TW201639934A - Surface protection film, and optical member - Google Patents

Abstract

Provided are a surface protection film with which it is possible to achieve anti-static properties and temporal stability in peeling electrostatic potential, and an optical member. The surface protection film of the present invention is provided with a base material having a first surface and a second surface, an anti-static layer provided on the first surface of the base material, and an adhesive layer formed from an adhesive composition on the second surface of the base material, wherein the surface protection film is characterized in that: the anti-static layer is formed from an anti-static composition containing polyaniline sulfonic acid and polythiophenes doped by polyanions as conductive polymer components, and a binder; and the mixture ratio (mass ratio) of the polyaniline sulfonic acid and the polythiophenes doped by polyanions is 90:10-10:90.

Description

Surface protection film and optical member Technical field

The present invention relates to 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 a second surface provided on the second surface of the substrate The adhesive layer, in detail, relates to a surface protective 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. In particular, it is useful as a surface protective film for the purpose of protecting surfaces such as a polarizing plate, a wavelength plate, a phase difference plate, an optical compensation film, a reflection sheet, and a brightness enhancement film used for a liquid crystal display or the like. .

Background technique

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 bonded to the object (protected body) through the adhesive layer, thereby protecting the object from damage or contamination during processing, transportation, and the like. For example, a panel of a liquid crystal display is provided by a polarizing plate or a wavelength plate through an adhesive layer. The optical member is formed by bonding to the liquid crystal cell. In the manufacture of the liquid crystal display panel, the polarizing plate bonded to the liquid crystal cell is temporarily wound into a roll, and is taken out from the roll, and then cut into a desired size corresponding to the shape of the liquid crystal cell. Here, in order to prevent the polarizing plate from being scratched by the conveyance roller or the like in the intermediate step, there is a measure for bonding the surface protection film to one surface or both surfaces (typically one side) of the polarizing plate. 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 rubbing 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, and when a voltage is applied to the liquid crystal in a state where the static electricity is left, there is a fear that the alignment of the liquid crystal molecules or the occurrence of panel defects may occur. Moreover, the presence of static electricity is a cause of attracting dust and causing a decrease in workability. Therefore, a method of performing antistatic treatment on the surface protective film has been carried out, 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 Document 1).

Further, in recent years, PEDOT (poly(3,4-ethylenedioxythiophene)/PSS (polystyrenesulfonic acid)) has been used for the conductive polymer used for imparting antistatic function to the surface layer of the surface protective film. Polythiophene type) is a water-dispersible type. However, when an antistatic layer is formed using the above conductive polymer, PSS (corresponding to a dopant) will be detached from PEDOT over time, causing surface resistivity or peeling off static electricity. The position rises, etc., and there are doubts about problems such as an increase in surface resistivity (deterioration) caused by oxidative degradation or photodegradation. When the rate rises (deterioration) or the like, static electricity is generated when the surface protective film is peeled off from the object, and there is a concern that a problem arises.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-255332

Summary of invention

Accordingly, the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a surface protective film and an optical member which can achieve antistatic properties and temporal stability of a peeling electrostatic potential.

In other words, the surface protection film of the present invention has a substrate having a first surface and a second surface, an antistatic layer provided on the first surface of the substrate, and a second surface formed on the substrate and An adhesive layer formed of an adhesive composition characterized in that the antistatic layer is formed of an antistatic agent composition containing polyaniline sulfonic acid as a conductive polymer component. And a polythiophene doped with a polyanion, and a binder; the blending ratio (mass ratio) of the polyaniline sulfonic acid to the polyanion-doped polythiophene is 90:10 to 10:90.

In the surface protective film of the present invention, the polythiophene is preferably poly(3,4-ethylenedioxythiophene) (PEDOT).

In the surface protective film of the present invention, the polyanion is preferably polystyrenesulfonic acid (PSS).

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

In the surface protection film of the present invention, the antistatic agent composition preferably contains a melamine crosslinking agent and/or an isocyanate 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 protection film of the present invention, the adhesive composition preferably contains a polyether compound.

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.

In the surface protection film of the present invention, the antistatic layer provided on the first surface (back surface) of the substrate is formed of an antistatic agent composition containing a specific conductive polymer component in a specific ratio, whereby It may be used to provide an antistatic property or peeling static which can be achieved by the aforementioned antistatic layer. A surface protective film and an optical member having a potential stability over time.

1‧‧‧Surface protection film

10‧‧‧Acrylic sheet

11‧‧‧Electrified prevention layer

12‧‧‧Substrate

13‧‧‧Adhesive layer

20‧‧‧Polar plate

30‧‧‧sample fixed table

40‧‧‧potentiometer

Fig. 1 is a schematic cross-sectional view showing a configuration 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.

Form for implementing the invention

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

<Overall construction of surface protection 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 useful as a processing or handling optical component (for example, as a liquid crystal display panel such as a polarizing plate or a wave plate). It is preferable to protect the surface protective film on the surface of the optical member when the optical member used for the element is used. Typically, the adhesive layer of the surface protective film is continuously formed, but is not limited by the form, and may be an adhesive layer formed with a regular or random pattern such as a dot or a stripe. Further, the surface protective film disclosed herein may be in the form of a roll or a sheet.

A typical configuration 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 12, and a second surface provided on the substrate 12 (on the opposite side to the antistatic layer 11). Adhesive layer 13 of the surface). The surface protective film 1 is used by attaching the adhesive layer 13 to a subject (protecting object, for example, a surface of an optical member such as a polarizing plate). The surface protective film 1 before use (that is, attached to the front of the object) may also be on the surface of the adhesive layer 13 The attached surface of the body is protected by at least a release liner which is a release surface on the side of the adhesive layer 13. Alternatively, the surface protective film 1 may be wound into a roll shape, and the adhesive layer 13 may be in contact with the back surface of the substrate 12 (the surface of the antistatic layer 11) to protect the surface thereof.

As shown in FIG. 1, the antistatic layer 11 is formed directly on the first surface of the substrate 12 (without other layers), and the antistatic layer 11 exposes the back surface of the surface protective film 1 (ie, the antistatic layer 11 is also In the form of a surface coating layer, a film with an antistatic layer of the antistatic layer 11 is provided on the substrate 12 compared to a configuration in which a surface coating layer and an antistatic layer are additionally provided (even using the film) The formed surface protective film is produced by reducing the number of layers constituting the surface protective film, and is also advantageous from the viewpoint of improving productivity and the like.

<Substrate>

The surface protective film of the present invention is characterized in that it has 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 is not particularly limited, but for example, transparency, mechanical strength, thermal stability, moisture shielding property, isotropic property, flexibility, dimensional stability, and the like are used. Those with excellent characteristics are preferred. In particular, if the substrate is flexible, the adhesive composition can be applied by a roll coater or the like, and it can be wound into a roll.

The base material (support) may, for example, be a polyester polymer such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) or polybutylene terephthalate; A cellulose-based polymer such as diacetyl cellulose or triacetyl cellulose; a polycarbonate polymer; an acrylic polymer such as polymethyl methacrylate or the like as a main resin component (a main component of a resin component, typically A plastic film composed of a resin material containing 50% by mass or more of the component is preferably used as the substrate. Other examples of the resin material include, as a resin material, 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. Further 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 polymerization. A vinyl chloride polymer, an ethylene butyral polymer, an aryl ester polymer, a polyoxymethylene polymer, or an epoxy polymer. It may be a substrate composed of a blend of two or more of the above polymers.

As the substrate, a plastic film composed of a transparent thermoplastic resin material can be preferably used. A polyester film is also preferred in the above plastic film. Here, the polyester film refers to a polymer material (polyester resin) having polyethylene terephthalate (PET) or polynaphthalene dicarboxylic acid as a main resin component. An ester bond such as ethylene glycol (PEN) or polybutylene terephthalate is used as a basic main skeleton. In addition to the excellent properties of the substrate as a surface protective film, such as excellent optical properties or dimensional stability, the polyester film is also inherently easy to charge.

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 is disposed) may be subjected to, for example, corona discharge treatment, A well-known or conventional surface treatment such as plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of a primer. Such a surface treatment can use, for example, a treatment for improving the adhesion between the substrate and the antistatic layer. It is preferred to use a surface treatment for introducing a polar group such as a hydroxyl group on 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 the side where the adhesive layer is formed). This surface treatment can improve the adhesion of the film 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 the substrate, and an antistatic treated plastic film can also be used as the substrate. By using the above-mentioned substrate, it is preferable since the charging of the surface protective film itself after peeling can be suppressed. Further, the base material is a plastic film, and the antistatic treatment of the plastic film can reduce the charging of the surface protection film itself, and the antistatic property of the object can be excellent. Further, a method of imparting an antistatic function is not particularly limited, and a conventionally known method can be used, and for example, an antistatic resin or a conductive polymer composed of an antistatic agent and a resin component is applied. A method of a conductive resin containing a conductive material, a method of vapor-depositing or plating a conductive material, a method of kneading an antistatic agent, or the like.

The thickness of the substrate is usually 5 to 200 μm, preferably about 10 to 150 μm. When the thickness of the base material is within the above range, it is preferable because it is excellent in the workability of the adherend and the peeling workability from the object.

<Antistatic layer (surface coating)>

The surface protection film of the present invention has a substrate having a first surface (back surface) and a second surface (surface opposite to the first surface), and is provided on the first surface of the substrate An antistatic layer (back surface) and an adhesive layer formed on the second surface of the substrate and formed of an adhesive composition, wherein the surface protection film is characterized in that the antistatic layer is composed of an antistatic agent The antistatic agent composition contains polyaniline sulfonic acid as a conductive polymer component, polythiophene doped with polyanion, and a binder, and the polyaniline sulfonic acid is doped with a polyanion as described above. The blending ratio (mass ratio) of the polythiophenes is 90:10 to 10:90. The surface protective film has an antistatic layer (surface coating), so that the antistatic property of the surface protective film and the temporal stability of the peeling electrostatic potential are improved, which is preferable. In particular, the polyaniline sulfonic acid is blended with the polyanion sulfonic acid in the foregoing range as compared with the case where the polyaniline sulfonic acid is blended separately or the polythiophene doped with the polyanion described above is blended in the foregoing range. When the polythiophene is doped, the stability over time of the antistatic property is improved, and the reason is presumed as follows. The polythiophene doped with polyanion is a polythiophene-supported polyanion-based anion group to form a complex, and the conductive mechanism is known to be a polythiophene-derived intramolecular conductive polythiophene produced in the composite body. The intermolecular conduction and the electrical conduction between the composite structures. Here, the conduction between the composite structures is determined by the rate because of the long distance between the molecules. In general, by using a polyaniline sulfonic acid which is a polythiophene-based polymer in combination, the polyaniline sulfonic acid becomes a connection between a complex of polythiophenes and polyanions, and is itself electrically conductive. Therefore, it is presumed that the conductivity between the composites can be improved, the antistatic property can be improved, and the stability can be increased. By using these together, it is very useful as a surface protective film system.

<Electrically conductive polymer>

The antistatic layer is characterized by containing polyaniline sulfonic acid and Sub-doped polythiophenes are used as conductive polymer components. By combining the above-mentioned conductive polymers, since the polyaniline sulfonic acid is responsible for the conduction between the polythiophene/polyanion composite structures, the conductivity is improved and the stability is stabilized. The antistatic property of the electrostatic layer and the peeling of the electrostatic potential over time are useful.

The conductive polymer is preferably used in an amount of from 1 to 1,000 parts by mass, more preferably from 5 to 750 parts by mass, based on 100 parts by mass of the binder contained in the antistatic layer (surface coating layer), more preferably 10 to 500 parts by mass. When the amount of the conductive polymer used is too small, the antistatic effect is small, and when the amount of the conductive polymer used is too large, there is a concern that the adhesion to the antistatic layer substrate is lowered and the transparency is lowered. .

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

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

The polythiophene used as the conductive polymer component may, for example, be polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene) or poly( 3-butylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-mercaptothiophene), poly(3-dodecylthiophene) ), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3-chlorothiophene), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-benzene Thiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3- Methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3- Octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene) , poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxy) Thiophene), poly(3,4-dihexyloxythiophene), poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-twenty) Dialkoxythiophene), poly(3,4-dioctadecyloxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propanedioxythiophene), poly( 3,4-butadioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3-methyl-4-ethoxythiophene), poly(3-carboxythiophene, poly( 3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxybutylthiophene). These may be used alone or in combination. Two or more types are used, and among them, poly(3,4-ethylenedioxythiophene) (PEDOT) is preferred from the viewpoint of conductivity.

The degree of polymerization of the polythiophene is preferably from 2 to 1,000, more preferably from 5 to 100. When it is in the above range, it is excellent in electrical conductivity.

