TW201900807A - Polarizer - Google Patents

Polarizer Download PDF

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Publication number
TW201900807A
TW201900807A TW107117370A TW107117370A TW201900807A TW 201900807 A TW201900807 A TW 201900807A TW 107117370 A TW107117370 A TW 107117370A TW 107117370 A TW107117370 A TW 107117370A TW 201900807 A TW201900807 A TW 201900807A
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Taiwan
Prior art keywords
meth
resin film
polarizer
acrylic resin
polarizing plate
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TW107117370A
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Chinese (zh)
Inventor
永安智
李正銀
藤田政大
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日商住友化學股份有限公司
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Publication of TW201900807A publication Critical patent/TW201900807A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • C09J129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09J139/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements

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

Abstract

The present invention provides a polarizing plate comprising a polarizer and a (meth) acrylic resin film, which has a good adhesion between the polarizer and the (meth) acrylic resin film after being placed under a wet heat environment (high temperature and high humidity environment). To provide a polarizing plate comprises a polarizer, a first adhesive layer, and a (meth) acrylic resin film in this order, and the first adhesive layer is a layer formed from an adhesive composition containing an oxazoline group-containing compound.

Description

偏光板    Polarizer   

本發明係有關偏光板。 The present invention relates to a polarizing plate.

可廣泛使用於以液晶顯示器為代表的圖像顯示器等之偏光板，通常具有在偏光片的單面或兩面上積層黏合如同保護膜之熱塑性樹脂膜的構成。偏光片與熱塑性樹脂膜間之黏合通常可使用接著劑。該接著劑已知有活性能量線硬化性接著劑或水性接著劑。[例如日本特開2009-008860號公報(專利文獻1)]。 It can be widely used in polarizing plates such as image displays such as liquid crystal displays, and usually has a structure in which a thermoplastic resin film, such as a protective film, is laminated on one or both sides of a polarizer. An adhesive is usually used for the adhesion between the polarizer and the thermoplastic resin film. This adhesive is known as an active energy ray hardening adhesive or an aqueous adhesive. [For example, Japanese Patent Application Laid-Open No. 2009-008860 (Patent Document 1)].

[先前技術文獻]     [Prior technical literature]     [專利文獻]     [Patent Literature]    

[專利文獻1]日本特開2009-008860號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2009-008860

本發明的目的是提供一種偏光板，係含有偏光片與(甲基)丙烯酸系樹脂膜的偏光板，其置於濕熱環境(高溫高濕環境)下之後，偏光片與(甲基)丙烯酸系樹脂膜之間的密合性良好。 An object of the present invention is to provide a polarizing plate, which is a polarizing plate containing a polarizer and a (meth) acrylic resin film. After being placed in a hot and humid environment (high temperature and high humidity environment), the polarizer and (meth) acrylic The adhesion between the resin films is good.

本發明係提供以下表示的偏光板。 The present invention provides a polarizing plate shown below.

[1]一種偏光板，係依序含有偏光片、第1接著劑層與(甲基)丙烯酸系樹脂膜，且前述第1接著劑層是由含有含噁唑啉基之化合物的接著劑組成物形成之層。 [1] A polarizing plate comprising a polarizer, a first adhesive layer and a (meth) acrylic resin film in this order, and the first adhesive layer is composed of an adhesive containing an oxazoline group-containing compound Layers of matter.

[2]如[1]項所述之偏光板，其中，前述接著劑組成物再含有乙醯乙醯基改質聚乙烯醇聚合物。 [2] The polarizing plate according to the item [1], wherein the adhesive composition further contains an ethyl acetamidine modified polyvinyl alcohol polymer.

[3]如[1]或[2]項所述之偏光板，係依序含有熱塑性樹脂膜、第2接著劑層、前述偏光片、前述第1接著劑層與前述(甲基)丙烯酸系樹脂膜。 [3] The polarizing plate according to [1] or [2], which comprises a thermoplastic resin film, a second adhesive layer, the polarizer, the first adhesive layer, and the (meth) acrylic system in this order. Resin film.

[4]如[1]至[3]項中任一項所述之偏光板，其中，前述第1接著劑層與前述(甲基)丙烯酸系樹脂膜係相接觸。 [4] The polarizing plate according to any one of [1] to [3], wherein the first adhesive layer is in contact with the (meth) acrylic resin film.

[5]如[4]項所述之偏光板，其中，前述(甲基)丙烯酸系樹脂膜與前述第1接著劑層相接觸面之水接觸角係80°以下。 [5] The polarizing plate according to the item [4], wherein a water contact angle of a contact surface between the (meth) acrylic resin film and the first adhesive layer is 80 ° or less.

[6]如[1]至[5]項中任一項所述之偏光板，其中，前述偏光片與前述第1接著劑層係相接觸。 [6] The polarizing plate according to any one of [1] to [5], wherein the polarizer is in contact with the first adhesive layer system.

[7]一種接著劑組成物，係偏光片與(甲基)丙烯酸系樹脂膜接著用之接著劑組成物，其含有含噁唑啉基之化合物。 [7] An adhesive composition comprising an oxazoline group-containing compound, and an adhesive composition for the subsequent use of a polarizer and a (meth) acrylic resin film.

[8]如[7]項所述之接著劑組成物，係再含有乙醯乙醯基改質聚乙烯醇聚合物。 [8] The adhesive composition according to item [7], which further contains an acetamidine modified polyvinyl alcohol polymer.

[9]如[7]或[8]項所述之接著劑組成物，係再含有水。 [9] The adhesive composition according to [7] or [8], further comprising water.

可提供一種偏光板，其置於濕熱環境(高溫高濕環境)下之後，偏光片與(甲基)丙烯酸系樹脂膜之間的密合性良好。 It is possible to provide a polarizing plate having good adhesion between a polarizer and a (meth) acrylic resin film after being placed in a hot and humid environment (high temperature and high humidity environment).

10‧‧‧(甲基)丙烯酸系樹脂膜 10‧‧‧ (meth) acrylic resin film

15‧‧‧第1接著劑層 15‧‧‧The first adhesive layer

20‧‧‧熱塑性樹脂膜 20‧‧‧ thermoplastic resin film

25‧‧‧第2接著劑層 25‧‧‧The second adhesive layer

30‧‧‧偏光片 30‧‧‧Polarizer

第1圖表示本發明的偏光板之層構成之一例的示意剖面圖。 FIG. 1 is a schematic cross-sectional view showing an example of a layer configuration of a polarizing plate of the present invention.

第2圖表示本發明的偏光板之層構成之另一例的示意剖面圖。 Fig. 2 is a schematic cross-sectional view showing another example of the layer configuration of the polarizing plate of the present invention.

<偏光板>     <Polarizer>    

本發明的偏光板係依序含有偏光片、第1接著劑層與(甲基)丙烯酸系樹脂膜，其中第1接著劑層是由含有含噁唑啉基的化合物之接著劑組成物形成的接著劑層。 The polarizing plate of the present invention sequentially includes a polarizer, a first adhesive layer, and a (meth) acrylic resin film, wherein the first adhesive layer is formed of an adhesive composition containing an oxazoline group-containing compound. Then the agent layer.

本發明的偏光板係置於濕熱環境(高溫高濕環境)下之後，偏光片與(甲基)丙烯酸系樹脂膜之間的密合性良好。 After the polarizing plate of the present invention is placed in a hot and humid environment (high temperature and high humidity environment), the adhesiveness between the polarizer and the (meth) acrylic resin film is good.

本說明書中「(甲基)丙烯酸基」係指選自丙烯酸基及甲基丙烯酸基所組成之群組中的至少1種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等的標示也是同樣。 The "(meth) acrylic group" in this specification means at least one selected from the group consisting of an acrylic group and a methacrylic group. The same applies to "(meth) acrylfluorenyl" and "(meth) acrylate".

[1]偏光板的構成     [1] Structure of polarizing plate    

將本發明的偏光板之層構成之例表示於第1圖及第2圖。 Examples of the layer configuration of the polarizing plate of the present invention are shown in FIGS. 1 and 2.

如第1圖所示，本發明的偏光板可以是含有偏光片30及於其一方的表面透過第1接著劑層15而積層黏合的(甲基)丙烯酸系樹脂膜10者。 As shown in FIG. 1, the polarizing plate of the present invention may include a polarizer 30 and a (meth) acrylic resin film 10 laminated and bonded to one surface through the first adhesive layer 15.

第1接著劑層15與(甲基)丙烯酸系樹脂膜10是以直接接觸為佳。 The first adhesive layer 15 and the (meth) acrylic resin film 10 are preferably in direct contact.

偏光片30與第1接著劑層15是以直接接觸為佳。 It is preferable that the polarizer 30 and the first adhesive layer 15 are in direct contact.

又如第2圖所示，本發明的偏光板也可以是含有偏光片30、於其一方之表面透過第1接著劑層15而積層黏合的(甲基)丙烯酸系樹脂膜10、以及於偏光片30的另一表面透過第2接著劑層25而積層黏合熱塑性樹脂膜20者。即，本發明的偏光板可以是依序含有熱塑性樹脂膜20、第2接著劑層25、偏光片30、第1接著劑層15與(甲基)丙烯酸系樹脂膜10者。 As shown in FIG. 2, the polarizing plate of the present invention may include a polarizing plate 30, a (meth) acrylic resin film 10 laminated and bonded to one surface through the first adhesive layer 15, and polarizing light. The other surface of the sheet 30 passes through the second adhesive layer 25 to laminate and adhere the thermoplastic resin film 20. That is, the polarizing plate of the present invention may include a thermoplastic resin film 20, a second adhesive layer 25, a polarizer 30, a first adhesive layer 15 and a (meth) acrylic resin film 10 in this order.

第2接著劑層25與熱塑性樹脂膜20是以直接接觸為佳。 It is preferable that the second adhesive layer 25 and the thermoplastic resin film 20 are in direct contact.

偏光片30與第2接著劑層25是以直接接觸為佳。 It is preferable that the polarizer 30 and the second adhesive layer 25 are in direct contact.

本發明的偏光板係以依序含有熱塑性樹脂膜20、第2接著劑層25、偏光片30、第1接著劑層15與(甲基)丙烯酸系樹脂膜10的偏光板為佳。 The polarizing plate of the present invention is preferably a polarizing plate containing the thermoplastic resin film 20, the second adhesive layer 25, the polarizer 30, the first adhesive layer 15 and the (meth) acrylic resin film 10 in this order.

本發明的偏光板並不侷限於第1圖及第2圖之例，可含有上述以外的其他層(或膜)。其他層可列舉：例如積層在(甲基)丙烯酸系樹脂膜10、熱塑性樹脂膜20及/或偏光片30的外表面之黏著劑層；積層在該黏著劑層的外表面之分離膜(也稱「剝離膜」。)；積層在(甲基)丙烯 酸系樹脂膜10、熱塑性樹脂膜20及/或偏光片30的外表面之保護膜(也稱「表面保護膜」。)；透過接著劑層或黏著劑層而積層在(甲基)丙烯酸系樹脂膜10、熱塑性樹脂膜20及/或偏光片30的外表面之光學機能性膜(或層)等。 The polarizing plate of the present invention is not limited to the examples shown in FIGS. 1 and 2, and may include layers (or films) other than those described above. Other layers include, for example, an adhesive layer laminated on the outer surface of the (meth) acrylic resin film 10, the thermoplastic resin film 20, and / or the polarizer 30; a separation film laminated on the outer surface of the adhesive layer (also It is called a "release film".); A protective film (also called a "surface protective film") laminated on the outer surfaces of the (meth) acrylic resin film 10, the thermoplastic resin film 20, and / or the polarizer 30; and a transmission adhesive A layer or an adhesive layer and an optically functional film (or layer) or the like laminated on the outer surfaces of the (meth) acrylic resin film 10, the thermoplastic resin film 20, and / or the polarizer 30.

[2]第1接著劑層     [2] The first adhesive layer    

第1接著劑層15係由含有含噁唑啉基的化合物(A)之接著劑組成物(S)形成之層。 The first adhesive layer 15 is a layer formed of an adhesive composition (S) containing an oxazoline group-containing compound (A).

含有噁唑啉基的化合物(A)係以含有噁唑啉基的聚合物為佳。 The oxazoline group-containing compound (A) is preferably an oxazoline group-containing polymer.

含有噁唑啉基的聚合物係分子內具有噁唑啉基的聚合物，並以側鏈具有噁唑啉基的聚合物為佳。聚合物的主鏈並無特別的限制，可以是例如由選自(甲基)丙烯酸基骨架、苯乙烯骨架等中的1種以上之骨架所形成。 The oxazoline group-containing polymer is a polymer having an oxazoline group in the molecule, and a polymer having an oxazoline group in a side chain is preferred. The main chain of the polymer is not particularly limited, and may be formed of, for example, one or more kinds of skeletons selected from a (meth) acrylic-based skeleton, a styrene skeleton, and the like.

含有噁唑啉基的聚合物可以在上述主鏈的側鏈具有噁唑啉基。 The oxazoline group-containing polymer may have an oxazoline group in a side chain of the main chain.

含有噁唑啉基的聚合物之較佳一例係含有由(甲基)丙烯酸基骨架形成的主鏈，且該主鏈的側鏈具有噁唑啉基之含有噁唑啉基的(甲基)丙烯酸系聚合物。 A preferred example of the oxazoline group-containing polymer is a (meth) acryl group-containing (methyl) group having a main chain formed of a (meth) acrylic group skeleton and a side chain of the main chain having an oxazoline group. Acrylic polymer.

含有噁唑啉基的聚合物為側鏈具有噁唑啉基時，雖然主鏈與噁唑啉基之間可以有連結基，但以主鏈與噁唑啉基係直接結合的聚合物為佳。 When the oxazoline group-containing polymer has an oxazoline group in its side chain, although a linking group may be present between the main chain and the oxazoline group, a polymer in which the main chain is directly bonded to the oxazoline group is preferred. .

噁唑啉基可列舉：例如2-噁唑啉基、3-噁唑啉基、4-噁唑啉基等。噁唑啉基係以2-噁唑啉基等為佳。 Examples of the oxazoline group include 2-oxazoline group, 3-oxazoline group, and 4-oxazoline group. The oxazoline group is preferably 2-oxazoline group or the like.

含有噁唑啉基的聚合物之數目平均分子量，係以5,000以上為佳，並以10,000以上更佳。數目平均分子量為上述範圍中時，傾向於顯示良好的密合性。含有噁唑啉基的聚合物之數目平均分子量通常是100,000以下。 The number average molecular weight of the oxazoline group-containing polymer is preferably 5,000 or more, and more preferably 10,000 or more. When the number average molecular weight is in the above range, good adhesion tends to be exhibited. The number average molecular weight of the oxazoline group-containing polymer is usually 100,000 or less.

含有噁唑啉基的聚合物之數目平均分子量，可藉由凝膠滲透層析儀測定作成標準聚苯乙烯換算值。 The number average molecular weight of the oxazoline group-containing polymer can be measured by a gel permeation chromatography to obtain a standard polystyrene conversion value.

含有噁唑啉基的聚合物之噁唑啉基量(含有噁唑啉基的聚合物之每1克固形分的噁唑啉基之莫耳數)，較佳的是0.4mmol/g‧固體以上10mmol/g‧固體以下。噁唑啉基量過高時難以獲得良好的密合性，噁唑啉基量少於上述的範圍時，恐使第1接著劑層15的耐水性降低。就此而言，含有噁唑啉基的聚合物之噁唑啉基量，係以3mmol/g‧固體以上9mmol/g‧固體以下更佳。 The amount of the oxazoline group of the oxazoline group-containing polymer (the mole number of the oxazoline group per 1 gram of solid content of the oxazoline group-containing polymer) is preferably 0.4 mmol / g‧solid Above 10mmol / g‧solid. When the amount of the oxazoline group is too high, it is difficult to obtain good adhesion. When the amount of the oxazoline group is less than the above range, the water resistance of the first adhesive layer 15 may be reduced. In this regard, the oxazoline group-containing amount of the oxazoline group-containing polymer is more preferably 3 mmol / g‧solids or more and 9 mmol / g‧solids or less.

接著劑組成物(S)為水性接著劑組成物(接著劑成分溶解於水中或分散在水中的接著劑)時，含有噁唑啉基的聚合物係以水性，即水溶性的聚合物或水分散性的聚合物為佳。就接著劑層的光學特性而言，含有噁唑啉基的聚合物係以水溶性的聚合物為佳。 When the adhesive composition (S) is an aqueous adhesive composition (adhesive in which the adhesive component is dissolved or dispersed in water), the oxazoline group-containing polymer is aqueous, that is, a water-soluble polymer or water. Dispersible polymers are preferred. In terms of the optical properties of the adhesive layer, the oxazoline group-containing polymer is preferably a water-soluble polymer.

