JP2015071736A - Coating film for transparent conductive base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating film for a transparent conductive base material hardly generating defects such as pattern failure when used for a transparent conductive laminate designed to have narrower pattern width.SOLUTION: There is provided a coating film for a transparent conductive raw material having a coating layer set on a single sided face of a multilayer polyester film consisting of at least 3 layer structure of both outer layers and an intermediate layer and satisfying following (1) and (2) at the same time by a coating liquid containing an acrylic resin and two or more kinds of crosslinkers, with a film thickness of 10 to 60 μm, and containing two kinds of particles having different average particle diameter in both outer layer, a polyester layer constituting both outer layer is 3 μm respectively and the softening point of both outer layer is higher than that of the polyester layer constituting the intermediate layer. 0<Ti≤20 (1) 0≤P≤300 (2), where Til represents the Ti element amount in the multilayer polyester film (ppm) and P represents the phosphorus element amount (ppm).

Description

  The present invention relates to a coated film used as a base material for a patterned transparent conductive layer used as a constituent base material for a touch panel, and a transparent conductive layer laminated on a film surface provided with no coating layer. The present invention relates to a coating film for a transparent conductive film substrate, which enables high-quality etching during etching and does not cause defects in the transparent conductive layer even after the crystallization step of the transparent conductive layer.

  Conventionally, in touch panel applications, various methods such as a resistive film method and a capacitance method are employed depending on the position detection method. Among them, there is a tendency to increase the spread of a capacitance method characterized by multipoint detection, high light transmittance, high resolution, and high response speed. There are two types of capacitive touch panels: surface type and projection type. The surface type consists of three layers: a cover, a transparent conductive layer, and a glass substrate. The projection type consists of a glass or plastic film, a transparent electrode layer, and a substrate layer equipped with an IC that performs arithmetic processing. The

  In the manufacturing process of the transparent conductive laminate, it is generally heat-processed after undergoing a patterning process. First, in order to form a transparent conductive film, an ITO film is formed by a sputtering method. Thereafter, the ITO film is patterned by a photoresist method or the like, and heat-treated at a temperature of about 150 ° C. or 180 ° C. to crystallize the ITO film, thereby obtaining a patterned transparent conductive laminate.

  When the pattern of the transparent conductive laminate is finished into the final touch panel member, it looks like a streak due to the difference in optical properties between the ITO film and the polyester base layer located thereunder There is. The pattern width of the ITO film has become narrower in recent years because the streaks of the pattern area are particularly noticeable when reflected over reflected light such as a fluorescent lamp, and the appearance quality of the final touch panel display product is reduced. There is a tendency to be designed.

  In general, particles are blended in the polyester film substrate mainly for the purpose of imparting slipperiness and preventing scratches in each step. If more particles are added and the surface roughness of the polyester film substrate is designed to be high, the handleability during processing of the substrate will increase, but if there is an aggregate of particles in the ITO pattern part, the photoresist This may have an adverse effect on the uniform patterning of the ITO layer by the method. In particular, in a transparent conductive laminate of a type designed with a narrower pattern width in recent years, there is a tendency for defects in patterning to occur frequently.

  On the other hand, if the polyester base material is not blended with particles, scratches that occur when the film passes through the roll path in each step occur on the entire surface of the film, and it is extremely difficult to process a transparent conductive laminate having a good appearance. It is.

JP 2007-200823 A JP2013-54517A

  The present invention has been made in view of the above circumstances, and the problem to be solved is that it is used for a transparent conductive laminate of a type designed to have a narrower pattern width when patterning an ITO film by a photoresist method or the like. The present invention relates to a coating film for a transparent conductive film substrate that is less likely to cause defects such as patterning failure, and is to provide a coating film suitable as a transparent conductive film substrate.

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

That is, the gist of the present invention is that an acrylic resin and two or more kinds of cross-linking agents are formed on one side of a multilayer polyester film which comprises at least three layers of both outer layers and intermediate layers and simultaneously satisfies the following formulas (1) and (2). The thickness of the polyester layer which comprises the coating layer provided with the coating liquid containing these, and the film thickness is 10-60 micrometers, contains two types of particle | grains from which an average particle diameter differs in both outer layers, and comprises both outer layers Are each 3 μm or less, and the softening point of both outer layers is higher than the softening point of the polyester layer constituting the intermediate layer.
0 <Ti ≦ 20 (1)
0 ≦ P ≦ 300 (2)
(In the above formula, Ti represents the amount of Ti element (ppm) in the multilayer polyester film, and P represents the amount of phosphorus element (ppm)).

  According to the coated film for a transparent conductive film substrate of the present invention, when patterning an ITO film by a photoresist method or the like, even when used for a transparent conductive laminate of a type designed to have a narrower pattern width, The present invention relates to a coated film for a transparent conductive film substrate that does not cause defects such as poor formation, and can provide a coated film that can be suitably used as a transparent conductive film substrate, and its industrial value is high.

  The coated film of the present invention needs to be a multilayer polyester film having at least three layers. The coated film referred to in the present invention is a polyester film extruded by a so-called extrusion method that is melt-extruded from an extrusion die, and is a film that is oriented in the biaxial direction of the vertical direction and the horizontal direction as necessary. is there.

  In the present invention, the polyester is obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. 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 polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN) and the like.

  The polyester used in the present invention may be a homopolyester or a copolyester. In the case of a copolyester, it is a copolymer containing 30 mol% or less of the third component. 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 acids (for example, P-oxybenzoic acid). Or 2 or more types are mentioned, As a glycol component, 1 type, or 2 or more types, such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1, 4- cyclohexane dimethanone neopentyl glycol, is mentioned.

In the present invention, in the multilayer polyester film constituting the coated film, it is necessary to use a titanium compound (Ti) and a phosphorus compound (P) in order to suppress oligomer precipitation, and the content of the compound (ppm) ), The following formulas (1) and (2) must be satisfied at the same time.
0 <Ti ≦ 20 (1)
0 ≦ P ≦ 300 (2)

  Regarding Ti, it is preferably in the range of 2 to 10 ppm. When Ti exceeds the upper limit of the above formula (1), an oligomer is by-produced in the step of melt-extruding polyester, and a film having low oligomer and high transparency cannot be obtained. In addition, it becomes difficult to deal with applications such as optical applications, particularly where the color tone of the coated film is important. On the other hand, with respect to P, the range of preferably 5 to 200 ppm, more preferably 0 to 100 ppm. When P exceeds the upper limit of the formula (2), gelation occurs at the time of polyester production, and it becomes a foreign substance to deteriorate the quality of the film. For example, it is difficult to cope with an inspection process involving optical evaluation such as a touch panel application. Become. By satisfying the above expressions (1) and (2) at the same time, it is possible to achieve a remarkable effect for reducing the amount of oligomers contained in the multilayer polyester film.

