JP2008023923A - Polyester film having antistatic coating layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coated film having good antistaticity and staining resistance, and exhibiting an excellent adequacy when used as, for example, a protective film of an optical member. <P>SOLUTION: This polyester film has an antistatic coating layer obtained by applying a coating liquid comprising the following components (A), (B) and (C) and drying it. The component (A) is an electron-conductive compound; the component (B) is one or more compounds selected from the group consisting of polyalkylene oxide (b1), glycerol (b2), polyglycerol (b3) and an alkylene oxide adduct (b4) to glycerol or polyglycerol, or derivatives thereof; and the component (C) is one or more compounds selected from the group consisting of an alkyl-based compound (c1), a fluorine compound (c2) and a silicone-based compound (c3), or derivatives thereof. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a film suitable for a surface protective film of a polarizing plate, a retardation plate or a viewing angle widening film, is transparent, has little charge when rubbed or peeled off, and easily removes dirt adhering to the surface. It relates to a film that can

  A protective film is attached to the surface of an optical member such as a polarizing plate (or a retardation plate) or a laminated body conforming thereto for the purpose of surface protection. In many cases, these protective films are removed by peeling after the assembly of the optical member is completed, but there is a problem in that static electricity is generated at the time of peeling and surrounding dust is caught.

  Polyester films represented by polyethylene terephthalate or polyethylene naphthalate are superior in mechanical strength, dimensional stability, flatness, heat resistance, chemical resistance, optical properties, etc., and cost performance. Used as a material. As an example of its use, there is a protective film that protects the surface of an optical member such as a polarizing plate from scratches and contamination, and a film in which an adhesive is applied to a polyester film substrate is used. It is easy to be charged at the time of delamination or the like, and in each process used as a protective film for an optical member, triboelectric charging or delamination charging occurs, causing problems such as adhesion of foreign matter and dust, electrostatic discharge failure, and the like.

  In addition, for the protective film attached, the surface of the protective film is easily contaminated with oils and fats, protruding or transferred adhesive, etc. in manual processes such as the re-peeling process and the inspection process. Is needed.

  In general, a method of applying an antistatic resin to the surface is applied to impart antistatic properties to the surface protective film (Patent Document 1).

  However, since such an antistatic resin has an ionic functional group having a high polarity, when it is exposed to an organic solvent or placed under a high humidity, the surface is whitened, causing a problem in the inspection process.

  The electronically conductive compound can also exhibit superior antistatic properties as compared with the ionic compound, and a film that is hardly affected by the solvent and humidity can be obtained. As the electroconductive compounds, various electroconductive organic compounds, especially conductive polymer compounds such as polyacetylene, polyphenylene, polyaniline, polypyrrole, polyisothianaphthene, and polythiophene have been proposed, and in particular, the polythiophene compound is applied to a film. Thus, a method for obtaining an antistatic film has been proposed (Patent Document 2).

  The polythiophene compound has excellent conductivity and exhibits high antistatic properties when applied to a film. However, in the case of a coating layer containing a polythiophene compound, when the coating layer is applied by a so-called in-line coating method in which the coating layer and the film are stretched together, sufficient antistatic performance is exhibited. It becomes difficult. This is because when the electronic conductive layer is stretched along with the stretching of the film, the electronic conductive layer cannot follow the stretching of the film while maintaining the conductive mechanism, and as a result, the conductive mechanism is broken. Conceivable. Further, the coating layer thus obtained is inferior in appearance, and is difficult to use for applications such as a surface protective film for optical members. For this reason, when a polythiophene compound is used, there is a demand for a method that exhibits excellent antistatic properties even in an in-line coating method and has few appearance defects.

  Moreover, the work which wipes off the surface with organic solvents, such as ethanol and toluene, is normally performed with respect to the contamination of the surface of a protective film. However, if the durability of the surface layer of the protective film is insufficient due to this operation, the surface is whitened by the wiping operation as described above. In addition, extra time is required for wiping, and the surface may be scratched by wiping, and characteristics that allow easy removal of contamination are also required.

Japanese Patent Laid-Open No. 7-26223 Japanese Patent Laid-Open No. 9-131843

  The present invention has been made in view of the above circumstances, and the solution is to have excellent antistatic properties and stain resistance. For example, when used as a protective film for an optical member, it has excellent suitability. It is to provide a coated film to be shown.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by providing a coating layer composed of a combination of specific types of compounds, and the present invention has been completed. It was.

