TW201736130A - Surface protection film, method for producing surface protection film, and optical member - Google Patents

Abstract

Provided are: a surface protection film which is capable of achieving antistatic properties, long-term stability of the peeling-charged electrostatic potential and print adhesion; a method for producing this surface protection film; and an optical member. A surface protection film according to the present invention is provided with: a base having a first surface and a second surface; an antistatic layer that is provided on the first surface of the base; and an adhesive layer that is formed on the second surface of the base with use of an adhesive composition. This surface protection film is characterized in that the antistatic layer is formed with use of an antistatic agent composition that contains a polyaniline sulfonic acid that serves as a conductive polymer component, a polyester resin that serves as a binder, and a melamine-based crosslinking agent that serves as a crosslinking agent.

Description

Surface protection film, method for manufacturing surface protection film, and optical member

The present invention relates to a surface protective film, a method of producing a surface protective film, and an optical member.

The present invention relates to a surface protection film comprising: a substrate having a first surface and a second surface; an antistatic layer provided on the first surface of the substrate; and the second surface of the substrate The adhesive layer is, in detail, a surface protection film having an antistatic function. The surface protective film of the present invention is suitable for use in applications such as plastic products which are prone to generate static electricity. Among them, it is particularly effective for protecting optical members (for example, polarizing plates, wavelength plates, phase difference plates, optical compensation films, reflective sheets, brightness enhancing films, hard coating films for touch panels, and the like for use in liquid crystal displays, etc.) A surface protective film such as a reflective film or a film having an anti-caking layer or the like.

The surface protective film (also referred to as a surface protective sheet) generally has a structure in which an adhesive layer is provided on a film-form substrate (support). The protective film is used for the purpose of protecting the object to be protected from damage or contamination during processing or transportation by adhering the adhesive layer to the object to be attached (protected body). For example, a liquid crystal display panel is formed by bonding an optical member such as a polarizing plate or a wave plate to a liquid crystal cell through an adhesive layer. In the manufacture of the liquid crystal display panel, the polarizing plate bonded to the liquid crystal cell is temporarily formed into a roll form, and then rolled out from the roll and cut into a desired size corresponding to the shape of the liquid crystal cell. At this time, in order to prevent the polarizing plate from being damaged by friction with the conveyance roller or the like in the intermediate step, measures for bonding the surface protection film to one surface or both surfaces (typically one side) of the polarizing plate are taken. The surface protective film can be peeled off when it is not needed.

In general, since the surface protective film or the optical member is made of a plastic material, electrical insulation is high, and static electricity is generated by friction or peeling. Therefore, when the surface protective film is peeled off from the optical member such as a polarizing plate, static electricity is likely to be generated. When a voltage is applied to the liquid crystal in a state where the static electricity remains, the alignment property of the liquid crystal molecules or the occurrence of panel defects may be impaired. Moreover, the presence of static electricity also causes dust to be attracted and causes workability to deteriorate. Therefore, it has been the case that the surface protective film is subjected to an antistatic treatment, for example, an antistatic layer is formed on the surface layer (surface coating, back layer) of the surface protective film or an antistatic coating is applied to impart antistatic effect. Function (refer to Patent Documents 1 and 2).

Further, in recent years, a conductive polymer used for imparting an antistatic function to a surface layer of a surface protective film is made of PEDOT (poly(3,4-ethylenedioxythiophene)/PSS (polystyrene sulfonate). (Polythiophene type) water-dispersible conductive polymer. However, the water-dispersible type, once stored in a dispersion state, generates aggregates, and a uniform antistatic layer cannot be formed, and derivatization is degraded. Further, in the case where the above-mentioned conductive polymer has been used to form an antistatic layer, PSS (corresponding to a dopant) may be detached from PEDOT over time, and surface resistivity or peeling electrostatic potential may rise, etc. There are also problems such as an increase in surface resistivity (deterioration) derived from oxidative degradation or photodegradation.

Further, when the surface resistivity is increased (deteriorated), static electricity is generated when the surface protective film is peeled off from the object to be attached, which causes a problem. Prior Technical Literature Patent Literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-223923

The present invention has been made in view of the above circumstances, and an object thereof is to provide a surface protective film and a surface which can achieve antistatic property, peel stability of electrostatic potential, and print adhesion. A method of manufacturing a protective film and an optical member. Means to solve the problem

That is, the surface protection film of the present invention is characterized by comprising: a substrate having a first surface and a second surface; an antistatic layer provided on the first surface of the substrate; and an adhesive composition formed on the base The adhesive layer of the second surface of the material, wherein the antistatic layer is formed using an antistatic agent composition containing polyaniline sulfonic acid as a conductive polymer component and as a binder A polyester resin and a melamine-based crosslinking agent as a crosslinking agent.

In the surface protection film of the present invention, the antistatic agent composition preferably contains a group selected from the group consisting of fatty acid guanamines, fatty acid esters, polyfluorene-based lubricants, fluorine-based lubricants, and wax-based lubricants. At least one type is used as a lubricant.

In the surface protection film of the present invention, the substrate is preferably a polyester film.

In the surface protection film of the present invention, the adhesive composition preferably contains at least one selected from the group consisting of an acrylic adhesive, an urethane adhesive, and a polyoxygen adhesive.

In the surface protective film of the present invention, the above-mentioned adhesive composition preferably contains an antistatic component.

The optical member of the present invention is preferably protected by the aforementioned surface protective film.

The method for producing a surface protective film of the present invention is the method for producing a surface protective film, characterized in that it comprises the step of preparing an antistatic agent composition containing a conductive polymer component. a polyaniline sulfonic acid, a polyester resin as a binder, and a melamine-based crosslinking agent as a crosslinking agent; and a step of preparing an antistatic layer, which is coated on the first side of the substrate to apply the antistatic agent The material was dried to prepare an antistatic layer. Effect of the invention

The antistatic layer provided on the first surface (back surface) of the surface protection film of the present invention is formed of an antistatic agent composition containing a specific conductive polymer component, a binder, and a crosslinking agent. The surface protective film having the following characteristics, the method for producing the surface protective film, and the optical member protected by the surface protective film can be effectively provided: the surface protective film can form a uniform antistatic layer, and the workability is also excellent, and the cause can be achieved. The excellent antistatic property of the antistatic layer or the stability with respect to the peeling electrostatic potential is also printed adhesiveness.

Hereinafter, embodiments of the present invention will be described in detail.

<Overall Structure of Surface Protective Film> The surface protective film disclosed herein is generally referred to as an adhesive sheet, an adhesive tape, an adhesive label, an adhesive film, etc., and is particularly suitable as an optical member (for example, as a polarizing plate, a wavelength plate, or the like). The optical member used for the display panel constituting the main component, an optical member used for a touch panel display such as a hard film, or the like, the surface protective film that protects the surface of the optical member during processing or transportation. The adhesive in the surface protective film is typically formed continuously, but is not limited to this form, and may be an adhesive layer formed into a regular or random pattern such as a dot or a stripe. Further, the surface protective film disclosed herein may also be in the form of a roll or a sheet.

A typical structural example of the surface protective film disclosed herein is schematically shown in FIG. The surface protection film 1 has a substrate (for example, a polyester film) 12, an antistatic layer 11 provided on the first surface of the substrate 12, and a second surface of the substrate 12 (opposite side to the antistatic layer 11). Adhesive layer 13 of the surface). The surface protection film 1 is used by attaching the adhesive layer 13 to a substrate (a surface to be protected, for example, an optical member such as a polarizing plate). The surface protective film 1 before use (that is, before attaching the object to be attached) may also be in a form in which the surface of the adhesive layer 13 (the attached surface to the object to be attached) is protected by the release liner, and the release liner is The side of at least the adhesive layer 13 is a peeling surface. Alternatively, the surface of the substrate 12 may be abutted against the back surface of the substrate 12 (the surface of the antistatic layer 11) by rewinding the surface protective film 1 into a roll shape to protect the surface thereof.

As shown in FIG. 1 , an antistatic layer 11 is formed directly on the first surface of the substrate 12 (without other layers), and the antistatic layer 11 is exposed on the back surface of the surface protective film 1 (ie, the antistatic layer 11 is exposed). A surface coating layer is provided, and a film with an antistatic layer of the antistatic layer 11 is provided on the substrate 12 compared to the structure in which the surface coating layer and the antistatic layer are additionally provided (even using the film) The surface protective film is also advantageous in that it can reduce the number of layers constituting the surface protective film from the viewpoint of improving productivity.

<Substrate> The surface protective film of the present invention is characterized by having a substrate having a first surface (back surface) and a second surface (surface opposite to the first surface). In the technique disclosed herein, the resin material constituting the substrate can be used without particular limitation, but it is preferable to use, for example, transparency, mechanical strength, thermal stability, moisture shielding property, isotropic property, flexibility, dimensional stability, and the like. Excellent characteristics. In particular, it is useful to apply an adhesive composition by a roll coater or the like by making the substrate flexible, and it can be wound into a roll.

The base material (support) is, for example, a plastic film composed of a resin material having a material of a main resin component (a component of a resin component, typically 50% by mass or more), as the base material. Preferably: polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate and other polyester polymers; diethyl phthalocyanine, triethylene sulfonate A cellulose-based polymer such as cellulose; a polycarbonate-based polymer; an acrylic polymer such as polymethyl methacrylate or the like. Other examples of the foregoing resin material include those having a styrene polymer such as polystyrene or acrylonitrile-styrene copolymer; polyethylene, polypropylene, polycyclic or descending; An olefin polymer such as an olefin structure or an ethylene-propylene copolymer; a chlorinated ethylene polymer; a amide amine polymer such as nylon 6, nylon 6,6 or an aromatic polyamine. Other examples of the resin material include a quinone imine polymer, a fluorene polymer, a polyether fluorene polymer, a polyether ether ketone polymer, a polyphenylene sulfide polymer, and a vinyl alcohol polymer. A vinylidene chloride polymer, an ethylene butyral polymer, an aryl ester polymer, a polyoxymethylene polymer, or an epoxy polymer. A substrate composed of a blend of two or more of the above polymers may also be used.

It is preferable to use a plastic film composed of a transparent thermoplastic resin material for the above substrate. Among the foregoing plastic films, a polyester film is preferred. Herein, the polyester film refers to a polymer material (polyester resin) having a main skeleton based on an ester bond as a main resin component, such as polyethylene terephthalate (PET) or polyethylene naphthalate. Diester (PEN), polybutylene terephthalate, and the like. On the one hand, the polyester film has excellent optical properties or dimensional stability and the like, and is preferable in terms of a substrate as a surface protective film, but on the other hand, it has a property of easily generating static electricity.

The resin material constituting the substrate may be blended with various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a colorant (pigment, dye, etc.), an antistatic agent, and an anti-caking agent, as needed. The first surface of the polyester film (the surface on which the antistatic layer side is to be provided) may be subjected to, for example, corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of a primer, and the like. A well-known or customary surface treatment. Such a surface treatment may be, for example, a treatment for improving the adhesion of the substrate to the antistatic layer. It is preferred to employ a surface treatment capable of introducing a polar group such as a hydroxyl group to the surface of the substrate. Further, the same surface treatment as described above may be applied to the second surface of the substrate (the surface on which the adhesive layer side is to be formed). The surface treatment may be a treatment for improving the adhesion of the substrate to the adhesive layer (the anchoring property of the adhesive layer).

The surface protective film of the present invention has an antistatic function by having an antistatic layer on a substrate, but it is also possible to further use an antistatic treated plastic film as the substrate. By using the above-mentioned substrate, the static electricity of the surface protective film itself is suppressed at the time of peeling, which is preferable. Further, the substrate is a plastic film, and by applying an antistatic treatment to the plastic film, the static electricity of the surface protection film itself can be reduced, and a surface protection film excellent in antistatic properties to the object can be obtained. Further, the method of imparting the antistatic function is not particularly limited, and a conventional method may be used, and for example, an antistatic resin composed of an antistatic agent and a resin component or a conductive resin containing a conductive polymer or a conductive material may be applied. The method is either a method of vapor-depositing or plating a conductive material, a method of mixing an antistatic agent, or the like.

The thickness of the substrate is usually 5 to 200 μm, and preferably about 10 to 100 μm. When the thickness of the base material is within the above range, it is excellent in workability for bonding the object to be attached and workability for peeling off the object to be attached, which is preferable.

< Antistatic layer (surface coating)> The surface protection film of the present invention is characterized in that the surface protection film has a base having a first surface (back surface) and a second surface (surface opposite to the first surface) And an antistatic layer provided on the first surface of the substrate, wherein the antistatic layer is formed using an antistatic agent composition containing polyaniline sulfonic acid as a conductive polymer component, A polyester resin as a binder and a melamine-based crosslinking agent as a crosslinking agent. Since the surface protective film has an antistatic layer (surface coating layer), it is preferable to improve the antistatic property of the antistatic layer and the temporal stability and the printing adhesion of the peeling electrostatic potential.

< Electroconductive polymer> The antistatic agent composition is characterized by containing polyaniline sulfonic acid as a conductive polymer component. By using the above-mentioned conductive polymer, the stability against time due to the antistatic property of the antistatic layer and the peeling of the electrostatic potential can be satisfied. Further, although the polyaniline sulfonic acid is "water-soluble", it can be immobilized in an antistatic layer by using a melamine-based crosslinking agent to be described later, thereby improving water resistance, and further, by using the aforementioned water-soluble conductive material. The aqueous solution of the polymer can obtain an antistatic layer excellent in surface resistivity over time, and is preferred. On the other hand, in the case where the conductive polymer used in forming the antistatic layer is "water-dispersible", the antistatic layer is formed by using a dispersion containing the water-dispersible conductive polymer, Since the aggregate is likely to be formed, it becomes difficult to form a uniform layer of the conductive polymer, and the obtained antistatic layer tends to have a deteriorated surface resistivity over time, which is not preferable.