The polyanion-based polymer having a constituent unit of an anionic group acts as a dopant on the polythiophene. Examples of the polyanion species include polystyrenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polyacrylsulfonic acid, polymethacrylic acid, and poly(2-acrylamidamine-2-methyl). Propane sulfonic acid), polyisoprene sulfonic acid, polysulfoethyl methacrylate, poly(4-sulfobutyl methacrylate), polymethylallyloxybenzene sulfonic acid, polyethylene carboxylic acid, Polystyrene carboxylic acid, polyallyl carboxylic acid, polypropylene carboxylic acid, polymethyl propylene carboxylic acid, poly(2-propenylamine-2-methylpropane carboxylic acid), polyisoprene carboxylate Acid, polyacrylic acid, polyphenylene phenyl acetylene, and the like. These may be individual polymers or may be two or more copolymers. Among them, from the viewpoint of improving dispersibility, the conductivity of the polythiophene is preferably polystyrenesulfonic acid (PSS).

The weight average molecular weight (Mw) of the polyanion is preferably from 1,000 to 1,000,000, more preferably from 2,000 to 500,000. When it is in the above range, it is excellent in the doping property and dispersibility of the polythiophene.

The commercially available product of the polyanion-doped polythiophene may, for example, be a trade name of BAYER Co., Ltd. of poly(3,4-ethylenedioxythiophene)/polystyrenesulfonic acid (PEDOT/PSS). "Bytron P", the trade name "SEPLEGYDA" manufactured by Shin-Etsu Chemical Co., Ltd., and the trade name "VERAZOL" manufactured by Synopsys Chemical Co., Ltd.

In the antistatic agent composition, the blending ratio (mass ratio) of the polyaniline sulfonic acid to the polyanion-doped polythiophene (the aforementioned polyaniline sulfonic acid: the polyanion group doped with the polyanion described above) Class)) 90:10~10:90, preferably 85:15~15:85, preferably 80:20~20:80. As long as it is within the above range, the surface resistivity can be suppressed, and in particular, the temporal stability of the surface resistivity is excellent, which is a preferable aspect. In addition, when the polyaniline sulfonic acid is used alone, since the initial conductivity is low, an increase in the peeling electrostatic potential or the surface resistivity is likely to occur over time, and when the polythiophene doped with the polyanion is used alone, the initial stage is Although the conductivity is high, the polyanion (corresponding to the dopant) tends to be detached from the polythiophene over time, so that it is less likely to cause an increase in the peeling electrostatic potential or the surface resistivity over time.

<Binder>

The antistatic layer is characterized in that it is solvent-resistant and mechanically strong. It contains a binder and is thermally stable. The binder may, for example, be an acrylic resin, an urethane acrylate resin, an acrylic styrene resin, an acrylic polyoxyl resin, a polyoxyn resin, a fluororesin, a styrene resin, a polyester resin, an acid alcohol resin, a polyamine. A urethane resin, a guanamine resin, a polyolefin resin, a polyazide resin, or such a modified or copolymerized resin. Further, the above resins may be used alone or in combination of two or more. In particular, it is preferable to use a polyester resin in the above resin from the viewpoint of excellent solvent resistance.

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 is preferably a structure having two compounds condensed, and is selected from polyvalent carboxylic acids (typically dicarboxylic acids) having two or more carboxyl groups in one molecule and derivatives thereof (the multivalent value) One or two or more compounds (polyvalent carboxylic acid component) of a carboxylic acid anhydride, an esterified product, a halide, or the like, and a polyhydric alcohol having two or more hydroxyl groups selected from one molecule (typically two One or two or more compounds (polyol components) of an alcohol.

Examples of the compound which is the above polyvalent carboxylic acid component can be used, and examples thereof include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, and alkylsuccinic acid. ±)-Malic acid, meso-tartaric acid, itaconic acid, maleic acid, methyl maleic acid, fumaric acid, methyl fumaric acid, acetylene dicarboxylic acid, pentane Acid, hexafluoroglutaric acid, methyl glutaric acid, glutaconic acid, adipic acid, dithioadipic acid, methyl adipic acid, dimethyl adipate, tetramethyl adipate, Methylene adipate, hexadiene diacid, galactosuccinic acid, pimelic acid, suberic acid, perfluorooctanoic acid, 3,3,6,6-tetramethyloctanedioic acid, sebacic acid , an aliphatic dicarboxylic acid such as azelaic acid, perfluorosebacic acid, tridecanedioic acid, dodecyl dicarboxylic acid, thirteen-based dicarboxylic acid, tetradecyl dicarboxylic acid; cycloalkyl dicarboxylic acid (eg, 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, decanoic acid, phenyl diacetic acid, phenyl dipropionic acid, naphthalene dicarboxylic acid, naphthalene dipropionic acid, biphenyl diacetic acid, Benzylpropionic acid, 3,3'-[4,4'-(methylenebis-pair-linked diphenyl)dipropionic acid, 4,4'-bibenzyldiacetic acid, 3,3'(4,4' - an aromatic dicarboxylic acid such as dibenzyl acid or dioxo-p-phenylenediacetic acid; or any of the above polyvalent carboxylic acids An anhydride; an ester of any of the above polyvalent carboxylic acids (which may be, for example, an alkyl ester, a monoester, a diester, etc.); an acid halide corresponding to any of the above polyvalent carboxylic acids (for example, a dicarboxylic acid) Chlorine).

Preferable examples of the compound which can be used as the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and acid anhydrides thereof; adipic acid and bismuth An aliphatic dicarboxylic acid such as an acid, azelaic acid, succinic acid, fumaric acid, maleic acid, humic acid or 1,4-cyclohexanedicarboxylic acid, and an acid anhydride thereof; and the aforementioned dicarboxylic acid Lower alkane A base ester (for example, a monool and an ester having 1 to 3 carbon atoms).

On the other hand, examples of the compound which can be used as the polyol component include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-butanediol. , 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4 - cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, Glycols such as 2-butyl-2-ethyl-1,3-propanediol, xylene alcohol, hydrogenated bisphenol A, and bisphenol A. As another example, an alkylene oxide adduct of such a compound (for example, an oxyethylene adduct or a propylene oxide adduct) may be mentioned.

The molecular weight of the polyester resin is a standard polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC), for example, about 1 × 10 ³ to 1.5 × 10 ⁵ (by 1 × 10). ³ ~ 6 × 10 ^{4 is} better). 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-1930, MD-1985, MD. -2000, the trade name of the chemical industry company, PLAS COAT Z-221, Z-446, Z-561, Z-565, Z-880, Z-3310, RZ-105, RZ-570, Z-730, Z-760, Z-592, Z-687, Z-690, PESRESIN A-110, A-120, A-124GP, A-125S, A-160P, A-520, A-613D, manufactured by Takamatsu Oil Co., Ltd. A-615GE, A-640, A-645GH, A-647GEX, A-680, A-684G, WAC-14, WAC-17XC, etc.

The adhesive of the antistatic layer (surface coating) may further contain a resin other than the polyester resin (for example, as long as the performance of the surface protective film disclosed herein (for example, performance such as antistatic property) is not greatly impaired. , acrylic resin, urethane acrylate resin, acrylic styrene resin, acrylic polyoxyl resin, polyoxyn oxy resin, fluororesin, styrene resin, acid alcohol resin, polyurethane resin, guanamine resin A polyolefin resin, a polyazide resin, or the like, or one or two or more resins selected from the modified or copolymerized resins. A preferred aspect of the technique disclosed herein is the case where the adhesive 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 proportion 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 layer (surface coating) of the technology disclosed herein is preferably selected from the group consisting of fatty acid amides, fatty acid esters, polyfluorene-based lubricants, fluorine-based lubricants and wax-based lubricants. At least one of the constituent groups is used as a lubricant. By using the lubricant, the peeling treatment is further performed on the surface of the antistatic layer (for example, a well-known release treatment agent such as a polyoxyalkylene release agent or a long-chain alkyl release agent is applied, and then dried. In the aspect of the treatment, an antistatic layer (surface coating) having both sufficient lubricity and printing adhesion can be obtained, which is preferable. As described above, the surface which is not subjected to the release treatment on the surface of the antistatic layer is preferably prevented from being whitened by the release treatment agent (for example, whitening caused by storage under heating and humidification conditions). Moreover, 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 perfluoroalkane, perfluorocarboxylic acid ester, fluorine-containing block copolymer, and polyether polymer having a fluorinated alkyl group. 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. For example, various waxes of (soft acid triglyceride, etc.) are mentioned. 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 ratio of the lubricant is too small, the lubricity tends to decrease. When the content ratio of the lubricant is too large, the printing adhesion or the back peeling force is lowered.

<crosslinker>

Preferably, the antistatic layer is selected from the group consisting of a decane coupling agent and an epoxy system. At least one of the group consisting of a crosslinking agent, a melamine crosslinking agent, and an isocyanate crosslinking agent is used as a crosslinking agent, and among them, it is preferable to use the melamine crosslinking agent and/or the isocyanate crosslinking agent in particular. kind. The conductive polymer component which is an essential component in forming the antistatic layer, that is, polyaniline sulfonic acid and polythiophene doped with polyanion can be fixed in the binder, so that it has excellent water resistance and solvent resistance. Sexuality, and can achieve the effect of improving the printing adhesion. In particular, by using a melamine-based crosslinking agent, water resistance or solvent resistance can be improved, and by using an isocyanate crosslinking agent, water resistance or printing adhesion can be improved, and by using the crosslinking agent in combination, Effectively improve water resistance, solvent resistance, and printing adhesion.

As the melamine-based crosslinking agent, melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine or the like can be used.

Further, the isocyanate crosslinking agent is preferably a blocked isocyanate crosslinking agent which is stable in an aqueous solution. As a specific example of the above-mentioned blocked isocyanate-based crosslinking agent, an isocyanate-based crosslinking agent (for example, an adhesive layer described later) which can be used in preparation of a general adhesive layer or an antistatic layer (surface coating layer) can be used. The isocyanate compound used in the production of alcohols, phenols, thiophenols, amines, quinones, anthraquinones, indoleamines, active methylene compounds, mercaptans, imines, Blocked by urea, diaryl compounds, and sodium hydrogen sulfite.

The antistatic layer in the technology disclosed herein may contain other antistatic components, antioxidants, colorants (pigments, dyes, etc.), fluidity adjusters (thixotropic agents, tackifiers, etc.), film forming aids as needed. Additives such as agents, surfactants (antifoaming agents, etc.), preservatives. Also, it can also contain as a conductivity An epoxy propyl compound, a polar solvent, a polyvalent aliphatic alcohol, an indoleamine compound, or the like.

<Formation of antistatic layer>

The antistatic layer (surface coating layer) can be preferably formed by a method comprising: imparting a liquid composition to the substrate, the liquid composition being an essential component such as the conductive polymer component, and optionally A liquid composition (a coating material for forming an antistatic layer, an antistatic agent composition) in which an additive to be used is dissolved or dispersed in a suitable solvent (water or the like). For example, a method of applying the above-mentioned coating material to the first surface of the substrate, drying it, and performing a curing treatment (heat treatment, ultraviolet treatment, or the like) as needed may be preferably used. The NV (non-volatile portion) of the coating material 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 coating material is preferably, for example, 0.05 to 0.50% by mass (for example, 0.10 to 0.40% by mass). By using such a low NV coating material, a more uniform antistatic layer can be formed.

The solvent for forming the coating material for an antistatic layer is preferably a component which can stabilize the formation component of the antistatic layer and can be dissolved or dispersed. The solvent may be an organic solvent, water, or a mixed solvent of these. The organic solvent may be one or more selected from the group consisting of esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone, and cyclohexanone; tetrahydrofuran (THF) and a cyclic ether such as an alkane; an aliphatic or alicyclic hydrocarbon such as n-hexane or cyclohexane; an aromatic hydrocarbon such as toluene or xylene; or a fat such as methanol, ethanol, n-propanol, isopropanol or cyclohexanol. a family or an alicyclic alcohol; an alkylene glycol monoalkyl ether (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), a glycol ether such as a dialkyl glycol monoalkyl ether, or the like. In a preferred embodiment, the solvent of the coating material is water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol).

Further, in order to enhance the dispersion stability to the solvent, a salt-based organic compound which can be coordinated as an ion pair or bonded to an anionic group of a polyanion can be contained. The salt-based organic compound is exemplified by an amine compound, an amine compound hydrochloride, a cationic emulsifier, a salt-based resin and the like.

