TWI752914B - Surface protection film for polarizing plate, polarizing plate, and manufacturing method of polarizing plate - Google Patents

Surface protection film for polarizing plate, polarizing plate, and manufacturing method of polarizing plate Download PDF

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TWI752914B
TWI752914B TW105123601A TW105123601A TWI752914B TW I752914 B TWI752914 B TW I752914B TW 105123601 A TW105123601 A TW 105123601A TW 105123601 A TW105123601 A TW 105123601A TW I752914 B TWI752914 B TW I752914B
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polarizing plate
meth
mass
film
protective film
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TW201714999A (en
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片岡賢一
天野立巳
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日商日東電工股份有限公司
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Health & Medical Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

本發明提供一種能夠增強剪切力，並且降低動摩擦力，同時謀求兼顧捲曲調節性及光滑性的偏光板用表面保護薄膜。 The present invention provides a surface protection film for a polarizing plate capable of enhancing shear force and reducing dynamic friction force, while achieving both curl controllability and smoothness.

本發明偏光板用表面保護薄膜的特徵在於，其係在支撐薄膜的一面或兩面具有由黏合劑組成物形成的黏合劑層的偏光板用表面保護薄膜，且前述黏合劑組成物含有(甲基)丙烯酸系聚合物及下述式所示的矽酮化合物，其中，前述(甲基)丙烯酸系聚合物至少含有具有碳原子數1~14的烷基的(甲基)丙烯酸系單體50~99.9質量%作為單體成分，相對於前述(甲基)丙烯酸系聚合物100質量份，含有前述矽酮化合物0.01質量份~未達1質量份，使前述黏合劑層以1cm2的黏合面積貼合於TAC偏光板，在23℃下黏貼上30分鐘後，在剪切方向以拉伸速度0.06mm/min進行拉伸時的剪切力為15N/cm2以上，使前述黏合劑層表面貼合於TAC偏光板，在23℃下黏貼上30分鐘後，從前述TAC偏光板剝離前述偏光板用表面保護薄膜，使亮度增強薄膜與前述TAC偏光板之黏貼過前述黏合劑層表面的面接觸，在施加了200g的載荷的狀態下，在與接觸面平行方向以拉伸速度100mm/min進行拉伸時的動摩擦力為1N以下。 The surface protective film for polarizing plates of the present invention is characterized in that it is a surface protective film for polarizing plates having an adhesive layer formed of an adhesive composition on one or both surfaces of a support film, and the adhesive composition contains (methyl) ) An acrylic polymer and a silicone compound represented by the following formula, wherein the (meth)acrylic polymer contains at least a (meth)acrylic monomer 50 to 50 having an alkyl group having 1 to 14 carbon atoms. 99.9% by mass as a monomer component, with respect to 100 parts by mass of the (meth)acrylic polymer, 0.01 part by mass to less than 1 part by mass of the aforementioned silicone compound is contained, and the aforementioned adhesive layer is adhered with an adhesive area of 1 cm 2 After being attached to the TAC polarizing plate for 30 minutes at 23°C, the shearing force during stretching at a tensile speed of 0.06mm/min in the shearing direction is 15N/ cm2 or more, so that the surface of the above-mentioned adhesive layer is attached. After attaching to the TAC polarizing plate for 30 minutes at 23°C, peel off the surface protective film for the polarizing plate from the TAC polarizing plate, so that the brightness enhancement film is in contact with the surface of the TAC polarizing plate pasted on the surface of the adhesive layer. , the dynamic friction force when stretched at a stretching speed of 100 mm/min in a direction parallel to the contact surface under a load of 200 g is 1 N or less.

Figure 105123601-A0202-11-0001-12
Figure 105123601-A0202-11-0001-12

式中，R及R’為甲基或苯基，R及R’可以相同，也可以不同。此外，m為0~3000，n為1~3000。 In the formula, R and R' are methyl or phenyl, and R and R' may be the same or different. In addition, m is 0 to 3000, and n is 1 to 3000.

Description

偏光板用表面保護薄膜、偏光板及偏光板之製造方法 Surface protection film for polarizing plate, polarizing plate, and manufacturing method of polarizing plate

本發明涉及偏光板用表面保護薄膜、藉由所述表面保護薄膜保護的偏光板、以及偏光板的製造方法。具體而言，涉及用於藉由黏貼於液晶顯示器所使用的偏光板來保護偏光板的表面的偏光板用表面保護薄膜。例如，偏光板用表面保護薄膜用於偏光板的製造商在偏光板出廠時的保護、液晶顯示器的製造商在顯示裝置(液晶模組)製造步驟時的偏光板保護用途等、各種步驟中偏光板的保護用途。此外，本發明涉及以偏光板用表面保護薄膜進行保護的偏光板，還涉及將矽酮化合物轉印到偏光板表面的矽酮化合物轉印型偏光板的製造方法。 The present invention relates to a surface protective film for a polarizing plate, a polarizing plate protected by the surface protective film, and a method for producing a polarizing plate. Specifically, it relates to a surface protection film for a polarizing plate for protecting the surface of a polarizing plate by sticking to a polarizing plate used for a liquid crystal display. For example, the surface protection film for polarizing plates is used for the protection of polarizing plates by manufacturers of polarizing plates at the time of delivery of the polarizing plates, the manufacturers of liquid crystal displays are used for the protection of polarizing plates in the production process of display devices (liquid crystal modules), etc., and polarizing in various steps. Protective use of the board. Furthermore, the present invention relates to a polarizing plate protected by a surface protective film for a polarizing plate, and also relates to a method for producing a silicone compound transfer type polarizing plate in which a silicone compound is transferred to the surface of the polarizing plate.

背景技術 Background technique

在運輸或向印刷基板安裝光學零件/電子零件時，藉由用規定的片包裝好的狀態、黏貼有黏合帶的狀態來對各個零件進行移送。其中，表面保護薄膜尤其被廣泛用於光學/電子零件領域。 When transporting or mounting optical components/electronic components on a printed circuit board, each component is transported in a state in which it is packaged in a predetermined sheet and in a state where an adhesive tape is attached. Among them, surface protection films are widely used in the field of optical/electronic parts in particular.

表面保護薄膜通常透過塗布於支撐薄膜側的黏合劑貼合於被黏附體，以防止被黏附體在加工、運送時產生的損傷、污染為目的而使用(專利文獻1)。例如，液晶顯 示器(LCD)面板藉由透過黏合劑使偏光板、波長板等光學構件貼合於液晶單元而形成。這些偏光板等光學構件透過黏合劑貼合有表面保護薄膜，以防止加工、運送時產生的損傷、污染。 The surface protection film is usually bonded to the adherend through an adhesive applied to the side of the support film, and is used for the purpose of preventing damage and contamination of the adherend during processing and transportation (Patent Document 1). For example, liquid crystal display A display (LCD) panel is formed by bonding optical members, such as a polarizing plate and a wavelength plate, to a liquid crystal cell through an adhesive. These optical members, such as polarizing plates, are bonded with a surface protective film through an adhesive to prevent damage and contamination during processing and transportation.

近年來，對用於LCD面板的偏光板而言，伴隨著LCD面板的薄型化，偏光板也被薄型化，由此，在組裝LCD面板時，亮度增強薄膜與偏光板的距離(間隔)也伴隨著薄型化而變窄，進而由於薄型化後的LCD面板或偏光板彎曲，亮度增強薄膜與偏光板接觸，造成偏光板產生損傷等問題。 In recent years, polarizing plates used for LCD panels have been thinned along with the thinning of LCD panels. Therefore, when assembling the LCD panel, the distance (interval) between the brightness enhancement film and the polarizing plate is also reduced. As the thickness becomes thinner, the thinned LCD panel or the polarizer is bent, and the brightness enhancement film is in contact with the polarizer, causing problems such as damage to the polarizer.

此外，對於偏光板本身而言，為了不產生不必要的捲曲、不想要的捲曲(所謂捲曲是指翹曲的現象，例如是指平板狀的物體整體地向任一方的面的一側翹曲的現象、平板狀的物體整體地翹曲成波狀的現象等)而要求捲曲調節性。當不必要的捲曲、不想要的捲曲產生時，處理性劣化，例如在將偏光板等黏貼於液晶單元時，有時產生夾入氣泡等不良狀況。 In addition, in order to prevent unnecessary curling and unwanted curling (the so-called curling refers to a phenomenon of warping, for example, a flat plate-shaped object is warped to one side of any surface as a whole) in the polarizing plate itself. A phenomenon in which a flat object is warped in a wavy shape as a whole, etc.), and curl adjustability is required. When unnecessary curling or unwanted curling occurs, handleability deteriorates, for example, when a polarizing plate or the like is attached to a liquid crystal cell, problems such as trapping of air bubbles may occur.

另一方面，藉由在表面保護薄膜的黏合劑層中配合起抗靜電劑作用的聚醚改性矽酮，聚醚改性矽酮微量轉印到被黏附體(例如，偏光板)表面，由此能夠對被黏附體賦予抗靜電性，進而，在被黏附體與構件接觸般的情況下，能夠降低被黏附體的動摩擦力，能夠謀求光滑性的提高、抑制被黏附體損傷的產生。另一方面，由於存在微量轉印到被黏附體表面的聚醚改性矽酮，被黏附體的剪切力降低，產生被黏附體的捲曲調節性劣化的問題。 On the other hand, by mixing polyether-modified silicone that acts as an antistatic agent in the adhesive layer of the surface protection film, the polyether-modified silicone is transferred to the surface of the adherend (for example, polarizing plate) in a small amount, Thereby, antistatic properties can be imparted to the adherend, and when the adherend is in contact with a member, the dynamic friction force of the adherend can be reduced, the smoothness can be improved, and the occurrence of damage to the adherend can be suppressed. On the other hand, due to the presence of a small amount of polyether-modified silicone transferred to the surface of the adherend, the shear force of the adherend is reduced, and the problem of deteriorating the curl controllability of the adherend occurs.

先行技術文獻 prior art literature 專利文獻 Patent Literature

專利文獻1：日本特開平9-165460號公報 Patent Document 1: Japanese Patent Application Laid-Open No. 9-165460

發明概要 Summary of Invention

因此，本發明的目的在於提供一種偏光板用表面保護薄膜，為了消除以往的表面保護薄膜的問題點，所述偏光板用表面保護薄膜能夠增強黏合劑層的剪切力，並且降低作為黏貼了表面保護薄膜後、剝離時的被黏附體的偏光板的動摩擦力，同時謀求兼顧偏光板的捲曲調節性及偏光板的光滑性。 Therefore, an object of the present invention is to provide a surface protective film for polarizing plates, which can enhance the shear force of the adhesive layer and reduce the amount of adhesive After the surface protection film is peeled off, the dynamic friction force of the polarizing plate of the adherend is aimed at both the curl controllability of the polarizing plate and the smoothness of the polarizing plate.

即，本發明偏光板用表面保護薄膜的特徵在於，其係在支撐薄膜的一面或兩面具有由黏合劑組成物形成的黏合劑層的偏光板用表面保護薄膜，且前述黏合劑組成物含有(甲基)丙烯酸系聚合物及下述式所示的矽酮化合物，其中，前述(甲基)丙烯酸系聚合物至少含有具有碳原子數1~14的烷基的(甲基)丙烯酸系單體50~99.9質量%作為單體成分，相對於前述(甲基)丙烯酸系聚合物100質量份，含有前述矽酮化合物0.01質量份~未達1質量份，使前述黏合劑層以1cm2的黏合面積貼合於TAC偏光板，在23℃下黏貼上30分鐘後，在剪切方向以拉伸速度0.06mm/min進行拉伸時的剪切力為15N/cm2以上，使前述黏合劑層表面貼合於 TAC偏光板，在23℃下黏貼上30分鐘後，從前述TAC偏光板剝離前述偏光板用表面保護薄膜，使亮度增強薄膜與前述TAC偏光板之黏貼過前述黏合劑層表面的面接觸，在施加了200g的載荷的狀態下，在與接觸面平行方向以拉伸速度100mm/min進行拉伸時的動摩擦力為1N以下。 That is, the surface protective film for polarizing plates of the present invention is characterized in that it is a surface protective film for polarizing plates having an adhesive layer formed of an adhesive composition on one or both surfaces of a support film, and the adhesive composition contains ( A meth)acrylic polymer and a silicone compound represented by the following formula, wherein the (meth)acrylic polymer contains at least a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms 50 to 99.9% by mass as a monomer component, relative to 100 parts by mass of the (meth)acrylic polymer, containing 0.01 part by mass to less than 1 part by mass of the aforementioned silicone compound, so that the aforementioned adhesive layer is adhered at a thickness of 1 cm 2 The area is attached to the TAC polarizing plate, and after sticking at 23 ° C for 30 minutes, the shear force when stretching is carried out at a tensile speed of 0.06 mm/min in the shearing direction is 15 N/cm 2 or more, so that the aforementioned adhesive layer is The surface is attached to the TAC polarizing plate, and after 30 minutes of pasting at 23 ° C, the surface protective film for the polarizing plate is peeled off from the aforementioned TAC polarizing plate, so that the brightness enhancement film and the aforementioned TAC polarizing plate are pasted over the surface of the aforementioned adhesive layer. In the case of surface contact, the dynamic friction force when stretched at a stretching speed of 100 mm/min in a direction parallel to the contact surface with a load of 200 g applied was 1 N or less.

Figure 105123601-A0305-02-0006-1
Figure 105123601-A0305-02-0006-1

(式中，R及R’為甲基或苯基，R及R’可以相同，也可以不同。此外，m為0~3000，n為1~3000。) (In the formula, R and R' are methyl or phenyl, and R and R' may be the same or different. In addition, m is 0 to 3000, and n is 1 to 3000.)

關於本發明的偏光板用表面保護薄膜，較佳前述黏合劑組成物含有具有烯化氧基的表面活性劑。 Regarding the surface protective film for polarizing plates of the present invention, it is preferable that the adhesive composition contains a surfactant having an alkylene oxide group.

關於本發明的偏光板用表面保護薄膜，較佳前述黏合劑組成物含有離子性化合物。 It is preferable that the said adhesive composition contains an ionic compound about the surface protection film for polarizing plates of this invention.

關於本發明的偏光板用表面保護薄膜，較佳前述(甲基)丙烯酸系聚合物含有具有羥基的(甲基)丙烯酸系單體作為單體成分。 As for the surface protection film for polarizing plates of this invention, it is preferable that the said (meth)acrylic-type polymer contains the (meth)acrylic-type monomer which has a hydroxyl group as a monomer component.

關於本發明的偏光板用表面保護薄膜，較佳前述(甲基)丙烯酸系聚合物含有具有羧基的(甲基)丙烯酸系單體作為單體成分。 As for the surface protection film for polarizing plates of this invention, it is preferable that the said (meth)acrylic-type polymer contains the (meth)acrylic-type monomer which has a carboxyl group as a monomer component.

本發明的偏光板較佳藉由前述偏光板用表面保護薄膜進行保護。 The polarizing plate of the present invention is preferably protected by the above-mentioned surface protective film for polarizing plates.

本發明的矽酮化合物轉印型偏光板的製造方法 較佳包括：使前述偏光板用表面保護薄膜的黏合劑層表面貼合於偏光板表面的步驟；及從前述偏光板表面剝離前述偏光板用表面保護薄膜，從而將前述偏光板用表面保護薄膜的黏合劑層中所含有的前述矽酮化合物轉印到前述偏光板表面的步驟。 The manufacturing method of the silicone compound transfer type polarizing plate of the present invention It preferably includes: the step of making the surface of the adhesive layer of the surface protection film for the polarizer adhere to the surface of the polarizer; and peeling off the surface protection film for the polarizer from the surface of the polarizer, so as to remove the surface protection film The step of transferring the silicone compound contained in the adhesive layer to the surface of the polarizing plate.

