TW201529316A - Surface protection film, method for manufacturing surface protection film, and optical member - Google Patents

Abstract

Provided are a surface protection film capable of achieving antistatic properties and durable stability in peeling electrostatic potential, a method for manufacturing the surface protection film, and an optical member. This surface protection film is provided with a substrate having a first surface and a second surface, an antistatic layer provided on the first surface of the substrate, and a pressure-sensitive adhesive layer provided on the second surface of the substrate, and is characterized in that the antistatic layer is formed from an antistatic composition containing polyaniline sulfonic acid as an electroconductive polymer component, a polyester resin as a binder, and an isocyanate crosslinking agent as a crosslinking agent.

Description

Surface protective film, method for producing surface protective film, and optical member

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

The present invention relates to a surface provided with a substrate having a first surface and a second surface, an antistatic layer provided on the first surface of the substrate, and an adhesive layer provided on the second surface of the substrate Protective film, in detail, the present invention relates to a surface protective film having an antistatic function. The surface protective film of the present invention is preferred for use in attaching to a plastic article or the like which is liable to generate static electricity. Among them, in particular, it is used as a surface protective film for the purpose of protecting the surface of a member such as a polarizing plate, a wave plate, a phase difference plate, an optical compensation film, a reflection sheet, or a brightness enhancement film for a liquid crystal display or the like. it works.

The surface protective film (also referred to as a surface protective sheet) usually has a structure in which an adhesive layer is provided on a film-form substrate (support). The protective film is bonded to the adherend (protected body) via the adhesive layer, thereby protecting the adherend from damage or contamination during processing, transportation, and the like. For example, a panel of a liquid crystal display is formed by bonding an optical member such as a polarizing plate or a wave plate to a liquid crystal cell via an adhesive layer. In the manufacture of the liquid crystal display panel, the polarizing plate bonded to the liquid crystal cell is temporarily formed into a roll form, and then taken out from the roll and cut into a desired size corresponding to the shape of the liquid crystal cell. Here, in order to prevent the polarizing plate from being damaged by friction with the conveying roller or the like in the intermediate step, a method of bonding the surface protective film to one side or both sides (typically, one side) of the polarizing plate is employed. The surface protective film is peeled off at an unnecessary stage.

Since the surface protective film or the optical member is usually made of a plastic material, electrical insulation is high, and static electricity is generated by friction or peeling. Therefore, when the surface protective film is peeled off from an optical member such as a polarizing plate, static electricity is likely to be generated. When a voltage is applied to the liquid crystal in a state where the static electricity remains, the alignment of the liquid crystal molecules is lost or the defects of the panel are caused. Moreover, the presence of static electricity can also be a cause of attracting dust or reducing workability. In this case, the surface protective film is subjected to an antistatic treatment, for example, by forming an antistatic layer or performing antistatic coating as a surface layer (top coat layer, back layer) of the surface protective film to impart an antistatic function ( Refer to Patent Documents 1 and 2).

Further, in recent years, as a conductive polymer for imparting an antistatic function to the surface layer of the surface protective film, PEDOT (poly(3,4-ethylenedioxythiophene))/PSS (polystyrenesulfonic acid) is used. (Polythiophene type) is a water-dispersible type. However, when the water-dispersed type is stored in a solution state, aggregates are generated, and a uniform antistatic layer cannot be formed, which causes a problem of poor workability. Further, when the antistatic layer is formed using the above conductive polymer, there is a case where the PSS (corresponding to a dopant) is detached from the PEDOT over time, and a surface resistance value or a peeling static voltage is increased. Further, problems such as an increase in the surface resistance value (deterioration) occur along with oxidative degradation or photodegradation.

In addition, when the surface resistance value or the like is increased (deteriorated), static electricity is generated when the surface protective film is peeled off from the adherend, and there is a problem.

[Previous Technical Literature] [Patent Literature]

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

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-255332

Therefore, the present invention has been intensively studied in view of the above circumstances, and as a result, provides a surface protective film and a surface protective film which can achieve antistatic property and time stability of peeling static voltage. Manufacturing method and optical member.

That is, the surface protection film of the present invention is characterized in that it comprises a substrate having a first surface and a second surface, an antistatic layer provided on the first surface of the substrate, and the second surface of the substrate An adhesive layer formed of an adhesive composition on the surface, and the antistatic layer is crosslinked by a polyaniline sulfonic acid as a conductive polymer component, a polyester resin as a binder, and an isocyanate crosslinking agent as a crosslinking agent. The antistatic agent composition of the agent is formed.

In the surface protective film of the present invention, it is preferred that the antistatic agent composition further contains a fatty guanamine as a lubricant.

The surface protective film of the present invention preferably has the above substrate as a polyester film.

In the surface protection film of the present invention, it is preferable that the pressure-sensitive adhesive composition contains at least one selected from the group consisting of an acrylic pressure-sensitive adhesive, an urethane-based pressure-sensitive adhesive, and a polyoxymethylene-based pressure-sensitive adhesive.

In the surface protective film of the present invention, it is preferred that the above adhesive composition contains an antistatic component.

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

The method for producing a surface protective film of the present invention is preferably a method for producing the surface protective film, and includes a step of preparing an aqueous solution containing the antistatic agent composition, and applying the aqueous solution to the substrate. The step of preparing an antistatic layer while drying on one side.

The surface protection film of the present invention is formed by using an antistatic layer provided on the first surface (back surface) of the substrate from an antistatic agent composition containing a specific conductive polymer component, a binder, and a crosslinking agent. A uniform antistatic layer can be formed, and workability is also excellent, and a surface protective film capable of achieving antistatic property and peeling static voltage stability based on the above-mentioned antistatic layer, a method for producing a surface protective film, and optical can be provided. Components are therefore more useful.

1‧‧‧Surface protection film

10‧‧‧Acrylic board

11‧‧‧Antistatic 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 static voltage.

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

<Overall structure of surface protective film>

The surface protective film disclosed herein is generally referred to as an adhesive sheet, an adhesive tape, an adhesive label, an adhesive film, or the like, and is particularly preferably used as an optical component (for example, as a component of a liquid crystal display panel such as a polarizing plate or a wave plate). The surface protective film that protects the surface of the optical component during processing or during transport. The adhesive layer in the surface protective film is typically formed continuously, but is not limited to this form, and may be, for example, an adhesive layer formed into a regular or random pattern such as a dot or a stripe. Further, the surface protective film disclosed herein may be in the form of a roll or a single piece.

A typical configuration example of the surface protective film disclosed herein is schematically shown in FIG. The surface protection film 1 includes a substrate (for example, a polyester film) 12, an antistatic layer 11 provided on the first surface 12 thereof, and an adhesive layer 13 disposed on the second surface of the substrate 12 (and The antistatic layer 11 is the surface on the opposite side). The surface protective film 1 is used by attaching the adhesive layer 13 to an adherend (protection target such as a surface of an optical component such as a polarizing plate). The surface protective film 1 before use (that is, before being attached to the adherend) may be a surface of the adhesive layer 13 (attached to the surface of the adherend) and a release liner which is a release surface from at least the adhesive layer 13 side. The form protected by the mat. Alternatively, the surface protective film 1 may be wound into a roll shape, whereby the adhesive layer 13 abuts against the back surface of the substrate 12 (the surface of the antistatic layer 11), and the surface thereof is protected.

As shown in FIG. 1 , the antistatic layer 11 is directly formed on the first surface of the substrate 12 (without intervening other layers), and the antistatic layer 11 is exposed to the back surface of the surface protective film 1 (ie, antistatic). The layer 11 is also a surface coating layer. The film 12 is provided with an antistatic layer 11 with an antistatic layer on the substrate 12 (the film is further used). and Since the surface protective film can reduce the number of layers constituting the surface protective film, it is also advantageous from the viewpoint of improving productivity.

<Substrate>

The surface protective film of the present invention is characterized in that it has a substrate comprising a first surface (back surface) and a second surface (surface opposite to the first surface). In the technique disclosed herein, the resin material constituting the substrate can be used without particular limitation, and for example, transparency, mechanical strength, thermal stability, water repellency, isotropy, flexibility, and size are preferably used. Excellent in stability and other characteristics. In particular, since the substrate has flexibility, the adhesive composition can be applied by a roll coater or the like, and can be wound into a roll shape, which is useful.

As the substrate (support), for example, a plastic material containing a resin material having a polymer as a main resin component (a main component of a resin component, typically a component of 50% by mass or more) is preferably used. The film is used as the above substrate: a polyester-based polymer such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polybutylene terephthalate; A cellulose-based polymer such as triacetonitrile cellulose; a polycarbonate-based polymer; an acrylic polymer such as polymethyl methacrylate; and the like. As another example of the above-mentioned resin material, a polymer such as a styrene polymer such as polystyrene or an acrylonitrile-styrene copolymer; a polyethylene or a polypropylene having a ring shape or a drop may be mentioned. An olefin polymer such as an olefin structure or an ethylene-propylene copolymer; a vinyl chloride polymer; a phthalamide polymer such as nylon 6, nylon 6,6 or an aromatic polyamine; and the like. 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 vinylidene chloride polymer, an ethylene butyral polymer, an aryl ester polymer, a polyoxymethylene polymer, or an epoxy polymer. It may also be a substrate comprising a mixture of two or more of the above polymers.

As the above substrate, a plastic film containing a transparent thermoplastic resin material can be preferably used. In the above plastic film, a more preferable aspect is to use a polyester film. Here, the so-called polyester film Means a polymer material having a main skeleton based on an ester bond such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polybutylene terephthalate (poly Ester resin) as a main resin component. The polyester film has preferable properties as a substrate of the surface protective film, such as excellent optical properties or dimensional stability, but on the other hand, if it is used as it is, it has a property of being easily charged.

Various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, and a colorant (pigment, dye, etc.) may be blended in the resin material constituting the substrate. The surface of the first surface of the polyester film (the surface on which the antistatic layer is provided) may be subjected to a known or conventional surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, Coating of the primer, and the like. Such a surface treatment may be, for example, a treatment for improving the adhesion between the substrate and the antistatic layer. Surface treatment such as introduction of a polar group such as a hydroxyl group (-OH group) onto the surface of the substrate can be preferably employed. 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). The surface treatment may be a treatment for improving the adhesion between the film and the adhesive layer (adhesion 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 a plastic film obtained by performing an antistatic treatment can also be used as the substrate. It is preferable to use the above substrate to suppress charging of the surface protective film itself at the time of peeling. Further, the substrate is a plastic film, and the plastic film is subjected to an antistatic treatment to reduce the charging of the surface protective film itself, and an antistatic property to the adherend can be obtained. In addition, the method of providing an antistatic function is not particularly limited, and a conventionally known method can be used. For example, a method of applying an antistatic resin containing an antistatic agent and a resin component or containing a conductive polymer, A method of conductive resin of a conductive material; a method of vapor-depositing or plating a conductive material; and 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 100 μm. When the thickness of the base material is in the above range, the adhesion to the adherend and the peeling workability from the adherend are excellent, which is preferable.

<antistatic layer (top coat)>

The surface protection film of the present invention is characterized in that it comprises 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 (back surface) An antistatic layer and an adhesive layer formed of the adhesive composition on the second surface of the substrate, wherein the antistatic layer contains polyaniline sulfonic acid as a conductive polymer component. It is formed of a polyester resin of a binder and an antistatic agent composition of an isocyanate crosslinking agent as a crosslinking agent. The surface protective film has an antistatic layer (top coat layer), and the antistatic property of the surface protective film and the stability over time of the peeling static voltage are improved, which is a preferable aspect.

<Electrically conductive polymer>

The antistatic layer is characterized by containing polyaniline sulfonic acid as a conductive polymer component. By using the above conductive polymer, the antistatic property based on the antistatic layer and the peeling static voltage with time can be satisfied. Further, the polyaniline sulfonic acid-based "water-soluble" can be fixed to the antistatic layer by using an isocyanate-based crosslinking agent described below to improve water resistance. By using an aqueous solution containing the above water-soluble conductive polymer, an antistatic layer excellent in surface resistance over time can be obtained, which is preferable. On the other hand, when the conductive polymer used for forming the antistatic layer is "water-dispersible", it is easy to form an antistatic layer using a solution containing the water-dispersible conductive polymer. Aggregates are generated, they are not uniformly coated, and the surface resistance value tends to deteriorate significantly over time, which is not preferable.

The amount of the conductive polymer to be used is preferably 10 to 200 parts by mass, more preferably 25 to 150 parts by mass, even more preferably 100 to 150 parts by mass, based on 100 parts by mass of the binder contained in the antistatic layer (top coat layer). 40 to 120 parts by mass. When the amount of the conductive polymer used is too small, the antistatic effect may be small. When the amount of the conductive polymer used is too large, the adhesion of the antistatic layer to the substrate may be lowered or the transparency may be lowered. Therefore, it is not good.

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

As a method of forming the above-described antistatic layer, a method of applying a coating material for forming an antistatic layer to a first surface of a substrate (support) and drying (or hardening) it may be employed as a method for preparing a coating. The conductive polymer component of the cloth material contains polyaniline sulfonic acid, a polyester resin as a binder, and an isocyanate crosslinking agent as a crosslinking agent as an essential component, and the above-mentioned essential component can be preferably dissolved in water. The resulting form (called an aqueous conductive polymer solution, or simply an aqueous solution). The conductive polymer aqueous solution can be prepared, for example, by dissolving a conductive polymer having a hydrophilic functional group (which can be synthesized by a method of copolymerizing a monomer having a hydrophilic functional group in the molecule) in water. Examples of the hydrophilic functional group include a sulfo group, an amine group, a decylamino group, an imido group, a hydroxyl group, a decyl group, a decyl group, a carboxyl group, a quaternary ammonium group, a sulfate group (-O-SO ₃ H), and a phosphoric acid group. An ester group (for example, -O-PO(OH) ₂ ) or the like. The hydrophilic functional group can also form a salt.

In addition, as a commercial item of the above-mentioned polyaniline sulfonic acid aqueous solution, the brand name "aqua-pass" manufactured by Mitsubishi Rayon Co., Ltd., etc. can be illustrated.

In the antistatic layer disclosed herein, the conductive polymer component contains polyaniline sulfonic acid (polyaniline type) as an essential component, but may contain, for example, one or two or more kinds of antistatic components (conductive). An organic conductive substance other than a polymer, an inorganic conductive substance, an antistatic agent, etc.). Furthermore, it is preferable that the antistatic layer is substantially free of an antistatic component other than the conductive polymer, that is, the antistatic component contained in the antistatic layer is substantially only The aspect in which the conductive polymer is formed.

Examples of the organic conductive material include a quaternary ammonium salt, a pyridinium salt, a cationic antistatic agent having a cationic functional group such as a primary amino group, a secondary amino group, and a tertiary amino group; a sulfonate or sulfuric acid; An anionic antistatic agent having an anionic functional group such as an ester salt, a phosphonate or a phosphate salt; an alkylbetaine and a derivative thereof, an imidazoline and a derivative thereof, a zwitterionic antistatic agent such as alanine and a derivative thereof; a nonionic antistatic agent such as an amino alcohol and a derivative thereof, glycerin and a derivative thereof, polyethylene glycol and a derivative thereof; An ionically conductive polymer obtained by polymerizing or copolymerizing monomers of an anionic, zwitterionic ionic conductive group (for example, a quaternary ammonium salt group); polythiophene, polyaniline, polypyrrole, polyethyleneimine A conductive polymer such as an allylamine polymer. These antistatic agents may be used alone or in combination of two or more.

Examples of the inorganic conductive material include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, and the like. Cobalt, copper iodide, ITO (indium oxide/tin oxide), ATO (antimony oxide/tin oxide), and the like. These inorganic conductive materials may be used alone or in combination of two or more.

Examples of the antistatic agent include a cationic antistatic agent, an anionic antistatic agent, a zwitterionic antistatic agent, and a nonionic antistatic agent, and the above-described cationic, anionic, and zwitterionic ionic conductivity. An ion conductive polymer obtained by polymerizing or copolymerizing a monomer.

