24 hours, and then dried at 60 ° C for 3 minutes to prepare an optical laminate. The thickness of the adhesive layer is about 0.1 m. [Example 2] The solid content ratio of the polyacrylic acid:decane coupling agent was changed to 1:0.3, and the adhesive composition was prepared by the same operation as in Example 1 (a). Further, an optical laminate was produced in the same manner as in Example 322672 40 201132505 1 (b) except that the adhesive composition was used. [Example 3] The solid content ratio of the polyacrylic acid: decane coupling agent was changed to 1:0. 4 ′ Others were prepared by the same operation as in Example 1 (a). Further, an optical laminate was produced in the same manner as in 1 (b) except that the adhesive composition was used. [Example 4] Using the 5% polyacrylic acid aqueous solution obtained in Production Example 2, the solid content ratio of the acrylic acid: decane coupling agent was 1: i to be mixed in the same manner as in the examples, and other examples were passed. The adhesive Z composition was prepared in the same manner as in Example 1 (a). Further, an optical layered body was produced in the same manner as in Example 1 (b) except that the adhesive composition was used. [Example 5] The 5% aqueous solution of the acrylic acid/itaconic acid copolymer obtained in Production Example 3 was mixed so that the solid content ratio of the copolymer: decane coupling agent was 1:0.2, and The adhesive composition was prepared by the same operation as in Example 1 (a). Further, an optical layered body was produced in the same manner as in Example 1 (b) except that the adhesive composition was used. [Example 6] The solid content ratio of the copolymer: decane coupling agent was changed to 1:0.3, and the adhesive composition was prepared by the same operation as in the first half of Example 5. Further, an optical layered body was produced in the same manner as in Example (b) except that the adhesive composition was used. [Example 7] 322672 201132505 t - A 5% aqueous solution of the acrylic acid/methyl acrylate copolymer obtained in Production Example 4 was used, and the solid content ratio of the copolymer: decane coupling agent was * 1: 〇 _ 3 The manner of mixing was carried out, except that the adhesive composition was prepared by the same operation as in Example 1 (a). Further, an optical layered body was produced in the same manner as in Example 1 (b) except that the adhesive composition was used. [Comparative Example 1] 20 ° / in polyvinylpyrrolidone. In the aqueous solution (manufactured by Nippon Shokubai Co., Ltd., trade name "K-85W"), 3 to glycidoxypropyltrimethoxy decane as a decane coupling agent is solidified with a polyvinylpyrrolidone decane coupling agent. The mixture was mixed in a manner of a weight ratio of 1:0.1, and further, by adding pure water to the mixture of 100 parts of polyvinylpyrrolidone in water, to prepare a binder composition. Using this adhesive composition, an optical laminate was produced in the same manner as in Example 1 (b). [Comparative Example 2] Instead of the adhesive composition composed of the polyacrylic acid aqueous solution, an acrylic adhesive having a thickness of 25/m was used, and the acrylic adhesive was used on one surface of the transparent glass substrate and in the examples. The same polarizing film surface which was not bonded to the polarizing plate protective film used in 1 was bonded. Then, at 5 〇. The high-pressure dad was treated at a pressure of 5 kg/cm 2 (about 0.5 MPa) for 20 minutes to prepare an optical laminate. [Comparative Example 3] An optical laminate 42 was produced in the same manner as in Example 1 (b) except for the binder composition composed of the polyacrylic acid aqueous solution, except that pure water was used. [Evaluation Test] (a) Durability Test The economical durability of the optical layered bodies produced in the above examples and comparative examples was evaluated by the following method. For the temperature at 8 进行. (When the heat resistance test is carried out for 1 hour under drying, the heat resistance test is carried out at a temperature of 6 (rc, relative humidity of 9〇% for 