Specific examples of the salt-based organic compound include methyloctylamine, methylbenzylamine, N-methylaniline, dimethylamine, diethylamine, diethanolamine, and N-methylethanolamine. Di-n-propylamine, diisopropylamine, methyl-isopropanolamine, dibutylamine, di-2-ethylhexylamine, aminoethylethanolamine, 3-amino-1-propanol, Isopropylamine, monoethylamine, 2-ethylhexylamine, tert-butylamine, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethyl An amine compound such as oxydecane, 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, monomethylamine, monoethylamine, stearic acidamine, etc. a hydrochloride of a grade II amine such as a hydrochloride of a first grade amine, a dimethylamine, a diethylamine or a distearylamine, a trimethylamine, a triethylamine, a stearin dimethylamine, etc. Grade 4 ammonium salt, such as a tertiary amine hydrochloride, stearic acid trimethylammonium chloride, distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, A hydrochloride of an ethanolamine such as monoethanolamine, diethanolamine or triethanolamine, or a hydrochloride of a polyethylene polyamine such as ethylenediamine or diethylene glycol triamine.

Specific examples of the cationic emulsifier include an alkylammonium salt, a alkylguanamine betain, an alkyl oxyalkylamine, and the like.

Specific examples of the above-mentioned salt-based resin include a polyester-based, acrylic-based, or urethane-based polymer copolymer, and a weight average molecular weight (Mw) of 1,000 to 1,000,000 is taken as an example. . When the weight average molecular weight of the salt-based resin is less than 1,000, sufficient steric hindrance is not obtained, and the dispersion effect is lowered. When the weight average molecular weight is more than 1,000,000, agglomeration may occur.

Further, the amine-based resin preferably has an amine value of 5 to 200 mgKOH/g. When the amount is less than 5 mgKOH/g, the interaction with the polyanion doped with polythiophene is likely to be insufficient, and a sufficient dispersion effect may not be obtained. On the other hand, when the amine valence of the salt-based resin is more than 200 mgKOH/g, the steric hindrance layer is less and the dispersion effect is insufficient as compared with the affinity portion of the polyanion doped with polythiophene. .

Examples of the salt-based resin include Solsperse 17000, Solsperse 20000, Solsperse 24000, Solsperse 32000 (manufactured by Zeneca Co., Ltd.), Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-170, Disperbyk-2000, Disperbyk. -2001 (manufactured by BIG Chemie), AJISPER PB711, AJISPER PB821, AJISPER PB822, AJISPER PB824 (manufactured by Ajinomoto Co., Ltd.), EPOMIN006, EPOMIN012, EPOMIN018 (made by SHOKUBAI Co., Ltd., Japan), EFKA4046, EFKA4300, EFKA4330, EFKA4510 (made by EFKA Co., Ltd.), DISPARLON DA-400N (made by Kusumoto Kasei Chemical Co., Ltd.), etc., can be used individually or in combination. In particular, AJISPER PB821, AJISPER PB822, and AJISPER PB824 are preferred from the viewpoint of dispersibility or conductivity at the time of use.

The amount of the above-mentioned salt-based compound is not limited, but it is in the range of 10 parts by mass to 100,000 parts by mass per 100 parts by mass of the polythiophene and the polyanion. It is better to add it inside.

<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, and more preferably from 3 to 60 nm. When the thickness of the antistatic layer is too small, it is difficult to form a uniform antistatic layer (for example, the thickness of the antistatic layer is large due to the difference in thickness between the positions), and therefore, the appearance of the surface protective film is likely to be uneven. On the other hand, when the thickness is too thick, there is a case where the properties (optical characteristics, dimensional stability, and the like) of the substrate are affected.

A preferred aspect of the surface protective film disclosed herein is a surface resistivity (Ω/□) measured on the surface of the antistatic layer, preferably less than 1.0×10 ¹¹ , preferably less than 5.0×10 ¹⁰ , more preferably The best is less than 1.0×10 ¹⁰ . The surface protective film which exhibits the surface resistivity in the above range can be preferably used for a surface protective film used in, for example, a process of processing or handling an article which is not resistant to static electricity such as a liquid crystal cell or a semiconductor device. Further, the surface resistivity can be calculated by using a commercially available insulation resistance measuring device at a surface resistivity measured under an ambient gas of 23 ° C and 50% RH.

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 (using, for example, an oily marker). The surface protective film is suitable for processing or transporting a subject (for example, an optical member) in a state in which a surface protective film is attached, and the surface protective film is labeled as a protective pair. The identification number of the elephant being used, etc. Therefore, it is preferable to use a surface protection film excellent in printability. For example, it is preferred that the solvent-based oil-based ink having a solvent of an alcohol type has high printing property. Further, it is preferable that the ink to be printed is not easily dropped by friction or transfer (that is, excellent in printing adhesion). Further, the surface protective film disclosed herein preferably has a solvent resistance which does not significantly change the appearance even when the printing is performed with an alcohol (for example, ethanol) in the case of correction or removal of printing.

The surface protective film disclosed herein can be carried out in addition to the substrate, the adhesive layer, and the antistatic layer in the form of including other layers. The configuration of the "other layer" can be exemplified as being between the second surface (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 (anchor layer), an antistatic layer, or the like which enhances the anchoring of the adhesive layer to the second surface. Alternatively, an antistatic layer may be disposed on the front surface of the substrate, and an anchor layer may be disposed on the antistatic layer, and a surface protective film having a structure of an adhesive layer may be disposed thereon.

<Adhesive Composition>

The surface protection film of the present invention has the above-mentioned adhesive layer, and the adhesive layer is formed of an adhesive composition. The adhesive composition may be any adhesive, and may be used without any particular limitation. For example, an acrylic adhesive, a urethane-based adhesive, a synthetic rubber-based adhesive, a natural rubber-based adhesive, a polyoxynoxy adhesive, or the like, and preferably an acrylic adhesive is selected from the group consisting of acrylic adhesives. At least one of the group consisting of a urethane-based pressure-sensitive adhesive and a polyoxymethylene-based pressure-sensitive adhesive is preferably an acrylic pressure-sensitive adhesive using a (meth)acrylic polymer.

When an acrylic pressure-sensitive adhesive is used as the pressure-sensitive adhesive layer, the raw material monomer constituting the (meth)acrylic polymer of the acrylic pressure-sensitive adhesive can be used to form a (meth) group having an alkyl group having 1 to 14 carbon atoms. An acrylic monomer is used as a main monomer. One type or two or more types of the above (meth)acrylic monomers can be used. By using the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the peeling force (adhesion) to the object (protected body) can be easily controlled to be low, and light peeling can be obtained. A surface protection film excellent in properties or 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.

Specific examples of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate. Ester, second butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, (methyl) Isodecyl 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, (meth) propyl N-dodecanoic acid ester, 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 peeling force (adhesion) against the object to be low, and it is excellent in re-peelability. .

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 monomer component 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 98% by mass. When the amount is less than 50% by mass, the proper wettability of the adhesive composition or the aggregation force of the adhesive layer will be deteriorated, which is not preferable.

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

By using the aforementioned hydroxyl group-containing (meth)acrylic monomer, the crosslinking of the adhesive composition can be easily controlled, and even the wettability of the flow can be easily controlled and the peeling force of the peeling can be easily improved (adhesion) Equilibrium. 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 or a polyether compound which is an antistatic component (antistatic agent). Antistatic properties also apply.

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-hydroxyl (meth)acrylate Octyl ester, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, N-hydroxymethyl (methyl) ) acrylamide and the like. In particular, it is preferred to use a hydroxyl group-containing (meth)acrylic monomer having 4 or more carbon atoms in the alkyl group to facilitate light peeling at the time of high-speed peeling.

The amount of the (meth)acrylic monomer having a hydroxyl group of 1 to 14 is preferably 25 parts by mass or less, more preferably 25 parts by mass or less, based on 100 parts by mass of the (meth)acrylic monomer having a hydroxyl group. 1 to 22 parts by mass, more preferably 2 to 20 parts by mass, and most preferably 3 to 18 parts by mass. When it is within the above range, it is preferred because the wetting property of the adhesive composition can be easily controlled to balance the cohesive force of the obtained adhesive layer.

Further, from the viewpoint of easily obtaining a balanced adhesive property, other polymerizable monomer components 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).

a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms and a hydroxyl group-containing (meth)acrylic monomer used in the (meth)acrylic polymer. As the polymerizable monomer, a carboxyl group-containing (meth)acrylic monomer can be used.

Examples of the carboxyl group-containing (meth)acrylic monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate.

The carboxyl group-containing (meth)acrylic monomer is preferably 5 parts by mass or less, and preferably 3 parts by mass or less, based on 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms. Preferably, it is 2 parts by mass or less. Preferably, the most preferred one is 0.01 parts by mass or more and less than 0.1 parts by mass. When the amount is more than 5 parts by mass, an acid functional group such as a carboxyl group having a large polarity is present, and when an ionic compound or a polyether compound which is an antistatic component (antistatic agent) is blended, the antistatic component or the like is used. The interaction of an acid functional group such as a carboxyl group interferes with ion conduction, and there is a concern that the conductivity is lowered and sufficient antistatic property is not obtained.

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. A polymerizable monomer other than an acrylic monomer, a hydroxyl group-containing (meth)acrylic monomer, and a carboxyl group-containing (meth)acrylic monomer. For example, a cohesive force such as a cyano group-containing monomer, a vinyl ester monomer, or an aromatic vinyl monomer can be suitably used. Heat resistance improving component, or a mercapto group-containing monomer, a quinone imine group-containing monomer, an amine group-containing monomer, an epoxy group-containing monomer, an N-propylene fluorenyl group A peeling force (adhesion) such as a porphyrin or a vinyl ether monomer is increased or a component having a functional group acting 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 an N-containing fluorenyl group are used. A nitrogen-containing monomer such as a porphyrin is preferred. By using a nitrogen-containing monomer, it is possible to ensure that a suitable peeling force (adhesive force) such as lifting or peeling does not occur, and a surface protective film having excellent shearing force can be obtained. These polymerizable monomers may be used alone or in combination of two or more.

Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

The above-mentioned monomer containing a guanamine group may, for example, be acrylamide, A Acrylamide, diethyl acrylamide, N-vinylpyrrolidone, N,N-dimethylpropenamide, N,N-dimethylmethacrylamide, N,N-diethyl Acrylamide, N,N-diethylmethacrylamide, N,N'-methylenebispropenylamine, N,N-dimethylaminopropylpropenylamine, N,N-di Methylaminopropyl 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 aminoethyl (meth) acrylate, N,N-dimethylaminoethyl (meth) acrylate or N,N-dimethylamino group. Propyl (meth) acrylate and the like.

Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl laurate.

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

Examples of the epoxy group-containing monomer include epoxypropyl (meth)acrylate, methyl epoxypropyl (meth)acrylate, allylepoxypropyl ether and the like.

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 a carbon number of 1 to 14 or a hydroxyl group-containing (meth)acrylic monomer or a carboxyl group-containing (meth)acrylic monomer may be used. The polymerizable monomer is 0 to 40% by mass based on 100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms. Preferably, it is preferably 0 to 30 parts by mass. When the above-mentioned other polymerizable monomer is used in the above range, when an ionic compound or a polyether compound as an antistatic component is used, good interaction and good removability can be appropriately adjusted.

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

The epoxy group-containing reactive monomer may be used alone or in combination of two or more. The total content of the monomeric component of the (meth)acrylic polymer is preferably 20% by mass or less. 10% by mass or less is 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 or the polyether compound becomes large, which hinders ion conduction and causes deterioration of antistatic property.

The oxygen-athane unit of the aforementioned epoxy group-containing reactive monomer can be Examples of the alkylene group having a carbon number of 1 to 6 are exemplified by an oxymethylene group, an oxygen-extended ethyl group, an oxygen-extended propyl group, and an oxygen-extended butyl group. 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, the matrix polymer can be enhanced with an ionic compound or a polyether compound as an antistatic component. It is compatible, and it is preferable to suppress leakage to the object, and a low-contaminant adhesive composition can be obtained.

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. A sexual surfactant or the like is exemplified.

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 interface having a (meth) acrylonitrile group or an allyl group. A reagent, a nonionic reactive surfactant, a cationic reactive surfactant, and the like.

The weight average molecular weight (Mw) of the (meth)acrylic polymer is preferably from 100,000 to 5,000,000, preferably from 200,000 to 4,000,000, and more preferably from 300,000 to 3,000,000. When the weight average molecular weight is less than 100,000, the cohesive force of the adhesive layer becomes small, and the adhesive tends to remain. 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 (for example, a polarizing plate) is insufficient, and the adhesive layer of the adherend and the surface protective film is formed. There is a tendency to cause expansion. Further, the weight average molecular weight means a GPC (gel (permeation (chromatography) measurement).