含有噁唑啉基的聚合物可使用市售品。具體上，可列舉株式會社日本觸媒製造Epocross WS-300、Epocross WS-500、Epocross WS-700(均為商品名)等含有噁唑啉基的丙烯酸聚合物；株式會社日本觸媒製造Epocross K-1000系列、Epocross K-2000系列、Epocross RPS系列(均為商品名)等含有噁唑啉基的丙烯酸/苯乙烯聚 合物。 As the oxazoline group-containing polymer, a commercially available product can be used. Specific examples include acrylic polymers containing oxazoline groups, such as Epocross WS-300, Epocross WS-500, and Epocross WS-700 (all trade names) made by Japan Catalyst Corporation; Epocross K made by Japan Catalyst Corporation -1000 series, Epocross K-2000 series, Epocross RPS series (all trade names) and other acrylic / styrene polymers containing oxazoline groups.

含有噁唑啉基的的聚合物也可同時併用2種以上。 The oxazoline group-containing polymer may be used in combination of two or more kinds.

就密合性、光學特性、耐水性之觀點而言，係以Epocross WS-300、Epocross WS-700等含有噁唑啉基的丙烯酸聚合物為佳。 From the viewpoints of adhesion, optical properties, and water resistance, acrylic polymers containing oxazoline groups such as Epocross WS-300 and Epocross WS-700 are preferred.

將接著劑組成物(S)的整體量作為100質量%時，含有噁唑啉基的的聚合物之含量係以0.1質量%以上30質量%以下為佳，並以0.5質量%以上20質量%以下更佳，而以1質量%以上15質量%以下又更佳。就置在濕熱環境(高溫高濕環境)下之後的偏光片30與(甲基)丙烯酸系樹脂膜10之間的密合性而言，係以將含有噁唑啉基的聚合物之含量設成上述的範圍以內為佳。 When the entire amount of the adhesive composition (S) is 100% by mass, the content of the oxazoline group-containing polymer is preferably from 0.1% by mass to 30% by mass, and from 0.5% by mass to 20% by mass. The following is more preferred, and more preferably from 1% by mass to 15% by mass. The adhesion between the polarizer 30 and the (meth) acrylic resin film 10 after being placed in a hot and humid environment (high temperature and high humidity environment) is based on setting the content of the oxazoline group-containing polymer to It is preferably within the above range.

接著劑組成物(S)可再含有乙醯乙醯基改質聚乙烯醇聚合物(B)。再含有乙醯乙醯基改質聚乙烯醇聚合物(B)有利於提高偏光片30與(甲基)丙烯酸系樹脂膜10之間的密合性。 The adhesive composition (S) may further contain an acetamidine-modified vinyl alcohol polymer (B). Containing acetoacetic acid modified polyvinyl alcohol polymer (B) further helps to improve the adhesion between the polarizer 30 and the (meth) acrylic resin film 10.

乙醯乙醯基改質聚乙烯醇聚合物(B)係指在側鏈導入乙醯乙醯基而改質的聚乙烯醇系聚合物。 The acetoacetic acid modified polyvinyl alcohol polymer (B) refers to a polyvinyl alcohol-based polymer modified by introducing an acetic acid ethyl group into a side chain.

構成乙醯乙醯基改質聚乙烯醇聚合物(B)的主鏈之聚乙烯醇系聚合物，可以是將乙酸乙烯酯均聚物之聚乙酸乙烯酯進行皂化處理而得的乙烯醇均聚物(完全皂化聚乙烯醇或部分皂化聚乙烯醇)，也可以是將乙酸乙烯酯與可和其共聚合的其他單體之共聚合物進行皂化處理而得之聚乙烯醇系共聚合物。 The polyvinyl alcohol-based polymer constituting the main chain of the ethyl acetate-modified vinyl alcohol polymer (B) may be a vinyl alcohol homopolymer obtained by saponifying a polyvinyl acetate homopolymer of polyvinyl acetate. Polymer (fully saponified polyvinyl alcohol or partially saponified polyvinyl alcohol), or a polyvinyl alcohol copolymer obtained by saponifying a copolymer of vinyl acetate and other monomers copolymerizable therewith .

可和乙酸乙烯酯共聚合的其他單體可列舉不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類及具有銨基的(甲基)丙烯醯胺類等。 Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamidoamines having an ammonium group.

乙醯乙醯基改質聚乙烯醇聚合物(B)的皂化度，通常是80莫耳%以上100莫耳%以下，並以85莫耳%以上為佳。 The saponification degree of the acetamidine-modified polyvinyl alcohol polymer (B) is usually 80 mol% or more and 100 mol% or less, and preferably 85 mol% or more.

乙醯乙醯基改質聚乙烯醇聚合物(B)的皂化度，可依照JIS K 6726：1994測定。 The saponification degree of the acetoacetic acid modified polyvinyl alcohol polymer (B) can be measured in accordance with JIS K 6726: 1994.

乙醯乙醯基改質聚乙烯醇聚合物(B)中乙醯乙醯基所致之改質度(改質量)，就密合性之觀點而言，通常是0.1莫耳%以上40莫耳%以下，並以0.5莫耳%以上40莫耳%以下為佳，而以1莫耳%以上20莫耳%以下更佳。改質度可由例如1H-NMR測定。 From the viewpoint of adhesion, the degree of modification (modification quality) caused by acetamidine in the acetamidine modified polyvinyl alcohol polymer (B) is usually 0.1 mol% or more and 40 mol. It is preferably less than 0.5% and more than 0.5% and less than 40%, and more preferably less than 1% and less than 20%. The degree of modification can be measured, for example, by 1 H-NMR.

就密合性之觀點而言，乙醯乙醯基改質聚乙烯醇聚合物(B)的平均聚合度係以100以上3,000以下為佳，並以500以上3,000以下更佳。 From the standpoint of adhesion, the average degree of polymerization of the acetoacetate-modified polyvinyl alcohol polymer (B) is preferably 100 or more and 3,000 or less, and more preferably 500 or more and 3,000 or less.

乙醯乙醯基改質聚乙烯醇聚合物(B)的平均聚合度，可依照JIS K 6726：1994測定。 The average degree of polymerization of the acetofluorene-modified polyvinyl alcohol polymer (B) can be measured in accordance with JIS K 6726: 1994.

相對於含有噁唑啉基的化合物(A)100質量份，乙醯乙醯基改質聚乙烯醇聚合物(B)的含量通常是1質量份以上300質量份以下，並以5質量份以上250質量份以下為佳，而以10質量份以上200質量份以下更佳。乙醯乙醯基改質聚乙烯醇聚合物(B)的含量為此範圍時，傾向於表現提高密合性的效果。 The content of the acetoacetamyl modified polyvinyl alcohol polymer (B) is usually 1 part by mass or more and 300 parts by mass or less, and 5 parts by mass or more based on 100 parts by mass of the oxazoline group-containing compound (A). 250 mass parts or less is preferable, and 10 mass parts or more and 200 mass parts or less is more preferable. When the content of the acetofluorene-modified polyvinyl alcohol polymer (B) falls within this range, the effect of improving the adhesion tends to be exhibited.

接著劑組成物(S)可再含有氮丙啶化合物(C)。氮丙啶化合物(C)係指分子內具有1個以上的氮丙啶環之化合物。氮丙啶化合物(C)係以分子內具有2個或3個氮丙啶環之化合物為佳。 The adhesive composition (S) may further contain an aziridine compound (C). The aziridine compound (C) refers to a compound having one or more aziridine rings in the molecule. The aziridine compound (C) is preferably a compound having two or three aziridine rings in the molecule.

氮丙啶化合物(C)係以單體為佳，氮丙啶化合物(C)的分子量可以是150以上1,000以下。 The aziridine compound (C) is preferably a monomer, and the molecular weight of the aziridine compound (C) may be 150 or more and 1,000 or less.

氮丙啶化合物(C)可以是市售品，具體上，可列舉株式會社日本觸媒製造Chemitite PZ-33、Chemitite DZ-22E(均是商品名)；MENADIONA公司製造CROSSLINKER CL-422、CROSSLINKER CL-427、CROSSLINKER CL-467(均是商品名)等氮丙啶系化合物。尤其就密合性之觀點而言，係以CROSSLINKER CL-427為佳。 The aziridine compound (C) may be a commercially available product, and specifically, Chemitite PZ-33 and Chemitite DZ-22E (both trade names) manufactured by Japan Catalyst Corporation; CROSSLINKER CL-422 and CROSSLINKER CL manufactured by Menadiona Corporation are listed. -427, CROSSLINKER CL-467 (all are trade names) and other aziridine-based compounds. Especially from the viewpoint of tightness, CROSSLINKER CL-427 is preferred.

相對於含有噁唑啉基的化合物(A)100質量份，氮丙啶化合物(C)的含量通常是0.1質量份以上50質量份以下，並以0.2質量份以上30質量份以下為佳，而以0.5質量份以上20質量份以下更佳。 The content of the aziridine compound (C) is usually from 0.1 to 50 parts by mass, and preferably from 0.2 to 30 parts by mass, with respect to 100 parts by mass of the oxazoline group-containing compound (A). More preferably, it is 0.5 mass part or more and 20 mass parts or less.

接著劑組成物(S)係以含有溶劑為佳。溶劑可列舉水、有機溶劑、或該等之混合物。溶劑係以含有水為佳，也可併用水與水溶性的有機溶劑。有機溶劑可列舉乙醇、1-甲氧基-2-丙醇等醇溶劑。 The adhesive composition (S) preferably contains a solvent. Examples of the solvent include water, organic solvents, and mixtures thereof. The solvent is preferably water-containing, and water and a water-soluble organic solvent may be used together. Examples of the organic solvent include alcohol solvents such as ethanol and 1-methoxy-2-propanol.

溶劑的主成分係以水為佳。主成分係指占有全溶劑的50質量%以上之意。 The main component of the solvent is preferably water. The main component means 50% by mass or more of the total solvent.

接著劑組成物(S)的固形分濃度通常是0.5質量%以上 20質量%以下，並以1質量%以上15質量%以下為佳。 The solid content concentration of the adhesive composition (S) is usually 0.5% by mass or more and 20% by mass or less, and preferably 1% by mass or more and 15% by mass or less.

固形分濃度係指含在接著劑組成物(S)中的溶劑以外之成分的合計濃度。 The solid content concentration refers to the total concentration of components other than the solvent contained in the adhesive composition (S).

接著劑組成物(S)可含有含噁唑啉基的化合物(A)、乙醯乙醯基改質聚乙烯醇聚合物(B)及溶劑以外的其他成分。 The adhesive agent composition (S) may contain components other than an oxazoline group-containing compound (A), an acetoacetamyl-modified polyvinyl alcohol polymer (B), and a solvent.

其他的成分可列舉多元醛、三聚氰胺系化合物、氧化鋯化合物、鋅化合物、乙二醛、乙二醛衍生物、水溶性環氧樹脂等硬化性成分或交聯劑；耦合劑、增黏劑、抗氧化劑、紫外線吸收劑、熱穩定劑、抗水解劑等添加劑。 Other components include polyhydric aldehydes, melamine compounds, zirconia compounds, zinc compounds, glyoxal, glyoxal derivatives, water-soluble epoxy resins and other hardening components or cross-linking agents; coupling agents, tackifiers, Antioxidants, UV absorbers, heat stabilizers, anti-hydrolytic agents and other additives.

接著劑組成物(S)係以水性接著劑為佳。即，接著劑組成物(S)係以將調配成分溶解於含水的溶劑而成之溶液，或將調配成分分散在含水的溶劑而成之分散體(例乳液)為佳。 The adhesive composition (S) is preferably an aqueous adhesive. That is, the adhesive composition (S) is preferably a solution obtained by dissolving a preparation component in an aqueous solvent, or a dispersion (such as an emulsion) obtained by dispersing the preparation component in an aqueous solvent.

接著劑組成物(S)的25℃之黏度，係以50mPa‧sec以下為佳，並以2mPa‧sec以上30mPa‧sec以下更佳，而以4mPa‧sec以上20mPa‧sec以下又更佳。25℃的黏度超過50mPa‧sec時，可能難以塗布均勻而造成塗布不均，同時，有可能產生管件阻塞等問題。 The viscosity of the adhesive composition (S) at 25 ° C is preferably 50 mPa · sec or less, more preferably 2 mPa · sec or more and 30 mPa · sec or less, and more preferably 4 mPa · sec or more and 20 mPa · sec or less. When the viscosity at 25 ° C exceeds 50 mPa‧sec, it may be difficult to apply uniformly and cause uneven coating, and at the same time, problems such as pipe blocking may occur.

接著劑組成物(S)的25℃之黏度，可用E型黏度計測定。 The viscosity of the adhesive composition (S) at 25 ° C can be measured with an E-type viscometer.

接著劑組成物(S)的25℃之pH是以3以上10以下為佳，並以4以上9以下更佳。接著劑組成物(S)的pH未達3時，可能使第1接著劑層15的耐水性不能充 分表現，接著劑組成物(S)的pH超過10時，可能使接著劑組成物(S)的適用期縮短。 The pH of the adhesive composition (S) at 25 ° C is preferably 3 or more and 10 or less, and more preferably 4 or more and 9 or less. When the pH of the adhesive composition (S) is less than 3, the water resistance of the first adhesive layer 15 may not be sufficiently expressed, and when the pH of the adhesive composition (S) exceeds 10, the adhesive composition (S) ) Shortened the applicable period.

接著劑組成物(S)的pH可利用pH計(例如HORIBA製「D-51」)測定。 The pH of the adhesive composition (S) can be measured with a pH meter (for example, "D-51" manufactured by HORIBA).

[3]偏光片     [3] Polarizer    

偏光片30係具有選擇性透過來自自然光某一方向之直線偏光的功能之膜。可列舉：例如於聚乙烯醇系樹脂膜吸附、配向有作為二色性色素的碘之碘系偏光片、聚乙烯醇系樹脂膜吸附、配向有作為二色性色素的二色性染料之染料系偏光片及塗布溶致液晶態(lyotropic liquid crystal state)二色性染料並經配向、固定化之塗布型偏光片等。此等偏光片可稱為選擇性透過來自自然光某一方向之直線偏光並吸收另一方向的直線偏光用之吸收型偏光片。 The polarizer 30 is a film having a function of selectively transmitting linearly polarized light from a certain direction of natural light. Examples include dyes adsorbed on a polyvinyl alcohol-based resin film, iodine-based polarizers having iodine as a dichroic pigment, and dyes adsorbed on polyvinyl alcohol-based resin films, and aligned on a dichroic dye as a dichroic dye. It is a polarizer and a coating-type polarizer coated with lyotropic liquid crystal state dichroic dye and aligned and fixed. These polarizers can be referred to as absorption-type polarizers that selectively transmit linearly polarized light from one direction of natural light and absorb linearly polarized light from the other direction.

偏光片30並不限於吸收型偏光片，也可以是選擇性透過來自自然光某一方向之直線偏光，並將另一方向的直線偏光反射之反射型偏光片，或是將另一方向的直線偏光散射之散射型偏光片，但就可見度變優之點而言，係以吸收型偏光片為佳。其中，係以聚乙烯醇系樹脂構成的聚乙烯醇系偏光片更佳，並以於聚乙烯醇系樹脂膜吸附、配向有碘或二色性染料等二色性色素的聚乙烯醇系偏光片又更佳，而以於聚乙烯醇系樹脂膜吸附、配向有碘的聚乙烯醇系偏光片尤佳。 The polarizer 30 is not limited to an absorption-type polarizer, but may be a reflective polarizer that selectively transmits linearly polarized light from one direction of natural light and reflects linearly polarized light in the other direction, or linearly polarized light in the other direction Scattering type polarizers, but in terms of better visibility, absorption type polarizers are preferred. Among them, a polyvinyl alcohol-based polarizer made of a polyvinyl alcohol-based resin is more preferred, and a polyvinyl alcohol-based polarized light having a dichroic dye such as iodine or a dichroic dye is adsorbed and aligned on the polyvinyl alcohol-based resin film. The sheet is more preferable, and a polyvinyl alcohol-based polarizer having iodine adsorbed and aligned with an iodine is particularly preferable.