The content of the conductive polymer is preferably 10 to 200 parts by mass, more preferably 25 to 150 parts by mass, still more preferably 40 to 120 parts by mass, per 100 parts by mass of the binder contained in the antistatic layer. When the content of the conductive polymer is too low, the antistatic effect is small, and if the content of the conductive polymer is too high, the adhesion of the antistatic layer to the substrate is lowered, and the transparency is lowered. The possibility is not appropriate.

The polyaniline sulfonic acid used as the conductive polymer component preferably has a weight average molecular weight (Mw) of 5 × 10 ⁵ or less and 3 × 10 ⁵ or less in terms of standard polystyrene measured by gel permeation chromatography (GPC). Preferably. Further, the weight average molecular weight of the conductive polymers is usually preferably 1 × 10 ³ or more, and more preferably 5 × 10 ³ or more.

The commercial product of the above-mentioned polyaniline sulfonic acid is exemplified by the trade name "aqua-pass" manufactured by Mitsubishi Rayon Co., Ltd., and the like.

The antistatic layer disclosed herein contains polyaniline sulfonic acid (polyaniline type) as an essential component in terms of a conductive polymer component, and may contain, for example, one or more other antistatic components (polyaniline sulfonate). An organic conductive substance other than acid, an inorganic conductive substance, an antistatic agent, etc.). Further, as a preferred embodiment, it is preferable that the antistatic layer contains substantially no antistatic component other than the conductive polymer, that is, the antistatic component contained in the antistatic layer is substantially only It is composed of polyaniline sulfonic acid as the conductive polymer component.

The organic conductive material may, for example, be a cationic antistatic agent having a cationic functional group such as a quaternary ammonium salt, a pyridinium salt, a first amine group, a second amine group or a third amine group; or a sulfonate or Anionic antistatic agents for anionic functional groups such as sulfates, phosphonates, and phosphate salts; zwitterionic antibiotics such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives Electrostatic agent; nonionic antistatic agent such as amino alcohol and its derivatives, glycerol and its derivatives, polyethylene glycol and its derivatives; having the above-mentioned cationic, anionic, zwitterionic ionic conductivity An ion-conducting polymer obtained by polymerizing or copolymerizing a monomer of a group (for example, a 4-stage ammonium salt group); a conductive polymer such as polythiophene, polyaniline, polypyrrole, polyethyleneimine or allylamine-based polymer and many more. These antistatic agents may be used alone or in combination of two or more.

The inorganic conductive substance may, for example, be tin oxide, cerium oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, cobalt, Copper iodide, ITO (indium oxide/tin oxide), ATO (antimony oxide/tin oxide), and the like. These inorganic conductive materials may be used alone or in combination of two or more.

The antistatic agent may, for example, be a cationic antistatic agent, an anionic antistatic agent, a zwitterionic antistatic agent, a nonionic antistatic agent, or a single having the above cationic, anionic or zwitterionic ionic conductive groups. An ion conductive polymer obtained by polymerization or copolymerization of a body.

< Binder> The antistatic layer is characterized in that a polyester resin as a binder is contained as an essential component in order to impart solvent resistance, mechanical strength, and thermal stability. The polyester resin is preferably a resin material containing a polyester as a main component (typically more than 50% by mass, preferably 75% by mass or more, for example, 90% by mass or more). The polyester preferably has a structure in which a polyvalent carboxylic acid component and a polyol component are condensed, that is, a polycarboxylic acid (typically a dicarboxylic acid) having two or more carboxyl groups in one molecule and One or two or more compounds (polycarboxylic acid component) of a derivative (an acid anhydride, an esterified product, a halide, etc.) of the polyvalent carboxylic acid, and a polyhydric alcohol selected from two or more hydroxyl groups in one molecule ( One or two or more compounds (polyol components) of a typical diol type).

Examples of the compound which is the above polyvalent carboxylic acid component may be oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, (±). - malic acid, meso-tartaric acid, itaconic acid, maleic acid, methyl maleic acid, fumaric acid, methyl fumaric acid, acetylene dicarboxylic acid, glutaric acid, Hexafluoroglutaric acid, methyl glutaric acid, glutaconic acid, adipic acid, dithioadipic acid, methyl adipic acid, dimethyl adipate, tetramethyl adipate, methylene Adipic acid, hexadiene diacid, galactose diacid, pimelic acid, suberic acid, perfluorooctanedioic acid, 3,3,6,6-tetramethylseic acid, sebacic acid, hydrazine Aliphatic dicarboxylic acids such as diacid, perfluorosebacic acid, tridecanedioic acid, dodecyl dicarboxylic acid, tridecyl dicarboxylic acid, tetradecyl dicarboxylic acid; cycloalkyl dicarboxylic acids (for example 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid), 1,4-(2-lower) Alkene dicarboxylic acid, 5-nor Ethylene-2,3-dicarboxylic acid (humic acid), adamantane dicarboxylic acid, cyclopentane dicarboxylic acid and other alicyclic dicarboxylic acids; phthalic acid, isophthalic acid, dithioisophthalene Formic acid, methyl isophthalic acid, dimethyl isophthalic acid, chloroisophthalic acid, dichloroisophthalic acid, terephthalic acid, methyl terephthalic acid, dimethyl terephthalic acid, Chloro terephthalic acid, bromine terephthalic acid, naphthalene dicarboxylic acid, oxonium dicarboxylic acid, stilbene dicarboxylic acid, biphenyl dicarboxylic acid, extended phenyl dicarboxylic acid, dimethyl linked phenyl Dicarboxylic acid, 4,4"-p-terephenylene dicarboxylic acid, 4,4"-terphenyl tetracarboxylic acid (4,4"-p-quaterphenyl Dicarboxylic acid), bibenzyl dicarboxylic acid, azobenzene dicarboxylic acid, o-carboxyphenylacetic acid, benzene diacetic acid, phenyl dipropionic acid, naphthalene dicarboxylic acid, naphthalene dipropionic acid, biphenyl diacetic acid, biphenyl dipropylene Acid, 3,3'-[4,4'-(methylenebis-p-linked diphenyl)dipropionic acid, 4,4'-bibenzyldiacetic acid, 3,3'(4,4'-bibenzyl An aromatic dicarboxylic acid such as dipropionic acid or oxydi-terephthalic acid; an acid anhydride of any of the above polycarboxylic acids; Esters of polycarboxylic acids of any one (e.g. alkyl esters; may be monoesters, diesters, etc.); a polycarboxylic acid corresponding to any of the above acid halide (e.g. acid chloride) and the like.

Preferred examples of the compound which the polyvalent carboxylic acid component can be used include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and acid anhydrides thereof; adipic acid and sebacic acid; An aliphatic dicarboxylic acid such as sebacic acid, succinic acid, fumaric acid, maleic acid, humic acid or 1,4-cyclohexanedicarboxylic acid, and an acid anhydride thereof; and a lower alkane of the above dicarboxylic acid a base ester (for example, an ester thereof with a unit cell having 1 to 3 carbon atoms).

Examples of the compound which can be used for the above polyol component include ethylene glycol, propylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, and neopentyl glycol. 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentane Alcohol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, hydrogenation Diols such as bisphenol A and bisphenol A. As another example, an alkylene oxide adduct of such a compound (for example, an ethylene oxide adduct or a propylene oxide adduct) may be mentioned.

The molecular weight of the polyester resin may be, for example, about 5×10 ³ to 1.5×10 ⁵ (preferably about 1×10 ⁴ to 6×10 ⁴ ), which is a standard polyphenylene measured by gel permeation chromatography (GPC). The number average molecular weight (Mn) in terms of ethylene. Further, the glass transition temperature (Tg) of the polyester resin may be, for example, 0 to 120 ° C (preferably 10 to 80 ° C).

The polyester resin may, for example, be manufactured by Toyobo Co., Ltd. under the trade names of VYLONAL MD-1100, MD-1200, MD-1245, MD-1335, MD-1480, MD-1500, MD-2000, and the trade name PLAS manufactured by Mutual Chemical Industry Co., Ltd. COAT Z-221, Z-446, Z-561, Z-565, Z-880, RZ-105, RZ-570, Z-592, Z-687, Z-690, PESRESIN A-110F manufactured by Takamatsu Oil Co., Ltd. A-120, A-124GP, A-125S, A-520, A-613D, A-615GE, A-640, A-645GH, A-647GEX, A-684G, and the like.

The antistatic layer may further contain a resin other than the polyester resin (for example, selected from the group consisting of acrylic resin and propylene) in a range that does not significantly impair the performance (for example, antistatic properties) of the surface protective film disclosed herein.醯-urethane resin, acrylonitrile-styrene resin, propylene fluorene-polyoxyl resin, polyoxyn oxy resin, polyazide resin, polyurethane resin, fluororesin, polyolefin resin, etc. One or two or more resins are used as a binder. One preferred aspect of the technology disclosed herein is the case where the binder of the antistatic layer consists essentially of only a polyester resin. For example, an antistatic layer having a ratio of the polyester resin in the binder of 98 to 100% by mass is preferred. The ratio of the binder in the entire antistatic layer may be, for example, 50 to 95% by mass, and usually 60 to 90% by mass.

< Lubricant> The antistatic agent composition used in forming the antistatic layer in the technique disclosed herein is preferably selected from the group consisting of fatty acid amides, fatty acid esters, polyfluorene-based lubricants, and fluorine-based compounds. At least one of a group consisting of a lubricant and a wax-based lubricant is used as a lubricant. In the case of the lubricant, even if the lubricant is not applied to the surface of the antistatic layer, a peeling treatment (for example, a coating of a polysulfide-based release agent or a long-chain alkyl-based release agent) is known. In the case of the treatment which is then dried, it is possible to obtain an antistatic layer having both sufficient lubricity and printing adhesion, and thus it is preferable. As described above, the surface of the antistatic layer is not further subjected to the release treatment, and it is preferable from the viewpoint of preventing whitening due to the release treatment agent (for example, whitening caused by storage under heating and humidification conditions). Further, it is also advantageous from the viewpoint of solvent resistance.

Specific examples of the fatty acid guanamine include, for example, decyl laurate, decyl palmitate, decylamine stearate, decyl octadecylamine, decyl hydroxystearate, decyl oleate, guanidine succinate. Amine, N-oil decyl palmitate, N-stearin, decylamine stearate, N-stearin decyl decylamine, N-oleyl stearate decylamine, N-stear mustard Acid amide, hydroxymethyl stearyl decylamine, methylene bis-stearate decylamine, ethylene bismuth decyl decylamine, ethylene bismuth laurate decylamine, ethylene bisstearate decylamine, ethylene bishydroxyl hard fat Acid amide, ethylene bisbehenate decylamine, hexamethylenebisstearate decylamine, hexamethylenebisbehenic acid decylamine, hexamethylene hydroxystearic acid decylamine, N,N '-Distearyl adipic acid decylamine, N,N'-distearyl decanoate, ethylene bis oleate, ethylene erucic acid decylamine, hexamethylene bis oleate , N,N'-dioleyl decanoic acid decylamine, N,N'-dioleyl decanoic acid decylamine, m-indole bis-stearic acid amide, m- bis bishydroxystearate Amine, N, N'-stearyl phthalate, decylamine and the like. These lubricants may be used alone or in combination of two or more.

Specific examples of the fatty acid esters include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl soft acid ester, 2-ethylhexyl stearate, and twenty Diacid monoglyceride, hexadecyl 2-ethylhexanoate, isopropyl myristate, isopropyl soft acid ester, cholesteryl isostearate, lauryl methacrylate, methyl oleate, Methyl laurate, methyl oleate, methyl stearate, tetradecyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate, Pentaerythritol tetrapalmitate, stearic acid stearate, isotridecyl stearate, 2-ethylhexanoic acid triglyceride, butyl laurate, octyl oleate, and the like. These lubricants may be used alone or in combination of two or more.

Specific examples of the polyfluorene-based lubricant include polydimethyl siloxane, polyether modified polydimethyl siloxane, amine modified polydimethyl siloxane, and epoxy modification. Polydimethyl methoxy oxane, methanol modified polydimethyl methoxy oxane, fluorenyl modified polydimethyl siloxane, carboxy modified polydimethyl oxa oxide, methyl hydrogen polyoxyl, A Propylene modified polydimethyl siloxane, phenol modified polydimethyl siloxane, sterol modified polydimethyl siloxane, aralkyl modified polydimethyl siloxane, halothane Modified dimethyl methoxy oxane, long chain alkyl modified polydimethyl siloxane, higher fatty acid modified ester modified polydimethyl siloxane, higher fatty acid guanamine modified polydimethyl A siloxane, a phenyl modified polydimethyl siloxane, and the like. These lubricants may be used alone or in combination of two or more.

Specific examples of the fluorine-based lubricant include perfluoroalkanes and perfluorocarboxylic esters. These lubricants may be used alone or in combination of two or more.

Specific examples of the wax-based lubricant include petroleum wax (such as paraffin), plant wax (such as palm wax), mineral wax (such as montan wax), higher fatty acid (such as ceric acid), and neutral fat. Various waxes (soft acid triglyceride, etc.). These lubricants may be used alone or in combination of two or more.

The ratio of the lubricant to the entire antistatic layer may be 1 to 50% by mass, and usually 5 to 40% by mass. When the content of the lubricant is too low, the lubricity tends to decrease. When the content of the lubricant is too high, the printing adhesion may be lowered.

< Crosslinking Agent> The antistatic layer described above is characterized by containing a melamine-based crosslinking agent as a crosslinking agent. By using the melamine-based crosslinking agent, the water-soluble polyaniline sulfonic acid which is an essential component in forming the antistatic layer can be immobilized in the binder, and the effect of excellent water resistance and printing adhesion can be achieved.