  The layer containing the titanium compound and the phosphorus compound preferably contains substantially no antimony element, usually 10 ppm or less, preferably 5 ppm or less, most preferably substantially free, ie 1 ppm or less. It is. If the amount of the antimony element is too large, it may be reduced by the phosphorus compound during melt extrusion and aggregate to cause foreign matters, or the film may become dark and the transparency may be insufficient.

  In the multilayer polyester film constituting the coated film of the present invention, the polyester constituting the layer containing the titanium compound and the phosphorus compound within the aforementioned range may be obtained by a melt polymerization reaction, but after the melt polymerization. If a raw material obtained by solid-phase polymerization of chipped polyester is used, it is preferably used because the amount of oligomers contained in the raw material can be reduced.

  In the multilayer polyester film of the present invention, the amount of the oligomer contained in the layer containing the titanium compound and the phosphorus compound within the above range is preferably 0.7% by weight or less, more preferably 0.5% by weight or less, particularly preferably. Is 0.3% by weight or less. When the amount of oligomer contained in the polyester layer is small, the amount of oligomer contained in the multilayer polyester film of the present invention is reduced, and the effect of preventing oligomer precipitation on the film surface is particularly high.

  In the present invention, it may be a film having a structure obtained by coextrusion laminating a polyester having a low oligomer content on the surface of at least one side of a layer composed of a polyester having a normal oligomer content. The effect of suppressing oligomer precipitation obtained in the present invention can be exhibited to a high degree.

  In the multilayer polyester film constituting the coated film in the present invention, it is necessary to have a multilayer configuration of at least three layers, and it is an essential requirement that both outermost polyester layers have a higher softening point than the intermediate layer. Is. Preferably, the difference in softening point between the polyester layers of the outermost layers and the intermediate layer is 3 ° C. or higher, preferably 5 ° C. or higher.

  As a specific method for satisfying the conditions, preferably by containing 80% or more of polyester having an oligomer (cyclic trimer) content of 0.5% by weight or less in the polyester layer constituting both outer layers The difference in the softening point can be expressed. When polyester with an oligomer content of more than 0.5% by weight is used, or when the content is less than 80%, the double-sided coated film is subjected to long-term heat treatment at 150 ° C and high tension. When used in severe processing conditions such as sputtering processes under conditions and durability tests in high-temperature and high-humidity atmospheres, film haze increases significantly, and after processing, optical properties or visibility In this case, it may be unsuitable for an optical member.

  The multilayer polyester film constituting the coated film of the present invention needs to be a multilayer polyester film composed of at least three polyester layers, and the polyester layer thickness of both outer layers needs to be 3 μm or less. The thickness of the polyester layer is preferably 2 μm or less. When the thickness of the polyester layer constituting both outer layers exceeds 3 μm, it may be difficult to obtain a coated film having a desired internal haze after heat-treating the coated film.

  In the present invention, when a polyester containing a titanium compound and having a low oligomer content is used, particularly when the polyester layers constituting both outer layers are laminated with a thickness of 3 μm or less, the film haze of the obtained film itself is reduced. It becomes possible to keep it smaller, and it is suitable for optical applications where a highly transparent coating film is required, for example, for touch panels.

  The film thickness in the coated film of the present invention is preferably in the range of 10 μm to 60 μm in consideration of processability for use. More preferably, the film thickness is in the range of 15 μm to 50 μm. When the film thickness is less than 10 μm, for example, when forming an ITO film by a sputtering method in order to form a transparent conductive film, the film strength is defeated by the processing tension, and wrinkles are generated and the desired transparent conductive film is formed. A film may be difficult to form. On the other hand, when the thickness exceeds 60 μm, the film becomes too strong, and when finished to the final touch panel product, the writing quality of the coated film of the present invention is reduced due to the cushioning effect of the adhesive layered on the coated layer surface. Or a problem such as a decrease in responsiveness of the touch panel may occur.

  In the coated film of the present invention, it is an essential requirement that the maximum roughness (St) of the film surface on which the coating layer is not provided is 300 nm or more and 550 nm or less. The maximum roughness (St) is preferably 350 nm or more and 500 nm or less. When the maximum roughness (St) is less than 300 nm, the film surface on which the coating layer is not provided becomes too smooth, and scratches may occur frequently during the formation of the multilayer polyester film. On the other hand, if the thickness exceeds 550 nm, the frequency of occurrence of disconnection of the wiring in the crystallization process of the transparent conductive layer may be increased particularly in the thinly patterned portion on the patterned transparent conductive film.

  In the coated film of the present invention, it is necessary to blend two kinds of particles having different average particle diameters in the multilayer polyester layer mainly for the purpose of imparting slipperiness and preventing the occurrence of scratches in each step. The kind of the particle to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness. Specific examples thereof include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and phosphoric acid. Examples of the particles include magnesium, kaolin, aluminum oxide, and titanium oxide. Further, the heat-resistant organic particles described in JP-B-59-5216, JP-A-59-217755 and the like may be used. Examples of other heat-resistant organic particles include thermosetting urea resins, thermosetting phenol resins, thermosetting epoxy resins, benzoguanamine resins, and the like. 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.

  On the other hand, 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.

  Although it does not specifically limit as an average particle diameter of the particle | grains mix | blended in a polyester film, Usually, 0.2 micrometer-1 micrometer, Preferably it is the range of 0.3 micrometer-0.6 micrometer. When particles having an average particle size of less than 0.2 μm are used, sufficient slipperiness cannot be imparted, so that the winding characteristics in the film production process tend to be inferior. Moreover, when the average particle diameter exceeds 1 μm, the degree of roughening of the film surface is large, and the maximum roughness (Rt) defined in the present invention may not be satisfied.

  Furthermore, the particle content in the polyester layer is usually in the range of 0.05 to 2.0% by weight, preferably 0.05 to 1.0% by weight. When the particle content is less than 0.05% by weight, the slipperiness of the film may be insufficient, resulting in poor appearance such as scratches during film processing. On the other hand, when adding over 2.0 weight%, film transparency may be inadequate.

  Among them, in the present invention, it is preferable to use cross-linked polymer particles when it is preferable to keep the internal haze of the coated film low.

