JP2014205754A - Laminate polyester film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester film that can be suitably used for applications requiring excellent precipitation prevention performance or the like of an ester cyclic trimer after a high-temperature treatment, and for example, a polyester film that can be suitably used for a polarizing plate of a liquid crystal display or a member of a transparent conductive layer of a touch panel.SOLUTION: A laminate polyester film is provided, which has a coating layer formed from a coating liquid containing a compound having an ammonium group on at least one surface of a polyester film, and further has a coating layer formed from a coating liquid containing a crosslinking agent by 30 wt.% or more with respect to a nonvolatile component on the above coating layer.

Description

  The present invention relates to a laminated polyester film, for example, a laminated polyester film that can be used for a polarizing plate of a liquid crystal display, a transparent conductive layer member of a touch panel, etc., and has less oligomer precipitation even after high temperature treatment. .

Polyester film has excellent transparency, strength, heat resistance, electrical properties, etc., so touch panel, polarizing plate protective film, prism lens film, light diffusion film, antireflection film, hard coat film, electromagnetic shielding film, It is used as a base material for molding.

  In particular, in recent years, the use of glass as a base material for a transparent conductive layer, which is increasingly used for touch panels and the like, is increasing. As such a transparent conductive laminate, a polyester film is used as a base material, and an ITO (indium tin oxide) film is generally formed on the transparent conductive layer by sputtering directly or via an anchor layer. .

  As a process of forming the transparent conductive layer, for example, it is allowed to stand at 150 ° C. for 1 hour for low heat shrinkage (Patent Document 1), and heat treatment is performed at 150 ° C. for ITO crystallization (Patent Document 2). There is processing of.

  However, as a problem of polyester film, when exposed to such high temperature and long time treatment, oligomers (low molecular weight component of polyester, especially ester cyclic trimer) contained in the film are precipitated and crystallized on the film surface. As a result, deterioration of visibility due to whitening of the external appearance of the film, defects in post-processing, contamination of the process and members, and the like occur. Therefore, the characteristics of the transparent conductive laminate having a polyester film as a base material may be insufficient.

  More recently, there has been a trend toward lower resistance in transparent conductive layers. When general ITO is used as the transparent conductive layer as the transparent conductive layer, it is necessary to increase the crystallinity of the ITO in order to reduce the resistance. In order to increase the crystallization, it is necessary to perform a heat treatment for a long time at a higher temperature than before. In that case, when a polyester film is used as the substrate, oligomers are more easily precipitated than before, and therefore a technique capable of preventing oligomer precipitation to a high degree has been desired.

JP 2007-42473 A JP 2007-200823 A

  The present invention has been made in view of the above circumstances, and the problem to be solved is, for example, the amount of ester cyclic trimer deposited on the film surface even after a long heat treatment step at a high temperature such as an ITO sputtering step. Is to provide a laminated polyester film that can suppress the increase in film haze

  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 at least one side of a polyester film has a coating layer formed from a coating solution containing a compound having an ammonium group, and further, 30 wt% or more based on the nonvolatile component on the coating layer. The present invention resides in a laminated polyester film having a coating layer formed from a coating solution containing a crosslinking agent.

  According to the polyester film of the present invention, there is little precipitation of the ester cyclic trimer on the film surface even in a heat treatment process at a high temperature for a long time, and for example, a film excellent in applications such as a touch panel can be provided. Target 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, titanium compounds and germanium compounds 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 the brightness of the film becomes high. Furthermore, since a germanium compound is expensive, it is more preferable to use a titanium compound.

  In the present invention, in order to suppress the precipitation amount of the ester cyclic trimer after the heat treatment, it is also possible to use a polyester having a low content of the ester cyclic trimer. As a method for producing a polyester having a low ester cyclic trimer content, a conventionally known method can be used. Examples thereof include a method of solid-phase polymerization after the production of a polyester.

  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 also possible. 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, the average particle diameter of particle | grains is 5 micrometers or less normally, Preferably it is 0.01-3 micrometers, More preferably, it is the range of 0.05-2 micrometers. When the average particle diameter exceeds 5 μm, the surface roughness of the film becomes too rough, which causes deterioration of transparency.