Further, the glass transition temperature (Tg) of the (meth)acrylic polymer is preferably 0 ° C or lower, more 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 to be used.

The polymerization method of the above (meth)acrylic polymer is not particularly limited, and it can be polymerized by a well-known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc., but particularly from the viewpoint of workability, or Solution polymerization system for the characteristics of the low contamination of the object (protected body) The preferred aspect. Further, the obtained polymer may be any of a random copolymer, a block copolymer, an interactive copolymer, a graft copolymer, and the like.

When a urethane-based adhesive is used for the above adhesive layer, any appropriate urethane-based adhesive can be used. A preferred example of such a urethane-based adhesive is exemplified by 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.

When a polyfluorene-based pressure-sensitive adhesive is used for the 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).

Moreover, the polyoxygen-based 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 adhesive layer>

The adhesive layer constituting the aforementioned adhesive layer in the surface protective film of the present invention The composition preferably contains an antistatic component, and the antistatic component preferably contains an ionic compound. The ionic compound may be exemplified by an alkali metal salt and/or an ionic liquid. By containing the ionic compound, excellent antistatic properties can be imparted. Further, an adhesive layer (using an antistatic component) obtained by crosslinking an adhesive composition containing an antistatic component as described above can be used for an antistatic body (for example, a polarizing plate) at the time of peeling. Antistatic property, which is a surface protection film that reduces contamination of the object. Therefore, as a problem of charging or pollution is a particularly serious problem. An antistatic surface protective film in the technical field related to electronic components is very useful.

Since the ionic dissociation property of the alkali metal salt is high, it is preferable from the viewpoint of exhibiting excellent antistatic energy even in a small amount of addition. As the alkali metal salt, for example, a cation derived from Li ⁺ , Na ⁺ , K ⁺ and Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF can be preferably used. 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 ^- anion formed from the metal salt. Preferred for use are 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 ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C and other lithium salts, 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 kinds.

Further, by using the ionic liquid as an antistatic component (antistatic agent), an adhesive layer having a high antistatic effect can be obtained without damaging the adhesive property. The reason why the excellent antistatic property can be obtained by using an ionic liquid is not clear. However, since the ionic liquid has a low melting point (melting point of 100 ° C or lower) as compared with a usual ionic compound, molecular motion is easy, and excellent resistance can be obtained. Static energy. In particular, when the antistatic property against the object is sought, it is known that a very small amount of the ionic liquid is transferred to the object, and it is found that excellent peeling antistatic property can be obtained in the object. In particular, an ionic liquid having a melting point of room temperature (25 ° C) or less can be more efficiently transferred to an object, and 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. In addition, since the ionic liquid has no vapor pressure (non-volatile), it does not disappear with time and has a characteristic of sustainable 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.

The ionic liquid is preferably one composed of an organic cation component and an anion component represented by the following general formulae (A) to (E). By these cationic ionic liquids, those having excellent antistatic properties are more preferable.

[Chemical 1]

R _a in the above formula (A) represents a hydrocarbon group having 4 to 20 carbon atoms, and a part of the hydrocarbon group may be a hetero atom-substituted functional group, and R _b and R _c may be the same or different, and represent hydrogen or a carbon number of 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 above 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, and 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, and 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.

Examples of the cation represented by the formula (A) include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a dihydropyrrole skeleton, a cation having a pyrrole skeleton, and the like. A porphyrin cation or the like.

Specific examples thereof include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methyl Pyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation, 1-ethyl- 1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation , 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butene Pyridone cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1 -dipropylpyrrolidone cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation, pyrrolidin-2-one cation, 1-propylpiperidine Ruthenium cation, 1-pentylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1-methyl 1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium Cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1- Butyl piperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1, 1-dipropyl piperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dibutylpiperidinium cation, 2-methyl-1-dihydropyrrole cation, 1- Ethyl-2-phenylphosphonium cation, 1,2-dimethylhydrazine cation, 1-ethylcarbazole cation, N-ethyl-N-methyl A porphyrin cation or 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 include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methyl Imidazolidinium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-mercapto-3-methylimidazolium cation, 1-dodecyl-3 -methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazole Pyridinium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, 1-(2-methoxyethyl)-3-methyl Imidazolium cation, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidine a cation, a 1,3-dimethyl-1,4-dihydropyrimidinium cation, a 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1, 4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1, a 4-dihydropyrimidinium cation, a 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation or the like.

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

Specific examples include 1-methylpyrazolium cations, and 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-trimethyldihydropyrazolium cation, and 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 via an alkenyl group or an alkoxy group, or even an epoxy group. Replacement, etc.

Specific examples include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetraamylammonium cation, tetrahexylammonium cation, tetraheptyl ammonium cation, and triethylmethylammonium cation. Tributylethylammonium cation, trimethylsulfonium ammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, epoxypropyltrimethyl Ammonium cation, trimethyl phosphonium cation, triethyl phosphonium cation, tributyl phosphonium cation, trihexyl phosphonium cation, diethyl methyl phosphonium cation, dibutyl ethyl phosphonium cation, dimethyl fluorenyl cation, Tetramethyl phosphonium cation, tetraethyl phosphonium cation, tetrabutyl phosphonium cation, tetrahexyl phosphonium cation, tetraoctyl phosphonium cation, triethylmethyl phosphonium cation, tributyl ethyl phosphonium cation, trimethyl fluorenyl a phosphonium cation, a diallyldimethylammonium cation, a tributyl-(2-methoxyethyl)phosphonium cation, and the like. Among them, the following is also preferred: triethylmethylammonium cation, tributylethylammonium cation, trimethylsulfonium ammonium cation, diethylmethyl phosphonium cation, dibutylethyl phosphonium cation, two Asymmetric tetraalkylammonium cation such as methylmercaptopurine cation, triethylmethylsulfonium cation, tributylethylphosphonium cation, trimethylsulfonium sulfonium cation, trialkylsulfonium cation, tetraalkylphosphonium a cation, or a N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, a propylene oxide trimethylammonium cation, a diallyldimethylammonium cation, N,N-dimethyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, N,N-dimethyl-N- Ethyl-N-amylammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N,N-dimethyl-N-ethyl-N-heptyl ammonium cation, N , N-dimethyl-N-ethyl-N-decyl ammonium cation, N,N-dimethyl-N,N-dipropyl ammonium cation, N,N-diethyl-N-propyl- N-butylammonium cation, N,N-dimethyl-N-propyl-N-amylammonium cation, N,N-dimethyl-N-propyl-N-hexylammonium cation, N,N- Dimethyl-N-propyl -N-heptyl ammonium cation, N,N-dimethyl-N-butyl-N-hexylammonium cation, N,N-diethyl-N-butyl-N-heptyl ammonium cation, N,N - dimethyl-N-pentyl-N-hexylammonium cation, N,N-dimethyl-N,N- Hexyl ammonium cation, trimethylheptyl ammonium cation, N,N-diethyl-N-methyl-N-propyl ammonium cation, N,N-diethyl-N-methyl-N-amyl ammonium a cationic, N,N-diethyl-N-methyl-N-heptyl ammonium cation, N,N-diethyl-N-propyl-N-amyl ammonium cation, triethyl propyl ammonium cation, Triethyl amyl ammonium cation, triethylheptyl ammonium cation, N,N-dipropyl-N-methyl-N-ethyl ammonium cation, N,N-dipropyl-N-methyl-N - amyl ammonium cation, N,N-dipropyl-N-butyl-N-hexylammonium cation, N,N-dipropyl-N,N-dihexyl ammonium cation, N,N-dibutyl- N-methyl-N-amylammonium cation, N,N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N -propyl-N-amyl ammonium cation.

The cation represented by the formula (E) is exemplified by a cation or the like. Further, specific examples of the RP in the above formula (E) include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, decyl, dodecyl, thirteen, and ten. Four bases, eighteen bases, etc.

On the other hand, the anion component is not particularly limited, and as long as it can satisfy an ionic liquid, for example, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF _{6 can 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.

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

Specific examples of the ionic liquid used in the present invention can be appropriately selected from the combination of the above cationic component and anionic component, and examples thereof include 1-butylpyridinium tetrafluoroboric acid and 1-butylpyridinium hexafluorophosphoric acid. 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonate Mercapto) quinone imine, 1-butyl-3-methylpyridinium bis(pentafluoroethanesulfonyl) quinone imine, 1-hexylpyridinium tetrafluoroborate, 1,1-dimethylpyrrolidine Bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propylpyrrolidine Bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-pentyl pyrrolidine Bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-heptylpyrrolidinium Bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1- Pyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexyl Pyrrolizinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropyl pyrrolidine Bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpyrrolidinium (Trifluoromethanesulfonyl) quinone imine, 1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-pentylpiperidinium bis(trifluoromethanesulfonyl) fluorene Amine, 1,1-dimethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1 -methyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl)pyrene , 1-ethyl-1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone , 1-ethyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(trifluoromethanesulfonyl) quinone imine, 1- Propyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1- Dimethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl 1-propylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1- Methyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1 -Methyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidine Bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrole Pyridinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptyl Pyrrolizinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dipropylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1-butyl Pyrrolizinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dibutylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propylpiperidinium bis ( Pentafluoroethanesulfonyl) quinone imine, 1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dimethylpiperidinium bis(pentafluoroethane sulfonate Indole, hydrazide, 1-methyl-1-ethylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-propylpiperidinium bis(pentafluoroethyl) Alkylsulfonyl) quinone imine, 1-methyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-pentylpiperidinium bis (five Fluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl- 1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-B N-butylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1 -ethyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dibutylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 2-methyl-1-dihydropyrrole tetrafluoroboric acid, 1-ethyl-2-phenylindole IV Fluoroboric acid, 1,2-dimethylindole tetrafluoroboric acid, 1-ethyloxazole tetrafluoroboric acid, 1-ethyl-3-methylimidazolium tetrafluoroboric acid, 1-ethyl-3-methyl Imidazolidinium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolidinium heptafluorobutylate, 1-ethyl-3- Methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolidinium perfluorobutane sulfonate, 1-ethyl-3-methyl Oxazolidine dicyandiamide, 1-ethyl-3-methylimidazolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolidinium bis(pentafluoroethylene) Alkylsulfonyl)imine, 1-ethyl-3-methylimidazolidinium (trifluoromethanesulfonyl)methyl metal compound, 1-butyl-3-methylimidazolium tetrafluoroboric acid , 1-butyl-3-methylimidazolium hexafluorophosphoric acid, 1-butyl-3-methylimidazolidinium trifluoroacetate, 1-butyl-3-methylimidazolidinium hexafluorobutane Ester, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolidinium perfluorobutanesulfonate, 1-butyl-3-methyl Imidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-hexyl-3-methylimidazolidinium bromide, 1-hexyl-3-methylimidazolidinium chloride, 1-hexyl-3-methyl Imidazolinium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazole Pyridinium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3- Propyl imidazolium bis(trifluoromethanesulfonyl) hydrazine Imine, 1-methylpyrazolium tetrafluoroboric acid, 2-methylpyrazolium tetrafluoroboric acid, 1-ethyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)醯imino, 1-propyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-2,3,5-trimethylpyridinium Oxazolium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl -2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-butyl-2,3,5-trimethylpyrazolium bis(pentafluoroethane Sulfhydryl) quinone imine, 1-ethyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-propyl-2,3,5 -trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoro Acetamide, 1-ethyl-2,3,5-trimethyldihydropyrazolium bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-2,3,5-trimethyl Dihydropyrazol bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-2,3,5-trimethyldihydropyrazolium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-2,3,5-trimethyldihydropyrazolium Bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-2,3,5-trimethyldihydropyrazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-butyl Bis-2,3,5-trimethyldihydropyrazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-2,3,5-trimethyldihydropyrazolium double (Trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethyldihydropyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1- Butyl-2,3,5-trimethyldihydropyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, tetraamylammonium trifluoromethanesulfonate, tetraamylammonium double (three Fluoromethanesulfonyl) ruthenium imine, tetrahexylammonium trifluoromethanesulfonate, tetrahexylammonium bis(trifluoromethanesulfonyl) ruthenium, tetraheptyl ammonium trifluoromethanesulfonate, tetraheptyl Ammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium double (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 trifluoromethanesulfonate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)anthracene Imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl) quinone imine, epoxypropyltrimethylammonium Fluoromethanesulfonate, epoxypropyltrimethylammonium bis(trifluoromethanesulfonyl) quinone imine, epoxypropyltrimethylammonium bis(pentafluoroethanesulfonyl) quinone imine, four Octyl sulfonium trifluoromethanesulfonate, tetraoctyl bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-propyl ammonium bis(trifluoromethane Sulfhydryl) quinone imine, N,N-dimethyl-N-ethyl-N-butylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-B --N-amyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-Dimethyl-N-ethyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-decyl ammonium (Trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N,N-dipropylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N -propyl-N-butyl Alkyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N- Dimethyl-N-propyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-heptyl ammonium bis(trifluoromethanesulfonate Indenylamine, N,N-dimethyl-N-butyl-N-hexylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-butyl- N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-pentyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N-dimethyl-N,N- Hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-propyl Alkyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) ruthenium, N,N- Diethyl-N-methyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-propyl-N-pentyl ammonium bis(trifluoromethane Sulfhydryl) sulfoximine, triethylpropylammonium bis(trifluoromethanesulfonyl) quinone imine, triethylammonium bis(trifluoromethanesulfonyl) ruthenium, triethylglycol Alkyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-methyl-N-ethylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N- Dipropyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-butyl-N-hexylammonium bis(trifluoromethanesulfonate Indenylamine, N,N-dipropyl-N,N- Hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dibutyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N- Dibutyl-N-methyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trioctylmethylammonium bis(trifluoromethanesulfonyl) quinone imine, N-methyl- N-ethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1- Butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolidinium (trifluoromethanesulfonyl) trifluoroacetamide, N -ethyl-N-methyl Phthalate cyanate, 4-ethyl-4-methyl 鎓 鎓 methyl carbonate and the like.

