JP5723509B2 - Laminated polyester film - Google Patents

Description

  The present invention relates to a laminated polyester film, and more particularly to a laminated polyester film having excellent transparency and antistatic properties.

  Polyester film is excellent in transparency, mechanical strength, dimensional stability, flatness, heat resistance, chemical resistance, etc. For example, a protective film that protects the surface of an optical member such as a polarizing plate from scratches and contamination. It is used for various applications such as a backlight unit, packaging, plate making, transfer, and building materials.

  Polyester films have a characteristic that they are easily charged due to static electricity as a problem common to plastic films. For example, in the case of a protective film used in the polarizing plate manufacturing process, it is attached to the polarizing plate via an adhesive or the like, but because of its easy charging property, friction charging or peeling charging occurs in each step, Problems such as adhesion of foreign matter and dust, and electrostatic discharge failures will occur.

  In order to solve these problems, a method of providing an antistatic coating layer on a polyester film has been proposed. However, in recent years, a film having higher transparency and less foreign matter has been demanded. Furthermore, in order to simplify the process, the protective film may not be peeled off, and the polarizing plate may be inspected while being attached, and a film having higher transparency than the film that has been used as a protective film is being demanded. .

  Conventionally, a technique of incorporating particles into a polyester film for the purpose of easy slipping has been common (Patent Documents 1 and 2). However, in the case of the method of incorporating particles in the polyester film, the haze of the film becomes high and becomes whitish, or when observed under a fluorescent lamp, graininess due to the particles is seen and visibility is deteriorated. There are also concerns that particles aggregated in various inspections may be detected as foreign matter.

  In order to solve these problems, a film that does not contain particles in a polyester film has also been proposed (Patent Document 3). However, in the case of a film containing no particles, there is a drawback that the slipperiness is poor and the film is easily damaged. A proposal has been made to form a coating layer containing particles on a uniaxially stretched polyester film to impart slipperiness. In the meantime, the slipperiness is poor and scratches are inevitable.

JP 2006-169467 A JP 2006-77148 A JP 2000-229355 A

  The present invention has been made in view of the above circumstances, and the problem to be solved is that it has excellent transparency and antistatic properties, for example, a good polyester film as a protective film used in the manufacturing process of polarizing plates. It is to provide.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that the use of a polyester film having a specific configuration can easily solve the above-described problems, and have completed the present invention.

That is, the gist of the present invention is that an unstretched polyester film has a coating layer formed by applying a coating liquid containing particles having a softening point of 120 to 270 ° C. and then stretching in at least one direction. And a laminated polyester film characterized by having a coating layer containing an antistatic agent on the coating layer.

  According to the polyester film of the present invention, a film excellent in transparency and antistatic property can be provided, and its industrial value is high.

  The polyester film constituting the polyester film in the present invention may have a single layer structure or a multilayer structure, and may have four or more layers as long as the gist of the present invention is not exceeded other than the two-layer or three-layer structure. It may be a multilayer and is not particularly limited. For example, it is possible to change the raw material of the surface layer and the intermediate layer into a three-layer structure for the purpose of effectively improving various properties using a polyester film with high functionality as the surface layer raw material.

  The polyester used in the present invention may be a homopolyester or a copolyester. In the case of a homopolyester, those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Typical polyester includes polyethylene terephthalate and the like. On the other hand, examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid (for example, p-oxybenzoic acid). 1 type or 2 types or more are mentioned, As a glycol component, 1 type or 2 types or more, such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexane dimethanol, neopentyl glycol, is mentioned.

There is no restriction | limiting in particular as a polymerization catalyst of polyester, A conventionally well-known compound can be used, For example, an antimony compound, a titanium compound, a germanium compound, a manganese compound, an aluminum compound, a magnesium compound, a calcium compound etc. are mentioned. Among these, a titanium compound and a germanium compound are preferable because they have high catalytic activity, can be polymerized in a small amount, and the amount of metal remaining in the film is small, so that foreign matter in the film is reduced. Furthermore, since a germanium compound is expensive, it is more preferable to use a titanium compound.

  In the polyester layer of the film of the present invention, particles can be blended mainly for the purpose of imparting slidability and preventing scratches in each step, but from the viewpoint of transparency, particles are not blended. It is preferable that When the particles are blended, the kind of the particles to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness, and specific examples thereof include, for example, silica, calcium carbonate, magnesium carbonate, barium carbonate, sulfuric acid. Examples thereof include inorganic particles such as calcium, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, and benzoguanamine resin. Furthermore, precipitated particles obtained by precipitating and finely dispersing a part of a metal compound such as a catalyst during the polyester production process can also be used.

  Moreover, when mix | blending particle | grains, the average particle diameter of particle | grains is 3 micrometers or less normally, Preferably it is the range of 0.01-1.5 micrometers. When the average particle diameter exceeds 3 μm, the film brightness decreases when the transparency of the film deteriorates, when the graininess due to the particles occurs and the visibility deteriorates, or when light scattering by the particles occurs. There is a case.

  The content of the particles depends on the average particle size, but in the polyester film layer containing the particles, it is usually in the range of 1000 ppm or less, preferably in the range of 500 ppm or less, more preferably in the range of 50 ppm or less (intentionally contained). Do not). If it exceeds 1000 ppm, the transparency may deteriorate, the graininess caused by particles may occur and the visibility may deteriorate, or the brightness of the film may decrease due to light scattering by the particles.

  The shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, a flat shape, and the like may be used. Moreover, there is no restriction | limiting in particular also about the hardness, specific gravity, a color, etc. These series of particles may be used in combination of two or more as required.

  The method for adding particles to the polyester layer is not particularly limited, and a conventionally known method can be adopted. For example, it can be added at any stage for producing the polyester constituting each layer, but it is preferably added after completion of esterification or transesterification.

  The polyester film of the present invention may contain an ultraviolet absorber in order to improve the weather resistance of the film and prevent deterioration of a material to be protected such as liquid crystal. The ultraviolet absorber is not particularly limited as long as it is a compound that absorbs ultraviolet rays and can withstand the heat applied in the production process of the polyester film.

  As the ultraviolet absorber, there are an organic ultraviolet absorber and an inorganic ultraviolet absorber. From the viewpoint of transparency, an organic ultraviolet absorber is preferable. Although it does not specifically limit as an organic type ultraviolet absorber, For example, a cyclic imino ester type, a benzotriazole type, a benzophenone type etc. are mentioned. From the viewpoint of durability, a cyclic imino ester type and a benzotriazole type are more preferable. It is also possible to use two or more ultraviolet absorbers in combination.