  Further, the content of particles in the polyester layer is usually less than 5% by weight, preferably in the range of 0.0003 to 3% 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. Further, when the particle content exceeds 5% by weight, the transparency of the film may be insufficient.

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, for example, to prevent deterioration of the liquid crystal or the like of a liquid crystal display used for a touch panel or the like. 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.

  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% can be 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 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.

  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, it is coated on any of an unstretched film obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, and a film after heat setting and before winding. Although not limited to the following, for example, when performing sequential biaxial stretching, as a preferred example in the present invention, a coating layer formed from a coating solution containing a compound having an ammonium group in an unstretched film is formed, Next, there is a method in which the film is stretched in the longitudinal direction (longitudinal direction) to form a uniaxially stretched film, on which a coating solution containing 30% by weight or more of a crosslinking agent is coated and then stretched in the transverse direction. 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. .

  In the present invention, at least one surface of the polyester film has a coating layer formed from a coating solution containing a compound having an ammonium group (hereinafter sometimes abbreviated as a first coating layer), and further the coating layer It is an essential requirement to have a coating layer (hereinafter sometimes abbreviated as a second coating layer) formed from a coating solution containing a crosslinking agent of 30% by weight or more with respect to the nonvolatile component. is there.

  The coating layer of the present invention is provided to prevent the ester cyclic trimer present in the polyester film from being deposited on the film surface by heat treatment. Even with only the first coating layer or the second coating layer, a film having good ester cyclic trimer precipitation prevention performance can be produced depending on the composition of the coating layer. However, the ester cyclic trimer is extremely precipitated even at a higher temperature and a longer heat treatment (for example, 1 hour or more at 180 ° C.), which is performed in the current trend toward lower resistance of the transparent conductive layer. It was difficult to realize such a design with a single coating layer.

  However, as a result of various studies, a first coating layer formed from a coating solution containing a compound having an ammonium group and a second coating formed from a coating solution containing 30% by weight or more of a crosslinking agent with respect to the nonvolatile component. It has been found that the anti-precipitation performance of the ester cyclic trimer can be improved to a high degree by employing a two-layer coating layer structure.

  The compound having an ammonium group used for forming the first coating layer of the present invention is a compound having an ammonium group in the molecule, and examples thereof include aliphatic amines, alicyclic amines, and ammonium amines of aromatic amines. . The compound having an ammonium group is preferably a polymer compound, for example, a polymer compound having an ammonium group from a polymer obtained by polymerizing a monomer containing an addition polymerizable ammonium group or a precursor of an ammonium group such as an amine, and the like. And are preferably used. As the polymer, a monomer containing an addition polymerizable ammonium group or a precursor of an ammonium group such as an amine may be polymerized alone, or it may be a copolymer of a monomer containing these and another monomer. May be.

  Specific examples of the polymer of the compound having an ammonium group include, but are not limited to, a polymer containing a constituent represented by the following formula (1) or the following formula (2). It is done. A single polymer or copolymer, or a plurality of other components may be copolymerized.

In the above formula (1), R ² is —O—, —NH— or —S—, R ³ is an alkylene group, or other structure capable of forming the structure of formula (1), R ¹ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, a phenyl group or the like, and these alkyl group and phenyl group may be substituted with the following groups. Substitutable groups include, for example, hydroxyl group, amino group, amide group, ester group, alkoxy group, phenoxy group, naphthoxy group, thioalkoxy group, thiophenoxy group, cycloalkyl group, trialkylammonium alkyl group, cyano group, Halogen.

In said formula (2), R < ¹ >, R < ² > is respectively independently an alkyl group, a phenyl group, etc., These alkyl groups and a phenyl group may be substituted by the group shown below. Substitutable groups include, for example, hydroxyl group, amino group, amide group, ester group, alkoxy group, phenoxy group, naphthoxy group, thioalkoxy group, thiophenoxy group, cycloalkyl group, trialkylammonium alkyl group, cyano group, 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.