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

In addition, the content (total amount) of the antistatic component is preferably 1 part by mass or less, more preferably 0.001 to 0.9 part by mass, even more preferably 0.005 to 0.8, based on 100 parts by mass of the (meth)acrylic polymer. The mass fraction is preferably 0.01 to 0.7 parts by mass. When it is within the above range, it is preferable because it can have both antistatic property and low pollution.

<Polyether compound of adhesive layer>

In the surface protection film of the present invention, it is preferred that the above-mentioned adhesive composition contains a polyether compound (polyether component), and it is preferable to use an organopolyoxane having an oxygen-containing alkylene chain to contain an aerobic alkylene. The organopolyoxane of the main chain is more preferred. By using the aforementioned organopolyoxane, it is presumed that the surface free energy of the surface of the adhesive is lowered to achieve light peeling.

As the above organopolyoxane, a well-known organopolyoxane having a polyoxyalkylene main chain can be suitably used, but it is preferably 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 chain may also be 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 above alkyl group or 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. By using the above-mentioned organooxane having an aerobic alkylene chain, it is presumed that a balance between compatibility with a (meth)acrylic polymer or an antistatic component can be obtained, and light peeling can be achieved.

Further, the above-mentioned organopolyoxane in the present invention can be used in the following constitution. 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 be an oxymethylene group, an oxygen-extended ethyl group or an oxygen-extended propyl group. For example, an oxygen-extended butyl group is also preferred, and an oxygen-extended ethyl group or an oxygen-extended propyl group is also preferred. Further, when both of R ₁ and R ₂ have an oxyalkylene chain, they may be the same or different.

Further, the hydrocarbon group of the oxygen alkylene chain may be a straight chain or a branch chain.

Further, the terminal of the oxyalkylene chain may be an alkoxy group or a hydroxyl group, and 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 will interact with the separator, and the adhesion (peeling) when the separator is peeled off from the surface of the adhesive layer The situation of rising power.

Further, n is an integer of 1 to 300, preferably 10 to 200, more preferably 20 to 150. When n is within the above range, it will be in a state of 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 (manufactured by Dow Corning), IM22 (made by Asahi Kasei WACKER Co., Ltd.), etc. These compounds may be used singly or in combination of two or more. .

Further, in addition to the (bonded) organooxane in the main chain having an alkylene chain, it is also possible to use an (oxygen) alkoxyalkylene (bonded) organic oxirane in the side chain, not on the side of the main chain. The chain employs a preferred aspect of the organooxane of the aerobic alkylene chain. As the above organopolyoxane, an organic polyoxyalkylene having a well-known polyoxyalkylene side chain can be suitably used, but it is preferably represented by the following formula.

[Chemical 5]

(wherein R ₁ is an organic group having 1 valence, 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 an integer of 0 to 1000. However, m, n is Not both 0. a and b are integers from 0 to 100. However, a and b are not 0 at the same time.)

Further, as the above-mentioned organopolyoxane in the present invention, for example, the following constitution can be used. 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 . R ₃ and R ₄ are those which increase the concentration of an antistatic component (for example, an ionic compound or the like) which is soluble in the polyoxyalkylene side chain, and either one of them is an ethylidene group or a propyl group. R ₅ may, for example, be an alkyl group such as a methyl group, an ethyl group or a propyl group, or a monovalent organic group having a mercapto group such as an ethyl fluorenyl group or a propyl fluorenyl group, and each may have 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. In the above organooxane having a polyoxyalkylene side chain, it is presumed that an organic oxane having a hydroxyl group-terminated polyoxyalkylene side chain is easily balanced in 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 singly 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 outside the above range, the contamination of the object is deteriorated.

The above-mentioned adhesive composition may also contain a polyoxyalkylene chain-containing compound which does not contain a polyether compound (polyether component) of a polysiloxane. By the inclusion of the aforementioned compound in the adhesive, the wettability of the object can be obtained. Excellent adhesive.

Specific examples of the polyoxyalkylene chain-containing compound not containing the polyoxyalkylene oxide include polyoxyalkylene alkylamine, polyoxyalkylene diamine, polyoxyalkylene fatty acid ester, and polyoxygen. 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 having a polyoxyalkylene chain a compound (and a derivative thereof), an acrylic acid compound having a polyoxyalkylene chain (and a derivative thereof), and the like. Further, a monomer containing a polyoxyalkylene chain may be blended as a polyoxyalkylene chain-containing compound in an acrylic polymer. The polyoxyalkylene chain-containing compound may be used singly or in combination of two or more.

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

Further, a specific example of the polyoxyalkylene chain-containing acrylic compound may be exemplified by an oxygen-extended alkyl (meth)acrylate polymer. The foregoing When the ionic compound is used as the antistatic component, the ionic compound is preferably 1 to 50, and 2 to 30. Good, better than 2~20. Further, the terminal of the oxyalkylene chain may be an original hydroxyl group or 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 alkyl (meth) acrylate, and the specific (meth) acrylate alkylene oxide In an example, the ethylene glycol group-containing (meth) acrylate is exemplified by methoxy-diethylene glycol (meth) acrylate and methoxy-triethylene glycol (methyl). a methoxy-polyethylene glycol (meth) acrylate type such as acrylate; ethoxy-diethylene glycol (meth) acrylate, ethoxy-triethylene glycol (meth) acrylate, etc. Oxy-polyethylene glycol (meth) acrylate type; butoxy-poly group such as butoxy-diethylene glycol (meth) acrylate, butoxy-triethylene glycol (meth) acrylate Ethylene glycol (meth) acrylate type; phenoxy-polyethylene glycol such as phenoxy-diethylene glycol (meth) acrylate or phenoxy-triethylene glycol (meth) acrylate ( Methyl) acrylate type; 2-ethylhexyl-polyethylene glycol (meth) acrylate, nonyl phenol-polyethylene glycol (meth) acrylate type, methoxy-dipropylene glycol (methyl) A methoxy-polypropylene glycol (meth) acrylate type such as acrylate.

Further, the monomer unit (component) may be a monomer unit (component) other than the above-mentioned (meth)acrylic acid alkylene oxide. Specific examples of the other monomer component include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and second butyl (meth)acrylate. ) tert-butyl acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, (A) Isooctyl acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate Acrylates and/or methacrylates having a C 1-14 alkyl group such as a diester, n-tride (meth)acrylate or n-tetradecyl (meth)acrylate.

Further, as the monomer unit (component) other than the above (meth)acrylic acid alkylene oxide, for example, a carboxyl group-containing (meth) acrylate, a phosphoric acid group-containing (meth) acrylate, and a cyanide group can be suitably used. (meth) acrylate, vinyl ester, aromatic vinyl compound, acid anhydride group-containing (meth) acrylate, hydroxyl group-containing (meth) acrylate, decyl group-containing (meth) acrylate Amino group-containing (meth) acrylate, epoxy group-containing (meth) acrylate, N-propylene fluorenyl group Porphyrins, vinyl ethers, and the like.

A preferred embodiment is a compound having at least a part of the polyoxyalkylene chain-containing compound having no polyoxyalkylene oxide having a (poly)ethylene oxide chain. By blending the compound containing the (poly)ethylene oxide chain, the compatibility of the matrix polymer with the antistatic component can be improved, and the extravasation to the object can be preferably inhibited, and the adhesive having low pollution can be obtained. Composition. Among them, an adhesive excellent in low contamination property particularly when a block copolymer having PPG-PEG-PPG is used 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 compound containing a polyoxyalkylene chain containing no organopolyoxyalkylene is suitable for a number average molecular weight (Mn) of 50,000 or less. When it is 200 to 30000, it is preferably 200 to 10000, and usually 200 to 5000 is preferably used. When Mn is more than 50,000, the compatibility with the acrylic polymer is lowered, and the adhesive layer tends to be whitened. When Mn is less than 200, contamination due to the above polyoxyalkylene compound is liable to occur. In addition, the Mn here is a value derived from 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). LATEMUL PD-420, LATEMUL PD-420, LATEMUL PD-450, EMULGEN120 (made by Kao), AQUALON HS-10, KH-10, NOIGEN EA-87, EA-137, EA-157, EA-167, EA- 177 (above, manufactured by Daiichi Kogyo Co., Ltd.).

The content of the polyether compound is preferably 0.01 to 3 parts by mass, more preferably 0.03 to 2 parts by mass, even more preferably 0.05 to 1 part by mass based on 100 parts by mass of the (meth)acrylic polymer. The best one is 0.05 to 0.5 parts by mass. When it is within the above range, it is preferable because it is easy to have both antistatic property and light peelability (repeelability).

<crosslinker>

The surface protective film of the present invention preferably contains a crosslinking agent in the above-mentioned adhesive composition. Further, in the present invention, the above-described adhesive composition is used as the adhesive layer. For example, when the (meth)acrylic polymer is contained in the above-mentioned adhesive, cross-linking is carried out by appropriately adjusting the constituent unit of the (meth)acryl-based polymer, the constitutional ratio, the selection of the crosslinking agent, and the addition ratio. ,Available A surface protection 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 cyclopropane derivative, a metal chelate compound or the like can be used, and in particular, an isocyanate compound is preferably used. 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. Cyclohexyl diisocyanate, isophorone diisocyanate (IPDI), alicyclic isocyanate such as 1,3-bis(isohydroxyoxymethyl)cyclohexane, 2,4-toluene diisocyanate, 4,4'- An aromatic isocyanate such as diphenylmethane diisocyanate or decyl diisocyanate (XDI), or an allophanate bond, a diurea bond, an iso-cyanuric bond, a uretdione bond, or a urea bond; a carbodiimide bond, a uretone imine bond, two A modified polyisocyanate modified body such as an 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 have both adhesiveness and repellency (adhesion to a curved surface), and a surface protective film which is more excellent in reliability can be obtained.

Further, when the above isocyanate compound (a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound) are used in combination, the blend ratio (mass ratio) of the two compounds is [2-functional isocyanate compound] / [3 functional or higher isocyanate The compound] (mass ratio) is preferably 0.1/99.9 to 50/50, preferably 0.1/99.9 to 20/80, more preferably 0.1/99.9 to 10/90, and 0.1/99.9 to 5/95. More preferably, the best is 0.1/99.9~1/99. It is preferable to adjust the adhesive layer which is excellent in adhesiveness and repellent property by blending in the said range.

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.) or the like.