構成聚乙烯醇系偏光片的聚乙烯醇系樹脂， 可使用將聚乙酸乙烯酯系樹脂進行皂化者。聚乙酸乙烯酯系樹脂除了乙酸乙烯酯的均聚物之聚乙酸乙烯酯以外，可列舉乙酸乙烯酯與可共聚合的其他單體之共聚合物等。可與乙酸乙烯酯共聚合的其他單體，可列舉不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類及具有銨基的(甲基)丙烯醯胺類等。 As the polyvinyl alcohol-based resin constituting the polyvinyl alcohol-based polarizer, a saponified polyvinyl acetate-based resin can be used. Examples of the polyvinyl acetate-based resin include copolymers of vinyl acetate and other copolymerizable monomers, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamidoamines having an ammonium group.

聚乙烯醇系樹脂的皂化度，通常是85莫耳%以上100莫耳%以下，並以98莫耳%以上為佳。聚乙烯醇系樹脂可加以改質，可使用：例如經醛類改質的聚乙烯縮甲醛或聚乙烯縮乙醛。聚乙烯醇系樹脂的平均聚合度通常是1,000以上10,000以下，並以1,500以上5,000以下為佳。聚乙烯醇系樹脂的平均聚合度，可依照JIS K 6726：1994求得。 The saponification degree of the polyvinyl alcohol resin is usually 85 mol% or more and 100 mol% or less, and preferably 98 mol% or more. The polyvinyl alcohol-based resin can be modified, and for example, polyvinyl acetal or polyvinyl acetal modified by aldehydes can be used. The average degree of polymerization of the polyvinyl alcohol resin is usually 1,000 to 10,000, and preferably 1,500 to 5,000. The average degree of polymerization of the polyvinyl alcohol resin can be obtained in accordance with JIS K 6726: 1994.

將此種聚乙烯醇系樹脂經製膜者，可使用作為偏光片30的原生膜。將聚乙烯醇系樹脂製膜的方法，並無特別的限制，可採用周知的方法。聚乙烯醇系原生膜的厚度係例如150μm以下，較佳為100μm以下(例如50μm以下)，5μm以上。 Those who pass such a polyvinyl alcohol-based resin into a film can use a native film of the polarizer 30. The method of forming a polyvinyl alcohol-type resin into a film is not specifically limited, A well-known method can be employ | adopted. The thickness of the polyvinyl alcohol-based primary film is, for example, 150 μm or less, preferably 100 μm or less (for example, 50 μm or less), and 5 μm or more.

偏光片30可藉由包含下述之方法製造，將乙烯醇系樹脂膜單軸延伸的步驟；藉由用二色性色素將聚乙烯醇系樹脂膜染色而吸附二色性色素的步驟；用硼酸水溶液處理(交聯處理)經吸附二色性色素的聚乙烯醇系樹脂膜的步驟；及經硼酸水溶液處理後的水洗步驟。 The polarizer 30 can be produced by a method including uniaxially stretching a vinyl alcohol-based resin film by a method described below; a step of adsorbing a dichroic pigment by dyeing a polyvinyl alcohol-based resin film with a dichroic pigment; A step of treating (cross-linking treatment) a boric acid aqueous solution with a polyvinyl alcohol-based resin film adsorbing a dichroic pigment; and a step of washing with a boric acid aqueous solution.

聚乙烯醇系樹脂膜的單軸延伸可在二色性 色素的染色前、與染色同時或染色之後進行。染色之後進行單軸延伸時，此單軸延伸也可在硼酸處理之前或硼酸處理中進行。又，也可在此等處理之複數個階段進行單軸延伸。 The uniaxial stretching of the polyvinyl alcohol-based resin film may be performed before the dyeing of the dichroic dye, simultaneously with the dyeing, or after the dyeing. When uniaxial stretching is performed after dyeing, this uniaxial stretching may also be performed before or during a boric acid treatment. In addition, uniaxial stretching may be performed in a plurality of stages of these processes.

當單軸延伸時，可用不同周速的輥間於一軸進行延伸，也可使用熱輥於一軸進行延伸。另外，單軸延伸可以是在大氣中進行延伸的乾式延伸，也可以是使用水等溶劑而使聚乙烯醇系樹脂膜在膨脹狀態中進行延伸的濕式延伸。延伸倍率通常是3倍以上8倍以下。 When uniaxial extension, it can be extended on one axis between rolls with different peripheral speeds, or it can be extended on one axis by hot rolls. The uniaxial stretching may be dry stretching in the air, or wet stretching in which the polyvinyl alcohol-based resin film is stretched in a swollen state using a solvent such as water. The stretching ratio is usually 3 times or more and 8 times or less.

以二色性色素將聚乙烯醇系樹脂膜染色的方法，可列舉：例如將該膜浸泡在含有二色性色素的水溶液中之方法等。二色性色素可使用碘或二色性有機染料。又，聚乙烯醇系樹脂膜係以在染色處理之前施加水的浸泡處理為佳。 Examples of a method for dyeing a polyvinyl alcohol-based resin film with a dichroic dye include a method of immersing the film in an aqueous solution containing a dichroic dye, and the like. As the dichroic pigment, iodine or a dichroic organic dye can be used. In addition, the polyvinyl alcohol-based resin film is preferably a dipping treatment in which water is applied before the dyeing treatment.

藉由碘的染色處理方法可列舉將聚乙烯醇系樹脂膜浸泡在含有碘及碘化鉀之水溶液中的方法等。此水溶液中的碘之含量係每100質量份的水為0.01質量份以上1質量份以下。碘化鉀的含量係每100質量份的水為0.5質量份以上20質量份以下。又，該水溶液的溫度可以是20℃以上40℃以下。 Examples of the dyeing treatment method with iodine include a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide. The content of iodine in this aqueous solution is 0.01 to 1 part by mass per 100 parts by mass of water. The content of potassium iodide is 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution may be 20 ° C or higher and 40 ° C or lower.

另一方面，藉由二色性有機染料的染色處理方法，可列舉將聚乙烯醇系樹脂膜浸泡在含有二色性有機染料的水溶液中之方法等。含有二色性有機染料的水溶液亦可含有硫酸鈉等無機鹽作為染色助劑。該水溶液中的二色性有機 染料之含量，相對於每100質量份的水可為1×10-4質量份以上10質量份以下。該水溶液的溫度可以是20℃以上80℃以下。 On the other hand, a method for dyeing a dichroic organic dye includes a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic organic dye. The aqueous solution containing a dichroic organic dye may contain an inorganic salt such as sodium sulfate as a dyeing auxiliary agent. The content of the dichroic organic dye in the aqueous solution may be 1 × 10 -4 parts by mass or more and 10 parts by mass or less per 100 parts by mass of water. The temperature of the aqueous solution may be from 20 ° C to 80 ° C.

經二色性色素染色後的硼酸處理方法，可列舉將經染色的聚乙烯醇系樹脂膜浸泡在含有硼酸之水溶液的方法等。使用碘作為二色性色素時，該含有硼酸的水溶液係以含有碘化鉀為佳。含有硼酸的水溶液中硼酸之量，相對於每100質量份的水可為2質量份以上15質量份以下。該水溶液中的碘化鉀之量，相對於每100質量份的水可為0.1質量份以上20質量份以下。該水溶液的溫度，可以是50℃以上，例如50℃以上85℃以下。 Examples of the boric acid treatment method after dichroic dyeing include a method of immersing the dyed polyvinyl alcohol-based resin film in an aqueous solution containing boric acid, and the like. When iodine is used as the dichroic dye, the boric acid-containing aqueous solution preferably contains potassium iodide. The amount of boric acid in the boric acid-containing aqueous solution may be 2 parts by mass or more and 15 parts by mass or less per 100 parts by mass of water. The amount of potassium iodide in the aqueous solution may be 0.1 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution may be 50 ° C or higher, for example, 50 ° C or higher and 85 ° C or lower.

硼酸處理後的聚乙烯醇系樹脂膜通常要進行水洗處理。水洗處理可藉由例如將經硼酸處理的聚乙烯醇系樹脂膜浸泡在水中而進行。水洗處理中的水之溫度，通常是5℃以上40℃以下。水洗後施加乾燥處理即可得偏光片30。 The polyvinyl alcohol-based resin film after the boric acid treatment is usually subjected to a water washing treatment. The water washing treatment can be performed by, for example, immersing a boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of the water in the water washing treatment is usually 5 ° C or higher and 40 ° C or lower. The polarizer 30 can be obtained by applying a drying treatment after washing with water.

乾燥處理可利用熱風乾燥機或遠紅外線加熱器進行。藉由在該偏光片30的單面使用接著劑組成物(S)將作為保護膜等的(甲基)丙烯酸系樹脂膜10加以黏合，即可得偏光板。可使用接著劑組成物將熱塑性樹脂膜20黏合在偏光片30的另一表面。 The drying process can be performed using a hot-air dryer or a far-infrared heater. A polarizing plate can be obtained by bonding the (meth) acrylic resin film 10 as a protective film or the like using an adhesive composition (S) on one side of the polarizer 30. The thermoplastic resin film 20 may be adhered to the other surface of the polarizer 30 using an adhesive composition.

又，偏光片30的製造方法之其他例，可列舉日本特開2000-338329號公報或日本特開2012-159778號公報所述之方法。此方法係在基材膜的表面塗布含有聚 乙烯醇系樹脂的溶液而設置樹脂層之後，將由基材膜與樹脂層形成的積層膜加以延伸，接著施加染色處理、交聯處理等，即由樹脂層形成偏光片層(偏光片層)。由基材膜與偏光片層形成的該偏光性積層膜，可將作為保護膜等的(甲基)丙烯酸系樹脂膜10黏合在偏光片層表面之後，將基材膜剝離去除，作成第1圖所示構成之偏光板。只要在剝離基材膜而露出的偏光片層表面再黏合熱塑性樹脂膜20，即形成第2圖所示構成之偏光板。 Moreover, as another example of the manufacturing method of the polarizing plate 30, the method described in Unexamined-Japanese-Patent No. 2000-338329 or the Unexamined-Japanese Patent No. 2012-159778 is mentioned. In this method, a solution containing a polyvinyl alcohol resin is coated on the surface of a base film to provide a resin layer, and then a laminated film formed of the base film and the resin layer is extended, followed by applying a dyeing treatment, a cross-linking treatment, or the like. The resin layer forms a polarizer layer (polarizer layer). This polarizing laminated film formed of a base film and a polarizer layer can be obtained by adhering a (meth) acrylic resin film 10 as a protective film or the like to the surface of the polarizer layer, peeling off the base film, and forming a first film. The polarizing plate of the structure shown in the figure. As long as the thermoplastic resin film 20 is adhered to the surface of the polarizer layer exposed after the base film is peeled off, a polarizing plate having a structure shown in FIG. 2 is formed.

偏光片30的厚度可作成40μm以下，並以30μm以下(例如20μm以下，再者15μm以下，又再者為10μm以下或8μm以下)為佳。若藉由日本特開2000-338329號公報或日本特開2012-159778號公報所述之方法，可更容易製造薄膜的偏光片30，偏光片30的厚度，可更容易作成例如20μm以下，再者15μm以下，又再者為10μm以下或8μm以下。偏光片30的厚度通常是2μm以上。減小偏光片30的厚度時，有利於偏光板乃至圖像顯示器的薄型化。 The thickness of the polarizer 30 may be 40 μm or less, and preferably 30 μm or less (for example, 20 μm or less, 15 μm or less, and 10 μm or 8 μm or less). If the method described in Japanese Patent Application Laid-Open No. 2000-338329 or Japanese Patent Application Laid-Open No. 2012-159778 can be used to manufacture the thin film polarizer 30, the thickness of the polarizer 30 can be more easily made, for example, 20 μm or less. It is 15 μm or less, and 10 μm or less or 8 μm or less. The thickness of the polarizer 30 is usually 2 μm or more. When the thickness of the polarizing plate 30 is reduced, it is advantageous to reduce the thickness of the polarizing plate and the image display.

[4](甲基)丙烯酸系樹脂膜     [4] (meth) acrylic resin film    

(甲基)丙烯酸系樹脂膜10可以是未延伸膜，也可以是經單軸或二軸延伸之膜的任一種。二軸延伸可以是同時朝2個延伸方向延伸的同時二軸延伸，也可以是朝第1方向延伸之後再朝與其不同方向的第2方向延伸之逐次二軸延伸。 The (meth) acrylic resin film 10 may be an unstretched film or a film stretched uniaxially or biaxially. The biaxial extension may be a simultaneous biaxial extension that extends simultaneously in two extension directions, or a sequential biaxial extension that extends in the first direction and then in a second direction that is different from the latter.

(甲基)丙烯酸系樹脂膜10係發揮保護偏光片30的機能之保護膜，也可以是兼具相位差膜等光學機能的保護膜。 The (meth) acrylic resin film 10 is a protective film that exerts the function of protecting the polarizer 30, and may be a protective film that also has optical functions such as a retardation film.

構成(甲基)丙烯酸系樹脂膜10的(甲基)丙烯酸系樹脂，係含有來自(甲基)丙烯酸系單體的構成單元之聚合物，(甲基)丙烯酸系單體可列舉甲基丙烯酸酯及丙烯酸酯。 The (meth) acrylic resin constituting the (meth) acrylic resin film 10 is a polymer containing a structural unit derived from a (meth) acrylic monomer. Examples of the (meth) acrylic monomer include methacrylic acid. Esters and acrylates.

甲基丙烯酸酯可列舉甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正-、異-或第三丁酯、甲基丙烯酸環己酯、甲基丙烯酸苯酯、甲基丙烯酸苯甲酯、甲基丙烯酸2-乙酯己酯、甲基丙烯酸2-羥酯乙酯等。 Examples of methacrylates include methyl methacrylate, ethyl methacrylate, n-, iso- or tert-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, and benzoyl methacrylate. Esters, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, and the like.

丙烯酸酯可列舉丙烯酸乙酯、丙烯酸正-、異-或第三丁酯、丙烯酸環己酯、丙烯酸苯酯、丙烯酸苯甲酯、丙烯酸2-乙酯己酯、丙烯酸2-羥酯乙酯等。 Examples of the acrylate include ethyl acrylate, n-, iso-, or tert-butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate. .

(甲基)丙烯酸系樹脂可以是僅由來自(甲基)丙烯酸的構成單元形成之聚合物，也可含有其他的構成單元。 The (meth) acrylic resin may be a polymer formed of only a structural unit derived from (meth) acrylic acid, or may contain other structural units.

1個較佳的實施形態中，(甲基)丙烯酸系樹脂係含有甲基丙烯酸甲酯或含有甲基丙烯酸甲酯與丙烯酸甲酯作為共聚合成分。 In a preferred embodiment, the (meth) acrylic resin contains methyl methacrylate or methyl methacrylate and methyl acrylate as copolymerization components.

1個較佳的實施形態中，(甲基)丙烯酸系樹脂可以是將甲基丙烯酸酯作成主要單體(含有50質量%以上)的聚合物，並以甲基丙烯酸酯與其他的共聚合成分共聚合之共聚合物為佳。 In a preferred embodiment, the (meth) acrylic resin may be a polymer in which methacrylate is used as a main monomer (containing 50% by mass or more), and methacrylate and other copolymerization components are used. Copolymerized copolymers are preferred.

上述的丙烯酸酯以外的其他共聚合成分可 列舉：例如2-(羥基甲基)丙烯酸甲酯、2-(1-羥基乙基)丙烯酸甲酯、2-(羥基甲基)丙烯酸乙酯、2-(羥基甲基)丙烯酸正-、異-或第三丁酯等羥基烷基丙烯酸酯類；甲基丙烯酸、丙烯酸等不飽和酸類；氯化苯乙烯、溴化苯乙烯等鹵化苯乙烯類；乙烯甲苯、α-甲基苯乙烯等取代苯乙烯類；丙烯腈、甲基丙烯腈等不飽和腈類；順丁烯二酸酐、檸康酸酐等不飽和酸酐類；苯基順丁烯二醯亞胺、環己基順丁烯二醯亞胺等不飽和醯亞胺類；等單官能單體。 Examples of other copolymerization components other than the above acrylates include methyl 2- (hydroxymethyl) acrylate, methyl 2- (1-hydroxyethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, and 2 -(Hydroxymethyl) acrylic acid such as n-, iso- or tert-butyl acrylate; unsaturated acids such as methacrylic acid and acrylic acid; halogenated styrenes such as chlorinated styrene and brominated styrene; Substituted styrenes such as vinyl toluene and α-methylstyrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated anhydrides such as maleic anhydride and citraconic anhydride; phenyl maleic acid Unsaturated fluorene imines such as imines, cyclohexyl cis butene difluorene imines; and other monofunctional monomers.