X ⁻ in the above formulas (1) and (2) can be appropriately selected within a range not impairing the gist of the present invention. For example, alkyl sulfate ion, alkyl sulfonate ion, halogen ion, phosphate, nitrate, carboxylate and the like can be mentioned.

A polymer having a component represented by Formula 1 is preferable because of excellent transparency of the resulting coating layer. In view of heat resistance and environmental aspects, X ⁻ is preferably not halogen.

  A compound represented by Formula 2 and other ammonium bases in the polymer main skeleton are excellent in heat resistance and are preferable.

  Moreover, the number average molecular weight of the compound which has an ammonium group is 1000-500000, Preferably it is 2000-350,000, More preferably, it is 5000-200000. When the molecular weight is less than 1000, the strength of the coating film may be weakened or the heat 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.

  The merit of using the above-mentioned compound having an ammonium group for the formation of the first coating layer is that the amount of ester cyclic trimer deposited on the film surface by heat treatment is suppressed, and depending on the method used, antistatic performance It is also possible to provide a high-performance film excellent in dust prevention.

  In the formation of the first coating layer, it is also possible to use a polymer in combination in order to improve the coating appearance, improve the transparency, and improve the adhesion to various layers. Specific examples of the polymer include polyester resin, acrylic resin, urethane resin, polyvinyl (polyvinyl alcohol, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, and starches. As a preferable polymer in the first coating layer, polyvinyl alcohol and acrylic resin are suitably used since the amount of ester cyclic trimer deposited on the film surface by heat treatment is suppressed, and polyvinyl alcohol is particularly preferable. In addition, polyester resin, acrylic resin, and urethane resin are preferably used from the viewpoint of applicability and adhesion, but depending on the composition of the coating layer, the amount of ester cyclic trimer deposited on the film surface by heat treatment is large. It may be necessary to proceed with caution.

  In order to strengthen the first coating layer, a crosslinking agent can be used in combination. Various known crosslinking agents can be used as the crosslinking agent, and examples include melamine compounds, oxazoline compounds, epoxy compounds, isocyanate compounds, carbodiimide compounds, aziridine compounds, and silane coupling compounds. Among these crosslinking agents, a melamine compound is preferably used because the amount of ester cyclic trimer deposited on the film surface by heat treatment can be suppressed.

  Furthermore, since the precipitation amount of the ester cyclic trimer on the film surface by the heat treatment can be effectively suppressed, a polyvalent aldehyde compound can be used in combination for forming the first coating layer.

  The polyvalent aldehyde compound is a compound having two or more aldehyde groups or a functional group derived from an aldehyde group in one molecule. For example, glyoxal, glutaraldehyde, terephthalaldehyde, cyclohexanedialdehyde, Polyhydric aldehyde compounds such as tricyclodecanedialdehyde, norbornane dialdehyde, suberaldehyde, compounds acetalized by reaction (protected) of those aldehyde groups, thioacetalized compounds, silyl etherified compounds, Examples thereof include nitrogenated compounds such as imine, iminium salt and enamine.

  The polyvalent aldehyde compound may be unstable and is preferably used in a form in which an aldehyde group is reacted (protected). In view of stability and reactivity in coating, a form reacted with a hydroxyl group-containing compound, particularly a polyhydric alcohol compound, is preferable, and among them, a type that forms a cyclic structure when reacted with an aldehyde group is more preferable.

  Examples of the polyhydric alcohol compound include polyhydric alcohols such as ethylene glycol, 1,3-propanediol, and glycerin, and saccharides such as glucose and galactose. Among them, saccharides are preferable in consideration of applicability.

  In addition, the polyhydric aldehyde compound is preferably an aliphatic polyhydric aldehyde compound or a derivative thereof in consideration of the strength of the coating layer and the coating appearance, and among them, glyoxal having a larger amount of aldehyde functional groups in particular, instead of molecular weight. preferable.

  Various known crosslinking agents can be used as the crosslinking agent used for forming the second coating layer of the present invention. For example, melamine compounds, oxazoline compounds, epoxy compounds, isocyanate compounds, carbodiimide compounds, aziridines Compounds, silane coupling compounds, and the like. Among these, it is preferable to use a melamine compound, an oxazoline compound, an epoxy compound, and a carbodiimide compound in that the precipitation prevention performance of the ester cyclic trimer can be improved to a higher degree, and a melamine compound is particularly preferable. In addition, any one of these crosslinking agents may be used, and two or more crosslinking agents may be used in combination.