That is, the gist of the present invention is characterized by having an antistatic coating layer formed by applying a coating solution containing the following components (A), (B) and (C) to one side of a polyester film and drying it. It exists in the polyester film.
(A): Electronically conductive compound (B): one selected from the group of polyalkylene oxide (b1), glycerin (b2), polyglycerin (b3), glycerin or an alkylene oxide adduct (b4) to polyglycerin Compound or derivative thereof (C): One or more compounds selected from the group consisting of alkyl compound (c1), fluorine compound (c2), and silicone compound (c3), or derivatives thereof

Hereinafter, the present invention will be described in detail.
The base film of the coated film of the present invention is made of polyester. Such polyesters include dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, 4,4′-diphenyldicarboxylic acid, 1,4-cyclohexyldicarboxylic acid or esters thereof. It is a polyester produced by melt polycondensation with glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol. Polyesters comprising these acid components and glycol components can be produced by arbitrarily using a commonly used method.
For example, a transesterification reaction between a lower alkyl ester of an aromatic dicarboxylic acid and a glycol, or a direct esterification of an aromatic dicarboxylic acid and a glycol, to form a substantially bisglycol of an aromatic dicarboxylic acid A method is employed in which an ester or a low polymer thereof is formed and then polycondensed by heating under reduced pressure. Depending on the purpose, an aliphatic dicarboxylic acid may be copolymerized.

  Typical examples of the polyester of the present invention include polyethylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, and the like. It may be a polymerized polyester and may contain other components and additives as necessary.

  The polyester film in the present invention can contain particles for the purpose of ensuring the film runnability and preventing scratches. Examples of such particles include inorganic particles such as silica, calcium carbonate, magnesium carbonate, calcium phosphate, kaolin, talc, aluminum oxide, titanium oxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide. Further, organic particles such as crosslinked polymer particles and calcium oxalate, and precipitated particles during the polyester production process can be used.

  The particle size and content of the particles used are selected according to the use and purpose of the film, but the average particle size is usually in the range of 0.01 to 5.0 μm. When the average particle diameter exceeds 5.0 μm, the film surface roughness tends to be too rough, or the particles tend to fall off from the film surface. When the average particle size is less than 0.01 μm, the surface roughness is too small and sufficient slipperiness may not be obtained. About particle | grain content, it is 0.0003 to 1.0 weight% normally with respect to polyester, Preferably it is the range of 0.0005 to 0.5 weight%. When the particle content is less than 0.0003% by weight, the slipperiness of the film may be insufficient. On the other hand, when the content exceeds 1.0% by weight, the transparency of the film is poor. It may be enough. Further, various stabilizers, lubricants, antistatic agents and the like can be appropriately added to the film.

  As a film forming method of the film of the present invention, a generally known film forming method can be adopted, and there is no particular limitation. For example, a sheet obtained by melt extrusion is first stretched 2 to 6 times at 70 to 145 ° C. by a roll stretching method to obtain a uniaxially stretched polyester film, and then perpendicular to the previous stretching direction in the tenter. A film is obtained by extending | stretching 2 to 6 times at 80-160 degreeC to the direction, and also heat-processing at 150-250 degreeC for 1 to 600 seconds. Further, at this time, a method of relaxing 0.1 to 20% in the longitudinal direction and / or the transverse direction in the heat treatment zone and / or the cooling zone at the heat treatment outlet is preferable.

  The polyester film in the present invention has a single layer or multilayer structure. In the case of a multilayer structure, the surface layer and the inner layer, or both surface layers can be made of different polyesters depending on the purpose.

  The polyester film of the present invention preferably has an antistatic coating layer on one side and a fine adhesive layer on the opposite side, but the antistatic coating layer is provided only on one side of the film. Even if it is provided, or provided on both sides and a fine adhesion layer is provided on one side, it is naturally included in the concept of the present invention.

Specifically, the antistatic coating layer in the present invention is a coating layer having a mechanism in which the surface specific resistance of the coating layer is low and charges are leaked. It can be said that the lower the surface resistivity of the coating layer, the better the antistatic property. If the surface resistivity is 1 × 10 ¹² Ω or less, it can be said to have antistatic properties, and if it is 1 × 10 ⁸ Ω or less, it can be said that the antistatic properties are extremely good.

  In the present invention, the electroconductive compound (A) is contained in the coating solution for providing the antistatic coating layer. In general, as an antistatic method for a polyester film, a method of applying a so-called ionic conductive compound such as an anionic compound or a cationic compound to the surface, a method of applying a hydrophilic nonionic compound such as polyethylene oxide to the surface, or a so-called method. There is a method of applying an electron conductive compound to the surface.