  In the polyester film of the present invention, conventionally known antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments, etc. may be added to the polyester film in the present invention as necessary in addition to the above-mentioned particles and ultraviolet absorbers. Can do.

  Although the thickness of the polyester film in this invention will not be specifically limited if it can be formed into a film as a film, Usually, 10-300 micrometers, Preferably it is the range of 20-250 micrometers.

Next, although the manufacture example of the polyester film in this invention is demonstrated concretely, it is not limited to the following manufacture examples at all. That is, a method of drying the polyester raw material pellets described above and cooling and solidifying the molten film extruded from the die with a cooling roll using a single screw extruder is preferable. In this case, in order to improve the flatness of the film, it is preferable to improve the adhesion between the film and the rotary cooling drum, and an electrostatic application adhesion method or a liquid application adhesion method is preferably employed. Next, the obtained unstretched film is stretched in the biaxial direction. In that case, first, a coating solution containing non-heat-resistant particles is applied to the unstretched film and dried to form a coating layer. Thereafter, the film is stretched in one direction by a roll or tenter type stretching machine. The stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times. Next, the film is stretched in the direction perpendicular to the first stretching direction. In that case, the stretching temperature is usually 70 to 170 ° C., and the stretching ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times. is there. Subsequently, heat treatment is performed at a temperature of 180 to 270 ° C. under tension or under relaxation within 30% to obtain a biaxially oriented film.
In the above-described stretching, a method in which stretching in one direction is performed in two or more stages can be employed.
In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges.

  In the present invention, the simultaneous biaxial stretching method can be adopted for the production of the polyester film constituting the polyester film. In the simultaneous biaxial stretching method, a coating solution containing non-heat-resistant particles is applied to the unstretched film, and the machine direction and the width direction are usually controlled at 70 to 120 ° C., preferably 80 to 110 ° C. The stretching ratio is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times. Subsequently, heat treatment is performed at a temperature of 170 to 270 ° C. under tension or relaxation within 30% to obtain a stretched oriented film. With respect to the simultaneous biaxial stretching apparatus that employs the above-described stretching method, a conventionally known stretching method such as a screw method, a pantograph method, or a linear driving method can be employed.

  In the present invention, a coating layer (hereinafter sometimes abbreviated as a first coating layer) is formed from a coating solution containing non-heat-resistant particles on at least one surface of an unstretched polyester film, and then at least in one direction. It is an essential requirement to have a coating layer containing an antistatic agent (hereinafter sometimes abbreviated as a second coating layer) on the coating layer and / or on the side opposite to the coating layer after stretching. To do.

  The present inventors include particles in a polyester film, and as a method for ensuring transparency and slipperiness, a change in the average particle diameter of the particles, a change in the addition amount of the particles, a layer of the polyester film containing the particles ( In the three-layer structure, only the outermost layer contains particles, and while improving the transparency, the method of changing the thickness of the slippery) has been studied, but both ensure high transparency and sufficient slipperiness. It was a difficult result.

  The first coating layer (non-heat-resistant particles) of the present invention is formed at the initial stage of the film production process, so that the first coating layer is formed on the unstretched film formed after melt extrusion and before the high temperature treatment. In these various processes, it is used to ensure sufficient slipperiness.

  In addition, usually when particles are present, they appear whitish due to light scattering, but when non-heat-resistant particles are used, they can be melted at a high temperature to reduce the particle size, deform, or be eliminated in a later step. In addition, they found that it was possible to reduce whitishness and realized high transparency.

  The formation of the first coating layer in the film of the present invention can be carried out at any stage from after the unstretched film formed after melt extrusion to before high temperature treatment. In particular, in order to prevent damage due to the roll, it is preferable to carry out at an initial stage. Moreover, in the method of extending | stretching by making it contact with films, such as a roll, since the damage to a film becomes large, forming in the step before extending | stretching is preferable.

  Furthermore, in order to increase transparency, it is necessary to treat at a temperature higher than the heat-resistant temperature (temperature at which heat is deformed) in order to reduce, deform, or eliminate the particle size by melting the non-heat-resistant particles in the subsequent process. Is preferable.

  The first coating layer in the film of the present invention is not limited to the following, for example, in sequential biaxial stretching, after the unstretched film is formed, the first coating layer is formed at an initial stage, and then A more suitable polyester film can be produced by performing the first stretching and then performing the high temperature treatment after the second stretching.

  The first coating layer in the film of the present invention may be formed on only one side of the film or may be formed on both sides in order to overcome, for example, a more easily damaged part. Moreover, in the case of both surfaces, the formation location may be the same or different.

  The non-heat resistant particles used in the present invention are particles having low heat resistance, and the particles are deformed at a high temperature. In particular, in the production process of the polyester film, the particles are deformed or dissolved in a process in which the temperature after film formation is high. However, for example, when selecting a method of stretching in contact with a film such as a roll in the first stretching, it is necessary to maintain a sufficient shape as particles in order to exhibit slipperiness in the stretching process. Some heat resistance is necessary.

  That is, the thermal characteristics required for the non-heat resistant particles are preferably those that do not undergo thermal deformation at a temperature of less than 120 ° C. and that undergo thermal deformation at a temperature of 120 ° C. or higher.

  The softening point of the non-heat resistant particles is preferably in the range of 120 to 270 ° C, more preferably in the range of 150 to 250 ° C, and still more preferably in the range of 180 to 230 ° C. When the temperature is lower than 120 ° C., when a method of stretching by contacting with a film such as a roll in the first stretching is selected, depending on the stretching temperature, thermal deformation of the particles may occur, and the slipping property is deteriorated. There are concerns. On the other hand, if the temperature exceeds 270 ° C., the final product may be a film in which the particles are not thermally deformed and remain whitish.

  The non-heat resistant particle is not particularly limited as long as it can maintain the above-mentioned thermal characteristics, but in general, the organic particles, i.e. Heat-resistant organic particles are preferred. In consideration of control of the size and shape of the particles and dispersibility in various solvents including water, the organic particles are more preferably of a high molecular type, that is, non-heat resistant polymer particles.

  As the non-heat-resistant polymer particles, cross-linked or non-cross-linked polymer particles can be used as long as the gist of the present invention is not impaired, but in order to make the thermal characteristics more suitable for the purpose of the present invention. More preferably, it is a non-crosslinked type, that is, a non-heat resistant non-crosslinked polymer particle.

  The non-crosslinking in the non-heat resistant non-crosslinked polymer particles is a polymer particle that does not have a three-dimensional structure or has a small number of heat resistance. For example, in the case of particles made of a polymerizable monomer as described later, the crosslinkable polymerizable monomer is preferably less than 5% by weight of the entire polymerizable monomer, and more preferably in the range of less than 1% by weight.