上述其他的單官能單體，可僅單獨使用1種，也可併用2種以上。 These other monofunctional monomers may be used alone or in combination of two or more.

也可使用多官能單體作為上述其他的共聚合成分。 A polyfunctional monomer can also be used as the other copolymerization component.

多官能單體可列舉：例如乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、九乙二醇二(甲基)丙烯酸酯、十四乙二醇二(甲基)丙烯酸酯等乙二醇或其寡聚物的兩末端羥基經(甲基)丙烯酸酯化者；丙二醇或其寡聚物的兩末端羥基經(甲基)丙烯酸酯化者；新戊二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、 丁二醇二(甲基)丙烯酸酯等二元醇的羥基經(甲基)丙烯酸酯化者；雙酚A、雙酚A的環氧烷加成物、或該等的鹵素取代物之兩末端羥基經(甲基)丙烯酸酯化者；三羥甲基丙烷、異戊四醇等多元醇經(甲基)丙烯酸酯化者，以及該等之末端羥基與(甲基)丙烯酸去水甘油酯的環氧基進行開環加成者；琥珀酸、己二酸、對苯二甲酸、鄰苯二甲酸、該等的鹵素取代物等二元酸，或該等的環氧烷加成物等與(甲基)丙烯酸去水甘油酯的環氧基進行開環加成者；(甲基)丙烯酸芳酯；二乙烯苯等芳香族二乙烯基化合物；等。 Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (methyl) (Meth) acrylates, nonaethylene glycol di (meth) acrylates, tetraethylene glycol di (meth) acrylates, and other oligomers of ethylene glycol or their oligomers are both (meth) acrylated (Methacrylic acid esterified at both terminal hydroxyl groups of propylene glycol or its oligomer; neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, butanediol di ( The hydroxyl groups of glycols such as (meth) acrylates are esterified with (meth) acrylic acid; bisphenol A, alkylene oxide adducts of bisphenol A, or both of these terminal hydroxyl groups are (Meth) acrylic esters; poly (methyl) acrylates such as trimethylolpropane and isopentyl alcohol; and those terminal hydroxyl groups and epoxy groups of (gly) methacrylate Those who carry out ring-opening additions; dibasic acids such as succinic acid, adipic acid, terephthalic acid, phthalic acid, halogenated substitutes, etc., or such alkylene oxide adducts, and (a Group) those having epoxy ring-opening addition of epoxy glyceride; aryl (meth) acrylate; aromatic divinyl compounds such as divinylbenzene; etc.

其中，以乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、新戊二醇二甲基丙烯酸酯為適用。 Among them, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and neopentyl glycol dimethacrylate are applicable.

(甲基)丙烯酸酯可以是藉由共聚合物所具有的官能基間之反應而改質者。該反應可列舉：例如(甲基)丙烯酸甲酯的甲酯基與2-(羥基甲基)(甲基)丙烯酸甲酯的羥基之高分子鏈內脫甲醇縮合反應、(甲基)丙烯酸的羧基與2-(羥基甲基)丙烯酸甲酯的羥基之高分子鏈內脫水縮合反應等。 The (meth) acrylate may be modified by a reaction between the functional groups of the copolymer. Examples of the reaction include demethylation condensation reaction in a polymer chain of a methyl group of methyl (meth) acrylate and a hydroxyl group of methyl 2- (hydroxymethyl) (meth) acrylate, and Dehydration condensation reaction of a carboxyl group with a hydroxyl group of methyl 2- (hydroxymethyl) acrylate in a polymer chain and the like.

(甲基)丙烯酸系樹脂的玻璃轉移溫度係以80℃以上160℃以下為佳。玻璃轉移溫度可藉由調整甲基丙烯酸酯系單體與丙烯酸酯系單體的聚合比、各別的酯基之碳鏈長及該等所具有的官能基之種類，以及相對於單體 整體多官能單體的聚合比而控制。 The glass transition temperature of the (meth) acrylic resin is preferably 80 ° C or higher and 160 ° C or lower. The glass transition temperature can be adjusted by adjusting the polymerization ratio of the methacrylate monomer to the acrylate monomer, the carbon chain length of each ester group, the kind of functional groups that they have, and the total monomer content. The polymerization ratio of the polyfunctional monomer is controlled.

提高(甲基)丙烯酸系樹脂的玻璃轉移溫度用之方式，在高分子的主鏈導入環結構也有效。環結構係以環狀酸酐結構、環狀醯亞胺結構及內酯結構等雜環結構為佳。具體上，可列舉戊二酸酐結構、琥珀酸酐結構等環狀酸酐結構；戊二醯亞胺結構、琥珀醯亞胺結構等環狀醯亞胺結構；丁內酯、戊內酯等內酯環結構。 The method for increasing the glass transition temperature of the (meth) acrylic resin is also effective in introducing a ring structure into the main chain of the polymer. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic amidine structure, and a lactone structure. Specific examples include cyclic acid anhydride structures such as glutaric anhydride structure and succinic anhydride structure; cyclic fluorene imine structures such as glutarimide imide structure and succinimide structure; lactone rings such as butyrolactone and valerolactone structure.

主鏈中的環結構之含量增大，可使(甲基)丙烯酸系樹脂的玻璃轉移溫度傾向增高。 The larger the content of the ring structure in the main chain, the higher the glass transition temperature of the (meth) acrylic resin.

環狀酸酐結構、環狀醯亞胺結構，可藉由下列方法導入：藉由順丁烯二酸酐、順丁烯二醯亞胺等具有環狀結構的單體共聚合而導入之方法；藉由聚合後脫水、脫甲醇縮合反應而導入環狀酸酐結構的方法；使胺基化合物反應而導入環狀醯亞胺結構的方法等。 The cyclic acid anhydride structure and the cyclic fluorene imine structure can be introduced by the following methods: a method by introducing copolymerization of a monomer having a cyclic structure such as maleic anhydride, maleimide and the like; A method of introducing a cyclic acid anhydride structure by dehydration and de-methanol condensation reaction after polymerization; a method of introducing a cyclic amidine imine structure by reacting an amine compound; and the like.

具有內酯環結構的樹脂(聚合物)，係在調製高分子鏈具有羥基與酯基的聚合物之後，藉由加熱，並視需要而在有機磷化合物等觸媒的存在下使所得的聚合物中的羥基與酯基環化縮合而形成內酯環結構之方法。 A resin (polymer) having a lactone ring structure is prepared by polymerizing a polymer having a hydroxyl group and an ester group in a polymer chain, and then heating the obtained polymer in the presence of a catalyst such as an organic phosphorus compound, if necessary. A method for cyclizing and condensing hydroxyl groups in an ester to form a lactone ring structure.

(甲基)丙烯酸系樹脂及由其形成之(甲基)丙烯酸系樹脂膜10，可視需要而含有添加劑。添加劑可列舉：例如滑劑、抗結塊劑、熱穩定劑、抗氧化劑、紫外線吸收劑、抗靜電劑、耐光劑、耐衝撃性改良劑、界面活性劑等。 The (meth) acrylic resin and the (meth) acrylic resin film 10 formed therefrom may contain additives as necessary. Examples of the additives include lubricants, anti-caking agents, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, lightfasteners, impact modifiers, and surfactants.

紫外線吸收劑可列舉水楊酸酯系化合物、二苯甲酮系化合物、苯並***系化合物、氰基丙烯酸酯系化合物、鎳 錯鹽系化合物等。 Examples of the ultraviolet absorber include a salicylate-based compound, a benzophenone-based compound, a benzotriazole-based compound, a cyanoacrylate-based compound, and a nickel salt-based compound.

就對膜之製膜性或膜的耐衝撃性等之觀點而言，(甲基)丙烯酸系樹脂可含有作為衝撃性改良劑的丙烯酸系橡膠粒。丙烯酸系橡膠粒係將以丙烯酸酯作為主體的彈性聚合物作為必需成分之粒子，實際上可列舉僅由此彈性聚合物形成之單層結構的橡膠粒或將此彈性聚合物作成1層的多層結構之橡膠粒。 The (meth) acrylic resin may contain acrylic rubber pellets as an impact modifier from the viewpoints of film forming properties and impact resistance of the film. Acrylic rubber particles are particles containing an elastic polymer mainly composed of acrylate as an essential component. Actually, a rubber layer having a single-layer structure formed only of the elastic polymer or a multilayer of the elastic polymer as a single layer can be cited. Structural rubber granules.

上述彈性聚合物之例，可列舉以丙烯酸酯作為主成分，使其與可共聚合的其他乙烯系單體及交聯性單體共聚合之交聯彈性共聚合物。 Examples of the elastic polymer include a crosslinked elastic copolymer having acrylate as a main component and copolymerized with other copolymerizable vinyl monomers and crosslinkable monomers.

作為彈性聚合物的主成分之丙烯酸酯，可列舉：例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等烷基的碳數為1以上8以下左右者，並以具有碳數4以上的烷基之丙烯酸烷酯為佳。 Examples of the acrylate as the main component of the elastic polymer include those having an alkyl group having a carbon number of 1 to 8 or less, such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Alkyl acrylate having an alkyl group having 4 or more carbon atoms is preferred.

上述可與丙烯酸酯共聚合的其他乙烯系單體，可列舉分子內具有1個聚合性碳-碳雙鍵的化合物，更具體言之，可列舉甲基丙烯酸甲酯等甲基丙烯酸酯；苯乙烯等芳香族乙烯化合物；丙烯腈等乙烯氰化合物等。 Examples of the other vinyl-based monomers copolymerizable with the acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylates such as methyl methacrylate; benzene Aromatic vinyl compounds such as ethylene; vinyl cyanide compounds such as acrylonitrile.

上述交聯性單體，可列舉分子內具有至少2個聚合性碳-碳雙鍵的交聯性化合物，更具體言之，可列舉乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯等多元醇的(甲基)丙烯酸酯類；(甲基)丙烯酸烯丙酯等(甲基)丙烯酸的烯酯；二乙烯苯等。 Examples of the crosslinkable monomer include crosslinkable compounds having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate and butanediol di (Meth) acrylates of polyols such as (meth) acrylates; allyl esters of (meth) acrylic acid such as allyl (meth) acrylate; divinylbenzene and the like.

丙烯酸系橡膠粒的平均直徑，通常是50nm 以上400nm以下。 The average diameter of the acrylic rubber particles is usually 50 nm to 400 nm.

相對於(甲基)丙烯酸系樹脂100質量份，丙烯酸系橡膠粒的含量，通常是5質量份以上50質量份以下。 The content of the acrylic rubber pellets is usually 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the (meth) acrylic resin.

經混合丙烯酸系橡膠粒的(甲基)丙烯酸系樹脂，可列舉市售品的「HT55X」(商品名住友化學(股))等。 Examples of the (meth) acrylic resin mixed with the acrylic rubber particles include "HT55X" (trade name: Sumitomo Chemical Co., Ltd.), which is a commercially available product.

(甲基)丙烯酸系樹脂膜10，可以是由不含橡膠粒的(甲基)丙烯酸系樹脂形成之層與由含橡膠粒的(甲基)丙烯酸系樹脂形成之層之積層體。 The (meth) acrylic resin film 10 may be a laminate of a layer formed of a (meth) acrylic resin not containing rubber particles and a layer formed of a (meth) acrylic resin containing rubber particles.

(甲基)丙烯酸系樹脂膜10的厚度，通常是5μm以上200μm以下，並以10μm以上120μm以下為佳，以10μm以上85μm以下更佳，而以15μm以上65μm以下又更佳。 The thickness of the (meth) acrylic resin film 10 is usually 5 μm or more and 200 μm or less, preferably 10 μm or more and 120 μm or less, more preferably 10 μm or more and 85 μm or less, and even more preferably 15 μm or more and 65 μm or less.

又，(甲基)丙烯酸系樹脂膜10為多層時，係以其整體的厚度在上述範圍內為佳。 When the (meth) acrylic resin film 10 has a plurality of layers, the entire thickness is preferably within the above range.

(甲基)丙烯酸系樹脂膜10，其外表面(與第1接著劑層15相反側之表面)可具備硬塗層、防眩層、抗反射層、光擴散層、抗靜電層、防污層、導電層等表面處理層(塗布層)。 The (meth) acrylic resin film 10 may include a hard coat layer, an anti-glare layer, an anti-reflection layer, a light diffusion layer, an antistatic layer, and an antifouling on the outer surface (the surface opposite to the first adhesive layer 15) Surface treatment layers (coating layers) such as layers and conductive layers.

就提高密合性之觀點而言，對於(甲基)丙烯酸系樹脂膜10的黏合面亦可進行皂化處理、電漿處理、電暈處理、底漆處理等表面改質處理。替代(甲基)丙烯酸系樹脂膜10的黏合面，可在該黏合面或在偏光片30的黏合面一起進行表面改質處理。 From the viewpoint of improving adhesion, the surface of the (meth) acrylic resin film 10 may be subjected to surface modification treatments such as saponification treatment, plasma treatment, corona treatment, and primer treatment. Instead of the bonding surface of the (meth) acrylic resin film 10, surface modification treatment may be performed on the bonding surface or the bonding surface of the polarizer 30 together.

(甲基)丙烯酸系樹脂膜與第1接著劑層接觸 時，(甲基)丙烯酸系樹脂膜與第1接著劑層的接觸面之水接觸角，係以80°以下為佳，並以70°以下更佳，而以65°以下又更佳。(甲基)丙烯酸系樹脂膜與第1接著劑層的接觸面之水接觸角，其下限並無特別的限制，但通常是20°以上。 When the (meth) acrylic resin film is in contact with the first adhesive layer, the water contact angle of the contact surface between the (meth) acrylic resin film and the first adhesive layer is preferably 80 ° or less, and 70 Below °° is better, and below 65 ° is even better. The lower limit of the water contact angle at the contact surface between the (meth) acrylic resin film and the first adhesive layer is not particularly limited, but it is usually 20 ° or more.

(甲基)丙烯酸系樹脂膜與第1接著劑層的接觸面之水接觸角為80°以下時，偏光片與(甲基)丙烯酸系樹脂膜之間的密合性，不僅在濕熱環境(高溫高濕環境)而且在室溫(例如23℃、相對濕度55%)下也良好。 When the contact angle of water between the (meth) acrylic resin film and the first adhesive layer is 80 ° or less, the adhesion between the polarizer and the (meth) acrylic resin film is not only in a hot and humid environment ( High-temperature and high-humidity environment) and also good at room temperature (for example, 23 ° C, 55% relative humidity).

(甲基)丙烯酸系樹脂膜與第1接著劑層的接觸面之水接觸角，可藉由施予例如上述的表面改質處理而得到所求的水接觸角。 The water contact angle at the contact surface between the (meth) acrylic resin film and the first adhesive layer can be obtained by, for example, applying the surface modification treatment described above.

[5]熱塑性樹脂膜     [5] Thermoplastic resin film    

熱塑性樹脂膜20係以具有透光性的熱塑性樹脂膜為佳。熱塑性樹脂膜例如可為由鏈狀聚烯烴系樹脂(聚丙烯系樹脂等)、環狀聚烯烴系樹脂(降冰片烯系樹脂等)等聚烯烴系樹脂；三乙醯基纖維素、二乙醯基纖維素等纖維素酯系樹脂；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯等聚酯系樹脂；聚碳酸酯系樹脂；(甲基)丙烯酸系樹脂；或該等的混合物、共聚合物等形成之膜。 The thermoplastic resin film 20 is preferably a thermoplastic resin film having translucency. The thermoplastic resin film may be, for example, a polyolefin resin such as a chain polyolefin resin (such as a polypropylene resin) or a cyclic polyolefin resin (such as a norbornene resin); triethylfluorene cellulose; diethylene glycol; Cellulose ester resins such as fluorenyl cellulose; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycarbonate resins; Base) acrylic resin; or a mixture of these, a copolymer, and the like.

熱塑性樹脂膜20為(甲基)丙烯酸系樹脂膜時，可引用有關(甲基)丙烯酸系樹脂膜10的上述記載。 When the thermoplastic resin film 20 is a (meth) acrylic resin film, the above description regarding the (meth) acrylic resin film 10 can be cited.