由於本發明的偏光板用表面保護薄膜能夠謀求剪切力的提高，因此在使偏光板用表面保護薄膜貼合於薄型化後的偏光板時，能夠抑制偏光板的捲曲的產生，能夠獲得捲曲調節性優異的偏光板，因而有用。此外，在將本發明的偏光板用表面保護薄膜在偏光板上黏貼剝離後組裝液晶顯示器面板時，由於即使在所述偏光板與亮度增強薄膜等接觸的情況下也可以將偏光板的動摩擦力抑制得較低，因此偏光板難以產生損傷，光滑性優異，因而有用。 Since the surface protective film for polarizing plates of the present invention can improve shear force, when the surface protective film for polarizing plates is bonded to a thinned polarizing plate, the occurrence of curling of the polarizing plate can be suppressed and curling can be obtained It is useful as a polarizing plate excellent in adjustability. In addition, when the liquid crystal display panel is assembled after sticking and peeling the surface protective film for a polarizing plate of the present invention on a polarizing plate, the dynamic friction force of the polarizing plate can be reduced even when the polarizing plate is in contact with a brightness enhancement film or the like. Since the suppression is low, the polarizing plate is less likely to be damaged, and it is useful because of its excellent smoothness.

1:偏光板用表面保護薄膜(表面保護薄膜) 1: Surface protection film for polarizer (surface protection film)

2:偏光板 2: polarizer

3:黏合劑層 3: Adhesive layer

4:支撐薄膜 4: Support film

5:附有偏光板用表面保護薄膜的偏光板(偏光板) 5: Polarizing plate (polarizing plate) with surface protection film for polarizing plate attached

10:丙烯酸板 10: Acrylic Sheet

20:TAC偏光板 20: TAC polarizer

30:樣品固定台 30: Sample fixing table

40:電位測定器 40: Potentiometer

圖1是本發明的較佳實施方式之附有偏光板用表面保護薄膜的偏光板的概略剖面圖。 1 is a schematic cross-sectional view of a polarizing plate with a surface protective film for a polarizing plate according to a preferred embodiment of the present invention.

圖2是表示剝離帶電壓的測定方法的說明圖。 FIG. 2 is an explanatory diagram showing a method of measuring the peeling charge voltage.

用以實施發明之形態 Form for carrying out the invention

以下，對本發明的實施方式進行詳細的說明。 Hereinafter, embodiments of the present invention will be described in detail.

<偏光板用表面保護薄膜(表面保護薄膜)的整體結構> <Overall structure of the surface protective film (surface protective film) for polarizing plates>

本發明偏光板用表面保護薄膜(以下，有時僅稱為“表 面保護薄膜”)通常是被稱為表面保護薄膜、黏合帶、黏合標籤、黏合薄膜等形態的物體，尤其適於作為在光學零件(例如，偏光板、波長板等作為液晶顯示器面板構成元件而使用的光學零件)的加工時、運送時對光學零件的表面進行保護的表面保護薄膜。雖然所述表面保護薄膜的黏合劑層通常連續地形成，但並不限定於如此的方式，例如也可以是形成點狀、條紋狀等規則的或隨機的圖案的黏合劑層。此外，此處揭示的表面保護薄膜可以是卷狀，也可以是片狀。 The surface protective film for polarizing plates of the present invention (hereinafter, may be simply referred to as "surface protection film") Surface protective film") is usually called a surface protective film, adhesive tape, adhesive label, adhesive film, etc., especially suitable for use in optical parts (for example, polarizers, wave plates, etc.) as liquid crystal display panel components. A surface protection film that protects the surface of optical parts during processing and transportation of optical parts used. Although the adhesive layer of the surface protection film is usually formed continuously, it is not limited to such a method. For example, it is also possible to It is an adhesive layer which forms regular or random patterns such as dots, stripes, etc. In addition, the surface protection film disclosed here may be in a roll shape or a sheet shape.

作為此處揭示的偏光板用表面保護薄膜(表面保護薄膜)的典型的構成例子，可以舉出在支撐薄膜(基材)的一面或兩面具有黏合劑層的表面保護薄膜、具備設置於支撐薄膜的一面的抗靜電層及設置於支撐薄膜的與抗靜電層相反一側的表面的黏合劑層的表面保護薄膜。表面保護薄膜係將該黏合劑層黏貼於被黏附體(作為保護對象的偏光板)並進行使用。使用前(即，向被黏附體黏貼前)的表面保護薄膜可以是黏合劑層的表面(向被黏附體的黏貼面)藉由至少黏合劑層側為剝離面的剝離襯墊進行保護的形態。或者，也可以是藉由表面保護薄膜捲繞成卷狀，黏合劑層與支撐薄膜的背面(抗靜電層的表面)抵接，從而保護其表面的形態。 As a typical structural example of the surface protective film (surface protective film) for polarizing plates disclosed here, a surface protective film having an adhesive layer on one or both surfaces of a support film (substrate), a surface protective film provided on a support film The antistatic layer on one side of the film and the surface protection film of the adhesive layer provided on the surface of the support film on the opposite side of the antistatic layer. The surface protective film is used by adhering the adhesive layer to the adherend (polarizing plate to be protected). The surface protective film before use (that is, before sticking to the adherend) may be a form in which the surface of the adhesive layer (the surface to be adhered to the adherend) is protected by a release liner with at least the side of the pressure-sensitive adhesive layer being the release surface . Alternatively, the surface protection film may be wound in a roll shape, and the adhesive layer may be in contact with the back surface (surface of the antistatic layer) of the support film to protect the surface.

<支撐薄膜> <Support Film>

本發明偏光板用表面保護薄膜(表面保護薄膜)的特徵在於，在支撐薄膜的一面或兩面具有由黏合劑組成物形成 的黏合劑層。雖然構成所述支撐薄膜的樹脂材料可以沒有特別限制地使用，但例如較佳使用透明性、機械強度、熱穩定性、水分屏蔽性、各向同性、可撓性、尺寸穩定性等特性優異的材料。特別是，藉由支撐薄膜具有可撓性，能夠用輥塗機等塗布黏合劑組成物，能夠捲繞成卷狀，因而有用。 The surface protective film (surface protective film) for polarizing plates of the present invention is characterized by having a support film formed of an adhesive composition on one or both surfaces of the support film. adhesive layer. Although the resin material constituting the support film can be used without particular limitation, for example, a resin material excellent in properties such as transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, flexibility, and dimensional stability is preferably used. Material. In particular, since the support film has flexibility, the adhesive composition can be applied by a roll coater or the like, and it can be wound into a roll shape, which is useful.

作為所述支撐薄膜(基材)，例如可以較佳使用塑膠薄膜作為所述支撐薄膜，其中，所述塑膠薄膜由以聚對苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚對苯二甲酸丁二醇酯等聚酯系聚合物；二醋酸纖維素、三醋酸纖維素等纖維素系聚合物；聚碳酸酯系聚合物；聚甲基丙烯酸甲酯等丙烯酸系聚合物等為主要樹脂成分(樹脂成分中的主成分、通常是占50質量%以上的成分)的樹脂材料構成。作為所述樹脂材料的其它例子，可以舉出以聚苯乙烯、丙烯腈-苯乙烯共聚物等苯乙烯系聚合物；聚乙烯、聚丙烯、具有環狀乃至降冰片烯結構的聚烯烴、乙烯-丙烯共聚物等烯烴系聚合物；氯乙烯系聚合物；尼龍6、尼龍6,6、芳香族聚醯胺等醯胺系聚合物等為樹脂材料的例子。進一步地，作為所述樹脂材料的其它例子，可以舉出醯亞胺系聚合物、碸系聚合物、聚醚碸系聚合物、聚醚醚酮系聚合物、聚苯硫醚系聚合物、乙烯醇系聚合物、偏二氯乙烯系聚合物、乙烯醇縮丁醛系聚合物、芳酯系聚合物、聚氧甲烯系聚合物、環氧系聚合物等。也可以是由上述聚合物的2種以上的混合物構成的支撐薄膜。 As the support film (substrate), for example, a plastic film can be preferably used as the support film, wherein the plastic film is made of polyethylene terephthalate (PET), polyethylene naphthalate Polyester-based polymers such as alcohol esters (PEN) and polybutylene terephthalate; cellulose-based polymers such as cellulose diacetate and cellulose triacetate; polycarbonate-based polymers; polymethyl methacrylate Acrylic polymers such as esters are composed of a resin material whose main resin component (the main component in the resin component, usually accounts for 50% by mass or more) of the resin material. Other examples of the resin material include styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer; polyethylene, polypropylene, polyolefins having cyclic or norbornene structures, ethylene - Olefin-based polymers such as propylene copolymers; vinyl chloride-based polymers; amide-based polymers such as nylon 6, nylon 6,6, and aromatic polyamides are examples of resin materials. Further, as other examples of the resin material, amide-imide-based polymers, silo-based polymers, polyether s-series polymers, polyether ether ketone-based polymers, polyphenylene sulfide-based polymers, Vinyl alcohol-based polymers, vinylidene chloride-based polymers, vinyl butyral-based polymers, arylate-based polymers, polyoxymethylene-based polymers, epoxy-based polymers, and the like. A support film composed of a mixture of two or more of the above polymers may be used.

作為所述支撐薄膜，可以較佳採用由透明的熱塑性樹脂材料構成的塑膠薄膜。在所述塑膠薄膜中，更佳的方式是使用聚酯薄膜。此處，所謂聚酯薄膜是指以聚合物材料(聚酯樹脂)為主要樹脂成分的薄膜，其中，所述聚合物材料具有以聚對苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚對苯二甲酸丁二醇酯等的酯鍵為基礎的主骨架。如此的聚酯薄膜具有光學特性、尺寸穩定性優異等作為表面保護薄膜的支撐薄膜的較佳特性，另一方面，其本身具有容易帶電的性質。 As the support film, a plastic film made of a transparent thermoplastic resin material can be preferably used. Among the plastic films, a polyester film is preferably used. Here, the term "polyester film" refers to a film containing a polymer material (polyester resin) as a main resin component, wherein the polymer material has polyethylene terephthalate (PET), polyethylene naphthalate Main skeleton based on ester bonds of ethylene formate (PEN) and polybutylene terephthalate. Such a polyester film has preferable properties such as excellent optical properties and dimensional stability as a support film for a surface protective film, and on the other hand, it has the property of being easily charged.

根據需要，也可以在所述構成支撐薄膜的樹脂材料中配合抗氧化劑、紫外線吸收劑、增塑劑、著色劑(顏料、染料等)等各種添加劑。也可以在所述支撐薄膜的一面(設置有黏合劑層的一側的表面)實施例如電暈放電處理、等離子體處理、紫外線照射處理、酸處理、鹼處理、塗布底塗劑等公知或慣用的表面處理。如此的表面處理可以是例如用於提高支撐薄膜與黏合劑層的密合性(黏合劑層的錨固性)的處理。可以較佳採用在支撐薄膜的表面導入羥基等極性基團如此的表面處理。 If necessary, various additives such as antioxidants, ultraviolet absorbers, plasticizers, colorants (pigments, dyes, etc.) may be blended with the resin material constituting the support film. Known or conventional methods such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, primer coating, etc. surface treatment. Such surface treatment may be, for example, treatment for improving the adhesion between the support film and the adhesive layer (anchoring property of the adhesive layer). A surface treatment such that polar groups such as hydroxyl groups are introduced into the surface of the support film can be preferably used.

此外，雖然本發明的表面保護薄膜也能夠在與支撐薄膜的黏合劑層相反的一側具有抗靜電層，但在具有抗靜電功能的情況下，還能夠使用經過抗靜電處理的塑膠薄膜作為所述支撐薄膜。由於藉由使用所述支撐薄膜能夠抑制剝離時表面保護薄膜本身的帶電，因此為佳。此外，支撐薄膜為塑膠薄膜，藉由對所述塑膠薄膜實施抗靜電處理 來減少表面保護薄膜本身的帶電，並且能夠獲得對被黏附體的抗靜電功能優異的塑膠薄膜。需要說明的是，作為賦予抗靜電功能的方法，沒有特別限制，可以使用以往公知的方法，例如可以舉出塗布含有由抗靜電劑及樹脂成分構成的抗靜電性樹脂、導電性聚合物、導電性物質的導電性樹脂的方法、蒸鍍或電鍍導電性物質的方法、或者混入抗靜電劑等的方法等。 In addition, although the surface protection film of the present invention can also have an antistatic layer on the side opposite to the adhesive layer of the supporting film, in the case of having an antistatic function, an antistatically treated plastic film can also be used as the protective film. the support film. The use of the support film is preferable because the electrification of the surface protection film itself at the time of peeling can be suppressed. In addition, the support film is a plastic film, and the antistatic treatment is performed on the plastic film. To reduce the charging of the surface protection film itself, and to obtain a plastic film with excellent antistatic function to the adherend. It should be noted that the method for imparting an antistatic function is not particularly limited, and conventionally known methods can be used, for example, coating an antistatic resin, a conductive polymer, a conductive A method of using a conductive resin of a conductive material, a method of vapor deposition or electroplating of a conductive material, or a method of mixing an antistatic agent or the like.

作為所述支撐薄膜的厚度，通常為1~200μm，較佳為5~100μm左右。當所述支撐薄膜的厚度在所述範圍內時，由於對作為被黏附體的偏光板的貼合操作性及從被黏附體的剝離操作性優異，因此為佳。 As a thickness of the said support film, it is 1-200 micrometers normally, Preferably it is about 5-100 micrometers. When the thickness of the support film is within the above-mentioned range, it is preferable since it is excellent in the workability of bonding to the polarizing plate as the adherend and the workability of peeling from the adherend.

<黏合劑組成物> <Adhesive composition>

本發明的偏光板用表面保護薄膜(表面保護薄膜)具有所述黏合劑層，所述黏合劑層是由黏合劑組成物形成的黏合劑層，作為所述黏合劑組成物，是含有(甲基)丙烯酸系聚合物的黏合劑組成物。 The surface protective film (surface protective film) for polarizing plates of the present invention has the adhesive layer, and the adhesive layer is an adhesive layer formed of an adhesive composition, and the adhesive composition contains ( based) adhesive compositions of acrylic polymers.

本發明中使用的所述黏合劑組成物含有(甲基)丙烯酸系聚合物，所述(甲基)丙烯酸系聚合物至少含有具有碳原子數1~14的烷基的(甲基)丙烯酸系單體50~99.9質量%作為單體成分，雖然只要是具有黏合性的(甲基)丙烯酸系聚合物就沒有特別限定，但其是使用具有碳原子數1~14的烷基的(甲基)丙烯酸系單體作為單體成分的(甲基)丙烯酸系聚合物，較佳為具有碳原子數4~14的烷基的(甲基)丙烯酸系單體。作為所述(甲基)丙烯酸系單體，可以使用1種或2種以 上作為主成分。需要說明的是，所謂本發明的(甲基)丙烯酸系聚合物是指丙烯酸系聚合物及/或甲基丙烯酸系聚合物，此外，所謂(甲基)丙烯酸酯是指丙烯酸酯及/或甲基丙烯酸酯。此外，所謂主成分是指在成分中配合最多的成分。 The adhesive composition used in the present invention contains a (meth)acrylic polymer containing at least a (meth)acrylic polymer having an alkyl group having 1 to 14 carbon atoms. 50 to 99.9% by mass of the monomer is not particularly limited as long as it is an adhesive (meth)acrylic polymer as a monomer component, but a (methyl) polymer having an alkyl group having 1 to 14 carbon atoms is used. ) acrylic monomer The (meth)acrylic polymer which is a monomer component is preferably a (meth)acrylic monomer having an alkyl group having 4 to 14 carbon atoms. As the (meth)acrylic-based monomer, one or two types of monomers may be used. as the main component. In addition, the (meth)acrylic polymer of the present invention refers to an acrylic polymer and/or a methacrylic polymer, and the (meth)acrylate refers to acrylate and/or methyl based acrylate. In addition, the so-called main component means the component which is compounded most among the components.