1 hour); and heating will be performed until 7 (rc) The state of the temperature is lowered to -35 ° C, and then the temperature is raised to 7 (the process of TC is used as a cycle (2 hours) and the cycle is repeated 6 times for the thermal shock test (indicated in the table as "HS test π") In the case, the optical laminates after the test were visually observed, and the results were classified according to the following criteria and summarized in Table 1. (Evaluation criteria for heat resistance, heat and humidity resistance test) ◎: No swelling or peeling was observed at all Change in appearance such as cracking of the polarizing film. 〇: The appearance change such as bulging, peeling, and cracking of the polarizing film is hardly observed. △: The appearance change such as bulging, peeling, and cracking of the polarizing film is slightly noticeable. Appearance changes such as bulging, peeling, and cracking of the polarizing film were apparent. (b) Evaluation of the workability The polarizing plate was bonded to the glass substrate, and after 3 hours (in Examples 1 to 7 and Comparative Examples 1 and 3) , in the third hour of the process of standing at room temperature for 24 hours, Further, in Comparative Example 2, in order to observe whether or not the polarizing plate can be peeled off from the glass substrate at a speed of 300 mm/min in the direction of 180 (reversely along the direction of the glass substrate surface) in the third hour after the completion of the high pressure dad treatment) The test piece was peeled off and the peeling test was performed, and the results were classified according to the following criteria and summarized in Table 1. 43 322672 201132505 % , (Reworkability evaluation standard) 〇: peelable. Table 1 _____________ * -1~- and polarizing plate $polarizing plate +i for heat and humidity resistance HS weight J1 Example No. Thickness test of adhesive wooding agent Test test Example 1 PAA substrate example 2 PAA Matrix Example 3 PAA Matrix Example 4 PAA Matrix Example 5 AIC Matrix Example 6 AIC Matrix Example 7 AMAC Matrix PVP Base i Comparative Example 2 Adhesive Comparative Example 3 System 屯# . //Μ y.// 3⁄4.仁ooooooo 7 7 7 7 7 7 7 //3⁄4.3⁄4 0 5 0 7 9 7 ◎◎◎◎◎◎◎ 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇△ 〇〇0X0 Wood PAA :Polyacrylic acid AIC: Acrylic/itaconic acid copolymer AMAC: Acrylic/propylene Methyl ester copolymer PVP: polyvinylpyrrolidone The optical laminates of Examples 1 to 7 are thin and excellent in durability and workability. On the other hand, a polyvinylpyrrolidone aqueous solution is used as a comparative example of the binder composition. The optical layered body of 1 was inferior in the durability test, and the optical layered body of Comparative Example 2 in which the acrylic adhesive was used for the adhesion of the glass and the polarizing plate was inferior in terms of thermal shock resistance and reworkability. Further, the optical laminate of Comparative Example 3 in which pure water was used for the adhesive was inferior in heat resistance and thermal shock resistance. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing the configuration of a basic layer of an optical layered body of the present invention. 44 322672 201132505. Fig. 2 is a schematic cross-sectional view showing a layer configuration of the optical layered body of the present invention. Fig. 3 is a schematic cross-sectional view showing another layer constitution of the optical layered body of the present invention. [Description of main component symbols] 1 Glass plate (liquid crystal early substrate) 2 Adhesive layer 3 Plastic sheet 5 Polarizing plate 6 Polarizing film 7 Transparent protective layer 8 Resin layer 10, 11, 12 Optical laminate 45 322672

Claims (1)