熱塑性樹脂膜20可以是未延伸膜、或經單 軸或二軸延伸之膜的任一種。二軸延伸可以是同時朝2個延伸方向延伸的二軸延伸，也可以是朝第1方向延伸之後再朝與此不同的第2方向延伸之逐次二軸延伸。 The thermoplastic resin film 20 may be an unstretched film or a film stretched uniaxially or biaxially. The biaxial extension may be a biaxial extension that extends in two extension directions at the same time, or a sequential biaxial extension that extends in a second direction after extending in the first direction.

熱塑性樹脂膜20可以是發揮保護偏光片30之機能的保護膜，也可以是兼具相位差膜等光學機能的保護膜。 The thermoplastic resin film 20 may be a protective film that exerts the function of protecting the polarizer 30, or a protective film that also has optical functions such as a retardation film.

鏈狀聚烯烴系樹脂係除了聚乙烯樹脂、聚丙烯樹脂等鏈狀烯烴的均聚物以外，可列舉由2種以上的鏈狀烯烴形成之共聚合物。 The chain polyolefin resin is a copolymer of two or more types of chain olefins, in addition to homopolymers of chain olefins such as polyethylene resins and polypropylene resins.

環狀聚烯烴系樹脂係含有以降冰片烯或四環十二烯(又名：二甲橋八氫萘(dimethanooctahydronaphthalene))或該等的衍生物為代表例之環狀烯烴作為聚合單元的樹脂之總稱。環狀聚烯烴系樹脂，可列舉環狀烯烴的開環(共)聚合物及其氫化物，環狀烯烴的加成聚合物，環狀烯烴與乙烯、丙烯等鏈狀烯烴或具有乙烯基的芳香族化合物之共聚合物，以及此等烯烴經不飽和羧酸或其衍生物改質的改質(共)聚合物等。 The cyclic polyolefin resin is a resin containing a norbornene or tetracyclododecene (also known as: dimethanooctahydronaphthalene) or a derivative thereof as a representative example of a cyclic olefin resin. Collectively. Examples of the cyclic polyolefin resin include ring-opened (co) polymers of cyclic olefins and hydrides thereof, addition polymers of cyclic olefins, cyclic olefins and chain olefins such as ethylene and propylene, or those having a vinyl group. Copolymers of aromatic compounds, and modified (co) polymers of these olefins modified by unsaturated carboxylic acids or their derivatives.

其中，以使用降冰片烯或多環降冰片烯單體等降冰片烯單體作為環狀烯烴之降冰片烯系樹脂為適用。 Among them, a norbornene-based resin using a norbornene monomer such as norbornene or a polycyclic norbornene monomer as a cyclic olefin is suitable.

纖維素酯系樹脂係纖維素中的羥基之至少一部分經乙酸酯化的樹脂，可以是一部分經乙酸酯化，一部分經其他酸酯化之混合酯。纖維素酯系樹脂係以乙醯基纖維素系樹脂為佳。 The cellulose ester-based resin is cellulose-based resin having at least a part of the hydroxyl groups acetated, and may be a mixed ester in which a part is acetated and a part is subjected to other acidification. The cellulose ester resin is preferably an ethyl cellulose resin.

乙醯基纖維素系樹脂可列舉三乙醯基纖維素、二乙醯基纖維素、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等。 Examples of the ethyl cellulose-based resin include triethyl cellulose, diethyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like.

聚酯系樹脂係含有酯鍵的上述纖維素酯系樹脂以外之樹脂，通常是由多元酸或其衍生物與多元醇的聚縮合物形成者。 Polyester-based resins are resins other than the above-mentioned cellulose ester-based resins containing an ester bond, and are usually formed from a polycondensate of a polybasic acid or a derivative thereof and a polyhydric alcohol.

聚酯系樹脂可列舉聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、聚對苯二甲酸丙二酯、聚萘二甲酸丙二酯、聚環己烷對苯二甲酸二甲酯、聚環己烷萘二甲酸二甲酯等。 Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, and polyethylene. Propylene naphthalate, polycyclohexane dimethyl terephthalate, polycyclohexane naphthalate, and the like.

其中，就機械性質、耐溶劑性、耐刮擦性、成本等之觀點而言，係以聚對苯二甲酸乙二酯為適用。聚對苯二甲酸乙二酯係指重複單元的80莫耳%以上為對苯二甲酸乙二酯構成的樹脂，可含有來自其他的共聚合成分之構成單元。 Among these, polyethylene terephthalate is suitable in terms of mechanical properties, solvent resistance, scratch resistance, cost, and the like. Polyethylene terephthalate refers to a resin composed of 80 mol% or more of repeating units composed of ethylene terephthalate, and may contain constituent units derived from other copolymerization components.

其他的共聚合成分，可列舉二羧酸成分或二元醇成分。 Examples of other copolymerization components include a dicarboxylic acid component and a diol component.

二羧酸成分可列舉間苯二甲酸、4,4’-二羧基二苯、4,4’-二羧基二苯甲酮、雙(4-羧基苯基)乙烷、己二酸、癸二酸、間苯二甲酸5-磺酸鈉、1,4-二羧基環己烷等。 Examples of the dicarboxylic acid component include isophthalic acid, 4,4'-dicarboxydiphenyl, 4,4'-dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, adipic acid, and sebacic acid. Acid, sodium 5-sulfoisophthalate, 1,4-dicarboxycyclohexane, etc.

二元醇成分可列舉丙二醇、丁二醇、新戊二醇、二乙二醇、環己二醇、雙酚A的環氧乙烷加成物、聚乙二醇、聚丙二醇、聚丁二醇等。 Examples of the glycol component include propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, and polybutadiene. Alcohol and so on.

二羧酸成分或二醇成分可視需要分別將2種以上組合使用。 If necessary, a dicarboxylic acid component or a diol component may be used in combination of two or more kinds.

又，上述二羧酸成分或二元醇成分亦可與對-羥基苯甲酸、對-羥基乙氧基苯甲酸、β-羥基乙氧基苯甲酸酸等羥基 羧酸併用。 The dicarboxylic acid component or glycol component may be used in combination with hydroxycarboxylic acids such as p-hydroxybenzoic acid, p-hydroxyethoxybenzoic acid, and β-hydroxyethoxybenzoic acid.

也可少量使用具有醯胺鍵、胺酯鍵、醚鍵、碳酸酯鍵等的二羧酸成分及/或二元醇成分作為其他的共聚合成分。 A dicarboxylic acid component and / or a diol component having a amine bond, an amine ester bond, an ether bond, a carbonate bond, or the like may be used in small amounts as other copolymerization components.

聚碳酸酯系樹脂係由碳酸與二元醇或雙酚形成之聚酯。其中就耐熱性、耐候性及耐酸性之觀點而言，係以分子鏈具有二苯基烷的芳香族聚酸酯為適用。 Polycarbonate resin is a polyester formed from carbonic acid and a diol or bisphenol. Among them, in terms of heat resistance, weather resistance, and acid resistance, an aromatic polyester having a diphenylalkane in the molecular chain is suitable.

聚碳酸酯可列舉2,2-雙(4-羥基苯基)丙烷(又名雙酚A)、2,2-雙(4-羥基苯基)丁烷、1,1-雙(4-羥基苯基)環己烷、1,1-雙(4-羥基苯基)異丁烷、1,1-雙(4-羥基苯基)乙烷等由雙酚衍生之聚碳酸酯。 Examples of the polycarbonate include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, and 1,1-bis (4-hydroxy Polycarbonates derived from bisphenol, such as phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) isobutane, 1,1-bis (4-hydroxyphenyl) ethane.

熱塑性樹脂膜20，係以纖維素酯系樹脂膜或環狀聚烯烴系樹脂膜為佳。 The thermoplastic resin film 20 is preferably a cellulose ester resin film or a cyclic polyolefin resin film.

熱塑性樹脂膜20可視需要含有添加劑。添加劑可列舉：例如滑劑、抗結塊劑、熱穩定劑、抗氧化劑、紫外線吸收劑、抗靜電劑、耐光劑、耐衝撃性改良劑、界面活性劑等。 The thermoplastic resin film 20 may contain additives if necessary. Examples of the additives include lubricants, anti-caking agents, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, lightfasteners, impact modifiers, and surfactants.

紫外線吸收劑可列舉水楊酸酯系化合物、二苯甲酮系化合物、苯並***系化合物、氰基丙烯酸酯系化合物、鎳錯鹽系化合物等。 Examples of the ultraviolet absorber include a salicylate-based compound, a benzophenone-based compound, a benzotriazole-based compound, a cyanoacrylate-based compound, and a nickel salt-based compound.

將偏光板使用在液晶顯示器等圖像顯示器時，藉由將含有紫外線吸收劑的熱塑性樹脂膜20或含有紫外線吸收劑的(甲基)丙烯酸系樹脂膜10配置在圖像顯示元件(例如液晶單元)的觀看側，可防止圖像顯示元件因紫外線而劣 化。 When a polarizing plate is used for an image display such as a liquid crystal display, a thermoplastic resin film 20 containing an ultraviolet absorber or a (meth) acrylic resin film 10 containing an ultraviolet absorber is disposed on an image display element (for example, a liquid crystal cell). ) On the viewing side to prevent deterioration of the image display element due to ultraviolet rays.

熱塑性樹脂膜20的厚度通常是5μm以上200μm以下，並以10μm以上120μm以下為佳，以10μm以上85μm以下更佳，而以15μm以上60μm以下又更佳。熱塑性樹脂膜20的厚度可以是50μm以下，也可以是40μm以下。將熱塑性樹脂膜20的厚度減小，有利於偏光板乃至圖像顯示器的薄型化。 The thickness of the thermoplastic resin film 20 is usually 5 μm or more and 200 μm or less, preferably 10 μm or more and 120 μm or less, more preferably 10 μm or more and 85 μm or less, and even more preferably 15 μm or more and 60 μm or less. The thickness of the thermoplastic resin film 20 may be 50 μm or less, or 40 μm or less. Reducing the thickness of the thermoplastic resin film 20 is advantageous for thinning the polarizing plate and even the image display.

熱塑性樹脂膜20可於其外表面(與第2接著劑層25相反側之表面)具備硬塗層、防眩層、抗反射層、光擴散層、抗靜電層、防污層、導電層等表面處理層(塗布層)。 The thermoplastic resin film 20 may be provided with a hard coat layer, an anti-glare layer, an anti-reflection layer, a light diffusion layer, an anti-static layer, an anti-fouling layer, a conductive layer, etc. on its outer surface (the surface opposite to the second adhesive layer 25). Surface treatment layer (coating layer).

就提高密合性之觀點而言，可對熱塑性樹脂膜20的黏合面進行皂化處理、電漿處理、電暈處理、底漆處理等表面改質處理。可替代熱塑性樹脂膜20的黏合面，而在該黏合面與偏光片30的黏合面一起進行表面改質處理。 From the viewpoint of improving the adhesiveness, a surface modification treatment such as saponification treatment, plasma treatment, corona treatment, and primer treatment can be performed on the adhesive surface of the thermoplastic resin film 20. Instead of the bonding surface of the thermoplastic resin film 20, a surface modification treatment may be performed on the bonding surface together with the bonding surface of the polarizer 30.

熱塑性樹脂膜20為乙酸纖維系樹脂膜時，就提高密合性之觀點而言，係以進行皂化處理為佳。皂化處理可列舉浸泡在如氫氧化鈉或氫氧化鉀的鹼性水溶液中之方法。 When the thermoplastic resin film 20 is an acetate fiber-based resin film, it is preferable to perform a saponification treatment from the viewpoint of improving adhesion. The saponification treatment may be a method of immersion in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.

[6]第2接著劑層     [6] The second adhesive layer    

形成第2接著劑層25的接著劑，可以是上述的接著劑組成物(S)，也可以是與此不同的其他接著劑組成物。第2接著劑層25係以由接著劑組成物(S)形成的接著劑層為 佳。 The adhesive for forming the second adhesive layer 25 may be the above-mentioned adhesive composition (S), or may be another adhesive composition different from this. The second adhesive layer 25 is preferably an adhesive layer formed of an adhesive composition (S).

第2接著劑層25可以是接著劑組成物的硬化物層。 The second adhesive layer 25 may be a cured product layer of the adhesive composition.

第1接著劑層15及第2接著劑層25是由接著劑組成物(S)形成時，該等接著劑組成物可以是相同的組成，也可以是不同的組成。 When the first adhesive layer 15 and the second adhesive layer 25 are formed of an adhesive composition (S), the adhesive compositions may have the same composition or different compositions.

其他的接著劑組成物，可列舉將接著劑成分溶解或分散在水中的週知之水性接著劑及含有活性能量線硬化性化合物的週知之活性能量線硬化性接著劑等。 Examples of other adhesive compositions include known aqueous adhesives in which an adhesive component is dissolved or dispersed in water, and known active energy ray-curable adhesives containing an active energy ray-curable compound.

水性接著劑組成物可列舉聚乙烯醇系樹脂或胺酯樹脂等將接著劑成分溶解或分散在水中而成的水性接著劑組成物。 Examples of the aqueous adhesive composition include an aqueous adhesive composition obtained by dissolving or dispersing an adhesive component in water, such as a polyvinyl alcohol resin or an amine ester resin.

含有聚乙烯醇系樹脂的水性接著劑，為了提高接著性，可含有多元醛、三聚氰胺系化合物、氧化鋯化合物、鋅化合物、乙二醛、乙二醛衍生物、水溶性環氧樹脂等硬化性成分或交聯劑。 The water-based adhesive containing a polyvinyl alcohol-based resin may contain a polyhydric aldehyde, a melamine-based compound, a zirconia compound, a zinc compound, glyoxal, a glyoxal derivative, and a water-soluble epoxy resin in order to improve adhesion. Ingredients or crosslinkers.

含有胺酯樹脂的水性接著劑，可列舉含有聚酯系離子聚合物型胺酯樹脂與具有去水甘油基氧基的化合物之水性接著劑。聚酯系離子聚合物型胺酯樹脂係指具有聚酯骨架的胺酯樹脂，係於其中導入少量離子性成分(親水成分)者。 Examples of the aqueous adhesive containing an amine ester resin include an aqueous adhesive containing a polyester-based ionic polymer-type amine ester resin and a compound having a dehydrated glyceryloxy group. The polyester-based ionic polymer-type amine ester resin refers to an amine ester resin having a polyester skeleton, and a small amount of an ionic component (hydrophilic component) is introduced therein.

活性能量線硬化性接著劑係受到紫外線、可見光、電子束、X線等活性能量線的照射而硬化之接著劑。使用活性能量線硬化性接著劑時，第2接著劑層25係該接著劑的硬化物層。 Active energy ray-curable adhesives are adhesives that are cured by irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays. When an active energy ray-curable adhesive is used, the second adhesive layer 25 is a cured product layer of the adhesive.

活性能量線硬化性接著劑可以是含有藉由陽離子聚合而硬化的環氧系化合物作為硬化性成分的接著劑，較佳的是含有環氧系化合物作為硬化性成分的紫外線硬化性接著劑。環氧系化合物係指分子內平均具有1個以上的環氧基之化合物，並以具有2個以上的環氧基為佳。環氧系化合物可僅使用1種，也可併用2種以上。 The active energy ray-curable adhesive may be an adhesive containing an epoxy-based compound hardened by cation polymerization as a hardening component, and an ultraviolet-curable adhesive containing an epoxy-based compound as a hardening component is preferred. The epoxy-based compound refers to a compound having an average of one or more epoxy groups in the molecule, and preferably has two or more epoxy groups. The epoxy-based compound may be used alone or in combination of two or more.

環氧系化合物可列舉：使芳香族多元醇的芳香環進行氫化反應而得的脂環式多元醇與環氧氯丙烷反應所得的氫化環氧系化合物(具有脂環式環的多元醇之去水甘油醚)；脂肪族多元醇或其環氧烷加成物的聚去水甘油醚等脂肪族環氧系化合物；分子內具有1個以上與脂環式環結合的環氧基之環氧系化合物的脂環式環氧系化合物等。 Examples of the epoxy-based compound include a hydrogenated epoxy-based compound obtained by reacting an alicyclic polyol obtained by hydrogenating an aromatic ring of an aromatic polyol with epichlorohydrin (a polyhydric alcohol having an alicyclic ring). Water glyceryl ether); aliphatic polyhydric alcohols such as aliphatic polyhydric alcohols or alkylene oxide adducts thereof; and epoxy resins having more than one epoxy group bonded to an alicyclic ring in the molecule Alicyclic epoxy compounds and the like.