  An ion conductive compound is a mechanism in which a hydrophilic ionic functional group interacts with moisture in the air, and charges are transferred by the generated ions. In addition to the method of applying a hydrophilic nonionic compound, the effect of moisture etc. is extremely high. It is easy to receive. Accordingly, in these antistatic methods, problems such as whitening of the surface may occur if the organic solvent is touched or placed under high humidity. In addition, the antistatic performance is often insufficient.

  On the other hand, a compound having electronic conductivity is less susceptible to moisture than the ion conductive compound as its mechanism, and the above-described problems are unlikely to occur. As the electronically conductive compound, various electronically conductive organic compounds, especially conductive polymer compounds such as polyacetylene, polyphenylene, polyaniline, polypyrrole, polyisothianaphthene, and polythiophene have been proposed. In the present invention, a polymer obtained by singly or copolymerizing thiophene or a thiophene derivative is preferable, and in particular, a compound composed of thiophene or a thiophene derivative is doped with another anionic compound, or an anion in the compound Those having a group and being self-doped are preferred because they exhibit excellent electrical conductivity. Examples of the compound (A) include those obtained by polymerizing a compound of the following formula (1) or (2) in the presence of a polyanion.

上記式中、Ｒ１およびＲ２は、それぞれ独立して、水素または炭素数が１〜２０の脂肪族炭化水素基、脂環族炭化水素基、芳香族炭化水素基、水酸基などを表す。

In the above formula, R1 and R2 each independently represent hydrogen or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a hydroxyl group, or the like.

上記式中、ｎは１〜４の整数を表す。

In said formula, n represents the integer of 1-4.

  Examples of the polyanion used at the time of polymerization include poly (meth) acrylic acid, polymaleic acid, polystyrene sulfonic acid and the like. These acids may be partially or completely neutralized.

  As a method for producing such a polymer, for example, a method as disclosed in JP-A-7-90060 can be employed.

  In the present invention, a particularly preferable embodiment is one in which n is 2 in the compound of the above formula (2) and polystyrene sulfonic acid is used as a polyanion.

  Moreover, the coating liquid for providing the antistatic coating layer in the present invention contains, as component (B), polyalkylene oxide (b1), glycerin (b2), polyglycerin (b3), glycerin or alkylene to polyglycerin. 1 or more types of compounds chosen from the group of an oxide adduct (b4), or its derivative (s) are contained.

  Preferable polyalkylene oxide (b1) or a derivative thereof is a structure containing an ethylene oxide or propylene oxide skeleton. If the alkyl chain in the alkylene oxide structure becomes too long, the hydrophobicity becomes strong, the uniform dispersibility in the coating solution deteriorates, and the antistatic property and transparency of the antistatic coating layer tend to deteriorate. . Particularly preferred is ethylene oxide.

  Glycerin and polyglycerin are compounds represented by the following general formula (3).

上記式中のｎが１の化合物がグリセリンであり、ｎが２以上の化合物はポリグリセリンである。本発明においては、式中のｎは、１〜２０の範囲が好ましく、より好ましくは２〜２０の範囲である。グリセリンを用いた場合、得られる帯電防止性塗布層の透明性が若干劣る場合がある。

The compound in which n is 1 in the above formula is glycerol, and the compound in which n is 2 or more is polyglycerol. In the present invention, n in the formula is preferably in the range of 1-20, more preferably in the range of 2-20. When glycerin is used, the transparency of the resulting antistatic coating layer may be slightly inferior.

  Further, the alkylene oxide adduct to glycerin or polyglycerin has a structure in which alkylene oxide or a derivative thereof is added and polymerized to the hydroxyl group of glycerin or polyglycerin represented by the general formula (3).

  Here, the structure of the alkylene oxide added or its derivative may differ for every hydroxyl group of glycerol or polyglycerol skeleton. Moreover, it is sufficient that it is added to at least one hydroxyl group in the molecule, and it is not necessary that alkylene oxide or a derivative thereof is added to all hydroxyl groups.

  A preferable alkylene oxide or derivative thereof added to glycerin or polyglycerin is a structure containing an ethylene oxide or propylene oxide skeleton. If the alkyl chain in the alkylene oxide structure becomes too long, the hydrophobicity becomes strong, the uniform dispersibility in the coating solution deteriorates, and the antistatic property and transparency of the antistatic coating layer tend to deteriorate. . Particularly preferred is ethylene oxide.