  As the polymer of the non-heat-resistant non-crosslinked polymer particles, conventionally known compounds can be used. For example, acrylic resin, styrene resin, vinyl resin, epoxy resin, urea resin, phenol resin, polyester resin, polyurethane resin , Polycarbonate resin, polyether resin and the like. Among these polymers, an acrylic resin, a styrene resin, and a vinyl resin formed from a polymerizable monomer having a carbon-carbon double bond are more preferable from the viewpoint that a compound having a desired thermal characteristic can be easily produced. In addition, in the case of these resins, since they are thermally deformed by high-temperature treatment, it is possible to prevent the particles from falling off. Furthermore, not only the function as particles, but also, for example, adhesion to various surface functional layers formed thereon It is also possible to develop other performances such as increasing.

  The polymerizable monomer having a carbon-carbon double bond refers to various carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, and salts thereof; 2 -Various hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroxyfumarate, monobutylhydroxyitaconate; Various (meth) acrylates such as (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate; (meth) acrylamide, diacetone acrylamide, N -Methylol Various nitrogen-containing compounds such as chloramide or (meth) acrylonitrile; various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene, various vinyl esters such as vinyl propionate; γ-methacrylic Various silicon-containing polymerizable monomers such as loxypropyltrimethoxysilane, vinyltrimethoxysilane, etc .; phosphorus-containing vinyl monomers; various vinyl halides such as vinyl fluoride, vinyl chloride, and biridene chloride; butadiene And various conjugated dienes.

  Among these, an acrylic resin obtained by polymerizing a (meth) acrylic polymerizable monomer as a main component is optimal. Also, a styrene / acrylic resin having a (meth) acrylic polymerizable monomer as a main component and copolymerized with a styrene derivative can be suitably used.

  That is, in the film of the present invention, the best form of the non-heat-resistant particles used for forming the first coating layer is the non-heat-resistant non-crosslinked acrylic resin particles and the non-heat-resistant non-crosslinked styrene / acrylic resin particles as described above. It is.

  When non-heat resistant non-crosslinked acrylic resin particles are used, the glass transition point of the resin particles is preferably in the range of 0 to 150 ° C, more preferably in the range of 50 to 120 ° C. When the temperature is lower than 0 ° C, there is a concern that the slipperiness cannot be sufficiently exhibited. When the temperature exceeds 150 ° C, there is a concern that the thermal deformation of the particles is not sufficient.

  The average particle diameter of the non-heat-resistant particles depends on the film thickness and cannot be generally specified, but is preferably in the range of 0.01 to 3 μm, more preferably in the range of 0.03 to 1 μm, and still more preferably 0.00. It is the range of 05-0.5 micrometer. When the average particle size is less than 0.01 μm, the slipperiness may not be sufficiently obtained. When the average particle size exceeds 3 μm, the particles are not sufficiently deformed and a whitish film remains. May end up.

  In the formation of the first coating layer in the film of the present invention, it is preferable to use various polymers and adhesive compounds in combination in order to hold the particles on the film. In particular, it is preferable to use a polymer in combination for the purpose of improving the appearance of coating, improving the transparency, and further improving the adhesion with various layers provided on the coating layer.

  Specific examples of the polymer include polyester resin, acrylic resin, urethane resin, polyvinyl (polyvinyl alcohol, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, and starches. Among these, it is preferable to use a polyester resin, an acrylic resin, a urethane resin, or polyvinyl alcohol from the viewpoints of particle retention and coatability. Moreover, when considering familiarity with a polyester film, a polyester resin is optimal.

  The polyester resin includes, for example, those composed of the following polyvalent carboxylic acid and polyvalent hydroxy compound as main constituent components. That is, as the polyvalent carboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4′-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6 -Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutar Acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic acid, trimellitic acid monopotassium salt and ester-forming derivatives thereof can be used. As the polyvalent hydroxy compound, ethylene Recall, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol , Neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol Polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate, and the like can be used. One or more compounds may be appropriately selected from these compounds, and a polyester resin may be synthesized by a conventional polycondensation reaction.

  The acrylic resin is a polymer composed of a polymerizable monomer having a carbon-carbon double bond, as typified by acrylic and methacrylic monomers. These may be either a homopolymer or a copolymer. Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer. Alternatively, a polymer (possibly a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyester solution or a polyester dispersion is also included. Similarly, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyurethane solution or polyurethane dispersion is also included. Similarly, a polymer obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in another polymer solution or dispersion (in some cases, a polymer mixture) is also included. Moreover, in order to improve adhesiveness, it is also possible to contain a hydroxyl group and an amino group.

  The polymerizable monomer having a carbon-carbon double bond is not particularly limited, but particularly representative compounds include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citracone. Various carboxyl group-containing monomers such as acids, and salts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxyl fumarate, Various hydroxyl group-containing monomers such as monobutylhydroxy itaconate; various monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate ( (Meth) acrylic acid esters; Various nitrogen-containing compounds such as meth) acrylamide, diacetone acrylamide, N-methylolacrylamide or (meth) acrylonitrile; various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene, vinyl propionate Various vinyl esters such as: Various silicon-containing polymerizable monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, etc .; Phosphorus-containing vinyl monomers; Various such as vinyl chloride and biridene chloride And various conjugated dienes such as butadiene.

  The urethane resin is a polymer compound having a urethane bond in the molecule. Usually, urethane resin is prepared by reaction of polyol and isocyanate. Examples of the polyol include polycarbonate polyols, polyester polyols, polyether polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination.

  Polycarbonate polyols are obtained from a polyhydric alcohol and a carbonate compound by a dealcoholization reaction. Examples of the polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Diol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylol heptane and the like can be mentioned. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Examples of polycarbonate polyols obtained from these reactions include poly (1,6-hexylene) carbonate, poly (3- And methyl-1,5-pentylene) carbonate.

  Polyester polyols include polycarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or their acid anhydrides. Product and polyhydric alcohol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol 2-methyl-2-propyl-1 3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propanediol, cyclohexane Diol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyl dialkanolamine, lactone diol, etc.).

  Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and the like.

  Examples of the polyisocyanate compound used for obtaining the urethane resin include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, α, α, α ′, α ′. -Aliphatic diisocyanates having aromatic rings such as tetramethylxylylene diisocyanate, aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl Methanzi Cyanate, alicyclic diisocyanates such as isopropylidene dicyclohexyl diisocyanates. These may be used alone or in combination.

  A chain extender may be used when synthesizing the urethane resin, and the chain extender is not particularly limited as long as it has two or more active groups that react with an isocyanate group. Alternatively, a chain extender having two amino groups can be mainly used.