本發明的表面保護薄膜相對於構成所述(甲基)丙烯酸系聚合物的單體成分總量，含有所述具有碳原子數1~14的烷基的(甲基)丙烯酸系單體50~99.9質量%，較佳為60~99質量%，更佳為70~98質量%，最佳為80~97質量%。藉由在所述範圍內，黏合劑組成物具有適度的潤濕性，黏合劑(層)的凝聚力也優異，因此為佳。 The surface protective film of the present invention contains the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms in an amount of 50 to 99.9 mass %, preferably 60 to 99 mass %, more preferably 70 to 98 mass %, and most preferably 80 to 97 mass %. Since the adhesive composition has moderate wettability and is excellent in the cohesive force of the adhesive (layer) by being within the above-mentioned range, it is preferable.

作為所述具有碳原子數1~14的烷基的(甲基)丙烯酸系單體的具體例，例如可以舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸正十三烷基酯、(甲基)丙烯酸正十四烷基酯等。 Specific examples of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylate. n-butyl acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, ( Isodecyl meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, and the like.

其中，在作為本發明的表面保護薄膜使用的情況下，作為較佳的(甲基)丙烯酸系單體，可以舉出(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙 烯酸正十二烷基酯、(甲基)丙烯酸正十三烷基酯、(甲基)丙烯酸正十四烷基酯等具有碳原子數6~14的烷基的(甲基)丙烯酸酯。藉由使用具有碳原子數6~14的烷基的(甲基)丙烯酸酯，從而容易將對被黏附體的黏合力控制得較低，成為再剝離性優異的表面保護薄膜。 Among them, when used as the surface protection film of the present invention, preferred (meth)acrylic monomers include hexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate. , n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, (meth) Isodecyl acrylate, (meth)propylene (Meth)acrylates having an alkyl group having 6 to 14 carbon atoms, such as n-dodecyl enoate, n-tridecyl (meth)acrylate, and n-tetradecyl (meth)acrylate . By using the (meth)acrylate having an alkyl group having 6 to 14 carbon atoms, it is easy to control the adhesive force to the adherend to be low, and it becomes a surface protection film excellent in releasability.

關於本發明的表面保護薄膜，較佳所述(甲基)丙烯酸系聚合物含有具有羥基的(甲基)丙烯酸系單體作為單體成分。由於所述羥基能夠容易地進行交聯的控制，因此成為較佳方式。此外，能夠提高黏合劑(層)的剪切力，藉由使所述黏合劑貼合於被黏附體，能夠抑制基於被黏附體的捲曲，能夠抑制黏合劑與被黏附體之間(界面)的滑動、偏移的產生，因此為佳。 As for the surface protection film of this invention, it is preferable that the said (meth)acrylic-type polymer contains the (meth)acrylic-type monomer which has a hydroxyl group as a monomer component. Since the above-mentioned hydroxyl group can easily control the crosslinking, it is a preferable form. In addition, the shear force of the adhesive (layer) can be increased, and by bonding the adhesive to the adherend, curling by the adherend can be suppressed, and the gap between the adhesive and the adherend (interface) can be suppressed. Sliding, offset generation, so it is better.

此外，所述(甲基)丙烯酸系聚合物藉由使用所述具有羥基的(甲基)丙烯酸系單體作為單體成分，變得容易控制黏合劑組成物的交聯等，進而變得容易控制因流動而引起的潤濕性的改善及黏合劑(層)的凝聚力、剪切力的平衡。進而，在向黏合劑中添加抗靜電劑的情況下，通常與可以作為交聯部位發揮作用的羧基、磺酸酯基等不同，由於羥基與作為抗靜電劑的離子性化合物等具有適度的相互作用，因此即使從抗靜電性方面考慮也較佳使用。 In addition, by using the (meth)acrylic monomer having the hydroxyl group as a monomer component in the (meth)acrylic polymer, it becomes easy to control the crosslinking of the adhesive composition and the like, and it becomes easy to Control the improvement of wettability caused by flow and the balance of cohesion and shear force of the adhesive (layer). Furthermore, when an antistatic agent is added to the binder, generally, unlike a carboxyl group, a sulfonate group, etc. that can function as a crosslinking site, the hydroxyl group has a moderate interaction with an ionic compound and the like as an antistatic agent. Therefore, it is preferable to use it even from the viewpoint of antistatic properties.

本發明的表面保護薄膜相對於構成所述(甲基)丙烯酸系聚合物的單體成分總量，較佳含有具有羥基的(甲基)丙烯酸系單體0.1~20質量%，更佳為1~15質量%，進一步更佳為2~12質量%。當在所述範圍內時，由於容易控制 黏合劑組成物的潤濕性及黏合劑(層)的凝聚力、剪切力的平衡，因此為佳。 The surface protective film of the present invention preferably contains 0.1 to 20 mass % of a (meth)acrylic monomer having a hydroxyl group, more preferably 1, with respect to the total amount of the monomer components constituting the (meth)acrylic polymer. -15 mass %, More preferably, it is 2-12 mass %. When within the stated range, due to easy control The wettability of the adhesive composition and the balance of the cohesive force and shear force of the adhesive (layer) are therefore preferred.

作為所述具有羥基的(甲基)丙烯酸系單體，例如可以舉出(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸12-羥基月桂酯、丙烯酸(4-羥基甲基環己基)甲酯、N-羥甲基(甲基)丙烯醯胺等。 Examples of the (meth)acrylic monomer having the hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. ester, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxydecyl (meth)acrylate) Hydroxymethylcyclohexyl) methyl ester, N-hydroxymethyl (meth) acrylamide, etc.

本發明的表面保護薄膜較佳所述(甲基)丙烯酸系聚合物含有具有羧基的(甲基)丙烯酸系單體作為單體成分。由於所述羧基能夠提高剪切力或者能夠防止經時的黏合力的增強，因此成為較佳方式。特別是，由於黏合劑(層)的剪切力提高，因此藉由使所述黏合劑貼合於被黏附體，能夠抑制基於被黏附體的捲曲，能夠抑制黏合劑與被黏附體之間(界面)的滑動、偏差的產生，因此為佳。 In the surface protective film of the present invention, the (meth)acrylic polymer preferably contains a (meth)acrylic monomer having a carboxyl group as a monomer component. Since the carboxyl group can increase the shear force or prevent the increase of the adhesive force over time, it is a preferable aspect. In particular, since the shear force of the adhesive (layer) is increased, by attaching the adhesive to the adherend, curling due to the adherend can be suppressed, and the gap between the adhesive and the adherend can be suppressed. It is preferable because of slippage of interface) and generation of deviation.

此外，藉由所述(甲基)丙烯酸系聚合物使用所述具有羧基的(甲基)丙烯酸系單體作為單體成分，能夠抑制表面保護薄膜(黏合劑層)的經時的黏合力的增強，再剝離性、黏合力增強抑制性、以及操作性優異，此外，黏合劑層的凝聚力及剪切力也優異，因此為佳。 In addition, by using the (meth)acrylic monomer having a carboxyl group as a monomer component in the (meth)acrylic polymer, the time-dependent adhesive force of the surface protective film (adhesive layer) can be suppressed. Reinforcement is preferred because it is excellent in re-peelability, inhibition of adhesive force enhancement, and handleability, and also in cohesive force and shear force of the adhesive layer.

本發明的表面保護薄膜相對於構成所述(甲基)丙烯酸系聚合物的單體成分總量，較佳含有具有羧基的(甲基)丙烯酸系單體未達2質量%，更佳為0.001~1.5質量%，進一步更佳為0.005~1質量%，最佳為0.01~0.5品質%。當 在所述範圍內時，能夠抑制經時的黏合力的增強，再剝離性、黏合力增強抑制性、以及操作性優異。此外，黏合劑層的凝聚力及剪切力也優異，因此為佳。需要說明的是，當存在大量極性作用大的羧基般的酸官能團時，在配合離子性化合物作為抗靜電劑的情況下，藉由羧基等酸官能團與離子性化合物相互作用，離子傳導被阻礙，導電效率降低，有可能導致無法獲得充分的抗靜電性，因此不為所欲。 The surface protective film of the present invention preferably contains less than 2 mass % of the (meth)acrylic monomer having a carboxyl group, more preferably 0.001, based on the total amount of the monomer components constituting the (meth)acrylic polymer. ~1.5 mass %, more preferably 0.005 to 1 mass %, and most preferably 0.01 to 0.5 mass %. when In the range described above, the increase in adhesive strength over time can be suppressed, and the re-peelability, the adhesive strength enhancement inhibition property, and the handleability are excellent. Moreover, since the cohesion force and shearing force of an adhesive bond layer are also excellent, it is preferable. It should be noted that when there are a large number of acid functional groups such as carboxyl groups having a large polar effect, when an ionic compound is compounded as an antistatic agent, ion conduction is hindered by the interaction of the acid functional group such as a carboxyl group with the ionic compound. There is a possibility that sufficient antistatic property cannot be obtained because the electrical conductivity efficiency is lowered, so it is not desired.

作為所述具有羧基的(甲基)丙烯酸系單體，例如可以舉出(甲基)丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基馬來酸、羧基聚己內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基四氫鄰苯二甲酸等。 Examples of the (meth)acrylic-based monomer having the carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, and 2-(meth)propylene. Ethyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethylphthalic acid, 2- (Meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylmaleic acid, carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acrylonitrile Oxyethyltetrahydrophthalic acid, etc.

此外，作為其它聚合性單體成分，從易於取得黏合性能的平衡的理由考慮，使玻璃化轉變溫度(Tg)為0℃以下(通常為-100℃以上)，在不損害本發明效果的範圍內，可以使用用於調整(甲基)丙烯酸系聚合物的玻璃化轉變溫度、剝離性的聚合性單體等。 In addition, as other polymerizable monomer components, the glass transition temperature (Tg) is set to 0°C or lower (usually -100°C or higher) in a range that does not impair the effects of the present invention, from the viewpoint of easily achieving a balance of adhesive properties. Inside, a polymerizable monomer for adjusting the glass transition temperature and releasability of the (meth)acrylic polymer can be used.

作為所述(甲基)丙烯酸系聚合物中使用的除所述具有羥基的(甲基)丙烯酸系單體、具有羧基的(甲基)丙烯酸系單體、以及具有碳原子數1~14的烷基的(甲基)丙烯酸系單體以外的其它聚合性單體，只要是在不損害本發明的特性的範圍內，就可以沒有特別限定地使用。例如，可以適 當使用含有氰基的單體、乙烯基酯單體、芳香族乙烯基單體等凝聚力/耐熱性提高成分、含有醯胺基的單體、含有醯亞胺基的單體、含有胺基的單體、含有環氧基的單體、N-丙烯醯嗎啉、乙烯基醚單體等具有黏合(黏接)力提高或作為交聯化基點發揮作用的官能團的成分。這些聚合性單體可以單獨使用，或者也可以混合使用2種以上。 In addition to the (meth)acrylic monomer having a hydroxyl group, the (meth)acrylic monomer having a carboxyl group, and the (meth)acrylic monomer having 1 to 14 carbon atoms used as the (meth)acrylic polymer Other polymerizable monomers other than the alkyl-based (meth)acrylic monomer can be used without particular limitations as long as they are within a range that does not impair the properties of the present invention. For example, it can be When using cohesion/heat resistance improving components such as cyano group-containing monomers, vinyl ester monomers, and aromatic vinyl monomers, amide group-containing monomers, amide group-containing monomers, amine group-containing monomers, etc. A monomer, an epoxy group-containing monomer, an N-acrylomorpholine, a vinyl ether monomer, and the like, a component having a functional group that improves adhesion (adhesion) or functions as a crosslinking base point. These polymerizable monomers may be used alone or in combination of two or more.

作為所述含有氰基的單體，例如可以舉出丙烯腈、甲基丙烯腈。 Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

作為所述乙烯基酯單體，例如可以舉出乙酸乙烯酯、丙酸乙烯酯、月桂酸乙烯酯等。 As said vinyl ester monomer, vinyl acetate, vinyl propionate, vinyl laurate, etc. are mentioned, for example.

作為所述芳香族乙烯基單體，例如可以舉出苯乙烯、氯苯乙烯、氯甲基苯乙烯、α-甲基苯乙烯、其它的取代苯乙烯等。 As said aromatic vinyl monomer, styrene, chlorostyrene, chloromethylstyrene, alpha-methylstyrene, other substituted styrene etc. are mentioned, for example.

作為所述含有醯胺基的單體，例如可以舉出丙烯醯胺、甲基丙烯醯胺、二乙基丙烯醯胺、N-乙烯基吡咯烷酮、N，N-二甲基丙烯醯胺、N，N-二甲基甲基丙烯醯胺、N，N-二乙基丙烯醯胺、N，N-二乙基甲基丙烯醯胺、N，N’-亞甲基雙丙烯醯胺、N，N-二甲基胺基丙基丙烯醯胺、N，N-二甲基胺基丙基甲基丙烯醯胺、雙丙酮丙烯醯胺等。 Examples of the amide group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N,N-dimethylacrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone , N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide, N,N'-methylenebisacrylamide, N , N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylate, diacetone acrylamide, etc.

作為所述含有醯亞胺基的單體，例如可以舉出環己基馬來醯亞胺、異丙基馬來醯亞胺、N-環己基馬來醯亞胺、衣康醯亞胺等。 Examples of the above-mentioned imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, itaconicimide, and the like.

作為所述含有胺基的單體，例如可以舉出(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N，N-二甲基胺基乙酯、(甲 基)丙烯酸N，N-二甲基胺基丙酯等。 Examples of the amine group-containing monomer include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (meth)acrylate base) N,N-dimethylaminopropyl acrylate and the like.

作為所述含有環氧基的單體，例如可以舉出(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯、烯丙基縮水甘油醚等。 As said epoxy group-containing monomer, glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, allyl glycidyl ether, etc. are mentioned, for example.

作為所述乙烯基醚單體，例如可以舉出甲基乙烯基醚、乙基乙烯基醚、異丁基乙烯基醚等。 As said vinyl ether monomer, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc. are mentioned, for example.

在本發明中，除所述具有羧基的(甲基)丙烯酸系單體、具有羥基的(甲基)丙烯酸系單體、以及具有碳原子數1~14的烷基的(甲基)丙烯酸系單體以外的其它聚合性單體在構成所述(甲基)丙烯酸系聚合物的單體成分總量(總單體成分)中，較佳為0~40質量%，更佳為0~30質量%。藉由在所述範圍內使用所述其它聚合性單體，可以適當地調節與能夠作為抗靜電劑使用的離子性化合物的良好的相互作用、以及良好的再剝離性。 In the present invention, in addition to the (meth)acrylic monomer having a carboxyl group, the (meth)acrylic monomer having a hydroxyl group, and the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms In the total amount of monomer components (total monomer components) constituting the (meth)acrylic polymer, other polymerizable monomers other than monomers are preferably 0 to 40% by mass, more preferably 0 to 30% by mass. quality%. By using the other polymerizable monomer within the above range, good interaction with an ionic compound that can be used as an antistatic agent and good re-peelability can be appropriately adjusted.