  In the present invention, particularly preferred embodiments of the compound (B) include polyglycerin (b3) and glycerin or an alkylene oxide adduct (b4) to polyglycerin. When polyalkylene oxide (b1) or glycerin (b2) is used, the appearance of the resulting antistatic coating layer may be slightly inferior. As the polyglycerin (b3), those having n of 2 to 20 in the compound of the above formula (3) are particularly preferred. Further, as the alkylene oxide adduct (b4) to glycerin or polyglycerin, a compound in which ethylene oxide or polyethylene oxide is added to the compound of the above formula (3) in which n is 2, The number of additions is particularly preferably in the range of 300 to 2000 in terms of the weight average molecular weight as the final compound (b4).

  In addition, in the alkylene oxide adduct to glycerin or polyglycerin, the copolymerization ratio of alkylene oxide or its derivative to the glycerin or polyglycerin skeleton is not particularly limited, but when the glycerin or polyglycerin moiety is 1 in terms of molecular weight ratio The alkylene oxide moiety is preferably 20 or less, more preferably 10 or less. When the ratio of the alkylene oxide or its derivative to the glycerin or polyglycerin skeleton is larger than this range, it becomes close to the characteristics when a normal polyalkylene oxide is used, and the antistatic coating layer obtained as described above. The appearance may be slightly inferior.

  Moreover, the coating liquid for providing the antistatic coating layer in the present invention is selected from the group consisting of an alkyl compound (c1), a fluorine compound (c2), and a silicone compound (c3) as the component (C). Contains more than one compound or derivative thereof.

  The alkyl compound is a compound having an olefin repeating unit represented by the following general formula, such as polyolefin, polyolefin wax, alkyl graft polymer and the like.

上記式中、Ｒは水素または炭素数が１〜６のアルキル基、ｎは１以上の整数、ｍは０または１以上の整数を表す。

In the above formula, R represents hydrogen or an alkyl group having 1 to 6 carbon atoms, n represents an integer of 1 or more, and m represents 0 or an integer of 1 or more.

  The fluorine compound in the present invention particularly refers to a compound having a fluorine-containing functional group with low polarity, and specifically includes a polymer containing a fluoroolefin or a perfluoroalkyl group. In particular, a polymer obtained by reacting a perfluoroalkyl group-containing ethylenically unsaturated monomer with another ethylenically unsaturated monomer has an affinity with a polyester film and other components constituting the coating layer. From the aspect of compatibility, it can be suitably used. Although it does not specifically limit as a perfluoroalkyl group containing ethylenically unsaturated monomer, For example, the compound shown by following General formula (4) is mentioned.

上記一般式（４）中、Ｒ^１はＨまたはＣＨ_３であり、Ｒ^２は炭素原子数が１〜１０のアルキレン基またはＣＯＮ（Ｒ^３）−Ｒ^４−、ＳＯ_２Ｎ（Ｒ^３）−Ｒ^４−であり、Ｒｆは炭素原子数が４〜２０のパーフルオロアルキル基である。Ｒ^３は炭素原子数が１〜４のアルキル基、Ｒ^４は炭素原子数が１〜１０のアルキレン基である。

In the general formula (4), R ¹ is H or CH ₃ , R ² is an alkylene group having 1 to 10 carbon atoms, CON (R ³ ) —R ⁴ —, SO ₂ N (R ³ ) — R ⁴ — and Rf is a perfluoroalkyl group having 4 to 20 carbon atoms. R ³ is an alkyl group having 1 to ⁴ carbon atoms, and R ⁴ is an alkylene group having 1 to 10 carbon atoms.

  The silicone compound in the present invention particularly refers to a compound having a silicone chain with low polarity, and specific examples include (modified) silicone oil, curable silicone resin and the like. Examples of (modified) silicone oil include modified silicone oil having a reactive organic group such as methacryl, epoxy, carbinol and the like. On the other hand, a specific example of the curable silicone resin may be a type having a curable silicone resin as a main component, or a modified silicone type by graft polymerization with an organic resin such as an acrylic resin, a urethane resin, an epoxy resin, or an alkyd resin. May be used. In particular, a modified silicone type by graft polymerization with an organic resin can be suitably used from the viewpoints of affinity with a polyester film and compatibility with other components constituting the coating layer.

In the coated film made according to the present invention, the weight of the compound (A) in the coating film is preferably 0.5 mg / m ² or more, and more preferably 1 mg / m ² or more. When the amount of the compound (A) is less than this, the antistatic property is often insufficient.