  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. From the viewpoint of preventing precipitation of the ester cyclic trimer, it preferably has more crosslinkable reactive groups such as hydroxyl groups, and more preferably has 4 or more. 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 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 10 mmol / g, more preferably 3 to 9 mmol / g, still more preferably 5 to 8 mmol in terms of the amount of the oxazoline group. / G. Use within the above range is preferable for preventing precipitation of the ester cyclic trimer.

  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.

  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 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.

  The content of the carbodiimide group contained in the carbodiimide-based 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 ~ 700. Use within the above range is preferable for preventing precipitation of the ester cyclic trimer.

  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.

  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.

  In addition, in the formation of the second coating layer, in the same manner as the formation of the first coating layer, it is possible to use a polymer in combination in order to improve the coating appearance, improve the transparency, and improve the adhesion to various layers. It is. Among these, polyester resins, acrylic resins, and urethane resins are preferably used from the viewpoints of applicability and adhesion. However, depending on the composition of the coating layer, the amount of precipitation of the ester cyclic trimer on the film surface by heat treatment may increase, so careful handling is necessary.

  In addition, particles can be used in combination for the purpose of blocking and improving slipperiness in forming the first coating layer and the second 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. The lower limit is preferably in the range of 0.01 μm or more, more preferably 0.02 μm or more in order to improve the slipperiness more effectively. Specific examples of the particles include silica, alumina, kaolin, calcium carbonate, and organic particles. Of these, silica and alumina-modified silica are preferable from the viewpoint of the stability and transparency of the coating solution.

  Further, in the range not impairing 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 formed as necessary for forming the coating layer. It is also possible to use a foaming agent, a dye, a pigment and the like in combination.

  As a ratio with respect to all the non-volatile components in the coating liquid forming the first coating layer in the film of the present invention, the compound having an ammonium group is usually in the range of 10 to 90% by weight, preferably in the range of 15 to 80% by weight. Preferably it is the range of 20-60 weight%. When outside the above range, the effect of preventing the precipitation of the ester cyclic trimer may be reduced, or the coating appearance may be deteriorated.

  As a ratio with respect to all the non-volatile components in the coating liquid which forms the 1st coating layer in the film of this invention, polyvinyl alcohol and an acrylic resin are the range of 90 weight% or less normally, Preferably it is the range of 5-70 weight%, More preferably. Is in the range of 10-50% by weight. Use within the above range is preferable for preventing precipitation of the ester cyclic trimer.

  As a ratio with respect to all the non-volatile components in the coating liquid forming the first coating layer in the film of the present invention, the crosslinking agent is usually in the range of 90% by weight or less, preferably in the range of 5 to 70% by weight, more preferably in the range of 10 to 10. It is in the range of 60% by weight. Use within the above range is preferable for preventing precipitation of the ester cyclic trimer. In particular, from the viewpoint of preventing precipitation of the ester cyclic trimer, the melamine compound is preferably in the range of 10 to 60% by weight as the crosslinking agent.

  As a ratio with respect to all the non-volatile components in the coating liquid which forms the 1st coating layer in the film of this invention, a polyhydric aldehyde type compound is the range of 50 weight% or less normally, Preferably it is the range of 2-30 weight%. Use within the above range is preferable for preventing precipitation of the ester cyclic trimer.

  As a ratio with respect to all the non-volatile components in the coating liquid for forming the second coating layer in the film of the present invention, the crosslinking agent is usually 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more, particularly preferably. Is in the range of 80% by weight or more. As the amount of the crosslinking agent is increased, the degree of crosslinking in the coating layer is improved, and the precipitation of the ester cyclic trimer can be more highly prevented. In particular, it is easy to improve performance by using all components except for a small amount of components such as particles used for imparting slipperiness without using a polymer as a crosslinking agent. Moreover, as a crosslinking agent, it is most preferable to use a melamine compound, and the amount is more effective in the range of 70 wt% or more.

