JP2017179023A - Laminate polyester film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate polyester film suppressing ester cyclic trimer precipitated from a film when exposed to a high temperature, and generating no defect associated with the ester cyclic trimer during film storing, film using, film processing or the like.SOLUTION: There is provided a laminate polyester film which is a polymer resin having a monomer with an acidic group of 5 mol% or more and has a layer formed from a coating liquid containing a resin having a (meth)acrylic acid ester and a melamine compound on at least a single sided surface of the polyester film.SELECTED DRAWING: None

Description

  The present invention relates to a laminated polyester film in which oligomers (low molecular weight components of polyester, particularly ester cyclic trimers) are less precipitated even after being exposed to a high temperature, for example.

  Polyester films are excellent in transparency, dimensional stability, mechanical properties, heat resistance, electrical properties, etc., and are used in various fields.

  In particular, in recent years, use as a base material for transparent conductive laminates, which are increasingly used for touch panels and the like, is increasingly used instead of glass. As such a transparent conductive laminate, there is one in which a polyester film is used as a base material and an ITO (indium tin oxide) film is formed by sputtering directly or via an anchor layer. Such a biaxially stretched polyester film is generally heat-processed.

  For example, there are treatments such as leaving for 1 hour at 150 ° C. for low heat shrinkage (Patent Document 1) and performing heat treatment at 150 ° C. for crystallization of ITO (Patent Document 2).

  However, as a problem of the polyester film, when exposed to such high temperature and long time treatment, the ester cyclic trimer contained in the film precipitates and crystallizes on the film surface. Decrease in visibility, post-processing defects, in-process and member contamination, etc. occur. Therefore, the characteristics of the transparent conductive laminate based on the polyester film cannot be said to be sufficiently satisfactory.

  Further, as a measure for preventing the precipitation of the ester cyclic trimer, for example, it is proposed to provide a curable resin layer made of a crosslinked product of a silicone resin and an isocyanate resin on a polyester film (Patent Document 3). However, the curable resin layer is formed by thermosetting, requires high-temperature treatment for dissociation of the blocking agent of the isocyanate resin, and is in a situation where curling and sagging are likely to occur during processing. Care must be taken in handling.

  Therefore, when taking measures to reduce the amount of ester cyclic trimer deposited by the coating layer, the coating layer itself has better heat resistance and the sealing performance of the ester cyclic trimer of the coating layer itself is better. It is in a situation where it is necessary.

JP 2007-42473 A JP 2007-200823 A JP 2007-320144 A

  The present invention has been made in view of the above circumstances, and the problem to be solved is to suppress, for example, ester cyclic trimers that are precipitated from the film when exposed to high temperatures. An object of the present invention is to provide a laminated polyester film that does not cause problems associated with ester cyclic trimers during processing.

  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 specific coating layer, and have completed the present invention.

  That is, the gist of the present invention is a polymer resin having 5 mol% or more of an acid group-containing monomer, and is formed from a coating solution containing a resin having a (meth) acrylate structure and a melamine compound. It exists in the laminated polyester film characterized by having a layer in the at least single side | surface of a polyester film.

  According to the laminated polyester film of the present invention, since the precipitation of the ester cyclic trimer from the surface is suppressed even after high-temperature and long-time treatment, an excellent appearance with no haze increase or generation of foreign matters Can be obtained, and its industrial utility value is high.

  The polyester film constituting the laminated 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 it does not exceed the gist of the present invention other than a two-layer or three-layer structure. It may be a multilayer, and is not particularly limited. It is preferable to have a multi-layer structure of two or more layers and to give each layer a characteristic so as to achieve multiple functions.

  The base film of the laminated polyester film of the present invention is made of polyester. Such polyester 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, the dicarboxylic acid component of the copolyester includes isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, p-oxybenzoic acid, etc.), etc. 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, titanium compounds and germanium compounds are preferable because they have high catalytic activity and can be polymerized in a small amount, and since the amount of metal remaining in the film is small, the transparency of the film becomes high. The compound is preferable because it is inexpensive.

  In this invention, in order to suppress the precipitation amount of the ester cyclic trimer after heat processing, manufacturing a film from polyester with little content of ester cyclic trimer is mentioned. Various known methods can be used as a method for producing a polyester having a low ester cyclic trimer content. Examples thereof include a method of solid-phase polymerization after polyester production.