  Examples of the chain extender having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. And glycols such as glycols. Examples of the chain extender having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine, and diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3- Propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- Aliphatic diamines such as decane diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isoprobilitincyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1 , 3-Bisaminomethylcyclohexa And alicyclic diamines such as

The urethane resin in the present invention may use a solvent as a medium, but preferably uses water as a medium. In order to disperse or dissolve the urethane resin in water, there are a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the urethane resin, and a water-soluble type. In particular, a self-emulsification type in which an ionic group is introduced into the skeleton of a urethane resin to form an ionomer is preferable because of excellent storage stability of the liquid and water resistance, transparency, and adhesion of the resulting coating layer.
Examples of the ionic group to be introduced include various groups such as a carboxyl group, sulfonic acid, phosphoric acid, phosphonic acid, quaternary ammonium salt, and the like, and a carboxyl group is preferable. As a method for introducing a carboxyl group into a urethane resin, various methods can be taken in each stage of the polymerization reaction. For example, there are a method of using a carboxyl group-containing resin as a copolymer component during prepolymer synthesis, and a method of using a component having a carboxyl group as one component such as polyol, polyisocyanate, and chain extender. In particular, a method in which a desired amount of carboxyl groups is introduced using a carboxyl group-containing diol depending on the amount of this component charged is preferred. For example, dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, bis- (2-hydroxyethyl) butanoic acid and the like are copolymerized with a diol used for polymerization of a urethane resin. Can do. The carboxyl group is preferably in the form of a salt neutralized with ammonia, amine, alkali metal, inorganic alkali or the like. Particularly preferred are ammonia, trimethylamine and triethylamine. In such a polyurethane resin, a carboxyl group from which the neutralizing agent has been removed in the drying step after coating can be used as a crosslinking reaction point by another crosslinking agent. Thereby, it is possible to further improve the durability, solvent resistance, water resistance, blocking resistance, and the like of the obtained coating layer, as well as excellent stability in a liquid state before coating.

  Moreover, in the 1st application layer in this invention, in order to improve an intensity | strength, you may use a crosslinking agent together. Various known crosslinking agents can be used as the crosslinking agent to be used in combination, and examples thereof include oxazoline compounds, epoxy compounds, melamine compounds, isocyanate compounds, carbodiimide compounds, aziridine compounds, and silane coupling compounds. .

  The oxazoline compound is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferable, and can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer. Addition polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like can be mentioned, and one or a mixture of two or more thereof can be used. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially. The other monomer is not limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer. For example, alkyl (meth) acrylate (the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, (meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; (meth) acrylamide, N-alkyl ( (Meth) acrylamide, N, N-dialkyl (meth) acrylamide, As the alkyl group, unsaturated amides such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group and cyclohexyl group); vinyl acetate Vinyl esters such as vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride And α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene, and the like, and one or more of these monomers can be used.

  The content of the oxazoline group contained in the oxazoline compound is usually 0.5 to 10 mmol / g, preferably 1 to 9 mmol / g, more preferably 3 to 8 mmol / g, and further preferably 4 to 6 mmol in terms of the amount of the oxazoline group. / G. Use within the above range is preferable because adhesion to various surface functional layers is improved.

  The epoxy compound is a compound having an epoxy group in the molecule, and examples thereof include condensates of epichlorohydrin with ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A and the like hydroxyl groups and amino groups, There are polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, and the like. Examples of the polyepoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane. Examples of the polyglycidyl ether and diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. , Polypropylene glycol diglycidyl ether, poly Examples of tetramethylene glycol diglycidyl ether and monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N′-tetraglycidyl-m-xylyl. Examples include range amine and 1,3-bis (N, N-diglycidylamino) cyclohexane.

  The melamine compound is a compound having a melamine skeleton in the compound. For example, an alkylolized melamine derivative, a compound partially or completely etherified by reacting an alcohol with an alkylolated melamine derivative, and these Mixtures can be used. As alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used. Moreover, as a melamine compound, either a monomer or a multimer more than a dimer may be sufficient, or a mixture thereof may be used. Further, a product obtained by co-condensing urea or the like with a part of melamine can be used, and a catalyst can be used to increase the reactivity of the melamine compound.

  The isocyanate compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate. Examples of isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, and aromatic rings such as α, α, α ′, α′-tetramethylxylylene diisocyanate. Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate Ne Alicyclic isocyanates such as bets are exemplified. Further, polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide modified products of these isocyanates are also included. These may be used alone or in combination. Among the above isocyanates, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.

  When used in the state of blocked isocyanate, the blocking agent includes, for example, bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, and alcohols such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol. Compounds, active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, lactam compounds such as ε-caprolactam and δ-valerolactam , Amine compounds such as diphenylaniline, aniline, ethyleneimine, acetanilide, acid amide compounds of acetic acid amide, formaldehyde, acetoald Examples include oxime compounds such as oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, and these may be used alone or in combination of two or more.

  In addition, the isocyanate compound in the present invention may be used alone, or may be used as a mixture or bond with various polymers. In the sense of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a bond with a polyester resin or a urethane resin.

  A carbodiimide-based compound is a compound having a carbodiimide structure, and is used for improving adhesion with a surface functional layer such as a hard coat layer that can be formed on a coating layer, and for improving wet heat resistance of the coating layer. It is what The carbodiimide compound is a compound having one or more carbodiimide or carbodiimide derivative structures in the molecule, but a polycarbodiimide compound having two or more in the molecule is more preferable for better adhesion and the like.

  The carbodiimide compound can be synthesized by a conventionally known technique, and generally a condensation reaction of a diisocyanate compound is used. The diisocyanate compound is not particularly limited, and any of aromatic and aliphatic compounds can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexa Examples include methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.

  Furthermore, in order not to lose the effect of the present invention, in order to improve the water solubility and water dispersibility of the polycarbodiimide compound, adding a surfactant, polyalkylene oxide, quaternary ammonium salt of dialkylamino alcohol, You may add and use hydrophilic monomers, such as a hydroxyalkyl sulfonate.

  These cross-linking agents are used in a design that improves the performance of the coating layer by reacting in the drying process or film forming process. It can be inferred that unreacted products of these crosslinking agents, compounds after the reaction, or mixtures thereof exist in the finished coating layer.

  Regarding the formation of the first coating layer in the film of the present invention, a coating solution prepared by adjusting the solid content concentration to about 0.1 to 80% by weight using the above-described series of compounds as a solution or dispersion of a solvent is used as an unstretched polyester. It is preferable to produce a polyester film in the manner of application on the film. In consideration of being inline in particular, it is more preferable that the solution is an aqueous solution or a water dispersion, but the coating solution contains a small amount of an organic solvent for the purpose of improving the dispersibility in water and improving the film forming property. You may do it. Moreover, only one type of organic solvent may be used, and two or more types may be used as appropriate.