As the melamine-based crosslinking agent, melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine, alkyl etherified melamine or the like can be used. Further, other crosslinking agents may be blended within a range that does not significantly impair the properties of the surface protective film disclosed herein (e.g., properties such as antistatic properties).

The antistatic layer in the technology disclosed herein may contain other antistatic agents, antioxidants, colorants (pigments, dyes, etc.), fluidity adjusters (thixotropic agents, tackifiers, etc.), and film forming assistants as needed. Additives such as surfactants (antifoaming agents, etc.) and preservatives. Further, it may contain a glycidyl compound as a conductivity enhancer, a polar solvent, a polyvalent aliphatic alcohol, an indoleamine compound, or the like.

< Formation of Antistatic Layer> The method for producing a surface protective film of the present invention comprises the step of preparing an antistatic agent composition containing polyaniline sulfonate as a conductive polymer component. An acid, a polyester resin as a binder, and a melamine-based crosslinking agent as a crosslinking agent; and a step of preparing an antistatic layer, which is coated on the first side of the substrate and dried to form the antistatic agent composition . In particular, the method for forming the antistatic layer can be suitably formed by modulating an antistatic agent composition (liquid composition, antistatic layer forming coating material) by the above-described steps. An essential component such as a polymer component and an additive to be used as needed are dissolved in a suitable solvent (water or the like), and the composition is applied to a substrate. For example, it is preferable to apply the antistatic agent composition to the first surface of the substrate, dry it, and perform a curing treatment (heat treatment, ultraviolet treatment, or the like) as necessary. The NV (nonvolatile content) of the antistatic agent composition may be, for example, 5% by mass or less (typically 0.05 to 5% by mass), and usually 1% by mass or less (typically 0.10 to 1% by mass). When the antistatic layer having a small thickness is formed, the NV of the antistatic agent composition is preferably 0.05 to 0.50% by mass (for example, 0.10 to 0.40% by mass). By using such a low NV antistatic agent composition, a more uniform antistatic layer can be formed.

In terms of the solvent constituting the antistatic agent composition, it is preferred to stabilize the forming component of the antistatic layer and dissolve it. The solvent may be an organic solvent, water, or a mixed solvent of these. As the organic solvent, one or two or more solvents selected from the group consisting of esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone, and cyclohexanone; and cyclic ethers such as tetrahydrofuran (THF) and dioxane can be used. An aliphatic or alicyclic hydrocarbon such as n-hexane or cyclohexane; an aromatic hydrocarbon such as toluene or xylene; an aliphatic or alicyclic group such as methanol, ethanol, n-propanol, isopropanol or cyclohexanol; Alcohols; glycol ethers such as alkylene glycol monoalkyl ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), dialkyl glycol monoalkyl ethers, and the like. In a preferred embodiment, the solvent of the antistatic agent composition is water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol).

< Properties of Antistatic Layer> The thickness of the antistatic layer in the technique disclosed herein is typically from 3 to 500 nm, preferably from 3 to 100 nm, preferably from 3 to 60 nm. When the thickness of the antistatic layer is too thin, it may be difficult to form a uniform antistatic layer (for example, the thickness of the antistatic layer may vary depending on the position), and thus the appearance of the surface protective film may be prone to uneven defects. On the other hand, when the thickness is too thick, there is a case where the properties of the substrate (optical characteristics, dimensional stability, etc.) are affected.

In a preferred aspect of the surface protective film disclosed herein, the surface resistivity (Ω/□) measured on the surface of the antistatic layer is preferably 1.0×10 ¹¹ or less, and preferably 5.0×10 ¹⁰ or less, more preferably It is 1.0 × 10 ¹⁰ or less. As the surface protective film which exhibits the surface resistivity in the above range, it is preferable to use a surface protective film which is used, for example, as a processing or conveyance process of an article which does not like static electricity such as a liquid crystal cell or a semiconductor device. Further, the surface resistivity can be determined from the measured surface resistivity by measuring in an environment of 23 ° C and 50% RH using a commercially available insulation resistance measuring device.

The surface protective film disclosed herein preferably has a property of being easily printed on the back surface (antistatic layer surface) with an aqueous ink or an oily ink (for example, using an oily marker). The surface protection film is adapted to mark the identification number of the object to be protected, etc., in the process of processing or transporting the object to be attached (for example, an optical member) in a state in which the surface protective film has been attached. On the aforementioned surface protective film. Therefore, it is preferable to use a surface protection film excellent in printing. For example, an oil-based ink of a type in which the solvent is an alcohol-based and contains a pigment is preferably highly printed. Further, the printed ink is preferably not easily dropped by rubbing or transfer (that is, excellent in printing adhesion). The surface protective film disclosed herein is also suitable for solvent resistance, so that even when printing with an alcohol (for example, ethanol), the printing does not cause a significant change in appearance when the printing is corrected or removed.

The surface protective film disclosed herein can also be subjected to other layers in addition to the substrate, the adhesive layer and the antistatic layer. The configuration of the "other layer" can be exemplified by being placed between the second side (front surface) of the substrate and the adhesive layer. The layer disposed between the front surface of the substrate and the adhesive layer may be, for example, an undercoat layer (an anchor layer) that enhances the anchoring of the adhesive layer to the second surface, an antistatic layer, or the like. A surface protective film having an antistatic layer disposed on the front surface of the substrate, an anchor layer disposed on the antistatic layer, and an adhesive layer disposed thereon may be used.

< Adhesive Composition> The surface protection film of the present invention has an adhesive layer formed by using an adhesive composition on the second surface of the substrate, and the adhesive composition can be used as long as it has transparency. It is used in a particularly limited manner. For example, an acrylic adhesive, an urethane-based adhesive, a synthetic rubber-based adhesive, a natural rubber-based adhesive, a polyoxyn-based adhesive, or the like can be used as the adhesive composition, and among them, a preferred one is selected. At least one selected from the group consisting of an acrylic adhesive, a urethane-based adhesive, and a polyoxygen-based adhesive, particularly preferred is acrylic acid using a (meth)acrylic polymer. Adhesive.

< Acrylic Adhesive> When an acrylic adhesive is used as the adhesive layer, the (meth)acrylic polymer constituting the acrylic adhesive may have a carbon number of 1 to 14 in the raw material of the polymer. The alkyl (meth)acrylic monomer is used as a main monomer. One type or two or more types of the (meth)acrylic monomer may be used as a main component. By using the above (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, it is easy to control the adhesion to the object to be attached (protected body) to a low adhesion, and light peelability can be obtained. Or a surface protection film excellent in removability. Further, the (meth)acrylic polymer in the present invention means an acrylic polymer and/or a methacrylic polymer, and the (meth)acrylate means an acrylate and/or a methacrylate. In addition, the "main component" in the present invention means a component which accounts for the largest amount of the total amount of constituent components, and is preferably more than 40% by mass, preferably more than 50% by mass, and more preferably more than 60% by mass.

Examples of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate. Base) butyl acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (methyl) ) n-octyl acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate , n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, and the like.

Among them, the surface protective film of the present invention is preferably a (meth)acrylic monomer having an alkyl group having 6 to 14 carbon atoms, and examples thereof include (meth)acrylic acid acrylate and (meth)acrylic acid 2- Ethylhexyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, Isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, and the like. In particular, by using a (meth)acrylic monomer having an alkyl group having 6 to 14 carbon atoms, it is easy to control the adhesion to the object to be adhered to a low adhesion, and it is excellent in removability.

In particular, the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms is contained in an amount of 50% by mass or more based on 100% by mass of the total of the monomer components constituting the (meth)acrylic polymer. Preferably, it is 60% by mass or more, more preferably 70 to 99% by mass, and most preferably 80 to 97% by mass. When it is less than 50% by mass, the moderate wettability of the adhesive composition or the cohesive force of the adhesive layer will be deteriorated, which is not preferable.

Moreover, it is preferable that the (meth)acrylic polymer constituting the acrylic pressure-sensitive adhesive contains a (meth)acrylic monomer having a hydroxyl group as a raw material monomer. One type or two or more types of the hydroxyl group-containing (meth)acrylic monomers may be used.

By using the above-mentioned hydroxyl group-containing (meth)acrylic monomer, the crosslinking of the adhesive composition can be easily controlled, and even the balance between improving the wettability due to flow and reducing the adhesion at the time of peeling is also Can be easily controlled. Further, unlike a carboxyl group or a sulfonate group which can be generally used as a crosslinking site, a hydroxyl group has an appropriate interaction with an ionic compound which is an antistatic component (antistatic agent), so it is also considered from the viewpoint of antistatic property. Suitable for use.

The hydroxyl group-containing (meth)acrylic monomer may, for example, be 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate. , 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxydodecyl (meth) acrylate, ( 4-hydroxymethylcyclohexyl)methacrylate, N-hydroxymethyl(meth)acrylamide, and the like. In particular, it is preferred to use a (meth)acrylic monomer having a hydroxyl group of 4 or more and having a hydroxyl group to facilitate light peeling at the time of high-speed peeling.

It is preferable to contain 15 parts by mass or less of the above-mentioned (meth)acrylic monomer having a hydroxyl group with respect to 100 parts by mass of the above (meth)acrylic monomer having 1 to 14 carbon atoms, and 1 to 13 masses. The amount is preferably 2 to 10 parts by mass, and 3 to 8 parts by mass. Within the above range, it is preferred to easily control the balance between the wettability of the adhesive composition and the cohesive force of the resulting adhesive layer.

Further, from the viewpoint that the balance of the adhesive property can be easily obtained, the other polymerizable monomer component can be used to adjust the glass transition temperature of the (meth)acrylic polymer or can be used within a range not impairing the effects of the present invention. The peelable polymerizable monomer or the like has a Tg of 0 ° C or lower (usually -100 ° C or higher).

The (meth)acrylic monomer having the alkyl group having 1 to 14 carbon atoms used in the (meth)acrylic polymer and other polymerizable groups other than the hydroxyl group-containing (meth)acrylic monomer The monomer can be a carboxyl (meth)acrylic monomer.

The (meth)acrylic monomer having a carboxyl group may, for example, be (meth)acrylic acid, carboxyethyl (meth)acrylate or carboxypentyl (meth)acrylate.

The (meth)acrylic monomer having a carboxyl group of 1 to 14 is preferably 5 parts by mass or less and 3 parts by mass based on 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms. Preferably, the amount is less than 1 part by mass, more preferably 0.2 part by mass or less, more preferably 0.01 part by mass or more and less than 0.1 part by mass. When it is more than 5 parts by mass, an acid functional group such as a carboxyl group having a large polar effect may be present in a large amount, and when it is blended with an ionic compound as an antistatic component, an acid functional group such as a carboxyl group may interact with the aforementioned ionic compound, thereby It is not suitable because ion conduction is hindered, conductivity is low, and sufficient antistatic property cannot be obtained. When it is in the above range, it is preferable to prevent the adhesion from increasing with time (adhesion prevention).

Further, in particular, for the purpose of taking out the peeling electrostatic properties and the adhesion preventing property, the (meth)acrylic monomer having a hydroxyl group and the (meth)acrylic monomer having a carboxyl group may be used in combination.

In addition, as long as the properties of the present invention are not impaired, the (meth) group having the alkyl group having 1 to 14 carbon atoms used in the (meth)acrylic polymer can be used without particular limitation. An acrylic monomer, a hydroxyl group-containing (meth)acrylic monomer, and a carboxyl group-containing (meth)acrylic monomer other than a polymerizable monomer. For example, a cyano group-containing monomer, a vinyl ester monomer, an aromatic vinyl monomer or the like, a cohesive heat resistance enhancing component, or a guanamine group-containing monomer, a quinone imine group-containing monomer, or the like may be used. The amine group monomer, the epoxy group-containing monomer, the N-propylene fluorenyl porphyrin, the vinyl ether monomer, and the like have a component which enhances the adhesion or functions as a crosslinking crosslinking point. Wherein, a cyano group-containing monomer, a guanamine group-containing monomer, a ruthenium group-containing monomer, an amine group-containing monomer, and a nitrogen-containing single sheet containing N-propylene fluorenyl porphyrin are used. The body is better. By using a nitrogen-containing monomer, it is advantageous to ensure proper adhesion without causing floating or peeling, and to obtain a surface protective film having excellent shearing force. These polymerizable monomers may be used singly or in combination of two or more.

The cyano group-containing monomer may, for example, be acrylonitrile or methacrylonitrile.

The vinyl ester monomer may, for example, be vinyl acetate, vinyl propionate or vinyl laurate.

Examples of the aromatic vinyl monomer include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and other substituted styrenes.

The hydrazine-containing monomer may, for example, be acrylamide, methacrylamide, diethyl acrylamide, N-vinyl pyrrolidone, N,N-dimethyl decylamine, N, N-dimethyl methacrylamide, N,N-diethyl acrylamide, N,N-diethyl methacrylamide, N,N'-methylenebis acrylamide, N, N-dimethylaminopropyl acrylamide, N,N-dimethylaminopropyl methacrylamide, diacetone acrylamide, and the like.

The quinone imine group-containing monomer may, for example, be cyclohexylmethylenediamine, isopropyl maleimide, N-cyclohexylmethyleneamine, methylene. Succinic acid succinate and the like.

The amino group-containing monomer may, for example, be an amine ethyl (meth) acrylate, N,N-dimethylamine ethyl (meth) acrylate or N,N-dimethylaminopropyl ( Methyl) acrylate or the like.

Examples of the epoxy group-containing monomer include a glycidyl (meth)acrylate, a methyl epoxypropyl (meth)acrylate, and an allyl epoxypropyl ether.

The vinyl ether monomer may, for example, be methyl vinyl ether, ethyl vinyl ether or isobutyl vinyl ether.