  Precipitation of ester cyclic trimer after heat treatment by designing a layer using a polyester raw material with a low content of ester cyclic trimer in the outermost polyester layer of the polyester film, with a polyester film comprising three or more layers A method of reducing the amount is also possible.

  In the polyester layer of the film of the present invention, particles can be blended mainly for the purpose of imparting slipperiness and preventing scratches in each step. 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, zirconium 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. Of these, silica particles and calcium carbonate particles are preferable because they are particularly effective in a small amount.

  Moreover, the average particle diameter of the particles is preferably 5.0 μm or less, and more preferably in the range of 0.01 to 3.0 μm. When the average particle diameter exceeds 5.0 μm, the surface roughness of the film becomes too rough, and problems may occur in various processes in the subsequent steps. Moreover, by using in the said range, haze is restrained low and it is easy to ensure transparency as the whole film.

  Further, the particle content in the polyester layer is preferably less than 5% by weight, more preferably in the range of 0.0003 to 1% by weight, and still more preferably in the range of 0.0005 to 0.5% by weight. When there are no or few particles, the transparency of the film becomes high and the film becomes a good film, but the slipperiness may be insufficient. There are cases where improvement is required. In addition, when the particle content is high, haze increases and lacks transparency. For example, during various inspections, defects such as difficulty of defect inspection for foreign matters may occur.

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.

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

  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, when producing a biaxially stretched polyester film, the polyester raw material described above is first melt-extruded from a die using an extruder, and the molten sheet is cooled and solidified with a cooling roll to obtain an unstretched sheet. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum, and an electrostatic application adhesion method or a liquid application adhesion method is preferably employed. Next, the obtained unstretched sheet is stretched in one direction by a roll or a 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-stage stretching direction at usually 70 to 170 ° C. and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times. Subsequently, a method of obtaining a biaxially oriented film by performing heat treatment at a temperature of 180 to 270 ° C. under tension or under relaxation within 30% is mentioned. 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 laminated polyester film. The simultaneous biaxial stretching method is a method in which the above-mentioned unstretched sheet is usually stretched and oriented in the machine direction and the width direction at a temperature controlled normally at 70 to 120 ° C., preferably 80 to 110 ° C. Is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times in terms of area magnification. Subsequently, heat treatment is performed at a temperature of 180 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.

  Next, formation of the coating layer which comprises the laminated polyester film in this invention is demonstrated. Regarding the coating layer, it may be provided by in-line coating which treats the film surface during the process of forming a polyester film, or offline coating which is applied outside the system on a once produced film may be adopted. More preferably, it is formed by in-line coating.

  In-line coating is a method of coating within the process of manufacturing a polyester film, and specifically, a method of coating at any stage from melt extrusion of a polyester to heat setting after stretching and winding up. Usually, coating is performed on either an unstretched sheet obtained by melting and rapid cooling, or a stretched uniaxially stretched film.

  Although not limited to the following, for example, in sequential biaxial stretching, a method of stretching in the transverse direction after coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) is particularly excellent. According to such a method, film formation and coating layer formation can be performed at the same time, so there is an advantage in manufacturing cost. In addition, in order to perform stretching after coating, the thickness of the coating layer can be changed by the stretching ratio. Compared to offline coating, thin film coating can be performed more easily.

  Further, by providing the coating layer on the film before stretching, the coating layer can be stretched together with the base film, whereby the coating layer can be firmly adhered to the base film. Furthermore, in the production of a biaxially stretched polyester film, the film can be restrained in the longitudinal and lateral directions by stretching while gripping the film end with a clip, etc. High temperature can be applied while maintaining the properties.

  Therefore, since the heat treatment performed after coating can be performed at a high temperature that cannot be achieved by other methods, the film forming property of the coating layer is improved, and the coating layer and the base film can be more firmly adhered to each other. Furthermore, a strong coating layer can be obtained.

  The coating layer of the present invention is a polymer resin having a monomer having an acid group of 5 mol% or more, and a layer formed from a coating solution containing a resin having a (meth) acrylic acid ester structure and a melamine compound. Is an essential requirement to have at least one side of the polyester film. The coating layer may contain compounds derived from other components.