The amount of the non-heat-resistant particles constituting the first coating layer in the film of the present invention is not particularly limited as long as the object is achieved. Further, since it depends on the thermal characteristics and size of the particles to be used and the film thickness of the first coating layer, it cannot be generally stated. However, the amount of only one side is a film after drying (before stretching), preferably 0. range 01~200mg / ^{m 2,} more preferably from 0.1~150mg / ^{m 2,} more preferably in the range of 1~70mg / ^{m 2.}

Moreover, since the coating amount of the first coating layer (after drying and before stretching) depends on the size of the particles, the stretching ratio, etc., it cannot be generally stated, but is preferably 0.001 to 5 g / m ² or less. The range is more preferably in the range of 0.01 to 3 g / m ² , still more preferably in the range of 0.05 to 1 g / m ² , and most preferably in the range of 0.1 to 0.7 g / m ² . When the coating amount is out of the above range, there are concerns about blocking, deterioration of the coating appearance, and dropout of particles.

  In the film of the present invention, the first coating layer may be formed by, for example, gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating. Conventionally known coating methods such as squeeze coating, impregnation coating, kiss coating, spray coating, calendar coating, extrusion coating, and the like can be used.

  Moreover, when forming a 1st application layer in a film, you may perform surface treatments, such as a corona treatment and a plasma treatment, as needed.

  Moreover, in this invention, after forming a 1st coating layer and extending | stretching at least to one direction, a 2nd coating layer is formed in order to provide antistatic performance. The second coating layer may be formed on the surface side on which the first coating layer is formed, or may be formed on the opposite surface side of the first coating layer. Moreover, you may form only in the single side | surface side of a film, and may form in both surfaces. Regarding the second coating layer, it may be provided by in-line coating, which treats the film surface during the process of forming a polyester film, or may be applied off-system on a once produced film. . Since the coating can be performed simultaneously with the film formation, the production can be handled at a low cost, and therefore in-line coating is preferably used.

  The in-line coating in the formation of the second coating layer is not limited to the following. For example, in the sequential biaxial stretching, the coating treatment can be performed particularly before the lateral stretching after the longitudinal stretching is finished. When the second coating layer is provided on the polyester film by in-line coating, coating can be performed simultaneously with film formation, and the coating layer can be processed at a high temperature in the heat treatment step of the stretched polyester film. A strong coating layer can be formed. Further, when coating is performed before transverse stretching, the thickness of the coating layer can be changed by the stretching ratio, and thin film coating can be performed more easily than offline coating. That is, a film suitable as a polyester film can be produced by in-line coating, particularly coating before stretching.

  That is, as one of the preferable production methods in the present invention, for example, an unstretched film is formed after melt extrusion, and then a first coating layer is formed and then longitudinal stretching is performed to further form a second coating layer, Then, it is the method of processing at high temperature, after performing horizontal extending | stretching.

  The second coating layer in the film of the present invention is provided for the purpose of facilitating the handling of the film, for example, to prevent sticking between films due to static electricity, or to prevent adhesion of foreign matter / dust. is there.

  The antistatic agent used for forming the second coating layer is used for lowering the surface resistance of the film surface, and there is no particular limitation, and a conventionally known antistatic agent can be used. A polymer type antistatic agent is preferred because of its good resistance to moist heat. Examples of the polymer type antistatic agent include quaternary ammonium salt compounds, polyether compounds, sulfonic acid compounds, betaine compounds, and conductive polymers.

  The quaternary ammonium salt compound is a compound containing a quaternary ammonium salt in the molecule, for example, a pyrrolidinium ring, a quaternized alkylamine, and a copolymer of these with acrylic acid or methacrylic acid, Examples thereof include quaternized N-alkylaminoacrylamides, vinylbenzyltrimethylammonium salts, 2-hydroxy-3-methacryloxypropyltrimethylammonium salts, and the like. Further, these may be combined or copolymerized with other resins. In addition, examples of anions that serve as counter ions of these quaternary ammonium salts include ions such as halogen ions, sulfonates, phosphates, nitrates, alkylsulfonates, and carboxylates.

  Among the quaternary ammonium salt compounds, a compound having a pyrrolidinium ring is more preferable in terms of excellent antistatic properties and heat stability.

  The compound having a pyrrolidinium ring is, for example, a polymer having a structure of the following formula (1).

In the above formula (1), each R ^1, R ² are independently an alkyl group, a phenyl group, these alkyl groups, a phenyl group may be substituted by the following groups. Substitutable groups are, for example, hydroxyl group, amide group, ester group, alkoxy group, phenoxy group, naphthoxy group, thioalkoxy, thiophenoxy group, cycloalkyl group, trialkylammonium alkyl group, cyano group, and halogen. R ¹ and R ² may be chemically bonded. For example, — (CH ₂ ) _m — (m is an integer of 2 to 5), —CH (CH ₃ ) CH (CH ₃ ) —, -CH = CH-CH = CH - , - CH = CH-CH = N -, - CH = CH-N = C -, - CH 2 OCH 2 -, - (CH 2) 2 O (CH 2) 2 - Etc.
Wherein X ^- represents a halogen ion, sulfonate, phosphate, nitrate, alkyl sulfonate, carboxylate and the like.

  In the present invention, the polymer of the above formula (1) is obtained by cyclopolymerizing a compound represented by the following formula (2) using a radical polymerization catalyst. The polymerization is carried out by using a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, tertiary butyl peroxide in a polar solvent such as water or methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile as a solvent. Although it can implement by a method, it is not limited to these. In the present invention, a compound having a polymerizable carbon-carbon unsaturated bond may be used as a copolymerization component.

  Moreover, the number average molecular weight of a quaternary ammonium salt compound is 1000-500000 normally, Preferably it is 2000-100000, More preferably, it is 5000-50000. When the molecular weight is less than 1000, the strength of the coating film may be weak or the heat resistance stability may be poor. On the other hand, when the molecular weight exceeds 500,000, the viscosity of the coating solution increases, and the handleability and applicability may deteriorate.

  Examples of polyether compounds include polyethylene oxide, polyether ester amide, acrylic resins having polyethylene glycol in the side chain, and the like.

  The sulfonic acid compounds are compounds containing sulfonic acid or sulfonate in the molecule, and examples thereof include polystyrene sulfonic acid.

Examples of the conductive polymer include polythiophene-based, polyaniline-based, polypyrrole-based, polyacetylene-based, and the like. Are preferably used.