In the present invention, a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, a (meth)acrylic monomer having a hydroxyl group, and a (meth)acrylic monomer having a carboxyl group are polymerized. The monomer is preferably 0 to 40 parts by mass, more preferably 0 to 30 parts by mass, per 100 parts by mass of the (meth)acrylic monomer having the alkyl group having 1 to 14 carbon atoms. In the case where an ionic compound is used as the antistatic agent, good interaction with the ionic compound and good removability can be appropriately adjusted by using the above other polymerizable monomer within the above range.

The monomer component of the (meth)acrylic polymer may further contain a reactive monomer containing an alkylene oxide group.

Further, the average addition mole number of the oxyalkylene unit of the epoxy group-containing reactive monomer is preferably from 1 to 40 from the viewpoint of compatibility with an ionic compound as an antistatic component. 3 to 40 is better, 4 to 35 is better, and 5 to 30 is better. When the average addition molar number is 1 or more, the effect of reducing the contamination of the object to be attached (protected body) is more effectively obtained. Further, when the average addition mole number is more than 40, the interaction with the ionic compound is large, and the viscosity of the adhesive composition is increased, which tends to be difficult to apply, which is not preferable. Further, the terminal of the oxyalkylene chain may be an original hydroxyl group or substituted with another functional group or the like.

The epoxy group-containing reactive monomer may be used singly or in combination of two or more kinds, and the total content thereof is preferably 20% by mass or less based on the total amount of the monomer components of the (meth)acrylic polymer. It is preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 4% by mass or less, particularly preferably 3% by mass or less, and more preferably 1% by mass or less. When the content of the epoxy group-containing reactive monomer is more than 20% by mass, the interaction with the ionic compound becomes large, and ion conduction is inhibited and the antistatic property is lowered, which is not preferable.

The oxyalkylene unit of the above-mentioned epoxy group-containing reactive monomer may, for example, be an alkylene group having a carbon number of 1 to 6, and examples thereof include an oxymethylene group, an oxygen-extended ethyl group, an oxygen-extended propyl group, and an oxygen group. Stretching butyl and so on. The hydrocarbyl group of the oxyalkylene chain may be linear or branched.

Further, the epoxy group-containing reactive monomer is preferably a reactive monomer having an oxirane group. By using a (meth)acrylic polymer containing a reactive monomer having an oxiranyl group as a matrix polymer, compatibility between the matrix polymer and the ionic compound can be enhanced, and the article can be oozing to the object to be attached. It is appropriately suppressed to obtain a low-pollution adhesive composition.

The epoxy group-containing reactive monomer may, for example, be a (meth)acrylic acid alkylene oxide adduct or a reactive substituent having a propylene group, a methacryloyl group or an allyl group in the molecule. Reactive surfactants and the like.

Specific examples of the (meth)acrylic acid alkylene oxide adduct include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polyethylene glycol-polypropylene glycol (methyl). Acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy Polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octyloxy polyethylene glycol (meth) acrylate, lauryl oxy polyethylene glycol (methyl Acrylate, stearyloxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, octyloxy polyethylene Glycol-polypropylene glycol (meth) acrylate, and the like.

Further, specific examples of the reactive surfactant include an anionic reactive surfactant having a (meth)acryl fluorenyl group or an allyl group, a nonionic reactive surfactant, and a cationic reactivity. Surfactant and the like.

The (meth)acrylic polymer is preferably from 100,000 to 5,000,000 in terms of weight average molecular weight (Mw), preferably from 200,000 to 2,000,000, more preferably from 300,000 to 800,000. When the weight average molecular weight is less than 100,000, the cohesive force of the adhesive layer tends to decrease, and the residual rubber tends to be generated. On the other hand, when the weight average molecular weight is more than 5,000,000, the fluidity of the polymer is lowered, and the wettability of the object to be attached (for example, a polarizing plate) is insufficient, and there is a relationship between the adhesive layer of the object to be attached and the surface protective film. The tendency to cause swelling. Further, the weight average molecular weight means a result measured by GPC (gel permeation chromatography).

Further, the glass transition temperature (Tg) of the (meth)acrylic polymer is preferably 0 ° C or lower, and preferably 10 ° C or lower (normally -100 ° C or higher). When the glass transition temperature is more than 0 ° C, the polymer does not easily flow, and for example, the wettability of the polarizing plate is insufficient, and there is a tendency that expansion occurs between the polarizing plate and the adhesive layer of the surface protective film. In particular, by setting the glass transition temperature to -61 ° C or lower, an adhesive layer excellent in wettability and light peelability to the polarizing plate can be easily obtained. Further, the glass transition temperature of the (meth)acrylic polymer can be adjusted to the above range by appropriately changing the monomer component or composition ratio used.

The polymerization method of the (meth)acrylic polymer is not particularly limited, and polymerization can be carried out by a well-known method such as solution polymerization, emulsion polymerization, bulk polymerization, or suspension polymerization, but particularly from the viewpoint of workability, Or, in terms of characteristics such as low contamination of the object to be attached (protected body), solution polymerization is preferred. Further, the obtained polymer may be any of a random copolymer, a bulk copolymer, an alternating copolymer, a graft copolymer, and the like.

< Aminoate-based adhesive> When a urethane-based adhesive is used for the adhesive layer, any appropriate urethane-based adhesive can be used. Such a urethane-based adhesive is preferably composed of a urethane resin (urethane-based polymer) obtained by reacting a polyol with a polyisocyanate compound. The polyhydric alcohol may, for example, be a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol or the like. The polyisocyanate compound may, for example, be diphenylmethane diisocyanate, toluene diisocyanate or hexamethylene diisocyanate.

< Polyoxygen-based Adhesive Agent> When a polyfluorene-based pressure-sensitive adhesive is used for the above-mentioned pressure-sensitive adhesive layer, any appropriate polyoxynitride-based pressure-sensitive adhesive can be used. Such a polyoxygen-based adhesive is preferably obtained by blending or agglomerating a polyoxynoxy resin (polyoxymethylene polymer or polyoxymethylene component).

Further, the polyadoxic adhesive may be an addition reaction-curable polyoxynoxy adhesive or a peroxide-curable polyoxynoxy adhesive. Among the above-mentioned polyoxynoxy adhesives, an addition reaction-curable polysulfoxy-based adhesive is preferred because no peroxide (benzyl peroxide, etc.) is used and no decomposition product is produced.

The hardening reaction of the addition reaction-hardening type polyoxynene-based adhesive is generally carried out by using a platinum catalyst to form a polyalkylhydroquinone-based adhesive. The method of hardening the object.

<Antistatic component of the adhesive layer> In the surface protective film of the present invention, the adhesive composition constituting the pressure-sensitive adhesive layer preferably contains an antistatic component, and the antistatic component preferably contains an ionic compound. The aforementioned ionic compound may, for example, be an alkali metal salt and/or an ionic liquid. By containing the ionic compound, excellent antistatic properties can be imparted. Further, as described above, an adhesive layer (using an antistatic component) obtained by crosslinking an adhesive composition containing an antistatic component can be used to prevent an antistatic coating (for example, polarized light) during peeling. The plate) acts as a static electricity, and the crucible constitutes a surface protective film which reduces contamination of the object to be attached. Therefore, it is quite useful as an antistatic surface protective film in the field of optical/electronic components related to static electricity or contamination, which is a particularly serious problem.

Since the above-mentioned alkali metal salt has high ion dissociation property, it exhibits excellent antistatic properties even in a small amount of addition, which is preferable from this point. The above alkali metal salt can be suitably used, for example, a metal salt composed of a cation of Li ⁺ , Na ⁺ , K ⁺ and an anion having the following ions: Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , SCN ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , C ₉ H ₁₉ COO ^- , CF ₃ COO ^- , C ₃ F ₇ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , C ₄ F ₉ SO ₃ ^- , C ₂ H ₅ OSO ₃ ^- , C ₆ H ₁₃ OSO ₃ ^- , C ₈ H ₁₇ OSO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , (C ₃ F ₇ SO ₂ ) ₂ N ^- , (C ₄ F ₉ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , HF ₂ ^- , (CN) ₂ N ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^- , (CH ₃ ) ₂ PO ₄ ^- , (C ₂ H ₅ ) ₂ PO ₄ ^- , CH ₃ (OC ₂ H ₄ ) ₂ OSO ₃ ^- , C ₆ H ₄ (CH ₃ )SO ₃ ^- , (C ₂ F ₅ ) ₃ PF ₃ ^- , CH ₃ CH(OH)COO ^- , And (FSO ₂ ) ₂ N ^- . It is preferred to use LiBr, LiI, LiBF ₄ , LiPF ₆ , LiSCN, LiClO ₄ , LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li (FSO ₂ ) a lithium salt such as ₂ N or Li(CF ₃ SO ₂ ) ₃ C, more preferably LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₃ F ₇ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(FSO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C. These alkali metal salts may be used singly or in combination of two or more.

Further, by using the ionic liquid as an antistatic component (antistatic agent), an adhesive layer having a high antistatic effect can be obtained without impairing the adhesive property. Although the detailed reason for obtaining excellent antistatic properties by using an ionic liquid is not clear, it is conceivable that the ionic liquid is lower in melting point than the general ionic compound (melting point of 100 ° C or lower), so that molecular motion is easy and excellent. Antistatic properties. In particular, in order to achieve an antistatic action on the object to be attached, since the ionic liquid system is extremely transferred to the object to be attached, it is desirable to obtain an excellent peeling antistatic property of the object to be attached. In particular, an ionic liquid having a melting point of not more than room temperature (25 ° C) is more effective in transferring the object to be attached, so that excellent antistatic property can be obtained.

Further, since the ionic liquid is liquid at 100 ° C or lower, it is easier to add, disperse or dissolve the adhesive than the solid salt. Further, since the ionic liquid has no vapor pressure (non-volatile), it does not disappear with time, and has characteristics of maintaining antistatic properties. Further, the ionic liquid system refers to a molten salt (ionic compound) having a melting point of 100 ° C or less and being in a liquid form.

As the ionic liquid, those composed of the organic cation component and the anion component represented by the following general formulae (A) to (E) are preferably used. Further, those having excellent antistatic properties are obtained by the ionic liquid having such cations.

[Chemical 1]

R _a in the above formula (A) represents a hydrocarbon group having 4 to 20 carbon atoms, and a part of the above hydrocarbon group may also be a hetero atom-substituted functional group; and R _b and R _c may be the same or different, and represent hydrogen or carbon number 1 To the hydrocarbon group of 16, a part of the aforementioned hydrocarbon group may also be a hetero atom-substituted functional group. However, when the nitrogen atom contains a double bond, there is no R _c .

R _d in the above formula (B) represents a hydrocarbon group having 2 to 20 carbon atoms, and a part of the hydrocarbon group may be a hetero atom-substituted functional group; and R _e , R _f and R _g may be the same or different and represent hydrogen. Or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the aforementioned hydrocarbon group may be a hetero atom-substituted functional group.

R _h in the above formula (C) represents a hydrocarbon group having 2 to 20 carbon atoms, and a part of the above hydrocarbon group may be a hetero atom-substituted functional group; R _i , R _j , and R _k may be the same or different and represent hydrogen. Or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the aforementioned hydrocarbon group may be a hetero atom-substituted functional group.

Z in the above formula (D) represents a nitrogen, sulfur, or phosphorus atom; R _l , R _m , R _n , and R _o may be the same or different, and represent a hydrocarbon group having 1 to 20 carbon atoms, and a part of the hydrocarbon group may also be used. It is a functional group substituted with a hetero atom. However, when Z is a sulfur atom, there is no R _o .

R _P in the above formula (E) represents a hydrocarbon group having 1 to 18 carbon atoms, and a part of the above hydrocarbon group may be a functional group substituted with a hetero atom.

The cation represented by the formula (A) may, for example, be a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a dihydropyrrole skeleton, a cation having a pyrrole skeleton, or a porphyrin cation.

Specific examples include 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, and 1-butyl-3,4-dimethylpyridinium cation. , 1-methyl-1-ethylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, pyrrolidin-2-one cation, 1-propylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 2-methyl-1-dihydropyrrole cation, 1- Ethyl-2-phenylphosphonium cation, 1,2-dimethylhydrazine cation, 1-ethylcarbazole cation, N-ethyl-N-methylmorpholine cation, and the like.

The cation represented by the formula (B) may, for example, be an imidazolium cation, a tetrahydropyrimidinium cation or a dihydropyrimidinium cation.

Specific examples thereof include, for example, 1,3-dimethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl group. 3-methylimidazolium cation, 1-mercapto-3-methylimidazolium cation, 1-tetrakisyl-3-methylimidazolium cation, 1-(2-methoxyethyl) 3-methylimidazolium cation, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6- Tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-Dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl- 1,6-dihydropyrimidinium cation, and the like.

The cation represented by the formula (C) may, for example, be a pyrazolium cation or a pyrazolinium cation.

Specific examples include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methyldihydropyrazolium cation, 1-ethyl-2,3, 5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation, 1- Ethyl-2,3,5-trimethyldihydropyrazolium cation, 1-propyl-2,3,5-trimethyldihydropyrazolium cation, 1-butyl-2,3,5 a trimethyldihydropyrazolium cation or the like.

The cation represented by the formula (D) may, for example, be a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, or a part of the aforementioned alkyl group substituted by an alkenyl group or an alkoxy group, or even substituted with an epoxy group. Wait.