<Binder>

The antistatic layer is characterized in that it contains a polyester resin as a binder as an essential component. The polyester resin is preferably a resin material containing a polyester as a main component (typically, it accounts for more than 50% by mass, preferably 75% by mass or more, for example, 90% by mass or more). Typically, the above polyester preferably has a polycarboxylic acid (typically a dicarboxylic acid) having two or more carboxyl groups selected from one molecule and a derivative thereof (an acid anhydride, an esterified product, and a halogenated polycarboxylic acid) One or two or more compounds (polycarboxylic acid component) and one or more compounds selected from polyhydric alcohols (typically diols) having two or more hydroxyl groups in one molecule (Polyol component) condensed structure.

Examples of the compound which can be used as the above polyvalent carboxylic acid component include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, and alkyl succinic acid. (for malic acid, meso-tartaric acid, itaconic acid, maleic acid, methyl maleic acid, fumaric acid, methyl fumaric acid, acetylene dicarboxylic acid, pentane Diacid, hexafluoroglutaric acid, methyl glutaric acid, glutaconic acid, adipic acid, dithioadipate, methyl adipic acid, dimethyl adipate, tetramethyl adipate , methylene adipate, muconic acid, galactosuccinic acid, pimelic acid, suberic acid, perfluorooctanoic acid, 3,3,6,6-tetramethyloctanedioic acid, sebacic acid, An aliphatic dicarboxylic acid such as sebacic acid, perfluorosebacic acid, tridecanedioic acid, dodecyl dicarboxylic acid, tridecyl dicarboxylic acid or tetradecyl dicarboxylic acid; cycloalkyl Carboxylic acid (for example, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid), 1,4-(2-lower) Alkene dicarboxylic acid, 5-nor Ethylene-2,3-dicarboxylic acid (bicycloheptylene dicarboxylic acid), adamantane dicarboxylic acid, octane dicarboxylic acid, etc. alicyclic dicarboxylic acid; phthalic acid, isophthalic acid, dithio Isophthalic acid, methyl isophthalic acid, dimethyl isophthalic acid, chloroisophthalic acid, dichloroisophthalic acid, terephthalic acid, methyl terephthalic acid, dimethyl p-benzene Dicarboxylic acid, chloroterephthalic acid, bromine terephthalic acid, naphthalene dicarboxylic acid, oxophthalic dicarboxylic acid, stilbene dicarboxylic acid, biphenyl dicarboxylic acid, extended biphenyl dicarboxylic acid, dimethyl extension Biphenyldicarboxylic acid, 4,4"-pair extended triphenyl dicarboxylic acid, 4,4"-paraphenylene dicarboxylic acid, bibenzyl dicarboxylic acid, azobenzene dicarboxylic acid, high phthalic acid Formic acid, phenyldiacetic acid, phenyldipropionic acid, naphthalene dipropionic acid, biphenyl diacetic acid, biphenyl dipropionic acid, 3,3'-[4,4'-(methylene two pairs of extension An aromatic dicarboxylic acid such as phenyl)dipropionic acid, 4,4'-bibenzyl diacetic acid, 3,3'-(4,4'-bibenzyl) dipropionic acid or oxydi-p-phenylenediacetic acid; An acid anhydride of any of the above polycarboxylic acids; an ester of any of the above polycarboxylic acids (for example, an alkyl ester, which may be a monoester, a diester, etc.); An acid halide corresponding to any polycarboxylic acid (for example, dimethyl hydrazine); and the like.

Preferred 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 sebacic acid; An aliphatic dicarboxylic acid such as azelaic acid, succinic acid, fumaric acid, maleic acid, bicycloheptene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and an anhydride thereof; a lower alkyl ester of a carboxylic acid (for example, an ester of a monool having 1 to 3 carbon atoms).

On the other hand, examples of the compound which can be used as the above polyol component include ethylene glycol, propylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butanediol, and 1,4- Butylene glycol, 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, 2-butyl-2-ethyl-1,3- Glycols such as propylene glycol, benzenedimethanol, hydrogenated bisphenol A, and bisphenol A. As another example, an alkylene oxide adduct of such a compound (for example, an ethylene oxide adduct, a propylene oxide adduct, etc.) is mentioned.

The molecular weight of the above polyester resin is, for example, from 5 × 10 ³ to 1.5 × 10 ⁵ by weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC). Good is 1×10 ⁴ ~6×10 ⁴ or so). Further, the glass transition temperature (Tg) of the polyester resin may be, for example, 0 to 120 ° C (preferably 10 to 80 ° C).

As the polyester resin, a commercially available product name "Vylonal" manufactured by Toyobo Co., Ltd., or the like can be used.

The antistatic layer (top coat layer) may further contain a resin other than the polyester resin (for example, selected from the group consisting of the properties of the surface protective film disclosed herein (for example, performance such as antistatic property). Acrylic resin, urethane acrylate resin, acrylic styrene resin, acrylic polyoxyn resin, polyoxyn oxy resin, polyazide resin, polyurethane resin, fluororesin, polyolefin resin, etc. One or two or more kinds of resins) are used as a binder. As a preferred aspect of the technology disclosed herein, the adhesive of the antistatic layer is substantially composed only of a polyester resin. For example, an antistatic layer in which the ratio of the binder of the polyester resin to the binder is 98 to 100% by mass is preferable. The ratio of the binder to the entire antistatic layer can be, for example, 50 to 95% by mass, and usually 60 to 90% by mass.

<Lubricant>

A preferred aspect of the antistatic layer (top coat) in the techniques disclosed herein is the use of fatty guanamine as a lubricant. By using fatty guanamine as a lubricant, even if the surface of the antistatic layer is not subjected to further release treatment (for example, coating a polysiloxane stripper, long In the aspect of the treatment of drying a known release treatment agent such as an alkyl group-based release agent, the antistatic layer (top coat layer) having sufficient slidability and printing adhesion can be obtained. The best way. In such a manner that the surface of the antistatic layer is not further subjected to the release treatment, the whitening caused by the release treatment agent (for example, whitening caused by storage under heating and humidification conditions) can be prevented. good. Moreover, it is also advantageous in terms of solvent resistance.

Specific examples of the above fatty guanamine include laurylamine, palm decylamine, stearylamine, behenamide, hydroxystearate, ceramide, sucrose, and N-oil palmitoyl. Amine, N-stearyl stearylamine, N-stearyl decylamine, N-oleyl stearylamine, N-stearyl glucosamine, hydroxymethyl stearylamine, methylene Bistearate, ethylidene, exoethyl bis-lauroside, ethyl bis-stearylamine, ethyl bishydroxystearylamine, ethyl bis-decylamine Hexamethylene distearylamine, hexamethylenebisammoniumamine, hexamethylene hydroxystearamide, N,N'-distearylhexamethyleneamine, N,N'-di Stearyl diamine, diethylamine, exoethylcandamine, hexamethylenebisoleamide, N,N'-dioleyl decylamine, N,N' - Dioleyl quinone diamine, p-xylylene bis stearylamine, p-xylylene bishydroxystearylamine, N, N'-stearyl methacrylamide, and the like. These lubricants may be used alone or in combination of two or more.

The ratio of the lubricant to the entire antistatic layer can be 1 to 50% by mass, and usually 5 to 40% by mass. When the content ratio of the lubricant is too small, the slidability tends to be lowered. If the content ratio of the lubricant is too large, there is a possibility that the printing adhesion is lowered.

The technique disclosed herein can be carried out in such a manner that the antistatic layer (top coat layer) contains other lubricants in addition to the above-mentioned fatty guanamine, without being greatly impaired and its application effect. Examples of the other lubricants include petroleum waxes (such as paraffin), mineral waxes (such as montan wax), higher fatty acids (such as waxy acid), and neutral fats (such as palmitic acid triglyceride). wax. Or in addition to the above wax, it may also be auxiliary to contain the usual aggregation An oxygen-based lubricant, a fluorine-based lubricant, or the like. The technique disclosed herein can be preferably carried out without substantially including the aspect of the polyfluorene-based lubricant, the fluorine-based lubricant or the like. However, without detracting from the application effect of the technology disclosed herein, it is not excluded to contain an antifoaming agent for other purposes other than as a lubricant (for example, as a coating material for forming an antistatic layer described below). a polyoxygen compound.

<crosslinker>

The above antistatic layer is characterized by containing an isocyanate crosslinking agent as a crosslinking agent. By using the above-mentioned isocyanate-based crosslinking agent, the water-soluble polyaniline sulfonic acid, which is an essential component, can be fixed to the binder when the antistatic layer is formed, and the water resistance is excellent, and the effect of improving the printing adhesion and the like can be achieved.

Moreover, it is preferable to use a blocked isocyanate type crosslinking agent which is stable even in an aqueous solution as the said isocyanate type crosslinking agent. Specific examples of the blocked isocyanate crosslinking agent include alcohols, phenols, thiophenols, amines, quinones, anthraquinones, indoleamines, and active methylene compounds. An isocyanate-based crosslinking agent which can be used in the preparation of a usual adhesive layer or an antistatic layer (top coat) such as a mercaptan, an imine, a urea, a diaryl compound or sodium hydrogen sulfite (for example) The isocyanate compound (isocyanate crosslinking agent) used for the adhesive layer described below is blocked.

The antistatic layer in the technology disclosed herein may contain other antistatic components, antioxidants, colorants (pigments, dyes, etc.), fluidity adjusters (thixotropic agents, tackifiers, etc.), and film forming aids as needed. Additives such as surfactants (antifoaming agents, etc.) and preservatives.

<Formation of antistatic layer>

The antistatic layer (top coat layer) can be preferably formed by dissolving an essential component such as the conductive polymer component and an additive used as needed in an appropriate solvent (water, etc.). The liquid composition (the coating material for forming an antistatic layer, the antistatic agent composition) thus obtained is applied to the substrate. For example, a method of applying the above coating material to the first side of the substrate and drying it, and optionally Hardening treatment (heat treatment, ultraviolet treatment, etc.) is required. The NV (nonvolatile content) of the coating material can 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). Suitable. In the case of forming an antistatic layer having a small thickness, it is preferable that the NV of the coating material is, for example, 0.05 to 0.50% by mass (for example, 0.10 to 0.40% by mass). As described above, a more uniform antistatic layer can be formed by using a coating material of low NV.

The solvent constituting the coating material for forming an antistatic layer is preferably one which can stably dissolve the constituent component of the antistatic layer. The solvent may be an organic solvent, water, or a mixed solvent of these. As the organic solvent, for example, one or two 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 two can be used. 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 alicyclic alcohol; alkylene glycol monoalkyl ether (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), dialkyl alkyl glycol monoalkyl ether and other glycol ethers; Wait. 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).

<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, more preferably from 3 to 60 nm. When the thickness of the antistatic layer is too small, it becomes difficult to form an antistatic layer uniformly (for example, the thickness of the antistatic layer varies greatly depending on the thickness of the antistatic layer), and therefore, the appearance of the surface protective film becomes The possibility of an uneven situation. On the other hand, if it is too thick, it may affect the characteristics (optical characteristics, dimensional stability, etc.) of the substrate.

In a preferred aspect of the surface protective film disclosed herein, the surface resistance value (Ω/□) measured as the surface of the antistatic layer is preferably less than 1.0×10 ¹¹ , more preferably less than 5.0 × 10 ¹⁰ , and further preferably less than 1.0 × 10 ¹⁰ . The surface protective film which exhibits the surface resistance value in the above range can be preferably used as a surface protective film used in processing or transporting of articles such as liquid crystal cells or semiconductor devices. Further, the surface resistance value can be calculated from the surface resistance value measured in an environment of 23 ° C and 50% RH using a commercially available insulation resistance measuring device.

The surface protective film disclosed herein preferably has a property that the back surface (the surface of the antistatic layer) can be easily printed by using an aqueous ink or an oily ink (for example, using an oily marker). The surface protective film is suitable for the identification number of the adherend to be protected, etc. in the process of processing or transporting the adherend (for example, an optical component) in a state in which the surface protective film is attached. It is described and displayed on the above surface protective film. Therefore, a surface protective film excellent in printability is preferred. For example, it is preferred that the oil-based ink of the type in which the solvent is alcohol-based and contains a pigment has high printing property. Further, it is preferable that the ink to be printed is not easily peeled off due to rubbing or turning (that is, excellent in printing adhesion). Further, the surface protective film disclosed herein preferably has solvent resistance to such an extent that the appearance does not change significantly even when printing is corrected by printing with an alcohol (for example, ethanol).

The surface protective film disclosed herein can be implemented in addition to the substrate, the adhesive layer, and the antistatic layer, and further includes other layers. The arrangement of the "other layer" may be, for example, between the first surface (back surface) of the substrate and the antistatic layer, between the second surface (front surface) of the substrate, and the adhesive layer. The layer disposed between the back surface of the substrate and the antistatic layer may be, for example, a layer containing an antistatic component (the above-described antistatic layer). The layer disposed between the front surface of the substrate and the adhesive layer may be, for example, an undercoat layer (an anchor layer), an antistatic layer, or the like which improves the adhesion of the adhesive layer to the second surface. A surface protective film having an antistatic layer disposed on the front surface of the substrate, an anchor layer disposed on the antistatic layer, and an adhesive layer disposed thereon may be used.

<Adhesive Composition>

The surface protective film of the present invention has the above-mentioned pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is formed of an adhesive composition. The adhesive composition can be used without any particular limitation as long as it has adhesiveness. For example, it can also be used. Acrylic adhesive, urethane system An adhesive, a synthetic rubber adhesive, a natural rubber adhesive, a polyoxygen adhesive, and the like, and more preferably selected from the group consisting of an acrylic adhesive, an urethane adhesive, and a polyoxygen adhesive. It is preferable to use an acrylic adhesive in at least one of the group consisting of, and a (meth)acrylic-type polymer is used for this acrylic adhesive.

When an acrylic pressure-sensitive adhesive is used as the pressure-sensitive adhesive layer, the (meth)acrylic polymer constituting the acrylic pressure-sensitive adhesive may be a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms. The raw material monomer constituting it. As the (meth)acrylic monomer, one type or two or more types may be used as a main component. By using the above (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, it is easy to control the adhesion to the adherend (protected body) to be low, and light peeling can be obtained. A surface protective film excellent in properties or removability. In the present invention, the (meth)acrylic polymer refers to an acrylic polymer and/or a methacrylic polymer, and the term "(meth)acrylate" refers to an acrylate and/or a methyl group. Acrylate. In addition, the term "main component" in the present invention means the component which is the most abundant in the total amount of components, and preferably means more than 40% by mass, more preferably more than 50% by mass, and still more preferably more than 60% by mass. .

Specific examples of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, second butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethyl methacrylate Ester, 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, examples of the surface protective film of the present invention include hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, and isooctyl (meth)acrylate. Ester, n-decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid Anthracene ester, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, etc. A (meth)acrylic monomer having an alkyl group of 6 to 14 is suitable. In particular, by using a (meth)acrylic monomer having an alkyl group having 6 to 14 carbon atoms, it is easy to control the adhesion to the adherend to be low, and it is excellent in removability.

In particular, it is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, based on 100% by mass of the total of the monomer components constituting the (meth)acrylic polymer. The (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms is preferably 80 to 93% by mass. If it is less than 50% by mass, the appropriate wettability of the adhesive composition or the cohesive force of the adhesive layer may be deteriorated, which is not preferable.

Moreover, in the adhesive composition of the present invention, it is preferred that the (meth)acrylic polymer contains a (meth)acrylic monomer having a hydroxyl group as a raw material monomer. As the (meth)acrylic monomer having a hydroxyl group, one type or two or more types may be used as a main component.

By using the above-mentioned (meth)acrylic monomer having a hydroxyl group, it is easy to control the crosslinking of the adhesive composition, etc., and it is easy to control the improvement of the wettability due to the flow and the balance of the adhesive force in the peeling. . Further, unlike a carboxyl group or a sulfonate group which can function as a crosslinking site, a hydroxyl group and an ionic compound as an antistatic component (antistatic agent) or an organopolyoxane having an oxygen alkyl chain It has a moderate interaction, and therefore can be suitably used in terms of antistatic property.