所述(甲基)丙烯酸系聚合物的重均分子量為10萬~500萬，較佳為20萬~400萬，進一步更佳為30萬~300萬。在重均分子量小於10萬的情況下，由於所得到的黏合劑(層)的凝聚力變小而具有發生殘膠的趨勢。另一方面，在重均分子量超過500萬的情況下，聚合物的流動性降低，對被黏附體(偏光板)的潤濕不充分，具有成為在被黏附體與表面保護薄膜的黏合劑組成物層之間產生的起泡的原因的趨勢。需要說明的是，重均分子量是指藉由GPC(凝膠滲透色譜法)測定而得到的值。 The weight average molecular weight of the (meth)acrylic polymer is 100,000 to 5 million, preferably 200,000 to 4 million, and more preferably 300,000 to 3 million. When the weight average molecular weight is less than 100,000, since the cohesion force of the obtained adhesive agent (layer) becomes small, there exists a tendency for adhesive residue to generate|occur|produce. On the other hand, when the weight average molecular weight exceeds 5,000,000, the fluidity of the polymer decreases, the wetting of the adherend (polarizing plate) is insufficient, and the adhesive composition becomes the adherend and the surface protective film. The tendency to cause blistering between layers. In addition, the weight average molecular weight means the value measured by GPC (gel permeation chromatography).

此外，所述(甲基)丙烯酸系聚合物的玻璃化轉變 溫度(Tg)較佳為0℃以下，更佳為-10℃以下，進一步更佳為-20℃以下(通常為-100℃以上)。在玻璃化轉變溫度高於0℃的情況下，聚合物難以流動，例如，對被黏附體(偏光板)的潤濕不充分，具有成為在被黏附體與表面保護薄膜的黏合劑組成物層之間產生的起泡的原因的趨勢。特別是藉由將玻璃化轉變溫度設為-61℃以下，可以容易地獲得對被黏附體的潤濕性及輕剝離性優異的黏合劑組成物。需要說明的是，(甲基)丙烯酸系聚合物的玻璃化轉變溫度可以藉由適當地改變所使用的單體成分、組成比而在所述範圍內進行調整。 In addition, the glass transition of the (meth)acrylic polymer The temperature (Tg) is preferably 0°C or lower, more preferably -10°C or lower, still more preferably -20°C or lower (usually -100°C or higher). When the glass transition temperature is higher than 0°C, the polymer is difficult to flow, for example, the wetting of the adherend (polarizing plate) is insufficient, and there is an adhesive composition layer that serves as a protective film between the adherend and the surface. The trend among the causes of blistering. In particular, by setting the glass transition temperature to be -61° C. or lower, an adhesive composition excellent in wettability to an adherend and light releasability can be easily obtained. In addition, the glass transition temperature of a (meth)acrylic-type polymer can be adjusted within the said range by suitably changing the monomer component and composition ratio used.

雖然本發明中使用的(甲基)丙烯酸系聚合物的聚合方法沒有特別限制，可以藉由溶液聚合、乳液聚合、本體聚合、懸浮聚合等公知的方法進行聚合，但特別是從操作性的觀點、對被黏附體(偏光板)的低污染性等特性方面考慮，更佳的方式是溶液聚合。此外，所得到的聚合物也可以是無規共聚物、嵌段共聚物、交替共聚物、接枝共聚物等的任一種。 The polymerization method of the (meth)acrylic polymer used in the present invention is not particularly limited, and the polymerization can be carried out by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. . Considering the characteristics of low pollution of the adhered body (polarizing plate), a better method is solution polymerization. In addition, the obtained polymer may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.

<矽酮化合物> <Silicone compound>

本發明的表面保護薄膜的特徵在於，所述黏合劑組成物含有下述式所示的矽酮化合物。雖然詳細的原因還不清楚，但藉由使用所述矽酮化合物，由於分子骨架中不含有醚基，因此能夠抑制所得到的黏合劑(層)的彈性模量變低，由於不會引起凝聚力及剪切力的降低，因此在使所述表面保護薄膜貼合於薄型化後的偏光板時，能夠抑制偏光板的 捲曲的產生，能夠獲得捲曲調節性優異的偏光板。 The surface protection film of the present invention is characterized in that the adhesive composition contains a silicone compound represented by the following formula. Although the detailed reason is not clear, by using the above-mentioned silicone compound, since the molecular skeleton does not contain an ether group, the elastic modulus of the obtained adhesive (layer) can be suppressed from being lowered, and the cohesion force is not caused. and shear force reduction, so when the surface protection film is bonded to the thinned polarizing plate, the polarizing plate can be suppressed from being damaged. The occurrence of curl can obtain a polarizing plate excellent in curl controllability.

Figure 105123601-A0305-02-0019-2
Figure 105123601-A0305-02-0019-2

上述式中，R及R’為甲基或苯基，R及R’可以相同，也可以不同。此外，m為0~3000，n為1~3000。 In the above formula, R and R' are methyl or phenyl, and R and R' may be the same or different. In addition, m is 0 to 3000, and n is 1 to 3000.

此外，作為上述矽酮化合物製劑的市售品的具體例，例如可以舉出KF-50-100cs(甲基苯基矽油)、KF-50-300cs(甲基苯基矽油)、KF-50-1000cs(甲基苯基矽油)、KF-50-3000cs(甲基苯基矽油)、KF-53(甲基苯基矽油)、KF-54(甲基苯基矽油)、KF-96-100cs(二甲基矽油)、KF-96-300cs(甲基苯基矽油)、KF-96-1000cs(二甲基矽油)、KF-96-3000cs(二甲基矽油)、KF-96-1萬cs(二甲基矽油)(信越化學公司製)等。 Moreover, as a specific example of the commercial item of the said silicone compound preparation, KF-50-100cs (methyl phenyl silicone oil), KF-50-300cs (methyl phenyl silicone oil), KF-50- 1000cs (methyl phenyl silicone oil), KF-50-3000cs (methyl phenyl silicone oil), KF-53 (methyl phenyl silicone oil), KF-54 (methyl phenyl silicone oil), KF-96-100cs ( Dimethyl silicone oil), KF-96-300cs (methyl phenyl silicone oil), KF-96-1000cs (dimethyl silicone oil), KF-96-3000cs (dimethyl silicone oil), KF-96-10,000 cs (Dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

本發明的表面保護薄膜的所述黏合劑組成物相對於所述(甲基)丙烯酸系聚合物100質量份，含有所述矽酮化合物0.01質量份~未達1質量份，較佳為0.02~0.98質量份，更佳為0.03~0.96質量份。當在所述範圍內時，能夠謀求剪切力與動摩擦力的並存，低污染性優異，因此為佳。 The adhesive composition of the surface protection film of the present invention contains 0.01 to less than 1 part by mass of the silicone compound, preferably 0.02 to 100 parts by mass of the (meth)acrylic polymer. 0.98 parts by mass, more preferably 0.03 to 0.96 parts by mass. Within the above range, coexistence of shear force and dynamic friction force can be achieved, and low contamination properties are excellent, which is preferable.

<具有烯化氧基的表面活性劑> <Surfactant having an alkylene oxide group>

關於本發明的表面保護薄膜，較佳所述黏合劑組成物含有具有烯化氧基的表面活性劑。藉由在所述黏合劑組成物中含有具有烯化氧基的表面活性劑，能夠進一步地獲得 對作為被黏附體的偏光板的潤濕性優異的黏合劑層，因此有用。 Regarding the surface protection film of the present invention, it is preferable that the adhesive composition contains a surfactant having an alkylene oxide group. By including a surfactant having an alkylene oxide group in the adhesive composition, it is possible to further obtain It is useful as an adhesive layer excellent in wettability to a polarizing plate as an adherend.

作為所述具有烯化氧基的表面活性劑的具體例，例如可以舉出聚氧化烯烷基胺、聚氧化烯二胺、聚氧化烯脂肪酸酯、聚氧化烯山梨糖醇酐脂肪酸酯、聚氧化烯烷基苯基醚、聚氧化烯烷基醚、聚氧化烯烷基烯丙基醚、聚氧化烯烷基苯基烯丙基醚等非離子性表面活性劑；聚氧化烯烷基醚硫酸酯鹽、聚氧化烯烷基醚磷酸酯鹽、聚氧化烯烷基苯基醚硫酸酯鹽、聚氧化烯烷基苯基醚磷酸酯鹽等陰離子性表面活性劑；另外，具有聚氧化烯鏈(聚烯基氧化物鏈)的陽離子性表面活性劑、兩離子性表面活性劑等。此外，所述具有烯化氧基的表面活性劑可以單獨使用，也可以組合使用2種以上。 Specific examples of the surfactant having an alkyleneoxy group include polyoxyalkylene alkylamines, polyoxyalkylene diamines, polyoxyalkylene fatty acid esters, and polyoxyalkylene sorbitan fatty acid esters, for example. , polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether, polyoxyalkylene alkyl phenyl allyl ether and other nonionic surfactants; polyoxyalkylene alkyl Anionic surfactants, such as base ether sulfate, polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkyl phenyl ether sulfate, polyoxyalkylene alkyl phenyl ether phosphate, etc.; A cationic surfactant, a zionic surfactant, etc. of an oxyalkylene chain (polyalkenyl oxide chain). Moreover, the surfactant which has the said alkylene oxide group may be used individually and may be used in combination of 2 or more types.

作為較佳的一種方式，上述具有烯化氧基的表面活性劑是至少一部分具有(聚)乙烯基氧化物鏈的化合物。除了基礎聚合物以外，藉由配合具有所述(聚)乙烯基氧化物鏈的化合物，在配合抗靜電劑的情況下，與抗靜電劑的相溶性得以提高，適當地抑制向作為被黏附體的偏光板的滲出，能夠獲得低污染性的黏合劑組成物。作為上述具有(聚)乙烯基氧化物鏈的化合物，所述化合物整體中所含的(聚)乙烯基氧化物鏈的質量較佳為5~90質量%，更佳為5~85質量%，進一步更佳為5~80質量%，最佳為5~75質量%。 As a preferred embodiment, the above-mentioned surfactant having an alkylene oxide group is a compound having at least a part of a (poly)vinyl oxide chain. When an antistatic agent is blended by blending a compound having the above-mentioned (poly)vinyl oxide chain in addition to the base polymer, the compatibility with the antistatic agent is improved, and the tendency to act as an adherend is appropriately suppressed. The exudation of the polarizing plate can be obtained, and the adhesive composition with low pollution can be obtained. As the compound having the above-mentioned (poly)vinyl oxide chain, the mass of the (poly)vinyl oxide chain contained in the entire compound is preferably 5 to 90% by mass, more preferably 5 to 85% by mass, More preferably, it is 5 to 80 mass %, and most preferably, it is 5 to 75 mass %.

作為上述具有烯化氧基的表面活性劑的數均分子量(Mn)，較佳為50000以下的數均分子量，更佳為 200~30000，進一步更佳為200~10000，特佳為200~5000的數均分子量。當數均分子量與50000相比過大時，則存在與丙烯酸系聚合物的相溶性降低、黏合劑層泛白的趨勢。當數均分子量與200相比過小時，則可能會容易產生由所述聚氧化烯化合物造成的污染。需要說明的是，此處所謂的數均分子量是指藉由GPC(凝膠滲透色譜法)獲得的聚苯乙烯換算的值。 The number average molecular weight (Mn) of the surfactant having an alkylene oxide group is preferably a number average molecular weight of 50,000 or less, more preferably 200-30,000, more preferably 200-10,000, particularly preferably 200-5,000 number average molecular weight. When the number average molecular weight is too large compared to 50,000, the compatibility with the acrylic polymer decreases, and the adhesive layer tends to be whitened. When the number average molecular weight is too small compared to 200, contamination by the polyoxyalkylene compound may easily occur. In addition, the number average molecular weight here means the polystyrene conversion value obtained by GPC (gel permeation chromatography).

此外，作為上述具有烯化氧基的表面活性劑的市售品的具體例，例如可以舉出Aqualon KH-10、Aqualon HS-10、Noigen EA-137、Hitenol NF-08(第一工業公司製)、Latemul PD-420(花王公司製)等。 In addition, as a specific example of the commercial item of the surfactant which has the said alkylene oxide group, Aqualon KH-10, Aqualon HS-10, Noigen EA-137, Hitenol NF-08 (made by Daiichi Kogyo Co., Ltd.) are mentioned, for example. ), Latemul PD-420 (made by Kao Corporation), etc.

作為上述具有烯化氧基的表面活性劑的含量，相對於所述(甲基)丙烯酸系聚合物100質量份，例如可以設為0~5質量份，較佳為0.01~2質量份，更佳為0.05~1質量份。只要在所述範圍內，在配合了抗靜電劑的情況下，就能夠獲得防止抗靜電劑的滲出的效果，因此為佳。 The content of the surfactant having an alkylene oxide group can be, for example, 0 to 5 parts by mass, preferably 0.01 to 2 parts by mass, relative to 100 parts by mass of the (meth)acrylic polymer, and more preferably 0.01 to 2 parts by mass. Preferably it is 0.05-1 mass part. When the antistatic agent is blended within the above range, the effect of preventing bleeding of the antistatic agent can be obtained, which is preferable.

而且，在所述黏合劑組成物中也可以含有丙烯酸低聚物。丙烯酸低聚物的重均分子量(Mw)較佳為1000以上且未達30000，更佳為1500以上且未達20000，進一步更佳為2000以上且未達10000。在用於本實施方式的表面保護用途(再剝離用)的丙烯酸系黏合劑組成物的情況下，作為增黏樹脂發揮功能，提高黏合(黏接)性，具有抑制表面保護薄膜的翹起的效果。 Moreover, an acrylic oligomer may be contained in the said adhesive composition. The weight average molecular weight (Mw) of the acrylic oligomer is preferably 1,000 or more and less than 30,000, more preferably 1,500 or more and less than 20,000, and still more preferably 2,000 or more and less than 10,000. In the case of the acrylic pressure-sensitive adhesive composition used for the surface protection application (for re-peeling) of the present embodiment, it functions as a tackifier resin, improves adhesion (adhesion), and suppresses the lifting of the surface protection film. Effect.

在所述丙烯酸低聚物中可以使用(甲基)丙烯酸 酯單體，例如可以舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛脂、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯般的(甲基)丙烯酸烷基酯；(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯般的(甲基)丙烯酸芳基酯；由萜烯化合物衍生物醇得到的(甲基)丙烯酸酯等。 (Meth)acrylic acid can be used in the acrylic oligomer Ester monomers, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, ( Isobutyl meth)acrylate, second butyl (meth)acrylate, 3rd butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, (meth)acrylic acid Hexyl ester, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, ( Isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (meth) (meth)acrylic acid alkyl ester; (meth)acrylic acid phenyl ester, (meth)acrylic acid aryl (meth)acrylic acid ester such as benzyl ester; (meth)acrylic acid ester obtained from terpene compound derivative alcohol, etc.