  Hereinafter, acrylic acid and methacrylic acid may be abbreviated as (meth) acrylic acid.

  The (meth) acrylic acid ester structure is a derivative in which a substituent is introduced into (meth) acrylic acid ester or (meth) acrylic acid ester.

  As (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-i-propyl, (meth) acrylic acid-n -Butyl, (meth) acrylic acid-i-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-i-octyl, (meth) acrylic acid-t -C1-C18 alkyl esters of acrylic acid and / or methacrylic acid such as octyl, (meth) acrylic acid-2-ethylhexyl, etc., and other C5-C12 cyclocarbons such as cyclohexyl acrylate Examples thereof include cycloalkyl esters and aralkyl esters having 7 to 12 carbon atoms of benzyl acrylate. Among these, from the viewpoint of the effect of preventing precipitation of the ester cyclic trimer by heat treatment, acrylic acid esters and methacrylic acid esters having an alkyl group having 4 or less carbon atoms at the terminal end of the ester are preferably used.

  The monomer having an acid group is an unsaturated compound containing one or more carboxyl groups, sulfonic acid groups, and phosphoric acid groups in the molecule. From the viewpoint of the effect of preventing precipitation of the ester cyclic trimer by heat treatment, a monomer having a carboxyl group is preferred.

  Monomers having an acid group include monomers having a carboxylic acid group such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and itaconic acid, sulfonic acid, xylene sulfonic acid, mesitylene sulfonic acid, and naphthalene. Examples thereof include monomers having a sulfonic acid such as sulfonic acid, and monomers having a phosphoric acid group such as phosphoric acid, diphosphoric acid, dimethylphosphoric acid, and dimethylallyldiphosphoric acid. From the viewpoint of the effect of preventing precipitation of the ester cyclic trimer by heat treatment, acrylic acid or methacrylic acid is preferable, and methacrylic acid is more preferable.

  The resin having 5 mol% or more of the monomer having an acid group, and the resin having a (meth) acrylic acid ester structure include other monomers capable of copolymerizing with the monomer having an acid group and the (meth) acrylic acid structure. It is also possible to combine polymerizable monomers. Examples of the copolymerizable monomer include various nitrogen-containing compounds such as (meth) acrylamide, diacetone acrylamide, N-methylol acrylamide or (meth) acrylonitrile, and various vinyls such as vinyl propionate and vinyl acetate. Esters; various silicon-containing polymerizable monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, etc .; phosphorus-containing vinyl monomers; various vinyl halides such as vinyl chloride and biridene chloride And various conjugated dienes such as butadiene.

  It is essential that the ratio of the monomer having an acid group in the resin having a (meth) acrylic acid ester structure is 5 mol% or more, which is a polymer resin having 5 mol% or more of the monomer having an acid group, Preferably it is 10-90 mol%, More preferably, it is 25-70 mol%, More preferably, it is the range of 40-60 mol%. When the ratio of the monomer having an acid group is less than 5 mol%, precipitation of the ester cyclic trimer by heat treatment cannot be effectively suppressed.

  As a ratio in the coating layer constituting the laminated polyester film in the present invention, the polymer resin having a monomer group having an acid group and having a (meth) acrylic acid ester structure is usually 1% by weight or more, Preferably it is 5 to 80 weight%, More preferably, it is 10 to 70 weight%, More preferably, it is the range of 25 to 40 weight%. When the amount is less than 1% by weight, precipitation of the ester cyclic trimer by heat treatment cannot be effectively suppressed. By using in the said range, precipitation of the ester cyclic | annular trimer on the film surface by heat processing can be suppressed.

  The melamine compound contained in the coating layer of the film of the present invention is a compound having a melamine skeleton in the compound. For example, an alcohol is reacted with an alkylolated melamine derivative or an alkylolated melamine derivative to partially Alternatively, fully etherified compounds and mixtures thereof 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.