Specific examples include tetramethylammonium cation, tetrabutylammonium cation, tetraamylammonium cation, tetrahexylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, and trimethylsulfonium. Alkyl ammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, epoxypropyltrimethylammonium cation, trimethylsulfonium cation, triethyl a phosphonium cation, a tributyl phosphonium cation, a trihexyl phosphonium cation, a diethyl methyl phosphonium cation, a dibutyl ethyl phosphonium cation, a dimethyl sulfonium cation, a tetramethyl phosphonium cation, a tetraethyl phosphonium cation, Tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethyl phosphonium cation, tributylethyl phosphonium cation, trimethylsulfonium cation, diallyldimethylammonium cation , a tributyl-(2-methoxyethyl) phosphonium cation, and the like. Among them, triethylmethylammonium cation, tributylethylammonium cation, trimethylsulfonium ammonium cation, diethylmethyl phosphonium cation, dibutylethyl phosphonium cation, dimethyl fluorenyl group are preferably used. An asymmetric tetraalkylammonium cation such as a phosphonium cation, a triethylmethyl phosphonium cation, a tributylethyl phosphonium cation, a trimethylsulfonium cation, a trialkyl phosphonium cation, a tetraalkyl phosphonium cation or N, N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, epoxypropyltrimethylammonium cation, diallyldimethylammonium cation, N,N-di Methyl-N-ethyl-N-heptyl ammonium cation, N,N-dimethyl-N-ethyl-N-decyl ammonium cation, N,N-dimethyl-N-propyl-N- Amyl ammonium cation, N,N-dimethyl-N-propyl-N-hexylammonium cation, N,N-dimethyl-N-propyl-N-heptyl ammonium cation, trimethylheptyl ammonium Cation, N,N-diethyl-N-methyl-N-propylammonium cation, N,N-diethyl-N-methyl-N-amylammonium cation, N,N-diethyl- N-methyl-N-heptyl ammonium cation, N,N-diethyl-N-propyl-N-amyl ammonium cation, trioctylmethyl ammonium cation, N-methyl-N-ethyl- N- Propyl-N-amyl ammonium cation.

The cation represented by the formula (E) is exemplified by a ruthenium cation or the like. Further, specific examples of R _P in the above formula (E) include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, a thirteen group, and a fourteenth. Base, eighteen base, etc.

On the other hand, the anion component is not particularly limited as long as it satisfies the ionic liquid, and for example, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^{- may be used.} , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , C ₄ F ₉ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , ( C ₂ F ₅ SO ₂ ) ₂ N ^- , (C ₃ F ₇ SO ₂ ) ₂ N ^- , (C ₄ F ₉ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ -, SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , HF ₂ ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- , ( CF ₃ SO ₂ )(CF ₃ CO)N ^- , C ₉ H ₁₉ COO ^- , (CH ₃ ) ₂ PO ₄ ^- , (C ₂ H ₅ ) ₂ PO ₄ ^- , C ₂ H ₅ OSO ₃ ^- , C ₆ H ₁₃ OSO ₃ ^- , C ₈ H ₁₇ OSO ₃ ^- , CH ₃ (OC ₂ H ₄ ) ₂ OSO ₃ ^- , C ₆ H ₄ (CH ₃ )SO ₃ ^- , (C ₂ F ₅ ) ₃ PF ₃ ^- , CH ₃ CH(OH)COO ^- , and (FSO ₂ ) ₂ N ^- and the like.

Further, an anion or the like represented by the following formula (F) can also be used as the anion component. [Chemical 2]

Further, among the anion components, in particular, an anion component of a fluorine atom is preferably used because a low melting point ionic liquid can be obtained.

Specific examples of the ionic liquid used in the present invention may be appropriately selected from the combination of the cationic component and the anionic component, and examples thereof include 1-butylpyridinium tetrafluoroborate and 1-butylpyridinium hexafluorophosphate. 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-3-methylpyridine Bis(pentafluoroethanesulfonyl) quinone imine, 1-hexylpyridinium tetrafluoroborate, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1 -Methyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-propane Isopiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexyl Piperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-hexylpyrrole Pyridinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 2-methyl-1-dihydropyrrole IV Fluoroboric acid Salt, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethylcarbazole tetrafluoroborate, 1-ethyl-3- Methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3 -methylimidazolidinium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolidinium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolidinium dicyanamide, 1-ethyl-3-methylimidazolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-3-methyl Imidazolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolidinium quinone (trifluoromethanesulfonyl) methide, 1-hexyl-3-methyl Imidazolidinium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate Salt, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 2-methylpyrazolium tetrafluoroborate, 1-ethyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) quinone imine, 1-propyl-2,3,5-trimethylpyrazolium (Trifluoromethanesulfonyl) quinone imine, 1-butyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl) quinone imine, tetraamyl ammonium trifluoromethane Acid salt, tetraamylammonium bis(trifluoromethanesulfonyl) quinone imine, tetrahexylammonium triflate, tetrahexylammonium bis(trifluoromethanesulfonyl) ruthenium, tetraheptyl ammonium Trifluoromethanesulfonate, tetraheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonic acid Salt, diallyldimethylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium bis(pentafluoroethanesulfonyl) quinone imine, N,N-diethyl --N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium Fluoromethanesulfonate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl Benzyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl) quinone imine, epoxypropyltrimethylammonium trifluoromethanesulfonate, epoxypropyl Trimethylammonium bis(trifluoromethanesulfonyl) quinone imine, epoxypropyltrimethylammonium bis(pentafluoroethanesulfonyl)pyrene Amine, tetraoctylfluorene trifluoromethanesulfonate, tetraoctylphosphonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-butylammonium double Trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl- N-ethyl-N-decyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-butylammonium bis(trifluoromethanesulfonyl) Yttrium imine, N,N-dimethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethanesulfonyl) Yttrium, N,N-diethyl-N-methyl-N-propylammonium bis(trifluoromethanesulfonyl) fluorene imine, N,N-diethyl-N-methyl-N- Amyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) fluorene imine, N, N -Diethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trioctylmethylammonium bis(trifluoromethanesulfonyl) quinone imine, N-A --N-ethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl)trifluoroacetate , 1-ethyl-3-methylimidazolidinium (trifluoromethanesulfonyl)trifluoroacetamide, N-ethyl-N-methyloxaline phthalocyanate, 4-ethyl-4 -Methyl phthalocyanine methyl carbonate and the like.

Further, the ionic liquid may be used singly or in combination of two or more.

For example, the above-mentioned anti-resistance is 100 parts by mass of a polymer which is a main component of the above-mentioned adhesive composition (for example, a (meth)acrylic polymer, a urethane polymer, a polyoxyl polymer, etc.) The content of the electrostatic component (ionic compound) is preferably less than 10 parts by mass, more preferably 5 parts by mass or less, more preferably 0.001 to 3 parts by mass, more preferably 0.005 to 0.9 parts by mass, and most preferably 0.01 to 0.5 parts by mass. When it is within the above range, it is preferable to have both antistatic property and low pollution property.

< Organic polyoxyalkylene having an oxyalkylene chain> In the surface protective film of the present invention, the above-mentioned adhesive composition preferably contains an organopolyoxane having an oxyalkylene chain, and contains an oxyalkylene group. The side chain organic polyoxane is preferred. It is presumed that by using the aforementioned organopolyoxane, the surface free energy of the surface of the adhesive is lowered to achieve light peeling.

The above organopolyoxane can be suitably used in the well-known organopolyoxane having a polyoxyalkylene main chain, but it is preferably the one represented by the following formula. [Chemical 3] (wherein R ₁ and/or R ₂ has an oxygen alkylene chain having 1 to 6 carbon atoms; and the alkylene group in the above oxygen alkyl chain may be linear or branched, and the terminal of the above oxygen alkyl chain may be The alkoxy group may also be a hydroxyl group. Further, any of R ₁ or R ₂ may be a hydroxyl group or an alkyl group or an alkoxy group, and a part of the alkyl group or the alkoxy group may be a hetero atom-substituted functional group. n is an integer from 1 to 300.)

The above organopolyoxyalkylene is used as a main chain comprising a site containing a decane (a oxane moiety), and an oxyalkylene chain is bonded to the end of the main chain. It is presumed that by using the organooxane of the above-described oxyalkylene chain, for example, the compatibility between the (meth)acrylic polymer and the ionic compound is balanced to achieve light peeling.

Further, in the present invention, for example, the following structure can be used as the organopolysiloxane. Specifically, R ₁ and/or R ₂ in the formula has an oxyalkylene chain containing a hydrocarbon group having 1 to 6 carbon atoms, and the oxyalkylene chain may, for example, be an oxymethylene group, an oxygen-extended ethyl group or an oxygen-extended group. The base, the oxygen-extended butyl group, etc., preferably with an oxygen-extended ethyl group or an oxygen-extended propyl group. Further, when both of R ₁ and R ₂ have an oxyalkylene chain, they may be the same or different. [Chemical 4]

Further, the hydrocarbon group of the oxygen alkylene chain may be linear or branched.

Further, the terminal of the oxyalkylene chain may be an alkoxy group or a hydroxyl group, and among them, an alkoxy group is preferred. When the separator is attached to the surface of the adhesive layer for the purpose of protecting the adhesive surface, the organic polyoxyalkylene having a hydroxyl group at the end interacts with the separator to adhere (peel) force when the separator is peeled off the surface of the adhesive layer. There will be a rise.

Further, n is an integer of 1 to 300, preferably 10 to 200, more preferably 20 to 150. When n is in the above range, it is preferable to balance the compatibility with the matrix polymer. Further, the molecule may have a reactive substituent such as a (meth)acrylinyl group, an allyl group or a hydroxyl group. The above organopolyoxane may be used singly or in combination of two or more.

Specific examples of the organopolyoxane of the aerobic alkylene chain include, for example, commercially available products under the trade names of X-22-4952, X-22-4272, X-22-6266, KF-6004, and KF-. 889 (above, Shin-Etsu Chemical Co., Ltd.), BY16-201, SF8427 (above, TORAY-Dow Corning Co., Ltd.), IM22 (made by Asahi Kasei WACKER Co., Ltd.), and the like. These compounds may be used singly or in combination of two or more.

Further, in addition to the organic oxirane having a main chain aoxyalkylene chain (bond), an organic oxane having a side chain oxyalkylene chain (bonding) may be used, and a side chain is used as compared with the main chain. The organic oxirane of the aerobic alkylene chain is preferable in that it is easy to achieve both antistatic property and low pollution. As the above-mentioned organopolyoxane, a well-known organopolyoxane having a polyoxyalkylene side chain can be suitably used, but it is preferably the following formula. [Chemical 5] (wherein R ₁ is a monovalent organic group, R ₂ , R ₃ and R ₄ are an alkylene group, R ₅ is a hydrogen or an organic group, and m and n are integers of 0 to 1000. However, m, n are not simultaneously It is 0. a and b are integers from 0 to 100. However, a and b cannot be 0 at the same time.)

Further, in the present invention, for example, the following structure can be used as the organopolysiloxane. Specifically, R ₁ in the formula may, for example, be an alkyl group such as a methyl group, an ethyl group or a propyl group; an aryl group such as a phenyl group or a tolyl group; or a monovalent organic group of an aralkyl group such as a benzyl group or a phenethyl group; The base may also have a substituent such as a hydroxyl group. As the R ₂ , R ₃ and R _{4 ,} a methylene group having a carbon number of 1 to 8 such as a methylene group, an exoethyl group or a propyl group can be used. Here, R ₃ and R ₄ are different alkylene groups, and R ₂ may be the same as or different from R ₃ or R ₄ . In order to increase the concentration of the ionic compound which is soluble in the side chain of the polyoxyalkylene, R ₃ and R ₄ are preferably either ethyl or propyl. R ₅ may, for example, be a monovalent organic group such as an alkyl group such as a methyl group, an ethyl group or a propyl group or a mercapto group such as an ethyl fluorenyl group or a propyl group, or a substituent such as a hydroxyl group. These compounds may be used singly or in combination of two or more. Further, the molecule may have a reactive substituent such as a (meth)acrylinyl group, an allyl group or a hydroxyl group. Among the above organic oxoxanes having a polyoxyalkylene side chain, it is presumed that an organic oxirane having a polyoxyalkylene side chain having a hydroxyl group terminal is easy to obtain a balance of compatibility. [Chemical 6]

Specific examples of the above-mentioned organic oxirane include, for example, commercially available products such as KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, and KF-640. , KF-642, KF-643, KF-6022, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, X-22-2516 (above, Shin-Etsu Chemical Industry Co., Ltd.) SF8428, FZ-2162, SH3749, FZ-77, L-7001, FZ-2104, FZ-2110, L-7002, FZ-2122, FZ-2164, FZ-2203, FZ-7001, SH8400 , SH8700, SF8410, SF8422 (above, TORAY (Dow Corning), TSF-4440, TSF-4441, TSF-4445, TSF-4450, TSF-4446, TSF-4452, TSF-4460 (manufactured by Momentive Performance Materials) ), BYK-333, BYK-307, BYK-377, BYK-UV3500, BYK-UV3570 (BIG Chemie (manufactured by Japan), etc.) These compounds may be used alone or in combination of two or more.

The HLB (Hydrophile-Lipophile Balance) value of the above-mentioned organodecane used in the present invention is preferably from 1 to 16, more preferably from 3 to 14. When the HLB value is out of the above range, the contamination of the object to be attached is deteriorated.

For example, the above-mentioned organic polymer (for example, a (meth)acrylic polymer, a urethane polymer, a polyoxyl polymer, etc.) as a main component of the above-mentioned adhesive composition with respect to 100 parts by mass The content of the polyoxyalkylene is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, still more preferably 0.05 to 1 part by mass, most preferably 0.05 to 0.5 part by mass. When it is in the above range, it is easy to have both antistatic property and light peelability (repeelability), which is preferable.

The above-mentioned adhesive composition may contain a polyoxyalkylene chain-containing compound which is a polyether component but does not contain an organopolysiloxane. In particular, when the surface protective film is peeled off from the optical member and then the optical member is attached to the other member with an adhesive or an adhesive, it can improve the wettability of the adhesive or the adhesive, and is preferably used.