  The proportion of the compound (A) in the antistatic coating layer is not limited, but the upper limit is preferably 90% by weight, more preferably 80%, and even more preferably 60%. When the ratio of the compound (A) is higher than this, the transparency of the coating film is often insufficient or the antistatic performance is insufficient. The lower limit is preferably 1%, more preferably 2%. When the ratio of the compound (A) is lower than this, the antistatic performance becomes insufficient, or the coating film for having sufficient antistatic performance becomes extremely thick. A thick coating film is not preferred because it tends to deteriorate the appearance and transparency, block the film, and increase the cost.

  The ratio of (A) to (B) in the antistatic coating layer is preferably in the range of 90/10 to 1/99 by weight, more preferably 70/30 to 1/99, and even more preferably. Is in the range of 50/50 to 2/98. Outside this range, the antistatic performance and the appearance of the coating film tend to deteriorate.

  The ratio of (C) in the antistatic coating layer is preferably 0.5 to 30%, more preferably 1 to 20%, still more preferably 2 to 20% of the entire coating film. When the ratio of (C) is more than 30%, the appearance is deteriorated and the coating film strength is easily lowered. On the other hand, when the ratio of (C) is lower than 0.5%, the dirt removal performance on the coating film surface tends to be insufficient.

  The coating solution used in the present invention may contain a surfactant in order to improve the coating property to the film. As this surfactant, it is more preferable to use a surfactant containing (poly) alkylene oxide, (poly) glycerin, or a derivative thereof in the structure, since it does not inhibit the antistatic property of the resulting coating layer.

  The coating solution used in the present invention may contain a crosslinking reactive compound as necessary. Crosslinking reactive compounds mainly improve the cohesiveness, surface hardness, scratch resistance, solvent resistance, and water resistance of the coating layer by crosslinking reactions with functional groups contained in other resins and compounds, or by self-crosslinking. be able to. As the crosslinking reactive compound that can be used, amino resins such as melamine, benzoguanamine, and urea, isocyanate, oxazoline, epoxy, and glyoxal are preferably used. Also included are polymer-type cross-linking reactive compounds having reactive groups in other polymer skeletons. Moreover, the compound which has these reactive groups can also be used as a part of compound (B). As these cross-linking reactive compounds, it is more preferable to use those containing (poly) alkylene oxide, (poly) glycerin or derivatives thereof in the structure without inhibiting the antistatic property of the resulting coating layer.

  If necessary, one or more water-soluble or water-dispersible binder resins can be used in combination. Examples of the binder resin include polyether resin, polyester resin, polyurethane resin, acrylic resin, vinyl resin, epoxy resin, amide resin, and the like. In these, each skeleton structure may have a composite structure substantially by copolymerization or the like. Examples of the binder resin having a composite structure include acrylic resin graft polyester, acrylic resin graft polyurethane, vinyl resin graft polyester, and vinyl resin graft polyurethane. By containing these resins, the strength of the resulting coating layer and the adhesion to the base film can be improved.

  The coating liquid used in the present invention includes an antifoaming agent, a coating property improver, a thickener, an organic lubricant, a release agent, organic particles, inorganic particles, an antioxidant, an ultraviolet absorber, a foaming agent, a dye, You may contain additives, such as a pigment. These additives may be used alone or in combination of two or more as necessary. Moreover, as these additives, it is more preferable to use those containing (poly) alkylene oxide, (poly) glycerin, or derivatives thereof in the structure without inhibiting the antistatic property of the resulting coating layer.

  The coating liquid in the present invention is preferably an aqueous solution or a water dispersion from the viewpoint of handling, working environment, and stability of the coating liquid composition, but water is the main medium. An organic solvent may be contained as long as it does not exceed the range.

  The antistatic coating layer according to the present invention is provided by applying a coating solution containing a specific compound to a film, and in the present invention, it is preferably provided by in-line coating in which coating is performed during film formation.

  In-line coating is a method of coating within the process of manufacturing a polyester film. Specifically, it is a method of coating at any stage from melt extrusion of polyester to biaxial stretching and then heat setting and winding. is there. Normally, it is coated on either a substantially amorphous unstretched sheet obtained by melting and quenching, then a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction), or a biaxially stretched film before heat setting. To do. Among these, a method in which a uniaxially stretched film is coated, dried in a tenter and stretched in the transverse direction, and further heat treated together with the base film is excellent. According to such a method, there is a merit in manufacturing cost because film formation and coating layer coating can be performed at the same time, thin film coating is easy to perform stretching after coating, and heat treatment applied after coating is performed, Since it is possible to make the temperature so high that it is difficult to achieve with other coating methods, the film forming property of the coating layer is improved, and the coating layer and the polyester film are firmly adhered. In particular, when the coating layer contains a cross-linking reactive compound, there is an advantage that the reaction residue hardly remains due to the high-temperature heat treatment of in-line coating. The presence of a reactive residue in the coating layer causes a reaction with the components of the overcoat layer when blocking when the film is wound into a roll or when another layer is provided on the coating layer in a later step. Sometimes unfavorable.

