TWI674195B - Coated film - Google Patents

Abstract

The present invention provides a component of an optical product, particularly when used as a microlens for LCD backlight and a base film of 稜鏡. Even if the back coating process is not performed, the antistatic performance of the back coating can be obtained. Various functions of abrasion performance and masking performance, maintain high brightness, can give bright and high-quality pictures, and have excellent optical performance and coating film corresponding to cost.

The coating film is a biaxially-stretched laminated polyester formed of a three-layer structure each using a polyester layer (A) and a polyester layer (C) as a surface layer and a polyester layer (B) as an intermediate layer. The (A) layer of the film has an easy-adhesion coating layer containing a polymer, the (C) layer has an antistatic coating layer containing a compound having an ammonium group, and the (C) layer contains an average particle diameter of 2.0 to 9.0 μm organic particles.

Description

Coated film

The present invention relates to a coating film suitable for use in optics, and more specifically, to a substrate for microlenses, cymbals, etc. for optical sheets used as a backlight for a liquid crystal display (hereinafter also simply referred to as LCD). In the coating film, in order to cope with the dramatic cost background in recent years, high brightness and high-quality screens can be maintained even without the previous back coating processing step of applying a back coating machine to a substrate film. Coating film with excellent optical performance and cost.

Previous polyester films, especially biaxially stretched films of polyethylene terephthalate and polyethylene naphthalate, have been widely used as magnetic tapes because of their excellent mechanical properties, heat resistance, and chemical resistance. Films for ferromagnetic films, photo films, packaging films, films for electronic components, electrical insulation films, metal laminated films, glass displays, and other films that are laminated to glass surfaces, and films for the protection of various components.

In recent years, polyester films have been widely used in various optical sheets, such as ITO-based diffuser sheets, microlens sheets, fluorene sheets, composite sheets, reflective plates, and touch panels. It can be used for various applications such as basic film of hard coating film, basic film for anti-reflection, basic film for explosion-proof display, and film for PDP filter.

Among these optical sheets, microlens sheets, cymbals, etc., which are used as backlights for LCDs, are processed on one side by a grinding rod having functions of microlenses, cymbals, and the like. The sheets are adhered to each other to prevent damage to other members and to shield the image of the light source lamp of the backlight unit, etc., and have been subjected to back coating processing having functions such as antistatic, abrasion (sliding), and shielding properties, but in recent years, In order to meet the demand for cost reduction of the stress, and without the back coating processing step previously performed, a back coating function can be provided to the polyester film for the substrate.

However, for example, in order to have the performance of shielding the image of a light source lamp in a backlight unit, a method generally used is a method of increasing the turbidity of a basic film. The specific method is to use silicon dioxide, calcium carbonate, magnesium carbonate, carbonic acid, etc. A method for adding inorganic particles such as barium, calcium sulfate, calcium phosphate, magnesium phosphate silicon oxide, kaolin, alumina, and titanium oxide to a thin film. However, in this method, a large number of particles are required for high turbidity in order to mask the image of the lamp. There are problems that the filter pressure is frequently increased during the film forming process and the filter needs to be exchanged, and the film is easily broken to cause poor productivity, and a large number of particles are required to increase the cost.

In addition, due to the large number of particles in the film, light reflection, scattering, absorption, etc. will be affected, so the required light transmittance of the original basic film will be reduced, and as a result, the brightness will be reduced, and clear high-definition and high-quality images cannot be obtained. The problem.

In order to avoid reducing the light transmittance due to the particles inside the film, That is, to reduce the brightness, a method of making the structure of the film into a multilayer system and adding particles only to the surface layer portion was considered. At this time, in order to perform various processes such as microlenses and cymbals on one side, only the unprocessed On the opposite side, a high turbidity can be achieved, which can shield the light source lamp. However, even if a large number of particles are added, the shielding effect is difficult to achieve. Moreover, the use of a large number of particles will cause the surface roughness of the film to be excessively rough, and the relative The problem of deterioration of the damage of other components.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2011-227436

Patent Document 2: Japanese Patent Application Laid-Open No. 2010-247481

In view of the above facts, the problem to be solved by the present invention is to provide a component of an optical product, especially a microlens or a base film for a backlight of an LCD, which can be obtained without back coating processing. The back coating has various functions of antistatic performance, abrasion performance, and shielding performance, maintains high brightness, can give clear and high-quality pictures, and has a coating film with excellent optical performance and cost.