Examples of the (meth)acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, acrylic acid (4-hydroxyl) Methylcyclohexyl)methyl ester, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol Monovinyl ether and the like. In particular, by using a (meth)acrylic monomer having a hydroxyl group of 4 or more and having a hydroxyl group, a high speed It is preferable that the light peeling at the time of peeling becomes easy.

100 parts by mass of the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms is preferably 15% by mass or less, more preferably 1 to 13% by mass, still more preferably 2% by mass. 11% by mass, and most preferably 3.5 to 10% by mass of the above-mentioned (meth)acrylic monomer having a hydroxyl group. If it is in the above range, it becomes easy to control the balance between the wettability of the adhesive composition and the cohesive force of the obtained adhesive layer, which is preferable.

In addition, as the other polymerizable monomer component, Tg can be used in the range of 0 ° C or less (usually -100 ° C or more) for the purpose of not impairing the effect of the present invention for the purpose of easily obtaining the balance of the adhesive performance. A polymerizable monomer such as a glass transition temperature or a releasable property of a methyl)acrylic polymer.

The (meth)acrylic monomer having the alkyl group having 1 to 14 carbon atoms used in the (meth)acrylic polymer and the (meth)acrylic monomer having the hydroxyl group as described above As the monomer, a (meth)acrylic monomer having a carboxyl group can be used.

Examples of the (meth)acrylic monomer having a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, and maleic acid. , fumaric acid, etc.

The (meth)acrylic monomer having a carboxyl group is preferably 10 parts by mass or less, more preferably 10 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. The amount is preferably not more than 3 parts by mass, more preferably 0.01 parts by mass or more and less than 1 part by mass. When the amount is more than 10 parts by mass, an acid functional group such as a carboxyl group having a large polarity is present in a large amount, and when an ionic compound is used as an antistatic component, an acid functional group such as a carboxyl group interacts with the ionic compound. The ion conduction is hindered, and the electric conduction efficiency is lowered, so that sufficient antistatic property cannot be obtained, which is not preferable.

Further, as the (meth)acrylic polymer, the (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms, a (meth)acrylic monomer having a hydroxyl group, and a carboxyl group are used. The polymerizable monomer other than the (meth)acrylic monomer can be used without particular limitation as long as it does not detract from the characteristics of the present invention. For example, a component containing a cyano group-containing monomer, a vinyl ester monomer, an aromatic vinyl monomer or the like to improve cohesive force and heat resistance, or a guanidine-containing monomer, a ruthenium-containing monomer, and an amine group may be suitably used. Monomer, epoxy-containing monomer, N-propylene fluorenyl A component such as a phenyl group or a vinyl ether monomer which has an adhesive property or a functional group which functions as a crosslinking crosslinking point. These polymerizable monomers may be used singly or in combination of two or more.

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

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 guanamine-containing monomer include acrylamide, methacrylamide, diethyl acrylamide, N-vinyl pyrrolidone, N,N-dimethyl decylamine, N, N. - dimethyl methacrylamide, N,N-diethyl acrylamide, N,N-diethyl methacrylamide, N,N'-methylenebis acrylamide, N,N - dimethylaminopropyl acrylamide, N,N-dimethylaminopropyl methacrylamide, diacetone acrylamide, and the like.

Examples of the quinone imine group-containing monomer include cyclohexylmethyleneimine, isopropyl maleimide, N-cyclohexylmethyleneimine, and iconimine. Wait.

Examples of the amine group-containing monomer include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and N,N-dimethylamine (meth)acrylate. Propyl ester and the like.

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

Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.

In the present invention, a (meth)acrylic monomer having an alkyl group having 1 to 14 carbon atoms a (meth)acrylic acid having a hydroxyl group-containing (meth)acrylic monomer or a carboxyl group-containing (meth)acrylic monomer other than the above-mentioned alkyl group having an alkyl group having 1 to 14 carbon atoms The monomer is 100 parts by mass, preferably 0 to 40 parts by mass, more preferably 0 to 30 parts by mass. When the above-mentioned other polymerizable monomer is used in the above range, when an ionic compound is used as an antistatic agent, a good interaction with the above ionic compound and good removability can be appropriately adjusted.

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

Further, the average addition mole number of the oxygen-extended alkyl unit as the epoxy group-containing reactive monomer is preferably 1 from the viewpoint of compatibility with the ionic compound as an antistatic component. ~40, more preferably 3~40, further preferably 4~35, especially preferably 5~30. When the average addition molar number is 1 or more, the effect of reducing the contamination by the adherend (protected body) tends to be obtained with high efficiency. Further, when the average addition molar number is more than 40, the interaction with the ionic compound is large, and the viscosity of the adhesive composition is increased to make it difficult to apply, which is not preferable. Further, the terminal of the oxygen alkyl chain may be directly a hydroxyl group, or may be substituted by another functional group or the like.

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

Examples of the oxygen-extended alkyl unit of the above-mentioned epoxy group-containing reactive monomer include those having a C 1 to 6 alkyl group, and examples thereof include an oxymethylene group, an oxyethyl group, and an oxy group. Propyl, oxybutylene, and the like. The hydrocarbyl group of the alkyl chain may be linear or branched. chain.

Further, it is more preferred that the epoxy group-containing reactive monomer is a reactive monomer having an oxiranyl group. By using a (meth)acrylic polymer containing a reactive monomer having an oxiranyl group as a base polymer, the compatibility of the base polymer with the ionic compound is improved, and the bleeding to the adherend is suitably suppressed. A low-contaminant adhesive composition can be obtained.

Examples of the epoxy group-containing reactive monomer include a (meth)acrylic acid alkylene oxide adduct or a reactive substitution such as an acrylonitrile group, a methacryl fluorenyl group, or an allyl group in the molecule. Based on reactive surfactants and the like.

Specific examples of the (meth)acrylic acid alkylene oxide adduct include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polyethylene glycol-polypropylene glycol (A). Acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, B Oxypoly polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octyloxy polyethylene glycol (meth) acrylate, lauryl oxy polyethylene glycol (A Acrylate, stearyloxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, octyloxy poly Ethylene glycol-polypropylene glycol (meth) acrylate or the like.

Moreover, as a specific example of the reactive surfactant, for example, an anionic reactive surfactant having a (meth)acryl fluorenyl group or an allyl group, a nonionic reactive surfactant, and a cationic reaction can be mentioned. Sexual surfactants, etc.

The weight average molecular weight (Mw) of the (meth)acrylic polymer is preferably from 100,000 to 5,000,000, more preferably from 200,000 to 4,000,000, and still 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 paste tends to remain. On the other hand, when the weight average molecular weight exceeds 5 million, the fluidity of the polymer is lowered, and the wetting of the adherend (for example, a polarizing plate) is insufficient, and This causes a tendency to foam between the adhesive layer and the adhesive layer of the surface protective film. Further, the weight average molecular weight means those measured by GPC (gel permeation chromatography).

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 higher than 0 ° C, the polymer is difficult to flow, and there is, for example, insufficient wetting of the polarizing plate, resulting in a tendency to foam 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, it is easy to obtain an adhesive layer which is excellent in wettability and light peelability to a polarizing plate. Further, the glass transition temperature of the (meth)acrylic polymer can be adjusted to the above range by appropriately changing the monomer component or composition ratio used.

The polymerization method of the (meth)acrylic polymer is not particularly limited, and polymerization can be carried out by a known method such as solution polymerization, emulsion polymerization, bulk polymerization or suspension polymerization, in particular, from the viewpoint of workability or adhesion. Solution polymerization is a better aspect in terms of characteristics such as low contamination of the body (protected body). Further, the obtained polymer may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer and the like.

When a urethane-based pressure-sensitive adhesive is used as the pressure-sensitive adhesive layer, any suitable urethane-based pressure-sensitive adhesive can be used as the urethane-based pressure-sensitive adhesive. As such a urethane-based pressure-sensitive adhesive, those containing a urethane resin obtained by reacting a polyol with a polyisocyanate compound are preferably used. Examples of the polyhydric alcohol include a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polycaprolactone polyol. Examples of the polyisocyanate compound include diphenylmethane diisocyanate, toluene diisocyanate, and hexamethylene diisocyanate.

When a polyfluorene-based adhesive is used for the above-mentioned adhesive layer, any suitable polyoxygen-based adhesive can be used as the polyoxygen-based adhesive. As such a polyoxynitride-based adhesive, those obtained by mixing or agglomerating a polyoxyxylene resin can be preferably used.

In addition, examples of the polyoxygenated adhesive include an addition reaction-curable polyoxynoxy adhesive or a peroxide-curable polyoxynoxy adhesive. In these polyoxygenated adhesives Among them, a peroxide (benzaldehyde peroxide, etc.) is not used, and an addition reaction hardening type polyoxynoxy adhesive is preferable from the viewpoint of not producing a decomposition product.

In the case of obtaining a polyalkyl polyoxynitride-based adhesive as a curing reaction of the addition reaction-curable polyoxynoxy adhesive, for example, a polyalkylhydroquinone is usually combined by a platinum catalyst. The method of hardening the object.

<Antistatic component in the adhesive layer>

In the surface protection film of the present invention, it is preferable that the adhesive composition constituting the pressure-sensitive adhesive layer contains an antistatic component, and more preferably contains an ionic compound as the antistatic component. Examples of the ionic compound include an alkali metal salt and/or an ionic liquid. By containing the ionic compound, excellent antistatic properties can be imparted. Further, as described above, the adhesive layer (using an antistatic component) obtained by crosslinking an adhesive composition containing an antistatic component is used to achieve an antistatic coating (for example, a polarizing plate) at the time of peeling. Anti-static, it becomes a surface protective film that reduces the contamination of the adherend. Therefore, it is very useful as an antistatic surface protective film in the technical field related to optical and electronic parts, which is a problem that is particularly problematic in terms of static electricity or contamination.

Since the above-mentioned alkali metal salt has high ion dissociation property, it is preferable in terms of an excellent antistatic property even in a small amount of addition. As the above alkali metal salt, for example, a cation containing Li ⁺ , Na ⁺ , K ⁺ and containing Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ can be suitably used. ^- , 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 ^- The metal salt of the anion. More preferably, LiBr, LiI, LiBF ₄ , LiPF ₆ , LiSCN, LiClO ₄ , LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li (FSO _{2 )} a lithium salt such as ₂ N or Li(CF ₃ SO ₂ ) ₃ C, more preferably LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₃ F ₇ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(FSO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C. These alkali metal salts may be used singly or in combination of two or more.

Further, by using the above ionic liquid as an antistatic component (antistatic agent), an adhesive layer having a high antistatic effect can be obtained without damaging the adhesive properties. The detailed reason for obtaining excellent antistatic properties by using an ionic liquid is not clear, and it is considered that the ionic liquid has a low melting point (melting point of 100 ° C or less) as compared with a usual ionic compound, so molecular motion is easy to obtain. Excellent anti-static ability. In particular, it is considered that when the antistatic property against the adherend is sought, the ionic liquid is extremely transferred to the adherend, whereby excellent anti-peeling electrostatic properties on the adherend are achieved. In particular, an ionic liquid having a melting point of room temperature (25 ° C) or less can be more efficiently transferred to an adherend, and thus excellent antistatic properties can be obtained.

Further, since the ionic liquid is liquid at any temperature of 100 ° C or lower, it is easier to add, disperse or dissolve into the adhesive than the solid salt. Further, since the ionic liquid has no vapor pressure (non-volatile), it has a feature that it does not disappear with time and can stably obtain antistatic properties. In addition, the ionic liquid system means a molten salt (ionic compound) having a melting point of 100 ° C or less and exhibiting a liquid state.

As the ionic liquid, those containing an organic cation component and an anion component represented by the following general formulae (A) to (E) are preferably used. By using the ionic liquid having such cations, it is possible to obtain further excellent antistatic ability.

[Chemical 1]

R _a in the above formula (A) represents _a hydrocarbon group having 4 to 20 carbon atoms, and may be a functional group in which a part of the above hydrocarbon group is substituted with a hetero atom, and R _b and R _{c are the} same or different and represent hydrogen or a carbon number of 1 to 16. The hydrocarbon group may also be a functional group in which a part of the above hydrocarbon group is substituted with a hetero atom. Wherein, in the case where the nitrogen atom contains a double bond, R _c does not exist.

R _d in the above formula (B) represents a hydrocarbon group having 2 to 20 carbon atoms, and may be a functional group in which a part of the above hydrocarbon group is substituted with a hetero atom, and R _e , R _f and R _{g are the} same or different and represent hydrogen or carbon. The hydrocarbon group of 1 to 16 may also be a functional group in which a part of the above hydrocarbon group is substituted with a hetero atom.

R _h in the above formula (C) represents a hydrocarbon group having 2 to 20 carbon atoms, and may be a functional group in which a part of the above hydrocarbon group is substituted with a hetero atom, and R _i , R _j and R _{k are the} same or different and represent hydrogen or carbon. The hydrocarbon group of 1 to 16 may also be a functional group in which a part of the above hydrocarbon group is substituted with a hetero atom.

Z in the above formula (D) represents a nitrogen, sulfur, or phosphorus atom, and R _l , R _m , R _n , and R _{o are the} same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms, and may be a part of the above hydrocarbon group. A functional group substituted with a hetero atom. Wherein in the case where 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 may be a functional group in which a part of the above hydrocarbon group is 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 pyrroline 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, and 1-butyl-4. -methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation, 1-B 1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidine Ruthenium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1 - butyl pyrrolidine cation, 1-ethyl-1-pentyl pyrrolidine cation, 1-ethyl-1-hexyl pyrrolidine cation, 1-ethyl-1-heptylpyrrolidinium cation, 1 , 1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation, pyrrolidin-2-one cation, 1-propyl Piperidinium 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- Pentamylpyridinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1- Ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidine Ruthenium cation, 1,1-dipropyl piperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dibutylpiperidinium cation, 2-methyl-1-pyrroline Cation, 1-ethyl-2-phenylphosphonium cation, 1,2-dimethylhydrazine cation, 1-ethylcarbazole cation, N-ethyl-N-methyl A porphyrin cation or the like.

Examples of the cation represented by the formula (B) include an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.

Specific examples include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3- Methylimidazolium 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-di Methylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, 1-(2-methoxyethyl)-3 -methylimidazole Ruthenium 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-tetrahydropyrimidinium cation , 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4 - dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1 , 2,3,4-tetramethyl-1,6-dihydropyrimidinium cation, and the like.

Examples of the cation represented by the formula (C) include a pyrazolium cation, a pyrazolinium cation, and the like.

Specific examples include 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, and 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-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-three Methylpyrazolium cations and the like.

Examples of the cation represented by the formula (D) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, or a part of the above alkyl group is substituted with an alkenyl group or an alkoxy group, and further a ring. Oxygen is the same as that.

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, glycidyl trimethyl 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 Ruthenium cation, diallyldimethylammonium A cation, a tributyl-(2-methoxyethyl)phosphonium cation or the like. Among them, it is preferred to use a triethylmethylammonium cation, a tributylethylammonium cation, a trimethylsulfonium ammonium cation, a diethylmethyl phosphonium cation, a dibutylethyl phosphonium cation, a dimethyl hydrazine. An asymmetric tetraalkylammonium cation such as a cation, a triethylmethyl phosphonium cation, a tributylethyl phosphonium cation, a trimethylsulfonium cation, a trialkyl phosphonium cation, a tetraalkyl phosphonium cation, or N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyl trimethylammonium cation, diallyldimethylammonium cation, N,N- Dimethyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, N,N-dimethyl-N-ethyl-N - amyl ammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N,N-dimethyl-N-ethyl-N-heptyl ammonium cation, N,N-di Methyl-N-ethyl-N-decyl ammonium cation, N,N-dimethyl-N,N-dipropylammonium cation, N,N-diethyl-N-propyl-N-butyl Ammonium cation, N,N-dimethyl-N-propyl-N-amyl ammonium cation, N,N-dimethyl-N-propyl-N-hexylammonium cation, N,N-dimethyl- N-propyl-N-g 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-dihexyl ammonium cation, trimethylheptyl ammonium cation, N,N-diethyl-N-methyl-N -propylammonium cation, N,N-diethyl-N-methyl-N-amylammonium cation, N,N-diethyl-N-methyl-N-heptyl ammonium cation, N,N- Diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylammonium ammonium cation, triethylheptyl ammonium cation, N,N-dipropyl-N- Methyl-N-ethylammonium cation, N,N-dipropyl-N-methyl-N-amylammonium cation, N,N-dipropyl-N-butyl-N-hexylammonium cation, N , N-dipropyl-N,N-dihexyl ammonium cation, N,N-dibutyl-N-methyl-N-amyl ammonium cation, N,N-dibutyl-N-methyl-N a hexyl ammonium cation, a trioctylmethyl ammonium cation, an N-methyl-N-ethyl-N-propyl-N-amyl ammonium cation.