  As a method for applying the coating solution to the polyester film, for example, a coating technique as shown in “Coating system” published by Yuji Harasaki, Tsuji Shoten, published in 1979 can be used. Specifically, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater, calendar coater And techniques such as an extrusion coater and a bar coater.

  In addition, in order to improve the applicability | paintability to the film of a coating agent and adhesiveness, you may give a chemical process, a corona discharge process, a plasma process, etc. to a film before application | coating.

The coating amount of the antistatic coating layer is usually 0.005 to 1.5 g / m ² , preferably 0.008 to 1.0 g / m ² , and more preferably 0.005 when viewed as the final coating. 01 to 0.5 g / m ² . If the coating weight is less than 0.005 g / ^{m 2} there is a possibility that sufficient performance is obtained, the coating layer in excess of 1.5 g / ^{m 2,} the appearance and transparency deteriorate or blocking of the film, cost It is easy to invite up.

  By providing a slightly adhesive layer on the opposite surface of the antistatic coating layer, it can be suitably used as an optical member surface protective film.

  As such a slightly adhesive layer, generally known adhesives such as an acrylic adhesive, a silicone adhesive, and a rubber adhesive can be used. Among these, an acrylic pressure-sensitive adhesive is preferable from the viewpoint of heat resistance and the like. Acrylic pressure-sensitive adhesives are mainly composed of various acrylic acid esters or methacrylic acid esters, copolymerized with various monomers, and are subjected to curing treatment by adding an isocyanate curing agent or the like thereto. Can be formed.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In addition, the evaluation method and the processing method of a sample in an Example and a comparative example are as follows.

(1) Transparency of coating layer (increased haze due to coating layer)
According to JIS-K7136, the haze of the film is measured with an integrating sphere turbidimeter NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the difference in haze between the film without the coating layer and the film with the coating layer is calculated. Then, an increase in haze due to the provision of the coating layer was obtained and evaluated as the transparency of the coating layer. It can be said that the smaller the haze rise, the better the transparency of the coating layer.
In particular, it can be said that when the haze difference is 0.5% or less in this method, the transparency is excellent, and when the difference is 0.2% or less, it is particularly excellent. On the other hand, when it exceeds 0.5%, the transparency is slightly inferior, and when it exceeds 1.0%, it can be said that the transparency is particularly inferior.

(2) Surface resistivity (Ω)
Based on the following method (2-1), the surface resistivity of the film coating layer was measured. Since the surface resistivity higher than 1 × 10 ⁸ Ω cannot be measured by the method (2-1), the method (2-2) was used for the sample that could not be measured by (2-1).
(2-1) Low resistivity meter manufactured by Mitsubishi Chemical Co., Ltd .: Loresta GP MCP-T600 was used, and after adjusting the sample for 30 minutes in a measurement atmosphere of 23 ° C. and 50% RH, the surface resistivity was measured.
(2-2) Using a high resistance measuring instrument made by Hewlett-Packard Japan: HP4339B and measuring electrode: HP16008B, measuring the surface resistivity after conditioning the sample for 30 minutes in a measurement atmosphere of 23 ° C. and 50% RH did.

(3) Solvent resistance: Taihei Rika Kogyo's special rubbing tester jig (5cm x 7cm, 500g) is wound with sheet-like cotton (Bencot made by Asahi Kasei Co., Ltd.), and 2ml of solvent is infiltrated there. A sample was prepared by wiping the surface of the sample 5 times (15 cm long range). Thereafter, the rubbed portion was visually observed and evaluated according to the following criteria. As the solvent, ethanol and toluene were used.
○: No change in appearance is observed at the rubbed area ×: Whitening is observed at the rubbed area

(4) Moisture resistance The film was stored in a constant temperature bath at 40 ° C. and 90% RH for 1 week, and the change in the appearance of the antistatic coating layer was visually evaluated.
○: No change in appearance ×: Appearance change such as whitening is observed

(5) Fine adhesive paste wiping test After the fine adhesive layer surface was rubbed against the surface of the antistatic coating layer, the adhered fine adhesive paste was wiped off with a sheet-like cotton (Bencot manufactured by Asahi Kasei Co., Ltd.). The results were evaluated according to the following criteria.
○: Can be easily wiped off ×: Adhesive glue is stuck and cannot be easily wiped off, or traces remain even after wiping off