Specific examples of the polyoxyalkylene chain-containing compound containing no organopolysiloxane described above include polyoxyalkylene alkylamines, polyoxyalkylene diamines, polyoxyalkylene fatty acid esters, and polyoxygen compounds. Alkylene sorbitan fatty acid ester, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether, polyoxyalkylene phenyl allyl ether, etc. Nonionic surfactant; polyoxyalkylene ether sulfate, polyoxyalkylene ether phosphate, polyoxyalkylene phenyl ether sulfate, polyoxyalkylene phenyl An anionic surfactant such as an ether phosphate; other, a cationic surfactant having a polyoxyalkylene chain (polyalkylene oxide chain) or a two-ionic surfactant, a polyether compound having a polyoxyalkylene chain (and derivatives thereof), acrylic acid compounds having polyoxyalkylene chains (and derivatives thereof), and the like. Further, the polyoxyalkylene chain-containing monomer may be blended in the acrylic polymer as a polyoxyalkylene chain-containing compound. The polyoxyalkylene chain-containing compound may be used singly or in combination of two or more.

Specific examples of the polyether compound having the above polyoxyalkylene chain include a block copolymer of polypropylene glycol (PPG)-polyethylene glycol (PEG), a block copolymer of PPG-PEG-PPG, and PEG-PPG. A block copolymer of PEG or the like is exemplified. The derivative of the above polyether compound having a polyoxyalkylene chain may be an etherified propyl group-terminated compound (PPG monoalkyl ether, PEG-PPG monoalkyl ether, etc.), and the terminal is acetylated. The oxygen-containing propyl group compound (terminal acetophenone PPG, etc.) and the like are exemplified.

Further, specific examples of the polyoxyalkylene chain-containing acrylic compound include a (meth)acrylate polymer having an alkylene group. In the case of the above oxygen-extended alkyl group, when an ionic compound is used as an antistatic component, from the viewpoint of coordination of the ionic compound, the addition molar number of the oxygen-desene unit is preferably from 1 to 50, and from 2 to 30. Good, 2~20 is better. Further, the terminal of the oxyalkylene chain may be an original hydroxyl group, or may be substituted with an alkyl group, a phenyl group or the like.

The monomer unit (component) of the above-mentioned (meth) acrylate polymer having an alkylene group is preferably a polymer containing an alkylene oxide (meth) acrylate, and the above alkyl (meth) acrylate Specific examples of the (meth) acrylate containing a glycol group include methoxy-diethylene glycol (meth) acrylate and methoxy-triethylene glycol (A). Methoxy-polyethylene glycol (meth) acrylate type such as acrylate; ethoxy-diethylene glycol (meth) acrylate, ethoxy-triethylene glycol (meth) acrylate Ethoxy-polyethylene glycol (meth) acrylate type; butoxy-diethylene glycol (meth) acrylate, butoxy-triethylene glycol (meth) acrylate and other butoxy - polyethylene glycol (meth) acrylate type; phenoxy-polyethylene glycol (phenoxy-diethylene glycol (meth) acrylate, phenoxy-triethylene glycol (meth) acrylate, etc. Alcohol (meth) acrylate type; 2-ethylhexyl-polyethylene glycol (meth) acrylate, nonyl phenol-polyethylene glycol (meth) acrylate type, methoxy-dipropylene glycol (A Methoxy-polypropylene glycol (meth) acrylate type, etc.

Further, as the monomer unit (component), other monomer units (components) other than the alkyl (meth)acrylate may be used. Specific examples of the other monomer component include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and second butyl (meth)acrylate. ) Third butyl acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylate Isooctyl ester, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, An acrylate and/or methacrylate having an alkyl group having 1 to 14 carbon atoms such as n-tridecyl (meth)acrylate or n-tetradecyl (meth)acrylate.

In addition, as the monomer unit (component) other than the alkyl (meth)acrylate, a carboxyl group-containing (meth) acrylate or a phosphate group-containing (meth) acrylate may be suitably used. a cyano group-containing (meth) acrylate, a vinyl ester, an aromatic vinyl compound, an acid anhydride group-containing (meth) acrylate, a hydroxyl group-containing (meth) acrylate, and a decyl group-containing (meth) group Acrylate, amine group-containing (meth) acrylate, epoxy group-containing (meth) acrylate, N-propylene fluorenyl porphyrin, vinyl ether, and the like.

In a preferred embodiment, the polyoxyalkylene chain-containing compound containing no organopolyoxyalkylene is at least a portion of a compound having a (poly)oxyethylidene chain. By blending the compound containing the (poly)oxyethylidene chain, the compatibility of the matrix polymer with the antistatic component can be improved, and the migration to the article can be preferably suppressed, and the adhesion with low pollution can be obtained. Agent composition. Among them, in particular, when a block copolymer of PPG-PEG-PPG is used, an adhesive excellent in low contamination can be obtained. The polyethylene oxide chain-containing compound has a mass of (poly)ethylene oxide chain of 5 to 90% by mass based on the total of the polyoxyalkylene chain-containing compound not containing the organopolysiloxane. Preferably, it is preferably 5 to 85% by mass, more preferably 5 to 80% by mass, and most preferably 5 to 75% by mass.

The molecular weight of the polyoxyalkylene chain-containing compound containing no organopolyoxyalkylene is suitably 5% or more, preferably 200 to 30,000, more preferably 200 to 10,000, and usually It is ideal to use 200~5000. When the Mn is more than 50,000, the compatibility with the (meth)acrylic polymer is lowered, and the adhesive layer tends to be whitened. When Mn is less than 200, it becomes easy to cause contamination by the above polyoxyalkylene compound. Here, the number average molecular weight (Mn) herein means a polystyrene-converted value measured by GPC (gel permeation chromatography).

In addition, specific examples of the commercially available product of the polyoxyalkylene chain-containing compound containing no organic polyoxane may be, for example, ADEKA Pluronic 17R-4 or ADEKA Pluronic 25R-2 (all manufactured by ADEKA). EMULGEN 120 (manufactured by Kao Corporation), AQUALON HS-10, KH-10, NOIGEN EA-87, EA-137, EA-157, EA-167, EA-177 (above, manufactured by Daiichi Kogyo Co., Ltd.) and the like.

The content of the polyoxyalkylene chain-containing compound containing no organopolyoxyalkylene may be, for example, 0.005 to 20 parts by mass, and preferably 0.01, per 100 parts by mass of the (meth)acrylic polymer. ~10 parts by mass, preferably 0.03 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, most preferably 0.1 to 0.9 parts by mass. When it is in the above range, it is easy to have both wettability and low contamination to the object to be attached.

< Crosslinking Agent> In the surface protective film of the present invention, the adhesive composition preferably contains a crosslinking agent. Further, in the present invention, the above-mentioned adhesive composition is used as an adhesive layer. For example, when the above-mentioned (meth)acrylic polymer is contained in the above-mentioned adhesive composition, the constituent unit of the (meth)acrylic polymer, the composition ratio, the selection and addition ratio of the crosslinking agent, and the like can be appropriately adjusted. Further, cross-linking is carried out to obtain a surface protective film (adhesive layer) which is more excellent in heat resistance.

As the crosslinking agent used in the present invention, an isocyanate compound, an epoxy compound, a melamine resin, an anthracene derivative, a metal chelate compound or the like can be used, and an isocyanate compound is particularly preferable. Further, these compounds may be used singly or in combination of two or more.

Examples of the isocyanate compound include aliphatic polyisocyanates such as trimethylene diisocyanate, butanediol diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate, and cyclopentyl diisocyanate. An aromatic isocyanate such as an alicyclic isocyanate such as cyclohexyl diisocyanate or isophorone diisocyanate (IPDI), 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate or decyl diisocyanate (XDI) And the aforementioned isocyanate compound is an allophanate bond, a diurea bond, an iso-cyanuric bond, a uretdione bond, a urea bond, a carbodiimide bond, a uretone imine bond,㗁 Modified polyisocyanate modified body such as oxadiazinetrione bond. Commercially available products include, for example, trade names TAKENATE 300S, TAKENATE 500, TAKENATE 600, TAKENATE D165N, TAKENATE D178N (above, Takeda Pharmaceutical Co., Ltd.), Sumidur T80, Sumidur L, Desmodur N3400 (above, manufactured by Bayer Urethane Co., Ltd.), Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (above, manufactured by Polyurethane Industrial Co., Ltd., Japan). These isocyanate compounds may be used singly or in combination of two or more kinds thereof, or a bifunctional isocyanate compound or a trifunctional or higher isocyanate compound may be used in combination. By using a crosslinking agent in combination, it is possible to achieve both adhesion and resistance to back-reflection (adhesion to a curved surface), and a surface protective film which is more excellent in reliability can be obtained.

In addition, when a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound are used in combination as the isocyanate compound, it is preferable to use a [2-functional isocyanate compound] / [3 functional or higher in terms of a blend ratio (mass ratio) of the two compounds. The isocyanate compound] (mass ratio) is blended in a manner of 0.1/99.9 to 50/50, and 0.1/99.9 to 20/80 is preferable, 0.1/99.9 to 10/90 is more preferable, and 0.1/99.9 to 5/95 is further Better, 0.1/99.9~1/99 is the best. The blending is carried out by adjusting to the above range, and it is an adhesive layer which is excellent in adhesion and reversibility, and is preferable.

The epoxy compound may, for example, be N,N,N',N'-tetraepoxypropyl-m-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) or 1,3-double (manufactured by Mitsubishi Gas Chemical Co., Ltd.). N,N-diepoxypropylaminomethyl)cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like.

The melamine-based resin may, for example, be hexamethylol melamine or the like. The anthracycline derivative is exemplified by a commercially available product name of HDU, TAZM, TAZO (above, manufactured by Mutual Pharmaceutical Co., Ltd.).

Examples of the metal component of the metal chelate compound include aluminum, iron, tin, titanium, nickel, and the like, and examples of the chelate synthesis include acetylene, ethyl acetonate acetate, and ethyl lactate.

The content of the crosslinking agent used in the present invention is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, per 100 parts by mass of the (meth)acrylic polymer used for the acrylic pressure-sensitive adhesive. It is preferably 0.5 to 10 parts by mass, and preferably 1.0 to 6 parts by mass. When the content is less than 0.01 parts by mass, the crosslinking formation state by the crosslinking agent is insufficient, the cohesive force of the obtained adhesive layer becomes small, and sufficient heat resistance is not obtained, and the residual rubber is also caused. tendency. On the other hand, when the content is more than 20 parts by mass, the cohesive force of the polymer is large, the fluidity is lowered, and the wetting of the object to be attached (for example, a polarizing plate) is insufficient, and the coating is adhered to the adhesive layer (adhesive layer). There is a tendency for the cause of swelling to occur between the agent composition layers. Further, when the amount of the crosslinking agent is high, the peeling static characteristics tend to be lowered. Further, these crosslinking agents may be used singly or in combination of two or more kinds.

The above-mentioned adhesive composition may further contain a crosslinking catalyst which can carry out any of the above crosslinking reactions more efficiently. Examples of the crosslinking catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, ginseng (acetonitrile) iron, ginseng-2,4-dione iron, and ginseng. (gly-2,4-dione) iron, ginseng (hepta-3,5-dione) iron, ginseng (5-methylhex-2,4-dione) iron, ginseng (xin-2,4- Diketone) iron, ginseng (6-methylheptane-2,4-dione) iron, ginseng (2,6-dimethylglyhen-3,5-dione) iron, ginseng (壬-2,4- Diketone) iron, ginseng (壬-4,6-dione) iron, ginseng (2,2,6,6-tetramethylhept-3,5-dione) iron, ginseng (tridecane-6, 8-dione) iron, ginseng (1-phenylbutane-1,3-dione) iron, ginseng (hexafluoroacetamidine) iron, ginseng (acetic acid ethyl acetate) iron, ginseng (acetamidine acetic acid - N-propyl) iron, ginseng (acetylacetate isopropyl) iron, ginseng (acetonitrile-n-butyl) iron, ginseng (acetic acid-t-butyl) iron, ginseng (acetonitrile acetic acid - third Butyl) iron, ginseng (methyl acetate) iron, ginseng (ethyl acetate) iron, ginseng (propionic acid-n-propyl) iron, ginseng (isopropyl acetate isopropyl) iron, ginseng ( Propionate-n-butyl) iron, ginseng (propionacetic acid-t-butyl) iron, ginseng (propionacetic acid-t-butyl) iron, ginseng (acetonitrile benzyl) iron, ginseng (C Dimethyl sulphate, iron, (Diethyl malonate) iron, trimethoxy iron, triethoxy iron, iron triisopropoxide chloride, such as iron and the second iron-based catalyst. These cross-linking catalysts may be used alone or in combination of two or more.

The content of the cross-linking catalyst is not particularly limited. For example, it is preferably about 0.0001 to 1 part by mass, and preferably 0.001 to 0.5 part by mass, per 100 parts by mass of the (meth)acryl-based polymer. When it is in the above range, the crosslinking reaction rate is fast when the adhesive layer is formed, and the life of the adhesive composition is also long, which is preferable.

Further, the above-mentioned adhesive composition may also contain an acrylic oligomer. The weight average molecular weight (Mw) of the acrylic oligomer is preferably 1,000 or more and less than 30,000, and more preferably 1,500 or more and less than 20,000, more preferably 2,000 or more and less than 10,000. The acrylic oligomer comprises a (meth)acrylic polymer which has a alicyclic structure (meth)acrylic monomer represented by the following formula as a monomer unit and is used as an acrylic adhesive. In this case, the function as a tackifying resin is exerted, the adhesion is improved, and the floating of the surface protective film is effectively suppressed. CH ₂ =C(R ¹ )COOR ² [wherein R ¹ is a hydrogen atom or a methyl group, and R ² is an alicyclic hydrocarbon group having an alicyclic structure]

In the above formula, the alicyclic hydrocarbon group R ² may, for example, be a cyclohexyl group, an isodecyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, a tricyclopentanyl group or a tricyclopentenyl group. An alicyclic hydrocarbon group or the like. Such an alicyclic hydrocarbon group-containing (meth) acrylate may, for example, be a cyclohexyl cyclohexyl (meth) acrylate, an isodecyl (meth) acrylate isodecyl ester, having a dicyclopentane An ester of an alkylcyclopentanyl (meth)acrylate or the like and an alicyclic alcohol of (meth)acrylic acid. By having a (meth)acrylic monomer having such a bulky structure as a monomer unit and present in the acrylic oligomer, the adhesion can be improved.