活性能量線硬化性接著劑，替代上述環氧系化合物可為該化合物或同時含有自由基聚合性的(甲基)丙烯酸系化合物作為硬化性成分。(甲基)丙烯酸系化合物，可列舉分子內具有1個以上的(甲基)丙烯醯氧基之(甲基)丙烯酸酯單體；使2種以上含有官能基的化合物反應而得之分子內具有至少2個(甲基)丙烯醯氧基的(甲基)丙烯酸酯寡聚物等含有(甲基)丙烯醯氧基之化合物。 The active-energy-ray-curable adhesive agent may be the compound or a radically polymerizable (meth) acrylic compound as a curable component instead of the epoxy-based compound. (Meth) acrylic compounds include (meth) acrylic acid ester monomers having one or more (meth) acryloxy groups in the molecule; and molecules obtained by reacting two or more types of compounds containing functional groups A (meth) acrylic acid oxy group-containing compound such as a (meth) acrylic acid ester oligomer having at least two (meth) acrylic acid groups.

活性能量線硬化性接著劑含有藉由陽離子聚合而硬化的環氧系化合物作為硬化性成分時，係以含有光陽離子聚合起始劑為佳。光陽離子聚合起始劑，可列舉：芳香族重氮鎓鹽；芳香族碘鎓鹽或芳香族硫鎓鹽等鎓鹽； 鐵-芳烴(arene)錯合物等。 When the active energy ray-curable adhesive contains an epoxy-based compound that is cured by cationic polymerization as a curable component, it is preferable to include a photocationic polymerization initiator. Examples of the photocationic polymerization initiator include: an aromatic diazonium salt; an onium salt such as an aromatic iodonium salt or an aromatic sulfonium salt; an iron-arene complex; and the like.

活性能量線硬化性接著劑含有(甲基)丙烯酸系化合物等自由基聚合性成分時，係以含有光自由基聚合起始劑為佳。光自由基聚合起始劑，可列舉：例如苯乙酮系起始劑、二苯甲酮系起始劑、安息香醚系起始劑、噻呫酮系起始劑、呫酮、芴酮、樟腦醌、苯甲醛、蒽醌等。 When the active energy ray-curable adhesive contains a radically polymerizable component such as a (meth) acrylic compound, it is preferable to include a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include acetophenone-based initiators, benzophenone-based initiators, benzoin-ether-based initiators, thienone-based initiators, fluorenone, fluorenone, Camphorquinone, benzaldehyde, anthraquinone, etc.

偏光板可以是含有黏著劑層替代第2接著劑層25者。即，可透過黏著劑層將熱塑性樹脂膜20黏合在偏光片30。該黏著劑層可引用後述的黏著劑層之記載。 The polarizing plate may include an adhesive layer instead of the second adhesive layer 25. That is, the thermoplastic resin film 20 can be adhered to the polarizer 30 through the adhesive layer. This adhesive layer can be referred to the description of the adhesive layer described later.

[7]偏光板的製造     [7] Manufacturing of polarizing plates    

藉由在偏光片30的一表面透過第1接著劑層15而積層接著(甲基)丙烯酸系樹脂膜10，可得第1圖所示構成的偏光板，藉由在偏光片30的另一表面透過第2接著劑層25再積層接著熱塑性樹脂膜20，可得第2圖所示構成的偏光板。 By laminating the (meth) acrylic resin film 10 through the first adhesive layer 15 on one surface of the polarizer 30, a polarizing plate having the structure shown in FIG. 1 can be obtained. The surface passes through the second adhesive layer 25, and then the thermoplastic resin film 20 is laminated, and a polarizing plate having a structure shown in FIG. 2 can be obtained.

製造具有(甲基)丙烯酸系樹脂膜10及熱塑性樹脂膜20兩者之偏光板時，此等膜可逐步的於各表面積層接著，也可將兩面的膜同時積層接著。 When manufacturing a polarizing plate having both a (meth) acrylic resin film 10 and a thermoplastic resin film 20, these films may be successively adhered to each surface area layer, or both surfaces of the film may be simultaneously laminated and adhered.

第1接著劑層15及/或第2接著劑層25，可以是接著劑組成物的硬化物層。 The first adhesive layer 15 and / or the second adhesive layer 25 may be a cured product layer of the adhesive composition.

將偏光片30與(甲基)丙烯酸系樹脂膜10接著的方法，可列舉將接著劑組成物(S)塗布在偏光片30及(甲基)丙烯酸系樹脂膜10的黏合面之任一方或其兩方，再 於其上積層另一方的黏合面，例如用黏合輥等上下推押而黏合的方法。 The method of adhering the polarizer 30 and the (meth) acrylic resin film 10 includes an application of the adhesive composition (S) to any one of the adhesion surfaces of the polarizer 30 and the (meth) acrylic resin film 10 or The two sides are laminated on top of each other, for example, a method of pushing up and down with an adhesive roller or the like to adhere.

在塗布接著劑組成物(S)時，可利用：例如刮刀片、線棒、模塗機、逗點式塗布機、凹板塗布機等各種塗布方式。同時，也可以使偏光片30及(甲基)丙烯酸系樹脂膜10兩者的黏合面成為內側之方式，一邊連續的供應，一邊使接著劑組成物(S)流延在其間。 When applying the adhesive composition (S), various coating methods such as a doctor blade, a wire rod, a die coater, a comma coater, and a gravure coater can be used. At the same time, the adhesive composition (S) may be cast therebetween while the adhesive surfaces of both the polarizer 30 and the (meth) acrylic resin film 10 are inside.

將偏光片30與(甲基)丙烯酸系樹脂膜10黏合之後，係以對含有偏光片30、第1接著劑層15與(甲基)丙烯酸系樹脂膜10的積層體施加加熱處理為佳。加熱處理的溫度，係例如40℃以上100℃以下，並以50℃以上90℃以下為佳。可藉由加熱處理去除接著劑組成物層中含有的溶劑。又，在接著劑組成物為硬化性的接著劑組成物時，可藉由該加熱處理而使其進行硬化、交聯反應。 After the polarizer 30 and the (meth) acrylic resin film 10 are adhered, it is preferable to apply a heat treatment to a laminate including the polarizer 30, the first adhesive layer 15, and the (meth) acrylic resin film 10. The temperature of the heat treatment is, for example, 40 ° C to 100 ° C, and preferably 50 ° C to 90 ° C. The solvent contained in the adhesive composition layer can be removed by heat treatment. When the adhesive composition is a curable adhesive composition, the heat treatment can be used to harden and crosslink the reaction.

以上的接著方法也可適用於偏光片30與熱塑性樹脂膜20的接著。 The above bonding method is also applicable to the bonding of the polarizer 30 and the thermoplastic resin film 20.

使用活性能量線硬化性接著劑時，視需要而進行接著劑組成物層的乾燥之後，照射活性能量線而使接著劑組成物層硬化。 When an active energy ray-curable adhesive is used, the adhesive composition layer is dried as necessary, and then the active energy ray is irradiated to harden the adhesive composition layer.

為了照射活性能量線而使用的光源，只要是可產生紫外線、電子束、X線等者即可。尤其適用具有波長400nm以下的發光分布之光源，例如低壓水銀燈、中壓水銀燈燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、激發微波水銀燈、金屬鹵素燈等。 The light source used for irradiating active energy rays may be any material that can generate ultraviolet rays, electron beams, X-rays, and the like. Particularly suitable for light sources with a light emission distribution below 400nm, such as low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, excited microwave mercury lamps, metal halide lamps, etc.

由接著劑組成物(S)形成的第1接著劑層15之厚度，係例如10nm以上10μm以下，並以20nm以上5μm以下為佳，以30nm以上1μm以下更佳，而以40nm以上500nm以下又更佳。由上述周知的水性接著劑形成之接著劑層，也可具有與此等相同程度的厚度。 The thickness of the first adhesive layer 15 formed of the adhesive composition (S) is, for example, 10 nm to 10 μm, preferably 20 nm to 5 μm, more preferably 30 nm to 1 μm, and more preferably 40 nm to 500 nm. Better. The adhesive layer formed of the above-mentioned known aqueous adhesive may have the same thickness.

由活性能量線硬化性接著劑形成的接著劑層之厚度，係例如10nm以上20μm以下，並以100nm以上10μm以下為佳，而以500nm以上5μm以下更佳。 The thickness of the adhesive layer formed of the active energy ray-curable adhesive is, for example, 10 nm to 20 μm, preferably 100 nm to 10 μm, and more preferably 500 nm to 5 μm.

第1接著劑層15與第2接著劑層25，其厚度可以相同，也可不同。 The thickness of the first adhesive layer 15 and the second adhesive layer 25 may be the same or different.

[8]偏光板的其他構成要素     [8] Other components of polarizing plate     [8-1]光學機能性膜     [8-1] Optical functional film    

為賦與所需的光學機能，偏光板可具備偏光片30以外的其他光學機能性膜，其合適之一例是相位差膜。 In order to impart a desired optical function, the polarizing plate may be provided with an optical functional film other than the polarizer 30, and a suitable example thereof is a retardation film.

如上述，(甲基)丙烯酸系樹脂膜10及/或熱塑性樹脂膜20可兼為相位差膜，但也可與此等膜分開積層相位差膜。後者之情況，相位差膜可透過黏着劑層或接著劑層而積層在(甲基)丙烯酸系樹脂膜10及/或熱塑性樹脂膜20的外表面。 As described above, the (meth) acrylic resin film 10 and / or the thermoplastic resin film 20 may also serve as a retardation film, but the retardation film may be laminated separately from these films. In the latter case, the retardation film can be laminated on the outer surfaces of the (meth) acrylic resin film 10 and / or the thermoplastic resin film 20 through an adhesive layer or an adhesive layer.

相位差膜可列舉由具有透光性的熱塑性樹脂之延伸膜構成的雙折射膜；經配向固定的盤狀液晶或向列液晶之膜；在基材膜上形成上述液晶層者等。 Examples of the retardation film include a birefringent film composed of a stretched film of a thermoplastic resin having translucency; a film of a discotic liquid crystal or a nematic liquid crystal fixed by alignment; and a liquid crystal layer formed on a substrate film.

基材膜通常是由熱塑性樹脂形成之膜，熱塑性樹脂之 一例，係三乙醯基纖維素等纖維素酯系樹脂。 The base film is usually a film made of a thermoplastic resin. One example of the thermoplastic resin is a cellulose ester resin such as triethylfluorinated cellulose.

可含在偏光板中的其他光學機能性膜(光學材料)之例為聚光板、亮度改善膜、反射層(反射膜)、半透過反射層(半透過反射膜)、光擴散層(光擴散膜)等。該等膜通常是在偏光板係配置在液晶單元背面側(背光側)之偏光板的情形設置。 Examples of other optically functional films (optical materials) that can be included in a polarizing plate are a light collecting plate, a brightness improving film, a reflective layer (reflective film), a semi-transparent reflective layer (semi-transparent reflective film), and a light diffusion layer (light diffusion). Film) and so on. These films are usually provided when a polarizing plate is a polarizing plate arranged on the back side (backlight side) of a liquid crystal cell.

聚光板係用於光路控制等目的者，且可附設稜鏡陣列片或透鏡陣列片、點附件片等。 The light collecting plate is used for light path control and other purposes, and can be provided with a 稜鏡 array sheet, a lens array sheet, a point attachment sheet, and the like.

亮度提高膜係以提高適用偏光板的液晶顯示器中之亮度的目的而使用。具體上，可列舉積層數片折射率的異方性相互不同之薄膜而以使反射率產生異方性的方式設計的反射型偏光分離片、在基材膜上支撐膽固醇液晶高分子的配向膜或其配向液晶層的圓偏光分離片等。 The brightness enhancement film is used for the purpose of improving the brightness in a liquid crystal display to which a polarizing plate is applied. Specific examples include reflective polarizing separation sheets that are laminated to form films having different anisotropies from each other and have anisotropy in reflectance, and an alignment film that supports a cholesteric liquid crystal polymer on a base film. Or a circularly polarized light separation sheet or the like that aligns the liquid crystal layer.

反射層、半透過反射層、光擴散層可為了將偏光板作成反射型、半透過型、擴散型的光學材料而分別設置。反射型的偏光板可使用在將來自觀看側之入射光反射而顯示型的液晶顯示器，因可省略背光等光源，故容易使液晶顯示器薄型化。半透過型的偏光板，可使用於在明亮處作為反射型，暗處顯示來自背光的光的型式之液晶顯示器。擴散型的偏光板，可使用於給予光擴散性而防止雲紋等顯示不良的液晶顯示器。反射層、半透過反射層及光擴散層可由周知的方法形成。 The reflective layer, the semi-transmissive reflective layer, and the light diffusion layer may be separately provided for making the polarizing plate into a reflective, semi-transmissive, or diffused optical material. The reflective polarizing plate can be used for a liquid crystal display that reflects incident light from the viewing side and displays it. Since a light source such as a backlight can be omitted, the liquid crystal display can be easily made thin. A transflective polarizer can be used as a reflective type in bright places and a liquid crystal display that displays light from the backlight in dark places. Diffusion-type polarizers can be used in liquid crystal displays that provide light diffusivity and prevent moire such as moire. The reflection layer, the transflective reflection layer, and the light diffusion layer can be formed by a known method.

[8-2]黏著劑層     [8-2] Adhesive layer    

本發明的偏光板可含有黏著劑層。黏著劑層可列舉將偏光板黏合在液晶單元等圖像顯示元件或其他的光學材料用之黏著劑層。在如第1圖所示的構成之偏光板中，該黏著劑層可積層在偏光片30的外表面，在如第2圖所示的構成之偏光板中，可積層在(甲基)丙烯酸系樹脂膜10或熱塑性樹脂膜20的外表面。 The polarizing plate of the present invention may contain an adhesive layer. Examples of the adhesive layer include an adhesive layer for adhering a polarizing plate to an image display element such as a liquid crystal cell or other optical materials. In the polarizing plate having the structure shown in FIG. 1, the adhesive layer may be laminated on the outer surface of the polarizer 30. In the polarizing plate having the structure shown in FIG. 2, it may be laminated with (meth) acrylic acid. The outer surface of the resin film 10 or the thermoplastic resin film 20.

黏著劑層使用的黏著劑，可使用將(甲基)丙烯酸系樹脂、或聚矽氧系樹脂、聚酯系樹脂、聚胺酯系樹脂、聚醚系樹脂等作成基礎聚合物者。其中，就透明性、黏著力、可靠性、耐候性、耐熱性、再加工性等觀點而言，係以(甲基)丙烯酸系黏著劑為佳。 As the adhesive used in the adhesive layer, a (meth) acrylic resin, or a silicone resin, a polyester resin, a polyurethane resin, a polyether resin, or the like can be used as a base polymer. Among these, from the viewpoints of transparency, adhesion, reliability, weather resistance, heat resistance, and reworkability, a (meth) acrylic adhesive is preferred.

(甲基)丙烯酸系黏著劑係將具有甲基、乙基、正-、異-或第三-丁基等碳數為20以下的烷基之(甲基)丙烯酸烷酯、與(甲基)丙烯酸或(甲基)丙烯酸羥基乙酯等含有官能基之(甲基)丙烯酸系單體，以使玻璃轉移溫度較佳成為25℃以下，更佳是成為0℃以下之方式加以調配，所得之重量平均分子量為10萬以上的(甲基)丙烯酸系樹脂係有用於作為基礎高分子。 The (meth) acrylic adhesive is an alkyl (meth) acrylate having an alkyl group having a carbon number of 20 or less such as methyl, ethyl, n-, iso-, or tert-butyl, and (meth) acrylate ) Acrylic acid or (meth) acrylic acid-containing hydroxyethyl (meth) acrylic monomers containing functional groups are blended so that the glass transition temperature is preferably 25 ° C or lower, and more preferably 0 ° C or lower. A (meth) acrylic resin having a weight average molecular weight of 100,000 or more is used as a base polymer.

於偏光板形成之黏著劑層，可藉由例如使黏著劑組成物溶解或分散在甲苯或乙酸乙酯等有機溶劑中而調製黏著劑液，將其直接塗布在偏光板的對象面而形成黏著劑層的方式，或在已施予離型處理的分離膜上形成片狀的黏著劑層，並將其轉移到偏光板的對象面之方式等進行。 The adhesive layer formed on the polarizing plate can be prepared by dissolving or dispersing the adhesive composition in an organic solvent such as toluene or ethyl acetate to prepare an adhesive liquid, and directly applying the liquid to the object surface of the polarizing plate to form an adhesive A method of forming an adhesive layer or a method of forming a sheet-shaped adhesive layer on a separation film that has been subjected to a release treatment and transferring the sheet-shaped adhesive layer to a target surface of a polarizing plate.