In view of the above-mentioned problems, the present inventors have intensively reviewed and found that, by using a thin film having a specific structure, the above problems can be easily solved and completed. this invention.

That is, the gist of the present invention is to provide a biaxial feature formed by a three-layer structure each including a polyester layer (A) and a polyester layer (C) as a surface layer and a polyester layer (B) as an intermediate layer. The (A) layer of the stretch-laminated polyester film has a polymer-adhesive coating layer, the (C) layer has an antistatic coating layer containing a compound having an ammonium group, and the (C) layer contains an average A coating film of organic particles with a particle diameter of 2.0 to 9.0 μm.

The coating film of the present invention can solve the cost reduction requirements in recent years in order to meet the drastic cost reduction without reducing the brightness. The basic films of the microlenses used as the backlight optical sheet for LCD and the thin films such as cymbals are not back-coated. During processing, the image of the light source lamp is developed, and a clear and high-definition picture cannot be obtained, and problems such as damage to other members and the bonding of the sheets to each other are caused, and high quality and corresponding costs are imparted. And because the non-back-coated processing layer is a polyester film itself containing organic particles, there is no unfavorable matter such as reduced performance and process pollution due to particle shedding, and it has extremely high industrial value.

The polyester used in the polyester film refers to a product obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic diol. Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the like; aliphatic diols such as ethylene glycol, diethylene glycol, trimethylene glycol, and tetramethyl glycol , Neopentyl glycol, 1,4- Cyclohexanedimethanol and the like. Typical polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylic acid (PEN), polybutylene terephthalate, and the like. The polyester may be an unpolymerized homopolymer or a dicarboxylic acid component other than 20 mol% or less in the dicarboxylic acid component as the main component and / or a diol component 20 mol% or less in the dicarboxylic acid component as the main component. A diol-like copolymerized polyester. It can also be a mixture of these.

Polyester can be obtained by previously known methods, such as a method of directly reacting a dicarboxylic acid with a diol to obtain a low degree of polymerization polyester, or a previously known transesterification catalyst can be used to make a lower alkyl ester of a dicarboxylic acid and a diol It is obtained by performing a polymerization reaction in the presence of a polymerization catalyst after the reaction. The polymerization catalyst used may be a known catalyst such as an antimony compound, a germanium compound, a titanium compound, or an aluminum compound, but when the content of the antimony compound is the antimony element, it is preferably 100 ppm or less, more preferably 50 ppm or less, and more preferably 10 ppm or less. Particularly preferred is a range of 2 ppm or less. When the above range is used, it is easy to reduce film unevenness.

In addition, the polyester can be fragmented after melt polymerization, and if necessary, solid phase polymerization can be performed under heating and reduced pressure or in an inert gas stream such as nitrogen to adjust the limiting viscosity and the like. The limiting viscosity of 80% by weight or more of the polyester constituting the film for the limiting viscosity of the polyester is preferably 0.50 dl / g or more, more preferably 0.50 to 0.90 dl / g, and even more preferably 0.55 to 0.80 dl / g. Particularly preferred is a range of 0.60 to 0.75 dl / g. When the above range is used, the manufacturability of the film can be improved, and a film having excellent mechanical strength and heat resistance is easily obtained.

On the surface layer (A) of the polyester film that can be used as a functional layer for backlights such as microlenses or cymbals, etc., in order to prevent the film from being scratched and the winding characteristics when the product is split by the main roll, etc. The purpose is to give slippery Sex particles. However, when there are no particular problems in the film-making process by preventing the film from being damaged and the winding characteristics when cutting the product through measures such as adjusting the roller material, adjusting the temperature of the roller, and removing the adherence of the roller, it is not necessary to add.

The type of particles to be added may be particles capable of imparting slipperiness, and is not particularly limited. Specific examples include silicon dioxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate silica, kaolin, and alumina. , Inorganic particles such as titanium oxide, acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, benzoguanamine resin and other organic particles. It is also possible to use particles in which metal compounds, such as catalysts, are precipitated due to precipitation and microdispersion during the polyester manufacturing process. Among them, from the viewpoint of showing the effect easily in a small amount, silica particles or calcium carbonate particles are preferred.

In addition, the shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, and a flat shape can be used. The hardness, specific gravity, and color are not particularly limited. These particles may be used in combination of two or more kinds if necessary.