The melamine-based resin may, for example, be hexamethylol melamine or the like. The anthracycline derivative is exemplified by a commercial 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 to be 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. 0.5 to 10 parts by mass is more preferable, and it is preferably 1.0 to 6 parts by mass. The aforementioned content is less than 0.01 mass In the case of the mixture, the crosslinking by the crosslinking agent is insufficient, and the cohesive force of the obtained adhesive layer is small, and sufficient heat resistance is not obtained, and the binder tends to remain. 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 (for example, a polarizing plate) is insufficient, and the adherend and the adhesive layer are formed ( There is a tendency for the cause of swelling to occur between the adhesive composition layers. Further, when the amount of the crosslinking agent is large, the peeling electrification property tends to decrease. 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. As the cross-linking catalyst, for example, tin-based catalyst such as dioctyltin dilaurate or dioctyltin dilaurate, ginseng (acetonitrile) iron, and ginseng (hexane-2,4-dione) can be used. Iron, ginseng (heptane-2,4-dione) iron, ginseng (heptane-3,5-dione) iron, ginseng (5-methylhexane-2,4-dione) iron, ginseng Octane-2,4-dione) iron, ginseng (6-methylheptane-2,4-dione) iron, ginseng (2,6-dimethylheptane-3,5-dione) iron , ginseng (-2,4-dione) iron, ginseng (-4,6-dione) iron, ginseng (2,2,6,6-tetramethylheptane-3,5-di Ketone) iron, ginseng (tridecane-6,8-dione) iron, ginseng (1-phenylbutane-1,3-dione) iron, ginseng (hexafluoroacetamidine) iron, ginseng (B)醯Ethyl acetate) iron, ginseng (acetonitrile-n-propyl) iron, ginseng (isopropyl acetate isopropyl) iron, ginseng (acetic acid-n-butyl) iron, ginseng (acetamidine acetic acid - second Butyl) iron, ginseng (acetic acid-t-butyl) iron, ginseng (methyl hydrazine acetate) iron, ginseng (acetic acid ethyl acetate) iron, ginseng (propylene acetate-n-propyl) iron, Ginseng (isopropylidene acetate) iron, ginseng (propionylacetate-n-butyl) iron, ginseng (propionacetic acid-t-butyl) iron, ginseng (propionacetic acid-t-butyl) iron, ginseng (acetic acid benzyl) Iron, ginseng (dimethyl malonate) iron, ginseng (C Iron-based catalysts such as diethyl diacid) iron, trimethoxy iron, triethoxy iron, iron triisopropoxide, and second iron chloride. 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, based on 100 parts by mass of the (meth)acryl-based polymer. When it is within the above range, the crosslinking reaction rate after the formation of the adhesive layer is fast, 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, 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 includes a (meth)acrylic polymer having a alicyclic structure-containing (meth)acrylic monomer represented by the following formula as a monomer unit, and is used as an acrylic adhesive. At the time, the function of imparting the resin to be adhered improves the adhesion and effectively suppresses the floating of the surface protective film.

CH ₂ =C(R ¹ )COOR ²

[In the above formula, R ¹ is a hydrogen atom or a methyl group, and R ² is an alicyclic hydrocarbon group having an alicyclic structure]

Examples of the alicyclic hydrocarbon group R ^{2 of the} above formula include a cyclohexyl group, an isodecyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, a tricyclopentanyl group, a tricyclopentenyl group, and the like. An alicyclic hydrocarbon group or the like. Such an alicyclic hydrocarbon group-containing (meth) acrylate may, for example, be a cyclohexyl (meth)acrylic acid cyclohexyl group, an isodecyl group (meth)acrylic acid isoindole, having a dicyclopentanyl group. An ester of an alicyclic alcohol of (meth)acrylic acid such as dicyclopentane (meth)acrylate. As described above, the acrylic monomer having a large volume structure is present as a monomer unit in the acrylic oligomer, and the adhesion can be improved.

The amount of the acrylic oligomer to be blended is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, even more preferably 0.2 to 5, based on 100 parts by mass of the (meth)acrylic polymer. The mass fraction is better, and it is preferably 0.3 to 2 parts by mass. By using the blending amount within the above range, it is expected to improve the peeling force (adhesive force) to the object, and it is expected to suppress the floating and to obtain a preferable aspect.

Further, the above-mentioned adhesive composition may contain other well-known additives, and may be appropriately added, for example, a powder such as a lubricant, a colorant or a pigment, a plasticizer, an adhesive agent, a low molecular weight polymer, or the like. Surface lubricants, leveling agents, antioxidants, preservatives, light stabilizers, UV absorbers, polymerization inhibitors, decane coupling agents, inorganic or organic fillers, metal powders, particulates, foils, and the like.

<Adhesive layer (surface protective film)

The surface protective film of the present invention is obtained by forming the above-mentioned adhesive layer on a substrate. In this case, the adhesion of the adhesive composition is generally performed after the application of the adhesive composition, and the crosslinking may be carried out after crosslinking. The adhesive layer composed of the adhesive composition is transferred to a substrate or the like.

Further, it is not particularly limited to a method of forming an adhesive layer on a substrate, for example, by coating the substrate with the above-described adhesive composition (solution), drying and removing the polymerization solvent, and the like, and then forming an adhesive layer on the substrate. . After that, the adjustment component of the adhesive layer is changed or the crosslinking reaction is adjusted. It can also be cured. 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.

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

Further, the total thickness of the surface protective film of the present invention is preferably 8 to 300 μm, more preferably 10 to 200 μm, and most preferably 20 to 100 μm. When it is in the above range, the adhesive properties (removability, adhesion, and the like), workability, and appearance characteristics are excellent, which is preferable. Further, the total thickness is intended to include the total thickness of all the layers of the substrate, the adhesive layer, and the antistatic layer.

<isolation sheet>

In the surface protective film of the present invention, for the purpose of protecting the adhesive surface, the separator may be attached to the surface of the adhesive layer.

The material constituting the separator is a paper or a plastic film, but it is preferable to use a plastic film from the viewpoint of excellent surface smoothness. The film is not particularly limited as long as it can protect the film of the adhesive layer, and For example: polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethyl pentylene film, polyvinyl chloride film, chlorinated ethylene copolymer film, polyethylene terephthalate film, A polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, or the like.

The thickness of the spacer is usually 5 to 200 μm, preferably about 10 to 100 μm. When it is in the above range, it is preferable because it is excellent in adhesion workability to the adhesive layer and peeling workability from the adhesive layer. If necessary, the release sheet may be subjected to mold release and antifouling treatment using 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. Antistatic treatment such as pinch type or vapor deposition type.

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 applications (surface protection film) for processing, transportation, and shipment, and to protect the optical member (polarizing plate, etc.). The surface system is useful. Especially for plastic products that are easy to generate static electricity, etc., it is an optical problem that becomes a very serious problem. In the technical field related to electronic components, it is very useful for antistatic applications.

[Examples]

In the following, several embodiments related to the present invention are described, but the invention is not limited by the specific examples. In addition, unless otherwise stated, the "parts" and "%" in the following description are the quality standards. Further, the blending amount (addition amount) in the table shows a solid component or a solid component ratio.

Further, each of the characteristics in the following description is measured or evaluated as follows.

<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: 10μl

Dissolution: THF

Flow rate: 0.6ml/min

Measuring temperature: 40 ° C

Column:

Sample column; TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2 sticks)

Reference column; TSKgel SuperH-RC (1 branch)

Detector: differential refractometer (RI)

Further, the weight average molecular weight was determined in terms of polystyrene. Further, when it is necessary to measure the number average molecular weight (Mn), it is measured in the same manner as the weight average molecular weight.

<glass transition temperature (Tg)>

The glass transition temperature Tg (° C.) was determined by the following formula using the glass transition temperature Tgn (° C.) of the homopolymer of each monomer and using the following literature values.

Formula: 1/(Tg+273)=Σ[Wn/(Tgn+273)]

[In the above formula, Tg (°C) represents the glass transition temperature of the copolymer, Wn(-) represents the mass fraction of each monomer, Tgn (°C) represents the glass transition temperature of the homopolymer of each monomer, and n represents Each monomer type. ]

Literature value:

2-ethylhexyl acrylate (2EHA): -70 ° C

N-butyl acrylate (BA): -55 ° C

4-hydroxybutyl acrylate (4HBA): -32 ° C

2-Hydroxyethyl acrylate (HEA): -15 ° C

Acrylic acid (AA): 106 ° C

N-vinylpyrrolidone (NVP): 80 ° C

Diethyl acrylamide (DEAA): 81 ° C

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

<Measurement of surface resistivity>

The surface resistivity was measured in accordance with JIS-K-6911 using a resistivity meter (manufactured by Mitsubishi Chemical Corporation, HILYSTA UP MCP-HT450 type) under an ambient gas having a temperature of 23 ° C and a humidity of 50% RH.

Furthermore, the surface resistivity (Ω/□) measured on the surface of the antistatic layer in the present invention is preferably less than 1.0 × 10 ¹¹ , more preferably less than 5.0 × 10 ¹⁰ , more preferably under the following conditions. It is less than 1.0×10 ¹⁰ , and the condition is: after application (initial), it is placed in the environment of direct irradiation of fluorescent light (400 lux) at room temperature (23 ° C × 50% RH) for 1 month (30 days). After (time), ultraviolet rays (high pressure mercury lamp, cumulative light amount: 4000 mJ/cm ² , irradiation time: 30 seconds) were further irradiated in an environment of 23 ° C × 50% RH and left to stand (UV irradiation). The surface protective film which exhibits the surface resistivity in the above range can be preferably used as, for example, a surface protective film used for processing or handling of an object which is not resistant to static electricity such as a liquid crystal cell or a semiconductor device. Further, after application, it means that the antistatic agent composition (solution) is applied and dried to form an antistatic layer. The following are the same.

<Identification (printing adhesion) evaluation>

After printing on the surface of the antistatic layer using a X Stamper manufactured by Shachihata Co., Ltd. under the measurement environment of 23 ° C × 50% RH, the product name CELLOTAPE (registered trademark) manufactured by Nichiban Co., Ltd. was attached from the top of the printing, and then peeled off. The condition was peeled off at a speed of 30 m/min and a peeling angle of 180 degrees. 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 × (printing failure), and 50% or more of the printing area was not peeled off and remained as ○ (printing property was good).

<Measurement of back peeling force>

The surface protective film of each example was cut into a width of 70 mm and a length of 100 mm, and the brand name CELLOTAPE (registered trademark) (width 24 mm, rubber-based adhesive tape) manufactured by Nichiban Co., Ltd., or the trade name No. manufactured by Nitto Denko Corporation was used. 31B (19 mm wide, acrylic adhesive tape) was pressure-bonded to the antistatic layer (back layer) of the surface protective film at a pressure of 0.25 MPa and a speed of 0.3 m/min. After leaving it in an environment of 23 ° C × 50% RH for 30 minutes, it was peeled off at a peeling speed of 0.3 m/min and a peeling angle of 180 degrees in the same environment, and the back peeling force at this time was measured (N/24 mm: for CELLOTAPE, Or N/19mm: for No. 31B).

Further, the back peeling force (N/24 mm: for CELLOTAPE) in the present invention is preferably 1 to 15 N/24 mm, preferably 2 to 13 N/24 mm, and more preferably 3 to 10 N/24 mm. Further, the back peeling force (N/19 mm: for No. 31B) is preferably 1 to 15 N/19 mm, more preferably 2 to 13 N/19 mm, more preferably It is 3~10N/19mm. If the back surface peeling force is too light (too low), the removable tape will not adhere to the back surface of the surface protective film, and the surface protective film will not be peeled off. When the back surface peeling force is too high, it will not be easily peeled off from the surface protective film. The removable tape is not good.

<Measurement of slidability (dynamic friction)>

The surface protective film was cut into a test piece having 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: 100 mm). 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 2 to 5, more preferably 2 to 4.8 or less, and still more preferably 3 to 4.5 or less. When it is located in the above range, when the object to which the surface protective film is attached is treated, it is possible to have both the slidability of the back surface of the surface protective film (the surface of the antistatic layer) and the back peeling force (adhesion). Sexuality is beneficial.

<Solvent resistance (appearance)>

The antistatic layer (back layer) of the surface protective film of each example was wiped back and forth 10 times with BEMCOT (manufactured by Asahi Kasei Textile Co., Ltd.) impregnated with ethanol, and the appearance change was visually observed, and the case where the antistatic layer was separated was evaluated as ×, The case where the antistatic layer was not separated was evaluated as ○.

<Solvent resistance (measurement of surface resistivity)>

The antistatic layer (back layer) of each surface protective film was wiped back and forth 10 times with BEMCOT (manufactured by Asahi Kasei Textile Co., Ltd.) impregnated with ethanol, and a resistivity meter was used under ambient gas at a temperature of 23 ° C and a humidity of 50% RH. Mitsubishi Chemical ANALYTECH, Hiresta UP MCP-HT450 type) measures surface resistivity according to JIS-K-6911.

Further, the surface resistivity (Ω/□) measured on the surface of the antistatic layer in the present invention is preferably less than 1.0 × 10 ¹¹ , preferably less than 5.0 × 10 ¹⁰ , more preferably less than 1.0 × 10 ¹⁰ . The surface protective film which exhibits the surface resistivity in the above range can preferably be used as a surface protective film used in processing or handling processes of an electrostatically resistant article such as a liquid crystal cell or a semiconductor device, for example, for erasing a surface. When the protective film is dirty and wiped with ethanol, the surface resistivity can be suppressed to be low.