  Analysis of the components in the coating layer can be performed by analysis of TOF-SIMS, ESCA, fluorescent X-rays, and the like, for example.

  When providing a coating layer by in-line coating, the above-mentioned series of compounds is applied as an aqueous solution or dispersion, and the coating solution adjusted to a solid content concentration of about 0.1 to 50% by weight as a guide is applied onto the polyester film. It is preferable to produce a laminated polyester film. In addition, an organic solvent may be contained in the coating solution for the purpose of improving the dispersibility in water, improving the film forming property, and the like within the range not impairing the gist of the present invention. Only one type of organic solvent may be used, or two or more types may be used as appropriate.

Regarding the laminated polyester film in the present invention, the coating amount of the coating layer provided on the polyester film (as the final film after drying and stretching) is usually 0.001 to 1 g / in each of the first coating layer and the second coating layer. range of m ^2, and preferably from 0.01 to 0.5 g / ^{m 2,} more preferably from 0.02~0.2g / ^{m 2.} When the coating amount is out of the above range, the precipitation prevention performance of the ester cyclic trimer is poor, the blocking of the coating layer may be deteriorated, or the coating appearance may be deteriorated.

  In the film of the present invention, as a method for forming the coating layer, 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 Conventionally known coating methods such as coating, impregnation coating, kiss coating, spray coating, calendar coating, extrusion coating, etc. can be used.

  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.

  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. From this viewpoint, in order to cope with high transparency, the film haze change amount (ΔHz) in the heat treatment (180 ° C., 90 minutes) is preferably 1.0% or less, more preferably 0.8% or less. More preferably, it is 0.5% or less. When ΔHz exceeds 1.0%, the visibility decreases as the film haze increases due to precipitation of the ester cyclic trimer, and is not suitable for applications that require high visibility, such as for touch panels. It may be appropriate.

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 (180 ° C., 90 minutes) of the laminated polyester film in the present invention is preferably 1.0 mg / m ² or less, more preferably 0.7 mg / m ² or less, and still more preferably 0.5 mg / m ² or less. If it exceeds 1.0 mg / m ² , in the subsequent step, for example, the amount of ester cyclic trimer precipitated increases with heat treatment for a long time in a high-temperature atmosphere such as 180 ° C. for 90 minutes, and the transparency of the film There is a concern that the performance may deteriorate or contamination of the process.

  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 haze It measured by JISK7136 using the haze meter HM-150 by Murakami Color Research Laboratory.

(3) Measuring method of film haze increase (ΔHz) by heat treatment 100 parts by weight of purple light 7600B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) on the surface opposite to the surface on which the (second) coating layer of the present invention is provided ) And Irgacure 651 5 parts by weight (manufactured by Ciba Specialty Chemicals Co., Ltd.) diluted with methyl ethyl ketone to a concentration of 30% by weight so that the thickness after curing is 3 μm, and hot-air drying set at 80 ° C. Dried for 1 minute in an oven. Next, using a high-pressure mercury lamp with an energy of 120 W / cm, irradiation for about 7 seconds at an irradiation distance of 100 mm, curing at 110 mJ / cm ² , and a laminated film provided with an active energy ray-curable resin layer on the film Obtained. The obtained laminated film was fixed by being overlapped with Kent paper with the (second) coating layer surface exposed, and was left to stand at 180 ° C. for 90 minutes in a nitrogen atmosphere for heat treatment. The haze of the laminated film subjected to the heat treatment was measured by the method (2) (haze 1). The difference (ΔHz = (haze 1) − (haze 2) from the haze (haze 2) measured by the method of (2) of the film (non-treated laminated polyester film of the present invention) before providing the active energy ray-curable resin layer). )). The lower ΔHz, the less precipitation of a relatively large size ester cyclic trimer by high temperature treatment, which is better.