此外，在所述丙烯酸低聚物中可以使用具有脂環式結構的(甲基)丙烯酸系單體，例如可以舉出甲基丙烯酸二環戊酯、丙烯酸二環戊酯、甲基丙烯酸二環戊基氧基乙酯、丙烯酸二環戊基氧基乙酯、甲基丙烯酸三環戊酯、丙烯酸三環戊酯、1-金剛烷基甲基丙烯酸酯、1-金剛烷基丙烯酸酯、2-甲基-2-金剛烷基甲基丙烯酸酯、2-甲基-2-金剛烷基丙烯酸酯、2-乙基-2-金剛烷基甲基丙烯酸酯、2-乙基-2-金剛烷基丙烯酸酯等(甲基)丙烯酸酯等。如此的(甲基)丙烯酸系單體可以單獨使用或組合使用2種以上。 In addition, a (meth)acrylic monomer having an alicyclic structure can be used for the acrylic oligomer, and examples thereof include dicyclopentyl methacrylate, dicyclopentyl acrylate, and bicyclo methacrylate. Amyloxyethyl, dicyclopentyloxyethyl acrylate, tricyclopentyl methacrylate, tricyclopentyl acrylate, 1-adamantyl methacrylate, 1-adamantyl acrylate, 2 -Methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl (meth)acrylates such as alkyl acrylates and the like. Such (meth)acrylic monomers can be used alone or in combination of two or more.

此外，所述丙烯酸低聚物除了所述(甲基)丙烯酸系單體成分單元之外，也可以使所述(甲基)丙烯酸系單體與能夠共聚的其它單體成分(共聚性單體)共聚來獲得。 In addition to the (meth)acrylic monomer component unit, the acrylic oligomer may contain the (meth)acrylic monomer and another monomer component (copolymerizable monomer) that can be copolymerized. ) are obtained by copolymerization.

所述丙烯酸低聚物的重均分子量(Mw)為1000以上且未達30000，較佳為1500以上且未達20000，進一步更佳為2000以上且未達10000。當重均分子量為30000以上時，黏合(黏接)性降低。此外，當重均分子量未達1000時，由於為低分子量，因此引起表面保護薄膜的黏合力的降低。 The weight average molecular weight (Mw) of the acrylic oligomer is 1,000 or more and less than 30,000, preferably 1,500 or more and less than 20,000, and still more preferably 2,000 or more and less than 10,000. When the weight average molecular weight is 30,000 or more, the adhesiveness (adhesion) decreases. In addition, when the weight average molecular weight is less than 1000, since the molecular weight is low, the adhesive force of the surface protection film is lowered.

關於本發明的表面保護薄膜，較佳所述黏合劑組成物不含有具有聚氧化烯鏈的有機聚矽氧烷。雖然能夠藉由使用所述有機聚矽氧烷來將表面保護薄膜(黏合劑層)的輕剝離化、偏光板的動摩擦力抑制得較低，但另一方面，會導致剪切力的降低，因此成為不為所欲的方式。需要說明的是，雖然剪切力降低的詳細原因不清楚，但可以推測為如下原因：由於在骨架中除了醚基之外還含有矽酮成分，因此獲得的黏合劑(層)的彈性模量變低，導致凝聚力降低及剪切力的降低。 Regarding the surface protection film of the present invention, preferably, the adhesive composition does not contain an organopolysiloxane having a polyoxyalkylene chain. Although the use of the organopolysiloxane can reduce the peeling of the surface protective film (adhesive layer) and the dynamic friction force of the polarizing plate can be reduced, on the other hand, the shear force is reduced, So it becomes the undesired way. It should be noted that although the detailed reason for the decrease in shear force is not clear, it is presumed to be the following reason: Since the skeleton contains a silicone component in addition to the ether group, the elastic modulus of the obtained adhesive (layer) becomes lower, resulting in a decrease in cohesion and a decrease in shear force.

<抗靜電劑> <Antistatic agent>

本發明的表面保護薄膜的所述黏合劑組成物可以含有抗靜電劑(抗靜電成分)，作為所述抗靜電劑，可以含有離子性化合物。作為所述離子性化合物，可以舉出鹼金屬鹽、及/或低熔點(熔點為150℃以下)的離子性化合物(離子液體等)。藉由含有這些離子性化合物，能夠賦予優異的抗靜電性。 The adhesive composition of the surface protection film of the present invention may contain an antistatic agent (antistatic component), and may contain an ionic compound as the antistatic agent. Examples of the ionic compound include alkali metal salts and/or ionic compounds (ionic liquids, etc.) having a low melting point (melting point of 150° C. or lower). By containing these ionic compounds, excellent antistatic properties can be imparted.

此外，相對於所述(甲基)丙烯酸系聚合物100質量份，所述抗靜電劑的含量較佳為1質量份以下，更佳為0.001~0.9質量份，進一步更佳為0.005~0.8質量份。當在所 述範圍內時，由於易於兼顧抗靜電性與低污染性，因此為佳。 In addition, the content of the antistatic agent is preferably 1 part by mass or less, more preferably 0.001 to 0.9 parts by mass, and still more preferably 0.005 to 0.8 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer. share. when in Within the above range, since it is easy to achieve both antistatic properties and low contamination properties, it is preferable.

<交聯劑> <Crosslinking agent>

關於本發明的表面保護薄膜，較佳所述黏合劑組成物含有交聯劑。此外，在本發明中，使用所述黏合劑組成物作為黏合劑層。例如，在所述黏合劑組成物含有所述(甲基)丙烯酸系聚合物的情況下，藉由適當地調節所述(甲基)丙烯酸系聚合物的構成單元、構成比率、交聯劑的選擇以及添加比率等進行交聯，能夠獲得耐熱性更優異的表面保護薄膜(黏合劑層)。 Regarding the surface protection film of the present invention, it is preferable that the adhesive composition contains a crosslinking agent. Furthermore, in the present invention, the adhesive composition is used as an adhesive layer. For example, in the case where the adhesive composition contains the (meth)acrylic polymer, the constituent units, constituent ratios, and crosslinking agents of the (meth)acrylic polymer are appropriately adjusted. It is possible to obtain a surface protective film (adhesive layer) with more excellent heat resistance by selecting and adding ratios and the like for crosslinking.

作為在本發明中使用的交聯劑，可以使用異氰酸酯化合物、環氧化合物、三聚氰胺系樹脂、氮丙啶衍生物、以及金屬螯合化合物等，特佳的方式是使用異氰酸酯化合物。此外，這些化合物可以單獨使用，也可以混合使用2種以上。 As the crosslinking agent used in the present invention, isocyanate compounds, epoxy compounds, melamine-based resins, aziridine derivatives, and metal chelate compounds can be used, and an isocyanate compound is particularly preferred. In addition, these compounds may be used alone or in combination of two or more.

作為所述異氰酸酯化合物，例如可以舉出三亞甲基二異氰酸酯、亞丁基二異氰酸酯、六亞甲基二異氰酸酯(HDI)、二聚酸二異氰酸酯等脂肪族多異氰酸酯類、環亞戊基二異氰酸酯、環亞己基二異氰酸酯、異佛爾酮二異氰酸酯(IPDI)等脂環族異氰酸酯類、2,4-甲苯二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯(XDI)等芳香族異氰酸酯類、將所述異氰酸酯化合物藉由脲基甲酸酯鍵、縮二脲鍵、異氰脲酸酯鍵、脲二酮鍵、脲鍵、碳化二亞胺鍵、脲酮亞胺鍵、惡二嗪三酮鍵等而改性了的多異氰 酸酯改性體。例如，作為市售品，可以舉出商品名Takenate 300S、Takenate 500、Takenate D165N、Takenate D178N(以上為三井化學公司製)、Sumidur T80、Sumidur L、Desmodur N3400(以上為住化拜耳聚胺酯公司製)、Millionate MR、Millionate MT、Coronate L、Coronate HL、Coronate HX(以上為日本聚胺酯工業公司製)等。這些異氰酸酯化合物可以單獨使用，可以混合使用2種以上，也可以並用2官能的異氰酸酯化合物及3官能以上的異氰酸酯化合物。藉由並用交聯劑，能夠兼顧黏合性及耐反彈性(對曲面的黏接性)，能夠獲得黏接可靠性更優異的表面保護薄膜(黏合劑層)。 Examples of the isocyanate compound include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), dimer acid diisocyanate, cyclopentylene diisocyanate, Alicyclic isocyanates such as cyclohexylene diisocyanate and isophorone diisocyanate (IPDI), 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate (XDI ) and other aromatic isocyanates, the isocyanate compounds are linked by an allophanate bond, biuret bond, isocyanurate bond, uretdione bond, urea bond, carbodiimide bond, uretonidene bond amine bond, oxadiazine trione bond, etc. modified polyisocyanide Ester modification. For example, commercial products include Takenate 300S, Takenate 500, Takenate D165N, Takenate D178N (the above are manufactured by Mitsui Chemicals Co., Ltd.), Sumidur T80, Sumidur L, Desmodur N3400 (the above are manufactured by Sumidur Bayer Polyurethane Co., Ltd.) , Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (the above are manufactured by Japan Polyurethane Industry Co., Ltd.), etc. These isocyanate compounds may be used alone, two or more types may be mixed and used, and a bifunctional isocyanate compound and a trifunctional or more functional isocyanate compound may be used in combination. By using a crosslinking agent in combination, both adhesion and rebound resistance (adhesion to a curved surface) can be achieved, and a surface protection film (adhesive layer) with more excellent adhesion reliability can be obtained.

作為所述環氧化合物，例如可以舉出N，N，N’，N’-四縮水甘油基-間二甲苯二胺(商品名TETRAD-X，三菱瓦斯化學公司製)、1,3-雙(N，N-二縮水甘油基胺基甲基)環己烷(商品名TETRAD-C，三菱瓦斯化學公司製)等。 Examples of the epoxy compound include N,N,N',N'-tetraglycidyl-m-xylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 1,3-bis (N,N-diglycidylaminomethyl)cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like.

作為所述三聚氰胺系樹脂，可以舉出六羥甲基三聚氰胺等。作為氮丙啶衍生物，例如可以舉出作為市售品的商品名HDU、TAZM、TAZO(以上為相互藥工公司製)等。 As said melamine-type resin, hexamethylol melamine etc. are mentioned. As an aziridine derivative, the trade name HDU, TAZM, and TAZO (the above are made by Mutual Pharmaceutical Co., Ltd.), which are commercially available products, can be mentioned, for example.

作為所述金屬螯合化合物，作為金屬成分可以舉出鋁、鐵、錫、鈦、鎳等，作為螯合成分可以舉出乙炔、乙醯乙酸甲酯、乳酸乙酯等。 Examples of the metal chelate compound include aluminum, iron, tin, titanium, nickel, and the like as the metal component, and acetylene, methyl acetoacetate, ethyl lactate, and the like as the chelate component.

相對於所述(甲基)丙烯酸系聚合物100質量份，本發明中使用的交聯劑的含量例如較佳含有0.01~10質量份，更佳含有0.5~8質量份，進一步更佳含有1~5質量份。在所述含量小於0.01質量份的情況下，由交聯劑引起的交 聯形成不充分，所得到的黏合劑層的凝聚力小，有時也無法獲得充分的耐熱性，此外具有成為殘膠的原因的趨勢。另一方面，在含量超過10質量份的情況下，聚合物的凝聚力大，流動性降低，對被黏附體(偏光板)的潤濕不充分，具有成為在被黏附體與黏合劑層(黏合劑組成物層)間產生的起泡的原因的趨勢。而且，當交聯劑量多時，具有剝離帶電特性降低的趨勢。此外，這些交聯劑可以單獨使用，或者可以混合使用2種以上。 The content of the crosslinking agent used in the present invention is, for example, preferably 0.01 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 1 part by mass relative to 100 parts by mass of the (meth)acrylic polymer. ~5 parts by mass. In the case where the content is less than 0.01 part by mass, cross-linking caused by the cross-linking agent Insufficient link formation, the cohesive force of the obtained adhesive bond layer is small, sufficient heat resistance may not be obtained, and there is a tendency that it becomes a cause of adhesive residue. On the other hand, when the content exceeds 10 parts by mass, the cohesive force of the polymer is large, the fluidity is lowered, the wetting of the adherend (polarizing plate) is insufficient, and the adherend and the adhesive layer (adhesion) are caused. The tendency of the cause of foaming between the agent composition layers). Furthermore, when the amount of crosslinking is large, there is a tendency that the peel charging characteristics are lowered. In addition, these crosslinking agents may be used alone or in combination of two or more.

為了使上述任一交聯反應更有效地進行，所述黏合劑組成物中還可以含有交聯催化劑。作為如此的交聯催化劑，例如可以使用二月桂酸二丁基錫、二月桂酸二辛基錫等錫系催化劑、三(乙醯丙酮)鐵、三(己烷-2,4-二酮)鐵、三(庚烷-2,4-二酮)鐵、三(庚烷-3,5-二酮)鐵、三(5-甲基己烷-2,4-二酮)鐵、三(辛烷-2,4-二酮)鐵、三(6-甲基庚烷-2,4-二酮)鐵、三(2,6-二甲基庚烷-3,5-二酮)鐵、三(壬烷-2,4-二酮)鐵、三(壬烷-4,6-二酮)鐵、三(2,2,6,6-四甲基庚烷-3,5-二酮)鐵、三(十三烷-6,8-二酮)鐵、三(1-苯基丁烷-1,3-二酮)鐵、三(六氟乙醯丙酮)鐵、三(乙醯乙酸乙酯)鐵、三(乙醯乙酸正丙酯)鐵、三(乙醯乙酸異丙酯)鐵、三(乙醯乙酸正丁酯)鐵、三(乙醯乙酸第二丁酯)鐵、三(乙醯乙酸第三丁酯)鐵、三(丙醯乙酸甲酯)鐵、三(丙醯乙酸乙酯)鐵、三(丙醯乙酸正丙酯)鐵、三(丙醯乙酸異丙酯)鐵、三(丙醯乙酸正丁酯)鐵、三(丙醯乙酸第二丁酯)鐵、三(丙醯乙酸第三丁酯)鐵、三(乙醯乙酸苄酯)鐵、三(丙二酸二甲酯)鐵、三(丙二酸二乙酯)鐵、三 甲氧基鐵、三乙氧基鐵、三異丙氧基鐵、氯化鐵等鐵系催化劑。這些交聯催化劑可以使用1種，也可以並用2種以上。 In order to make any of the above-mentioned cross-linking reactions proceed more efficiently, the adhesive composition may further contain a cross-linking catalyst. As such a crosslinking catalyst, for example, tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris(acetylacetone)iron, tris(hexane-2,4-dione)iron, Tris(heptane-2,4-dione)iron, Tris(heptane-3,5-dione)iron, Tris(5-methylhexane-2,4-dione)iron, Tris(octane) -2,4-dione)iron, tris(6-methylheptane-2,4-dione)iron, tris(2,6-dimethylheptane-3,5-dione)iron, tris(2,6-dimethylheptane-3,5-dione)iron (nonane-2,4-dione)iron, tris(nonane-4,6-dione)iron, tris(2,2,6,6-tetramethylheptane-3,5-dione) Iron, Tris(tridecane-6,8-dione)iron, Tris(1-phenylbutane-1,3-dione)iron, Tris(hexafluoroacetone acetone)iron, Tris(acetylacetate) ethyl)iron, tris(acetonitrile-n-propylacetate)iron, tris(acetonitrile-isopropylacetate)iron, tris(acetonitrile-n-butylacetate)iron, tris(2-butylacetate)iron, Tris(3-butylacetate)iron, tris(methylpropylacetate)iron, tris(ethylacetate)iron, tris(n-propylacetate)iron, isopropyl tris(propylacetate) ester) iron, tris(propylacetate-n-butyl acetate)iron, tris(2-butylpropylacetate)iron, tris(tertiary butylacetate)iron, tris(acetoxybenzyl acetate)iron, tris(2-butylacetate)iron (dimethylmalonate)iron, tris(diethylmalonate)iron, tris(diethylmalonate)iron Iron-based catalysts such as iron methoxy, iron triethoxide, iron triisopropoxide, and iron chloride. These crosslinking catalysts may be used alone or in combination of two or more.