黏著劑層的厚度雖然是配合其接著力等而決，但以1μm以上50μm以下的範圍為適當，並以2μm以上40μm以下為佳。 Although the thickness of the adhesive layer depends on the adhesive force and the like, it is preferably in a range of 1 μm to 50 μm, and more preferably in a range of 2 μm to 40 μm.

偏光板可含有上述的分離膜。分離膜可以是由聚乙烯等聚乙烯系樹脂、聚丙烯等聚丙烯系樹脂、聚對苯二甲酸乙二酯等聚酯系樹脂等形成之膜。其中，並以聚對苯二甲酸乙二酯的延伸膜為佳。 The polarizing plate may contain the above-mentioned separation film. The separation membrane may be a membrane formed of a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, a polyester resin such as polyethylene terephthalate, and the like. Among them, a stretched film of polyethylene terephthalate is preferred.

黏著劑層可視需要含有玻璃纖維、玻璃粒、樹脂粒、由金屬粉或其他的無機粉末形成之充填劑、顏料、著色劑、抗氧化劑、紫外線吸收劑、抗靜電劑等。 The adhesive layer may contain glass fibers, glass particles, resin particles, fillers made of metal powder or other inorganic powders, pigments, colorants, antioxidants, ultraviolet absorbers, antistatic agents, etc., as needed.

抗靜電劑可列舉：例如離子性化合物、導電性微粒、導電性高分子等，但以離子性化合物為適用。 Examples of the antistatic agent include ionic compounds, conductive fine particles, and conductive polymers. However, ionic compounds are suitable.

構成離子性化合物的陽離子成分可以是無機陽離子，也可以是有機陽離子。 The cation component constituting the ionic compound may be an inorganic cation or an organic cation.

有機陽離子可列舉吡啶鎓陽離子、咪唑鎓陽離子、銨陽離子、硫鎓陽離子、磷鎓陽離子、哌啶鎓陽離子、吡咯啶鎓陽離子等；無機陽離子可列舉鋰離子、鉀離子等。 Examples of organic cations include pyridinium cations, imidazolium cations, ammonium cations, sulfonium cations, phosphonium cations, piperidinium cations, and pyrrolidinium cations; and inorganic cations include lithium ions, potassium ions, and the like.

另一方面，構成離子性化合物的陰離子成分可以是無機陰離子，也可以是有機陰離子，但就提供抗靜電性能優異的離子性化合物而言，係以含有氟原子的陰離子成分為佳。含有氟原子的陰離子成分可列舉六氟磷酸鹽陰離子[(PF6 -)]、雙(三氟甲烷磺醯基)醯亞胺陰離子[(CF3SO2)2N-]陰離子、雙(氟磺醯基)醯亞胺陰離子[(FSO2)2N-]陰離子等。 On the other hand, the anionic component constituting the ionic compound may be an inorganic anion or an organic anion, but in terms of providing an ionic compound having excellent antistatic properties, an anionic component containing a fluorine atom is preferred. An anionic component containing a fluorine atom include hexafluorophosphate anion [(PF 6 -)], bis (trifluoromethane sulfonic acyl) acyl imide anion [(CF 3 SO 2) 2 N -] anion, bis (fluoromethyl sulfo acyl) acyl imide anion [(FSO 2) 2 N - ] anion.

[8-3]保護膜     [8-3] Protective film    

本發明的偏光板可含有保護其表面(典型的是(甲基)丙烯酸系樹脂膜10或熱塑性樹脂膜20的表面)用之保護膜。保護膜可在偏光板黏合在例如圖像顯示元件或其他的光學材料之後，將其連同所具有之黏著劑層一起剝離去除。 The polarizing plate of the present invention may contain a protective film for protecting the surface thereof (typically, the surface of the (meth) acrylic resin film 10 or the thermoplastic resin film 20). After the protective film is adhered to, for example, an image display element or other optical material, the protective film can be peeled off together with the adhesive layer.

保護膜係由例如基材膜與積層在其上的黏著劑層構成。有關黏著劑層可引用上述記載。 The protective film is composed of, for example, a base film and an adhesive layer laminated thereon. Regarding the adhesive layer, the above description can be cited.

構成基材膜的樹脂為例如聚乙烯類的聚乙烯系樹脂、聚丙烯類的聚丙烯系樹脂、聚對苯二甲酸乙二酯或聚萘二甲酸乙二酯類的聚酯系樹脂、聚碳酸酯系樹脂等的熱塑性樹脂。較佳的是聚對苯二甲酸乙二酯等聚酯系樹脂。 The resin constituting the base film is, for example, polyethylene-based polyethylene-based resin, polypropylene-based polypropylene-based resin, polyethylene terephthalate or polyethylene naphthalate-based polyester resin, or polymer A thermoplastic resin such as a carbonate resin. Polyester resins such as polyethylene terephthalate are preferred.

<液晶面板及液晶顯示器>     <LCD panel and LCD display>    

本發明的偏光板可使用於液晶面板及液晶顯示器。液晶面板含有液晶單元與配置在其兩面的偏光板。液晶顯示器含有液晶面板與背光。 The polarizing plate of the present invention can be used in a liquid crystal panel and a liquid crystal display. The liquid crystal panel includes a liquid crystal cell and polarizing plates arranged on both sides thereof. The liquid crystal display includes a liquid crystal panel and a backlight.

本發明的偏光板可配置在液晶單元的單面或兩面。偏光板與液晶單元間的黏著，可使用黏著劑層。 The polarizing plate of the present invention can be arranged on one or both sides of a liquid crystal cell. For the adhesion between the polarizing plate and the liquid crystal cell, an adhesive layer can be used.

液晶單元可以是任何一種，例如代表薄膜電晶體型的主動矩陣驅動型液晶單元、代表超扭曲向列型的單純矩陣驅動型液晶單元等，可使用各種的液晶單元形成液晶面板及液晶顯示器。設在液晶單元兩面之偏光板，可以是相同者，也可以是不同者。 The liquid crystal cell may be any type, for example, an active matrix driving liquid crystal cell representing a thin film transistor type, a simple matrix driving liquid crystal cell representing a super twisted nematic type, and the like. Various liquid crystal cells may be used to form a liquid crystal panel and a liquid crystal display. The polarizing plates provided on both sides of the liquid crystal cell may be the same or different.

[實施例]     [Example]    

以下，雖然是呈示實施例以更具體的說明本發明，但本發明並非侷限於此等例者。表示含有量或使用量的%及份，如無特別的說明，係質量基準。 In the following, the present invention is more specifically described by presenting examples, but the present invention is not limited to these examples. Contents and percentages and parts used, unless otherwise specified, are based on quality.

表1中，含噁唑啉基的聚合物(A)及乙醯基乙醯基改質聚乙烯醇(B)，係分別簡稱為(A)、(B)。 In Table 1, the polymer (A) containing an oxazoline group and the modified polyvinyl alcohol (B) with an ethyl amidino group are abbreviated as (A) and (B), respectively.

(製造例1：甲基(丙烯酸)系樹脂膜的製作)     (Manufacturing example 1: Production of a methyl (acrylic) resin film)    

準備甲基丙烯酸甲酯/丙烯酸甲酯=96%/4%(質量比)的共聚合物作為(甲基)丙烯酸系樹脂。又，準備一種具有三層結構的彈性體粒子作為橡膠粒，其最內層是由使用甲基丙烯酸甲酯與少量的甲基丙烯酸烯丙酯聚合而成的硬質聚合物所形成，中間層是由使用丙烯酸丁酯為主成分，並使用苯乙烯及少量的甲基丙烯酸烯丙酯聚合而成的軟質彈性體所形成，最外層是使用甲基丙烯酸甲酯與少量的丙烯酸乙酯聚合而成之硬質聚合物，且至中間層的彈性體之平均粒徑為240nm者。又，此橡膠粒中，最內層與中間層的合計質量，係整體粒子的70%。 As a (meth) acrylic resin, a copolymer of methyl methacrylate / methyl acrylate = 96% / 4% (mass ratio) was prepared. In addition, an elastomer particle having a three-layer structure is prepared as a rubber particle. The innermost layer is formed of a hard polymer polymerized by using methyl methacrylate and a small amount of allyl methacrylate. The intermediate layer is It is formed by using butyl acrylate as the main component, and using styrene and a small amount of allyl methacrylate polymerized soft elastomer. The outermost layer is made of methyl methacrylate and a small amount of ethyl acrylate. It is a hard polymer and the average particle diameter of the elastomer to the intermediate layer is 240 nm. In this rubber pellet, the total mass of the innermost layer and the intermediate layer is 70% of the total pellets.

利用超級混合機，將上述(甲基)丙烯系樹脂68.5質量%、上述橡膠粒29.6質量%及株式會社ADEKA社製造的紫外線吸收劑「Adekastab LA 31」1.9質量%混合，利用二軸押出機熔融混練作成顆粒。將此顆粒投入65mm 單軸押出機中，透過設定溫度275℃的T型模具押出，夾住具有鏡面的兩個拋光輥膜的兩面、冷卻，獲得 厚度60μm的(甲基)丙烯酸系樹脂膜。 Using a super mixer, 68.5% by mass of the (meth) acrylic resin, 29.6% by mass of the rubber pellets, and 1.9% by mass of the ultraviolet absorber "Adekastab LA 31" manufactured by ADEKA Corporation were mixed and melted by a biaxial extruder. Knead into granules. Put this particle into 65mm In a uniaxial extruder, extrude through a T-shaped mold at a set temperature of 275 ° C., clamp both sides of two polishing roll films with mirror surfaces, and cool to obtain a (meth) acrylic resin film with a thickness of 60 μm.

(製造例2：偏光片的製作)     (Manufacturing Example 2: Production of Polarizer)    

將平均聚合度約2,400、皂化度99.9莫耳%以上且厚度60μm的聚乙烯醇膜浸泡在30℃的純水中之後，在30℃浸泡在碘/碘化鉀/水的質量比為0.02/2/100之水溶液中。然後，在56.5℃，浸泡在碘化鉀/硼酸/水的質量比為12/5/100之水溶液中。隨後，以8℃的純水洗淨之後，在65℃乾燥，獲得碘已吸附配向在聚乙烯醇中的偏光片。延伸主要是於碘染色及硼酸處理的步驟進行，全延伸倍率是5.5倍，所得的偏光片之厚度是23μm。 A polyvinyl alcohol film having an average degree of polymerization of about 2,400, a degree of saponification of 99.9 mol% or more, and a thickness of 60 μm was immersed in pure water at 30 ° C, and then the mass ratio of iodine / potassium iodide / water was 0.02 / 2 / 100% aqueous solution. Then, it was immersed in an aqueous solution having a mass ratio of potassium iodide / boric acid / water of 12/5/100 at 56.5 ° C. Subsequently, it was washed with pure water at 8 ° C, and then dried at 65 ° C to obtain a polarizer having iodine adsorbed and aligned in polyvinyl alcohol. The stretching is mainly performed in the steps of iodine staining and boric acid treatment, the full stretching ratio is 5.5 times, and the thickness of the obtained polarizer is 23 μm.

<實施例1>     <Example 1>     (1)接著劑組成物的調製     (1) Preparation of adhesive composition    

將表1所示的成分以表1所示的調配量與作為溶劑的純水一起混合，調製成接著劑組成物(接著劑水溶液)。表1所示的各成分之調配量的單位是質量份，各成分的調配量是換算固形分之量。獲得的接著劑組成物中之固形分濃度(此處所謂固形分濃度，係指接著劑組成物中的成分(A)、(B)及(C)之合計濃度。其他例中亦同。)係設為2.0質量%。 The components shown in Table 1 were mixed with pure water as a solvent at the compounding amount shown in Table 1 to prepare an adhesive composition (adhesive aqueous solution). The unit of the blending amount of each component shown in Table 1 is part by mass, and the blending amount of each component is the amount converted into solid content. Solid content concentration in the obtained adhesive composition (herein, the “solid content concentration” refers to the total concentration of the components (A), (B), and (C) in the adhesive composition. The same applies to other examples.) It is set to 2.0% by mass.

(2)偏光板的製作     (2) Fabrication of polarizing plate    

在上述製造例1中製作的(甲基)丙烯酸系樹脂膜之單面施加電暈處理，在該(甲基)丙烯酸系樹脂膜已施加電暈 處理之面與已施加皂化處理的三乙醯基纖維素(TAC)膜[Konica Minolta Opt(股)製造的商品名「KC2UAW」，厚度：25μm]之單面，利用棒塗機塗布上述(1)中調製的接著劑組成物。以使接著劑組成物層成為偏光片側的方式將(甲基)丙烯酸系樹脂膜積層在上述製造例2中製作的偏光片之一面，並於另一面積層經皂化的TAC膜，獲得具有(甲基)丙烯酸系樹脂膜/接著劑組成物層/偏光片/接著劑組成物層/TAC膜之層構成的積層體。將該積層體通過熱風乾燥機進行80℃、300秒的加熱處理之後，使其在25℃熟成72小時，製作成偏光板。 Corona treatment was applied to one side of the (meth) acrylic resin film produced in Production Example 1, and the corona-treated surface of the (meth) acrylic resin film and triethylpyridine to which saponification treatment was applied were applied. The single-sided surface of a cellulose-based (TAC) film [KC2UAW, manufactured by Konica Minolta Opt Co., Ltd., thickness: 25 [mu] m] was coated with the adhesive composition prepared in (1) above using a bar coater. A (meth) acrylic resin film was laminated on one side of the polarizer produced in the above Production Example 2 so that the adhesive composition layer was on the polarizer side, and a saponified TAC film was laminated on the other area to obtain Base) A laminated body composed of a layer of an acrylic resin film / adhesive composition layer / polarizer / adhesive composition layer / TAC film. This laminated body was heat-treated with a hot air dryer at 80 ° C for 300 seconds, and then aged at 25 ° C for 72 hours to prepare a polarizing plate.

(3)濕熱處理後的密合性評估     (3) Evaluation of adhesion after wet heat treatment    

依照下述，評估上述(2)中獲得的偏光板中之(甲基)丙烯酸系樹脂膜與偏光片之間經濕熱處理後之密合性。 The adhesion between the (meth) acrylic resin film and the polarizer in the polarizing plate obtained in the above (2) after wet heat treatment was evaluated in accordance with the following.

在偏光板中的(甲基)丙烯酸系樹脂膜之表面施加電暈放電處理，在該電暈放電處理面黏合(甲基)丙烯酸系黏著劑片作成附黏著劑層的偏光板。從獲得的附黏著劑層的偏光板裁切寬度25mm、長度約200mm的試驗片，將其黏著劑層面黏合在鈉玻璃基板。 A corona discharge treatment is applied to the surface of the (meth) acrylic resin film in the polarizing plate, and a (meth) acrylic adhesive sheet is bonded to the corona discharge treated surface to form a polarizing plate with an adhesive layer. A test piece having a width of 25 mm and a length of about 200 mm was cut from the obtained polarizer with an adhesive layer, and the adhesive layer was bonded to a soda glass substrate.

在溫度85℃、相對濕度85%的環境下，保管該試驗片48小時之後，在溫度23℃、相對濕度55%的環境下保管一夜。 After storing the test piece for 48 hours in an environment at a temperature of 85 ° C and a relative humidity of 85%, it was stored overnight in an environment at a temperature of 23 ° C and a relative humidity of 55%.

其次，將刀片放入(甲基)丙烯酸系樹脂膜與偏光片之間，在長度方向從末端剝離30mm，用萬能拉伸試驗機[(股) 島津製作所製造的商品名「AG-1」]之握把部分握住該剝離部分。將該狀態的試驗片在溫度23℃、相對濕度55%的周圍環境中，依照JIS K 6854-2：1999「接著劑-剝離接著強度試驗方法-第2部分：剝離180度」，以握把移動速度300mm/分鐘進行剝離試驗，求得握把部分的30mm除外之170mm長度之平均剝離力，將此力作為密合力。將結果表示於表1中。表1中，「※」，係指因密合力高，進行上述剝離試驗時，(甲基)丙烯酸系樹脂膜與偏光片之間的界面產生剝離之前，(甲基)丙烯酸系樹脂膜或偏光片會破裂。 Next, the blade was placed between the (meth) acrylic resin film and the polarizer, and 30 mm was peeled from the end in the longitudinal direction, and a universal tensile testing machine [(share) Shimadzu Corporation's trade name "AG-1"] was used. The grip portion holds the peeling portion. The test piece in this state was held in a surrounding environment at a temperature of 23 ° C and a relative humidity of 55% in accordance with JIS K 6854-2: 1999 "Adhesives-Peeling Adhesive Strength Test Method-Part 2: Peeling 180 degrees". A peeling test was performed at a moving speed of 300 mm / minute, and an average peeling force of 170 mm in length except for 30 mm of the grip portion was obtained, and this force was used as the adhesion force. The results are shown in Table 1. "*" In Table 1 means that the (meth) acrylic resin film or polarized light was peeled before the interface between the (meth) acrylic resin film and the polarizer was peeled when the peeling test was performed due to high adhesion. The film will burst.