Examples of the cation represented by the formula (E) include a phosphonium cation and the like. Further, specific examples of R _P in the above formula (E) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, and a tridecyl group. , tetradecyl, octadecyl and the like.

On the other hand, the anion component is not particularly limited as long as it satisfies the ionic liquid, and for example, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF _{6 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, as the anion component, an anion or the like represented by the following formula (F) can also be used.

Further, as the anion component, in particular, in terms of obtaining an ionic liquid having a low melting point, it is preferred to use an anion component of a fluorine atom.

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 tetrafluoroborate and 1-butylpyridinium hexafluorophosphate. Phosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis ( Iridin, 1-butyl-3-methylpyridinium bis(pentafluoroethanesulfonyl)imide, 1-hexylpyridinium tetrafluoroborate, 1,1-dimethylpyrrolidine Bis(trifluoromethanesulfonate)imide, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonate)imide, 1-methyl-1-propylpyrrolidinium bis (three Fluorosulphonium)imine, 1-methyl-1-butylpyrrolidinium bis(trifluoromethanesulfonate)imide, 1-methyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonate) Imine, 1-methyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonate)imide, 1-methyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonate)imide, 1 -ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonate)imide, 1-ethyl-1-butylpyrrolidinium bis(trifluoromethanesulfonate)imide, 1-ethyl- 1-pentylpyrrole Bis(trifluoromethanesulfonate)imide, 1-ethyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonate)imide, 1-ethyl-1-heptylpyrrolidinium bis(trifluoro Methanesulfonate)imine, 1,1-dipropylpyrrolidinium bis(trifluoromethanesulfonate)imide, 1-propyl-1-butylpyrrolidinium bis(trifluoromethanesulfonate)imide 1,1-dibutylpyrrolidinium bis(trifluoromethanesulfonate)imide, 1-propylpiperidinium bis(trifluoromethanesulfonate)imide, 1-pentylpiperidinium bis (three Fluoromethanesulfonate, imine, 1,1-dimethylpiperidinium bis(trifluoromethanesulfonate)imide, 1-methyl-1-ethylpiperidinium bis(trifluoromethanesulfonate) Amine, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonate)imide, 1-methyl-1-butylpiperidinium bis(trifluoromethanesulfonate)imide, 1- Methyl-1-pentylpiperidinium bis(trifluoromethanesulfonate)imide, 1-methyl-1-hexylpiperidinium bis(trifluoromethanesulfonate)imide, 1-methyl-1- Heptyl piperidinium bis(trifluoromethanesulfonate)imide, 1-ethyl-1-propylpiperidinium bis(trifluoromethanesulfonate)imide, 1-ethyl-1-butylpiperidine Bis(trifluoromethanesulfonate)imide, 1-ethyl-1-pentylpiperidinium bis(trifluoromethanesulfonate)imide, 1-ethyl-1-hexylpiperidinium bis(trifluoro Methotrexate Amine, 1-ethyl-1-heptylpiperidinium bis(trifluoromethanesulfonate)imide, 1,1-dipropylpiperidinium bis(trifluoromethanesulfonate)imide, 1-propyl 1-butylpiperidinium bis(trifluoromethanesulfonate)imide, 1,1-dibutylpiperidinium bis(trifluoromethanesulfonate)imide, 1,1-dimethylpyrrolidinium Bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(pentafluoro Ethylene sulfonate) imine, 1-methyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonate) Imine, 1-methyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1- Ethyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1 -Pentylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpyrrolidine Bis(pentafluoroethanesulfonyl)imide, 1,1-dipropylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-propyl-1-butylpyrrolidinium bis ( Isoammine, 1,1-dibutylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-pentyl Isopiperidine bis(pentafluoroethanesulfonyl)imide, 1,1-dimethylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-ethylpiperidinium bis ( Pentafluoroethanesulfonate)imine, 1-methyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-butylpiperidinium bis(pentafluoroethanesulfonate醯) imine, 1-methyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl 1-butylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexyl Piperidine bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1,1-dipropylpiperidinium bis (five Isoammine, 1-propyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1,1-dibutylpiperidinium bis(pentafluoroethanesulfonate) Amine, 2-methyl-1-pyrrole Porphyrin tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethylcarbazole tetrafluoroborate, 1-B 3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3- Methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl 3-methylimidazolium dicyanamide salt, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonate)imide, 1-ethyl-3-methylimidazolium bis(pentafluoroethyl) Sulfo]imine, 1-ethyl-3-methylimidazolium tris(trifluoromethanesulfonyl)methide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl 3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl- 3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonate) Imine, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium , 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1 -octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1 ,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonate)imide, 1-methylpyrazolium tetrafluoroborate, 2-methylpyrazolium tetrafluoroborate, 1- Ethyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonate)imide, 1-propyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonate) Imine, 1-butyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonate)imide, 1-ethyl-2,3,5-trimethylpyrazolium double (pentafluoroethanesulfonate) imine, 1-propyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl)imide, 1-butyl-2,3,5-three Methylpyrazolium bis(pentafluoroethanesulfonyl)imide, 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 (three Fluoromethanesulfonyl)trifluoroethane Amine, 1-ethyl-2,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonate)imide, 1-propyl-2,3,5-trimethylpyrazoline (trifluoromethanesulfonate) imine, 1-butyl-2,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonate)imide, 1-ethyl-2,3,5- Trimethylpyrazolinium bis(pentafluoroethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl)imide, 1-butyl Base-2,3,5-trimethylpyrazolinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazoline bis(trifluoromethanesulfonate Mercapto) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3 , 5-trimethylpyrazolinium bis(trifluoromethanesulfonyl)trifluoroacetamide, tetraamylammonium triflate, tetraamylammonium bis(trifluoromethanesulfonate)imide, Tetrahexylammonium trifluoromethanesulfonate, tetrahexylammonium bis(trifluoromethanesulfonate)imide, tetraheptyl ammonium trifluoromethanesulfonate, tetraheptyl ammonium bis(trifluoromethanesulfonate)imide, tetrafluoro Diallyldimethylammonium borate, diallyldimethylammonium triflate, diallyldimethylammonium bis(trifluoromethanesulfonate)imide, diallyldimethyl Ammonium Bis(pentafluoroethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-difluoromethanesulfonate Ethyl-N-methyl-N-(2-methoxyethyl)ammonium, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoro Methanesulfonate)imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl)imide, glycidyl trifluoromethanesulfonate Trimethylammonium, glycidyl trimethylammonium bis(trifluoromethanesulfonate)imide, glycidyl trimethylammonium bis(pentafluoroethanesulfonyl)imide, tetraoctylfluorene trifluoromethane Acid salt, tetraoctyl bis(trifluoromethanesulfonate) imine, N,N-dimethyl-N-ethyl-N-propylammonium bis(trifluoromethanesulfonate)imide, N,N - dimethyl-N-ethyl-N-butylammonium bis(trifluoromethanesulfonate)imide, N,N-dimethyl-N-ethyl-N-amylammonium bis(trifluoromethanesulfonate醯) imine, N,N-dimethyl-N-ethyl-N-hexyl ammonium bis(trifluoromethanesulfonate) imine, N,N-dimethyl-N-ethyl-N-heptyl Ammonium bis(trifluoromethanesulfonate)imide, N,N-dimethyl-N-ethyl-N-methylammonium bis(trifluoromethanesulfonate)imide, N,N-dimethyl-N , N-dipropylammonium bis(trifluoromethanesulfonate)imide, N,N-dimethyl-N-propyl- N-butylammonium bis(trifluoromethanesulfonate)imide, N,N-dimethyl-N-propyl-N-amylammonium bis(trifluoromethanesulfonate)imide, N,N-di Methyl-N-propyl-N-hexylammonium bis(trifluoromethanesulfonate)imide, N,N-dimethyl-N-propyl-N-heptyl ammonium bis(trifluoromethanesulfonate) Amine, N,N-dimethyl-N-butyl-N-hexyl ammonium bis(trifluoromethanesulfonate)imide, N,N-dimethyl-N-butyl-N-heptyl ammonium double ( Trifluoromethanesulfonate)imine, N,N-dimethyl-N-pentyl-N-hexylammonium bis(trifluoromethanesulfonate)imide, N,N-dimethyl-N,N-di Hexyl ammonium bis(trifluoromethanesulfonate)imide, trimethylheptyl ammonium bis(trifluoromethanesulfonate)imide, N,N-diethyl-N-methyl-N-propylammonium bis ( Trifluoromethanesulfonate, imine, N,N-diethyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonate)imide, N,N-diethyl-N-methyl -N-heptyl ammonium bis(trifluoromethanesulfonate) imine, N,N-diethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonate)imide, triethyl propyl Ammonium bis(trifluoromethanesulfonate)imide, triethylammonium bis(trifluoromethanesulfonate)imide, triethylheptylammonium bis(trifluoromethanesulfonate)imide, N,N -dipropyl-N-methyl-N-ethylammonium bis(trifluoromethanesulfonate)imide, N,N-dipropyl-N-methyl -N-amylammonium bis(trifluoromethanesulfonate)imide, N,N-dipropyl-N-butyl-N-hexylammonium bis(trifluoromethanesulfonate)imide, N,N-di propyl-N,N-dihexylammonium bis(trifluoromethanesulfonate)imide, N,N-dibutyl-N-methyl-N-amylammonium bis(trifluoromethanesulfonate)imide, N,N-dibutyl-N-methyl-N-hexyl ammonium bis(trifluoromethanesulfonate)imide, trioctylmethylammonium bis(trifluoromethanesulfonate)imide, N-methyl- N-ethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonate)imide, 1-butylpyridinium (trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl -3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, N-ethyl -N-methyl Lanthanum thiocyanate, 4-ethyl-4-methyl Lanthanum methyl carbonate salt and the like.

As the ionic liquid described above, a commercially available product can be used, or it can be synthesized as follows. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained, and the halide method described in the document "Ion Liquid - The Forefront and Future of Development -" (CMC) is generally used. , hydroxide method, acid ester method, wrong law, and neutralization method.

Hereinafter, the halide method, the hydroxide method, the acid ester method, the wrong method, and the neutralization method will be described by taking a nitrogen-containing phosphonium salt as an example thereof, and other sulfur-containing phosphonium salts, phosphorus-containing phosphonium salts, and the like. Other ionic liquids can also be obtained by the same method.

The halide method is a method which is carried out by a reaction represented by the following formulas (1) to (3). First, a tertiary amine is reacted with an alkyl halide to obtain a halide (reaction formula (1), and halogen is chlorine, bromine, or iodine). The obtained halide is reacted with an acid (HA) or a salt (MA, M is a cation which forms a salt with a target anion such as ammonium, lithium, sodium or potassium) having an anionic structure (A ^- ) of a target ionic liquid to obtain a target. Ionic liquid (R ₄ NA).

(1) R ₃ N+RX→R ₄ NX (X:Cl, Br, I) (2) R ₄ NX+HA→R ₄ NA+HX (3)R ₄ NX+MA→R ₄ NA+MX (M: NH ₄ , Li, Na, K, Ag, etc.)

The hydroxide method is a method carried out by a reaction as shown in (4) to (8). First, the halide (R ₄ NX) is subjected to ion exchange membrane method electrolysis (reaction formula (4)), OH type ion exchange resin method (reaction formula (5)) or reaction with silver oxide (Ag ₂ O) ( The hydroxide (R ₄ NOH) is obtained by the reaction formula (6)) (halogen is chlorine, bromine or iodine). The obtained hydroxide is obtained by the reaction of the reaction formulas (7) to (8) in the same manner as the above-described halogenation method to obtain a target ionic liquid (R ₄ NA).

(4) R ₄ NX+H ₂ O→R ₄ NOH+1/2H ₂ +1/2X ₂ (X:Cl,Br,I) (5)R ₄ NX+P-OH→R ₄ NOH+PX (P-OH: OH type ion exchange resin) (6) R ₄ NX+1/2Ag ₂ O+1/2H ₂ O→R ₄ NOH+AgX (7)R ₄ NOH+HA→R ₄ NA +H ₂ O (8)R ₄ NOH+MA→R ₄ NA+MOH (M:NH ₄ , Li, Na, K, Ag, etc.)

The acid ester method is a method carried out by a reaction as shown in (9) to (11). First, a tertiary amine (R ₃ N) is reacted with an acid ester to obtain an acid ester compound (reaction formula (9). The acid ester is an ester of a mineral acid such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid or carbonic acid or methanesulfonic acid. Acid, methylphosphonic acid, acid esters such as formic acid, etc.). The obtained acid ester compound is subjected to a reaction of the reaction formulas (10) to (11) in the same manner as the above halogenation method to obtain a target ionic liquid (R ₄ NA). Further, an ionic liquid can be directly obtained by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as an acid ester.

The wrong law is a method performed by a reaction as shown in (12) to (15). First, a quaternary ammonium halide (R ₄ NX), a quaternary ammonium hydroxide (R ₄ NOH), a quaternary ammonium carbonate (R ₄ NOCO ₂ CH ₃ ), etc., and hydrogen fluoride (HF) or Ammonium fluoride (NH ₄ F) is reacted to obtain a fluorinated quaternary ammonium salt (reaction formulae (12) to (14)). An ionic liquid can be obtained by subjecting the obtained fluorinated quaternary ammonium salt to a fluorine compound such as BF ₃ , AlF ₃ , PF ₅ , AsF ₅ , SbF ₅ , NbF ₅ or TaF ₅ (reaction formula (15). )).

(12) R ₄ NX+HF→R ₄ NF+HX (X:Cl,Br,I) (13)R ₄ NY+HF→R ₄ NF+HY (Y:OH, OCO ₂ CH ₃ (14) R ₄ NY+NH ₄ F→R ₄ NF+NH ₃ +HY (Y:OH, OCO ₂ CH ₃ ) (15)R ₄ NF+MF _n-1 →R ₄ NMF _n (MF _{n- 1} : BF ₃ , AlF ₃ , PF ₅ , AsF ₅ , SbF ₅ , NbF ₅ , TaF _{5 ,} etc.)

The neutralization method is carried out by a reaction as shown in (16). By subjecting the tertiary amine to HBF ₄ , HPF ₆ , CH ₃ COOH, CF ₃ COOH, CF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) ₃ CH, (C ₂ F ₅ SO ₂ ) ₂ NH and other organic acids are obtained by reaction.

[7] (16) R ₃ N+HZ→R ₃ HN ⁺ Z ^- [HZ:HBF ₄ , HPF ₆ , CH ₃ COOH, CF ₃ COOH, CF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ NH , (CF ₃ SO ₂ ) ₃ CH, (C ₂ F ₅ SO ₂ ) ₂ NH and other organic acids]

R represented by the above formulas (1) to (16) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may be a functional group in which one of the above hydrocarbon groups is substituted with a hetero atom.

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

In addition, the content of the ionic compound 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 part by mass, based on 100 parts by mass of the (meth)acrylic polymer. Preferably, it is 0.01 to 0.5 parts by mass. If it is in the above range, it is easy to have both antistatic property and low pollution property, and therefore it is preferable.

<Organic polyoxane having an oxygen alkyl chain>

In the surface protective film of the present invention, it is preferred that the above-mentioned adhesive composition contains an organic polyoxyalkylene having an oxygen-extended alkyl chain, and more preferably an organic polyoxyalkylene having an oxygen-extended alkyl main chain. It is presumed that by using the above organopolyoxane, the surface free energy of the surface of the adhesive is lowered, and light peeling is achieved.