  In the formation of the second coating layer of the film of the present invention, a polymer or a crosslinking agent used for the formation of the first coating layer is used in combination for the purpose of improving the coating appearance, transparency, and coating film strength. It is possible.

  In addition, for the formation of the second coating layer of the film of the present invention, for example, polyalkylene oxide, glycerin, polyglycerin, glycerin or alkylene to polyglycerin is used to improve the coating appearance and reduce the surface resistance. It is also possible to use a polyol compound or a polyether compound such as an oxide adduct in combination.

  Preferred as the polyalkylene oxide or derivative thereof is a compound having an ethylene oxide or propylene oxide structure. If the alkyl group in the alkylene oxide structure is too long, the hydrophobicity becomes strong, the uniform dispersibility in the coating solution tends to deteriorate, and the antistatic property tends to deteriorate. Particularly preferred is polyethylene oxide. Moreover, the thing of 200-2000 is more preferable in a weight average molecular weight.

  Polyglycerol is a compound in which two or more glycerols are polymerized, and the degree of polymerization is preferably in the range of 2-20. When glycerin is used, transparency 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 to the hydroxyl group of glycerin or polyglycerin.

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

  Moreover, what is preferable as an alkylene oxide or its derivative added to glycerol or polyglycerol is a compound which has ethylene oxide or a propylene oxide structure. If the alkyl chain in the alkylene oxide structure becomes too long, the hydrophobicity becomes strong, the uniform dispersibility in the coating solution tends to deteriorate, and the antistatic property and transparency tend to deteriorate. Particularly preferred is ethylene oxide. The number of additions is preferably in the range of 250 to 2000 in terms of the number average molecular weight as the final compound, and more preferably in the range of 300 to 1000.

  Moreover, in the formation of the second coating layer of the film of the present invention, a release agent can be used in combination for improving scratch resistance and slipperiness. Examples of the release agent include waxes, fluorine compounds, long chain alkyl compounds, silicone compounds, and the like. The combined use of the release agent can be suitably used particularly for applications in which various surface functional layers are not provided on the second coating layer.

  Moreover, in the range which does not impair the main point of this invention, it is also possible to use a particle together with the formation of the 2nd coating layer of the film of this invention for the purpose of the blocking property of a coating layer, slipperiness improvement, etc.

  Furthermore, as long as it does not impair the gist of the present invention, the above-mentioned coating layer is formed with an antifoaming agent, a coating property improver, a thickener, an organic lubricant, an ultraviolet absorber, an antioxidant, a foam as necessary. Agents, dyes, pigments and the like can be used.

  As a ratio with respect to all the non-volatile components in the coating liquid forming the second coating layer constituting the laminated polyester film in the present invention, the antistatic agent is usually in the range of 1 wt% or more, preferably in the range of 10 to 80 wt%. More preferably, it is in the range of 20 to 60% by weight. When the amount is less than 1% by weight, the antistatic property is not sufficient, and dust may be attached, or handling may be deteriorated due to sticking of a film. However, when a conductive polymer is used as the antistatic agent, it is usually in the range of 0.1% by weight or more, preferably in the range of 0.5 to 80% by weight, more preferably in the range of 1 to 60% by weight. If it is less than% by weight, the antistatic property is not sufficient, and dust adhesion may occur, or handling may be deteriorated due to sticking of the film. In addition, when the amount is large, there is a concern that the cost increases.

  Analysis of the final form of the non-heat-resistant particles used for forming the first coating layer, and other components in the first and second coating layers, for example, TOF-SIMS, ESCA, fluorescent X-rays, various surfaces, It can be performed by cross-sectional observation or the like.

  When the second coating layer is provided by in-line coating, the above-mentioned series of compounds is applied as an aqueous solution or water dispersion, and a coating solution adjusted to a solid content concentration of about 0.1 to 50% by weight is applied onto the polyester film. It is preferable to produce a polyester film as described above. Moreover, in the range which does not impair the main point of this invention, a small amount of organic solvents may be contained in the coating liquid for the purpose of improving dispersibility in water, improving film-forming properties, and the like. Only one type of organic solvent may be used, or two or more types may be used as appropriate.

Respect laminated polyester film of the present invention, the coating amount of the second coating layer provided on the polyester film is usually 0.002~1.0g / ^{m 2,} more preferably 0.005 to 0.5 / ^{m 2,} further Preferably it is the range of 0.01-0.2 g / m < ² >. If the coating amount is less than 0.002 g / m ^2, sufficient adhesion may not be obtained, and if it exceeds 1.0 g / m ² , the appearance, transparency, and film blocking properties may be deteriorated. There is sex.

  In the present invention, the method of providing the second coating layer includes, for example, gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, Conventionally known coating methods such as impregnation coating, kiss coating, spray coating, calendar coating, and extrusion coating can be used.

  In the present invention, the drying and curing conditions for forming the second coating layer on the polyester film are not particularly limited. For example, when the coating layer is provided by off-line coating, it is usually 3 at 80 to 250 ° C. The heat treatment should be performed for ˜40 seconds, preferably 100 to 180 ° C. for 3 to 40 seconds.

  On the other hand, when forming a 2nd application layer by in-line coating, it is good to heat-process normally for 3 to 200 seconds at 70-270 degreeC.

  Further, irrespective of off-line coating or in-line coating, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination as required. The polyester film constituting the polyester film in the present invention may be subjected to surface treatment such as corona treatment or plasma treatment in advance.

  The polyester film in the present invention can be used for applications requiring excellent transparency, and its internal haze is preferably in the range of 0.0 to 1.0%, more preferably 0.0 to 0.5%. More preferably, it is 0.0 to 0.3% of range. When the internal haze exceeds 1.0%, even if various surface functional layers are provided on the film, the haze cannot be sufficiently lowered, and the whitish color remains as a film. Cannot be achieved.

  The haze of the polyester film in the present invention cannot be generally stated when various surface functional layers are provided on the film because the surface haze can be lowered, but is preferably in the range of 0.0 to 2.0%, more preferably. Is in the range of 0.0 to 1.5%, more preferably in the range of 0.0 to 1.0%. If it exceeds 2.0%, the appearance of the film may be poor, or even if various surface functional layers are provided, the haze cannot be lowered sufficiently, and the visibility may be insufficient.

The surface resistivity of the second coating layer in the film of the present invention is preferably in the range of 1 × 10 ¹² Ω or less, more preferably in the range of 1 × 10 ¹¹ Ω or less, and still more preferably in the range of 1 × 10 ¹⁰ Ω or less. is there. When the surface resistivity exceeds 1 × 10 ¹² Ω, the film is not sufficiently static-proof, so that sticking of a film or adhesion of dust may occur.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. The measurement method and evaluation method used in the present invention are as follows.