  As a ratio in the coating layer which comprises the laminated polyester film in this invention, a melamine compound is 1 weight% or more normally, Preferably it is 10 to 90 weight%, More preferably, it is 20 to 80 weight%, More preferably, it is 35 to 70 weight%. % Range. When the amount is less than 1% by weight, precipitation of the ester cyclic trimer by heat treatment cannot be effectively suppressed. By using in the said range, precipitation of the ester cyclic | annular trimer on the film surface by heat processing can be suppressed. Moreover, when using an epoxy compound together as a crosslinking agent, precipitation of the ester cyclic trimer to the film surface by heat processing can be suppressed even if a melamine compound is 35 weight% or less.

  In the formation of the coating layer of the film of the present invention, various known crosslinking agents other than the melamine compound can be used in combination in order to reduce film haze or improve the adhesiveness with the topcoat layer when a topcoat layer is provided. is there. Known crosslinking agents include epoxy compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, silane coupling compounds, and the like. Among these, from the viewpoint of reducing the film haze, an epoxy compound, an isocyanate compound, and a carbodiimide compound are preferably used, and more particularly, an epoxy compound is preferably used from the viewpoint of suppressing precipitation of an ester cyclic trimer. However, when a large amount of a crosslinking agent other than a melamine compound other than epoxy is used in combination, precipitation of the ester cyclic trimer cannot be effectively suppressed.

  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 isocyanate compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate. Examples of the 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, 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 to improve adhesion with various surface functional layers that can be formed on a coating layer and to improve the heat and humidity resistance of the coating layer. is there. 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.

  A carbodiimide-based compound is a compound having a carbodiimide structure, and is used to improve adhesion with various surface functional layers that can be formed on a coating layer and to improve the heat and humidity resistance of the coating layer. is there. 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.

  The content of the carbodiimide group contained in the carbodiimide compound is a carbodiimide equivalent (weight of the carbodiimide compound to give 1 mol of carbodiimide group [g]), and is usually 100 to 1000, preferably 250 to 800, more preferably 300. It is in the range of ˜650. By using it in the above range, the durability of the coating film is improved.

  As a ratio in the coating layer constituting the laminated polyester film in the present invention, when an epoxy compound is used as a crosslinking agent other than a melamine compound, it is preferably 80% by weight or less, more preferably 60% by weight or less, and further preferably 50% by weight. % Or less. When using a crosslinking agent other than the melamine compound and the epoxy compound, it is preferably 80% by weight or less, more preferably 60% by weight or less, and further preferably 30% by weight or less. When it exceeds 80% by weight, precipitation of the ester cyclic trimer by heat treatment cannot be effectively suppressed.

  Further, in the formation of the coating layer of the film of the present invention, a polymer can be used in combination for improving the coating appearance. However, when used in combination, if the amount is too large, precipitation of the ester cyclic trimer by heat treatment may not be effectively suppressed.

  Specific examples of the polymer include a resin containing a (meth) acrylic acid ester structure composed of a monomer having no acid group of 5 mol% or more, a polyester resin, a urethane resin, polyvinyl (polyvinyl alcohol, etc.), and conductive. Examples include polymers, polyalkylene glycols, polyalkyleneimines, methylcellulose, hydroxycellulose, and starches.

  In addition, particles can be used in combination for the purpose of blocking and improving slipperiness in forming the coating layer. The average particle diameter is preferably 1.0 μm or less, more preferably 0.5 μm or less, and particularly preferably 0.2 μm or less from the viewpoint of transparency of the film. Further, the lower limit is preferably 0.01 μm or more, more preferably 0.03 μm or more, and particularly preferably a range larger than the film thickness of the coating layer in order to improve the slipperiness more effectively. Specific examples of the particles include silica, alumina, kaolin, calcium carbonate, and organic particles. Among these, silica is preferable from the viewpoint of transparency.

  Furthermore, as long as it does not impair the gist of the present invention, an antifoaming agent, a coating property improver, a thickener, an organic lubricant, an antistatic agent, an ultraviolet absorber, and an antioxidant are necessary for forming a coating layer. Agents, foaming agents, dyes, pigments and the like can be used in combination.