As the above organopolyoxane, a known organopolyoxyalkylene having a polyoxyalkylene chain main chain can be suitably used, and it is preferably represented by the following formula.

(wherein R ₁ and/or R ₂ has an alkylene chain having a carbon number of 1 to 6, and the alkyl group in the above alkyl chain may be a straight chain or a branched chain, and the above oxygen alkyl chain The terminal may be an alkoxy group or a hydroxyl group. Further, any of R ₁ or R ₂ may be a hydroxyl group, or may be an alkyl group or an alkoxy group, or may be a part of the above alkyl group or alkoxy group through a hetero atom. Substituted functional group. n is an integer from 1 to 300)

The above organopolyoxyalkylene is used as a main chain having a site containing a decane (a decane moiety), and an alkylene chain is bonded to the terminal of the main chain. It is presumed that the (meth)acrylic polymer and ionicity are obtained by using the above organic siloxane having an oxygen alkyl chain. The balance of the compatibility of the compounds enables light stripping.

Moreover, as the above-mentioned organopolyoxane in the present invention, for example, the following constitution can be used. Specifically, R ₁ and/or R ₂ in the formula has an oxygen-extended alkyl chain having a hydrocarbon group having 1 to 6 carbon atoms, and examples of the oxygen-extended alkyl chain include an oxymethylene group and an oxyethyl group. And an oxypropyl group, an oxybutyl group or the like, and among them, an oxy group or an oxypropyl group is preferred. Further, in the case where both of R ₁ and R ₂ have an oxygen-extended alkyl chain, they may be the same or different.

Further, the hydrocarbon group of the above oxygen alkyl chain may be a straight chain or a branched chain.

Further, the terminal of the above oxygen alkyl chain may be an alkoxy group or a hydroxyl group, and more preferably an alkoxy group. In the case where the separator is attached to the surface of the adhesive layer in order to protect the adhesive surface, the organic polyoxyalkylene having a hydroxyl group at the end sometimes causes interaction with the separator, and when the separator is peeled off from the surface of the adhesive layer Adhesion (peeling) force rises.

Further, n is an integer of 1 to 300, preferably 10 to 200, more preferably 20 to 150. When n is in the above range, the balance with the compatibility with the base polymer is obtained, which is a preferable aspect. 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 having an oxygen-extended alkyl chain include, for example, commercially available products, and the product names are X-22-4952, X-22-4272, X-22-6266, and KF-6004. , KF-889 (above manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-201, SF8427 (above manufactured by Dow Corning Toray), IM22 (Asahi Kasei Wacker Co., Ltd.) Manufacturing) and so on. These compounds may be used singly or in combination of two or more.

Further, in addition to the organic siloxane having a main chain having an oxygen-extended alkyl chain, an organic oxane having a side chain having an oxygen-extended alkyl chain may be used, and the main chain has oxygen. A more preferred aspect is the use of an organic oxoxane having an oxygen-extended alkyl chain in the side chain as compared to the organic oxirane having an alkyl chain. As the above organopolyoxane, a known organopolyoxyalkylene having a polyoxyalkylene side chain can be suitably used, and it is preferably represented by the following formula.

(wherein R ₁ is a monovalent organic group, R ₂ , R ₃ and R ₄ are an alkylene group, R ₅ is a hydrogen or an organic group, and m and n are integers of 0 to 1000. Among them, m and n are different The time is 0. a and b are integers from 0 to 100, where a and b are not 0)

Moreover, as the above-mentioned organopolyoxane in the present invention, for example, the following constitution can be used. Specifically, R ₁ in the formula is an organic group represented by 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 an alkyl group such as a benzyl group or a phenethyl group. Each may have a substituent such as a hydroxyl group. As 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 and R ₃ or R ₄ may be the same or different. In order to increase the concentration of the ionic compound soluble in the polyoxyalkylene side chain, it is preferred that either of R ₃ and R ₄ is an exoethyl or a propyl group. R ₅ may be an organic group exemplified by an alkyl group such as a methyl group, an ethyl group or a propyl group, or a fluorenyl group such as an ethyl fluorenyl group or a propyl 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. It is presumed that among the above organic oxoxanes having a polyoxyalkylene side chain, an organic oxirane having a polyoxyalkylene-containing side chain having a hydroxyl group terminal is easy to obtain a balance of compatibility, and thus is preferable.

Specific examples of the above-mentioned organic decane are commercially available as KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, 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 Manufactured by Shin-Etsu Chemical 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 manufactured by Dow Corning Toray), TSF-4440, TSF-4441, TSF-4445, TSF-4450, TSF-4446, TSF-4452, TSF-4460 (Momentive Performance Materials) Made by the company), BYK-333, BYK-307, BYK-377, BYK-UV3500, BYK-UV3570 (manufactured by BYK-Chemie Japan Co., Ltd.). These compounds may be used singly or in combination of two or more.

As the above-mentioned organic decane which is used in the present invention, the HLB (Hydrophile-Lipophile Balance) value is preferably from 1 to 16, more preferably from 3 to 14. If the HLB value is outside the above range, the contamination to the adherend is deteriorated, which is not preferable.

Further, the above organic polymerization is carried out with respect to 100 parts by mass of the above (meth)acrylic polymer. The content of the decane is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, still more preferably 0.05 to 1 part by mass, most preferably 0.05 to 0.5 part by mass. When it is in the above range, it is easy to have both antistatic property and light peelability (repeelability), which is preferable.

<crosslinker>

In the surface protective film of the present invention, it is preferred that the above adhesive composition contains a crosslinking agent. Further, in the present invention, the above adhesive composition is used to form an adhesive layer. For example, when the above-mentioned (meth)acrylic polymer is contained in the above-mentioned adhesive, the constituent unit of the (meth)acrylic polymer, the constituent ratio, the selection of the crosslinking agent, the addition ratio, and the like are appropriately adjusted. Cross-linking provides a surface protective film (adhesive layer) which is more excellent in heat resistance.

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

Examples of the isocyanate compound (isocyanate crosslinking agent) include aliphatic polyisocyanates such as trimethylene diisocyanate, butyl diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate; Cycloaliphatic isocyanate such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis(isocyanatemethyl)cyclohexane; 2,4-toluene diisocyanate , 4,4'-diphenylmethane diisocyanate, benzene dimethyl diisocyanate (XDI) and other aromatic isocyanates; by allophanate bond, biuret bond, isocyanurate bond, urea Diketone bond, urea bond, carbodiimide bond, uretonimine bond, two A polyisocyanate modified product obtained by modifying the above isocyanate compound, such as a triketone bond. For example, as a commercial item, the product names Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (above, manufactured by Takeda Pharmaceutical Co., Ltd.), Sumidur T80, Sumidur L, and Desmodur N3400 (above by Sumika Bayer Urethane) Manufacturing), Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (above manufactured by Japan Polyurethane Industry Co., Ltd.) and the like. These isocyanate compounds may be used singly or in combination of two or more kinds, and a bifunctional isocyanate compound may be used in combination with a trifunctional or higher isocyanate compound. 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.

In the case where a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound are used in combination as the isocyanate compound (isocyanate crosslinking agent), the compounding ratio (weight ratio) of the two compounds is preferably [2 functional The isocyanate compound]/[3 functional or higher isocyanate compound] (weight ratio) is 0.1/99.9 to 50/50, more preferably 0.1/99.9 to 20/80, and still more preferably 0.1/99.9 to 10/90. More preferably, it is 0.1/99.9~5/95, and the best is 0.1/99.9~1/99. It is preferable to adjust to the above range and to form an adhesive layer excellent in adhesion and repellent resistance.

Examples of the epoxy compound include N, N, N', N'-tetraglycidyl-m-xylylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) or 1,3-double (manufactured by Mitsubishi Gas Chemical Co., Ltd.). N,N-diglycidylaminomethyl)cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like.

Examples of the melamine-based resin include hexamethylol melamine and the like. The aziridine derivative is, for example, a commercially available product under the trade names of HDU, TAZM, TAZO (the above is manufactured by Mutual Pharmaceutical Co., Ltd.).

Examples of the metal chelating compound include aluminum, iron, tin, titanium, and nickel. Examples of the chelating component include acetylene, ethyl acetacetate, and ethyl lactate.

The content of the crosslinking agent used in the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, even more preferably 100 parts by mass based on 100 parts by mass of the (meth)acrylic polymer. It is contained in an amount of 0.5 to 5 parts by mass, preferably 1.0 to 2.5 parts by mass. When the content is less than 0.01 parts by mass, the crosslinking formation by the crosslinking agent becomes insufficient, and the cohesive force of the obtained adhesive layer becomes small, and sufficient resistance cannot be obtained. In the case of heat, there is a tendency to cause the paste to remain. On the other hand, when the content exceeds 10 parts by mass, the cohesive force of the polymer is large, the fluidity is lowered, the wetting of the adherend (for example, a polarizing plate) is insufficient, and the adherend is caused. There is a tendency to foam between the adhesive layer (adhesive composition layer). Further, when the amount of the crosslinking agent is large, the peeling static characteristics tend to be lowered. Further, these crosslinking agents may be used singly or in combination of two or more.

Further, the above-mentioned adhesive composition may further contain a crosslinking catalyst for allowing any of the above crosslinking reactions to proceed more efficiently. As the crosslinking catalyst, for example, tin-based catalyst such as dibutyltin dilaurate or dioctyltin dilaurate; tris(acetonitrile)iron and tris(hexane-2,4-dione) can be used. Iron, tris(heptane-2,4-dione) iron, tris(heptane-3,5-dione) iron, tris(5-methylhexane-2,4-dione) iron, tri ( Octane-2,4-dione)iron, tris(6-methylheptane-2,4-dione)iron, tris(2,6-dimethylheptane-3,5-dione)iron , tris(decane-2,4-dione)iron, tris(decane-4,6-dione)iron, tris(2,2,6,6-tetramethylheptane-3,5-di Ketone) iron, tris(tridecane-6,8-dione)iron, tris(1-phenylbutane-1,3-dione)iron, tris(hexafluoroacetamidine)iron, tris(b)醯 ethyl acetate) iron, tris(ethylene acetate acetate) iron, tris(acetate isopropyl acetate) iron, tris(ethylene acetoacetate n-butyl ester) iron, tris(ethylene acetate second butyl acetate) Iron, tris(ethylene acetoacetate), iron, tris(ethyl acetate) iron, tris(ethyl acetate) iron, tris(n-propyl acetate) iron, tris(propyl acetate) Isopropyl ester) iron, tris(n-butyl acetate) iron, tris(propylene diacetate) butyl, tris(trimethylene acetate), iron, tris(ethyl acetate) , iron (trimethyl malonate) iron, tris (diethyl malonate) iron, trimethoxy iron, triethoxy iron, triisopropoxy iron, ferric chloride and other iron-based catalysts . These crosslinking catalysts may be used alone or in combination of two or more.

The content (amount of use) of the cross-linking catalyst is not particularly limited. For example, it is preferably about 0.0001 to 1 part by mass, more preferably 0.001 to 100 parts by mass of the (meth)acryl-based polymer. 0.5 parts by mass. If it is within the above range, the crosslinking reaction speed is faster when the adhesive layer is formed, and the pot life of the adhesive composition becomes longer, which becomes a preferable state. kind.

The above-mentioned adhesive composition may also contain a polyoxyalkylene-containing chain compound containing no organopolyoxyalkylene. By containing the above compound in the adhesive, an adhesive which is more excellent in wettability to the adherend can be obtained.

Specific examples of the polyoxyalkylene group-containing compound containing no organopolyoxyalkylene include polyoxyalkylene alkylamine, polyoxyalkylene diamine, and polyoxyalkylene fatty acid. Ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allylate, polyoxyalkylene Nonionic surfactants such as alkylalkyl phenyl allyl ether; polyoxyalkylene alkyl alkyl ether sulfate, polyoxyalkylene alkyl phosphate phosphate, polyoxyalkylene alkyl phenyl Anionic surfactants such as ether sulfates, polyoxyalkylene alkyl phenyl ether phosphates; other cationic surfactants or diionics having polyoxyalkylene chains (polyalkylene oxide chains) A surfactant, a polyether compound having a polyoxyalkylene chain (and derivatives thereof), an acrylic compound having a polyoxyalkylene chain (and derivatives thereof), and the like. Further, a polyoxyalkylene group-containing monomer may be formulated as a polyoxyalkylene-containing chain compound in the acrylic polymer. The polyoxyalkylene group-containing chain compound may be used singly or in combination of two or more.

Specific examples of the polyether compound having a polyoxyalkylene chain include a block copolymer of polypropylene glycol (PPG)-polyethylene glycol (PEG), a block copolymer of PPG-PEG-PPG, and Block copolymer of PEG-PPG-PEG, and the like. Examples of the derivative of the polyether compound having a polyoxyalkylene chain include an etherified oxypropyl group-containing compound (PPG monoalkyl ether, PEG-PPG monoalkyl ether, etc.), and terminal B. An oxylated propyl-containing compound (terminal acetophenone PPG, etc.).

Further, specific examples of the acrylic compound having a polyoxyalkylene chain include a (meth) acrylate polymer having an oxygen alkyl group. The oxygen-extended alkyl group has an addition molar number of from 1 to 50, more preferably from 2 to 30, still more preferably from 2 to 20, from the viewpoint of the coordination ionic compound. . Again, at the end of the above oxygen chain The terminal may be directly a hydroxyl group or may be substituted with an alkyl group, a phenyl group or the like.

The (meth) acrylate polymer having an oxygen alkyl group is preferably a polymer containing (meth)acrylic acid alkylene oxide as a monomer unit (component) as a specific one of the above (meth)acrylic acid alkylene oxide. Examples thereof include a (meth) acrylate having a glycol group, for example, a methoxy group such as methoxydiethylene glycol (meth) acrylate or methoxy triethylene glycol (meth) acrylate. Polyethylene glycol (meth) acrylate type; ethoxypolyethylene glycol (meth) acrylate, ethoxy triethylene glycol (meth) acrylate and other ethoxypolyethylene glycol (methyl Acrylate type; butoxy polyethylene glycol (meth) acrylate type such as butoxy diethylene glycol (meth) acrylate, butoxy triethylene glycol (meth) acrylate; phenoxy Phenoxy polyethylene glycol (meth) acrylate type such as diethylene glycol (meth) acrylate or phenoxy triethylene glycol (meth) acrylate; 2-ethylhexyl polyethylene glycol A methoxypolypropylene glycol (meth) acrylate type such as (meth) acrylate, nonylphenol polyethylene glycol (meth) acrylate type, or methoxy dipropylene glycol (meth) acrylate.

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

Further, as the monomer unit (component) other than the (meth)acrylic acid alkylene oxide, a carboxyl group-containing (meth) acrylate, a phosphate group-containing (meth) acrylate, or a cyano group may be suitably used. (meth) acrylate, vinyl ester, aromatic vinyl compound, acid anhydride group-containing (meth) acrylate, hydroxyl group-containing (meth) acrylate, guanamine-containing (meth) acrylate Amino group-containing (meth) acrylate, epoxy group-containing (meth) acrylate, N-propylene fluorenyl group Porphyrins, vinyl ethers, and the like.

As a more preferable aspect, the above polyoxyalkylene group-containing compound containing no organopolyoxyalkylene is a compound having at least a part of a (poly)ethylene oxide chain. By blending the above-mentioned (poly)ethylene oxide chain-containing compound, the compatibility between the base polymer and the antistatic component is improved, and the bleeding to the adherend is appropriately suppressed, whereby a low-pollution adhesive composition can be obtained. Among them, in particular, in the case of using a block copolymer of PPG-PEG-PPG, an adhesive excellent in low contamination is obtained. The polyoxyethylene oxide chain-containing compound preferably has a (poly)ethylene oxide chain in an amount of from 5 to 90% by mass based on the total of the polyoxyalkylene group-containing compound containing no organopolyoxyalkylene. More preferably, it is 5 to 85% by mass, further preferably 5 to 80% by mass, most preferably 5 to 75% by mass.

The molecular weight of the polyoxyalkylene group-containing compound containing no organopolyoxyalkylene, the number average molecular weight (Mn) is preferably 50,000 or less, more preferably 200 to 30,000, and still more preferably 200 to 10,000. Suitable for use from 200 to 5000. When Mn is too large than 50,000, the compatibility with the acrylic polymer is lowered, and the adhesive layer tends to be whitened. If Mn is too small as 200, there is a possibility that contamination due to the above polyoxyalkylene alkyl compound is likely to occur. Here, the term "Mn" as used herein means a value in terms of polystyrene obtained by GPC (gel permeation chromatography).

In addition, as a specific example of the commercial product containing the polyoxyalkylene chain-containing compound of the above-mentioned organic polyoxane, for example, Adeka Pluronic 17R-4 and Adeka Pluronic 25R-2 (all of which are manufactured by ADEKA Co., Ltd.) are mentioned. , Emulgen 120 (made by Kao Corporation) and so on.

The amount of the polyoxyalkylene group-containing compound containing no polyoxyalkylene oxide is, for example, 0.005 to 20 parts by mass, preferably 0.01 to 10 parts by mass, per 100 parts by mass of the acrylic polymer. More preferably, it is 0.05 to 5 parts by mass, and most preferably 0.1 to 1 part by mass. If the amount is too small, the effect of preventing the bleed out of the antistatic component is lowered, and if it is too large, there is a possibility that the contamination due to the polyoxyalkylene compound is likely to occur. Sex.

Further, an acrylic oligomer may be contained in the above adhesive composition. The weight average molecular weight 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, further preferably 2,000 or more and less than 10,000. The acrylic oligomer is a (meth)acrylic polymer containing a (meth)acrylic monomer having an alicyclic structure represented by the following formula (17) as a monomer unit, and is used. In the case of an acrylic-based adhesive, it functions as an adhesive-imparting resin, and improves adhesion, and is effective in suppressing the swelling of the surface protective film.

CH ₂ =C(R ¹ )COOR ² (17)

[In the formula (17), 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 in the formula (17) include a cyclohexyl group and a different An alicyclic hydrocarbon group such as a dicyclopentyl group or the like. Examples of the (meth) acrylate having such an alicyclic hydrocarbon group include cyclohexyl (meth) acrylate having a cyclohexyl group, and having a different (meth)acrylic acid An ester, an ester of (meth)acrylic acid such as dicyclopentyl (meth)acrylate having a dicyclopentyl group, and an alicyclic alcohol. By making the acrylic oligomer contain an acrylic monomer having a relatively large volume as a monomer unit, the adhesion can be improved.

Further, in the present embodiment, the alicyclic hydrocarbon group constituting the acrylic oligomer preferably has a bridged ring structure. The bridge ring structure refers to an alicyclic structure of three or more rings. By making the acrylic oligomer have a structure having a larger volume as a bridge ring structure, the adhesion of the acrylic adhesive composition for re-peeling (acrylic surface protective film for re-peeling) can be further improved.

Examples of the alicyclic hydrocarbon group R ² having a bridged ring structure include a dicyclopentanyl group represented by the following formula (3a), a dicyclopentenyl group represented by the following formula (3b), and the following formula. (3c) The adamantyl group represented by the following formula (3d), a tricyclopentenyl group represented by the following formula (3e), and the like. Further, in the case of synthesizing an acrylic oligomer or when UV polymerization is used in the production of an adhesive composition, it is difficult to cause polymerization inhibition, and it has an alicyclic structure having a triple ring or more having a bridged ring structure. In the (meth)acrylic monomer, a dicyclopentyl group represented by the following formula (3a) or an adamantyl group represented by the following formula (3c), and the following formula (3d) can be suitably used. The (meth)acrylic monomer having a saturated structure such as a tricyclopentyl group represented as a monomer constituting the acrylic oligomer.

Further, examples of the (meth)acrylic monomer having an alicyclic structure having three or more rings having a bridged ring structure include dicyclopentyl methacrylate, dicyclopentyl acrylate, and A. Dicyclopentyloxyethyl acrylate, dicyclopentyloxyethyl acrylate, tricyclopentyl methacrylate, tricyclopentyl acrylate, 1-adamantyl methacrylate, acrylic acid 1- Adamantyl ester, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, acrylic acid 2 (Meth) acrylate such as ethyl-2-adamantyl ester. These (meth)acrylic monomers may be used singly or in combination of two or more.

The acrylic oligomer of the present embodiment may be a homopolymer of a (meth)acrylic monomer having an alicyclic structure, or may be a (meth)acrylic monomer having an alicyclic structure. Copolymer with other (meth) acrylate monomers or copolymerizable monomers.

Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate. Butyl methacrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Amyl ester, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (A) Ethyl acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, (meth) acrylate An alkyl (meth)acrylate such as an alkyl ester; An aryl (meth)acrylate such as phenyl (meth)acrylate or benzyl (meth)acrylate; a (meth) acrylate obtained from a terpene compound derivative alcohol; and the like. Such (meth) acrylate may be used singly or in combination of two or more.

Further, in addition to the above (meth) acrylate component unit, the acryl oligomer may be obtained by copolymerizing another monomer component (copolymerizable monomer) copolymerizable with (meth) acrylate.

Examples of the other monomer copolymerizable with the (meth) acrylate include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, itaconic acid, maleic acid, and antibutene. a carboxyl group-containing monomer such as acid, crotonic acid or methacrylic acid; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, (methyl) a (meth)acrylic acid alkoxyalkyl ester monomer such as butoxyethyl acrylate or ethoxypropyl methacrylate; a salt such as an alkali metal salt of (meth)acrylic acid; Di(meth)acrylate, di(meth)acrylate of diethylene glycol, di(meth)acrylate of triethylene glycol, di(meth)acrylate of polyethylene glycol, propylene glycol a di(meth)acrylate monomer of di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate or the like (poly)alkylene glycol a poly (meth) acrylate monomer such as trimethylolpropane tri(meth) acrylate; a vinyl ester such as vinyl acetate or vinyl propionate; Ethylene, (meth) acrylate, 2-chloroethyl acrylate and the like halogenated vinyl compounds; vinyl-2- Oxazoline, 2-vinyl-5-methyl-2- Oxazoline, 2-isopropenyl-2- Oxazoline and the like Polymerizable compound of oxazoline group; polymerizable compound containing aziridine group such as (meth) acrylonitrile aziridine or 2-aziridine ethyl (meth)acrylate; allyl glycidol Ethylene ether, glycidyl (meth)acrylate, epoxy group-containing vinyl monomer such as 2-ethyl ester glycidyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, a hydroxyl group-containing vinyl monomer such as 2-hydroxypropyl methacrylate, a lactone and an addition product of 2-hydroxyethyl (meth) acrylate; in polypropylene glycol, polyethylene glycol, polytetraethylene a terminal bond of a methylene glycol, a polytetramethylene glycol, a copolymer of polyethylene glycol and polypropylene glycol, a copolymer of polytetramethylene glycol and polyethylene glycol, etc. a macromonomer of an unsaturated group such as an acrylonitrile group, a styryl group or a vinyl group; a fluorine-containing vinyl monomer such as a fluorine-substituted alkyl (meth)acrylate; maleic anhydride and itaconic anhydride; An acid group-containing monomer; an aromatic vinyl compound monomer such as styrene, α-methylstyrene or vinyl toluene; 2-chloroethyl vinyl ether, monochlorovinyl acetate Reactive halogen-containing vinyl monomers; (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-di (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-methylolpropane (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-propylene fluorenyl Hydrazine-containing vinyl monomer such as porphyrin; N-(methyl) propylene oxymethylene butyl quinone imine, N-(methyl) propylene fluorenyl-6-oxy hexamethylene Butadiene imine monomer such as butadiene imine, N-(methyl)propenyl-8-oxyhexamethylenebutaneimine; N-cyclohexylmethyleneimine , N-isopropyl maleimide, N-lauryl maleimide, N-phenyl maleimide, etc., maleimide-based monomer; N -methyl Ikonide, N-ethyl Ikonide, N-butyl Ikonide, N-octyl Ikonide, N-2-ethylhexyl Iccomia Ikonide imine monomer such as amine, N-cyclohexyl Ikonium imine, N-lauryl Icinoimine; N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidine Ketone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperidone N-vinylpyrene , N-vinylpyrrole, N-vinylimidazole, N-vinyl Oxazole, N-(methyl)propenyl-2-pyrrolidone, N-(methyl)propenylpyridinium, N-(methyl)propenylpyrrolidine, N-vinyl Porphyrin, N-vinylpyrazole, N-vinyl iso Oxazole, N-vinylthiazole, N-vinylisothiazole, N-vinyl anthracene a nitrogen-containing heterocyclic monomer; N-vinyl carboxamide; an internal guanamine monomer such as N-vinyl caprolactam; a cyanoacrylate monomer such as (meth)acrylonitrile; Aminoethyl acrylate, N,N-dimethylaminoethyl (meth) acrylate, N,N-dimethylaminoethyl (meth) acrylate, third butyl (meth) acrylate Aminoalkyl (meth) acrylate monomer such as arylaminoethyl ester; quinone imine containing monomer such as cyclohexylmethyleneimine or isopropyl maleimide; Isocyanate group-containing monomer such as 2-isocyanatoethyl methacrylate; vinyl trimethoxy decane, γ-methyl propylene oxypropyl trimethoxy decane, allyl trimethoxy decane, trimethoxy An organic ruthenium-containing vinyl monomer such as alkyl propylallylamine or 2-methoxyethoxytrimethoxy decane; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, methacrylic acid (4) -hydroxymethyl a hydroxyl group-containing monomer such as a hydroxyalkyl (meth) acrylate such as a methyl group; a tetrahydrofurfuryl (meth) acrylate, a (meth) acrylate having a fluorine atom, and a poly(oxy) (meth) acrylate. An acrylate monomer having a hetero ring, a halogen atom or a ruthenium atom; an olefin monomer such as isoprene, butadiene or isobutylene; and a vinyl ether such as methyl vinyl ether or ethyl vinyl ether. Monomer; olefin or diene such as ethylene, butadiene, isoprene, isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; and free radicals at the end of the monomer obtained by polymerizing a vinyl group A macromonomer of a polymerizable vinyl group or the like. These monomers may be copolymerized with the above (meth) acrylate, either singly or in combination.

Examples of the acrylic oligomer include a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA), cyclohexyl methacrylate (CHMA) and methacrylic acid. Copolymer (IBXMA) copolymer, methyl methacrylate (MMA) and methacrylic acid Copolymer (IBXMA) copolymer, cyclohexyl methacrylate (CHMA) and acrylonitrile Copolymer of porphyrin (ACMO), copolymer of cyclohexyl methacrylate (CHMA) and diethyl acrylamide (DEAA), 1-adamantyl acrylate (ADA) and methyl methacrylate (MMA) Copolymer, dicyclopentyl methacrylate (DCPMA) and methacrylic acid Copolymer of ester (IBXMA), copolymer of dicyclopentyl methacrylate (DCPMA) and methyl methacrylate (MMA), dicyclopentyl methacrylate (DCPMA) and N-vinyl-2 a copolymer of pyrrolidone (NVP), a copolymer of dicyclopentyl methacrylate (DCPMA) and hydroxyethyl methacrylate (HEMA), dicyclopentyl methacrylate (DCPMA) and acrylic acid ( Copolymer of AA), dicyclopentyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), methacrylic acid Ester (IBXMA), acrylic acid Ester (IBXA), dicyclopentyl acrylate (DCPA), 1-adamantyl methacrylate (ADMA), 1-adamantyl acrylate (ADA), methyl methacrylate (MMA) Polymer, etc.

Further, the acrylic oligomer may be introduced with a functional group reactive with an epoxy group or an isocyanate group. Examples of such a functional group include a hydroxyl group, a carboxyl group, an amine group, a phosphonium group, and a mercapto group, and a monomer having such a functional group may be used (copolymerization) in the production of an acrylic oligomer.

When the acrylic oligomer is a copolymer of a (meth)acrylic monomer having an alicyclic structure and another (meth) acrylate monomer or a copolymerizable monomer, it has a fat. The content ratio of the (meth)acrylic monomer having a ring structure is 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more, based on the total of the monomers constituting the acrylic oligomer. It is preferably 30% by mass or more (usually less than 100% by mass, preferably 90% by mass or less). When the (meth)acrylic monomer having an alicyclic structure is contained in an amount of 5 mass% or more, the adhesion can be improved without lowering the transparency.

The acrylic oligomer has a weight average molecular weight of 1,000 or more and less than 30,000, preferably 1,500 or more and less than 20,000, more preferably 2,000 or more and less than 10,000. When the weight average molecular weight is 30,000 or more, the adhesion is lowered. Further, when the weight average molecular weight is less than 1,000, the molecular weight is low, and thus the adhesion of the surface protective film is lowered.

The amount of the acrylic oligomer to be added is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass based on 100 parts by mass of the (meth)acrylic polymer. The amount of the component is preferably 0.2 to 5 parts by mass, more preferably 0.3 to 2 parts by mass. By using the blending amount in the above range, the adhesion to the adherend is improved, and the suppression of the bulge is easily achieved, which is a preferable aspect.

Further, other additives may be contained in the above-mentioned adhesive composition. For example, a powder such as a coloring agent or a pigment, a surfactant, a plasticizer, an adhesion-imparting agent, and a low molecular weight may be appropriately added depending on the intended use. Polymers, surface lubricants, leveling agents, antioxidants, anticorrosives, light stabilizers, UV absorbers, polymerization inhibitors, decane coupling agents, inorganic or organic fillers, metal powders, particulates, foils, etc. .

<Adhesive layer, surface protective film>

The surface protective film of the present invention is formed by forming the above-mentioned adhesive layer on a substrate. In this case, the crosslinking of the adhesive composition is usually performed after the application of the adhesive composition, but it may also be carried out after crosslinking. The adhesive layer of the adhesive composition is transferred onto a substrate or the like.

Further, the method of forming the pressure-sensitive adhesive layer on the substrate is not particularly limited. For example, the above-mentioned pressure-sensitive adhesive composition (solution) can be applied onto a substrate, and a polymerization solvent or the like can be dried and removed to form a substrate. Made with an adhesive layer. Thereafter, aging may be performed for the purpose of adjusting the component transfer of the adhesive layer or adjusting the crosslinking reaction. Further, when the surface protective film is formed by applying the pressure-sensitive adhesive composition to a substrate, one or more solvents other than the polymerization solvent may be newly added to the pressure-sensitive adhesive composition, so that the substrate can be uniformly applied to the substrate. on.

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

The surface protective film of the present invention is usually produced in such a manner that the thickness of the above-mentioned adhesive layer is from 3 to 100 μm, preferably from about 5 to 50 μm. When the thickness of the adhesive layer is within the above range, it is easy to obtain a balance between moderate removability and adhesion, which is preferable.

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

<separator>

In the surface protective film of the present invention, a spacer may be attached to the surface of the adhesive layer in order to protect the adhesive surface as needed.

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

The thickness of the separator is usually 5 to 200 μm, preferably about 10 to 100 μm. When it is in the above range, the adhesion to the adhesive layer and the workability of the self-adhesive layer are excellent, which is preferable. The release sheet may be subjected to mold release, antifouling treatment, or coating using a polyfluorene-based, fluorine-based, long-chain alkyl-based or fatty amide-based release agent, cerium oxide powder or the like as needed. Antistatic treatment of type, kneading type, vapor deposition type, etc.

The optical member of the present invention is preferably protected by the above surface protective film. Since the surface protective film has excellent antistatic property and peeling static voltage stability over time, it can be used for surface protection applications (surface protective film) such as processing, transportation, and shipment, and therefore protects the optical member (polarizing plate, etc.). The surface is useful. In particular, it can be used for a plastic product or the like which is likely to generate static electricity. Therefore, it is very useful for antistatic use in the technical field related to optical and electronic parts where static electricity is a particularly serious problem.

[Examples]

Hereinafter, some embodiments related to the present invention will be described, but it is not intended to The invention is limited to those shown in this specific example. In addition, as long as there is no special statement, the "parts" and "%" in the following descriptions are the quality standards. Further, the blending amount (addition amount) in the table indicates the ratio of the solid content or the solid content.