(1) Measuring method of intrinsic viscosity of polyester 1 g of polyester from which other polymer components and pigments incompatible with polyester have been removed are weighed accurately, and 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) is added. And dissolved at 30 ° C.

(2) Measuring method of average particle diameter of particles The film was observed using an electron microscope (S-4500 manufactured by HITACHI), and the average value of the particle diameters of 10 particles was defined as the average particle diameter. The non-heat resistant particles were observed on the film before the high temperature process, that is, after the longitudinal stretching and before the transverse stretching.

(3) Measuring method of internal haze Using haze meter HZ-2 manufactured by Suga Test Instruments Co., Ltd., the film was immersed in ethanol and measured according to JIS K 7136.

(4) Measuring method of haze It measured by JISK7136 using the haze meter HM-150 by Murakami Color Research Laboratory.

(5) Film surface roughness (Sa)
Using a three-dimensional non-contact surface shape measurement system (MN537N-M100, manufactured by Ryoka System Co., Ltd.), the roughness Sa of the film on the cooled and solidified surface side before the high-temperature process, that is, after the longitudinal stretching and before the transverse stretching is determined. It was measured. When the Sa is less than 5 nm, the slipperiness is poor, and there is a concern that scratches may occur when coming into contact with a roll or the like in a stretching process or the like. A more preferable form is 5 nm or more.

(6) Transparency evaluation method When the film is visually observed under a three-wavelength light region type fluorescent lamp, the particle feeling (dots due to particles in the film) is not observed and there is a clear feeling. The case where there was a particle feeling or the case where whitishness was observed was taken as x.

(7) Method of measuring surface resistivity of second coating layer Based on the method of (7-1) below, the surface resistivity of the second coating layer was measured. In the method (7-1), since the surface resistivity lower than 1 × 10 ⁸ Ω cannot be measured sufficiently, the method (7-2) was used for the sample that could not be measured in (7-1).
(7-1) A high resistance measuring instrument manufactured by Hewlett-Packard Japan: HP4339B and measuring electrode: HP16008B were used, and the polyester film was fully conditioned in a measurement atmosphere of 23 ° C. and 50% RH, and then applied at an applied voltage of 100V. The surface resistance value of the second coating layer after a minute was measured.
(7-2) Mitsubishi Chemical's low resistivity meter: Loresta GP MCP-T600, the sample was conditioned for 30 minutes in a measurement atmosphere of 23 ° C. and 50% RH, and then the surface resistivity of the second coating layer was determined. It was measured.

(8) Method for evaluating dust adhesion of second coating layer After the humidity of the polyester film is sufficiently adjusted in a measurement atmosphere of 23 ° C. and 50% RH, the second coating layer is rubbed 10 times with a cotton cloth. This was brought close to the finely crushed cigarette ash and the ash adhesion was evaluated according to the following criteria.
○: Even if the film is brought into contact with ash, it does not adhere. Δ: When the film is brought into contact with ash, it adheres a little.

(9) Method of measuring softening point Using a flow tester CFT-500D manufactured by Shimadzu Corporation, the temperature at which half of the non-heat resistant particles flowed out was measured as the softening point.

The polyester used in the examples and comparative examples was prepared as follows.
<Method for producing polyester (A)>
100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, 30 ppm of ethyl acid phosphate with respect to the resulting polyester, and 100 ppm of magnesium acetate tetrahydrate with respect to the resulting polyester as the catalyst at 260 ° C. in a nitrogen atmosphere at 260 ° C. The reaction was allowed to proceed. Subsequently, 50 ppm of tetrabutyl titanate was added to the produced polyester, the temperature was raised to 280 ° C. over 2 hours and 30 minutes, the pressure was reduced to 0.3 kPa in absolute pressure, and melt polycondensation was further performed for 80 minutes to obtain the intrinsic viscosity. 0.63 polyester (A) was obtained.

<Method for producing polyester (B)>
100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, and magnesium acetate tetrahydrate as a catalyst were subjected to an esterification reaction at 225 ° C. in a nitrogen atmosphere at 900 ppm with respect to the produced polyester. Subsequently, 3500 ppm of orthophosphoric acid was added to the produced polyester, and 70 ppm of germanium dioxide was added to the produced polyester. The temperature was raised to 280 ° C. over 2 hours and 30 minutes, and the pressure was reduced to an absolute pressure of 0.4 kPa. After 85 minutes of melt polycondensation, polyester (B) having an intrinsic viscosity of 0.64 was obtained.

<Method for producing polyester (C)>
In the production method of the polyester (A), the same method as the production method of the polyester (A) is used except that 0.5% by weight of silica particles having an average particle size of 0.1 μm is added to the produced polyester before melt polymerization. Thus, polyester (C) was obtained.

<Method for producing polyester (D)>
In the production method of polyester (A), the same method as the production method of polyester (A) is used except that 0.5% by weight of silica particles having an average particle diameter of 3.2 μm is added to the produced polyester before melt polymerization. Thus, polyester (D) was obtained.

Examples of compounds constituting each coating layer are as follows.
(Example compounds)
Non-heat-resistant particles: (IA) Non-heat-resistant non-crosslinked acrylic particles having an average particle size of 0.09 μm, a softening point of 210 ° C., and a glass transition point of 60 ° C. copolymerized with a composition of methyl methacrylate / butyl acrylate = 80/20 Non-heat-resistant particles: (IB) Non-heat-resistant non-crosslinked styrene / acrylic resin particles having an average particle size of 0.37 μm, a softening point of 220 ° C., and a glass transition point of 110 ° C., copolymerized with a composition of methyl methacrylate / styrene = 70/30 Silica particles: (IC) Silica particles having an average particle size of 0.30 μm Silica particles: (ID) Silica particles having an average particle size of 0.07 μm

・ Polyester resin: (IIA)
Water dispersion of polyester resin copolymerized with the following composition: Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene glycol / 1,4-butanediol / diethylene glycol = 56/40/4 // 70/20/10 (mol%)

・ Acrylic resin: (IIB)
Aqueous dispersion of acrylic resin polymerized with the following composition: Emulsion polymer of ethyl acrylate / n-butyl acrylate / methyl methacrylate / N-methylol acrylamide / acrylic acid = 65/21/10/2/2 (% by weight) (emulsifier: Anionic surfactant)

・ Urethane resin (IIC)
Water of polyester polyurethane resin formed from isophorone diisocyanate unit: terephthalic acid unit: isophthalic acid unit: ethylene glycol unit: diethylene glycol unit: dimethylolpropanoic acid unit = 12: 19: 18: 21: 25: 5 (mol%) Dispersion.