  The thickness of the coating layer is usually in the range of 0.003 μm to 1 μm, preferably 0.005 μm to 0.5 μm, more preferably 0.00 as the thickness of the coating layer on the finally obtained film. It is in the range of 01 μm to 0.2 μm. When the thickness is less than 0.003 μm, the amount of ester cyclic trimer precipitated from the film may not be sufficiently reduced. On the other hand, when the thickness is larger than 1 μm, problems such as deterioration of the appearance of the coating layer and easy blocking may occur.

  Examples of methods for applying a coating solution to a polyester film include air doctor coating, blade coating, rod coating, bar coating, knife coating, squeeze coating, impregnation coating, reverse roll coating, transfer roll coating, gravure coating, and kiss roll coating. Conventional coating methods such as cast coating, spray coating, curtain coating, calendar coating, and extrusion coating can be used.

  In order to improve the applicability and adhesion of the coating agent to the film, the film may be subjected to chemical treatment, corona discharge treatment, plasma treatment or the like before coating.

  For the laminated polyester film in the present invention, for example, for a touch panel, a high degree of transparency may be required even after being exposed to a high temperature atmosphere for a long time. The initial film haze is preferably 5.0% or less, more preferably 3.0% or less, and still more preferably 1.5% or less. When the initial film haze exceeds 5.0%, the visibility is poor and may be inappropriate for applications that require high visibility, such as for touch panels.

  From this point of view, in order to cope with high transparency, the film haze change amount in heat treatment (150 ° C., 90 minutes) is preferably 1.0% or less, more preferably 0.7% or less, and still more preferably It is 0.0 to 0.5% of range. When the amount of change in film haze exceeds 1.0%, the visibility decreases as the film haze rises due to the precipitation of the ester cyclic trimer. For example, for a touch panel, a high degree of visibility is required. It may be inappropriate for the application.

Further, from the viewpoint of the precipitation amount of the ester cyclic trimer, the amount of the ester cyclic trimer extracted from the film surface by dimethylformamide by heat treatment (150 ° C., 90 minutes) of the laminated polyester film in the present invention is preferably 1.0 mg / ^{m 2} or less, more preferably 0.8 mg / ^{m 2} or less, more preferably 0.0~0.6mg / ^{m 2} or less. In the case where it exceeds 1.0 mg / m ² , in the subsequent step, for example, the precipitation amount of the ester cyclic trimer increases with heat treatment in a high temperature atmosphere such as 150 ° C. for 90 minutes, and the transparency of the film There is a concern that the yield may be greatly reduced due to a decrease in the performance or contamination of the process.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to a following example, unless the summary is exceeded. In addition, the evaluation method in an Example and a comparative example is as follows.

(1) Method for measuring the intrinsic viscosity of polyester 1 g of polyester from which other polymer components and pigments incompatible with polyester have been removed are precisely weighed, 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 size (d50: μm) Integration (weight basis) 50% in equivalent spherical distribution measured using centrifugal sedimentation type particle size distribution measuring device (SA-CP3 type manufactured by Shimadzu Corporation) Was the average particle size.

(3) Measuring method of film thickness of coating layer The surface of the coating layer was dyed with RuO ₄ and embedded in an epoxy resin. Thereafter, the section prepared by ultramicrotomy stained with RuO _4, a coating layer cross-section was measured by using a TEM (Hitachi High Technologies Corporation H-7650, accelerating voltage 100 kV).

(5) Heat treatment method of the film The sample is fixed with the Kent paper in a state where the measurement surface of the sample is exposed, and is left to stand at 150 ° C. for 90 minutes in a nitrogen atmosphere for heat treatment.

(6) Measuring method of film haze Film haze was measured for the sample film according to JIS-K-7136 with a haze meter “HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd.

(7) Method for measuring change in film haze by heat treatment On the surface of the polyester film opposite to the surface provided with the coating layer to be measured, 80 parts by weight of dipentaerythritol hexaacrylate, 2-hydroxy-3-phenoxy A mixed coating solution of 20 parts by weight of propyl acrylate, 5 parts by weight of a photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 200 parts by weight of methyl ethyl ketone was applied so that the dry film thickness was 3 μm. And cured to form a hard coat layer. The haze of the film on which the hard coat layer was formed was measured by the method (5). Subsequently, after heating by the method of (4) term, haze was measured by the method of (5). The difference between the haze after heat treatment and the haze before heat treatment was calculated and used as the amount of change in film haze. The lower the film haze change amount, the less the ester cyclic trimer is precipitated by the high temperature treatment, which is better.