The average particle diameter of the particles used in the layer (A) is preferably from 0.01 to 3.3 μm, and more preferably from 1.5 to 3.0 μm. When the average particle diameter is less than 0.01 μm, the particles are likely to aggregate and make the dispersion insufficient, and when it exceeds 3.3 μm, the surface roughness of the film is excessively rough, and microlenses and cymbals cannot be uniformly processed, and microlenses occur It is unsuitable to deteriorate the optical properties of 稜鏡 processing.

In addition, the content of the particles with respect to the content in the (A) layer is preferably 0.35% by weight or less, more preferably 0.15% by weight or less, more preferably 0.05% by weight or less, and the lower limit thereof is preferably 0.0001% by weight. Added amount When it exceeds 0.35 wt%, the surface roughness of the film is excessively rough, and it is impossible to uniformly process the microlenses and cymbals, thereby deteriorating optical characteristics such as brightness.

In addition, the layer (C) maintains the characteristics of high brightness, and at the same time, it can provide the functions of shielding the image of the light source lamp and the abrasion resistance to prevent damage to other members, and it contains organic particles. Thing. The organic particles used may be previously known organic particles, such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, benzoguanamine resin, melamine resin, polysiloxane resin, and the like. Among these, especially when considering optical characteristics such as brightness and shielding properties, an acrylic resin, a styrene resin, or an acrylic-styrene copolymer resin is preferred. In consideration of thermal stability, an inactive type is preferable, and a crosslinked type is more preferable. These organic particles can be used alone or in combination of two or more.

The average particle diameter of the organic particles needs to be in the range of 2.0 to 9.0 μm, preferably 2.5 to 8.0 μm, and more preferably 3.0 to 7.0 μm, and more preferably 3.5 to 5.5 μm. When the average particle diameter is less than 2.0 μm, a large number of particles are required in order to achieve the shielding property, so the cost efficiency is small, and the light transmittance and brightness are reduced. In addition, when the average particle diameter exceeds 9.0 μm, the filter pressure is greatly increased during the film forming process, which deteriorates the productivity and easily causes film breakage. At this time, although the filter sieve was considered to be enlarged, the foreign matter in the film was increased, and there was a problem that it was difficult to obtain a high-quality picture. When the above range is used, the decrease in brightness can be avoided, and a thin film having excellent optical characteristics can be easily manufactured.

The content of the organic particles in the (C) layer constituting the surface layer is preferably 0.05 to 2.5% by weight, and more preferably 0.1 to 1.5% by weight, and more preferably The range is 0.2 to 1.0% by weight. When the above range is used, the shielding property for the light image for shielding the light source for the purpose of the present invention which is sufficient without lowering the brightness can be achieved. In addition, it is difficult for the surface roughening degree to be excessively rough when there are too many particles, and the damage to other members is significantly deteriorated.

When the organic particles are measured by a thermogravimeter, the 5% thermal decomposition temperature in an inactive environment is preferably 300 ° C or higher, and more preferably 310 ° C or higher. When the above range is used, the yellowish tone of the light transmission of the film can be reduced due to the occurrence of thermal deterioration, so it is easy to prevent the decrease in brightness and appearance quality.

The thickness of the polyester film may be in a range in which a film can be formed, and is not particularly limited, but is preferably in a range of 50 to 300 μm.

The total light transmittance of the polyester film is preferably 88% or more, more preferably 89% or more, and more preferably 90% or more. This type of film has high turbidity and excellent light transmission, so it can be used for optical applications. It is not suitable for optics when the total light transmittance is less than 88%.

The turbidity of the polyester film is preferably 6.0 to 30.0%, and more preferably 6.0 to 20.0%. If the turbidity is too high, the total light transmittance will be reduced and the brightness will be insufficient. Therefore, it is not suitable for optical use, and it will worsen the damage to other components. When it is too low, the image of the light source lamp cannot be achieved.

In the heat shrinkage of a polyester film at 150 ° C for 30 minutes, the film length direction (MD) is preferably 1.8% or less, and more preferably 1.5% or less. The film width direction (TD) is preferably 1.0% or less, more preferably 0.8%, and even more preferably 0.5% or less. When it is used as a component of a display product within the above range, it is easy to avoid the heat of the lamp for the light source of the backlight and the peripheral components, which affects the dimensional stability of the thin film forming the film, and can be particularly suppressed. The curling phenomenon occurs at the edge of the sheet, which can prevent the picture quality from being deteriorated due to screen distortion and speckle. The method for adjusting the heat shrinkage rate may be adjusting the temperature and stretching ratio of the film forming step.