(4) (Second) Method for Measuring Ester Cyclic Trimer (Ethylene Terephthalate Cyclic Trimer) Precipitated on the Surface of Coating Layer The polyester film is heated in air at 180 ° C. for 90 minutes. Thereafter, the heat-treated film is formed into a box shape with the measurement surface ((second) 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 (dimethylformamide) was placed in the box prepared by the above method and allowed to stand for 3 minutes, after which 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, column: “MCI GEL ODS 1HU” manufactured by Mitsubishi Chemical Corporation, column temperature: 40 ° C., flow rate: 1 ml / min, detection wavelength: 254 nm), and oligomer in DMF The amount was determined, and this value was divided by the film area contacted with DMF to obtain the amount of the film surface oligomer (mg / m ² ). The amount of 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)>
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. 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 polyester (C) is produced using the same method as the production method of the polyester (A) except that 0.2 parts by weight of silica particles having an average particle diameter of 1.6 μm is added before the melt polymerization. Got.

Examples of compounds constituting each coating layer are as follows.
(Example compounds)
Compound containing ammonium group: (I) Water dispersion 2- (trimethylammonio) ethyl methacrylate / butyl methacrylate / ethyl methacrylate = 75/15/10 (% by weight) having the following composition, the counter ion being monomethyl sulfate ion A copolymer having a number average molecular weight of 150,000.

・ Melamine compounds: (IIA) Hexamethoxymethylolmelamine ・ Oxazoline compounds: (IIB)
Oxazoline group-containing acrylic polymer Epocross (registered trademark) (Oxazoline group amount = 7.7 mmol / g, manufactured by Nippon Shokubai Co., Ltd.)
Epoxy compound: (IIC) polyglycerol polyglycidyl ether

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

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

・ Polyester resin: (IIIC)
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%)

・ Multivalent aldehyde compounds: (IV)
A polyvalent aldehyde compound obtained by reacting glyoxal with anhydrous glucose.

-Particles: (VA) silica particles having an average particle size of 0.07 µm · Particles: (VB) alumina-modified silica particles having an average particle size of 0.02 µm

Example 1:
A mixed raw material in which polyesters (A), (B), and (C) were mixed at a ratio of 87%, 3%, and 10%, 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. Coextruded with a layer structure of layers (surface layer / intermediate layer / surface layer = 1: 18: 1 discharge amount) and cooled and solidified to obtain an unstretched film. Thereafter, the aqueous coating solution A1 shown in Table 1 below is applied to one side of the unstretched film and dried, and the coating amount (as the final film after drying and stretching) is 0.03 g / m ^2. A film having was obtained. Subsequently, the film was stretched 3.4 times in the machine direction at a film temperature of 85 ° C. using the difference in peripheral speed of the roll, and then the aqueous coating solution B1 shown in Table 1 below was applied to the first coating layer side of the longitudinally stretched film. Then, the film was led to a tenter, stretched 4.0 times at 120 ° C in the transverse direction, heat treated at 230 ° C, then relaxed 2% in the transverse direction, and the coating amount applied (as the final film after drying and stretching) ) Obtained a polyester film with a thickness of 125 μm having a second coating layer of 0.10 g / m ² . When the obtained polyester film was evaluated, the film haze increase (ΔHz) by heat treatment 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 2-7:
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 below, the finished polyester film was good in that the haze increase due to heat treatment was small and the amount of ester cyclic trimer precipitated was small.

Comparative Example 1:
In Example 1, a polyester film was obtained in the same manner as in Example 1 except that the first coating layer and the second coating layer were not provided on the unstretched film. When the finished polyester film was evaluated, as shown in Table 2 below, the haze increase due to heat treatment was large, the amount of ester cyclic trimer precipitated was also large, and there was concern about visibility and process contamination. .

Comparative Examples 2-5:
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, and obtained the polyester film. As shown in Table 2, the finished polyester film was found to have a large haze increase due to heat treatment or a large amount of ester cyclic trimer.

  The film of the present invention causes little precipitation of the ester cyclic trimer on the film surface even in a heat treatment process at a high temperature for a long time, and can be suitably used for applications such as a touch panel.

Claims (1)

A coating solution having a coating layer formed from a coating solution containing a compound having an ammonium group on at least one surface of the polyester film, and further containing a crosslinking agent of 30% by weight or more based on the nonvolatile component on the coating layer A laminated polyester film comprising a coating layer formed from