(8) Measurement of amount of ester cyclic trimer deposited on the surface of the laminated polyester film The polyester film is heated in air at 150 ° C. for 90 minutes. Thereafter, the heat-treated film is formed into a box shape with the measurement surface (coating layer) as the inner surface so that the upper part is 10 cm in length and width and the height is 3 cm. Next, 4 ml of DMF (dimethylsulfoamide) was placed in the box prepared by the above method and allowed to stand for 3 minutes, and then DMF was recovered and subjected to liquid chromatography (manufactured by Shimadzu Corporation: LC-7A, mobile phase A: Acetonitrile, mobile phase B: 2% aqueous acetic acid solution, column: “MCI GEL ODS 1HU” manufactured by Mitsubishi Chemical Corporation, column temperature: 40 ° C., flow rate: 1 ml / min, detection wavelength: 254 nm) The amount of the ester cyclic trimer was determined, and this value was divided by the film area in contact with DMF to obtain the amount of the film surface ester cyclic trimer (mg / m ² ). The ester cyclic trimer in DMF was determined from the peak area ratio between the standard sample peak area and the measured sample peak area (absolute calibration curve method). The standard sample was prepared by accurately weighing the pre-sorted ester cyclic trimer and dissolving it in accurately measured DMF.

The polyester used in the examples and comparative examples was prepared as follows.
<Method for producing polyester (A)>
Using 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol as starting materials, 0.09 parts by weight of magnesium acetate tetrahydrate as a catalyst is placed in the reactor, the reaction start temperature is set to 150 ° C., and the methanol is distilled off gradually. The reaction temperature was raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially terminated. After adding 0.04 part by weight of ethyl acid phosphate to this reaction mixture, 0.04 part by weight of antimony trioxide was added, and a polycondensation reaction was carried out for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.63 due to a change in stirring power of the reaction tank, and the polymer was discharged under nitrogen pressure. The intrinsic viscosity of the obtained polyester (A) was 0.63.

<Method for producing polyester (B)>
In the polyester (A) production method, after adding 0.04 part by weight of ethyl acid phosphate, 0.2 part by weight of silica particles having an average particle diameter of 2 μm and 0.04 part by weight of antimony trioxide are added to obtain the intrinsic viscosity. A polyester (B) was obtained using the same method as the production method of the polyester (A) except that the polycondensation reaction was stopped at a time corresponding to 0.65. The obtained polyester (B) had an intrinsic viscosity of 0.65.

Examples of compounds constituting the coating layer are as follows.
-Resin (IA) which is a polymer resin having a monomer having an acid group of 5 mol% or more and having a (meth) acrylate structure:
Acrylic resin copolymerized with methacrylic acid / n-butyl acrylate / n-butyl methacrylate / ethyl acrylate / ethyl methacrylate = 49/14/9/24/4 (mol%). Resin (IB) which is a polymer resin and has a (meth) acrylic acid ester structure:
Acrylic resin copolymerized with methacrylic acid / ethyl acrylate / ethyl methacrylate / isobutyl methacrylate = 37/43/7/13 (mol%). It is a polymer resin having 5 mol% or more of monomers having acid groups, and (meth) Resin having an acrylate structure (IC):
Acrylic resin copolymerized with methacrylic acid / n-butyl acrylate / n-butyl methacrylate / ethyl methacrylate = 25/28/15/32 (mol%). Polymer resin having 5 mol% or more of acid group-containing monomer. Resin (ID) having a (meth) acrylic ester structure:
Acrylic resin copolymerized with methacrylic acid / ethyl acrylate / n-butyl methacrylate / isobutyl methacrylate = 5/20/45/30 (mol%)