The content of the above-mentioned (meth)acrylic polymer is preferably 0.01 to 10 parts by mass, preferably 0.1 to 7 parts by mass, and preferably 0.2 to 5 by mass, based on 100 parts by mass of the above-mentioned (meth)acrylic polymer. More preferably, it contains 0.3~2 parts by mass. By using the content in the above range, it is possible to improve the adhesion to the object to be attached, and it is easy to obtain the effect of suppressing the floating, which is preferable.

Further, the above-mentioned adhesive composition may contain other well-known additives, and a powder such as a lubricant, a colorant, a pigment, a surfactant, a plasticizer, an adhesive agent, and a low amount may be appropriately added depending on the intended use. Molecular weight polymer, surface lubricant, leveling agent, antioxidant, preservative, light stabilizer, ultraviolet absorber, polymerization inhibitor, decane coupling agent, inorganic or organic filler, metal powder, particulate, foil Things and so on.

< Adhesive layer and surface protective film> The surface protective film of the present invention is obtained by forming the above-mentioned adhesive layer on the second surface of the substrate. In this case, the adhesive is generally applied after applying the adhesive composition. The cross-linking of the composition may also transfer the adhesive layer composed of the crosslinked adhesive composition to a substrate or the like.

Further, the method of forming the adhesive layer on the substrate is not particularly limited. For example, the adhesive composition is formed on the substrate by applying the adhesive composition (solution) to the substrate, drying and removing the polymerization solvent, and the like. . Thereafter, it may be cured for the purpose of adjusting the component transfer of the adhesive layer or adjusting the crosslinking reaction. Further, when the surface protective film is formed by applying the adhesive composition to the substrate, one or more solvents other than the polymerization solvent may be added to the adhesive composition to uniformly coat the substrate.

Further, as a method of forming the adhesive layer in the production of the surface protective film of the present invention, a well-known method for producing an adhesive tape can be used. Specific examples thereof include roll coating, gravure coating, reverse roll coating, roll brushing, spray coating, air knife coating, and extrusion coating using a die coater.

In the surface protection film of the present invention, the thickness of the adhesive layer is usually about 3 to 100 μm, and preferably about 5 to 50 μm. When the thickness of the adhesive layer is within the above range, it is preferable to obtain a suitable balance between re-peelability and adhesion.

Further, the total thickness of the surface protective film of the present invention is preferably from 1 to 400 μm, more preferably from 10 to 200 μm, and most preferably from 20 to 100 μm. When it is in the above range, the adhesive properties (removability, adhesion, etc.), workability, and appearance characteristics are excellent, and it is preferable. Further, the total thickness means a total thickness of all layers including a substrate, an adhesive layer, an antistatic layer, and an antistatic layer.

< Separator> In the surface protection film of the present invention, a spacer is attached to the surface of the adhesive layer for the purpose of protecting the adhesive surface as needed.

The material constituting the spacer is a paper or a plastic film, but a plastic film is preferably used from the viewpoint of excellent surface smoothness. The film is not particularly limited as long as it is a film that can protect the pressure-sensitive adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, and a polymethyl pentene film. A polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate film, or the like.

The thickness of the spacer is usually 5 to 200 μm, and preferably about 10 to 100 μm. When it is in the above range, it is preferable that the adhesiveness of the adhesive layer and the peeling workability of the self-adhesive layer are excellent. The separator may also be subjected to release and antifouling treatment by a polyfluorene-based, fluorine-based, long-chain alkyl or fatty acid amide-based release agent, cerium oxide powder, or the like, or a coating type or ruthenium may be applied as needed. Antistatic treatment such as combination and evaporation.

The optical member of the present invention is preferably protected by the aforementioned surface protective film. Since the surface protective film is excellent in antistatic property and stability over time of the peeling electrostatic potential, it can be used for surface protection (surface protection film) during processing, transportation, and shipping, and protects the optical member (polarized light). The surface of the board, etc.) is useful. In particular, it can be used in a plastic product or the like which is likely to generate static electricity, and is therefore very useful for an antistatic use in the field of optical electronic components in which static electricity is a serious problem. Example

In the following, several embodiments relating to the invention are described, but are not intended to limit the invention to those illustrated in the embodiments. In addition, the "parts" and "%" in the following descriptions or tables are based on the mass basis unless otherwise specified, and indicate solid components or active ingredients.

Further, each of the characteristics in the following description was measured or evaluated in the following manner.

< Measurement of Weight Average Molecular Weight (Mw)> The weight average molecular weight (Mw) was measured using a GPC apparatus (HLC-8220GPC) manufactured by Tosoh Corporation. The measurement conditions are as follows.

Sample concentration: 0.2% by mass (THF solution) Sample injection amount: 10 μl Dissolution: THF Flow rate: 0.6 ml/min Measurement temperature: 40 ° C Column: Sample column; TSKguardcolumn SuperHZ-H (1 branch) + TSKgel SuperHZM-H (2 branches) Reference column; TSKgel SuperH-RC (1 branch) ・Detector: Differential refractometer (RI) In addition, the weight average molecular weight is determined by the value of polystyrene. Further, when it is necessary to measure the number average molecular weight (Mn), the measurement is carried out in the same manner as the weight average molecular weight.

< Glass Transfer Temperature (Tg)> The glass transition temperature Tg (° C.) is obtained by the following literature using the following literature values of the glass transition temperature Tgn (° C.) of the homopolymer of each monomer.

Formula: 1/(Tg+273)=Σ[Wn/(Tgn+273)] [wherein, Tg(°C) is the glass transition temperature of the copolymer, Wn(-) is the mass fraction of each monomer, and Tgn (°C) is The glass transition temperature of the homopolymer of each monomer, and n is the kind of each monomer. Literature value: 2-ethylhexyl acrylate (2EHA): -70 ° C n-butyl acrylate (BA): -55 ° C 2-hydroxyethyl acrylate (HEA): -15 ° C 4-hydroxybutyl acrylate (HBA): -32 ° C Acrylic acid (AA): 106 ° C

In addition, the literature values refer to "Composite Design and New Use of Acrylic Resin" (published by the Central Business Development Center Publishing Department) and "Polymer Handbook" (John Wiley & Sons).

< Measurement of surface resistivity> A resistivity meter (Hiresta UP MCP-HT450 type manufactured by Mitsubishi Chemical Corporation, manufactured by Mitsubishi Chemical Corporation) was used in an ambient gas having a temperature of 23 ° C and a humidity of 50% RH, and the measurement was carried out in accordance with JIS-K-6911. Further, the surface resistivity (Ω/□) in the present invention is preferably 1.0 × 10 ¹¹ or less in the initial stage and at room temperature (23 ° C × 50% RH) for one week (7 days). Preferably, it is 5.0 × 10 ¹⁰ or less, more preferably 1.0 × 10 ¹⁰ or less. As the surface protective film which exhibits the surface resistivity in the above range, it is preferable to use a surface protective film which is used, for example, as a processing or conveyance process of an article which does not like static electricity such as a liquid crystal cell or a semiconductor device.

< Measurement of the polarizing plate peeling electrostatic potential (polarizing plate side)> The surface protective film 1 of each example was cut into a width of 70 mm and a length of 130 mm, and the release liner was peeled off, and as shown in FIG. A polarizing plate 20 (manufactured by Mitsubishi Rayon Co., Ltd., trade name "ACRYLATE", thickness: 1 mm, width: 70 mm, length: 100 mm), which is made of acryl plate 10 (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 70 mm, length) : 100 mm) The surface protective film 1 was pressed with a hand-held roller on the surface so that the end portion of one side protruded from the end portion of the polarizing plate 20 by 30 mm. The sample was allowed to stand in an environment of 23 ° C × 50% RH for one day, and then fixed to a predetermined position of the sample fixing table 30 having a height of 20 mm. The end portion of the surface protective film 1 which protruded from the polarizing plate 20 by 30 mm was fixed by an automatic winder (not shown), and peeled off at a peeling angle of 150° and a peeling speed of 10 m/min. The potential of the surface of the object (polarizing plate) which is generated at this time is measured by a potential measuring machine 40 (type "KSD-0103" manufactured by Kasuga Electric Co., Ltd.) which is fixed at a height of 100 mm from the center of the polarizing plate 20. The polarizing plate peels off the electrostatic potential." The measurement was carried out in an environment of 23 ° C and 50% RH. In addition, after leaving for one week (7 days) in an environment of 23 ° C × 50% RH, "the polarizing plate peeling electrostatic potential with time" was measured in the same manner as in the "initial polarizing plate peeling electrostatic potential". The measurement was carried out in an environment of 23 ° C and 50% RH. In addition, the "polarizing plate peeling electrostatic potential" is a peeling electrostatic potential from the antistatic layer and the adhesive layer constituting the surface protective film of the present invention, and contributes to antistatic property. The polarizing plate peeling electrostatic potential (kV) (absolute value, initial value, and elapsed time) in the present invention is preferably 0.8 or less, preferably 0.7 or less, more preferably 0.5 or less. When it is within the above range, it is possible to prevent damage such as liquid crystal display driving, for example, and it is preferable.

<Measurement of peeling electrostatic potential on the film side (antistatic layer side of the surface protective film)> The surface protective film 1 was applied from the polarizing plate 20 at a peeling angle of 150° and a peeling speed of 10 m/min, as in the measurement of the peeling electrostatic potential of the polarizing plate. Surface peeling. The electric potential of the surface protective film 1 which was produced at this time was measured by a potential measuring machine 40 (type "KSD-0103" manufactured by Kasuga Electric Co., Ltd.) which was fixed at a height of 100 mm from the center of the surface protective film 1, "the initial film side" Stripping the electrostatic potential". The measurement was carried out in an environment of 23 ° C and 50% RH. In addition, after leaving for one week (7 days) in an environment of 23 ° C × 50% RH, "the polarizing plate peeling electrostatic potential with time" was measured in the same manner as in the "initial polarizing plate peeling electrostatic potential". The measurement was carried out in an environment of 23 ° C and 50% RH. In addition, the "film-side peeling electrostatic potential" is a peeling electrostatic potential from the antistatic layer constituting the surface protective film of the present invention, and contributes to antistatic property. The film side peeling electrostatic potential (kV) (absolute value, initial value, and elapsed time) in the present invention is preferably 0.8 or less, preferably 0.7 or less, more preferably 0.5 or less. When it is in the above range, the surface protective film after peeling is not electrostatically charged and is excellent in workability, so that it is preferable.

<Measurement of slidability (dynamic friction)> The surface protection film was cut into a width of 70 mm and a length of 100 mm, and bonded to an acrylic plate (trade name "ACRYLATE", manufactured by Mitsubishi Rayon Co., Ltd., thickness: 1 mm, width: 70 mm) , length: 100mm), prepare test pieces. The back surface of the test piece (the surface of the antistatic layer) was placed face down on a smooth PET film which was kept horizontal, and a load of 1.5 kg was placed on the test piece. The test piece loaded with the load was attached to a tensile tester using a non-stretchable wire, and the test piece was horizontally stretched at a measurement temperature of 25 ° C at a tensile speed of 300 mm/min and a tensile distance of 300 mm. The average value (n=3) of the dynamic frictional force (N) applied to the test piece was taken. Further, the slidability (dynamic friction) (N) in the present invention is preferably 5 or less, more preferably 4.5 or less, still more preferably 4 or less. When it is in the above range, the slidability of the back surface of the substrate (the surface of the antistatic layer) is good when the article to which the surface protective film has been attached is treated, which is advantageous in terms of workability.

< Evaluation of Printing (Printing Adhesion)> After printing on the surface of the antistatic layer using X Stamper manufactured by Shachihata Co., Ltd. under a measurement environment of 23 ° C × 50% RH, Nichiban Co., Ltd. was attached from the top of the printing. CELLOTAPE (registered trademark) was peeled off at a peeling speed of 30 m/min and a peeling angle of 180°. After that, the surface after peeling was visually observed, and the case where 50% or more of the printing area was peeled off was evaluated as (poor printing property), and 50% or more of the printing area was not peeled off and remained as ○ (printing property was good).

Hereinafter, a method of preparing a sample (surface protective film) of the examples and the comparative examples will be described.

< Preparation of Solution for Antistatic Layer (1)> A polyester resin VYLONAL MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder was added to a mixed solvent of water/ethanol (1/3) as conductivity. Polymer polyaniline sulfonic acid (aqua-PASS, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co., Ltd.), melamine-based crosslinking agent (SUMIMAL M-50W, manufactured by Sumitomo Chemical Co., Ltd.) as a crosslinking agent, and as a lubricant The oleic acid decylamine is 100 parts by mass of the solid content of the binder, 75 parts by mass of the conductive polymer, and 5 parts by mass of the crosslinking agent based on the solid content, and the lubricant is The solid content was 30 parts by mass, and the mixture was stirred for about 20 minutes to be sufficiently mixed. In this manner, a solution for the antistatic layer (1) having an NV of about 0.4% was prepared (see Table 1).

< Preparation of Solution for Antistatic Layer (2)> A polyester resin VYLONAL MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder was added to a mixed solvent of water/ethanol (1/3) as conductivity. Polymer polyaniline sulfonic acid (aqua-PASS, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co., Ltd.) and melamine crosslinking agent (SUMIMAL M-50W, manufactured by Sumitomo Chemical Co., Ltd.) as a crosslinking agent, bonding agent The amount of the solid content is 100 parts by mass, the conductive polymer is 75 parts by mass in terms of the solid content, and the crosslinking agent is 5 parts by mass in terms of the solid content, and the mixture is stirred for about 20 minutes to be sufficiently mixed. In this manner, a solution for the antistatic layer (2) having an NV of about 0.4% was prepared (see Table 1).