<Measurement of 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 after peeling off the release liner, as shown in Fig. 2, the acrylic sheet 10 (manufactured by Mitsubishi Rayon Co., Ltd., trade name " ACRYLATE, thickness: 1 mm, width: 70 mm, length: 100 mm) The polarizing plate 20 (made by Nitto Denko Co., Ltd., SEG1423DU polarizing plate, width: 70 mm, length: 100 mm), the surface protective film 1 was pressed by a hand roller. The end of one side protrudes 30 mm from the end of the polarizing plate 20.

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 of the surface protective film 1 which protrudes from the polarizing plate 20 by 30 mm is fixed by an automatic winder (not shown) The part was 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 device 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 it at room temperature (23 ° C × 50% RH) and directly irradiating the light of a fluorescent lamp (400 lux) for one month (30 days), it is the same as the "dissociation of the polarizing plate of the initial polarizing plate". Ground, measuring the "dissociation of the polarizing plate over time", irradiating ultraviolet rays (high-pressure mercury lamp, cumulative light amount: 4000 mJ/cm ² , irradiation time: 30 seconds) in an environment of 23 ° C × 50% RH, and measuring "irradiation UV" The polarizing plate was then stripped of the electrostatic potential, and the measurements were carried out in an environment of 23 ° C × 50% RH.

Further, the polarizing plate peeling electrostatic level is derived from the peeling electrostatic potential of the antistatic layer and the adhesive layer constituting the surface protective film of the present invention, and contributes to antistatic property.

In the polarizing plate of the present invention, the electrostatic potential (kV) (absolute value, initial value, time, and UV exposure) is preferably 0.6 or less, preferably 0.5 or less, and more preferably 0.4 or less. When it is in the above range, for example, it is possible to prevent damage such as liquid crystal display driving, and it is preferable.

<Measurement of film side peeling electrostatic potential (antistatic layer side of surface protective film)>

The surface protective film 1 was peeled off from the surface of 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. The potential of the surface protective film 1 generated at this time is fixed to The potential measuring device 40 (type "KSD-0103" manufactured by Kasuga Electric Co., Ltd.) at a position of a height of 100 mm in the center of the surface protective film 1 measures "initial film side peeling electrostatic potential". The measurement was carried out in an environment of 23 ° C and 50% RH.

In addition, after leaving it at room temperature (23 ° C × 50% RH) and directly irradiating the light of the fluorescent lamp (400 lux) for one month (within 30 days), the "electrode position at the initial film side is peeled off". Similarly, the "film-side peeling electrostatic potential" was measured, and ultraviolet rays were irradiated in an environment of 23 ° C × 50% RH (high-pressure mercury lamp, cumulative light amount: 4000 mJ/cm ² , irradiation time: 30 seconds), and then "UV was measured. The film side peeled off the electrostatic potential after the irradiation, and the measurement was performed in an environment of 23 ° C × 50% RH.

Further, the film side peeling electrostatic level is derived from the peeling electrostatic potential of the antistatic layer constituting the surface protective film of the present invention, and contributes to antistatic property.

In the present invention, the film side peeling electrostatic potential (kV) (absolute value, initial period, time, and UV exposure) is preferably 0.6 or less, preferably 0.5 or less, and more preferably 0.4 or less. When it is in the above range, the surface protective film after peeling is not charged, and workability is excellent, so that it is preferable.

<Preparation of Antistatic Layer A with Water Dispersion>

The binder is a polyester resin VYLONAL MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.), and the conductive polymer is polyaniline sulfonic acid (aqua-pass, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co., Ltd.) and poly( 3,4-ethylenedioxythiophene) (PEDOT) / polystyrenesulfonic acid (PSS) (Baytron P, H, C, manufactured by Starck), the cross-linking agent is a hexamethylene group of diisopropylamine block a hetero-isocyanate of a diisocyanate, the lubricant is a decylamine oleate of a fatty acid decylamine; a solid component meter is added to a mixed solvent of water/ethanol (1/1) 100 parts by mass of a binder, 80 parts by mass of a polyaniline sulfonic acid, a solid content meter of 20 parts by mass of PEDOT/PSS, a solid content meter of 10 parts by mass of a crosslinking agent, and a solid content meter 10 mass The lubricant is stirred for about 20 minutes to allow it to be thoroughly mixed. Thus, an aqueous dispersion of the antistatic layer A having an NV of about 0.4% was prepared.

<Preparation of Antistatic Layer B with Water Dispersion>

The binder is a polyester resin VYLONAL MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.), and the conductive polymer is polyaniline sulfonic acid (aqua-pass, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co., Ltd.) and poly( 3,4-ethylenedioxythiophene) (PEDOT) / polystyrenesulfonic acid (PSS) (Baytron P, H, C, manufactured by Starck), the crosslinking agent is methoxylated methylol melamine, lubricant Methanol-modified polydimethyl siloxane (polystyrene-based lubricant) (BY16-201, TORAY (manufactured by Dow Corning); solid content meter 100 in a mixed solvent of water/ethanol (1/1) 50 parts by mass of the polyaniline sulfonic acid, 30 parts by mass of the PEDOT/PSS of the solid content meter, 10 parts by mass of the cross-linking agent of the solid content meter, and 10 parts by mass of the solid content meter The lubricant was stirred for about 20 minutes to be sufficiently mixed, etc. Thus, an aqueous dispersion of the antistatic layer B having an NV of about 0.4% was prepared.

<Preparation of Antistatic Layer C with Water Dispersion>

The binder is a polyester resin VYLONAL MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.), and the conductive polymer is polyaniline sulfonic acid (aqua-pass, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co., Ltd.) and poly( 3,4-ethylenedioxythiophene) (PEDOT) / polystyrenesulfonic acid (PSS) (Baytron P, H, C, manufactured by Starck), cross-linking agent is diammonium block of hexamethylene A hetero-isocyanate of a diisocyanate and a methoxymethylol melamine, and the lubricant is a fluorine-containing block copolymer of a fluorine-based lubricant (MODIPER F200, manufactured by Nippon Oil Co., Ltd.); in water/ethanol ( To the mixed solvent of 1/1), a binder of 100 parts by mass of a solid content meter, a mass fraction of 25 parts by mass of polyaniline sulfonic acid, a solid content meter of 25 parts by mass of PEDOT/PSS, and a solid content meter 10 are added. Each part of the crosslinking agent and the solid content of 10 parts by mass of the lubricant were stirred for about 20 minutes to be sufficiently mixed. Thus, an aqueous dispersion of the antistatic layer C having an NV of about 0.4% was prepared.

<Preparation of Antistatic Layer D with Water Dispersion>

The binder is a polyester resin VYLONAL MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.), and the conductive polymer is polyaniline sulfonic acid (aqua-pass, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co., Ltd.) and poly( 3,4-ethylenedioxythiophene) (PEDOT) / polystyrenesulfonic acid (PSS) (Baytron P, H, C, manufactured by Starck), the crosslinking agent is methoxylated methylol melamine, lubricant a palm wax of a wax-based lubricant; a binder of 100 parts by mass of a solid content meter, a mass fraction of 20 parts by mass of polyaniline sulfonic acid, and a solid content in a mixed solvent of water/ethanol (1/1) 80 parts by mass of PEDOT/PSS, a solid content meter of 10 parts by mass of a crosslinking agent, and a solid content of 20 parts by mass of a lubricant were stirred for about 20 minutes to be sufficiently mixed. Thus, an aqueous dispersion of the antistatic layer D having an NV of about 0.4% was prepared.

<Preparation of antistatic layer K with water dispersion>

The adhesive is acrylic resin (methyl methacrylate / n-butyl acrylate / cyclohexyl methacrylate = 6 / 2 / 1 copolymer), conductive polymer is polyaniline sulfonic acid (aqua-PASS, weight Average molecular weight of 40,000, Mitsubishi RAYON Co., Ltd.) and poly(3,4-ethylenedioxythiophene) (PEDOT)/polystyrenesulfonic acid (PSS) (Baytron P, H, C, manufactured by Starck), methoxylation of a crosslinking agent Methylol melamine; 100 parts by mass of a solid content meter binder, 25 parts by mass of polyaniline sulfonic acid, and 75 parts by mass of a solid content meter in a mixed solvent of water/ethanol (1/1) The PEDOT/PSS and the solid content meter were mixed with 10 parts by mass of a crosslinking agent, and the mixture was stirred for about 20 minutes to be sufficiently mixed. Thus, an aqueous dispersion of the antistatic layer K of about 0.4% of NV was prepared.

<Preparation of antistatic layer E~J with water dispersion>

Further, according to the blending contents of Table 1, the aqueous dispersion of the antistatic layer E to J was obtained in the same manner as the preparation method of the above-mentioned antistatic layer A to D aqueous dispersion.

<Preparation of Antistatic Layer L with Water Dispersion>

The binder is a polyester resin VYLONAL MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.), and the conductive polymer is polyaniline sulfonic acid (aqua-pass, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co., Ltd.) and poly( 3,4-ethylenedioxythiophene) (PEDOT) / polystyrenesulfonic acid (PSS) (Baytron P, H, C, manufactured by Starck), the cross-linking agent is a hexamethylene group of diisopropylamine block A hetero-isocyanate of a diisocyanate, a lubricant is a fluorine-containing block copolymer of a fluorine-based lubricant (MODIPER F200, manufactured by Nippon Oil Co., Ltd.); and a solid component is added to a mixed solvent of water/ethanol (1/1) 100 parts by mass of a binder, 25 parts by mass of a polyaniline sulfonic acid, a solid content meter of 25 parts by mass of PEDOT/PSS, a solid content meter of 10 parts by mass of a crosslinking agent, and a solid content meter 170 parts by mass of the lubricant was stirred for about 20 minutes to allow it to be thoroughly mixed. Thus, the antistatic layer L with a NV of about 0.4% is prepared. Dispersions.

<Preparation of Antistatic Layer M with Water Dispersion>

The binder was a polyester resin VYLONAL MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.), and the conductive polymer was polyaniline (weight average molecular weight: 15,000, manufactured by Aldrich Co., Ltd.) and poly(3,4-ethylenedioxygen). Thiophene) (PEDOT) / polystyrene sulfonic acid (PSS) (Baytron P, H, C, manufactured by Starck), the crosslinking agent is methoxylated methylol melamine, and the lubricant is used as a wax-based lubricant. Palmitol wax; 100 parts by mass of a solid content meter binder, 10 parts by mass of polyaniline, and 90 parts by mass of PEDOT/PSS of a solid content meter in a mixed solvent of water/ethanol (1/1) A solid content metering agent of 10 parts by mass of a crosslinking agent or a solid content of 20 parts by mass of a lubricant was stirred for about 20 minutes to be sufficiently mixed. Thus, an aqueous dispersion of the antistatic layer M having an NV of about 0.4% was prepared.

<Preparation of Acrylic Polymer 1 for Adhesive Layer>

100 parts by mass of 2-ethylhexyl acrylate (2EHA) and 4 parts by mass of 2-hydroxyethyl acrylate (HEA) were fed into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler. 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator, and 157 parts by mass of ethyl acetate, and nitrogen gas was introduced while slowly stirring, and the liquid temperature in the flask was maintained at about 65 °C. The polymerization reaction was carried out for 6 hours to prepare an acrylic polymer 1 solution (40% by mass). The acrylic polymer 1 had a weight average molecular weight of 540,000 and a glass transition temperature (Tg) of -68 °C.

<Preparation of Acrylic Polymer 8 for Adhesive Layer>

With stirring feather root, thermometer, nitrogen inlet tube, cooler In the neck flask, 100 parts by mass of 2-ethylhexyl acrylate (2EHA), 10 parts by mass of 4-hydroxybutyl acrylate (4HBA), 0.02 parts by mass of acrylic acid (AA), and 0.1 part by mass of N- were fed. Vinylpyrrolidone (NVP), 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator, and 157 parts by mass of ethyl acetate, while introducing nitrogen gas while slowly stirring, maintaining the inside of the flask The polymerization was carried out for 6 hours at a liquid temperature of about 65 ° C to prepare an acrylic polymer 8 solution (40% by mass). The acrylic polymer 8 had a weight average molecular weight of 540,000 and a glass transition temperature (Tg) of -67 °C.

<Preparation of Acrylic Polymers 2 to 7, 9 and 10 for Adhesive Layer>

Acrylic polymers 2 to 7, 9 and 10 were obtained in the same manner as in the preparation of the acrylic polymer 1 or 8 for the above-mentioned pressure-sensitive adhesive layer. Further, the components other than the monomer component are blended in the same amount as the acrylic polymer 1.