又，以獲得的密合力之測定值為基礎，用以下的3個階段評估(甲基)丙烯酸系樹脂膜與偏光片之間經濕熱處理後之密合性。將結果一起表示於表1中。 In addition, based on the measured values of the obtained adhesion force, the adhesion between the (meth) acrylic resin film and the polarizer after wet heat treatment was evaluated in the following three stages. The results are shown together in Table 1.

A：密合力超過5N。 A: Adhesion exceeds 5N.

B：密合力在1至5N的範圍。 B: The adhesive force is in the range of 1 to 5N.

C：密合力未達1N。 C: The adhesion is less than 1N.

<實施例2至37、比較例1>     <Examples 2 to 37, Comparative Example 1>    

除了將調配成分及該等的調配量變更成如表1所示以外，與實施例1相同操作，調製成接著劑組成物。 Except having changed the compounding component and the compounding amount as shown in Table 1, it carried out similarly to Example 1, and prepared the adhesive composition.

將所得的接著劑組成物中之固形分濃度一起表示於表1中。 The solid content concentrations in the obtained adhesive composition are shown in Table 1.

再者，除了使用獲得的接著劑組成物以外，與實施例1相同操作製作偏光板，測定(甲基)丙烯酸系樹脂膜與偏光片之間經濕熱處理後之密合力，亦評估濕熱處理後的密合 力。將結果表示於表1中。 Furthermore, a polarizing plate was produced in the same manner as in Example 1 except that the obtained adhesive composition was used, and the adhesion between the (meth) acrylic resin film and the polarizer after wet heat treatment was measured, and the wet heat treatment was also evaluated. Of adhesion. The results are shown in Table 1.

表1所示之各成分的詳細情形如下述。 The details of each component shown in Table 1 are as follows.

a1：株式會社日本觸媒製造的商品名「Epocross WS-300」[具有2-噁唑啉基作為側鏈的含有噁唑啉基的丙 烯酸系聚合物之水溶液，固形分濃度：10質量%，噁唑啉價(理論值)：130g固體/當量，噁唑啉基量(理論值)：7.7mmol/g，固體，數平均分子量：4×104，重量平均分子量：12×104)] a1: Trade name "Epocross WS-300" manufactured by Nippon Catalytic Corporation [an aqueous solution of an oxazoline group-containing acrylic polymer having a 2-oxazoline group as a side chain, solid content concentration: 10% by mass, Oxazoline valence (theoretical value): 130 g solid / equivalent, oxazoline group amount (theoretical value): 7.7 mmol / g, solid, number average molecular weight: 4 × 10 4 , weight average molecular weight: 12 × 10 4 )]

a2：株式會社日本觸媒製造的商品名「Epocross WS-500」[具有2-噁唑啉基作為側鏈的含有噁唑啉基的丙烯酸系聚合物之溶液(溶劑：水及1-甲氧基-2-丙醇)、固形分濃度：39質量%、噁唑啉價(理論值)：220g固體/當量，噁唑啉基量(理論值)：4.5mmol/g，固體，數平均分子量：2×104，重量平均分子量：7×104)] a2: Trade name "Epocross WS-500" manufactured by Nippon Shokusen Co., Ltd. [A solution of an oxazoline group-containing acrylic polymer having a 2-oxazoline group as a side chain (solvent: water and 1-methoxy 2-propanol), solid content concentration: 39% by mass, oxazoline valence (theoretical value): 220 g solid / equivalent, oxazoline group amount (theoretical value): 4.5 mmol / g, solid, number average molecular weight : 2 × 10 4 , weight average molecular weight: 7 × 10 4 )]

a3：株式會社日本觸媒製造的商品名「Epocross WS-700」[具有2-噁唑啉基作為側鏈的含有噁唑啉基的丙烯酸系聚合物之水溶液，固形分濃度：25質量%、噁唑啉價(理論值)：220g固體/當量，噁唑啉基量(理論值)：4.5mmol/g，固體，數平均分子量：2×104，重量平均分子量：4×104)] a3: Trade name "Epocross WS-700" manufactured by Nippon Catalytic Corporation [an aqueous solution of an oxazoline group-containing acrylic polymer having a 2-oxazoline group as a side chain, solid content concentration: 25% by mass, Oxazoline valence (theoretical value): 220 g solids / equivalent, oxazoline group amount (theoretical value): 4.5 mmol / g, solid, number average molecular weight: 2 × 10 4 , weight average molecular weight: 4 × 10 4 )]

b1：日本合成化學工業株式會社製造的商品名「GOHSENEX Z-100」[乙醯乙醯基改質聚乙烯醇，平均聚合度：500，皂化度：98.5莫耳%以上] b1: Trade name "GOHSENEX Z-100" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. [Ethyl ethyl acetate modified polyvinyl alcohol, average degree of polymerization: 500, degree of saponification: 98.5 mole% or more]

b2：日本合成化學工業株式會社製造的商品名「GOHSENEX Z-200」[乙醯乙醯基改質聚乙烯醇，平均聚合度：1100，皂化度：99.0莫耳%以上] b2: Trade name "GOHSENEX Z-200" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. [Ethyl ethyl acetate modified polyvinyl alcohol, average polymerization degree: 1100, saponification degree: 99.0 mole% or more]

b3：日本合成化學工業株式會社製造的商品名「GOHSENEX Z-300」[乙醯乙醯基改質聚乙烯醇，平均聚 合度：1700，皂化度：98.0至99.0莫耳%] b3: Trade name "GOHSENEX Z-300" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. [Ethyl ethyl acetate modified polyvinyl alcohol, average degree of polymerization: 1700, degree of saponification: 98.0 to 99.0 mole%]

c1：MENADIONA公司製造的商品名「CROSSLINKER CL-427」[分子內具有3個氮丙啶環的下述化合物] c1: Trade name "CROSSLINKER CL-427" manufactured by MENADIONA [the following compound having three aziridine rings in the molecule]

d1：日本合成化學工業株式會社製造的商品名「Safelink SPM-01」[乙醛酸鹽系的交聯劑，固形分濃度：10質量%] d1: Trade name "Safelink SPM-01" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. [glyoxylate crosslinking agent, solid content concentration: 10% by mass]

<實施例38>     <Example 38>     (1)水接觸角之測定     (1) Measurement of water contact angle    

在上述製造例1中製作的(甲基)丙烯酸系樹脂膜之黏合面以表2表示的放電量(W‧分鐘/平方米)施加電暈處理。在(甲基)丙烯酸系樹脂膜經施加電暈處理的面滴下水8.0μL，利用Data Physics製造的接觸角測量裝置「OCA35」，以液滴法測定靜置180秒後的水接觸角。 A corona treatment was applied to the adhesive surface of the (meth) acrylic resin film produced in the above Production Example 1 at the discharge amount (W · min / m 2) shown in Table 2. 8.0 μL of water was dropped on the surface of the (meth) acrylic resin film to which the corona treatment was applied, and a contact angle measuring device “OCA35” manufactured by Data Physics was used to measure the water contact angle after standing for 180 seconds by the droplet method.

(2)偏光板的製作     (2) Fabrication of polarizing plate    

在(甲基)丙烯酸系樹脂膜經施加電暈處理之面與經施加皂化處理的三乙醯基纖維素(TAC)膜[Konica Minolta Opt(股)製造的商品名「KC2UAW」，厚度：25μm]之單面，利用棒塗機塗布上述實施例35中調製的接著劑組成物。以 使接著劑組成物層成為偏光片側之方式，在上述製造例2中製作的偏光片之一面積層(甲基)丙烯酸系樹脂膜，在另一面積層經皂化的TAC膜，獲得具有(甲基)丙烯酸系樹脂膜/接著劑組成物層/偏光片/接著劑組成物層/TAC膜之層構成的積層體。將該積層體通過熱風乾燥機進行80℃、300秒的加熱處理之後，在25℃熟成72小時，製作成偏光板。 Corona treated surface of (meth) acrylic resin film and saponified triethyl cellulose (TAC) film [KC2UAW's product name, manufactured by Konica Minolta Opt Co., Ltd., thickness: 25 μm ], The adhesive composition prepared in Example 35 was applied with a bar coater. One area layer (meth) acrylic resin film of the polarizer produced in the above Production Example 2 so that the adhesive composition layer was on the polarizer side, and the other area layer was saponified TAC film to obtain ) A laminated body composed of a layer of an acrylic resin film / adhesive composition layer / polarizer / adhesive composition layer / TAC film. This laminated body was heat-treated at 80 ° C. for 300 seconds with a hot air dryer, and then aged at 25 ° C. for 72 hours to prepare a polarizing plate.

(3)初期密合力的評估     (3) Evaluation of initial adhesion    

依照下述，評估上述(2)中獲得的偏光板中之(甲基)丙烯酸系樹脂膜與偏光片之間的初期密合性。初期密合性係指施加後述的濕熱處理前之偏光板，製作後在溫度23℃、相對濕度55%的環境下保管之偏光板的密合性。 The initial adhesion between the (meth) acrylic resin film and the polarizer in the polarizing plate obtained in the above (2) was evaluated in accordance with the following. The initial adhesiveness refers to the adhesiveness of a polarizing plate stored under an environment of a temperature of 23 ° C. and a relative humidity of 55% after the polarizing plate before the wet heat treatment described later is applied.

在偏光板中的(甲基)丙烯酸系樹脂膜之表面施加電暈放電處理，並在該電暈放電處理面黏合(甲基)丙烯酸系黏著劑片作成附黏著劑層的偏光板。從獲得的附黏著劑層的偏光板裁切寬度25mm、長度約200mm的試驗片，將其黏著劑層面黏合在鈉玻璃基板。 A corona discharge treatment is applied to the surface of the (meth) acrylic resin film in the polarizing plate, and a (meth) acrylic adhesive sheet is bonded to the corona discharge treated surface to form a polarizing plate with an adhesive layer. A test piece having a width of 25 mm and a length of about 200 mm was cut from the obtained polarizer with an adhesive layer, and the adhesive layer was bonded to a soda glass substrate.

其次，將刀片放入(甲基)丙烯酸系樹脂膜與偏光片之間，在長度方向從末端剝離30mm，用萬能拉伸試驗機[(股)島津製作所製造的商品名「AG-1」]之握把部分握住該剝離部分。將該狀態的試驗片在溫度23℃、相對濕度55%的周圍環境中，依照JIS K 6854-2：1999「接著劑-剝離接著強度試驗方法-第2部分：剝離180度」，以握把移動速度300mm/分鐘進行剝離試驗，求得握把部分的30mm除外之 170mm的長度之平均剝離力，將此力作為密合力。將結果表示於表2中。又，表2中的「不可能」，係指刀片未能切入(甲基)丙烯系樹脂膜與偏光片之間，表示密合力非常高。 Next, the blade was placed between the (meth) acrylic resin film and the polarizer, and 30 mm was peeled from the end in the longitudinal direction, and a universal tensile tester [trade name "AG-1" manufactured by Shimadzu Corporation was used] The grip portion holds the peeling portion. The test piece in this state was held in a surrounding environment at a temperature of 23 ° C and a relative humidity of 55% in accordance with JIS K 6854-2: 1999 "Adhesives-Peeling Adhesive Strength Test Method-Part 2: Peeling 180 degrees". A peeling test was performed at a moving speed of 300 mm / minute, and an average peeling force of a length of 170 mm other than 30 mm of the grip portion was obtained, and this force was used as the adhesion force. The results are shown in Table 2. In addition, "impossible" in Table 2 means that the blade failed to cut between the (meth) acrylic resin film and the polarizer, and showed that the adhesive force was very high.

(4)濕熱處理後的密合性評估     (4) Evaluation of adhesion after wet heat treatment    

與以上所述之方法相同，進行測定及評估。表2中，「※」，係指因密合力高，進行上述剝離試驗時，在(甲基)丙烯酸系樹脂膜與偏光片之間的界面產生剝離之前，(甲基)丙烯酸系樹脂膜或偏光片會破裂。 Measurement and evaluation were performed in the same manner as described above. “*” In Table 2 means that the (meth) acrylic resin film or the (meth) acrylic resin film or The polarizer will break.

同時，以獲得的密合力之測定值為基礎，用以下的3個階段評估(甲基)丙烯酸系樹脂膜與偏光片之間的濕熱處理後之密合性。將結果一起表示於表2中。 At the same time, based on the measured values of the obtained adhesion force, the adhesion after wet heat treatment between the (meth) acrylic resin film and the polarizer was evaluated in the following three stages. The results are shown together in Table 2.

A：密合力超過5N。 A: Adhesion exceeds 5N.

B：密合力在1至5N的範圍。 B: The adhesive force is in the range of 1 to 5N.

C：密合力未達1N。 C: The adhesion is less than 1N.

<實施例39及實施例40>     <Example 39 and Example 40>    

除了電暈處理中的放電量如表2表示以外，與實施例38相同操作製作成偏光板。又，進行獲得的偏光板之初期密合力、濕熱處理後的密合性之評估。 A polarizing plate was produced in the same manner as in Example 38 except that the discharge amount in the corona treatment is shown in Table 2. In addition, the initial polarizing force of the obtained polarizing plate and the adhesiveness after the wet heat treatment were evaluated.

Claims (9)

一種偏光板，係依序含有偏光片、第1接著劑層與(甲基)丙烯酸系樹脂膜，且前述第1接著劑層是由含有含噁唑啉基之化合物的接著劑組成物形成之層。     A polarizing plate includes a polarizer, a first adhesive layer, and a (meth) acrylic resin film in this order. The first adhesive layer is formed of an adhesive composition containing an oxazoline group-containing compound. Floor.     如申請專利範圍第1項所述之偏光板，其中，前述接著劑組成物再含有乙醯乙醯基改質聚乙烯醇聚合物。     The polarizing plate according to item 1 of the scope of the patent application, wherein the aforementioned adhesive composition further contains an acetamidine-modified vinyl alcohol polymer.     如申請專利範圍第1或2項所述之偏光板，係依序含有熱塑性樹脂膜、第2接著劑層、前述偏光片、前述第1接著劑層與前述(甲基)丙烯酸系樹脂膜。     The polarizing plate according to item 1 or 2 of the scope of patent application contains a thermoplastic resin film, a second adhesive layer, the polarizer, the first adhesive layer, and the (meth) acrylic resin film in this order.     如申請專利範圍第1至3項中任一項所述之偏光板，其中，前述第1接著劑層與前述(甲基)丙烯酸系樹脂膜係相接觸。     The polarizing plate according to any one of claims 1 to 3, wherein the first adhesive layer is in contact with the (meth) acrylic resin film.     如申請專利範圍第4項所述之偏光板，其中，前述(甲基)丙烯酸系樹脂膜與前述第1接著劑層相接觸面之水接觸角係80°以下。     The polarizing plate according to item 4 of the scope of patent application, wherein a water contact angle of a contact surface between the (meth) acrylic resin film and the first adhesive layer is 80 ° or less.     如申請專利範圍第1至5項中任一項所述之偏光板，其中，前述偏光片與前述第1接著劑層係相接觸。     The polarizing plate according to any one of claims 1 to 5, wherein the polarizer is in contact with the first adhesive layer system.     一種接著劑組成物，係偏光片與(甲基)丙烯酸系樹脂膜接著用之接著劑組成物，其含有含噁唑啉基之化合物。     An adhesive composition comprising a polarizer and a (meth) acrylic resin film, and an adhesive composition containing an oxazoline group-containing compound.     如申請專利範圍第7項所述之接著劑組成物，係再含有乙醯乙醯基改質聚乙烯醇聚合物。     The adhesive composition as described in item 7 of the scope of the patent application, which further contains acetoacetic acid modified polyvinyl alcohol polymer.     如申請專利範圍第7或8項所述之接著劑組成物，係再含有水。     The adhesive composition according to item 7 or 8 of the patent application scope further contains water.    
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JP6439794B2 (en) * 2014-05-30 2018-12-19 住友化学株式会社 Polarizing plate with adhesive and liquid crystal display device
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CN108931833B (en) 2023-11-14

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