  The crosslinked polymer particles used in the present invention can be usually obtained as follows. That is, a compound (J) having only one aliphatic unsaturated bond in a molecule is copolymerized with a compound (K) having two or more aliphatic unsaturated bonds in the molecule as a crosslinking agent. It is obtained. Examples of (J), which is a component of the copolymer, include acrylic acid, crotonic acid, methacrylic acid, and their lower alkyl esters such as methyl ester and ethyl ester, or glycidyl ester, maleic anhydride and its alkyl Derivatives, vinyl glycidyl ether, vinyl acetate, acrylonitrile, styrene and substituted products thereof. Examples of the compound (K) include divinylbenzene, ethylene glycol dimethacrylate, butylene glycol acrylate and the like.

  Typical examples of these copolymers include a copolymer of methacrylic acid and divinylbenzene, styrene and divinylbenzene, and methacrylic acid and ethylene glycol dimethacrylate. In the present invention, the compound (J) A cross-linked polymer may be obtained by using a plurality of compounds (K).

  Furthermore, in the outermost polyester layer constituting the multilayer polyester film of the present invention, it is preferable to use aluminum oxide particles together as a dispersant in order to prevent aggregation of the crosslinkable polymer particles. The average particle diameter of the aluminum oxide particles used in the present invention is preferably in the range of 0.01 to 0.3 μm. When the average particle diameter of the aluminum oxide particles is out of the above range, the dispersion effect as a dispersant may be poor.

  Specific examples of the aluminum oxide particles used in the present invention include γ-type and δ-type aluminum oxides produced by flame hydrolysis using anhydrous aluminum chloride as a raw material.

  In the present invention, the method of blending the particles with the polyester is not particularly limited, and a known method can be adopted. For example, it can be added at any stage of producing the polyester, but it is preferably added as a slurry dispersed in ethylene glycol or the like at the stage of esterification or before the start of the polycondensation reaction after completion of the transesterification reaction, The polycondensation reaction may proceed. Also, a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material, or a blending of dried particles and a polyester raw material using a kneading extruder. It is done by methods.

  In the coated film of the present invention, the polyester film having a multi-layer structure has functions such as adhesiveness, antistatic property, slipperiness, releasability and the like within the stretch process and / or subsequent film within the range not impairing the gist of the present invention. In order to impart the above, a coating layer may be formed on the film surface or a surface treatment such as a corona treatment may be performed.

  In the coated film of the present invention, a coated layer may be provided for the purpose of improving the adhesion with the hard coat layer processed thereon, improving the slipperiness during processing, and the like. 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. Since the coating can be performed simultaneously with the film formation, the production can be handled at a low cost, and therefore in-line coating is preferably used.

  The in-line coating is not limited to the following, but for example, in the sequential biaxial stretching, the coating treatment can be performed particularly before the lateral stretching after the longitudinal stretching is finished. When the coating layer is provided on the polyester film by in-line coating, it is possible to apply at the same time as the film formation, and the coating layer can be processed at a high temperature in the heat treatment process of the polyester film after stretching. Performances such as adhesion to various surface functional layers that can be formed on the layer and heat-and-moisture resistance can be improved. Moreover, when coating before extending | stretching, the thickness of an application layer can also be changed with a draw ratio, and compared with off-line coating, uniform coating can be performed with a thin film. That is, a film suitable as a polyester film can be produced by in-line coating, particularly coating before stretching.

  In this invention, it is preferable to have the coating layer formed by apply | coating the coating liquid containing an acrylic resin, an epoxy compound, and an oxazoline compound on the single side | surface of a polyester film.

  The coating layer in this invention can improve adhesiveness with a hard-coat layer, various thermosetting layers, and an active energy ray hardening layer.

  As a result of various investigations, adhesion with the hard coat layer is further improved by forming a coating layer containing an acrylic resin and containing at least two types of crosslinking agents such as epoxy compounds or oxazoline compounds. I found out that

  The acrylic resin used in the present invention is a polymer comprising a polymerizable monomer having a carbon-carbon double bond, as typified by acrylic and methacrylic monomers. These may be either a homopolymer or a copolymer. Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer. Alternatively, a polymer (possibly a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyester solution or a polyester dispersion is also included. Similarly, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyurethane solution or polyurethane dispersion is also included. Similarly, a polymer obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in another polymer solution or dispersion (in some cases, a polymer mixture) is also included.

  The polymerizable monomer having a carbon-carbon double bond is not particularly limited, but particularly representative compounds include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citracone. Various carboxyl group-containing monomers such as acids, and salts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxyl fumarate, Various hydroxyl group-containing monomers such as monobutylhydroxy itaconate; various monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate ( (Meth) acrylic acid esters; Various nitrogen-containing vinyl monomers such as (meth) acrylimide, diacetone acrylamide, N-methylol acrylamide or (meth) acrylonitrile; various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene, Various vinyl esters such as vinyl acetate and vinyl propionate; γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, “Silaplane FM-07” (methacryloyl silicon macromer) manufactured by Chisso Corporation Various silicon-containing polymerizable monomers; phosphorus-containing vinyl monomers; vinyl chloride, biliden chloride, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafur Various vinyl halides such as Russia propylene; various conjugated dienes such as butadiene and the like.

  In order to improve the adhesion with the hard coat layer, it is also possible to use an acrylic resin containing a functional group such as a hydroxyl group, an amino group, or an amide group.

  In the coating layer formation in the film of the present invention, the coating layer of the coating layer is strengthened, has sufficient adhesion with various hard coat layers, and is crosslinked to improve the heat and heat resistance after these layers are formed. It is preferable to use an epoxy compound and an oxazoline compound as the agent.

  As an epoxy compound, the compound containing an epoxy group in a molecule | numerator, its prepolymer, and hardened | cured material are mentioned, for example. Examples include condensates of epichlorohydrin with hydroxyl groups and amino groups such as ethylene glycol, polyethylene glycol, glycerin, polyglycerin, and bisphenol A, and polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, and the like. is there. 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, trimethylol. Examples of the propane 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, propylene glycol diglycidyl ether. Ether, polypropylene glycol diglycidyl ether, Ritetramethylene glycol diglycidyl ether and monoepoxy compounds include, for example, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N ′,-tetraglycidyl-m. -Xylylenediamine, 1,3-bis (N, N-diglycidylamino) cyclohexane and the like.

  An oxazoline compound is a compound having an oxazoline group in the molecule. In particular, a polymer containing an oxazoline group is preferable, and it 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.