Melamine compound (II): hexamethoxymethylol melamine Epoxy compound (IIIA): polyglycerol polyglycidyl ether.
-Carbodiimide compound (IIIB): Polycarbodiimide compound Carbodilite (carbodiimide equivalent = 600, manufactured by Nisshinbo Co., Ltd.)
Isocyanate compound (IIIC): Block polyisocyanate obtained by the following production method 1000 parts of hexamethylene diisocyanate was stirred at 60 ° C., and 0.1 part of tetramethylammonium capryate was added as a catalyst. After 4 hours, 0.2 part of phosphoric acid was added to stop the reaction, and an isocyanurate type polyisocyanate composition was obtained. 100 parts of the obtained isocyanurate type polyisocyanate composition, 42.3 parts of methoxypolyethylene glycol having a number average molecular weight of 400, and 29.5 parts of propylene glycol monomethyl ether acetate were charged and maintained at 80 ° C. for 7 hours. Thereafter, the reaction solution temperature was kept at 60 ° C., 35.8 parts of methyl isobutanoyl acetate, 32.2 parts of diethyl malonate, and 0.88 part of 28% methanol solution of sodium methoxide were added and kept for 4 hours. 58.9 parts of n-butanol was added and held at a reaction solution temperature of 80 ° C. for 2 hours, and then 0.86 part of 2-ethylhexyl acid phosphate was added to obtain a blocked polyisocyanate.

Particle (IV): Silica particles having an average particle size of 0.07 μm Melamine crosslinking catalyst (V): 2-amino-2-methylpropanol hydrochloride Acrylic resin (VIA): acrylic acid / methyl acrylate / ethyl acrylate / isobutyl Acrylic resin copolymerized with methacrylate / = 3/20/38/39 (mol%).
Acrylic resin (VIB): Acrylic resin copolymerized with methyl methacrylate / ethyl methacrylate / hydroxyethyl methacrylate / ethylene glycol = 40/13/30/17 (mol%)

Example 1:
The mixed raw materials obtained by mixing the polyesters (A) and (B) at a ratio of 90% and 10%, respectively, are used as the outermost layer (surface layer) raw material, and only the polyester (A) is used as the intermediate layer raw material in two extruders. Each is supplied, melted at 285 ° C., and then coextruded in a layer configuration of two types and three layers (surface layer / intermediate layer / surface layer = 1: 8: 1 discharge amount) on a cooling roll set at 40 ° C. Cooled and solidified to obtain an unstretched sheet. Next, the film was stretched 3.4 times in the longitudinal direction at a film temperature of 85 ° C. using the difference in peripheral speed of the roll, and then the coating solution 1 shown in Table 1 below was applied to one side of the longitudinally stretched film, which was led to a tenter. Polyester having a thickness of 50 μm having a coating layer having a thickness of 0.05 μm after being stretched 4.3 times at 110 ° C. in the transverse direction and heat-treated at 235 ° C. and then 2% relaxed in the transverse direction. A film was obtained.

  The amount of change in film haze due to heat treatment of the obtained polyester film was small, and the amount of ester cyclic trimer precipitated was small and good. The properties of this film are shown in Table 2 below.

Examples 2-16:
In Example 1, it manufactured similarly to Example 1 except having changed the coating agent composition into the coating agent composition shown in Table 1, and obtained the polyester film. As shown in Table 2, the finished polyester film had a small amount of change in film haze due to heat treatment, and the precipitation amount of the ester cyclic trimer was small and good.

Comparative Example 1:
In Example 1, it manufactured like Example 1 except not providing an application layer, and obtained the polyester film. When the completed laminated polyester film was evaluated, as shown in Table 2, the amount of change in film haze due to heat treatment was greatly increased, and precipitation of ester cyclic trimers was also large.

Comparative Examples 2-5:
A polyester film was obtained in the same manner as in Example 1. When the finished laminated polyester film was evaluated, the amount of change in film haze was greatly increased, and precipitation of the ester cyclic trimer due to heat treatment was large, and there was concern about process contamination.

  The film of the present invention is used for applications that require the performance that the film is exposed to a high temperature atmosphere for a long time, and the increase in film haze is as small as possible and the precipitation of ester cyclic trimer is small even after a severe heat treatment step. For example, the laminated polyester film can be suitably used as a base material of a transparent conductive laminate.

Claims (1)

At least one surface of the polyester film is a polymer resin having 5 mol% or more of an acid group-containing monomer and formed from a coating solution containing a resin having a (meth) acrylic acid ester structure and a melamine compound. A laminated polyester film characterized by comprising: