TW200916314A - Surface protective film - Google Patents

Abstract

The surface protective film of this invention comprises a substrate and a coating layer with a thickness between 20nm to 50nm on the substrate. The coating layer comprises a composition containing (A) a conductive polymer having a polythiophene structure and an electron-accepting polyacid structure, (B) melamine resin, (C) polyester resin, and (D) polyorganosiloxane. In this invention, the amount of (A) is controlled by the manner that the product (<alpha>) of coating layer thickness and the mass ratio of the conductive polymeric ingredient (A) to the total mass of the conductive polymeric ingredient (A), melamine resin (B), polyester resin (C), and polyorganosiloxane (D) becomes 6nm to 15nm.

Description

200916314 IX. Description of the Invention [Technical Field] The present invention relates to a surface protective film mainly used for a polarizing plate. [Prior Art] Products such as electronic equipment, optical components, and electrochemical products are stored at the time of manufacture for the purpose of preventing scratches or breakage, preventing the adhesion of dirt or dust, and preventing dust or moisture from entering the interior. A surface protection film that protects various products or members is used for transportation, transportation, and the like. The surface protective film used in the above application is generally formed by using a plastic film as a substrate, and an adhesive layer is formed on one surface of the substrate, and the adhesive layer is attached to various products or members. . Therefore, the surface protective film is peeled off when various products or members are used after storage, transportation, transportation, and transportation, but the surface protective film used in the electronic device is electrically charged. 'There is a flaw in the electronic circuit, so the surface protection film requires antistatic properties. In addition, in the case of the surface protective film, if the surface (the side opposite to the adhesive layer) is contaminated, it may become a contaminated product or a member or a foreign matter may be mixed in the product, so the surface is also required to have antifouling properties. . Further, in the case of the surface protective film, since the adhesive tape attached to the surface of the film is peeled off from the peeling of the product or the member, the tape peeling force on the surface of the film is also required to be high. In addition, since there are many printings such as lot numbers on the surface protective film, printing density is also required to be high. -4- 200916314 As for the surface of the surface protection film, for example, dust or dirt is attached, and dirt during work is used. Further, since the surface protective film used in the polarizing plate cuts the polarizing plate in a state in which the surface protective film is attached, the chips (especially the chips of the adhesive layer) which are generated at the time of cutting are also It adheres to its surface and there is also a contamination due to the chips. If the cause of the contamination of the surface protective film is roughly different, it can be distinguished as adhesion of dust due to charging of the surface of the surface protective film, adhesion of dirt due to wettability of the surface of the surface protective film, or adhesion of the adhesive layer. Therefore, if the surface of the surface protective film has antistatic properties and low wettability (if the water repellency is high), it can be said that the antifouling property is high. Such a surface protective film is proposed, for example, in Patent Documents 1 to 3. In Patent Documents 1 and 2, a surface protective film which imparts antistatic properties is proposed, and an antistatic layer containing a conductive high molecular weight such as polyaniline or polyolefin is provided on the substrate. Further, Patent Document 3 proposes an optical protective film having antistatic properties, scratch resistance, easy-to-cleanness of contaminants, printability, and the like, and is provided on an antistatic layer, and further provided with a surface protective layer. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-246874 (Patent Document 3) Japanese Laid-Open Patent Publication No. Hei No. Hei. No. 2006-142769. The problem is that the conductive polymer contained in the surface protective film of the above-mentioned Patent Documents 1 and 2 differs from the liquid antistatic agent in that it is difficult to cause volatilization or elution due to long-term storage. However, if an antistatic layer containing a conductive polymer is provided, the water repellency of the surface of the film is lowered, and the antifouling property is insufficient. In order to solve this problem, when a water repellency is imparted by using a rhodium-based surfactant or a fluorine-based surfactant, the tape peeling force or the printing adhesion is lowered. Further, when the content ratio of the conductive polymer is high, the scratch resistance is lowered. Further, in the protective film of Patent Document 3, in order to form a two-layer structure of the antistatic layer and the surface protective layer, it is necessary to apply the coating twice, and the cost becomes high. An object of the present invention is to provide a surface protective film which can be used as a single layer coating to solve the above problems, and which is low in cost and has excellent antistatic property and stain resistance while being excellent in scratch resistance. The layer is also excellent in tape peeling force and printing adhesion. (Means for Solving the Problem) The present inventors have found that a conductive polymer component (A), a melamine resin (B), a polyester resin (C) having a polyolefin structure and an electron-accepting polybasic acid structure are combined. The organic decane (D) is used as a component contained in the coating of the surface protective film to simultaneously achieve antistatic properties and antifouling properties. The present inventors have further found that the content of the conductive polymer -6 - 200916314 component of the above (A) is controlled within a certain range irrespective of the thickness of the coating layer, and antistatic property, scratch resistance, tape peeling property, and A coating with excellent balance of printing adhesion. The present invention has been completed based on these novel findings. That is, the present invention is a surface protective film characterized by comprising a substrate and a coating having a thickness of 20 nm to 500 nm on the surface of the substrate, the coating comprising a polythiophene-containing structure and an electron-accepting polybasic acid. a conductive polymer component having a structure, a melamine resin, a polyester resin, and a composition of an organic siloxane, wherein the conductive polymer component is the conductive polymer component contained in the composition, and the melamine The product of the mass ratio of the total mass of the resin, the above polyester resin and the above organic decane to the thickness of the coating layer is 6 nm to 15 nm. The composition for forming the surface coating of the substrate of the surface protective film of the present invention contains not only the conductive polymer component (A) which imparts antistatic property but also the organic siloxane which imparts water repellency and scratch resistance ( D), therefore, can have both antistatic properties and antifouling properties. Further, since the composition contains the melamine resin (B) and the polyester resin (C), it has sufficient strength and higher scratch resistance and is excellent in transparency. The content of the conductive polymer component (A) in the composition is too small to exhibit an antistatic effect, and if too much, the strength of the coating layer is lowered, and according to the present invention, the content of the conductive polymer component (A) is It is controlled to a certain range regardless of the thickness of the coating, and the antistatic effect and strength can be fully exerted. The present invention may also be constituted as follows. (1) The organic oxirane (1) by mass based on the total mass of the conductive polymer component 200916314 (A), the melamine resin (B), and the polyester resin (C). The content ratio of D) is 〇. 1 to 1.0 parts by mass. According to this configuration, a surface protective film having a coating layer excellent in water repellency, printing property, and tape peeling property can be obtained. (2) In the above composition, the ratio of the total mass of the melamine resin (B) to the polyester resin (C) is 400 to 2000 parts by mass based on 100 parts by mass of the conductive polymer component (A). According to this configuration, it is preferable to obtain a surface protective film having a coating excellent in scratch resistance. (3) In the above composition, an adhesive layer may be formed on a surface opposite to a surface on which the substrate is formed with the coating layer. According to this configuration, even if the adhesive is not additionally applied, the surface protective film can be adhered to the surface of the member such as the polarizing plate by the adhesive layer. (4) In the above composition, the conductive polymer component (A) may further comprise a polyethylene dioxythiophene and a polystyrene sulfonate. If so configured, a surface protective film of a coating having a higher antistatic property can be obtained. (5) In the above composition, the polyester resin (C) may be a water-dispersible polyester into which a sulfonic acid metal salt group is introduced. According to this configuration, the polyester in the coating layer can be uniformly dispersed, and a surface protective film having a high transparency and a good appearance can be obtained. (Effect of the Invention) -8 - 200916314 According to the present invention, it is possible to provide a surface protective film having a coating layer excellent in antistatic property and antifouling property and excellent in scratch resistance, and excellent in tape peeling force and printing adhesion. . [Embodiment] The surface protection film of the present invention comprises a substrate having a conductive polymer component (A), a melamine resin (B), a polyester resin (C), and an organic chopping chamber ( The composition of d) is formed to have a thickness of 20 nm to 5 Å Onm. &lt;Substrate&gt; The substrate of the surface protective film of the present invention is not particularly limited as long as it has transparency and heat resistance necessary for the application, and is, for example, polyethylene terephthalate (PET). Polyester polymer such as polyethylene naphthalate; cellulose polymer such as diethyl hydrazine cellulose or triethylene fluorenyl cellulose; acrylic polymer such as polymethyl methacrylate Polystyrene, acrylonitrile/styrene copolymer (AS resin), etc.; styrenic polymer; polyphthalate polymer; norbornene polymer; polyethylene, polypropylene, ethylene, propylene copolymerization a polyolefin-based polymer such as a material; a vinyl chloride-based polymer; a guanamine-based polymer such as nylon or an aromatic polyamine; a quinone-based polymer; a fluorene-based polymer; a polyether fluorene-based polymer; An epoxy polymer or the like. These polymers may be used in combination of two or more kinds. The thickness of the substrate depends on the use and the type of the polymer, but is usually 10 to 200 / / m', preferably 10 to 100 / zni. If it is not reached, there is a case where the surface protective film cannot maintain sufficient strength as in 200916314, and if it exceeds 100 #m', the surface protective film becomes heavy, so that there is a load on the member using the surface protective film. &lt;Coating&gt; After coating a composition containing the conductive polymer component (A), the melamine resin (B), the polyester resin (C), and the organic decane (D) on the surface of the substrate, for example, 1 0 0 to 1 5 0 ° C was dried by heating, thereby forming the resulting coating. Before the coating is formed, the coated surface of the substrate (the surface on which the coating is formed) may be subjected to an easy subsequent treatment such as corona discharge, ultraviolet ray irradiation, electric paddle treatment, squeegee etching treatment, primer treatment, or the like. Hereinafter, the composition containing the conductive polymer component (A), the melamine resin (B), the polyester resin (C), and the organic siloxane (D) is also referred to as "coating composition". &lt;Coating composition&gt; The coating composition coated on the surface of the substrate to form a coating is usually used as a water-soluble or water-dispersible composition. Hereinafter, each component contained in the coating composition will be specifically described. (Conductive polymer component (A)) The conductive polymer component (A) contained in the coating composition is a component having a polythiophene structure and an electron-accepting polybasic acid structure. Examples of the conductive polymer component include a composition containing a polythiophene and a polybasic acid, a copolymer of a polythiophene and a polybasic acid, and a compound having a polysulfonated thiophene and the like. Polymer. Among these, a composition containing a polythiophene and a polybasic acid is preferred. The composition containing a polythiophene and a polybasic acid is exemplified by a polymer having a constituent unit represented by the following formula (1) or (r) and a polymer having a constituent unit containing a sulfonic acid ion or a carboxylic acid ion (multiple The composition of acid). [Chemical 1]

Wherein R1 and R2 are each independently represented by a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, or a group represented by -R3-X (wherein R3 is a single bond, sub Methyl or a C 2 to 6 alkylene group, X is a hydroxyl group, a carboxyl group, a carboxylate group, an amine group, a (substituted) aminomethyl fluorenyl group, a halogen atom, a phosphate group or an oxirane group)] . -11 - 200916314 U 2

(Γ) [wherein R1 and R2 are each independently represented by a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, or R1 and R2 may be bonded to each other to form -OR4- (R4 represents a methylene group or an alkylene group having 2 to 4 carbon atoms). As the polythiophene represented by the above formula (1) or formula (1'), polythiophene, polyethylene oxide thiophene, polyalkylthiophene or the like can be preferably used. As the polymer (polyacid) having a constituent unit containing a sulfonic acid ion or a carboxylic acid ion, polycarboxylic acid, polymethacrylic acid, polymaleic acid or the like polycarboxylic acid; polystyrenesulfonic acid, polyvinylsulfonate; A polysulfonic acid such as an acid, and polystyrenesulfonic acid is preferably used. The copolymer of the polythiophene and the polybasic acid may, for example, be a copolymer of a constituent unit represented by the above formula (1) or formula (Γ) and a constituent unit containing a sulfonic acid ion or a carboxylic acid ion. Further, a polymer having a compound having a thiophene structure such as polysulfonated thiophene and an acid structure is preferably exemplified in the above formula (1) or formula (1') -19. 200916314 R1 and R2 have at least one of A polymer of constituent units of a sulfonic acid group. In the conductive polymer component, the ratio of the polythiophene structure to the polybasic acid is preferably a polythiophene structure: polybasic acid = 1:1 to 3 (mass ratio). These conductive polymer components are preferably mixed into a coating composition which is dissolved or dispersed in a single solvent such as water or alcohol or a water-soluble solvent containing two or more kinds. (melamine resin (B)) The melamine resin (B) contained in the coating composition is used for imparting sufficient strength, surface hardness and scratch resistance to the coating layer. As the melamine, an alkylated melamine resin such as a methylated melamine resin or a butylated melamine resin, or a methylol type melamine resin or an imine type melamine resin is preferably used. Further, it is preferable to use a melamine-formaldehyde resin containing melamine of the above structure. As preferred commercial products, for example, Cymel 3 00, Cymel 301, Cymel 303, Cymel 3 50, Cymel 73 6, Cymel 73 8, Cymel 3 70, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 701, Cymel 266, Cymel 267, Cymel 2 8 5, Cymel 232, Cymel 23 5, Cymel 23 8, Cymel 1141, Cymel 272, Cymel 254, Cymel 235, Cymel 202, Cymel 1156' Cymel 1158 (above is Cytec Industries, Japan) Inc (share) manufacturing). The melamine resin used in the present invention is preferably added by dissolving or dispersing in water or an aqueous solvent of -13-200916314. (Polyester Resin (C)) The polyester resin (C) contained in the coating composition is a polymer component which forms a coating layer, and forms a film excellent in transparency with respect to the strength of the substrate. In the present invention, a water-dispersible polyester is preferably used as the polyester resin, and a polyester having excellent water dispersibility can be obtained by introducing a hydrophilic functional group into the polymer (details will be described later). In the present invention, as the polyester resin, those which are commercially available or can be synthesized by the following methods can be used. The polyester resin used in the present invention is a polycarboxylic acid (dicarboxylic acid, dicarboxylic acid ester, dicarboxylic acid halide, etc.) and a glycol, which are heated and condensed in the presence of a catalyst as needed to synthesize a linear chain. The polyester is obtained by depolymerizing a linear polyester having a trivalent or higher hydroxycarboxylic acid to synthesize a branched polyester resin, if necessary. Further, these linear or branched polyesters may be subjected to a reduced pressure polycondensation reaction as needed to be polymerized. As the catalyst for polycondensation of the dicarboxylic acid and the diol compound, a protonic acid such as sulfuric acid or p-toluenesulfonic acid, an oxide or a salt of a heavy metal, an organometallic compound such as titanium, tin or lead, or the like can be used. As the catalyst for reacting the dicarboxylic acid ester with the diol compound, an acetate or carbonate compound such as lead, zinc, manganese, calcium, cobalt or cadmium, or an oxide of magnesium metal, zinc, lead, antimony or bismuth can be used. . As the catalyst for reacting the dicarboxylic acid halide with the diol compound, an alkaline catalyst such as -14-200916314 pyridine or triethylamine can be used. As the dicarboxylic acid, for example, oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, (±)-malic acid, di-tartaric acid, and Kang acid, maleic acid, methyl maleic acid, fumaric acid, methyl fumaric acid, acetylene dicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methyl glutaric acid, glutaconic acid, Diacid, dithioadipate, methyl adipic acid, dimethyl adipate, tetramethyladipate, methylene adipate, hexadiene diacid, galactose diacid, giga Acid, suberic acid, perfluorooctanoic acid, 3,3,6,6-tetramethylsuberic acid, azelaic acid, sebacic acid, perfluorosebacic acid, undecanedioic acid, dodecane An aliphatic carboxylic acid such as a diacid, a tridecanedioic acid or a tetradecanedioic acid; a cycloalkyldicarboxylic acid, a hexahydrophthalic acid, a 1,6-cyclohexanedicarboxylic acid, 1,4-( Norbornene) alicyclic carboxylic acid such as dicarboxylic acid, bicycloalkyl dicarboxylic acid, adamantane dicarboxylic acid or spiroheptane dicarboxylic acid; phthalic acid, isophthalic acid, dithioisophthalene Formic acid, methyl isophthalic acid, dimethyl isophthalic acid, chlorobenzene Formic acid, dichloroisophthalic acid, terephthalic acid, methyl terephthalic acid, dimethyl terephthalic acid, chloroterephthalic acid, bromine terephthalic acid, naphthalene dicarboxylic acid, oxoquinone Carboxylic acid, hydrazine dicarboxylic acid, biphenyl dicarboxylic acid, biphenyl dicarboxylic acid, dimethyl biphenyl dicarboxylic acid, 4, 4 &quot;-p-triphenyl dicarboxylic acid ' 4, 4 &quot;- p-Tetraphenyldicarboxylic acid, bibenzyldicarboxylic acid, azobenzenedicarboxylic acid, homophthalic acid, phenyldiacetic acid, phenyldipropionic acid, naphthalene dicarboxylic acid 'naphthalene dipropionic acid , biphenyl diacetic acid 'biphenyl dipropionic acid, 3,3, [4,4|-(methylene-di-p-biphenyl) dipropionic acid], 4,4,-bibenzyl diacetic acid And an aromatic dicarboxylic acid such as 3,3' (4,4'-bibenzyl)dipropionic acid, oxydi-p-phenylenediacetic acid or the like; and esters such as alkyl esters thereof - 200916314 Compound; carboxylic acid halide of carboxylic acid chloride or the like. These may be used singly or in combination of two or more. Preferred as the dicarboxylic acid are aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and the like; adipic acid, sebacic acid, sebacic acid, succinic acid, and rich An aliphatic dicarboxylic acid such as horse acid, maleic acid, hemicarboxylic acid, 1,6-cyclohexanedicarboxylic acid, or the like; and a lower alkane of the dicarboxylic acid Base ester and the like. As the diol compound, for example, ethylene glycol, propylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3, butanediol, 1,4-butanediol, neopentyl glycol, 1, 5 are exemplified. - pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-I,5-pentanediol, 2 -methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, xylene glycol, hydrogenated bisphenol A, Ethylene oxide or propylene oxide adduct of bisphenol A or the like. These may be used alone or in combination of two or more. The water-dispersible polyester which is preferably used in the present invention can be obtained by introducing one or more kinds of hydrophilic functional groups such as a sulfonic acid metal salt, a carboxyl group, an ether group or a phosphoric acid group into the resin as exemplified below. When introducing a sulfonate group into the molecule, it is preferred to use, for example, 5-sodium sulfonic acid isophthalic acid, 5-ammonium sulfonic acid isophthalic acid, 4-sodium sulfonic acid isophthalic acid, 4-methyl sulfonic acid. Isophthalic acid '2-sodium sulfonic acid terephthalic acid, 5-potassium acid extended isophthalic acid, 4-potassium sulfonic acid isophthalic acid, 2-potassium sulfonic acid isophthalic acid, sodium sulfonic acid succinic acid Or a sulfonic acid alkali metal salt or a sulfonic acid amine salt compound, a bisphenol A-alkylene oxide adduct containing a sodium sulfonate salt, and a hydroquinone alkylene oxide adduct containing a potassium sulfonate. polymerization. -16- 200916314 When introducing an ether group into a molecule, for example, diethylene glycol alcohol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene neopentyl glycol ethylene oxide adduct, neopentyl can be used. Glycol propylene oxide plus a glycol containing an ether linkage. As for the method of introducing a carboxyl group into the molecule, after the polyester, under normal pressure and nitrogen atmosphere, the benzoic acid anhydride, the liver, the pyromellitic acid liver, the sodium sulphate liver, the 1,8-naphthyl dimethyl hydride Anhydride hexane dicarboxylic anhydride, cyclohexane-1,2,3,4-tetracarboxylic acid-3,4-anhydride, anhydrous trimellitic acid, 5-(2,5-dioxotetrahydro-3- a method of imparting an acid value to a 3-cyclohexene-1,2-dicarboxylic anhydride or a naphthalene-1,8:4,5-tetracarboxylic dianhydride or a later addition thereof; or a molecular weight In the oligomer state before the introduction, the acid anhydride is introduced, and the polycondensation is carried out under pressure, and the polymer is quantitatively quantified. In the case where the acid value is introduced into the polyester, the target acid value is easily obtained, and the former is introduced into the carboxyl group. When the aqueous dispersion of the polyester resin is produced, it is preferred to neutralize the carboxyl group on the surface of the particle with a basic substance in order to stabilize the particle. Among them, the basic substance which can be used for the neutralization can be an amine represented by ammonia or an inorganic salt represented by sodium hydroxide, potassium hydroxide or hydrogen. For this reason, it is preferable to consider the volatility problem, or the problem that the coating remains in the coating at the time of the coating, and the like.

The polyester resin used in the present invention is a resin-polymerized phthalic acid, 1,2-, which is converted into a polystyrene by a gel permeation layer, and has a weight average molecular weight of preferably I, triethylene glycol, or the like. Cycloethylene glycol bis-3-methyl- and the like are selected as 1 polyester by high reduction method or the like. Better. The polarity of the dispersed micro-equivalent, such as lithium triethylamine, etc., is measured by the appropriate method of selection. 5,000~ -17- 200916314 150,000' is more preferably i〇, 〇〇〇 ~60,000. Further, the glass transition temperature (Tg) of the polyester resin used in the present invention is usually from 0 to 100 ° C, more preferably from 10 to 80 ° C. (Organic siloxane (D)) The organic siloxane (D) contained in the coating composition is used for forming a film excellent in water repellency and excellent in scratch resistance. As the organic oxirane used in the present invention, a decane compound having a functional group having a hydroxyl group, an amine group, an epoxy group or a thiol group at the terminal is preferably used, and an organic hydrazine represented by the following formula (3) is preferably used. Oxytomane. [Chemical 3] R5 R5

R5 R5 (wherein R5 is independently an alkyl group having 1 to 3 carbon atoms, and R6 is each independently a methylene group or a C 2 to 6 alkyl group, and R 7 is independently a hydroxyl group, an amine group, an epoxy group or The thiol group, η is an integer of 1 to 1 ,, and m is an integer of 1 to 20). As the organosiloxane which is preferably used, a compound wherein R7 is a hydroxyl group in the above formula (3). The organic oxime having a hydroxyl group at the terminal is generally excellent in compatibility with each component of the coating composition of the water-soluble or water-dispersible composition. Further, a compound in which R5 is a methyl group is preferably used in comparison with -18-200916314 in terms of availability. The organic oxirane used in the present invention may also be a mixture of the above organic oxirane of the formula and other oxiranes. Other oxoxanes may, for example, be alkyltrioxanes such as methyltrimethoxydecane, ethyltrimethoxydecanemethoxydecane, butyltrimethoxydecane, etc.; dimethyldimethoxydecane, diethyl Dialkyl dialkoxy decanes such as dimethoxy fluorenyl dimethoxy decane, diethyl diethoxy decane, dimethyl decane, etc.; octamethylcyclotetradecane oxirane . (Proportion of A, B, C, and D) The above (A), (B), (C), and (D) are included. In the following description, "(A) ~ (D) 夕 " (A), (B), (C) and (D)". The content ratio of the conductive polymer component (A) is usually from 1.2 to 20 parts by mass, preferably from 1.2 to 20 parts by mass, based on 100 parts by mass of the total mass of the component (D). If the content of the component (A) exceeds a part, the melamine resin (B) and the polyester resin (C) are insufficient, and the resulting coating may have reduced scratch resistance. The present invention is characterized in that the content of the conductive component (A) in the coating composition is set to satisfy the thickness of the layer of the conductive poly (A) with respect to the total mass of the components (A) to (D). The product (α) becomes 値6nm~l 5nm. When α値, sufficient antistatic property cannot be obtained, and if it exceeds 15 nm, [3] indicates that the compound, propyl trioxydecane, methylethylenedioxyoxygen, etc. have a ratio such as h" means (A) ~ parts by mass, ! The mass ratio of the proportion of the proportion of the polymer composition of 75 masses and the amount of the coating of less than 6 nm are -19-200916314. The coating becomes deteriorated in scratch resistance or transparency. In other words, in the present invention, by controlling the conductive polymer component (the content of A to a certain range regardless of the thickness of the coating layer, it is possible to obtain no antistatic property, antifouling property, scratch resistance, tape peeling force, Surface protection film with excellent balance such as imprintability. The ratio of (B), (C), and (D) is preferably the following. The total mass of melamine (B) and polyester resin (C) is relatively high. When the ratio of the polymer component (A) to 100 parts by mass is 400 parts by mass, a coating excellent in scratch resistance can be obtained. The polyester resin (C) is relatively good with respect to the melamine resin (B). When the ratio is 100 to 300 parts by mass, a layer excellent in scratch resistance can be obtained, and the organic siloxane (D) is preferably used with respect to the conductive polymer component (A melamine resin (B) and polyester resin (C). The ratio of the total mass of 100 parts is preferably from 0 · 1 to 1 · 0 parts by mass. The content of (D) is less than that of less than 1 part by mass, and if the water repellency of the obtained coating is insufficient, 1 · 〇质量份, the printing of the resulting coating or the lack of tape stripping. (Solvent) In the coating composition used in the present invention, it is preferred that the component (D) and other components described later are dissolved or dispersed in water or an agent. A water-soluble organic compound can also be a mixture of water and a water-soluble organic solvent. As for the water, it is only coated with a coating of 2000 parts by mass. 'Quality case, exogenous solvent soluble -20- 200916314 The organic solvent is preferably an alcohol such as methanol, ethanol, isopropanol or n-butanol. The solid content concentration in the coating composition is preferably from 1 to 10% by mass based on the total mass of the coating composition. More preferably, it is 1 to 5% by mass. (Other components) In the present invention, the coating composition may also contain a petroleum resin for printing ink. The petroleum resin may be exemplified by rosin resin, rosin ester resin, acrylic resin, Ester resin, cellulose resin, phenol resin, alkyl phenol resin, alkyd resin, olefin resin, bismuth resin, coumarone resin, xylene resin, alkyd resin or maleic acid modified rosin resin, rich Horse acid modification An acid modified product such as a scented resin or a cerium-modified rosin resin, a hydrogenated rosin resin, a hydrogenated product such as a hydrogenated terpene resin, or the like, which may be used alone or in a mixture of a plurality of kinds, and may be a natural product or a natural product. The purified product may also be a composite polymerized with a petroleum resin of dicyclopentadiene (DCPD) or C5 to C9 as a raw material. Among them, most of them are contained in a printing ink, preferably an alkylphenol resin or a rosin. The modified resin, or an acid-modified product thereof, or the like, is preferably an acid-modified alkylphenol resin or an acid-modified rosin resin in terms of water dispersibility. The average molecular weight of the petroleum resin is from 1,000 to 500,000. Preferably, it is 1000 0~100000. When the average molecular weight is less than 1,000, the adhesiveness of the petroleum resin becomes large, and the bite of the surface film is liable to occur. If it exceeds 500,000, the dispersibility of the coating composition is deteriorated. The softening point of the petroleum resin is preferably 5 〇 ° C to 2 00 ° C, more preferably l 〇 crc 〜 15 〇 t:. When the softening point is less than 5 (TC, the adhesion at room temperature becomes large at -21 to 1631614, and it becomes easy to cause the bite of the surface film. If it exceeds 20 ° C, the drying step after coating the coating composition is In the case where the petroleum resin is added in an amount of more than 5% by mass based on the total amount of the solid content in the coating composition, since the strength of the protective film is lowered, it is preferred that the total amount of the solid component in the coating composition is 0. In the present invention, the coating composition may contain particles which impart scratch resistance or slidability to the film. As the particles, the lifting force is inorganic particles or organic particles, and as the inorganic particles, for example, oxidation is carried out. Bismuth, alumina, zinc oxide, potassium oxide, calcium oxide, chromium oxide, antimony oxide, tungsten oxide, magnesium oxide, titanium oxide, antimony oxide, antimony oxide, cobalt oxide, iron oxide 'phosphorus oxide, oxidized fierce, tin oxide, a metal oxide such as indium oxide, cerium oxide, cerium oxide, calcium carbonate, carbonic acid clock, cerium carbonate, calcium citrate, calcium titanate, calcium sulfate, barium sulfate, or molybdenum sulfide, barium sulfide, tungsten sulfide, a composite of one or more of boron, nickel iodide, etc., and its hydrate, or kaolin, clay, talc, mica, bentonite, hydrotalcite, zeolite, pyrophyllite, carbon black, black lead, etc. Mineral particles. Examples of the organic particles include polyethylene, polypropylene, ketone resin, styrene resin, norbornene resin, fluororesin, polyacetal, guanamine resin, amidoxime resin, acrylic resin, Thermoplastic resin such as ester resin, polyfluorene, butyl diene resin, liquid crystal polymer, epoxy resin, xylene resin, oxime resin, diallyl phthalate resin, vinyl ester resin, oxime resin, furan resin , thermosetting resin such as quinone imine resin, urethane resin, maleic acid resin, melamine resin, urea resin, etc., natural product of poly-22- 200916314 cellulose, cellulose derivative, polyterpene resin, etc. The composition of one or more selected from the group consisting of a polymer and a derivative thereof may also be a mixture. The inorganic particles and the organic particles may be used singly or as a composite. The surface and the cost are preferably cerium oxide and clay. The shape of the particles is not particularly limited, and a spherical shape, a plate shape, a needle shape, a hollow shape, or an indefinite shape may be used, and it is preferably a spherical shape. The dispersibility is good, and it may be a surface treatment by a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, or an oxygen, fluorine, or the like. It is preferably 0.01 to 10/m, and the specific surface area is preferably 50 to 5 Å Om/g. If the average particle diameter is less than 〇.〇i#m or the specific surface area is less than 50 m2/g, the scratch resistance, The slidability imparting property is deteriorated, and it is easy to cause problems due to secondary aggregation. Further, when the average particle diameter exceeds 10 m or the specific surface area exceeds 500 m 2 /g, the optical properties of the film are deteriorated. The scratch resistance and slidability are exhibited. From the viewpoint of the nature, the amount of the particles added is preferably from 质量1% by mass to 5% by mass based on the total amount of the solid content in the coating composition. The coating composition may contain various surfactants which impart water dispersion stability and impart moisture to the substrate. The surfactant may, for example, be a cationic surfactant, an anionic surfactant, an ionic surfactant such as an amphoteric surfactant, a nonionic surfactant such as a fatty acid, a rhodium-based surfactant, or a fluorine-based interface. Active agent, fluorinated fluorine-based surfactant. In the coating composition, in addition to the above components, the ionic liquid, or the anti-plastic, rubber, emulsion, organic solvent, coating material may be used to the extent that the effect of the present invention is not impaired. An oxidizing agent, an anti-aging agent, a UV absorber, a flame retardant, a dye, a pigment, a slip agent, an antifungal agent, a plasticizer, a pH adjuster, a wetting agent, and the like. &lt;Adhesive layer&gt; In the present invention, an adhesive layer may be formed on the surface of the substrate opposite to the surface on which the coating layer is formed. In the surface protective film, the adhesive layer has a function of adhering the film to the surface of a member such as a polarizing plate. The adhesive contained in the adhesive layer is preferably an adhesive resin or a sulfonated polymer composed of a (meth)acrylic acid alkyl ester resin. The adhesive layer comprising a sulfonated polymer has a high antistatic property. The adhesive layer can be obtained by applying an adhesive composition containing the above adhesive resin component to a substrate and drying it. Hereinafter, the adhesive resin and the sulfonated polymer contained in the adhesive composition will be described. (Adhesive resin) The (meth)acrylic acid alkyl ester resin used as the adhesive resin is composed of a resin having adhesiveness as a main component of (meth)acrylic acid alkyl ester. As the alkyl (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, ( N-hexyl methacrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, -24- 200916314 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, Isodecyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc. In particular, an alkyl (meth)acrylate having an alkyl group having 4 to 12 carbon atoms is preferred, and an alkyl (meth)acrylate having an alkyl group having 6 to 12 carbon atoms is more preferred. The alkyl (meth)acrylates may be used singly or in combination of two or more. In the present invention, the above-mentioned (meth)acrylic acid alkyl esters and other polymerizable monomers can be used as the adhesive resin. As the other polymerizable monomer, for example, an unsaturated carboxylic acid such as (meth)acrylic acid, crotonic acid, fumaric acid or isaconic acid or a salt thereof; an unsaturated carboxylic acid such as maleic anhydride or isocanic anhydride; Anhydrides; 2-methyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-methyl propyl methacrylate, 2-hydroxybutyl (meth) acrylate (meth)acrylic acid 3_ butyl butyl ester, 4-hydroxybutyl (meth) acrylate, etc. (meth) propylene acid basal ester; 2-methyl methacrylate Ethyl vinegar, (meth) propylene acid 2 methoxy propyl ester, (meth) acrylate 3 methoxy propyl vinegar, (meth) acrylate 2 methoxy butyl acrylate, (meth) acrylate (meth)acrylic acid alkoxyalkyl esters of 3-methoxybutyl vinegar, C methyl methacrylate 4 methoxybutyl acrylate; (meth) acrylonitrile, chloropropene susceptibility, ammoniated yttrium An amino group-containing monomer such as 2-cyanoethyl (meth)acrylate; (meth) acrylamide, Ν-methyl (meth) acrylamide, hydrazine, hydrazine-dimethyl ( Methyl) propylene Amine, hydrazine-hydroxymethyl (meth) acrylamide, hydrazine, hydrazine-di-methyl (meth) acrylamide, N-methoxymethyl-25- 200916314 (meth) acrylamide Monomers containing amidino group; vinyl esters such as vinyl acetate and vinyl propionate; halogenated vinyls such as vinyl chloride and vinylidene chloride; aromatic vinyl compounds such as styrene and methylstyrene a monofunctional monomer such as an unsaturated aliphatic hydrocarbon such as ethylene, butadiene or isoprene, or ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, or glycerin Tris(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, methylenebis(meth)acrylamide, exoethyl bis(methyl) A polyfunctional monomer such as acrylamide or divinylbenzene. Among these, (meth)acrylic acid, (meth)acrylonitrile, etc. are preferable, and acrylic acid, acrylonitrile, etc. are preferable. These other polymerizable monomers may be used singly or in combination of two or more. The amount of the (meth)acrylic acid alkyl ester used in the production of the alkyl (meth)acrylate resin is preferably from 50 to 100% by mass, more preferably from 90 to 100% by mass, based on the total of the monomers. . Further, the weight average molecular weight of the (meth)acrylic acid alkyl ester-based resin (the same applies to the polystyrene according to the GPC method, the same applies hereinafter) is preferably 10 or more, more preferably 30 or more. . At this time, if the weight average molecular weight of the (meth)acrylic acid alkyl ester-based resin is less than 10,000, adhesion problems such as sticking residue may occur. Further, the glass transition point (hereinafter referred to as "Tg") of the (meth)acrylic acid alkyl ester-based resin is preferably from -8 〇 to -l 〇 ° C 'better than -80 to -3 (TC. -26 - 200916314 (sulfonated polymer) The sulfonated polymer contained in the adhesive layer can be exemplified by, for example, a sulfonate of a total of 1 ny = olefin polymer, or a sulfonate of a hydride of a conjugated diene polymer. a sulfonated conjugated diene polymer; a sulfonate of an aromatic vinyl polymer such as polystyrene; a sulfonate of a sulfonic acid group-containing monomer such as styrene sulfonic acid; The acidified aromatic vinyl polymer or the like is preferably a sulfonated conjugated diene polymer or a polystyrenesulfonic acid, preferably a sulfonated conjugated diene polymer. The olefin polymer can be obtained by sulfonating a polymer containing a conjugated diene monomer as a constituent unit or a hydride thereof (hereinafter, the polymer and the hydride are collectively referred to as a "conjugated diene-based basic polymer"). The conjugated diene monomer used in the conjugated diene base polymer is preferably a combination of carbon numbers 4 to 10. More preferably, it is a compound having a carbon number of 4 to 8, preferably a compound having a carbon number of 4 to 10. As the conjugated diene monomer, for example, 1,2-butadiene, 1,3-butadiene can be exemplified. 1,2-butadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene, 1,4 -hexadiene, 1,5-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl_ 1,3·butadiene, 1,2-heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, i,6-heptadiene, 2, 3-heptadiene, 2,5-heptadiene, 3,4-heptadiene, 3,5-heptadiene, cyclopentadiene, dicyclopentadiene, ethylidene norbornene, etc. In particular, it is preferably U3_butadiene or isoprene. These conjugated diene monomers may be used singly or in combination of two or more. Further, in the conjugated diene base polymer, Other polymerizable monomers exemplified as the polymerizable monomer of the alkyl (meth)acrylate may be used together with the conjugated diene monomer -27-200916314. In the conjugated diene base polymer, Conjugated diene monomer And other polymerizable monomers as needed, in the polymerization polymerization of free radical polymerization initiators such as hydrogen peroxide, benzophenone, azobisisobutyronitrile or n-butyl lithium, sodium naphthalate, sodium metal, etc. In the presence of a starting agent, a known solvent is usually used, and it is usually synthesized by polymerization at -10 Torr to +150 ° C, preferably at 〇 130 ° C. Further, as a conjugated diene-based base polymer, A partially or fully hydrogenated hydride which is one of the double bond moieties remaining in the conjugated diene base polymer may be used. This hydrogenation may use a known hydrogenation catalyst or a known method. However, the hydrogenation of the acidified ruthenium is produced. In the case of a second polymer, either hydrogenation or sulfonic acid may be carried out first. In the case of the copolymer, the conjugated diene-based base polymer may be a random copolymer or a block copolymer, and in the case of a block copolymer, an AB type, a ruthenium type, or the like may be used. Special restrictions. As the preferred conjugated diene base polymer, for example, poly-1,3-butadiene, polyisoprene, 1,3-butadiene/styrene random copolymer, 1, 3-butadiene-styrene diblock copolymer, styrene-1,3-butadiene-styrene ternary block copolymer, 1,3-butadiene-styrene-1,3- Butadiene ternary block copolymer, isoprene/styrene random copolymer, isoprene-styrene diblock copolymer, styrene-isoprene-styrene Metablock copolymer, isoprene-styrene-isoprene-28- 200916314 ternary block copolymer, hydride of these polymers, in addition to ethylene/propylene/conjugate a diene-based random copolymer, etc., among which, more preferably a 1,3-butadiene-styrene diblock copolymer, a styrene-butadiene-styrene ternary block copolymer ' 1,3-butadiene-styrene-1,3-butadiene ternary block copolymer, isoprene-styrene diblock copolymer, benzene-iso-iso-amyl - phenylethyl ternary block copolymer, isoprenoid-styrene-isoprene Or those ternary block copolymer having a hydride, etc. of the conjugated block copolymer or a hydride-based unit of a diene and an aromatic diene unit. The weight average molecular weight of the basic polymer of the conjugated secondary storage system is preferably 1,000 or more and more preferably 5,000 or more, more preferably 5,000 to 400,0 Å. At this time, if the average molecular weight of the conjugated diene base polymer is less than 1, the sulfonated conjugated diene polymer has a tendency to bleed out from the surface of the adhesive layer, causing the adhesion to change over time. On the other hand, if it exceeds 4 〇〇, 〇〇〇, there is a tendency to decrease productivity. The sulfonated conjugated diene polymer in the present invention can be obtained by sulfonating a double bond moiety in a conjugated dibasic unit in the conjugated di-based base polymer by using a sulfonating agent. This sulfonation reaction is such that the double bond of the conjugated diene unit is ring-opened to a single bond or the double bond is retained thereby to replace the hydrogen atom with a sulfonic acid (salt) group. Further, when another polymerizable monomer is used, for example, an aromatic vinyl-based unit may be sulfonated in addition to the conjugated diene unit. The content of the sulfonic acid (salt) group in the acidified conjugated diene polymer is usually 0.1 to ό mmol/g', preferably 〇5 to 5 mmol/g. At this time, if the content of the acid (salt) base of sulfonate -29- 200916314 is less than 0.1 millimoles per gram, the antistatic energy of the obtained adhesive composition is insufficient. On the other hand, when it exceeds 6 millimoles per gram. 'It is detrimental to the transparency of the resulting adhesive layer. The weight average molecular weight of the polystyrene sulfonate is preferably 1, more than 〇〇〇, more preferably 5,0 Å or more, and most preferably 5,000 to 4,000 Å. In this case, if the weight average molecular weight is less than 1,000', the polystyrene sulfonic acid bleeds out from the surface of the adhesive layer, and the adhesion tends to change over time. On the other hand, if it exceeds 400,000 Å, the productivity tends to decrease. In the present invention, the sulfonated polymer may be used singly or in combination of two or more. (Adhesive Composition) The adhesive composition used in the present invention may contain an adhesive resin and a sulfonated polymer in the following proportions. The blending ratio of the adhesive resin is preferably from 40 to 99.9% by mass, more preferably from 50 to 99.5 % by mass, based on the total amount of the adhesive resin and the sulfonated polymer, and the blending ratio of the sulfonated polymer is preferably It is 60 to 0.1% by mass, more preferably 50 to 〇_5% by mass. At this time, the amount of the adhesive resin is less than 40 mass. /. It is difficult to ensure sufficient anti-static energy. On the other hand, if it exceeds 99.9% by mass, it is difficult to ensure sufficient adhesion. In the present invention, the adhesive composition can be obtained by, for example, (a) mixing an adhesive resin with a sulfonated polymer' (b) polymerizing a monomer capable of obtaining an adhesive resin in the presence of an acid-extended polymer. The method is made, preferably the method of (b). In the adhesive group -30-200916314 obtained by the method (b), a composition in which an emulsion in which a sulfonated polymer and an adhesive polymer are composited is dispersed in an aqueous medium is preferred. The average particle diameter of the above emulsion is preferably from 60 to 500 nm, more preferably from 90 to 300 nm. At this time, if the average particle diameter of the obtained emulsion is less than 60 nm, the viscosity of the obtained adhesive composition becomes too high, and on the other hand, if it exceeds 500 nm, the adhesive strength tends to decrease. Further, the solid content (nonvolatile matter) of the adhesive composition is usually 10 to 70% by mass, preferably 20 to 60% by mass. This solid component can be adjusted by chasing the aqueous medium or by removing a portion of the aqueous medium. (Formation of Adhesive Layer) The above-mentioned adhesive composition can be applied on the surface opposite to the side on which the coated surface of the substrate is formed and dried to form an adhesive layer. In order to improve the adhesion between the substrate and the adhesive layer, the adhesive forming surface of the substrate may be subjected to a corona treatment or the like before the application of the adhesive composition. The thickness of the adhesive layer after drying can be appropriately adjusted depending on the use of the surface protective film, but it is usually 5 to 50 / / m, more preferably 10 to 30 μm. (Examples) Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In the following description, the parts and % are based on mass unless otherwise specified. &lt;Example 1&gt; -31 - 200916314 (1) Preparation of coating composition The product name "DANATRON P502RG" manufactured by Nagase ChemteX (shares) having a solid content of 16.67 parts was added to a screw bottle at room temperature. As a conductive polymer component (a) 'Cymel 3 70" manufactured by CYTEC Industries Co., Ltd. of Japan, which has a solid content of 41.67 parts (isopropanol/isobutanol solution of methylated melamine formaldehyde resin, solid content concentration) 8 8 % ) As a melamine resin (B ), the product name "Vylonal MD-1480" (a saturated aqueous solution of a polyester resin, a solid content concentration of 25 % by mass) manufactured by Toyobo Co., Ltd. having a solid content of 4.67 parts is used. The polyester resin (C) and the product name "BY16-201" (hydroxyalkyl-terminated dimethyl oxyalkylene) manufactured by Toray Dow Corning Co., Ltd. having a solid content of 0.2 parts are used as the organic decane (D). And 79.68 parts of a mixed solvent of 50 parts of ion-exchanged water and 50 parts of isopropyl alcohol was added, and the mixture was stirred for 30 minutes to obtain a coating composition having a solid concentration of 3.0%. The composition of "DANATRON P5〇2RG" used as the conductive polymer component (A) is "polyethylenedioxythiophene/polystyrene sulfonate/polyester resin: 3 · 9 mass%, water: 9 6 · 1% by mass". The polyester resin contained in (A) is a polyethylene glycol terephthalic acid 5-sodium sulfonic acid isophthalic acid polycondensate. (2) Preparation of Coating The coating composition obtained in (1) was applied to a polyethylene terephthalate film (substrate) having a thickness of 38/zm using a bar coater at 140 ° C. After drying for 2 minutes, a 40 nm thick coating was formed to prepare a surface-32-200916314 protective film of the present invention. The α 値 of the obtained surface protective film was 6.6 5 nm. The obtained surface protective film was subjected to the following performance evaluation test, and the results are shown in Table 1. &lt;Performance evaluation test&gt; (1) Surface specific resistance 値 (described as "SR" in Table 1) In the atmosphere of 23 tx relative humidity of 60%, 'use high resistance meter (product name: HIRESTA-UP, model number) : MCP-HT45 0 (manufactured by Mitsubishi Chemical Corporation), the surface specific resistance 涂层 of the coating layer was measured after applying a voltage of 100 V for 30 seconds. If the surface specific resistance 値 is 1 Ε + 11 (Ω / 〇) or less, it is judged to have sufficient antistatic property. (2) Water contact angle 2 μ of pure water was dropped on the surface of the coating, and the water contact angle was measured after dropping for 3 seconds. The measurement was carried out using a contact angle meter (product name: contact angle meter, model: CA-X (Kyowa Interface Science Co., Ltd.)), and the measurement was 70. Above, it is judged that it has sufficient water repellency. (3) Non-woven fabric using scratch resistance (product name: Bencotte, model: Μ-3 (manufactured by Asahi Kasei Fibers Co., Ltd.), with a load of about 50 g/cm2 on the surface of the coating film 1 turn back and forth] and visually observing the surface damage State, and the objectivity is evaluated by the following criteria: 〇: no damage -33- 200916314 △: identifiable damage is 5 or more and 10 or less X: identifiable damage is above 1 〇 or the coating is whitened (4 ) Printing adhesion (described as "printing" in Table 1) Embossing the imprinted ink on the surface of the coating (product name: ΤΑΤ embossed ink, model: quick-drying multi-purpose STSG-1 red (Shachihata (share) ))), and dried for 2 minutes. Subsequently, the cymbal adhesive tape (registered trademark, model: CT-24 (manufactured by Nichiban)) was attached to the printed matter, and the load evaluation test was performed after conditioning for 2 minutes. Machine (product name: small universal load evaluation test machine, model: MODEL 1308S, use load weight single product name: singular digital push-pull gauge, model: MODEL RX-1 (AIKOH engineering (share) manufacturing) , at a braking speed of 5.5m/min The bell was pulled down to remove the adhesive tape (registered goods) and the peeling of the printed matter was observed, and the printing adhesion was evaluated on the following basis: 〇: the printed matter was not peeled off Δ: the printed matter was peeled off X: the printed matter could not be replaced by the exclusion Embossing (5) Tape peeling force The polyester tape No31B (manufactured by Nitto Denko Co., Ltd.) is attached to the surface of the coating, and is adhered to the 2kg drum one time, at a relative humidity of 60% at 23 ° C. The humidity was adjusted for 1 hour under ambient gas. Then, the load evaluation test machine was used (product name: small universal load evaluation test machine, type -34-200916314: MODEL 1308S, load cell name: high performance digital push-pull table type) : MODEL RX-1 (manufactured by AIKOH Engineering Co., Ltd.), the peeling force of the peeling speed 〇.3 m/min was measured. If the peeling force was measured at 3,000 g/25 mm or more, it was judged that the peeling force was high. (6) Fog Turbid turbidity (haze turbidity) Using a turbidity measuring machine made by Siiga test machine (product name: TM double-arm automatic fogging computer, type: HZ-2), according to ·!^-K7 1 3 6, The haze was measured and evaluated according to the following criteria. The smaller the haze, the better the transparency. 〇: less than 5 %; △: 5 % or more, less than 10%; X: 10% or more <Examples 2 to 14, Comparative Examples 1 to 10> In addition to use The coating composition was prepared in the same manner as in Example 1 except for the components (A) to (D) shown in Table 1. The coating compositions were applied in the same manner as in Example 1. On the surface of the substrate, a coating layer having a thickness shown in Table 1 was formed to prepare a surface protective film, and each surface protective film was subjected to an evaluation test. The results are shown in Table 1. In Table 1, the results of the test evaluation, the amounts of the components (A) to (D), the coating thickness, and α値 which were prepared in Examples 1 to 14 and Comparative Examples 1 to 10 were shown. &lt;Comparative Example 1 1 to 1 8 &gt; Instead of Nagase -35- 200916314 used as the conductive polymer component (A)

The DANATRON P502RG manufactured by ChemteX Co., Ltd. was prepared in the same manner as in Example 1 except that 16-6 parts of the antistatic agents (a2), (a3), (a4) or (a5) were used. Each of the coating compositions was applied to the surface of the substrate in the same manner as in Example 1 to form a coating layer having a thickness shown in Table 1 to prepare a surface protective film, and each surface protective film was subjected to an evaluation test. The results are shown in Table 1. The details of the antistatic agent (a2), (a3), (a4) or (a5) are as follows. A2: Four-stage hinged cationic antistatic agent (trade name: Elgan 264WAX 'Nippon Oils and Fats Co., Ltd., solid content concentration: 1% by mass) a3 : Polyacrylic acid quaternary ammonium cationic antistatic agent (trade name: BONDEIP-PAioo 'K0NISHI (stock), solid content concentration: 3% by mass) a4 : Anionic antistatic agent (trade name: CHEMISTATE 3500, manufactured by Sanyo Chemical Industry Co., Ltd., solid content concentration: 1% by mass) a5 : Polypyrrole-based conductive polymer (trade name: ρργΐ2, manufactured by Jiuling Oil Chemical Industry Co., Ltd., solid content concentration: 8% by mass) Further, in Table 1, 'Comparative Example 1 1 to 18 (A) One of the digits shows the type of antistatic agent "(a2), (a3), (a4) or (a5)" and its amount of use (inside the number of brackets). In Table 1, in the α field of Comparative Example 1 1 to 18 and the total field of (A) to (D), * indicates that the component (a) is (a2), (a3), (a4) or ( A5) Replace the calculated enthalpy. That is, 'Comparative Example 1 1~1 8' table! The number of the fields in (a) to (D) total -36 - 200916314 is described as antistatic agent (a2), (a3), (a4) or (a5), and (B) to (d). sum. Further, in the present specification, (B) to (D) mean (b), (c), and (D). In the 'Comparative Examples 1 1 to 18, the alpha column number 値 is described as an antistatic agent (a2), (a3), (a4) or (a5) with respect to the antistatic agents (a2) and (a3), The mass ratio of (a4) or (a5) and (B) to (D) is calculated by multiplying the thickness of the coating. &lt;Comparative Example 1 9 &gt; Instead of the product name "BY1 6-201" (hydroxyalkyl-terminated dimethyl oxyalkylene) manufactured by Toray Dow Corning Co., Ltd., which is used as the organic decane (D) In the same manner as in Example 1, except that the (d2) fluororesin (trade name: DICKGUARD NH-15' manufactured by Dainippon Ink Chemicals Co., Ltd.) was used, a coating composition was prepared. The coating composition was applied to the surface of the substrate in the same manner as in Example 1 to form a coating layer having a thickness shown in Table 1, and a surface protective film was prepared. Each surface protective film was subjected to an evaluation test, and the results are shown in Table 1. Further, in Table 1, in the (D) block of Comparative Example 19, it means that the amount of use (the number in parentheses) is shown using the above (d2)'. The ratio of Table 1 is shown in the α field and the total column (A) to (D) in Example 1 and the * indicates that the component (D) is replaced by (d2). That is, in the comparative example 19, the total number of columns (a) to (D) in Table 1 is described as the sum of (A), (B), (C) and (d2). In addition, in Comparative Example 19, 〇: the number of columns is described as (a) component phase - 37 - mass ratio of (A), (B), (C), and (d2) is multiplied by the coating. The thickness calculated by the thickness.