Moreover, each characteristic 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 Super HZ-H (1) + TSKgel Super HZM-H (2)

Reference column: TSKgel Super H-RC (1 root)

Detector: Differential Refractometer (RI)

Further, the weight average molecular weight is determined by a value in terms of polystyrene.

<glass transition temperature (Tg)>

The glass transition temperature Tg (° C.) is obtained by using the following literature value as the glass transition temperature Tgn (° C.) of the homopolymer of each monomer, and is obtained by the following formula (18).

Equation (18): 1/(Tg+273)=Σ[Wn/(Tgn+273)]

Wherein Tg(°C) represents the glass transition temperature of the copolymer, Wn(-) represents the weight fraction of each monomer, Tgn (°C) represents the glass transition temperature of the homopolymer of each monomer, and n represents each single Type of body]

Literature value: 2-ethylhexyl acrylate (2EHA): -70 ° C

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

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

Acrylic acid (AA): 106 ° C

In addition, as a literature value, reference is made to "Synthesis, design, and new use of acrylic resin" (issued by the Central Business Development Center Publishing Department) and "Polymer Handbook" (John Wiley & Sons).

<Measurement of surface resistance value>

The measurement was carried out in accordance with JIS-K-6911 using a resistivity meter (manufactured by Mitsubishi Chemical Corporation, manufactured by Mitsubishi Chemical Corporation, Hiresta UP MCP-HT450) under an environment of a temperature of 23 ° C and a humidity of 50% RH.

Further, as the surface resistance value (Ω/□) in the present invention, the initial period and the standing at room temperature (23 ° C × 50% RH) for one week (7 days) are preferably less than 1.0 × 10 ^{11 is more} preferably less than 5.0 × 10 ¹⁰ , and further preferably less than 1.0 × 10 ¹⁰ . The surface protective film which exhibits the surface resistance value in the above range can be preferably used as a surface protective film used in processing or transporting of articles such as liquid crystal cells or semiconductor devices.

<Measurement of polarizing plate peeling static voltage (polarizing plate side)>

The surface protective film 1 of each example was cut into a size of 70 mm in width and 130 mm in length, and after peeling off the release liner, as shown in FIG. 2, one end portion of the surface protective film 1 was extended from the end of the polarizing plate 20 by 30 mm. , by a hand press roll, a polarizing plate 20 bonded to a pre-decomposed acrylic plate 10 (manufactured by Mitsubishi Rayon Co., Ltd., trade name "Acrylite", thickness: 1 mm, width: 70 mm, length: 100 mm) Surface manufactured by Electrician Company, SEG1423DU polarizing plate, width: 70mm, length: 100mm).

The sample was allowed to stand in an environment of 23 ° C × 50% RH for one day, and then placed at a specific position of the sample fixing table 30 having a height of 20 mm. The end portion of the surface protective film 1 extending from the polarizing plate 20 by 30 mm is fixed to an automatic winder (not shown) so that the peeling angle becomes 150° and the peeling speed is set. Peeling was performed in such a manner that the degree became 10 m/min. The potential of the surface of the adherend (polarizing plate) generated at this time was measured as an "initial" by the potential measuring machine 40 (model "KSD-0103" manufactured by Kasuga Electric Co., Ltd.) which is fixed at a position 100 mm higher than the center of the polarizing plate 20. The polarizing plate peels off the static voltage." The measurement was carried out in an environment of 23 ° C and 50% RH.

In addition, after leaving it for 7 days in an environment of 23 ° C × 50% RH, the "polarized plate peeling static voltage over time" was measured in the same manner as in the "initial polarizing plate peeling static voltage". The measurement was carried out in an environment of 23 ° C × 50% RH.

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

The polarizing plate peeling static voltage (kV) (initial and transit time is an absolute value) of the present invention is preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.5 or less. If it is in the above range, for example, it is possible to prevent damage of the liquid crystal driver or the like, and it is preferable.

<Measurement of film side peeling static voltage (antistatic layer side of surface protective film)>

The surface protective film 1 was peeled off from the surface of the polarizing plate 20 so as to have a peeling angle of 150° and a peeling speed of 10 m/min, in the same manner as the measurement of the peeling static voltage of the polarizing plate. The potential of the surface protective film 1 generated at this time was measured by the potential measuring machine 40 (model "KSD-0103" manufactured by Kasuga Electric Co., Ltd.) which was fixed at a position 100 mm higher than the center of the surface protective film 1 as the "initial film". Side peeling static voltage". The measurement was carried out in an environment of 23 ° C and 50% RH.

Further, after standing for 7 days in an environment of 23 ° C × 50% RH, the "polarization plate peeling static voltage over time" was measured in the same manner as in "initial polarizing plate peeling static voltage". The measurement was carried out in an environment of 23 ° C × 50% RH.

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

The film side peeling static voltage (kV) (initial and time-lapse absolute values) of the present invention is preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.5 or less. If it is the above range In the inside, the surface protective film after peeling is not charged, and the workability is excellent, so that it is preferable.

<Measurement of slidability (dynamic friction)>

The surface protective film was cut into a size of 70 mm in width and 100 mm in length, and bonded to an acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name "Acrylite", thickness: 1 mm, width: 70 mm, length: 100 mm) to prepare a test piece. The back surface of the test piece (the surface of the antistatic layer) was placed downward on a smooth PET film which was kept horizontal, and a load of 1.5 kg was applied to the test piece. The test piece loaded with the load was mounted on 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.

Further, the slidability (dynamic frictional force) (N) in the present invention is preferably 5 or less, more preferably 4.5 or less, still more preferably 4 or less. When it is in the above range, when the adherend to which the surface protective film is attached is treated, the slidability of the back surface of the substrate (the surface of the antistatic layer) is good, which is advantageous in terms of workability.

<Evaluation of printing (printing adhesion)>

After printing on the surface of the antistatic layer using an X stamper manufactured by Shachihata Co., Ltd. under the measurement environment of 23 ° C × 50% RH, attached Sellotape (registered trademark) manufactured by Nichiban Co., Ltd., and then peeling speed. Peeling was carried out under conditions of 30 m/min and a peeling angle of 180°. Then, the surface after the peeling was visually observed, and the case where the printing area was peeled off by 50% or more was evaluated as × (printing failure), and 50% or more of the printing area was not peeled off and remained as ○ (printing property was good) ).

<Preparation of Acrylic Polymer (I) for Adhesive Layer>

To a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler, 100 parts by mass of 2-ethylhexyl acrylate (2EHA), 10 parts by mass of 4-hydroxybutyl acrylate (4HBA), and acrylic acid (AA) were added. 0.02 parts by mass of 2,2'-couple as a polymerization initiator 0.2 parts by mass of nitrogen diisobutyronitrile and 157 parts by mass of ethyl acetate, nitrogen gas was introduced while stirring slowly, and the liquid temperature in the flask was maintained at around 65 ° C for 6 hours to prepare an acrylic polymer (I). ) solution (40% by mass). The acrylic polymer (I) had a weight average molecular weight of 540,000 and a glass transition temperature (Tg) of -67 °C.

<Preparation of Acrylic Polymer (II) for Adhesive Layer>

Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler, 100 parts by mass of 2-ethylhexyl acrylate (2EHA) and 4 parts by mass of 2-hydroxyethyl acrylate (HEA) were added as a polymerization. 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a starting agent 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 around 65 ° C for 6 hours. Thus, an acrylic polymer (II) solution (40% by mass) was prepared. The acrylic polymer (II) had a weight average molecular weight of 540,000 and a glass transition temperature (Tg) of -68 °C.

<Preparation of Acrylic Polymer (III) for Adhesive Layer>

To a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler, 100 parts by mass of 2-ethylhexyl acrylate (2EHA), 10 parts by mass of 4-hydroxybutyl acrylate (4HBA), and acrylic acid (AA) were added. 0.05 parts by mass of 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 stirring slowly, and the temperature in the flask was maintained at 65 ° C. A polymerization reaction was carried out for 6 hours in the vicinity to prepare an acrylic polymer (III) solution (40% by mass). The acrylic polymer (III) had a weight average molecular weight of 540,000 and a glass transition temperature (Tg) of -67 °C.

<Preparation of Acrylic Polymer (IV) for Adhesive Layer>

To a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler, 100 parts by mass of 2-ethylhexyl acrylate (2EHA), 10 parts by mass of 4-hydroxybutyl acrylate (4HBA), and acrylic acid (AA) were added. 0.1 parts by mass of 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 stirring slowly, and the temperature in the flask was maintained at 65 ° C. 6 hours of polymerization in the vicinity, from Further, an acrylic polymer (IV) solution (40% by mass) was prepared. The acrylic polymer (IV) had a weight average molecular weight of 540,000 and a glass transition temperature (Tg) of -67 °C.

[Preparation of Acrylic Oligomers]

Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, a cooler, and a dropping funnel, 100 parts by mass of toluene and dicyclopentyl methacrylate (DCPMA) (trade name: FA-513M, Hitachi Chemical Co., Ltd.) were charged. 60 parts by mass, 40 parts by mass of methyl methacrylate (MMA) and 3.5 parts by mass of methyl thioglycolate as a chain transfer agent. Then, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator was introduced, and the reaction was carried out at 70 ° C for 2 hours, followed by reaction at 80 ° C. After 4 hours, the reaction was carried out at 90 ° C for 1 hour to obtain an acrylic oligomer solution (51% by mass). The acrylic oligomer had a weight average molecular weight of 4,000 and a glass transition temperature (Tg) of 144 °C.

[Preparation of Acrylic Adhesive Solution (A)]

The acrylic polymer (I) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and hexamethylene group as a crosslinking agent was added to 500 parts by mass of the solution (100 parts by mass of the solid content). 3.5 parts by mass of a diisocyanate isocyanurate body (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) (3.5 parts by mass of a solid component), dibutyltin dilaurate (1% by mass ethyl acetate solution) as a crosslinking catalyst 3 parts by mass (0.03 parts by mass of the solid content) was mixed and stirred to prepare an acrylic pressure-sensitive adhesive solution (A).

[Preparation of Acrylic Adhesive Solution (B)]

The above acrylic polymer (I) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of the solution (100 parts by mass of the solid content) was added to the organic polyoxyl Alkane (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 10% to obtain 2 parts by mass of a solution (0.2 parts by mass of solid content), and an alkali metal salt of bis(trifluoroethylene) as an antistatic agent using ethyl acetate Methanesulfonate) Lithium imide (LiN(CF ₃ SO ₂ ) ₂ : LiTFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) diluted to 1% to obtain 15 parts by mass of a solution (solid content: 0.15 parts by mass) as a crosslinking agent 3.5 parts by mass of an isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) (3.5 parts by mass of solid content), and dibutyltin dilaurate (1% by mass) as a crosslinking catalyst 3 parts by mass of the ethyl acetate solution (0.03 parts by mass of the solid content) was mixed and stirred to prepare an acrylic adhesive solution (B).

[Preparation of Acrylic Adhesive Solution (C)]

The acrylic polymer (II) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and hexamethylene group as a crosslinking agent was added to 500 parts by mass of the solution (100 parts by mass of the solid content). 3.5 parts by mass of a diisocyanate isocyanurate body (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) (3.5 parts by mass of a solid component), dibutyltin dilaurate (1% by mass ethyl acetate solution) as a crosslinking catalyst 3 parts by mass (0.03 parts by mass of the solid content) was mixed and stirred to prepare an acrylic adhesive solution (C).

[Preparation of Acrylic Adhesive Solution (D)]

The above acrylic polymer (I) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of the solution (100 parts by mass of the solid content) was added to the organic polyoxyl Alkane (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 10% to obtain 2 parts by mass of a solution (0.2 parts by mass of solid content), and 1-ethyl group as an antistatic agent, i.e., an ionic liquid, using ethyl acetate 5-methylimidazolium bis(trifluoromethanesulfonate)imide (EMITFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) diluted to 1% to obtain 15 parts by mass of a solution (solid content of 0.15 parts by mass) as a crosslinking agent 2 parts by mass of the isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) (solid content: 2 parts by mass) and 1,3-bis(isocyanatemethyl)cyclohexane (manufactured by Mitsui Chemicals, Takenate 600) 0.3 parts by mass (solid content: 0.3 parts by mass), dibutyltin dilaurate (1% by mass ethyl acetate solution) as a crosslinking catalyst, 3 parts by mass (solid content 0.03 mass) The mixture was stirred and mixed to prepare an acrylic adhesive solution (D).

[Preparation of Acrylic Adhesive Solution (E)]

The above acrylic polymer (I) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of the solution (100 parts by mass of the solid content) was added to the organic polyoxyl Alkane (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 10% to obtain 2 parts by mass of a solution (0.2 parts by mass of solid content), and 1-ethyl group as an antistatic agent, i.e., an ionic liquid, using ethyl acetate 5-methylimidazolium bis(fluorosulfonyl)imide (EMIFSI, manufactured by Dai-Il Pharmaceutical Co., Ltd.) diluted to 1% to obtain 15 parts by mass of a solution (solid content of 0.15 parts by mass) as a crosslinking agent 2 parts by mass of the isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) (solid content: 2 parts by mass) and 1,3-bis(isocyanatemethyl)cyclohexane ( Manufactured by Mitsui Chemicals Co., Ltd., Takenate 600) 0.3 parts by mass (solid content: 0.3 parts by mass), dibutyltin dilaurate (1% by mass ethyl acetate solution) as a crosslinking catalyst, 3 parts by mass (solid content: 0.03 parts by mass) And mixing and stirring to prepare an acrylic adhesive solution (E).

[Preparation of Acrylic Adhesive Solution (F)]

The above acrylic polymer (I) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of the solution (100 parts by mass of the solid content) was added to the organic polyoxyl Alkane (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 10% to obtain 2 parts by mass of a solution (0.2 parts by mass of solid content), and 1-ethyl group as an antistatic agent, i.e., an ionic liquid, using ethyl acetate 15-Methylimidazolium trifluoromethanesulfonate (EMITFS, manufactured by First Industrial Pharmaceutical Co., Ltd.) diluted to 1% of a solution of 15 parts by mass (solid content of 0.15 parts by mass), as a crosslinking agent 2 parts by mass of methyl isocyanate isocyanurate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) (solid content: 2 parts by mass) and 1,3-bis(isocyanatemethyl)cyclohexane (Mitsui Chemicals) Made by the company, Takenate 600) 0.3 parts by mass (solid content: 0.3 parts by mass), dibutyltin dilaurate (1% by mass ethyl acetate solution) as a crosslinking catalyst, 3 parts by mass (solid content: 0.03 parts by mass), The mixture was stirred and mixed to prepare an acrylic adhesive solution (F).

[Preparation of Acrylic Adhesive Solution (G)]

The above acrylic polymer (I) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of the solution (100 parts by mass of the solid content) was added to the organic polyoxyl 20 parts by mass of a solution obtained by diluting to 1% of an alkane (KF-6004, manufactured by Shin-Etsu Chemical Co., Ltd.) (0.2 parts by mass of a solid content), and 1-butyl group as an antistatic agent, that is, an ionic liquid, using ethyl acetate 3-5-methylpyridinium bis(trifluoromethanesulfonate)imide (BMPTFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) diluted to 1% to obtain 15 parts by mass of a solution (solid content: 0.15 parts by mass) as a crosslinking agent 3 parts by mass of a trimer adduct of trimethylolpropane/toluene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) (solid content: 3 parts by mass), dibutyltin dilaurate as a crosslinking catalyst (1 mass% of ethyl acetate solution) 3 parts by mass (0.03 parts by mass of the solid content), and the mixture was stirred and mixed to prepare an acrylic pressure-sensitive adhesive solution (G).