・ Polyvinyl alcohol: (IID)
Polyvinyl alcohol having a saponification degree of 88 mol% and a polymerization degree of 500

・ Acrylic resin: (IIE)
Emulsion polymer of ethyl acrylate / n-butyl acrylate / N-methylol acrylamide / acrylic acid = 88/10/1/1 (wt%) (emulsifier: nonionic surfactant)

・ Hexamethoxymethylolmelamine (IIIA)

・ Oxazoline compounds: (IIIB)
Acrylic polymer having oxazoline group and polyalkylene oxide chain EPOCROS (registered trademark) (oxazoline group amount = 4.5 mmol / g, manufactured by Nippon Shokubai Co., Ltd.)

・ Antistatic agent (conductive polymer): (IVA)
An Orgacon ICP1010 manufactured by Agfa Gebalt, made of polyethylene dioxythiophene and polystyrene sulfonic acid.

・ Antistatic agent (quaternary ammonium salt compound): (IVB)
Polymer polymerized with the following composition having a pyrrolidinium ring in the main chain: Diallyldimethylammonium chloride / dimethylacrylamide / N-methylolacrylamide = 90/5/5 (mol%). Number average molecular weight 30000.

・ Polyether compounds: (V)
Polyethylene oxide adduct to diglycerin structure, number average molecular weight 350.

Example 1:
A mixed raw material in which polyesters (A) and (B) are mixed at a ratio of 97% and 3%, respectively, is used as a raw material for the outermost layer (surface layer), and polyesters (A) and (B) are respectively at a ratio of 97% and 3%. Each of the mixed raw materials is fed to two extruders as a raw material for the intermediate layer, melted at 285 ° C., and then two types and three layers (surface layer / intermediate layer / A non-stretched film was obtained by co-extrusion and cooling solidification with a layer structure of (surface layer = 1: 6: 1 discharge amount). Thereafter, an aqueous coating solution A1 shown in Table 1 below was applied to both sides of the unstretched film and dried to obtain a film having a first coating layer having a coating amount (after drying) of 0.2 g / m ² . Next, the film was stretched 3.4 times in the longitudinal direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then the aqueous coating solution B1 shown in Table 2 below was applied to both surfaces of the longitudinally stretched film. Then, the film was stretched 4.0 times at 120 ° C. in the transverse direction and heat-treated at 230 ° C., and then relaxed by 2% in the transverse direction, and the coating amount of the coating layer (after drying and stretching) was 0.03 g / m ^2. A polyester film having a thickness of 50 μm and having a second coating layer was obtained. When the obtained polyester film was evaluated, the transparency was good, the roughness of the film after longitudinal stretching was sufficient, and the surface resistivity was low and good. The properties of this film are shown in Table 5 below.

Examples 2 to 19:
In Example 1, it manufactured like Example 1 except having changed an application agent composition into an application agent composition shown in Tables 1-3, and obtained a polyester film. As shown in Table 5 below, the finished polyester film had good transparency, sufficient film roughness after longitudinal stretching, and good low surface resistivity.

Example 20:
A mixed raw material in which polyesters (A), (B), and (C) were mixed at a ratio of 96%, 3%, and 1%, respectively, was used as a raw material for the outermost layer (surface layer), and polyesters (A) and (B) were each 97 %, 3% of the mixed raw material is used as an intermediate layer raw material, each is supplied to two extruders, melted at 285 ° C., and then on a cooling roll set at 40 ° C. The film was coextruded and cooled and solidified with a layer structure of layers (surface layer / intermediate layer / surface layer = 1: 6: 1 discharge amount) to obtain an unstretched film. Thereafter, an aqueous coating solution A1 shown in Table 1 below was applied to both sides of the unstretched film and dried to obtain a film having a first coating layer having a coating amount (after drying) of 0.2 g / m ² . Next, the film was stretched 3.4 times in the longitudinal direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then the aqueous coating solution B1 shown in Table 2 below was applied to both surfaces of the longitudinally stretched film. Then, the film was stretched 4.0 times at 120 ° C. in the transverse direction and heat-treated at 230 ° C., and then relaxed by 2% in the transverse direction, and the coating amount of the coating layer (after drying and stretching) was 0.03 g / m ^2. A polyester film having a thickness of 50 μm and having a second coating layer was obtained. When the obtained polyester film was evaluated, the transparency was good, the roughness of the film after longitudinal stretching was sufficient, and the surface resistivity was low and good. The properties of this film are shown in Table 5 below.

Comparative Example 1:
In Example 1, it manufactured like Example 1 except not providing a 1st coating layer in an unstretched film, and obtained the polyester film. When the finished polyester film was evaluated, as shown in Table 6 below, the film after longitudinal stretching had a small roughness and was likely to be damaged.

Comparative Examples 2-4:
In Example 1, it manufactured like Example 1 except having changed a coating agent composition into the coating agent composition shown in following Table 1, 2, 4, and obtained the polyester film. As shown in Table 6, the finished polyester film has a high haze and is whitish as a film, or when the film is not sufficiently rough after longitudinal stretching, or has a high surface resistivity and is antistatic. Some cases were inferior in nature.

Comparative Example 5
A mixed raw material in which polyesters (A), (B), and (D) were mixed at a ratio of 92%, 3%, and 5%, respectively, was used as a raw material for the outermost layer (surface layer), and polyesters (A) and (B) were each 97 %, 3% of the mixed raw material is used as an intermediate layer raw material, each is supplied to two extruders, melted at 285 ° C., and then on a cooling roll set at 40 ° C. The film was coextruded and cooled and solidified with a layer structure of layers (surface layer / intermediate layer / surface layer = 1: 6: 1 discharge amount) to obtain an unstretched film. Next, the film was stretched 3.4 times in the longitudinal direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then the aqueous coating solution B1 shown in Table 2 below was applied to both surfaces of the longitudinally stretched film. Then, the film was stretched 4.0 times at 120 ° C. in the transverse direction and heat-treated at 230 ° C., and then relaxed by 2% in the transverse direction, and the coating amount of the coating layer (after drying and stretching) was 0.03 g / m ^2. A polyester film having a thickness of 50 μm was obtained. When the obtained polyester film was evaluated, a particle feeling was observed and the film was whitish. The properties of this film are shown in Table 6 below.

  The film of this invention has the outstanding transparency and antistatic property, for example, can be utilized suitably for uses, such as a protective film used in the process of polarizing plate manufacture.

Claims (1)

After applying a coating liquid containing particles having a softening point of 120 to 270 ° C. on at least one side of the unstretched polyester film, the coating layer is formed by stretching in at least one direction. A laminated polyester film comprising a coating layer containing an antistatic agent.