雖然所述交聯催化劑的含量沒有特別限制，但例如相對於所述(甲基)丙烯酸系聚合物100質量份，較佳約為0.0001~1質量份，更佳為0.001~0.5質量份。當在所述範圍內時，形成黏合劑層時交聯反應的速度快，黏合劑組成物的適用期也變長，因此成為較佳方式。 Although the content of the crosslinking catalyst is not particularly limited, for example, it is preferably about 0.0001 to 1 part by mass, and more preferably about 0.001 to 0.5 part by mass with respect to 100 parts by mass of the (meth)acrylic polymer. When it is in the said range, the rate of the crosslinking reaction when forming an adhesive bond layer becomes high, and the pot life of an adhesive composition becomes long, and it becomes a preferable form.

而且，所述黏合劑組成物中可以含有產生酮-烯醇互變異構性的化合物作為交聯阻滯劑。例如，在含有交聯劑的黏合劑組成物或配合交聯劑而得到使用的黏合劑組成物中，可以較佳採用含有所述產生酮-烯醇互變異構性的化合物的方式。由此，抑制交聯劑配合後的黏合劑組成物的過度的黏度增強、凝膠化，可以實現延長黏合劑組成物的適用期的效果。在至少使用異氰酸酯化合物作為所述交聯劑的情況下，含有產生酮-烯醇互變異構性的化合物尤其有意義。該技術例如在所述黏合劑組成物為有機溶劑溶液或無溶劑的形態的情況下可以較佳適用。 Furthermore, the adhesive composition may contain a compound that produces keto-enol tautomerism as a crosslinking retarder. For example, in an adhesive composition containing a cross-linking agent or an adhesive composition obtained by blending a cross-linking agent, an aspect that contains the compound that produces the keto-enol tautomerism can be preferably used. Thereby, excessive viscosity increase and gelation of the adhesive composition after blending of the crosslinking agent can be suppressed, and the effect of prolonging the pot life of the adhesive composition can be achieved. In the case of using at least an isocyanate compound as the crosslinking agent, it is of particular interest to contain a compound which produces keto-enol tautomerism. This technique can be preferably applied, for example, when the adhesive composition is in the form of an organic solvent solution or a solvent-free form.

作為所述產生酮-烯醇互變異構性的化合物，可以使用各種β-二羰基化合物。作為具體例，可以舉出乙醯丙酮、2,4-己二酮、3,5-庚二酮、2-甲基己烷-3,5-二酮、6-甲基庚烷-2,4-二酮、2,6-二甲基庚烷-3,5-二酮等β-二酮類；乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸異丙酯、乙醯乙酸第三丁酯等乙醯乙酸酯類；丙醯乙酸甲酯、丙醯乙酸乙酯、丙醯乙酸異丙酯、丙醯乙酸第三丁酯等丙醯乙酸酯類； 異丁醯乙酸甲酯、異丁醯乙酸乙酯、異丁醯乙酸異丙酯、異丁醯乙酸第三丁酯等異丁醯乙酸酯類；丙二酸甲酯、丙二酸乙酯等丙二酸酯類等。其中，作為較佳的化合物，可以舉出乙醯丙酮及乙醯乙酸酯類。如此的產生酮-烯醇互變異構性的化合物可以單獨使用，也可以組合使用2種以上。 As the compound that produces the keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples include acetone acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2, β-diketones such as 4-diketone, 2,6-dimethylheptane-3,5-dione, etc.; Acetyl acetate such as tert-butyl acetate; propyl acetate such as methyl propyl acetate, ethyl propyl acetate, isopropyl propyl acetate, tert-butyl propyl acetate, etc.; Isobutyryl acetate, methyl isobutyrate, ethyl isobutyrate, isopropyl isobutyrate, tert-butyl isobutyrate, etc.; methyl malonate, ethyl malonate, etc. Malonates, etc. Among them, acetylacetone and acetylacetate are mentioned as preferable compounds. Such a compound that produces keto-enol tautomerism may be used alone or in combination of two or more.

所述產生酮-烯醇互變異構性的化合物的含量相對於所述(甲基)丙烯酸系聚合物100質量份，例如可以採用0.1~20質量份，通常採用0.5~15質量份(例如為1~10質量份)較為合適。當所述化合物的量過少時，有時難以發揮充分的使用效果。另一方面，當超過需要過多地使用所述化合物時，有時殘留於黏合劑層，使凝聚力降低。 The content of the compound that produces keto-enol tautomerism relative to 100 parts by mass of the (meth)acrylic polymer can be, for example, 0.1 to 20 parts by mass, usually 0.5 to 15 parts by mass (for example, 0.5 to 15 parts by mass). 1 to 10 parts by mass) is suitable. When the amount of the compound is too small, it may be difficult to exhibit a sufficient use effect. On the other hand, when the said compound is used excessively more than necessary, it may remain|survive in an adhesive bond layer, and cohesion force may fall.

而且，在用於本發明的表面保護薄膜的黏合劑組成物中，也可以含有其它公知的添加劑，例如可以根據使用的用途適當添加著色劑、顏料等粉體、增塑劑、增黏劑、低分子量聚合物、表面潤滑劑、流平劑、抗氧化劑、防腐劑、光穩定劑、紫外線吸收劑、阻聚劑、矽烷偶聯劑、無機或有機的填充劑、金屬粉、粒子狀或箔狀物等。 Further, the adhesive composition used for the surface protective film of the present invention may contain other known additives, for example, powders such as colorants, pigments, plasticizers, tackifiers, Low molecular weight polymers, surface lubricants, leveling agents, antioxidants, preservatives, light stabilizers, UV absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, particles or foils objects, etc.

本發明的表面保護薄膜的特徵在於，在所述支撐薄膜的一面或兩面具有由所述黏合劑組成物形成(使黏合劑組成物交聯而形成)的黏合劑層。雖然所述黏合劑組成物的交聯通常在黏合劑組成物的塗布後進行，但也可以將由交聯後的黏合劑組成物形成的黏合劑層轉印到支撐薄膜等。此外，雖然在所述支撐薄膜上形成黏合劑層的方法並不特別重要，但例如可以藉由將所述黏合劑組成物塗布於 支撐薄膜、乾燥去除聚合溶劑等從而在支撐薄膜上形成黏合劑層來製作。之後，也可以為了調整黏合劑層的成分轉移、調整交聯反應等進行養護。此外，在將黏合劑組成物塗布於支撐薄膜上來製作表面保護薄膜時，為了能夠均勻地塗布在支撐薄膜上，也可以在所述黏合劑組成物中新添加聚合溶劑以外的一種以上的溶劑。 The surface protection film of the present invention is characterized by having an adhesive layer formed of the adhesive composition (formed by crosslinking the adhesive composition) on one or both surfaces of the support film. Although the crosslinking of the adhesive composition is usually performed after the application of the adhesive composition, the adhesive layer formed of the crosslinked adhesive composition may be transferred to a support film or the like. In addition, although the method of forming the adhesive layer on the support film is not particularly important, for example, the adhesive composition can be coated on The support film is dried to remove the polymerization solvent, etc., thereby forming an adhesive layer on the support film to manufacture. After that, curing may be performed in order to adjust the component transfer of the adhesive layer, adjust the crosslinking reaction, and the like. In addition, when applying the adhesive composition on the support film to produce a surface protection film, one or more solvents other than the polymerization solvent may be newly added to the adhesive composition in order to allow the adhesive composition to be uniformly coated on the support film.

此外，作為製造本發明的表面保護薄膜時的黏合劑層的形成方法，可以使用黏合片(表面保護薄膜)類的製造中使用的公知的方法。具體而言，例如可以舉出輥塗、凹版塗布、反向塗布、輥刷、噴塗、氣刀塗布法、利用模塗布機等的擠出塗布法等。 Moreover, as the formation method of the adhesive bond layer at the time of manufacture of the surface protection film of this invention, the well-known method used for manufacture of an adhesive sheet (surface protection film) can be used. Specifically, for example, roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating method, extrusion coating method using a die coater, etc. are mentioned.

通常，本發明的表面保護薄膜的上述黏合劑層的厚度較佳製作為3~100μm，更佳製作為5~50μm左右。當黏合劑層的厚度在所述範圍內時，由於容易獲得適度的再剝離性與黏合(黏接)性的平衡，因此為佳。 Generally, the thickness of the said adhesive bond layer of the surface protection film of this invention is preferably made 3-100 micrometers, More preferably, it is about 5-50 micrometers. When the thickness of the pressure-sensitive adhesive layer is within the above-mentioned range, it is easy to obtain a balance between moderate re-peelability and adhesion (adhesion), which is preferable.

<隔片> <Spacer>

在本發明的表面保護薄膜中，根據需要以保護黏合劑層的黏合面為目的，可以使隔片貼合於黏合劑層表面。 In the surface protection film of the present invention, if necessary, for the purpose of protecting the adhesive surface of the pressure-sensitive adhesive layer, a separator may be bonded to the surface of the pressure-sensitive adhesive layer.

雖然作為構成所述隔片的材料有紙、塑膠薄膜，但從表面平滑性優異的觀點考慮較佳使用塑膠薄膜。作為該薄膜，只要是能夠保護所述黏合劑層的薄膜就沒有特別限定，例如可以舉出聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對苯二甲酸乙二醇酯薄膜、聚對苯二 甲酸丁二醇酯薄膜、聚胺酯薄膜、乙烯-乙酸乙烯酯共聚物薄膜等。 Although there are paper and a plastic film as a material constituting the spacer, a plastic film is preferably used from the viewpoint of excellent surface smoothness. The film is not particularly limited as long as it can protect the adhesive layer, and examples thereof include polyethylene films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, PVC film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene terephthalate Butylene formate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

所述隔片的厚度通常為5~200μm，較佳為10~100μm左右。當在所述範圍內時，由於對黏合劑層的貼合操作性及從黏合劑層的剝離操作性優異，因此為佳。根據需要，也可以對所述隔片進行借助矽酮系、氟系、長鏈烷烴系或脂肪酸醯胺系的脫模劑、二氧化矽粉末等進行的脫模及防污處理、或塗布型、混入型、蒸鍍型等抗靜電處理。 The thickness of the separator is usually 5-200 μm, preferably about 10-100 μm. It is preferable that it is in the said range, since the lamination workability|operativity with respect to an adhesive bond layer and the peeling workability from an adhesive bond layer are excellent. If necessary, the separator may be subjected to mold release and antifouling treatment by a silicone-based, fluorine-based, long-chain alkane-based or fatty acid amide-based mold release agent, silica powder, or the like, or a coating type. , mixed type, evaporation type and other antistatic treatment.

本發明的表面保護薄膜也可以藉由除了支撐薄膜(基材)及黏合劑層之外還含有抗靜電層等其它的層的方式實施獲得。 The surface protective film of this invention can also be implemented and obtained by carrying out the form containing other layers, such as an antistatic layer, in addition to a support film (substrate) and an adhesive bond layer.

<偏光板> <Polarizer>

本發明的偏光板較佳為藉由所述偏光板用表面保護薄膜(表面保護薄膜)進行保護的偏光板。由於所述表面保護薄膜能夠謀求剪切力的提高，因此在使偏光板用表面保護薄膜貼合於薄型化後的偏光板時，能夠抑制偏光板的捲曲的產生，能夠獲得捲曲調節性優異的偏光板，因此有用。此外，在將所述表面保護薄膜在偏光板上黏貼剝離後組裝液晶顯示器面板時，由於即使在所述偏光板與亮度增強薄膜等接觸的情況下，也可以將偏光板的動摩擦力抑制得較低，因此偏光板難以產生損傷，光滑性優異，因此有用。需要說明的是，如圖1所示，所述偏光板(附有表面保護薄膜的偏光板5)藉由將偏光板用表面保護薄膜1的黏合劑層3 的表面黏貼於偏光板2的表面來保護偏光板表面以防止損傷、塵埃等。 The polarizing plate of the present invention is preferably a polarizing plate protected by the above-mentioned surface protective film for a polarizing plate (surface protective film). Since the above-mentioned surface protective film can improve the shear force, when the surface protective film for a polarizing plate is bonded to a thinned polarizing plate, it is possible to suppress the occurrence of curling of the polarizing plate, and it is possible to obtain a film having excellent curling controllability. Polarizers are therefore useful. In addition, when the liquid crystal display panel is assembled after sticking and peeling the surface protection film on the polarizing plate, the dynamic friction force of the polarizing plate can be suppressed relatively even when the polarizing plate is in contact with the brightness enhancement film or the like. Low, the polarizing plate is less likely to be damaged, and it is useful because of its excellent smoothness. It should be noted that, as shown in FIG. 1 , the polarizing plate (the polarizing plate 5 with the surface protective film) is formed by applying the adhesive layer 3 of the surface protective film 1 for the polarizing plate to the adhesive layer 3 . The surface of the polarizing plate is pasted on the surface of the polarizing plate 2 to protect the surface of the polarizing plate from damage, dust, etc.

<矽酮化合物轉印型偏光板的製造方法> <Manufacturing method of silicone compound transfer polarizing plate>

本發明的矽酮化合物轉印型偏光板的製造方法較佳包括：使所述偏光板用表面保護薄膜的黏合劑層表面貼合於所述偏光板表面的步驟；及從所述偏光板表面剝離所述偏光板用表面保護薄膜，從而使所述偏光板用表面保護薄膜的黏合劑層中含有的所述矽酮化合物轉印到所述偏光板表面的步驟。藉由將所述黏合劑層表面黏貼到所述偏光板表面，從而在分子骨架中不含偏析於所述黏合劑層表面的醚基的矽酮化合物轉印到所述偏光板表面，之後，由於即使剝離所述表面保護薄膜，也會在所述偏光板表面微量殘留有所述矽酮化合物，因此獲得的偏光板能夠將動摩擦力抑制得較低，即使在偏光板與亮度增強薄膜等接觸了的情況下偏光板本身也難以產生損傷，光滑性優異，因此有用。 The manufacturing method of the silicone compound transfer type polarizing plate of the present invention preferably includes: the step of attaching the surface of the adhesive layer of the surface protection film for polarizing plate to the surface of the polarizing plate; The step of peeling off the surface protective film for polarizing plates and transferring the silicone compound contained in the adhesive layer of the surface protective film for polarizing plates to the surface of the polarizing plate. By sticking the surface of the adhesive layer to the surface of the polarizing plate, the silicone compound that does not contain ether groups segregated on the surface of the adhesive layer in the molecular skeleton is transferred to the surface of the polarizing plate, and then, Since the silicone compound remains in a small amount on the surface of the polarizing plate even if the surface protection film is peeled off, the obtained polarizing plate can suppress the dynamic friction force low even when the polarizing plate is in contact with a brightness enhancement film or the like Even if the polarizing plate itself is damaged, it is very useful because of its excellent smoothness.