[Preparation of Acrylic Adhesive Solution (H)]

The acrylic polymer (III) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of the solution (100 parts by mass of the solid content) was added to the organic polyoxyl Alkane (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 10% to obtain 4 parts by mass of a solution (solid content 0.4 parts by mass), and an alkali metal salt bis (trifluoroethylene) as an antistatic agent using ethyl acetate Methanesulfonate) Lithium imide (LiN(CF ₃ SO ₂ ) ₂ : LiTFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) diluted to 1% to obtain 30 parts by mass of a solution (solid content: 0.3 parts by mass), as a crosslinking agent 3 parts by mass of the isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) (solid content: 3 parts by mass) and 1,3-bis(isocyanatemethyl)cyclohexane ( Manufactured by Mitsui Chemicals Co., Ltd., Takenate 600) 0.3 parts by mass (solid content: 0.3 parts by mass), dibutyltin dilaurate (1% by mass ethyl acetate solution) as a crosslinking catalyst, 3 parts by mass (solid content: 0.03 parts by mass) And mixing and stirring to prepare an acrylic adhesive solution (H).

[Preparation of Acrylic Adhesive Solution (I)]

The above acrylic polymer (IV) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of the solution (100 parts by mass of the solid content) was added to the organic polyoxyl oxide by using ethyl acetate. Alkane (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 10% to obtain 4 parts by mass of a solution (solid content 0.4 parts by mass), and an alkali metal salt bis (trifluoroethylene) as an antistatic agent using ethyl acetate Methanesulfonate) Lithium imide (LiN(CF ₃ SO ₂ ) ₂ : LiTFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) diluted to 1% to obtain 30 parts by mass of a solution (solid content: 0.3 parts by mass), as a crosslinking agent 3 parts by mass of the isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) (solid content: 3 parts by mass) and 1,3-bis(isocyanatemethyl)cyclohexane ( Manufactured by Mitsui Chemicals Co., Ltd., Takenate 600) 0.5 parts by mass (0.5 parts by mass of solid content), 3 parts by mass of dibutyltin dilaurate (1% by mass ethyl acetate solution) as cross-linking catalyst (solid content 0.03 parts by mass) And mixing and stirring to prepare an acrylic adhesive solution (I).

[Preparation of Acrylic Adhesive Solution (J)]

The above acrylic polymer (I) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of the solution (100 parts by mass of the solid content) was added to the organic polyoxyl Alkane (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 10% to obtain 2 parts by mass of a solution (0.2 parts by mass of solid content), and an alkali metal salt of bis(trifluoroethylene) as an antistatic agent using ethyl acetate Methanesulfonate) Lithium imide (LiN(CF ₃ SO ₂ ) ₂ : LiTFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) diluted to 1% to obtain 15 parts by mass of a solution (solid content: 0.15 parts by mass) as a crosslinking agent 3.5 parts by mass of the isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) (3.5 parts by mass of the solid component) and 1,3-bis(isocyanatemethyl)cyclohexane ( Manufactured by Mitsui Chemicals Co., Ltd., Takenate 600) 0.3 parts by mass (solid content: 0.3 parts by mass), as a crosslinking catalyst, iron(III) pyruvate (1% by mass ethyl acetate solution) 0.5 parts by mass (solid content 0.005 parts by mass), and mixing and stirring were carried out to prepare an acrylic adhesive solution (J).

[Preparation of Acrylic Adhesive Solution (K)]

The above acrylic polymer (I) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of the solution (100 parts by mass of the solid content) was added to the organic polyoxyl oxide by using ethyl acetate. Alkane (x-22-6266, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 10% to obtain 2 parts by mass of a solution (0.2 parts by mass of solid content), and an alkali metal salt as an antistatic agent using ethyl acetate ( Trifluoromethanesulfonate) Lithium imide (LiN(CF ₃ SO ₂ ) ₂ : LiTFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) diluted to 1% and obtained 15 parts by mass of a solution (solid content: 0.15 parts by mass) as cross-linking The isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) 3 parts by mass (solid content: 3 parts by mass) and 1,3-bis(isocyanatemethyl)cyclohexane 0.3 parts by mass (solid content: 0.3 parts by mass) of alkane (manufactured by Mitsui Chemicals, Inc., Takenate 600), dibutyltin dilaurate (1% by mass ethyl acetate solution) as a crosslinking catalyst, 3 parts by mass (solid content 0.03) The mass part) was mixed and stirred to prepare an acrylic adhesive solution (K).

[Preparation of Acrylic Adhesive Solution (L)]

The above acrylic polymer (I) solution (40% by mass) was diluted to 20% by mass with ethyl acetate, and 500 parts by mass of the solution (100 parts by mass of the solid content) was added to the organic polyoxyl Alkane (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 10% to obtain 2 parts by mass of a solution (0.2 parts by mass of solid content), and an alkali metal salt of bis(trifluoroethylene) as an antistatic agent using ethyl acetate Methanesulfonate) Lithium imide (LiN(CF ₃ SO ₂ ) ₂ : LiTFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) diluted to 1% to obtain 15 parts by mass of a solution (solid content: 0.15 parts by mass), using ethyl acetate 5 parts by mass of the solution obtained by diluting the above acrylic oligomer solution to 10% by mass (0.5 parts by mass of the solid content), and an isocyanurate body of hexamethylene diisocyanate as a crosslinking agent (Japanese polyurethane industry) Co., Ltd., Coronate HX) 3.5 parts by mass (3.5 parts by mass of solid content) and 1,3-bis(isocyanatemethyl)cyclohexane (manufactured by Mitsui Chemicals, Takenate 600) 0.3 parts by mass (solid content 0.3 mass) a part of dibutyltin dilaurate (1 mass% acetic acid) as a cross-linking catalyst Ester solution) 3 parts by mass (0.03 parts by mass of solid content), mixing and stirring, to prepare an acrylic adhesive solution (L).

[Preparation of urethane-based adhesive solution (M)]

For the quality of the Sanminx GP3000 (manufactured by Sanyo Chemical Co., Ltd., Mn=3000) of 13 mass parts of a polyol having three hydroxyl groups as a polyol having three hydroxyl groups as a polyol, Mn = 3,000 (prepared by Asahi Glass Co., Ltd., Mn = 10000) 2 parts by mass of Sannix GP1000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 1000) of a polyol having three hydroxyl groups, and 18 parts by mass of an isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, as a catalyst 0.04 parts by mass of ethyl acetate (III) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 210 parts by mass of ethyl acetate as a diluent solvent, thereby obtaining a urethane-based pressure-sensitive adhesive solution (M). Further, as a raw material of the urethane-based adhesive solution, all of the raw materials were 100% in concentration except for the solvent.

[Preparation of urethane-based adhesive solution (N)]

A urethane-based adhesive is obtained by the same method as the above-described urethane-based adhesive solution (M), except that 0.08 parts by mass of a tin-based catalyst dibutyltin dilaurate is used as a catalyst. Solution solution (N).

[Preparation of urethane-based adhesive solution (O)]

Further, 30 parts by mass of isopropyl myristate (Exceparl IPM, manufactured by Kao Corporation) as a wettability improver, and 0.5 parts by mass of Irganox 1010 (manufactured by BASF Corporation) as an antioxidant were added, in addition to the above amine. The urethane-based adhesive solution (O) is obtained in the same manner as the urethane-based adhesive solution (M).

[Preparation of urethane-based adhesive solution (P)]

Further, 0.1 parts by mass of an organic polyoxane (KF-6004, manufactured by Shin-Etsu Chemical Co., Ltd.) as an antistatic component, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIFSI, A urethane-based pressure-sensitive adhesive solution (P) is obtained by the same method as the above-described urethane-based pressure-sensitive adhesive solution (O), except that the amount of the urethane-based adhesive solution (O) is 0.5 parts by mass.

[Preparation of polyoxygenated adhesive solution (Q)]

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

[Preparation of polyoxygenated adhesive solution (R)]

"X-40-3229" (solid content 60% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.) and "CAT-PL" as a platinum catalyst, which are 100 parts by mass of the solid content of the polyoxynene-based adhesive -50T" (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass, organic polyoxane (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 parts by mass, lithium bis(trifluoromethanesulfonate)imide (LiN (CF _{3 )} SO ₂ ) ₂ : LiTFSI (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.3 parts by mass of 100 parts by mass of toluene as a solvent to obtain a polyoxynoxy-based adhesive solution (R).

<Preparation of aqueous solution for antistatic layer (C), (G) and (H)>

To a mixed solvent of water/ethanol (1/3), a polyester resin Vylonal MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder in an amount of 100 parts by mass of the solid content component, and a solid content component are added. 75 parts by mass of polyaniline sulfonic acid (aquapass, weight average molecular weight 40,000 manufactured by Mitsubishi Rayon Co., Ltd.) as a conductive polymer, and 10 parts by mass of a solid content component as a crosslinking agent The isocyanuric acid-blocked hexamethylene diisocyanate isocyanurate body, and 30 parts by mass of the oily amide as a lubricant in an amount of the solid content, was stirred for about 20 minutes and thoroughly mixed. Thus, an aqueous solution for an antistatic layer (C) having an NV of about 0.4% was prepared.

Further, based on the contents of the formulation of Table 4, an aqueous solution for the antistatic layer (G) and an aqueous solution for the antistatic layer (H) were prepared in the same manner as the aqueous solution of the antistatic layer (C).

<Preparation of aqueous solution for antistatic layer (D)>

To a mixed solvent of water/ethanol (1/3), a polyester resin Vylonal MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder in an amount of 100 parts by mass of the solid content component, and a solid content component are added. 75 parts by mass of polyaniline as a conductive polymer Sulfonic acid (aquapass, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co., Ltd.), 10 parts by mass of the solid content component, and diisopropylamine-terminated hexamethylene diisocyanate as a crosslinking agent The cyanurate body was stirred for about 20 minutes and thoroughly mixed. Thus, an aqueous solution for an antistatic layer (D) having an NV of about 0.4% was prepared.

<Preparation of aqueous solution for antistatic layer (E)>

To a mixed solvent of water/ethanol (1/1), a polyester resin Vylonal MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder in an amount of 100 parts by mass of the solid content component, and a solid content component are added. 50 parts by mass of a conductive polymer containing poly(3,4-ethylenedioxythiophene) (PEDOT) 0.5% and polystyrenesulfonic acid (weight average molecular weight 150,000) (PSS) 0.8% An aqueous solution (Bytron P, manufactured by HC Stark Co., Ltd.) and a melamine-based crosslinking agent were stirred for about 20 minutes to be thoroughly mixed. Thus, an aqueous solution for an antistatic layer (E) having an NV of about 0.4% was prepared.

<Preparation of aqueous solution for antistatic layer (F)>

To a mixed solvent of water/ethanol (1/3), a polyester resin Vylonal MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder in an amount of 100 parts by mass of the solid content component, and a solid content component are added. 75 parts by mass of polyaniline sulfonic acid (aquapass, weight average molecular weight 40,000 manufactured by Mitsubishi Rayon Co., Ltd.) as a conductive polymer was weighed and mixed well for about 20 minutes. Thus, an aqueous solution for an antistatic layer (C) having an NV of about 0.4% was prepared.

<Preparation of substrate with antistatic layer>

On one side (the first side), a corona-treated surface of 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 was subjected to corona treatment to dry. Any one of the antistatic layers (C) to (H) described above is applied so as to have a thickness of 15, 30, or 45 nm. The coated product was heated at 130 ° C for 1 minute and dried to prepare a substrate having an antistatic layer having an antistatic layer on the first side of the PET film.

<Example 1> [Production of surface protective film]

The acrylic pressure-sensitive adhesive solution (A) is applied to the surface of the substrate (antistatic layer-attached substrate) having the antistatic layer opposite to the antistatic layer, and heated at 130 ° C for 1 minute to form An adhesive layer having a thickness of 15 μm. Then, a polyfluorene-treated surface of a polyethylene terephthalate film (thickness: 25 μm) which is a separator which is subjected to polyfluorination treatment was bonded to the surface of the above-mentioned pressure-sensitive adhesive layer to prepare a surface protective film.

<Example 15>

Applying the above urethane-based adhesive solution (N) to the surface of the substrate (antistatic layer with an antistatic layer) having the antistatic layer opposite to the antistatic layer, and heating at 130 ° C Minutes to form an adhesive layer having a thickness of 10 μm. Then, a polyfluorene-treated surface of a polyethylene terephthalate film (thickness: 25 μm) which is a separator which is subjected to polyfluorination treatment was bonded to the surface of the above-mentioned pressure-sensitive adhesive layer to prepare a surface protective film.

<Example 19>

The polyoxygen-based adhesive solution (Q) is applied to the surface of the substrate (antistatic layer-attached substrate) having the antistatic layer opposite to the antistatic layer, and heated at 150 ° C for 1 minute. Thus, an adhesive layer having a thickness of 10 μm was formed. Then, a polyfluorene-treated surface of a polyethylene terephthalate film (thickness: 25 μm) which is a separator which is subjected to polyfluorination treatment was bonded to the surface of the above-mentioned pressure-sensitive adhesive layer to prepare a surface protective film.

<Examples 2 to 14 and Comparative Examples 1 to 3>

A surface protective film was produced in the same manner as in Example 1 based on the contents of the formulations of Table 1, Table 4, and Table 5.

<Examples 16 to 18>

A surface protective film was produced in the same manner as in Example 15 based on the contents of the preparations of Table 2, Table 4, and Table 5.

<Example 20>

Surfaces were produced in the same manner as in Example 19 based on the contents of Tables 3 to 5 Protective film.

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

According to Table 6, it was confirmed that in all the examples, the surface resistance value and the film side peeling static voltage which the antistatic layer functions are excellent, and further, the isocyanate crosslinking agent is used as the crosslinking agent used for the antistatic layer. The printing is also excellent in adhesion. In addition, in the second embodiment in which the antistatic component is blended in the adhesive layer, the polarizing plate peeling static voltage is also excellent, and in the first embodiment in which the lubricant is blended in the antistatic layer, the slidability is obtained. Also excellent.

On the other hand, according to Table 6, it can be confirmed that in Comparative Examples 1 and 2, when a water-dispersible conductive polymer (PEDOT/PSS) is used as a component constituting the antistatic layer, when preparing an antistatic layer Agglomerates were observed in the aqueous solution used, not only the surface resistance value of the antistatic layer acting on time (measured after 1 week at room temperature), but also the film side peeling static voltage from the antistatic layer was not obtained. The desired effect comes from the antistatic layer and the adhesive layer. The polarizing plate peeling static voltage also did not achieve the desired effect. The reason for this is not clear, and it is presumed that the antistatic property of the entire surface protective film is deteriorated due to deterioration of the antistatic layer. Further, in Comparative Example 2 in which the antistatic component was blended in the adhesive layer, the polarizing plate peeling static voltage was particularly poor as a result.

Further, in Comparative Example 3, it was confirmed that a water-soluble conductive polymer (polyaniline sulfonic acid) was used as a component constituting the antistatic layer, but an isocyanate crosslinking agent was not used as a crosslinking agent, so the printing was closely bonded. Poor sex.

[Industrial availability]

When the surface protective film disclosed herein is used for manufacturing an optical member used as a constituent element of a liquid crystal display panel, a plasma display panel (PDP), an organic electroluminescence (EL) display or the like, it is suitably used as a carrier to protect the optical. Surface protection film for components. In particular, it is used as a surface protective film (optical surface protection film) 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. )it works.

Claims (7)

A surface protective film comprising: a substrate having a first surface and a second surface; an antistatic layer provided on the first surface of the substrate; and the second surface of the substrate The adhesive layer formed of the adhesive composition, and the antistatic layer is composed of polyaniline sulfonic acid as a conductive polymer component, a polyester resin as a binder, and an isocyanate crosslinking agent as a crosslinking agent. An electrostatic agent composition is formed. The surface protective film of claim 1, wherein the antistatic agent composition further contains a fatty guanamine as a lubricant. The surface protective film of claim 1, wherein the substrate is a polyester film. The surface protective film of claim 1, wherein the adhesive composition contains at least one selected from the group consisting of an acrylic adhesive, an urethane-based adhesive, and a polyoxygen-based adhesive. The surface protective film of claim 1, wherein the above adhesive composition contains an antistatic component. An optical member characterized in that it is protected by a surface protective film according to any one of claims 1 to 5. A method of producing a surface protective film according to any one of claims 1 to 5, comprising: a step of preparing an aqueous solution containing the above antistatic agent composition, and The aqueous solution is applied to the first surface of the substrate and dried to prepare an antistatic layer.