The total thickness of the polyester film at the time of measurement is approximately 1000 μm, and the tone reflection method y value when a plurality of polyester films are overlapped in a range of 900 μm to 1000 μm is preferably in a range of 0.3230 or less. A range of 0.3225 or less is more preferable, a range of 0.3220 or less is more preferable, and a preferable lower limit range is 0.3180. When the y value of the hue reflection method exceeds 0.3230, the yellow tone of the film will be enhanced. When used as a display, the hue of the screen will be deteriorated due to its use form, and the brightness will be reduced. In addition, when a color difference occurs between the sheets, the color tone of the backlight on the light source side needs to be appropriately adjusted when assembling each sheet in the backlight unit, and when corresponding to the backlight of the light source LED in recent years, the light source color of the LED tends to be yellowish, and The enhanced yellow tone makes the screen yellow, so these sheets cannot be used when corresponding to the backlight of the LED.

In order to make the film have this color tone, the amount of catalyst can be reduced as much as possible by selecting catalysts and auxiliaries in the production of polyester raw materials, or in the polymerization and film formation without making the polyester to a higher temperature than necessary, and not pulling Long melting time.

In order to cope with cost reduction, the present invention can be used in the intermediate layer with regard to the regenerates from the flange portion, the main roll flange portion, and the main roll lower roll portion that occur during the production of the film, without departing from the spirit of the present invention. (B). When regenerating the (B) layer, since the organic particles added in the (C) layer will be mixed into the B layer, the amount of organic particles added to the (C) layer can be suppressed within the range of maintaining abrasion resistance to increase cost benefits. .

When layer (B) uses regeneration, except for turbidity and hue specifications In addition, it is preferably 60% by weight or less with respect to the (B) layer in terms of film forming stability for reducing the limiting viscosity.

The surface orientation (ΔP) of the polyester film is preferably 0.161 or more. When the surface orientation is 0.160 or less, the thickness feel when used as a biaxially stretched polyester film is increased, and the planarity of the film is deteriorated. Therefore, it is impossible to uniformly perform microlens processing and 稜鏡 processing, which may cause microlenses and 稜鏡The various optical properties are uneven, and some of the spots and screen spots with low brightness occur, which will cause uneven shielding performance of the light image used by the light source, and uneven unevenness with respect to other components.

The total amount of oligomers (ester cyclic terpolymers) deposited on the surface of the polyester film after heat treatment at 180 ° C for 10 minutes is preferably 15 mg / m ² or less, more preferably 10.0 mg / m. ² or less, particularly preferably 8.0 mg / m ² or less. When the amount of oligomers deposited on the surface of the film exceeds 15 mg / m ² , the oligomers on the surface crystallize and dissolve into the functional layer provided on the film, thereby affecting the characteristics and the like.

In order to make the amount of oligomers deposited on the surface of the film after the heat treatment fall into the above range, polyesters with less oligomer content in the (A) layer and (C) layer constituting the surface layer can be used, and set during online / offline The coating layer is used to suppress the precipitation of oligomers on the surface of the film, and the amount of oligomers deposited on the surface of the film after the heat treatment is within the above range.

The polyester film can be co-extruded to form a laminated structure, but the thickness of the (A) layer and (C) layer constituting the surface layer at this time is preferably in a range of 2.0 to 20.0 μm, and more preferably in a range of 3.0 to 15.0 μm. When the thickness is less than 2.0 μm, it is difficult to adjust the absolute amount of particles contained in each layer, and it is impossible to adjust Obtain sufficient optical characteristics. There is also the fear of particles falling off. In addition, when it exceeds 20.0 μm, it is difficult to adjust not only the particle content but also sufficient optical characteristics, and the film tends to easily curl.

In addition, additives such as an ultraviolet absorber and a dye may be added to layer B of the intermediate layer constituting the film.

The method for producing a polyester film will be described in detail below, but the invention is not particularly limited to the following examples as long as it conforms to the gist of the invention.