作為使所述偏光板用表面保護薄膜的黏合劑層表面貼合於所述偏光板表面的步驟，雖然其黏貼時間沒有特別限制，但例如在23℃、50%RH的條件下，較佳黏貼15分鐘以上。只要在所述範圍內，所述矽酮化合物就能夠從黏合劑表面充分地向偏光板表面轉印(轉移)，因此成為較佳方式。 As the step of sticking the surface of the adhesive layer of the surface protection film for polarizing plates to the surface of the polarizing plate, although the sticking time is not particularly limited, for example, under the conditions of 23°C and 50% RH, it is preferable to stick more than 15 minutes. As long as it is within this range, the silicone compound can be sufficiently transferred (transferred) from the surface of the adhesive to the surface of the polarizing plate, which is a preferable form.

實施例 Example

以下，對具體地表示本發明的構成及效果的實施例等進行說明，但本發明並不限定於此。需要說明的是， 對實施例等的配合內容及特性評價，以下述的方式進行測定。此外，在表1中，示出了黏合劑組成物的配合比例、及得到的(甲基)丙烯酸系聚合物的物理性質，在表2中，示出了得到的偏光板用表面保護薄膜(表面保護薄膜)、及黏貼了所述表面保護薄膜後的偏光板的特性評價的結果。 Hereinafter, although the Example etc. which show the structure and effect of this invention concretely are demonstrated, this invention is not limited to this. It should be noted, The content of compounding and characteristic evaluation of Examples and the like were measured in the following manner. In addition, in Table 1, the mixing ratio of the adhesive composition and the physical properties of the obtained (meth)acrylic polymer are shown, and in Table 2, the obtained surface protection film for polarizing plates ( surface protective film), and the results of the evaluation of the properties of the polarizing plate after the surface protective film was pasted.

<評價> <Evaluation>

以下，記載了具體的測定/評價方法。 Hereinafter, specific measurement/evaluation methods are described.

<重均分子量(Mw)的測定> <Measurement of weight average molecular weight (Mw)>

重均分子量(Mw)使用TOSOH株式會社製GPC裝置(HLC-8220GPC)進行測定。測定條件如下所述。 The weight average molecular weight (Mw) was measured using a GPC apparatus (HLC-8220GPC) manufactured by TOSOH Corporation. The measurement conditions are as follows.

樣品濃度：0.2質量%(THF溶液) Sample concentration: 0.2 mass % (THF solution)

樣品注入量：10μl Sample injection volume: 10μl

洗脫液：THF Eluent: THF

流速：0.6ml/min Flow rate: 0.6ml/min

測定溫度：40℃ Measurement temperature: 40℃

柱： column:

樣品柱；TSKguardcolumn SuperHZ-H(1根)+TSKgel SuperHZM-H(2根) Sample column; TSKguardcolumn SuperHZ-H (1)+TSKgel SuperHZM-H (2)

參比柱；TSKgel SuperH-RC(1根) Reference column; TSKgel SuperH-RC (1 piece)

檢測器：差示折射計(RI) Detector: Differential Refractometer (RI)

需要說明的是，重均分子量以聚苯乙烯換算值求得。 In addition, the weight average molecular weight was calculated|required by polystyrene conversion value.

<玻璃化轉變溫度(Tg)的理論值> <Theoretical value of glass transition temperature (Tg)>

玻璃化轉變溫度Tg(℃)使用下述文獻值作為利用各單體形成的均聚物的玻璃化轉變溫度Tgn(℃)，藉由下述式求 得。 Glass transition temperature Tg (° C.) Using the following literature value as the glass transition temperature Tgn (° C.) of the homopolymer formed from each monomer, it was calculated by the following formula have to.

式：1/(Tg+273)=Σ[Wn/(Tgn+273)] Formula: 1/(Tg+273)=Σ[Wn/(Tgn+273)]

(式中，Tg(℃)表示共聚物的玻璃化轉變溫度，Wn(-)表示各單體的質量分率，Tgn(℃)表示利用各單體形成的均聚物的玻璃化轉變溫度，n表示各單體的種類。〕 (in the formula, Tg(°C) represents the glass transition temperature of the copolymer, Wn(-) represents the mass fraction of each monomer, Tgn(°C) represents the glass transition temperature of the homopolymer formed by each monomer, n represents the type of each monomer.]

文獻值： Literature value:

丙烯酸2-乙基己酯(2EHA)：-70℃ 2-ethylhexyl acrylate (2EHA): -70°C

丙烯酸(AA)：106℃ Acrylic (AA): 106℃

丙烯酸2-羥乙酯(HEA)：-15℃ 2-Hydroxyethyl acrylate (HEA): -15℃

丙烯酸4-羥丁酯(4HBA)：-32℃ 4-Hydroxybutyl acrylate (4HBA): -32°C

需要說明的是，文獻值參照了“丙烯酸樹脂的合成/設計及新用途開發”(中央經營開發中心出版部發行)及“Polymer Handbook(聚合物手冊)”(John Wiley & Sons)。 In addition, the literature value refers to "synthesis/design of acrylic resin and development of new applications" (published by the Central Business Development Center Publishing Department) and "Polymer Handbook (Polymer Handbook)" (John Wiley & Sons).

<剪切力的測定> <Measurement of Shear Force>

將表面保護薄膜切割成寬度10mm、長度100mm的大小，剝離了黏貼到表面保護薄膜的黏合劑層表面的隔片後，以所述表面保護薄膜的黏合劑層的黏合(黏接)面積為1cm2的方式使其貼合於TAC(三醋酸纖維素)偏光板(日東電工公司製、SEG1423DU偏光板、寬度：25mm、長度：100mm)，在室溫(23℃×50%RH)下靜置30分鐘後，以拉伸速度0.06mm/min在剪切方向進行拉伸，將此時的最大載荷(N/cm2)作為剪切力。 Cut the surface protective film into a size of 10 mm in width and 100 mm in length, peel off the spacer attached to the surface of the adhesive layer of the surface protective film, and take the adhesive (bonding) area of the adhesive layer of the surface protective film as 1 cm 2 to make it stick to a TAC (triacetate cellulose) polarizing plate (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 25mm, length: 100mm), and let it stand at room temperature (23℃×50%RH) After 30 minutes, stretching was performed in the shearing direction at a stretching speed of 0.06 mm/min, and the maximum load (N/cm 2 ) at this time was taken as the shearing force.

需要說明的是，所述剪切力(N/cm2)為15以上，較佳為15~50，更佳為20~40。只要所述剪切力在所述範圍 內，黏貼了表面保護薄膜的作為被黏附體的偏光板就能夠承受將要捲曲時產生的剪切方向的力，由於不會產生表面保護薄膜的滑動、偏移，能夠抑制被黏附體的捲曲，因此為佳。 It should be noted that the shear force (N/cm 2 ) is 15 or more, preferably 15-50, more preferably 20-40. As long as the shearing force is within the above range, the polarizing plate as the adherend to which the surface protection film is attached can withstand the force in the shearing direction when it is about to be curled. It is preferable because it can suppress the curling of the adherend.

<動摩擦力(光滑性)的測定> <Measurement of dynamic friction force (smoothness)>

在切割成寬度5cm、長度15cm的大小的TAC偏光板(日東電工公司製，SEG1423DU偏光板)的TAC面的整個面黏貼表面保護薄膜的黏合劑層表面，在23℃×50%RH下放置30分鐘後，從TAC面剝離表面保護薄膜。 A TAC polarizing plate (manufactured by Nitto Denko Co., Ltd., SEG1423DU polarizing plate) cut into a size of 5 cm in width and 15 cm in length was adhered to the entire surface of the TAC surface of the adhesive layer of the surface protection film, and left at 23°C × 50% RH for 30 After minutes, the surface protective film was peeled off from the TAC side.

接著，使TAC偏光板之黏貼過黏合劑層表面的面(TAC面)與亮度增強薄膜(住友3M公司製、DBEF-D2-280)接觸作為試驗片。在該試驗片上，承載載荷200g。使用沒有伸縮性的線將所述承載了載荷的試驗片安裝到拉伸試驗機上，在測定溫度25℃下，以拉伸速度100mm/min、拉伸距離50mm的條件在TAC面與亮度增強薄膜的接觸面的平行方向(水平方向)進行拉伸，求得施加到試驗片的動摩擦力(N)的平均值(n=3)。 Next, the surface (TAC surface) of the TAC polarizing plate pasted on the surface of the adhesive layer was brought into contact with a brightness enhancement film (manufactured by Sumitomo 3M, DBEF-D2-280) as a test piece. On this test piece, a load of 200 g was applied. The load-bearing test piece was mounted on a tensile tester using a wire without stretchability, and at a measurement temperature of 25°C, the TAC surface and brightness were enhanced under the conditions of a tensile speed of 100 mm/min and a tensile distance of 50 mm. The film was stretched in the parallel direction (horizontal direction) of the contact surface, and the average value (n=3) of the dynamic friction force (N) applied to the test piece was obtained.

需要說明的是，所述動摩擦力(N)為1以下，較佳為0.9以下，更佳為0.8以下。當在所述範圍內時，能夠使偏光板的動摩擦力降低，能夠謀求抑制偏光板表面產生的損傷，能夠謀求光滑性的提高，因而有利。 In addition, the said dynamic friction force (N) is 1 or less, Preferably it is 0.9 or less, More preferably, it is 0.8 or less. Within the above range, the dynamic friction force of the polarizing plate can be reduced, the damage to the surface of the polarizing plate can be suppressed, and the smoothness can be improved, which is advantageous.

<損傷的有無> <presence of damage>

藉由目測觀察測定了所述動摩擦力後的TAC偏光板表面(TAC面)的損傷的產生情況。 The occurrence of damage on the surface of the TAC polarizing plate (TAC surface) after the dynamic friction force was measured by visual observation.

沒有損傷的情況：○、產生損傷的情況：× When there is no damage: ○, when there is damage: ×

<剝離帶電壓的測定> <Measurement of peeling charge voltage>

將偏光板用表面保護薄膜(表面保護薄膜)切割成寬度70mm、長度130mm的大小，剝離黏貼於表面保護薄膜的黏合劑層表面的隔片後，在貼合於經預先除電的丙烯酸板(厚度：2mm、寬度：70mm、長度：100mm)的TAC偏光板(日東電工公司製、SEG1423DU偏光板、寬度：70mm、長度：100mm)表面(TAC面)，以一方的端部突出30mm的方式藉由手壓輥進行壓接。在23℃×50%RH下放置一天后，如圖2所示，將樣品設置於規定的位置。將突出30mm的一方的端部固定於自動捲繞機，以剝離角度150°、剝離速度30m/min的方式進行剝離。藉由固定於偏光板中央位置的電位測定器(春日電機公司製、KSD-0103)測定此時產生的偏光板表面的電位(剝離帶電壓：絕對值、kV)。測定在23℃×50%RH的環境下進行。 Cut the surface protective film (surface protective film) for polarizing plates into a size of 70 mm in width and 130 mm in length, peel off the spacer attached to the surface of the adhesive layer of the surface protection film, and attach it to a pre-static acrylic plate (thickness). : 2mm, width: 70mm, length: 100mm) TAC polarizing plate (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 70 mm, length: 100 mm) surface (TAC surface), with one end protruding 30 mm by Hand pressure roller for crimping. After standing for one day at 23° C.×50% RH, as shown in FIG. 2 , the sample was set at a predetermined position. The one end portion protruding by 30 mm was fixed to an automatic winder, and peeled at a peeling angle of 150° and a peeling speed of 30 m/min. The potential (peeling charge voltage: absolute value, kV) on the surface of the polarizing plate generated at this time was measured with a potentiometer (KSD-0103, manufactured by Kasuga Electric Co., Ltd.) fixed at the center of the polarizing plate. The measurement was performed in an environment of 23°C×50%RH.

<污染性> <pollution>

將表面保護薄膜切割成寬度50mm、長度80mm的大小，剝離黏貼於表面保護薄膜的黏合劑層表面的隔片後，黏貼於切割成寬度70mm、長度100mm的TAC偏光板(日東電工公司製、SEG1423DU偏光板)表面(TAC面)，在23℃×50%RH下放置1天后，剝離表面保護薄膜，藉由目測進行污染性的確認。 Cut the surface protection film into a size of 50mm in width and 80mm in length, peel off the spacer attached to the surface of the adhesive layer of the surface protection film, and paste it on a TAC polarizer cut into a width of 70mm and a length of 100mm (manufactured by Nitto Denko Co., Ltd., SEG1423DU). The polarizing plate) surface (TAC surface) was left to stand at 23° C.×50% RH for 1 day, and then the surface protective film was peeled off, and contamination was confirmed by visual inspection.

沒有污染的情況：○、有污染的情況：× Without pollution: ○, With pollution: ×

<製備方法> <Preparation method>

以下，記載了具體的(甲基)丙烯酸系聚合物、黏合劑組成物等的製備方法。需要說明的是，表1中的配合量(份數)表示固體成分量。 Hereinafter, the preparation method of a specific (meth)acrylic-type polymer, an adhesive composition, etc. is described. In addition, the compounding quantity (parts) in Table 1 shows the solid content amount.

<實施例1> <Example 1>

<(甲基)丙烯酸系聚合物的製備> <Preparation of (meth)acrylic polymer>

在具備攪拌葉片、溫度計、氮氣導入管、冷卻器的四口燒瓶中加入丙烯酸2-乙基己酯(2EHA)100質量份、丙烯酸4-羥丁酯(4HBA)10質量份、丙烯酸(AA)0.02質量份、作為聚合引發劑的2,2’-偶氮二異丁腈0.2質量份、乙酸乙酯157質量份，一邊緩慢攪拌一邊導入氮氣，將燒瓶內的液溫保持在65℃左右，進行聚合反應6小時，製備出(甲基)丙烯酸系聚合物溶液(40質量%)。所述丙烯酸系聚合物的重均分子量(Mw)為54萬，玻璃化轉變溫度(Tg)為-67℃。 100 parts by mass of 2-ethylhexyl acrylate (2EHA), 10 parts by mass of 4-hydroxybutyl acrylate (4HBA), and acrylic acid (AA) were placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler. 0.02 parts by mass, 0.2 parts by mass of 2,2'-azobisisobutyronitrile as polymerization initiators, and 157 parts by mass of ethyl acetate, nitrogen gas was introduced while stirring slowly, and the liquid temperature in the flask was maintained at about 65°C, The polymerization reaction was performed for 6 hours to prepare a (meth)acrylic polymer solution (40% by mass). The weight average molecular weight (Mw) of the acrylic polymer was 540,000, and the glass transition temperature (Tg) was -67°C.