< Preparation of Solution for Antistatic Layer (3)> A polyester resin VYLONAL MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder was added to a mixed solvent of water/ethanol (1/1) as conductivity. The polymer contains an aqueous solution (Bytron P, manufactured by HC Stark Co., Ltd.) containing poly(3,4-ethylenedioxythiophene) (PEDOT) 0.5% and polystyrene sulfonate (weight average molecular weight 150,000) (PSS) 0.8%. The amount of the solid content of the binder is 100 parts by mass, the amount of the conductive polymer is 50 parts by mass, and the melamine-based crosslinking agent (SUMIMAL M-50W, manufactured by Sumitomo Chemical Co., Ltd.) is 5 in terms of solid content. The mass parts were stirred for about 20 minutes to allow thorough mixing. In this manner, a solution for the antistatic layer (3) having an NV of about 0.4% was prepared (see Table 1). Further, the obtained antistatic layer (3) was visually confirmed for the presence of aggregates by a solution.

< Preparation of Solution for Antistatic Layer (4)> A polyester resin VYLONAL MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder was added to a mixed solvent of water/ethanol (1/3), and as a conductive material. Polyaniline sulfonic acid (aqua-PASS, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co., Ltd.), the binder is 100 parts by mass in terms of solid content, and the conductive polymer is calculated as solid content. 75 parts by mass, stirred for about 20 minutes to allow thorough mixing. In this manner, a solution for the antistatic layer (4) having an NV of about 0.4% was prepared (see Table 1).

[Table 1]

<Preparation of Substrate with Antistatic Layer> Transparent polyethylene terephthalate (PET) film (polyester film/base) having a thickness of 38 μm, a width of 30 cm and a length of 40 cm which has been subjected to corona treatment on one side (first side) The material of the antistatic layer (1) to (4) was applied to the corona-treated surface to have a thickness of 30 nm after drying. The coated product was dried by heating at 130 ° C for 1 minute to prepare a substrate with an antistatic layer having an antistatic layer on the first side of the PET film.

< Preparation of (meth)acrylic polymer 1 for an adhesive layer> In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, 95 parts by mass of 2-ethylhexyl acrylate was added ( 2EHA), 5 parts by mass of 2-hydroxyethyl acrylate (HEA), 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator, and 150 parts by mass of ethyl acetate, while slowly Nitrogen gas was introduced while stirring, and the liquid temperature in the flask was maintained at about 65 ° C for 6 hours to prepare a (meth)acrylic polymer 1 solution (40% by mass). The (meth)acrylic polymer 1 had a weight average molecular weight of 560,000 and a glass transition temperature (Tg) of -68 ° C (see Table 2).

<Preparation of (meth)acrylic polymers 2 and 3 for adhesive layer> The (meth)acrylic polymerization was carried out in the same manner as in the preparation method of the (meth)acrylic polymer 1 for the adhesive layer. Items 2 and 3. Further, the components other than the monomer component were blended in the same amount as the (meth)acrylic polymer 1 (see Table 2).

[Table 2]

[Preparation of Acrylic Adhesive (1) Solution] The (meth)acrylic polymer 1 solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass (solid content: 100 parts by mass) To the solution, 3.5 parts by mass (3.5 parts by mass of solid component) of hexamethylene isocyanate trimeric isocyanate (manufactured by Nippon Polyurethane Co., Ltd., Coronate HX: C/HX) was added as a crosslinking agent. And 3 parts by mass (solid content: 0.03 parts by mass) of dibutyltin dilaurate (dibutyltin dilaurate) (1% by mass ethyl acetate solution) as a crosslinking catalyst, and mixing and stirring to prepare an acrylic adhesive Solution (1) solution (refer to Table 3).

[Preparation of Acrylic Adhesive (2) to (4) Solution] The acrylic acid-based polymer 1 to 3 was used in the same manner as in the preparation method of the acrylic adhesive (1) solution, and acrylic acid was obtained. Adhesive (2) ~ (4) solution (refer to Table 3).

[table 3]

[Preparation of a urethane-based adhesive (5) solution] A urethane-based adhesive (5) solution is obtained by blending a polyol, a crosslinking agent, a catalyst, and a diluent solvent under the following conditions: The alcohol is a polyol having three hydroxyl groups, "PREMINOL S3011" (manufactured by Asahi Glass Co., Ltd., Mn = 10000), 85 parts by mass, and a three-hydroxyl polyol "SANNIX GP3000" (manufactured by Sanyo Chemical Co., Ltd., Mn = 3000) 13 parts by mass. 2 parts by mass of a polyol having three hydroxyl groups, "SANNIX GP1000" (manufactured by Sanyo Chemical Co., Ltd., Mn = 1000); and a crosslinking agent: 18 parts by mass of an isocyanate compound (Coronate HX, manufactured by Japan Polyurethane Co., Ltd.); The medium was 0.04 parts by mass of acetonitrile iron (III) (e (acetonitrile) iron) (manufactured by Tokyo Chemical Industry Co., Ltd.); and the diluted solvent was 210 parts by mass of ethyl acetate. Further, the raw material of the urethane-based adhesive solution was a raw material having a concentration of 100% except for the solvent (refer to Table 4).

[Preparation of a urethane-based adhesive (6) solution] In addition to 0.1 mass part of an organooxyalkylene chain (KF-6004, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.3 parts by mass of anti-oxyalkylene chain 1-ethyl-3-methylimidazolidinium bis(fluorosulfonyl) quinone imine (EMIFSI, manufactured by Dai-ichi Kogyo Co., Ltd.) having the electrostatic component and the above-mentioned urethane-based adhesive (5) The solution of the urethane-based adhesive (6) was prepared in the same manner as the solution (refer to Table 4).

[Table 4]

[Preparation of a solution of a polyoxygenated adhesive (7)] A polyoxynoxy-based adhesive "X-40-3229" having a solid content of 100 parts by mass (solid content: 60% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass of platinum catalyst "CAT-PL-50T" (manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 parts by mass of toluene as a solvent to obtain a solution of a polyoxygen-based adhesive (7) (see Table 5) .

[Preparation of the solution of the polyoxygen-based adhesive (8)] The polyoxynoxy-based adhesive "X-40-3229" (solid content: 60% by mass), manufactured by Shin-Etsu Chemical Co., Ltd. ), 0.5 parts by mass of a platinum catalyst "CAT-PL-50T" (manufactured by Shin-Etsu Chemical Co., Ltd.), 0.2 parts by mass of an organic alkyl oxane having an oxygen-lowering alkyl chain (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.3 parts by mass of an antistatic component lithium bis(trifluoromethanesulfonyl) quinone imine (LiN(CF ₃ SO ₂ ) ₂ :LiTFSI, manufactured by Tokyo Chemical Industry Co., Ltd.), and 100 parts by mass of a solvent toluene to obtain a polyfluorene Oxygen-based adhesive (8) solution (refer to Table 5).

[table 5]

< Example 1><Preparation of surface protective film> The acrylic adhesive (1) solution was applied to a surface of a substrate having the antistatic layer (substrate with an antistatic layer) opposite to the antistatic layer. (The second side of the substrate) was heated at 130 ° C for 1 minute to form an adhesive layer having a thickness of 15 μm. Next, a polyethylene terephthalate film (thickness 25 μm) which has been subjected to polysilicon treatment as a separator on one side is attached to the surface of the above-mentioned adhesive layer with its polyoxygenated surface to form a surface. Protective film (refer to Tables 1-3 and 6).

< Examples 2 to 6 and Comparative Examples 1 to 4> A surface protective film was produced in the same manner as in Example 1 (see Tables 1 to 3 and 6).

< Example 7><Preparation of surface protective film> The solution of the above-described urethane-based adhesive (5) was applied to the above-mentioned substrate having an antistatic layer (substrate with an antistatic layer) and antistatic On the opposite side of the layer, it was heated at 130 ° C for 1 minute to form an adhesive layer having a thickness of 15 μm. Next, a polyethylene terephthalate film (thickness 25 μm) which has been subjected to polysilicon treatment as a separator on one side is attached to the surface of the above-mentioned adhesive layer with its polyoxygenated surface to form a surface. Protective film (refer to Tables 1, 4 and 6).

< Example 8> A surface protective film was produced in the same manner as in Example 9 except that the urethane-based pressure-sensitive adhesive (6) solution was used (see Tables 1, 4 and 6).

< Example 9><Preparation of surface protective film> The solution of the above polyoxygenated adhesive (7) was applied to the substrate (antistatic layer-attached substrate) having the antistatic layer as opposed to the antistatic layer. On the surface, it was heated at 150 ° C for 1 minute to form an adhesive layer having a thickness of 15 μm. Next, a polyethylene terephthalate film (thickness 25 μm) which has been subjected to a fluorine treatment as a separator on one side is adhered to the surface of the above-mentioned adhesive layer with a polyfluorinated surface to form a surface protection. Film (refer to Tables 1, 5 and 6).

< Example 10> A surface protective film was produced in the same manner as in Example 9 except that the above-mentioned polyoxynitride-based adhesive (8) solution was used (see Tables 1, 5 and 6).

Table 6 shows the results of various measurements and evaluations of the surface protective films of the examples and the comparative examples.

In addition, the abbreviations in Tables 2 to 5 are explained below. The abbreviations in other tables are based on the examples and comparative examples. [Monomer] 2EHA: 2-ethylhexyl acrylate BA: n-butyl acrylate HEA: 2-hydroxyethyl acrylate HBA: 4-hydroxybutyl acrylate AA: Acrylic acid

[ Organic Polyoxane] KF353: Organic Polyoxane with Oxygen Streptane Chain (HLB Value: 10) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-353) KF6004: Organic Polymer with Oxyl-Strept Chain Hexane (HLB value: 9) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6004)

[ Polyether component] HS10: First industrial pharmaceutical company, trade name "AQUALON HS-10" (anionic surfactant) EA137: First Industrial Pharmaceutical Co., Ltd., trade name "NOIGEN EA-137" (nonionic surfactant)

[ Antistatic component (ionic compound)] LITFSI: lithium bis(trifluoromethanesulfonyl) quinone imine (alkali metal salt, manufactured by Tokyo Chemical Industry Co., Ltd.) (active ingredient 100%) BMPTFSI: 1-butyl-3 -methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (ionic liquid, manufactured by Sigma Aldrich, liquid at 25 ° C) (active ingredient 100%)

[ Crosslinking agent] C/HX: Heterotrimeric cyanide of hexamethylene diisocyanate (manufactured by Japan Polyurethane Co., Ltd., trade name: Coronate HX) (active ingredient 100%) TAKENATE 600:1,3 - bis(methyl isocyanate) cyclohexane (manufactured by Mitsui Chemicals, Inc., trade name: TAKENATE 600) (active ingredient 100%)

[Table 6]

From the evaluation results of the above Table 6, it was confirmed that all of the examples were based on the antistatic property of the antistatic layer and the stability of the peeling electrostatic potential (surface resistivity and film side peeling electrostatic potential) and printing adhesion. Excellent in all aspects. Further, it was confirmed that the example in which the lubricant was used in forming the antistatic layer was excellent in lubricity, and the antistatic property (polarizing plate peeling electrostatic potential) of the example in which the antistatic component was used in forming the adhesive layer was also observed. excellent.

On the other hand, in the comparative example, according to the evaluation results of the above Table 6, the antistatic layer was not formed from the desired antistatic agent composition, so that the antistatic property due to the antistatic layer and the peeling electrostatic potential were not obtained. The stability of time and the characteristics of all the characteristics of printing adhesion.

1‧‧‧Surface protection film
10‧‧‧Acrylic sheet
20‧‧‧Polar plate
30‧‧‧sample fixed table
40‧‧‧potentiometer
11‧‧‧Antistatic layer
12‧‧‧Substrate
13‧‧‧Adhesive layer

Fig. 1 is a schematic cross-sectional view showing a structural example of a surface protective film of the present invention. Fig. 2 is an explanatory view showing a method of measuring the peeling electrostatic potential.

no

Claims (7)

A surface protection film characterized by comprising: a substrate having a first surface and a second surface; an antistatic layer disposed on the first surface of the substrate; and an adhesive layer using an adhesive composition And forming the second surface of the substrate; the antistatic layer is formed by using an antistatic agent composition containing polyaniline sulfonic acid as a conductive polymer component and as a binder A polyester resin and a melamine-based crosslinking agent as a crosslinking agent. The surface protective film according to claim 1, wherein the antistatic agent composition is selected from the group consisting of fatty acid guanamine, fatty acid ester, polyfluorene-based lubricant, fluorine-based lubricant, and wax-based lubricant. At least one of them is used as a lubricant. The surface protective film of claim 1 or 2, wherein the substrate is a polyester film. The surface protection film according to any one of claims 1 to 3, wherein the adhesive composition contains a group selected from the group consisting of an acrylic adhesive, an urethane adhesive, and a polyoxygen adhesive. At least one of them. The surface protection film according to any one of claims 1 to 4, wherein the aforementioned adhesive composition contains an antistatic component. An optical member characterized in that it is protected by a surface protective film according to any one of claims 1 to 5. A method of producing a surface protective film, characterized in that the surface protective film is as described in any one of claims 1 to 5, the manufacturing method comprising the steps of: modulating an antistatic agent composition, the antistatic agent The composition contains polyaniline sulfonic acid as a conductive polymer component, a polyester resin as a binder, and a melamine-based crosslinking agent as a crosslinking agent; and a step of preparing an antistatic layer, which is the first of the foregoing substrates The antistatic agent composition was applied to the surface and dried to prepare an antistatic layer.