First, the polyester chips which have been dried by a known method or are not dried are supplied to a melting and extruding device, and are heated and melted at a temperature above the melting point of each polymer. Secondly, the melted polymer is extruded from the die, and quenched and solidified on a rotary cooling drum to a temperature below the glass transition temperature to obtain a substantially amorphous unaligned sheet. At this time, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum. In the present invention, it is better to use an electrostatic application method and / or a liquid coating method.

Then, the obtained sheet is stretched in a biaxial direction to form a thin film. The specific stretching conditions are preferably that the aforementioned unstretched sheet is stretched at 70 to 145 ° C in a longitudinal direction of 2.7 to 5 times, to obtain a longitudinal uniaxially stretched film, and then stretched in a horizontal direction at 3 to 5 times at 90 to 160 ° C. Then, heat treatment is performed at 210 to 240 ° C for 10 to 600 seconds. It is also preferable to relax the longitudinal direction and / or transverse direction by 2-20% in the highest temperature zone of the heat treatment and / or the cooling zone of the heat treatment exit at this time. Further, if necessary, re-longitudinal extension and re-lateral extension may be added.

The three-layer laminated film can be obtained by using three polyester melt extruder, that is, co-extrusion method. The structure of the layer may be a thin film composed of A / B / C obtained by using A raw material, B raw material, and C raw material.

In order to be able to be used on the microlenses used as the optical sheet of the LCD backlight and the thin sheets of the cymbal, the present invention is required to provide and improve the close contact with various functional layers such as the microlens resin and the cypress resin. And (A) the coating layer (easy-adhesion coating layer) is imparted to the surface side of (A). In addition, the (C) layer on the opposite side needs to be provided with a coating layer (antistatic coating layer) containing a compound having an ammonium group for improving antistatic properties and abrasion resistance.

When the coating layer is used to treat the surface of the film during the film-forming process of the polyester film, it can be set by the on-line coating method, and once the film is coated by the system, the offline coating method can be used. Among them, those formed by a wire coating method are preferred.

The in-line coating method is a method of coating in the manufacturing process of a polyester film, and specifically, a method in which the polyester can be coated at any stage in the heat-fixing and rewinding after the polyester is melted and extruded. Generally, it can be applied to any one of unstretched sheet obtained after melting and quenching, uniaxially stretched film after stretching, biaxially stretched film before heat fixing, or film before coiling after heat fixing. In addition, the method is not limited to the following method. For example, in the case of sequential biaxial stretching, a method of coating the uniaxially stretched film obtained by stretching the longitudinal direction (longitudinal direction) in particular and then extending the transverse direction is preferred. With this method, the film can be formed and the coating layer can be formed at the same time, which is conducive to manufacturing costs. In addition, the thickness of the coating layer can be changed by the stretching ratio when stretching after coating, so it is easier to perform thin film than offline coating. Coated. In addition, when a coating layer is provided on the film before stretching, the coating layer and the substrate film can be simultaneously stretched, so that the coating layer and the substrate film are more strongly and closely adhered. In addition, when manufacturing a biaxially stretched polyester film, the end of the film is stretched by the holder to restrain the vertical and horizontal directions of the film. Therefore, high temperature can be applied during the heat fixing process without wrinkles and maintaining flatness. The heat treatment after coating can achieve a high temperature that cannot be achieved by other methods, so the film-forming property of the coating layer can be improved, and the coating layer and the substrate film can be stronger and closer to each other to obtain a strong coating layer, which can improve Adhesiveness to various functional layers formed on the coating layer, and moisture and heat resistance.

As the easily-adhesive coating layer on the (A) layer side of the polyester film, various polymers known previously can be used.

Specific examples of the polymer include urethane resin, polyester resin, acrylic resin, polyethylene (polyvinyl alcohol, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, etc.), polyalkylene glycol, and polyalkylene oxide. Amine, methyl cellulose, hydroxy cellulose, starch, etc. Among them, from the viewpoint of improving the adhesion with the functional layer provided on the coating layer, urethane resin, acrylic resin, and polyester resin are preferred, and urethane resin and acrylic resin are more preferred. In particular, it is preferable to use a urethane resin from the viewpoint of improving the adhesion to an optical functional layer such as a fluorene layer or a microlens layer.

The urethane resin refers to a polymer compound having a urethane bond in a molecule. Generally, the urethane resin is obtained by the reaction of a polyol and an isocyanate. Polyols, such as polycarbonate polyols, polyester polyols, polyether polyols, polyolefin polyols, acrylic polyols, etc. These compounds can be used alone or in combination.