  In the coated film of the present invention, a binder polymer other than an acrylic resin is used in combination to improve the coated surface shape, improve the visibility when various hard coat layers are formed on the coated surface, and improve the transparency. Is also possible.

  The “binder polymer” used in the present invention is a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) according to a polymer compound safety evaluation flow scheme (sponsored by the Chemical Substance Council in November 1985). ) Is a polymer compound having a molecular weight of 1000 or more and having a film-forming property.

  Specific examples of the binder polymer include polyester resin, urethane resin, polyvinyl (polyvinyl alcohol, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches, and the like. Can be mentioned. Among these, it is preferable to use a polyester resin in combination from the viewpoint of improving the coated surface and adhesion.

  Moreover, it is also possible to contain particle | grains for the improvement of the slipperiness of a coating layer, or a blocking improvement. Examples of the particles used include inorganic particles such as silica, alumina, and metal oxide, or organic particles such as crosslinked polymer particles.

  Furthermore, as long as it does not impair the gist of the present invention, the coating layer has an antifoaming agent, a coating property improving agent, a thickener, an organic lubricant, an antistatic agent, an ultraviolet absorber, an antioxidant, foaming as necessary. Agents, dyes and the like may be contained.

  In the present invention, the content of the acrylic resin in the coating layer is usually 20 to 90% by weight, preferably 25 to 85% by weight, and more preferably 30 to 80% by weight. When the amount is less than 20% by weight, the adhesion may not be sufficient due to the small amount of the acrylic resin component, and when it exceeds 90% by weight, the coating layer becomes brittle due to the small amount of the crosslinking agent component, and the adhesion is not sufficient. In some cases, the heat and humidity resistance may not be sufficient.

  In this invention, the quantity of the compound derived from the epoxy compound and oxazoline compound which occupies in a coating layer is 10-80 weight% normally, Preferably it is 15-75 weight%, More preferably, it is 20-70 weight%. When the amount is less than 10% by weight, the coating layer becomes brittle and may not sufficiently withstand moisture and heat. When the amount exceeds 80% by weight, the adhesion may not be sufficient. Moreover, it is preferable that at least one of an epoxy compound and an oxazoline compound exceeds 5 weight%. When both are 5 wt% or less, the adhesion to the active energy ray-curable resin layer may not be stable when exposed to high temperature and high humidity conditions for a long time.

  Moreover, the coating layer of the film of the present invention comprises a surfactant, an antifoaming agent, a coating property improving agent, a thickener, an organic lubricant, organic particles, inorganic particles, an antioxidant, an ultraviolet absorber, a foaming agent, It may contain additives such as dyes and pigments. These additives may be used alone or in combination of two or more as necessary.

As long as water is the main medium, the coating agent may contain a small amount of an organic solvent for the purpose of improving dispersion in water or improving the film-forming performance. It is necessary to use the organic solvent as long as it is soluble in water. Examples of the organic solvent include aliphatic or alicyclic alcohols such as n-butyl alcohol, n-propyl alcohol, isopropyl alcohol, ethyl alcohol, and methyl alcohol, glycols such as propylene glycol, ethylene glycol, and diethylene glycol, n-butyl cellosolve, Glycol derivatives such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether, ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate and amyl acetate, ketones such as methyl ethyl ketone and acetone, amides such as N-methylpyrrolidone Can be mentioned.
These organic solvents may be used in combination of two or more as required.

  Moreover, you may use together heat treatment and active energy ray irradiation, such as ultraviolet irradiation, as needed irrespective of offline coating or in-line coating as needed. The polyester film constituting the laminated polyester film in the present invention may be subjected to surface treatment such as corona treatment or plasma treatment in advance. Such a coat may be either single-sided or double-sided. The coating material may be either water-based and / or solvent-based for off-line coating, but is preferably water-based or water-dispersed for in-line coating.

  The coating liquid used in the present invention is preferably an aqueous solution or an aqueous dispersion in terms of handling and working environment, but contains water as the main medium and contains an organic solvent as long as it does not exceed the gist of the present invention. You may do it.

  Although there is no restriction | limiting in particular in the solid content density | concentration of a coating liquid, Usually, 0.3 to 65 weight%, Preferably it is 0.5 to 30 weight%, More preferably, it is 1 to 20 weight%. When the concentration is too high or too low than these ranges, it may be difficult to provide a coating layer having a thickness necessary for fully expressing the function.

  The thickness of a coating layer is dry thickness, and is 0.003-1.5 micrometers normally, Preferably it is 0.01-0.5 micrometer, More preferably, it is 0.01-0.3 micrometer. If the thickness of the coating layer is less than 0.003 μm, sufficient performance may not be obtained, and if it exceeds 1.5 μm, blocking between films tends to occur.

  As a coating method of the coating agent, for example, a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, or a coating apparatus other than these as shown in Yuji Harasaki, Tsuji Shoten, published in 1979, “Coating Method” Can be used.

  In the present invention, it is preferable to contain inorganic particles or organic particles in the coating layer in order to further improve the slipperiness, adhesion and the like. The compounding amount of the particles in the coating agent is usually 0.5 to 10% by weight, preferably 1 to 5% by weight. When the blending amount is less than 0.5% by weight, the blocking resistance may be insufficient. When the blending amount exceeds 10% by weight, the transparency of the film is hindered and the image sharpness tends to be lowered.

  Examples of the inorganic particles include silicon dioxide, alumina, zirconium oxide, kaolin, talc, calcium carbonate, titanium oxide, barium oxide, carbon black, molybdenum sulfide, and antimony oxide. Among these, silicon dioxide is easy to use because it is inexpensive and has various particle sizes.

  Examples of the organic particles include polystyrene or polyacrylate polymethacrylate in which a crosslinked structure is achieved by a compound (for example, divinylbenzene) containing two or more carbon-carbon double bonds in one molecule.

  The above inorganic particles and organic particles may be surface-treated. Examples of the surface treatment agent include a surfactant, a polymer as a dispersant, a silane coupling agent, a titanium coupling agent, and the like. The content of the particles in the coating layer is preferably 10% by weight or less, more preferably 5% by weight or less as an appropriate addition amount that does not impair the transparency.

  The coating layer may contain an antifoaming agent, a coating property improving agent, a thickener, an antioxidant, an ultraviolet absorber, a foaming agent, a dye, a pigment, and the like.

  In addition, the multilayer polyester film constituting the coated film of the present invention may be mixed with other thermoplastic resins such as polyethylene naphthalate and polytrimethylene terephthalate as long as the gist of the present invention is not impaired. Can do. Moreover, you may mix | blend coloring agents, such as a ultraviolet absorber, antioxidant, surfactant, a fluorescent whitening agent, a lubricant agent, a light-shielding agent, a matting agent, and a dye, a pigment.

  The maximum roughness of the anchor layer surface after the heat treatment (180 ° C., 90 minutes) in the double-side coated film in which the anchor layer is provided on the film surface on which the coating layer is not provided using the coated film in the present invention (St ) Preferably satisfies the range of 300 to 550 nm, more preferably 350 nm to 500 nm.

  Conventionally, a transparent conductive film using a polyester film base material has a problem that a white cloudy phenomenon occurs and a delicate image cannot be displayed when laminated on a polyester base material or when a constituent base material for a touch panel is laminated. Was holding.

  The inventors of the present application considered that the maximum roughness (St) of the outermost surface in the multilayer polyester film substrate constituting the coated film is one of the causes (estimation) of the increase in internal haze of the transparent conductive film itself.

  Immediately before laminating the transparent conductive layer, the maximum roughness (St) of the outermost surface of the film (corresponding to the outermost surface of the film after laminating the anchor layer in the present invention) is suppressed to a low level, which is estimated to be derived from the oligomer of the film. It is considered possible to solve the white clouding phenomenon considered to be caused (estimated) by the formation of new protrusions.

  In the coated film in the present invention, the internal haze of the coated film is preferably 0.4% or less, more preferably 0.2% or less. When it is out of the range, problems such as white clouding may occur when the transparent conductive layer is laminated and bonded to the adhesive layer.

  On the other hand, in the coated film in the present invention, a transparent conductive film is generally laminated on the film surface on which the coating layer is not provided via an anchor layer. In that case, in the crystallization process of ITO which is a constituent material of the transparent conductive film, the polyester constituting the coating film is exposed by exposing the coating film to a high temperature atmosphere such as 150 ° C. for 1 hour or 180 ° C. for 90 minutes. It is considered that an oligomer (mainly a cyclic trimer) that is considered to be derived from a film base material is deposited and crystallized on the film surface after heat treatment to newly form protrusions. As a result, it is surmised that there is a problem that after the patterned transparent conductive film is laminated, there is a large difference in level between the place where the conductive film exists and the place where the conductive film does not exist, resulting in poor appearance. (For example, Patent Document 2)

  With regard to such problems, the present inventors have found that such problems can be solved if the oligomer derived from the polyester film can be reduced to such an extent that coarse protrusions are not formed after heat treatment.

  In the coated film of the present invention, a hard coat layer containing a binder polymer having an acrylate structure is preferably provided on the coated layer in consideration of durability when the transparent conductive layer is laminated.

  In the present invention, specific examples of the binder polymer having an acrylate structure constituting the hard coat layer include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, epoxy acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylol propane tri Acrylate, dimethylol tricyclodecane diacrylate, tetramethylene glycol tetraacrylate, 2-hydroxy-1,3-diaacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2- Bis [4- (acryloxyethoxy) phenyl] propane, dicyclopentenyl acrylate, tricyclodecanyl acrylate, tris (acryloxyethyl) ) Isocyanurate, urethane acrylate and the like. These may be used individually by 1 type and may use 2 or more types together. Furthermore, what used the said acrylate as the methacrylate may be used together, may be used individually by 1 type, and may use 2 or more types together. In addition, “Technical Information Association” issued on December 21, 2010, “How to select and use functional acrylates” has a description about specific examples.

  In the present invention, as specific examples of the photopolymerization initiator used for curing the binder polymer having the acrylate structure, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl- Phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1 -One, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4 -Methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -bu Non-1,2 (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like. Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Examples of titanocene-based photopolymerization initiators include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. Is mentioned. Examples of the oxime ester polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, 2- (2-hydroxy And ethoxy) ethyl ester. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

  Regarding the hard coat layer in the present invention, the coating thickness (after drying) is preferably in the range of 1 to 15 μm, more preferably 1 to 10 μm, and most preferably 1 to 5 μm. When the thickness (after drying) is less than 1 μm, it may be difficult to obtain an active energy ray-curable resin layer having a desired hardness. On the other hand, when the thickness exceeds 15 μm, an active energy ray-curable resin layer is provided. The film surface on the other side becomes too flat, and when the film is wound up in a roll shape, a defect such as scratches on the film may occur.

In the coated film in the present invention, it is preferable that a transparent conductive film is laminated on the film surface on which the coating layer is not provided via an anchor layer.
As for the anchor layer composition, acrylic resin, urethane resin, melamine resin, alkyd resin, siloxane polymer, organosilane condensate and the like can be mentioned. These compositions may be used alone, or two or more of them may be used in combination as long as the gist of the present invention is not impaired.

Moreover, as a constituent material of the transparent conductive film, a metal oxide is preferably used from the viewpoint of transparency, durability, and weather resistance. In particular, indium tin oxide (ITO), antimony-containing indium tin oxide ( ATO), tin oxide, zinc oxide (ZnO), indium zinc oxide (In ₂ O ₃ —ZnO) and the like are particularly preferably used.

  The method for forming the transparent conductive film is not particularly limited, and a conventionally known method can be employed. Specific examples include vacuum deposition, sputtering, and ion plating.

  An anchor coating can be applied between the transparent conductive film and the multilayer polyester film substrate as necessary for the purpose of improving adhesion and improving the appearance. The constituent material of the anchor coat layer is not particularly limited. For example, among inorganic substances, silicon oxide, aluminum oxide, magnesium fluoride and the like are preferably used. Among organic substances, acrylic resin, urethane resin, melamine resin, polyester resin, melamine resin, polycarbonate resin, polyolefin resin, polyvinyl resin, polyvinyl alcohol resin, organic silane polymer and the like are preferably used.

The formed transparent conductive film is patterned by etching. The shape of the pattern depends on the design of the touch panel that is the final product, but the finest details of the patterned portion are preferably in the range of 1 μm to 15 μm, and more preferably in the range of 5 μm to 15 μm.
When the finest part of the patterned part is less than 1 μm, the conductive part is too thin and the possibility of disconnection with a slight impact tends to increase. On the other hand, when the finest detail of the patterned portion exceeds 15 μm, streaks of the patterned portion are noticeable, and the appearance quality when finished as a final touch panel display product is deteriorated.

The transparent conductive film patterned by the etching process is heated and crystallized.
It is preferable that the temperature of heat processing is the range of 100 to 150 degreeC normally. When the temperature is lower than 100 ° C., there is a high possibility that the crystallization of the transparent conductive film does not proceed sufficiently. On the other hand, when the temperature exceeds 150 ° C., the oligomer component precipitates from the polyester substrate and the transparency of the entire transparent conductive film is high. There is a possibility that side effects such as falling will occur. However, in recent years, in the transparent conductive film formation process, from the viewpoint of productivity improvement, in the ITO crystallization process, the heat treatment temperature tends to be further increased to shorten the heat treatment time. Is a more serious problem.

  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. In the examples and comparative examples, “parts” means “parts by weight”. The measuring method used in the present invention is as follows.

(1) Measurement of 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. It was dissolved and measured at 30 ° C.

(2) Average particle size (d50) and particle size distribution The particle size was measured by a sedimentation method based on Stokes' resistance law using a centrifugal sedimentation type particle size distribution analyzer SA-CP3 manufactured by Shimadzu Corporation.

Particle size distribution (r)
The particle size distribution was determined in the same manner as the average particle size measurement method. Integration was performed from the large particle side in the equivalent sphere distribution, and the particle size distribution ratio (R) was calculated from the following equation.
(R) = particle diameter when particle cumulative weight is 25% / particle diameter when particle cumulative weight is 75%

(3) Measuring method of amount of oligomer contained in polyester raw material About 200 mg of the polyester raw material is weighed and dissolved in 2 ml of a mixed solvent of chloroform / HFIP (hexafluoro-2-isopropanol) ratio 3: 2. After dissolution, add 20 ml of chloroform, and then add 10 ml of methanol little by little. The precipitate is removed by filtration, and the precipitate is further washed with a mixed solvent having a chloroform / methanol ratio of 2: 1. The filtrate / washing solution is collected, concentrated by an evaporator, and then dried. After the dried product was dissolved in 25 ml of DMF (dimethylformamide), this solution was supplied to liquid chromatography (manufactured by Shimadzu Corporation: LC-7A) to determine the amount of oligomer in DMF, and this value was obtained as a chloroform / HFIP mixed solvent. Divide by the amount of the polyester raw material dissolved in the amount to make the amount of oligomers contained (% by weight). The amount of oligomer 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 oligomer (cyclic trimer) collected in advance and dissolving it in DMF accurately measured. The concentration of the standard sample is preferably in the range of 0.001 to 0.01 mg / ml.

The conditions for the liquid chromatograph were as follows.
Mobile phase A: Acetonitrile Mobile phase B: 2% acetic acid aqueous solution Column: “MCI GEL ODS 1HU” manufactured by Mitsubishi Chemical Corporation
Column temperature: 40 ° C
Flow rate: 1 ml / min Detection wavelength: 254 nm

(4) Thickness of Laminated Polyester Layer After fixing a small piece of film with an epoxy resin, it was cut with a microtome, and the cross section of the film was observed with a transmission electron micrograph. Two of the cross-sections are observed in parallel with the film surface, and the interface is observed by light and dark. The distance between the two interfaces and the film surface was measured from 10 photographs, and the average value was defined as the laminated thickness.

(5) Quantitative determination of metal element and phosphorus element amount in polyester film Using a fluorescent X-ray analyzer (model “XRF-1500” manufactured by Shimadzu Corporation) under the conditions shown in Table 1 below, the film FP method The amount of elements in the film was determined by single sheet measurement, and the detection limit in this method is usually about 1 ppm.

(6) Measurement of softening point of each polyester layer of multilayer polyester film After confirming the layer structure of the sample film in advance as described in (4), in the exposed film cross-section, one central portion of each polyester layer is placed at Nano Navi II. / E-Sweep / nano-TA2 (manufactured by SII Nanotechnology) was measured under the following measurement conditions, and the average value of N = 3 was used as the softening point of the polyester layer. In addition, regarding the measured value, the tangent in each curve of a temperature rising curve and a temperature falling curve was drawn from the obtained measurement chart, and the intersection of the tangent was calculated | required. Next, a point passing through the intersection of the obtained tangent lines and intersecting the measurement temperature axis perpendicularly was defined as a softening point.
"Measurement condition"
Temperature increase rate: 5 ° C / sec
Probe: Thermal cantilever AN2-200
Measurement temperature range: normal temperature (23 ° C) to 300 ° C
Measurement atmosphere: atmospheric pressure

(7) Internal haze of coated film According to JIS-K-7136, the haze value of a glass cell filled with an ethanol solution was measured using a haze meter manufactured by Suga Test Co., Ltd. (touch panel type haze computer HZ-2). It was set to 0%, and the test piece was measured in a state immersed in the same cell.

(8) Wiring disconnection evaluation after patterning of transparent conductive film In a double-sided coated film with a hard coat layer, 95 wt.% Of indium oxide in an atmosphere of 0.4 Pa composed of 95% argon gas and 5% oxygen gas on the anchor layer. %, A 25 nm thick ITO film (transparent conductive thin film) was formed by a reactive sputtering method using a sintered body material of 5% by weight of tin oxide. After applying a patterned photoresist on the ITO film (most detail: 5 μm, 10 μm, 15 μm) and drying and curing, the obtained ITO film was made into 4% hydrogen chloride aqueous solution (manufactured by Wako Pure Chemical Industries). It was immersed in and etched. The obtained patterned ITO film was crystallized by heat treatment at 180 ° C. for 90 minutes. 100 locations of the ITO film after patterning obtained are inspected with an optical microscope (Keyence Corp., digital microscope model number: VHX-200) at a magnification of 40 times, and the presence or absence of breakage of ITO is inspected. The wire disconnection after the transparent conductive film patterning was evaluated according to the following criteria.
<< Anchor layer composition >>
Silane compound (Colcoat P (manufactured by Colcoat))
A 1% strength solution was prepared using isopropyl alcohol.
<Criteria>
○: Disconnection of ITO wiring is not confirmed. Δ: Disconnection of ITO wiring is not confirmed, but cracking of wiring is confirmed. ×: Disconnection of ITO wiring is confirmed at one or more places.

(9) Evaluation method of adhesion 1 As a hard coat layer coating solution, 100 parts by mass of resin (Halus Hybrid UV-G301 manufactured by Nippon Shokubai Co., Ltd.), 10 parts by mass of isocyanate (manufactured by Sumika Bayer Urethane, Desmodur N-3200), 100 parts by mass of toluene and 100 parts by mass of methyl ethyl ketone were prepared, and a hard coat layer having a thickness of 15 g / m ² was formed by applying and heat curing on the coating layer of the sample film. After that, 10 × 10 cross cut is applied to the hard coat layer, and a 18 mm wide tape (Cello Tape (registered trademark) CT-18 manufactured by Nichiban Co., Ltd.) is applied on the hard coat layer. After peeling off rapidly, the peeled surface is observed. For the larger peeled area, ○ if the peeled area is 5% or less, Δ if it exceeds 5% and 30% or less, and × if it exceeds 30%. It was.

(10) Evaluation method of adhesion 2 As a coating solution for a hard coat layer, 60 parts by mass of dipentaerythritol hexaacrylate, 6 parts by mass of 2-hydroxy-3-phenoxypropyl acrylate, a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) ) 4 parts by mass, 200 parts by mass of methyl ethyl ketone were prepared, applied onto the coating layer of the sample film, and cured by irradiating with ultraviolet rays to form a hard coat layer having a thickness of 10 g / m ² . Immediately thereafter (initial), after 150 hours in an environment of 80 ° C./90% RH (wet heat test), a 10 × 10 cross-cut was made on the hard coat layer, and then a 18 mm wide tape (Nichiban) Cellotape (registered trademark) CT-18 manufactured by Co., Ltd. was affixed and peeled off rapidly at a peeling angle of 180 degrees, and then the peeled surface was observed. The peeled area was 5% relative to the larger peeled area. In the following, it was evaluated as ◯ if it exceeded 5% and 30% or less, and × if it exceeded 30%.

(11) Processing suitability of coated film At the time of sputtering processing in (8), the film flatness of the processed part was visually evaluated. <Criteria>
○: The processed portion of the film is well processed without waviness and wrinkles in the entire width direction. ×: Waviness and wrinkles are generated in the processed portion of the film, and it cannot be processed uniformly in the width direction.

(12) Cushion effect of adhesive (practical property substitution evaluation)
A non-carrier film “KF4 # 50” manufactured by New Tack Kasei Co., Ltd. was peeled off and separated onto the surface of the hard coat layer of the double-side coated film with a hard coat layer. Next, the heavy release side separator was peeled off and bonded to a plate glass ("float plate glass (5 mm thickness)") manufactured by Nippon Sheet Glass Co., Ltd., to prepare a double-sided coated film (hard coat layer side) / adhesive layer / glass structure. The structure was brought into contact with the pen tip of a ballpoint pen from the double-side coated film side, and the cushioning effect of the adhesive was subjected to sensory evaluation according to the following criteria.
<Criteria>
○: While the pen is in contact, the adhesive layer follows the contacted area. When contact is stopped, the follow-up deformation of the adhesive layer is restored (you can feel the cushion effect)
×: Even if the pen is brought into contact, the adhesive layer is not deformed and the cushion effect cannot be felt.

(13) Maximum surface roughness (St) measurement of film surface Non-contact using the measurement surface of the sample film as the measurement surface of the sample film using the direct phase detection interferometry, so-called two-beam interference method using Michelson interference The surface roughness (St) was measured by a surface measurement system “Micromap 512” manufactured by Micromap. Note that the measurement wavelength is 530 nm, the objective lens is 20 ×, and the 20 ° field of view is measured. Among the measurement values measured in total, the average value of 10 points excluding the maximum and minimum values is adopted. The surface roughness (St) was used. According to the above measurement method, in the coated film, after providing an anchor layer on the film surface where the coating layer before heat treatment is not provided and the film surface where the coating layer is not provided, after heat treatment at 180 ° C. for 90 minutes, The maximum roughness (St) of the anchor layer surface was measured.

<Manufacture of polyester>
[Production method of polyester (A)]
Using 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol as starting materials, adding tetrabutoxy titanate as a catalyst to the reactor, setting the reaction start temperature to 150 ° C., and gradually increasing the reaction temperature as methanol is distilled off. It was 230 degreeC after 3 hours. After 4 hours, the transesterification reaction was substantially terminated. This reaction mixture was transferred to a polycondensation tank and subjected to a polycondensation reaction 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 is stopped at a time corresponding to an intrinsic viscosity of 0.55 due to a change in the stirring power of the reaction vessel, and the polymer is discharged under nitrogen pressure, and the intrinsic viscosity is 0.59 and contains an oligomer (cyclic trimer). A quantity of 0.89% by weight of polyester A was obtained.

[Production method of polyester (B)]
Polyester (A) was pre-crystallized at 160 ° C. in advance, and then solid-phase polymerized in a nitrogen atmosphere at a temperature of 220 ° C., limiting viscosity 0.72 and oligomer (cyclic trimer) content 0.46% by weight. Polyester (B) was obtained.

[Production method of polyester (C)]
Starting from 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol, magnesium acetate / tetrahydrate is added as a catalyst to the reactor, the reaction start temperature is set to 150 ° C., and the reaction temperature is gradually increased as methanol is distilled off. Was raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially terminated. This reaction mixture was transferred to a polycondensation tank, orthophosphoric acid was added, and then germanium dioxide was added to conduct a polycondensation reaction 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 vessel, and the polymer was discharged under nitrogen pressure to obtain a polyester (C) having an intrinsic viscosity of 0.63. .

[Production method of polyester (D)]
In the production method of polyester (A), divinylbenzene cross-linked polystyrene particles having an average particle diameter of 0.4 μm were prepared in the same manner except that the content to the polyester was 0.5% by weight. ) The obtained polyester (D) had an intrinsic viscosity of 0.59 and an oligomer (cyclic trimer) content of 0.87% by weight.

[Production method of polyester (E)]
In the production method of the polyester (A), it is produced in the same manner except that the aluminum oxide particles dispersed in ethylene glycol having an average particle diameter of 60 nm are added so that the content of the particles with respect to the polyester is 1.5% by weight, Polyester (E) was obtained. The obtained polyester (E) had an intrinsic viscosity of 0.59 and an oligomer (cyclic trimer) content of 0.87% by weight.

[Production method of polyester (F)]
In the manufacturing method of polyester (D), it manufactured similarly except having added the divinylbenzene crosslinked polystyrene particle | grain with an average particle diameter of 0.7 micrometer, and obtained polyester (F). The obtained polyester (F) had an intrinsic viscosity of 0.59 and an oligomer (cyclic trimer) content of 0.87% by weight.

[Production method of polyester (G)]
In the manufacturing method of polyester (D), it manufactured similarly except having added divinylbenzene crosslinked polystyrene particles with an average particle diameter of 0.2 micrometer, and obtained polyester (F). The obtained polyester (F) had an intrinsic viscosity of 0.59 and an oligomer (cyclic trimer) content of 0.87% by weight.

Example 1:
The above-mentioned polyester (B), (C), (D), and (E) are mixed at a ratio of 75%, 10%, 10%, and 5%, respectively. Using the raw material of B as the raw material of the B layer, each was supplied to two extruders, melted at 285 ° C each, and then cooled to 40 ° C using the A layer as the outermost layer (surface layer) and the B layer as the intermediate layer On the drum, two types and three layers (ABA) were coextruded so as to have a thickness composition ratio of A: B: A = 2: 19: 2, and cooled and solidified to obtain a non-oriented sheet. Next, the film was stretched 3.4 times in the machine direction at a film temperature of 85 ° C. using the difference in roll peripheral speed, and then the coating layer (after drying) composed of the following coating solution was applied to 0.030 g / m 2. After that, this longitudinally stretched film was guided to a tenter, stretched 4.3 times in the transverse direction at 120 ° C., heat treated at 225 ° C. for 5 seconds, and then wound on a roll to form a coated film having a thickness of 23 μm. Got.

[Preparation of coating solution]

Examples of compounds constituting the coating layer are as follows.
(Example compounds)
Acrylic resin: (IA) Aqueous dispersion of acrylic resin polymerized with the following composition: ethyl acrylate / n-butyl acrylate / methyl methacrylate / N-methylol acrylamide / acrylic acid = 65/21/10/2/2 (% by weight) Emulsion polymer (emulsifier: anionic surfactant)
Acrylic resin: (IB) Aqueous dispersion of acrylic resin polymerized with the following composition: ethyl acrylate / methyl methacrylate / 2-hydroxyethyl methacrylate / N-methylol acrylamide / acrylic acid = 65/28/3/2/2 (% by weight ) Emulsion polymer (emulsifier: anionic surfactant)

Polyester resin: (II) A water dispersion of a 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%)

Epoxy compound: (III) Denacol EX-521 (manufactured by Nagase ChemteX), which is polyglycerol polyglycidyl ether

・ Oxazoline compounds: (IVA)
Acrylic polymer Epocros WS-500 having an oxazoline group and a polyalkylene oxide chain (manufactured by Nippon Shokubai, containing about 38% by weight of 1-methoxy-2-propanol solvent)
・ Oxazoline compounds: (IVB)
Oxazoline group-containing acrylic polymer Epocros WS-300 (manufactured by Nippon Shokubai)

  Particles: (V) Silica sol with an average particle diameter of 65 nm

In the obtained coated film, an anchor layer composed of the following anchor layer composition was coated on the surface of the film on which the anchor layer was not provided so that the coating amount (after drying) was 0.1 g / m 2, and then 100 ° C. It heat-processed for 1 minute and obtained the coating film in which the anchor layer was provided.
<Anchor layer composition>
Colcoat P (manufactured by Colcoat)
A 1% strength solution was prepared using isopropyl alcohol.
Furthermore, in the double-side coated film, the coating film was dried by heating a hard coat layer composition composed of the following hard coat layer composition on the coating layer at 60 ° C. for 1 minute. Thereafter, ultraviolet light with an integrated light quantity of 300 mJ / cm ² was irradiated with a high-pressure mercury lamp to obtain a double-side coated film with a hard coat layer having a coating amount (after drying) of 2 μm (after drying).
<Hard coat layer composition>
Binder (Nippon Paint “Luciferal NAB-007” 100 parts by weight Acrylic fine particles (Sekisui Plastics Co., Ltd. trade name “BMSA-18GN” (average particle size 0.8 μm) 0.1 part by weight) A hard coat layer composition having a solid content of 40% by weight was prepared by dispersing in ketone.

Examples 2-14:
In Example 1, a coating film was obtained in the same manner as in Example 1 except that the coating layer, the raw material composition, and the thickness configuration were different.

Comparative Example 1:
In Example 1, except that polyesters (A), (C), (D), and (E) were mixed in proportions of 84% and 16% as raw materials for the A layer, respectively, in the same manner as in Example 1, A coated film was obtained.

Comparative Example 2:
In Example 1, a coating film was obtained in the same manner as in Example 1 except that the type of coating layer was changed.

Comparative Example 3:
In Example 1, a coating film was obtained in the same manner as in Example 1 except that the type of coating layer was changed.

Comparative Example 4:
In Example 1, a coating film was obtained in the same manner as in Example 1 except that the type of coating layer was changed.

Comparative Example 5:
In Example 1, a coated film was obtained in the same manner as in Example 1 except that the thickness component ratio was A: B: A = 2: 5: 2 and the obtained film thickness was 9 μm.

Comparative Example 6:
In Example 1, a coated film was obtained in the same manner as in Example 1 except that the thickness component ratio was A: B: A = 2: 71: 2 and the obtained film thickness was 75 μm.

Comparative Example 7:
In Example 1, a coated film was obtained in the same manner as in Example 1 except that the thickness component ratio was A: B: A = 4: 15: 4.

Comparative Examples 8-11:
In Example 1, the coating film was obtained by the same method as Example 1 except the raw material of A layer differing.

  The characteristics of each film obtained in the above Examples and Comparative Examples are shown in Tables 1 to 5 below.

  The coated film of the present invention has good heat resistance, transparency, and good visibility after laminating a patterned transparent conductive layer, for example, for a transparent conductive film substrate, and is suitable for a touch panel, for example. Industrial value is high.

Claims (3)

Provided with a coating solution containing an acrylic resin and two or more types of crosslinking agents on one side of a multilayer polyester film that comprises at least three layers of both outer and intermediate layers and simultaneously satisfies the following formulas (1) and (2) The film thickness is 10 to 60 μm, the two outer layers contain two kinds of particles having different average particle diameters, and the thicknesses of the polyester layers constituting the outer layers are each 3 μm or less, A coated film for a transparent conductive film substrate, characterized in that the softening point of both outer layers is higher than the softening point of the polyester layer constituting the layer.
0 <Ti ≦ 20 (1)
0 ≦ P ≦ 300 (2)
(In the above formula, Ti represents the amount of Ti element (ppm) in the multilayer polyester film, and P represents the amount of phosphorus element (ppm)). The double-sided coating film for transparent conductive film base materials of Claim 1 which has an anchor layer in the film surface opposite to the surface which has a coating layer. The double-sided coating film for transparent conductive film base materials of Claim 1 or 2 which has a hard-coat layer on a coating layer.