The polyester raw materials used in Examples and Comparative Examples are as follows.
(Polyester 1): Polyethylene terephthalate having substantially no particle and having an intrinsic viscosity of 0.66

(Polyester 2): Polyethylene terephthalate having an intrinsic viscosity of 0.66 containing 0.6 part by weight of amorphous silica having an average particle diameter of 2.5 μm

Moreover, the following was used as a coating composition.
(A1): Baytron P AG manufactured by Starck Co., Ltd., consisting of polyethylene dioxythiophene and polystyrene sulfonic acid

(G1): Charol DC-902P manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which is a polymer having a pyrrolidinium ring in the main chain

(B1): Polyglycerin in which n = 10 in the formula (3)
(B2): Polyethylene oxide adduct to the polyglycerol skeleton in which n = 2 in the formula (3). Average molecular weight 350

(C1): Johnson wax 26 manufactured by Johnson Polymer Co., which is an aqueous dispersion of oxidized polyethylene wax
(C2): in a glass reaction vessel, _CF 3 _{(CF 2)} a perfluoroalkyl group-containing acrylate _{n CH 2 CH 2 OCOCH = CH} 2 (n = 5~11, n average = 9) 80.0 g 20.0 g of acetoacetoxyethyl methacrylate, 0.8 g of dodecyl mercaptan, 354.7 g of deoxygenated pure water, 40.0 g of acetone, 1.0 g of C ₁₆ H ₃₃ N (CH ₃ ) ₃ Cl and C ₈ H ₁₇ C ₆ H ₄ O (CH ₂ CH ₂ O) nH (n = 8) (3.0 g) was added, 0.5 g of azobisisobutylamidine dihydrochloride was added, and the mixture was copolymerized at 60 ° C. for 10 hours with stirring under a nitrogen atmosphere. Fluorine-containing resin emulsion obtained.

(D1): Erastron MF-25 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which is a block type isocyanate having a polyalkylene oxide skeleton
(D2): Becamine J-101 manufactured by Dainippon Ink and Chemicals, which is a methylated methylol melamine

(E1): Water-dispersible polyester resin having a molar ratio of terephthalic acid / isophthalic acid / sulfoisophthalic acid / ethylene glycol / 1,4-butanediol of 55/40/5/65/35

(F1): Nonionic surfactant having a structure having polyethylene oxide in the side chain, represented by the following formula

上記式中のｍ、ｎはエチレンオキサイドの付加モル数を示す整数であり、ここではｍ＋ｎ＝１０となるものを用いた。

M and n in the above formula are integers indicating the number of moles of ethylene oxide added, and here m + n = 10.

Comparative Example 1:
Polyester 1 and Polyester 2 are blended at a weight ratio of 80/20, sufficiently dried, heated and melted to 280 to 300 ° C., extruded into a sheet form from a T-shaped base, and surface temperature using an electrostatic adhesion method. It cooled and solidified, making it closely_contact | adhere to a 40-50 degreeC mirror surface cooling drum, and the unstretched polyethylene terephthalate film was created. This film was stretched 3.7 times in the longitudinal direction while passing through a heating roll group at 85 ° C. to obtain a uniaxially oriented film. This uniaxially oriented film was guided to a tenter stretching machine, stretched 4.0 times in the width direction at 100 ° C., and further heat treated at 230 ° C. to obtain a biaxially oriented polyethylene terephthalate film having a film thickness of 38 μm. The properties of this film are shown in Table 2 below.

  Next, on one side of this film, an isocyanate curing agent (manufactured by Nippon Polyurethane Co., Ltd., coronate) is used as a slightly adhesive layer for 100 parts (solid weight part) of an acrylic adhesive (Teikoku Chemical Co., Ltd., SG-800). HL) Apply 10 parts (parts by weight of solids) of the coating liquid using a bar coater, dry and cure the coating film at 100 ° C. for 2 minutes, provide a 20 μm thick adhesive layer, and protect the surface A film was created. The evaluation results of the obtained surface protective film are shown in Table 3 below.

  In Comparative Example 1, since the antistatic coating layer was not provided, the results shown in Table 2 were directly evaluated on the polyester film surface.