Polycarbonate polyols are obtained by a dealcoholization reaction between polyols and carbonate compounds. Polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Glycol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexane dimethyl Alcohol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol Alcohol, 3,3-dimethylolheptane, etc. Carbonate compounds such as dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethyl carbonate, etc. Polycarbonate polyols obtained by these reactions, such as poly (1,6 -Hexyl) carbonate, poly (3-methyl-1,5-pentyl) carbonate, and the like.

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

Polyether polyols include, for example, polyethylene glycol, polypropylene glycol, polyethylene glycol, polytetramethylene glycol, polyhexamethylene glycol, and the like.

In order to improve the adhesion with the functional layer, it is more preferable to use polycarbonate polyol and polyester polyol among the above-mentioned polyols.

Polyisocyanate compounds used in the production of urethane resins such as methylenediisocyanate, xylylenediisocyanate, methylenediphenyldiisocyanate, methylenediisocyanate, naphthalenediisocyanate, toluidinediamine Aromatic diisocyanates such as isocyanates, α, α, α ', α'-tetramethylxylene diisocyanate and other aliphatic diisocyanates diisocyanates with aromatic rings, methylidene diisocyanates, methylidene diisocyanates, Lysine diisocyanate, trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, Dicyclohexyl methane diisocyanate, alicyclic diisocyanate, etc. such as isopropylidene dicyclohexyl diisocyanate. These can be used alone or in combination.

When synthesizing urethane resin, a chain extender may be used. The chain extender may be one having two or more reactive groups reactive with isocyanate groups. There is no particular limitation. Generally, a chain having two hydroxyl groups or amine groups is mainly used. Extender.

Chain extender with 2 hydroxyl groups such as aliphatic ethylene glycol such as ethylene glycol, propylene glycol, butanediol, aromatic ethylene glycol such as xylylene glycol, dihydroxyethoxybenzene, etc. Ethylene glycol, such as pentanediol hydroxytrimethyl acetate, etc. In addition, a chain extender having two amine groups such as aromatic diamine, methylenediamine, xylylenediamine, diphenylmethanediamine, etc. Hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2- Aliphatic diamines such as ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1-amino- 3-amino Methyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidenecyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1 Cycloaliphatic diamines such as 3-bisaminomethylcyclohexane and the like.

The urethane resin may be a substance using a solvent as a medium, but is preferably a substance using water as a medium. It may be a forced emulsification type in which a urethane resin is dispersed or dissolved in water using an emulsifier, or a self-emulsification type or a water-soluble type in which a hydrophilic group is introduced into the urethane resin. In particular, the self-emulsifying type in which an ionic group is introduced into the structure of the urethane resin and an ionic bond is polymerized can obtain excellent liquid storage stability and water resistance, transparency, and adhesion of the obtained coating layer. .

The ionic group to be introduced includes various materials such as a carboxyl group, a sulfonic acid, a phosphoric acid, a phosphonic acid, and a quaternary ammonium salt, but a carboxyl group is preferred. The method for introducing the carboxyl group into the urethane resin may be a method performed in each stage of the polymerization reaction. For example, when synthesizing a prepolymer, a method in which a resin having a carboxyl group is used as a copolymerization component, or a method in which a component having a carboxyl group is used as a component of a polyol, a polyisocyanate, a chain extender, or the like. Particularly preferred is a method of using a carboxyl group-containing diol and introducing a desired amount of carboxyl group by the amount of the component added. For example, compared with diols used in the polymerization of urethane resins, it can be used with dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, and bis- (2- Hydroxyethyl) butyric acid copolymerization. The carboxyl group is preferably in the form of a salt obtained by neutralization with ammonia, amines, alkali metals, or inorganic bases. Particularly preferred are ammonia, trimethylamine, and triethylamine. This type of polyurethane resin may be a carboxyl group which is shed by a neutralizing agent during the drying process after coating, and is used as a crosslinking reaction point using other crosslinking agents. In addition to the liquid state before coating In addition to excellent stability, it can further improve the durability, solvent resistance, water resistance, and barrier resistance of the resulting coating layer.

Acrylic resin refers to a polymer formed by a polymerizable monomer having a carbon-carbon double bond represented by an acrylic-based or methacrylic-based monomer. These may be any of a single polymer or a copolymer. Copolymers of these polymers with other polymers (such as polyesters, polyurethanes, etc.) are also included. Examples are block copolymers and graft copolymers. Also included is a polymer obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyester solution or a polyester dispersion (in some cases, a polymer mixture). A polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyurethane solution or a polyurethane dispersion is similarly contained. Similarly, a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in another polymer solution or dispersion. Moreover, in order to improve adhesiveness, you may contain a hydroxyl group and an amine group.

The above-mentioned polymerizable monomer having a carbon-carbon double bond is not particularly limited, and specific representative compounds such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid are contained. Hydroxyl monomers and salts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl Hydroxyl fumarate and monobutyl hydroxyitaconate monomers containing various hydroxyl groups; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Various (meth) acrylates like butyl (meth) acrylate and lauryl (meth) acrylate; (meth) acrylamide, diacetone-propyl Various nitrogen-containing compounds such as enamine, N-methylol acrylamide, or (meth) acrylonitrile; various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene, Various vinyl esters like vinyl propionate; γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane and other silicon-containing polymerizable monomers; phosphorus-containing vinyl monomers ; Various vinyl halides such as vinyl chloride and vinylidene chloride; various conjugated diene like butadiene.

The polyester resin refers to a product composed of a polycarboxylic acid and a polyhydroxy compound as a main constituent as described below. That is, as the polycarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, and 1,5-naphthalene can be used. Dicarboxylic acids, and 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfo Phthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, pyromellitic acid, pyromellitic acid, trimellitic anhydride, Phthalic anhydride, p-hydroxybenzoic acid, trimellityl monopotassium salt, and ester-forming derivatives of these, etc. Polyhydric hydroxy compounds can be ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol , P-xylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol , Dimethylolpropionic acid, glycerol, trimethylolpropane, sodium dimethylolethanesulfonate, potassium dimethylolpropionate, and the like. One or more of these compounds can be appropriately selected, and a polyester resin can be synthesized by a conventional polycondensation reaction.

In addition, in the above polymers, when the fluorene layer and the microlens layer tend to have high brightness in recent years, it is difficult to ensure the adhesion of the general resin system, so it is better to further improve the adhesion. Therefore, it is preferable to introduce carbon-carbon. Double bond. When the coating layer easily contains a carbon-carbon double bond, the double bond and the carbon-carbon double bond forming the compound used for the erbium layer and the microlens layer will react to form a common bond when irradiated with ultraviolet rays. Improve adhesion.

The polymer used to introduce the carbon-carbon double bond can be any of the above polymers, but from the viewpoint of adhesion, urethane resin, acrylic resin, and polyester resin are particularly preferred. The best form is urethane. The ester resin contains a carbon-carbon double bond.

A carbon-carbon double bond-containing urethane resin refers to a substance containing a carbon-carbon double bond in a urethane resin, which may be contained in a compound capable of forming a fluorene layer and a microlens layer. The carbon-carbon double bond reaction product can be introduced into a urethane resin using known materials such as acrylate, methacrylate, vinyl, allyl, and the like.

Various substituents can be introduced into the carbon-carbon double bond, such as methyl, ethyl, and other alkyl groups, phenyl, halogen, ester, and amido groups, or they can have a conjugated double bond-like structure. In addition, the content of the substituent is not particularly limited, and any one of a 1-substituent, a 2-substituent, a 3-substituent, or a 4-substituent may be used. In consideration of the reactivity, the 1-substituent or the 2-substituent is preferred, and the 1-substituent is preferred. Substitute.

Considering the reactivity of easy introduction of urethane resin and the carbon-carbon double bond contained in the compound forming the fluorene layer and the microlens layer, it is preferably an acrylate group or a methacrylate group. Unsubstituted C An acrylate group or a methacrylate group is preferable, and an acrylate group having no substituent is particularly preferable.

The ratio of the carbon-carbon double bond portion (C = C portion, molecular weight 24) to the entire urethane resin is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, and more preferably 1.5% by weight. %the above. When the ratio of the carbon-carbon double bond portion to the entire resin is 0.5% by weight or more, it can effectively improve the adhesion to the resin and microlens resin. Especially considering high brightness, it can increase the relative refractive index. Resin adhesion.