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CO σ &gt; OT 00 G &gt; σ &gt; CO 0 01 co σ &gt; co O) CO - Eo CO T - (O inch · co cd 5 cb co cd co CO ίο cd CO — &lt;q cd CO «J1 &lt;q cd &lt;〇cd 0 1 CO CSJ CO 0 1 CO CM CO od CNJ CO CsJ CO oo CM CO CM CO £ &lt;b 5 CO »»-s cd s ( 0 /-~N 5 cb CSJ (D CO CO (0 £ €0 CO CO 5 CD f /-N 5 (£} V^1 ra CD cd s-✓ LO (C CO CD to (0 Bu co cd CM CO in CO 卜CO &lt;Λ 〇»—CSJ CO inch T— CM CO inch to &lt;〇卜00 σ&gt; o ▼— T~ CSi CO inch l〇&lt;D r- 00 05 sm 闺200916314 &lt;Results And investigation> (1) With respect to the surface protective films of Comparative Examples 1 to 4, 1 1, 13, 15, and 17, the surface specific resistance 値 is large and sufficient antistatic property cannot be obtained.In the comparative examples 1 to 4, it is considered that a 値 is 2 or less, and it is considered that if the amount of the component (A) is controlled so that α 値 is 6 or more, sufficient antistatic performance can be obtained. Comparative Example 1 in which sufficient antistatic property could not be obtained 1 , 1 3 , 1 5 , 1 7 Comparative Example 1 in which sufficient antistatic property was obtained 2, 1 4 '1 6 and 18, the former (D) component The amount is larger and the latter has less (D) components. However, in Example 8, although the amounts of the components (D) of Comparative Examples 11, 13, 15, and 17 were the same, sufficient antistatic properties were obtained. The eighth embodiment and the comparative examples 11, 13, 15, and 17 differ only in the use of the conductive polymer component (A) having a polythiophene structure and an electron-accepting polybasic acid structure, and the use of other antistatic agents. Therefore, it is considered that the conductive polymer component (A) having a polythiophene structure and an electron-accepting polybasic acid structure can exhibit sufficient antistatic properties. (2) The water contact angle of the surface protective film of Comparative Examples 12, 14, and 16 was less than 70 °, and the water repellency was not sufficient. In Comparative Examples 12, 14, and 16, a quaternary cation-based antistatic agent or an anionic antistatic agent was used instead of the component (A), and this was considered to cause a decrease in water repellency. (3) The surface protective films of Comparative Examples 1, 3, 5 to 8, 10, 17, and 18 have low scratch resistance. The low scratch resistance of Comparative Examples 1 and 3 is considered to be caused by α値 being less than 6-39-200916314. Therefore, it is considered that the total mass of the (B) component and the (C) component is also small relative to the (A) component. influential. The low scratch resistance of Comparative Examples 5 to 8, 1 is considered to be caused by α値 being larger than i 5 . Comparative Example 1 The low scratch resistance of 7 and 18 was considered to be caused by using a polypyrrole-based conductive polymer instead of the conductive polymer component (A) having a polythiophene structure and an electron-accepting polybasic acid structure. (4) The surface protective film of Examples 1 to 14 had a low haze of less than 5%, and was excellent in transparency. Thus, the surface protective film of the present invention can be preferably used for optical film applications. (5) According to the present invention, a conductive polymer component (A) having a polythiophene structure and an electron-accepting polybasic acid structure, a melamine resin (B), a polyester resin (C), and an organic decane (D) are used. The coating composition and the amount of the component (A) are controlled so that α値 becomes 6 nm to 15 nm, and the surface of the coating having excellent antistatic properties such as scratch resistance, tape peeling force, and printing adhesion can be provided. Protective film. According to the present invention, in the above coating layer, since it is preferable to contain the components (A), (B), (C), and (D) as much as possible and control the amount of the component (A) so that Q: 値 becomes 6 nm 〜1. The 5 nm coating composition coats the substrate and is therefore inexpensive. &lt;Other Embodiments&gt; The present invention is not limited to the above-described embodiments and the embodiments described in the drawings. For example, the following embodiments are also included in the scope of the present invention. -40- 200916314 (1) In the above embodiment, as the conductive polymer component (A), a composition containing poly(ethylenedioxythiophene), polystyrene sulfonate, and polyacetate may be used, but it may be used. A copolymer of a polythiophene and a polybasic acid or a poly(acidified thiophene). (2) In the above embodiment, the surface protective film having no adhesive layer is shown, but the adhesive layer is formed on the surface of the substrate opposite to the coating forming surface. -41 -

Claims (1)

200916314 X. Patent Application Area 1. A surface protection film characterized by having: a substrate, and a thickness on the surface of the substrate of 20 nm to 500 nm. The coating layer is formed by using a polythiophene structure and electron acceptability. The conductive polymer component, the melamine resin, and the polyester tree oxime composition are formed, wherein the conductive polymer component is the conductive polymer component, the melamine resin ester resin, and the organic component described above. The mass ratio of the total mass of the decane is 6 nm to 15 nm with the above coating. 2. The surface protective film according to the first aspect of the invention, wherein the composition of the conductive polymer component, the total mass of the resin and the polyester resin is 100 parts by mass, and the content of the superoxane is 0.1 to 0.1%. 1.0 parts by mass. 3. The surface protection sheet according to claim 1 or 2, wherein the composition of the melamine resin and the polyester resin is 400 to 2000 parts by mass with respect to the conductive polymer component. 4. The surface protection sheet according to claim 1 or 2, wherein the surface layer is opposite to the surface of the substrate on which the coating layer is formed. 5. The surface protective film according to item 3 of the patent application, wherein the substrate is formed with a coating on the opposite side of the surface of the coating layer, a polybasic acid, and a thickness of the poly layer. Among the above melamines, the organic stone film, wherein 100 parts by mass of the film, on which the adhesive layer is formed in the layer with the adhesive-42-200916314. 6. The surface protection film according to any one of claims 1, wherein the conductive polymer component comprises a polyethylenedioxythiophene and a polystyrene sulfonate. 7. The surface protection film of claim 3, wherein the conductive polymer component comprises a polyethylene dioxythiophene and a polystyrene sulfonate. 8. The surface protection film of claim 4, wherein in the composition, the conductive polymer component comprises a polyethylene dioxythiophene and a polystyrene sulfonate. 9. The surface protection film according to any one of claims 1, 2, 5, 7, and 8, wherein the polyester resin is a water-dispersible polyester into which a metal sulfonate group is introduced. . 10. The surface protective film of claim 3, wherein the polyester resin is a water-dispersible polyester into which a metal sulfonate group is introduced. The surface protective film of claim 4, wherein the polyester resin is a water-dispersible polyester into which a metal sulfonate group is introduced. 12. The surface protective film of claim 6 wherein the polyester resin is a water-dispersible polyester into which an acid-expanding metal salt group is introduced. -43- 200916314 The seven-character single-character list is the map of the generation of the map. The table of the representative figure is the table of the case. ' 'Nothing is not eight. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention. :no