Example 1:
In the same process as Comparative Example 1, one side of the uniaxially oriented film after stretching in the longitudinal direction was uniformly treated at about 30 W / m ² · min using a corona treatment machine. Next, a coating composition as shown in Table 1 below was applied to the surface subjected to the discharge treatment. Subsequently, this film was led to a tenter stretching machine, and the coating composition was dried using the heat. Thereafter, the same procedure as in Comparative Example 1 was performed, and 0.023 g / m ² on a base film having a film thickness of 38 μm. The coating film which laminated | stacked the quantity of the antistatic coating layer was obtained. The properties of this film are shown in Table 2. When evaluating the transparency of the coating layer, the film haze value of 3.9% of Comparative Example 1 was used as the haze value of the film without the coating layer (the same applies to the following Examples and Comparative Examples).

  Next, on the surface opposite to the surface on which the coating layer of the film was provided, a slightly adhesive layer was provided in the same manner as in Comparative Example 1 to prepare a surface protective film. Table 3 shows the evaluation results of the obtained surface protective film.

Example 2:
In the same process as in Example 1, the coating solution was changed as shown in Table 1, and an antistatic coating layer having an amount of 0.022 g / m ² was laminated on a base film having a film thickness of 38 μm. A film was obtained. The properties of this film are shown in Table 2.

  Furthermore, it carried out similarly to Example 1, and was set as the surface protection film which provided the slightly adhesion layer on the opposite surface to the application layer. Table 2 shows the evaluation results of the obtained surface protective film.

Example 3:
In the same process as in Example 1, the coating solution was changed as shown in Table 1, and an antistatic coating layer having an amount of 0.024 g / m ² was laminated on a base film having a film thickness of 38 μm. A film was obtained. The properties of this film are shown in Table 2.

  Furthermore, it carried out similarly to Example 1, and was set as the surface protection film which provided the slightly adhesion layer on the opposite surface to the application layer. Table 2 shows the evaluation results of the obtained surface protective film.

Example 4:
In the same process as in Example 1, the coating solution was changed as shown in Table 1, and an antistatic coating layer having an amount of 0.024 g / m ² was laminated on a base film having a film thickness of 38 μm. A film was obtained. The properties of this film are shown in Table 2.

  Furthermore, it carried out similarly to Example 1, and was set as the surface protection film which provided the slightly adhesion layer on the opposite surface to the application layer. Table 2 shows the evaluation results of the obtained surface protective film.

Example 5:
In the same process as in Example 1, the coating solution was changed as shown in Table 1, and an antistatic coating layer having an amount of 0.016 g / m ² was laminated on a base film having a film thickness of 38 μm. A film was obtained. The properties of this film are shown in Table 2.

  Furthermore, it carried out similarly to Example 1, and was set as the surface protection film which provided the slightly adhesion layer on the opposite surface to the application layer. Table 2 shows the evaluation results of the obtained surface protective film.

Comparative Example 2:
In the same process as in Example 1, the coating solution was changed as shown in Table 1, and an antistatic coating layer having an amount of 0.012 g / m ² was laminated on a base film having a film thickness of 38 μm. A film was obtained. The properties of this film are shown in Table 2.

  Furthermore, it carried out similarly to Example 1, and was set as the surface protection film which provided the slightly adhesion layer on the opposite surface to the application layer. Table 2 shows the evaluation results of the obtained surface protective film.

Comparative Example 3:
In the same process as in Example 1, the coating solution was changed as shown in Table 1, and an antistatic coating layer having an amount of 0.034 g / m ² was laminated on a base film having a film thickness of 38 μm. A film was obtained. The properties of this film are shown in Table 2.

  Furthermore, it carried out similarly to Example 1, and was set as the surface protection film which provided the slightly adhesion layer on the opposite surface to the application layer. Table 2 shows the evaluation results of the obtained surface protective film.

  The coating amount means the solid content weight of the coating layer composition per area of the finally obtained coating film.

  The film of the present invention can be suitably used as an optical member protective film such as a polarizing plate.

Claims (3)

A polyester film comprising an antistatic coating layer formed by applying a coating solution containing the following components (A), (B) and (C) to one side of a polyester film and drying it.
(A): Electronically conductive compound (B): one selected from the group of polyalkylene oxide (b1), glycerin (b2), polyglycerin (b3), glycerin or an alkylene oxide adduct (b4) to polyglycerin Compound or derivative thereof (C): One or more compounds selected from the group consisting of alkyl compound (c1), fluorine compound (c2), and silicone compound (c3), or derivatives thereof The polyester film according to claim 1, wherein the electron conductive compound (A) is a polymer obtained by polymerizing thiophene or a thiophene derivative. A polyester film for protecting a surface of an optical member, comprising a slightly adhesive layer on a surface opposite to the antistatic coating layer of the polyester film according to claim 1 or 2.