201132505 Λ , 七、申請專利範圍： 1. 一種光學積層體，其係由玻璃板和塑料片經由黏接劑層 貼合而成，其中，所述黏接劑層是由以主要單體為分子 内具有至少一個稀煙性雙鍵和至少一個缓基的化合物 的聚合物作為主成分的水系黏接劑組成物所形成者。 2. 如申請專利範圍第1項所述的光學積層體，其中，所述 水系黏接劑組成物還含有矽烷偶合劑。 3. 如申請專利範圍第1或2項所述的光學積層體，其中， 所述水系黏接劑組成物還含有交聯劑。 4. 如申請專利範圍第1或2項所述的光學積層體，其中， 所述黏接劑層具有5ym以下的厚度。 5. 如申請專利範圍第1或2項所述的光學積層體，其中， 所述玻璃板為液晶單元基板。 6. 如申請專利範圍第1或2項所述的光學積層體，其中， 所述塑料片是具有在聚乙烯醇系樹脂上吸附有二色性 色素並使其取向而成的偏振膜的偏振板。 7. 如申請專利範圍第6項所述的光學積層體，其中，所述 偏振板具備所述偏振膜和在其至少一個面上形成的透 明保護層。 8. 如申凊專利範圍f 7項所述的光學積層體，其中，所述 偏振板具備所述偏振膜和在其一個面上所形成的透明 保護層，與所述透明保護層處於相反側的偏振膜面經由 所述黏接劑層直接貼合在所述液晶單元基板上。 9. 如申請專利範圍f 7項所述的光學積廣體，其中，所述 322672 1 201132505 Λ 層以Χ及層Μ 、在其—個面上形成的透明保護 二立#杯二所述偏振膜的另一個面上的相位差板，該 ^所㈣接劑層貼合在所述液晶單元基 板上。 10. 種在玻璃板上貼合有塑料片的光學積層體的製造方 法’其具備如下步驟： 黏接劑組成物層形成步驟，係在_板和塑料片的各 自貼&amp;面中的至）—個面上設置黏接劑組成物的層，所述 黏接劑組祕的層純含主轉料分子内1有至少一 個稀烴性雙鍵和至少—個麟的聚合物的水溶液而形成； 貼合步驟，係經由該黏接劑組成物之層貼合所述玻 璃板和所述塑料片； 檢查步驟，係檢查通過所述貼合步，驟而得到的貼合 品’將查出有缺陷的貼合品取出至生產線外；以及 硬化步驟’係使存在於未經所述檢查步驟查出缺陷 的貼合品中的黏接劑組成物的層硬化。 11. 如申請專利範圍第10項所述的方法，其中，所述玻璃 板為液晶單元基板，所述塑料片是具有在聚乙烯醇系樹 脂上吸附有二色性色素並使其取向而成的偏振膜的偏 振板。 12. 如申凊專利範圍第10或11項所述的方法，其且有如下 構成，即對於通過所述檢查步驟而查出缺陷的貼合品， 將塑料片剝下，然後將玻璃板返回到所述黏接劑組成物 層形成步驟中。 322672 2201132505 Λ , VII, the scope of application for patents: 1. An optical laminate, which is formed by bonding a glass plate and a plastic sheet via an adhesive layer, wherein the adhesive layer is composed of a main monomer A water-based adhesive composition having a polymer of at least one compound having a smoky double bond and at least one slow group as a main component. 2. The optical laminate according to claim 1, wherein the aqueous binder composition further contains a decane coupling agent. 3. The optical layered body according to claim 1 or 2, wherein the water-based adhesive composition further contains a crosslinking agent. 4. The optical layered body according to claim 1 or 2, wherein the adhesive layer has a thickness of 5 μm or less. 5. The optical laminate according to claim 1 or 2, wherein the glass plate is a liquid crystal cell substrate. 6. The optical layered body according to the first or second aspect of the invention, wherein the plastic sheet has a polarization of a polarizing film obtained by adsorbing and orienting a dichroic dye on a polyvinyl alcohol resin. board. 7. The optical layered body according to claim 6, wherein the polarizing plate is provided with the polarizing film and a transparent protective layer formed on at least one surface thereof. 8. The optical layered body according to claim 7, wherein the polarizing plate is provided with the polarizing film and a transparent protective layer formed on one surface thereof, on the opposite side to the transparent protective layer The polarizing film surface is directly bonded to the liquid crystal cell substrate via the adhesive layer. 9. The optical product according to claim 7, wherein the 322672 1 201132505 Λ layer is formed by a layer of Χ and Μ , a transparent protective erection formed on one surface thereof The phase difference plate on the other surface of the film is bonded to the liquid crystal cell substrate. 10. A method for producing an optical laminate in which a plastic sheet is bonded to a glass sheet, which has the following steps: a step of forming an adhesive composition layer, in each of the affixing and surface of the _ plate and the plastic sheet a layer of adhesive composition, the layer of the adhesive agent layer containing an aqueous solution of at least one of a dilute hydrocarbon double bond and at least a lining polymer in the main conversion molecule. Forming; a bonding step of bonding the glass plate and the plastic sheet through a layer of the adhesive composition; an inspection step of inspecting a laminate obtained by the bonding step, and checking The defective laminate is taken out of the production line; and the hardening step 'cures the layer of the adhesive composition present in the laminate that has not been detected by the inspection step. 11. The method according to claim 10, wherein the glass plate is a liquid crystal cell substrate, and the plastic sheet has a dichroic dye adsorbed on a polyvinyl alcohol resin and oriented. The polarizing plate of the polarizing film. 12. The method of claim 10, wherein the method further comprises peeling off the plastic sheet for the laminate that has been found to be defective by the inspection step, and then returning the glass sheet. To the adhesive composition layer forming step. 322672 2
TW100100263A 2010-01-06 2011-01-05 Optical laminate member and method for making same TWI526318B (en)

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