<黏合劑組成物的製備> <Preparation of adhesive composition>

用乙酸乙酯將上述(甲基)丙烯酸系聚合物溶液(40質量%)稀釋至20質量%，向該溶液500質量份(固體成分100質量份)中加入作為非矽酮系的聚醚的聚氧化乙烯-1-(烯丙氧基甲基)烷基醚硫酸銨(第一工業製藥公司製、Aqualon KH-10)0.3質量份(固體成分0.3質量份)、作為不含醚基的矽酮化合物的甲基苯基矽油(信越化學公司製、KF-50-100cs)0.1質量份(固體成分0.1質量份)、作為抗靜電劑的離子性化合物的雙(三氟甲烷磺醯)亞胺鋰(東京化成工業公司製、LiTFSI)0.15質量份(固體成分0.15質量份)、以及作為交聯劑的為脂肪族系異氰酸酯化合物的六亞甲基二異 氰酸酯的異氰脲酸酯體(TOSOH公司製、Coronate HX：C/HX)3質量份(固體成分3質量份)、作為交聯催化劑的二月桂酸二丁基錫(1質量%乙酸乙酯溶液)2質量份(固體成分0.02質量份)，進行混合攪拌，製備出黏合劑組成物(溶液)。 The above-mentioned (meth)acrylic polymer solution (40 mass %) was diluted to 20 mass % with ethyl acetate, and 500 mass parts of the solution (solid content 100 mass parts) was added as a non-silicone-based polyether. Polyoxyethylene-1-(allyloxymethyl)alkyl ether ammonium sulfate (Daiichi Kogyo Pharmaceutical Co., Ltd., Aqualon KH-10) 0.3 parts by mass (solid content 0.3 parts by mass), as ether group-free silicon 0.1 part by mass (0.1 part by mass of solid content) of methylphenyl silicone oil of ketone compound (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50-100cs), bis(trifluoromethanesulfonyl)imide as ionic compound of antistatic agent Lithium (manufactured by Tokyo Chemical Industry Co., Ltd., LiTFSI) 0.15 parts by mass (solid content 0.15 parts by mass), and hexamethylene diiso which is an aliphatic isocyanate compound as a crosslinking agent Isocyanurate of cyanate ester (Tosoh Corporation, Coronate HX: C/HX) 3 parts by mass (solid content 3 parts by mass), dibutyltin dilaurate (1 mass % ethyl acetate) as a crosslinking catalyst solution) 2 parts by mass (solid content 0.02 parts by mass), mixed and stirred to prepare an adhesive composition (solution).

<抗靜電處理薄膜的製作> <Production of antistatic treatment film>

藉由將抗靜電劑(Solvex公司製、Microsolver RMd-142、以氧化錫及聚酯樹脂為主成分)10重量份用由水30重量份及甲醇70重量份構成的混合溶劑進行稀釋，製備出抗靜電劑溶液。 Prepared by diluting 10 parts by weight of an antistatic agent (Solvex, Microsolver RMd-142, mainly composed of tin oxide and polyester resin) with a mixed solvent consisting of 30 parts by weight of water and 70 parts by weight of methanol Antistatic agent solution.

使用邁耶棒(Mayer Bar)將得到的抗靜電劑溶液塗布到作為支撐薄膜的聚對苯二甲酸乙二醇酯(PET)薄膜(厚度：38μm)上，藉由在130℃下乾燥1分鐘來去除溶劑，形成抗靜電層(厚度：0.2μm)，製作出抗靜電處理薄膜。 The obtained antistatic agent solution was applied on a polyethylene terephthalate (PET) film (thickness: 38 μm) as a support film using a Mayer Bar, by drying at 130° C. for 1 minute To remove the solvent, an antistatic layer (thickness: 0.2 μm) was formed, and an antistatic treatment film was produced.

<偏光板用表面保護薄膜的製作> <Production of surface protection film for polarizing plate>

將上述黏合劑組成物(溶液)塗布於與上述抗靜電處理薄膜的抗靜電層相反的一面，在130℃下加熱2分鐘，形成厚度15μm的黏合劑層。接著，使作為一面實施了矽酮處理的隔片的聚對苯二甲酸乙二醇酯薄膜(厚度25μm)的矽酮處理面貼合於所述黏合劑層的表面，製作出偏光板用表面保護薄膜。 The above-mentioned adhesive composition (solution) was applied on the side opposite to the antistatic layer of the above-mentioned antistatic treatment film, and heated at 130° C. for 2 minutes to form an adhesive layer with a thickness of 15 μm. Next, the silicone-treated surface of the polyethylene terephthalate film (thickness: 25 μm), which is one side of the silicone-treated separator, was bonded to the surface of the adhesive layer to produce a surface for polarizing plates. protective film.

<實施例2~8及比較例1~3> <Examples 2 to 8 and Comparative Examples 1 to 3>

基於表1的配合比例，與實施例1相同地製作出偏光板用表面保護薄膜。需要說明的是，表1中的配合量表示固體成分。 Based on the compounding ratio of Table 1, it carried out similarly to Example 1, and produced the surface protective film for polarizing plates. In addition, the compounding quantity in Table 1 shows solid content.

根據上述評價方法，做出了獲得的偏光板用表面保護薄膜(表面保護薄膜)、及黏貼了所述表面保護薄膜後的偏光板的特性評價的結果。在表2中示出了獲得的結果。 According to the above-mentioned evaluation method, the obtained surface protective film for polarizing plates (surface protective film) and the results of the evaluation of the properties of the polarizing plate to which the surface protective film was pasted were obtained. The results obtained are shown in Table 2.

Figure 105123601-A0305-02-0038-3
Figure 105123601-A0305-02-0038-3

以下，對表1中的簡稱進行說明。 Hereinafter, the abbreviations in Table 1 will be described.

<構成(甲基)丙烯酸系聚合物的單體成分> <Monomer components constituting the (meth)acrylic polymer>

2EHA：丙烯酸2-乙基己酯 2EHA: 2-ethylhexyl acrylate

AA：丙烯酸(具有羧基的(甲基)丙烯酸系單體) AA: Acrylic acid ((meth)acrylic monomer having a carboxyl group)

HEA：丙烯酸2-羥乙酯(具有羥基的(甲基)丙烯酸系單體) HEA: 2-hydroxyethyl acrylate ((meth)acrylic monomer having a hydroxyl group)

4HBA：丙烯酸4-羥丁酯(具有羥基的(甲基)丙烯酸系單體) 4HBA: 4-hydroxybutyl acrylate ((meth)acrylic monomer having a hydroxyl group)

<交聯劑> <Crosslinking agent>

C/L：芳香族系異氰酸酯化合物、三羥甲基丙烷/甲苯二異氰酸酯三聚體加成物，TOSOH公司製，商品名：Coronate L C/L: Aromatic isocyanate compound, trimethylolpropane/toluene diisocyanate trimer adduct, manufactured by TOSOH, trade name: Coronate L

C/HX：脂肪族系異氰酸酯化合物、六亞甲基二異氰酸酯的異氰脲酸酯體，TOSOH公司製，商品名：Coronate HX C/HX: aliphatic isocyanate compound, isocyanurate of hexamethylene diisocyanate, manufactured by TOSOH, brand name: Coronate HX

<聚醚> <Polyether>

KH-10：聚氧化乙烯-1-(烯丙氧基甲基)烷基醚硫酸銨、第一工業製藥公司製、商品名：Aqualon KH-10 KH-10: Polyoxyethylene-1-(allyloxymethyl)alkyl ether ammonium sulfate, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., trade name: Aqualon KH-10

HS-10：聚氧化乙烯壬基丙烯基苯基醚硫酸銨、第一工業製藥公司製、商品名：Aqualon HS-10 HS-10: Polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., trade name: Aqualon HS-10

NF-08：聚氧化乙烯苯乙烯化苯基醚硫酸銨、第一工業製藥公司製、商品名：Hitenol NF-08 NF-08: Polyoxyethylene styrenated phenyl ether ammonium sulfate, manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., trade name: Hitenol NF-08

EA-137：聚氧化乙烯苯乙烯化苯基醚、第一工業製藥公司製、商品名：Noigen EA-137 EA-137: Polyoxyethylene styrenated phenyl ether, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., trade name: Noigen EA-137

KF353：聚醚改性矽酮、信越化學公司製、商品名：KF-353 KF353: Polyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-353

<矽酮化合物> <Silicone compound>

KF-50-100cs：甲基苯基矽油、信越化學公司製、商品名：KF-50-100cs KF-50-100cs: methylphenyl silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-50-100cs

KF-50-1000cs：甲基苯基矽油、信越化學公司製、商品名：KF-50-1000cs KF-50-1000cs: methylphenyl silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-50-1000cs

KF-50-3000cs：甲基苯基矽油、信越化學公司製、商品名：KF-50-3000cs KF-50-3000cs: Methyl phenyl silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-50-3000cs

KF-96-100cs：二甲基矽油、信越化學公司製、商品名：KF-96-100cs KF-96-100cs: Dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96-100cs

KF-96-1000cs：二甲基矽油、信越化學公司製、商品名：KF-96-1000cs KF-96-1000cs: Dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96-1000cs

KF-96-3000cs：二甲基矽油、信越化學公司製、商品名：KF-96-3000cs KF-96-3000cs: Dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96-3000cs

<抗靜電劑(離子性化合物)> <Antistatic agent (ionic compound)>

LiTFSI：雙(三氟甲烷磺醯)亞胺鋰、東京化成工業公司製 LiTFSI: lithium bis(trifluoromethanesulfonyl)imide, manufactured by Tokyo Chemical Industry Co., Ltd.

Figure 105123601-A0305-02-0040-4
Figure 105123601-A0305-02-0040-4

從上述表2的評價結果可以確認，在所有的實施例中，藉由使用具有配合了分子骨架中不含醚基的矽酮化合物的黏合劑層的偏光板用表面保護薄膜，從而具有所需的剪切力及動摩擦力，能夠謀求兼顧捲曲調節性及光滑性，能夠抑制對偏光板的污染、損傷的產生。 From the evaluation results in Table 2 above, it was confirmed that in all the examples, by using the surface protective film for polarizing plates having the adhesive layer in which the silicone compound not containing an ether group in the molecular skeleton was blended, the required surface protection films were obtained. The shear force and the dynamic friction force can achieve both the curl controllability and the smoothness, and the occurrence of contamination and damage to the polarizing plate can be suppressed.

另一方面，從上述表2的結果來看，在比較例1中，由於沒有配合所述矽酮化合物，因此不能將動摩擦力抑制得較低。在比較例2中確認了，由於沒有配合所述矽酮化合物而配合了聚醚改性矽酮，因此剪切力變低。此外，在比較例3中確認了，雖然使用了所述矽酮化合物，但是由於配合超過規定量，因此觀察到了污染，在實用性上存在問題。 On the other hand, from the result of the said Table 2, in the comparative example 1, since the said silicone compound was not mix|blended, the dynamic friction force could not be suppressed low. In Comparative Example 2, it was confirmed that the shear force was low because the silicone compound was not compounded but the polyether-modified silicone was compounded. In addition, in Comparative Example 3, although the above-mentioned silicone compound was used, it was confirmed that contamination was observed because the compounding amount exceeded the predetermined amount, and there was a problem in practicality.

Claims (5)

一種偏光板用表面保護薄膜，其特徵在於，係在支撐薄膜的一面或兩面具有由黏合劑組成物形成的黏合劑層的偏光板用表面保護薄膜，且前述黏合劑組成物含有(甲基)丙烯酸系聚合物及下述式所示的矽酮化合物，其中，前述(甲基)丙烯酸系聚合物至少含有具有碳原子數1~14的烷基的(甲基)丙烯酸系單體50~97質量%、具有羥基的(甲基)丙烯酸系單體2~20質量%、及具有羧基的(甲基)丙烯酸系單體0.001~未達2質量%作為單體成分，相對於前述(甲基)丙烯酸系聚合物100質量份，含有前述矽酮化合物0.01質量份~未達1質量份，使前述黏合劑層以1cm2的黏合面積貼合於TAC偏光板，在23℃下黏貼上30分鐘後，在剪切方向以拉伸速度0.06mm/min進行拉伸時的剪切力為15N/cm2以上，使前述黏合劑層表面貼合於TAC偏光板，在23℃下黏貼上30分鐘後，從前述TAC偏光板剝離前述偏光板用表面保護薄膜，使亮度增強薄膜與前述TAC偏光板之黏貼過前述黏合劑層表面的面接觸，在施加了200g的載荷的狀態下，在與接觸面平行方向以拉伸速度100mm/min進行拉伸時的動摩擦力為1N以下，[化1]
Figure 105123601-A0305-02-0043-5
 式中，R及R’為甲基或苯基，R及R’可以相同，也可以不同，此外，m為0~3000，n為1~3000。 A surface protective film for polarizing plates, characterized in that it is a surface protective film for polarizing plates having an adhesive layer formed by an adhesive composition on one or both sides of a support film, and the adhesive composition contains (methyl) An acrylic polymer and a silicone compound represented by the following formula, wherein the (meth)acrylic polymer contains at least 50 to 97 (meth)acrylic monomers having an alkyl group having 1 to 14 carbon atoms. mass %, 2 to 20 mass % of the (meth)acrylic monomer having a hydroxyl group, and 0.001 to less than 2 mass % of the (meth)acrylic monomer having a carboxyl group as monomer components, relative to the aforementioned (meth) ) 100 parts by mass of acrylic polymer, containing 0.01 part by mass to less than 1 part by mass of the above-mentioned silicone compound, the above-mentioned adhesive layer is bonded to the TAC polarizing plate with a bonding area of 1 cm 2 , and pasted at 23 ° C for 30 minutes After that, the shear force when stretching at a tensile speed of 0.06 mm/min in the shearing direction is 15 N/cm 2 or more, and the surface of the aforementioned adhesive layer is attached to the TAC polarizing plate, and it is attached at 23 ° C for 30 minutes. Then, peel off the surface protection film for the polarizing plate from the TAC polarizing plate, make the brightness enhancement film and the surface of the TAC polarizing plate pasted on the surface of the adhesive layer contact, and apply a load of 200g. The dynamic friction force when stretched at a stretching speed of 100 mm/min in the plane-parallel direction is 1 N or less, [Chemical 1]
Figure 105123601-A0305-02-0043-5
 In the formula, R and R' are methyl or phenyl, R and R' may be the same or different, and m is 0-3000, and n is 1-3000. 如請求項1之偏光板用表面保護薄膜，其中前述黏合劑組成物含有具有烯化氧基的表面活性劑。 The surface protective film for polarizing plates according to claim 1, wherein the adhesive composition contains a surfactant having an alkylene oxide group. 如請求項1或2之偏光板用表面保護薄膜，其中前述黏合劑組成物含有離子性化合物。 The surface protective film for polarizing plates according to claim 1 or 2, wherein the adhesive composition contains an ionic compound. 一種偏光板，其特徵在於，藉由請求項1至3中任一項之偏光板用表面保護薄膜進行保護。 A polarizing plate characterized by being protected by the surface protective film for a polarizing plate according to any one of claims 1 to 3. 一種矽酮化合物轉印型偏光板之製造方法，其特徵在於，包括：使請求項1至3中任一項之偏光板用表面保護薄膜的黏合劑層表面貼合於偏光板表面的步驟；及從前述偏光板表面剝離前述偏光板用表面保護薄膜，從而將前述偏光板用表面保護薄膜的黏合劑層中所含有的前述矽酮化合物轉印到前述偏光板表面的步驟。 A method for producing a silicone compound transfer type polarizer, comprising: the step of attaching the surface of the adhesive layer of the surface protection film for polarizer according to any one of claims 1 to 3 to the surface of the polarizer; And the step of peeling the surface protective film for polarizing plates from the surface of the polarizing plate, and transferring the silicone compound contained in the adhesive layer of the surface protective film for polarizing plates to the surface of the polarizing plate.
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KR102568434B1 (en) * 2018-06-22 2023-08-18 산진 옵토일렉트로닉스 (쑤저우) 컴퍼니 리미티드 Method for deriving polarizer proper cutting condition
US20200407507A1 (en) * 2019-06-28 2020-12-31 Skc Co., Ltd. Polymer film, front plate and display device comprising same
CN114573747A (en) * 2022-03-15 2022-06-03 东胜化学(上海)有限公司 Acrylate polymer for antistatic pressure-sensitive adhesive and preparation method thereof

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