<Preparation of Acrylic Adhesive 1 Solution for Adhesive Layer>

The acrylic polymer 1 solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 3.5 parts by mass (solid content: 3.5 parts by mass) was added to 500 parts by mass of the solution (100 parts by mass of the solid component). Cross-linking catalyst of a cross-linked hexamethylene diisocyanate isomeric cyanuric acid (manufactured by Nippon Polycarbonate Co., Ltd., Coronate HX: C/HX) and 3 parts by mass (solid content: 0.03 parts by mass) Dibutyltin dilaurate (1% by mass ethyl acetate solution) was mixed and stirred to prepare an acrylic adhesive 1 solution.

<Preparation of Acrylic Adhesive 10 Solution for Adhesive Layer>

The acrylic polymer 10 solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and an organic polycondensation diluted to 10% by ethyl acetate was added to 500 parts by mass of the solution (100 parts by mass of the solid component). 2 parts by mass of a solution of a decane (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) (solid content: 0.2 parts by mass) and 15 parts by mass (solid content: 0.15 parts by mass) of an alkali metal salt as an antistatic component, that is, ethyl acetate Diluted into 1% lithium bis(trifluoromethane hydrazide) quinone imine (LiN(CF ₃ SO ₂ ) ₂ :LiTFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) solution, 1.0 part by mass (solid content: 1.0 part by mass) of a crosslinking agent Iso-polyisocyanate of hexamethylene diisocyanate (manufactured by Nippon Polycarbonate Co., Ltd., Coronate HX: C/HX), and 0.3 parts by mass (solid content: 0.3 parts by mass) of 1,3-double ( Isohydrooxymethyl)cyclohexane (TAKENATE 600, manufactured by Mitsui Chemicals, Inc.), 0.5 parts by mass (solid content: 0.005 parts by mass) of crosslinked catalyst iron (III) acetamidine acetone (1% by mass ethyl acetate solution) Thereafter, the mixture was stirred and mixed to prepare an acrylic adhesive 10 solution.

<Preparation of Acrylic Adhesive 2~9 Solution for Adhesive Layer>

An acrylic adhesive 2 to 9 solution was obtained in the same manner as in the above-described method of preparing the acrylic adhesive 1 or 10.

<Preparation of urethane-based adhesive 11 solution>

The polyol, the crosslinking agent, the catalyst, and the diluent solvent were blended under the following conditions to obtain an urethane-based adhesive 11 solution: the polyol was a polyol having three hydroxyl groups, PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) 85 parts by mass of a polyol having three hydroxyl groups, SANNIX GP3000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 3000), 13 parts by mass, and a polyol having three hydroxyl groups, SANNIX GP1000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 1000) 2 mass Crosslinker is an isocyanate compound (CoronateHX: C/HX, Japan Polyurethane Co., Ltd. 18 parts by mass; the catalyst was 0.04 parts by mass of iron (III) acetamidine acetone (manufactured by Tokyo Chemical Industry Co., Ltd.); and the dilution solvent was 210 parts by mass of ethyl acetate. Further, the raw material of the urethane-based adhesive solution is a raw material having a concentration of 100% except for the solvent.

<Preparation of urethane-based adhesive 12 solution>

The urethane-based pressure-sensitive adhesive 12 solution was obtained in the same manner as the above-described urethane-based pressure-sensitive adhesive 11 solution except that the catalyst was 0.08 parts by mass of dibutyltin dilaurate using a tin-based catalyst.

<Preparation of urethane-based adhesive 13 solution>

In addition to the above-mentioned amine group, in addition to 30 parts by mass of isopropyl myristate (EXCEPARL IPM, manufactured by Kao), and 0.5 parts by mass of Irganox 1010 (manufactured by BASF Corporation) as an antioxidant, The urethane-based adhesive 11 solution was obtained in the same manner to obtain a urethane-based adhesive 13 solution.

<Preparation of urethane-based adhesive 14 solution>

In addition to a polyether compound (KF-6004, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.1 parts by mass of an antistatic component of 1-ethyl-3-methylimidazolidinium bis(fluorosulfonyl) quinone imine The urethane-based pressure-sensitive adhesive 14 solution was obtained in the same manner as the above-described urethane-based pressure-sensitive adhesive 13 solution, except for 0.5 parts by mass of EMIFSI (manufactured by Daiichi Seiki Co., Ltd.).

<Preparation of Polyoxyl Adhesive 15 Solution>

100 parts by mass of the polyoxynoxy-based adhesive "X-40-3229" (solid content: 60% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.5 part by mass of platinum catalyst "CAT-PL-" 50T" (manufactured by Shin-Etsu Chemical Co., Ltd.), 100 parts by mass of toluene as a solvent to obtain a solution of a polyoxynoxy-based adhesive 15.

<Preparation of Polyoxyl Adhesive 16 Solution>

In addition to a polyether compound (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.2 parts by mass of an antistatic component of lithium bis(trifluoromethanesulfonyl) quinone imine (LiN(CF ₃ SO ₂ ) ₂ A polyfluorene-based adhesive 16 solution was obtained in the same manner as the above-mentioned polyoxygen-based adhesive 15 solution, except that 0.3 parts by mass of LiTFSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

<Modulation of substrate with antistatic layer>

The antistatic layer (A) was coated on a transparent polyethylene terephthalate (PET) film (polyester film) having a thickness of 38 μm, a width of 30 cm, and a length of 40 cm so as to have a thickness of 20, 30, and 45 nm after drying. ) ~(K) Any of the aqueous dispersions. The coating was heated at 130 ° C for 1 minute and dried to prepare a substrate with an antistatic layer having an antistatic layer on the first side of the PET film.

<Example 1>

<Production of surface protective film>

The acrylic adhesive 1 solution was applied to the surface of the substrate having the antistatic layer (substrate with an antistatic layer) opposite to the antistatic layer, and further heated at 130 ° C for 1 minute to form an adhesive having a thickness of 15 μm. Floor. Next, a polyfluorinated epoxy-treated surface of a polyethylene terephthalate film (thickness: 25 μm) which was subjected to a polyfluorene-treated separator on one surface was bonded to the surface of the pressure-sensitive adhesive layer to prepare a surface protective film.

<Example 11>

<Production of surface protective film>

Applying the solution of the urethane-based adhesive 11 to the surface of the substrate having the antistatic layer (substrate with an antistatic layer) opposite to the antistatic layer, and heating at 130 ° C for 1 minute to form a thickness 10 μm adhesive layer. Next, a polyfluorinated epoxy-treated surface of a polyethylene terephthalate film (thickness: 25 μm) which was subjected to a polyfluorene-treated separator on one surface was bonded to the surface of the pressure-sensitive adhesive layer to prepare a surface protective film.

<Example 15>

<Production of surface protective film>

The polyfluorene-based adhesive 15 solution was applied to the surface of the substrate (antistatic layer-attached substrate) having the antistatic layer opposite to the antistatic layer, and further heated at 150 ° C for 1 minute to form a thickness of 10 μm. Adhesive layer. Next, a polyfluorinated epoxy-treated surface of a polyethylene terephthalate film (thickness: 25 μm) which was subjected to a polyfluorene-treated separator on one surface was bonded to the surface of the pressure-sensitive adhesive layer to prepare a surface protective film.

<Examples 2 to 10, Example 17, Example 18, and Comparative Examples 1 to 5>

A surface protective film was produced in the same manner as in Example 1 in accordance with the blending contents of Tables 1 to 3.

<Examples 12 to 14>

A surface protective film was produced in the same manner as in Example 11 in accordance with the blending contents of Tables 1 and 4.

<Example 16>

According to the blending contents of Tables 1 and 5, and in the same manner as in the embodiment 15, As a surface protection film.

The results of the above various measurements and evaluations of the surface protective films of the examples and the comparative examples are shown in Table 6.

Furthermore, the abbreviation in Table 2 and Table 3 will be described below. The abbreviations in other tables are based on the examples.

[monomer composition]

2EHA: 2-ethylhexyl acrylate

BA: n-butyl acrylate

4HBA: 4-hydroxybutyl acrylate

HEA: 2-hydroxyethyl acrylate

AA: Acrylic

NVP: N-vinylpyrrolidone

DEAA: diethyl acrylamide

[Polyether compound]

KF353: an organopolyoxane having an oxyalkylene chain (HLB value: 10) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-353)

KF6004: an organopolyoxane having an oxygen-extended alkyl chain (HLB value: 9) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6004)

HS10: First Industrial Pharmaceutical Co., Ltd., 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, east Jinghuacheng Industrial Co., Ltd.) (100% active ingredient)

BMPTFSI: 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (ionic liquid, manufactured by Sigma Aldrich, liquid at 25 ° C) (active ingredient 100%)

EMIFSI: ionic liquid: 1-ethyl-3-methylimidazolidinium bis(fluorosulfonyl) quinone imine (ionic liquid, manufactured by Daiichi Kogyo Co., Ltd.) (active ingredient 100%)

[crosslinking agent]

C/HX: isomeric cyanuric acid of hexamethylene diisocyanate (manufactured by Japan Polyurethane Co., Ltd., trade name: Coronate HX) (active ingredient 100%)

C/L: trimethylolpropane/toluene diisocyanate (manufactured by Japan Polyurethane Industry Co., Ltd., trade name: Coronate L) (active ingredient: 75%)

TAKENATE 600: 1,3-bis(isocyanatomethyl)cyclohexane (manufactured by Mitsui Chemicals, Inc., trade name: TAKENATE 600) (active ingredient 100%)

[crosslinking catalyst]

Sn: dibutyltin dilaurate (dibutyltin dilaurate) (manufactured by Tokyo Chemical Industry Co., Ltd.)

Fe: ginseng (acetonitrile) iron (iron (III) acetonitrile) (manufactured by Tokyo Chemical Industry Co., Ltd.)

In all of the examples in Table 6, it was confirmed that the surface resistivity, the film side peeling electrostatic potential, and the like, and the ionic compound and the polyether compound doped with the antistatic agent, the polarizing plate peeled off the electrostatic potential. It is excellent, and when the lubricant is blended in the antistatic layer, the slidability is also excellent. When the antistatic component is blended in the adhesive layer, the polarizing plate is also excellent in peeling off the electrostatic potential. Further, in Example 17 using an acrylic resin as a binder, it was confirmed that the solvent resistance was also excellent in the examples using the polyester resin.

On the other hand, it can be confirmed from Table 6 that in Comparative Examples 1 to 5, since the conductive polymer constituting the antistatic layer was not blended in the desired ratio, the surface resistivity after the irradiation of UV or the peeling of the film side was static. The bit is worse than the embodiment. In particular, in Comparative Example 5, since the polyaniline sulfonic acid of its own doping type was replaced with an externally doped polyaniline, a polyanion (PSS) (corresponding to doping) was generated with time. In the case of detachment from polythiophene (PEDOT), it was confirmed that the surface resistivity over time was inferior to that of the examples.

Industrial availability

The surface protection film disclosed herein is suitable as a surface protection film for protecting the optical member when manufacturing or handling an optical member, which is used as a liquid crystal display panel, a plasma display panel (PDP), and an organic electroluminescence. (EL) Components such as displays. It is especially useful as a surface protection film (optical) for optical members such as a polarizing plate (polarizing film) for a liquid crystal display panel, a wave plate, a phase difference plate, an optical compensation film, a brightness enhancement film, a light diffusion sheet, and a reflection sheet. Use a surface protection film).

Claims (11)

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 formed on the substrate and composed of an adhesive The surface protective film is characterized in that the antistatic layer is formed of an antistatic agent composition containing polyaniline sulfonic acid as a conductive polymer component and An anionic doped polythiophene and a binder; the blending ratio (mass ratio) of the polyaniline sulfonic acid to the polyanion-doped polythiophene is 90:10 to 10:90. The surface protective film of claim 1, wherein the polythiophene is poly(3,4-ethylenedioxythiophene) (PEDOT). The surface protective film of claim 1 or 2, wherein the polyanionic polystyrene sulfonic acid (PSS) is used. The surface protection film according to any one of claims 1 to 3, wherein the binder is a polyester resin. The surface protection film according to any one of claims 1 to 4, wherein the antistatic agent composition contains a melamine-based crosslinking agent and/or an isocyanate-based crosslinking agent as a crosslinking agent. The surface protection film according to any one of claims 1 to 5, wherein the antistatic agent composition is selected from the group consisting of fatty acid amides, fatty acid esters, polyfluorene-based lubricants, fluorine-based lubricants, and wax-based lubricants. At least one of the groups consisting of the agents serves as a lubricant. The surface protection film according to any one of claims 1 to 6, wherein the substrate is a polyester film. The surface protection film according to any one of claims 1 to 7, 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 8, wherein the above-mentioned adhesive composition contains a polyether compound. The surface protection film according to any one of claims 1 to 9, wherein the aforementioned adhesive composition contains an antistatic component. An optical member characterized by being protected by a surface protective film according to any one of claims 1 to 10.