In addition, a cross-linking agent may be used in combination in order to strengthen the adhesion of the coating film of the coating layer to the sacrifice layer, the microlens layer, and the like, and to improve the moisture and heat resistance.

Examples of the crosslinking agent include oxazoline compounds, epoxy compounds, melamine compounds, isocyanate compounds, carbodiimide compounds, silane coupling compounds, and the like. Among them, from the viewpoint of improving adhesion, an oxazoline compound, an epoxy compound, an isocyanate compound, and a carbodiimide compound are preferred, and two or more of these crosslinking agents are used in combination, and oxazoline is particularly used in combination. The compound and the epoxy compound can particularly improve adhesion, and it is preferable.

An oxazoline compound is a compound having an oxazoline group in the molecule, particularly preferably a polymer containing an oxazoline group, which is obtained by polymerizing a monomer containing an additional polymerizable oxazoline group alone or with other monomers . Monomers containing additional polymerizable oxazoline groups such as 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-isopropene And the like may be one or two or more kinds. Among them, 2-isopropenyl-2-oxazoline is preferable because it is easily available in industry. Other monomers may be monomers that can be copolymerized with monomers containing additional polymerizable oxazoline groups, without limitation, such as alkyl (meth) acrylates (alkyl groups such as methyl, ethyl, n-propyl (Meth) acrylic acid esters such as methyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl); acrylic acid, methacrylic acid, itaconic acid, horse Unsaturated carboxylic acids such as maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and their salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); acrylonitrile, methacrylonitrile, etc. Saturated nitriles; (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, (alkyl such as methyl, ethyl, n -Propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, etc.), unsaturated amines; vinyl acetate, vinyl propionate, etc. Vinyl esters; 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 Class; α, β- of styrene, α-methylstyrene, etc. Unsaturated aromatic monomer, one kind of these or two or more of the monomers may be used.

The content of the oxazoline group contained in the oxazoline compound is generally 0.5 to 10 mmol / g, preferably 1 to 10 mmol / g, and more preferably 2 to 8 mmol / g, and more preferably A range of 3 to 7 mmol / g. From the viewpoint of improving adhesion, it is preferable to use the above range.

The epoxy compound is a compound having an epoxy group in the molecule, for example, a condensate of epichlorohydrin with a hydroxyl group or an amine group of ethylene glycol, polyethylene glycol, glycerol, polyglycerin, bisphenol A, etc. Compound, two Epoxy compounds, monoepoxy compounds, glycidylamine compounds, and the like. Polyepoxy compounds such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tri (2-hydroxyethyl) isocyanate, glycerin poly Glycidyl ether, trimethylolpropane polyglycidyl ether, diepoxy compounds such as neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, monoepoxy compounds such as allyl glycidyl Glyceryl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, glycidylamine compounds such as N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylamino) cyclohexane and the like.

The isocyanate-based compound refers to a compound having an isocyanate derivative structure represented by an isocyanate or a block isocyanate. Isocyanates such as, for example, aromatic isocyanates of methylenephenyl diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, methylene diisocyanate, naphthalene diisocyanate, α, α, α ', α' -Tetramethylxylylene diisocyanate and other aliphatic isocyanates with aromatic rings, dimethyl diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethyldiisocyanate, hexamethylidene Aliphatic isocyanates such as methyl diisocyanate, cyclohexane diisocyanate, methyl cyclohexane diisocyanate, isophorone diisocyanate, methyl bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl Cycloaliphatic isocyanates, such as diisocyanates. For another example, the biuret, trimeric isocyanate, and uretdione of these isocyanates Polymers, carbodiimide modifiers, etc. polymers or derivatives. These can be used alone or in combination. Among the above isocyanates, in order to avoid yellowing due to ultraviolet rays, it is better to use aliphatic isocyanates or alicyclic isocyanates than aromatic isocyanates.

When used in the state of a block isocyanate, the blocking agent such as a phenolic compound such as bisulfite, phenol, cresol, ethylphenol, propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, Alcohol compounds such as ethanol, dimethyl malonate, propylene glycol diethyl ester, methyl ethyl acetate, ethyl ethyl acetate, ethyl acetone and other active methylene compounds, butyl mercaptan, dodecane Thiol-based compounds such as thiol, ε-caprolactam, δ-pentalactam and other lactam-based compounds, diphenylaniline, aniline, ethyleneimine and other amine-based compounds, ethyl Benzidine, acetamide acetamide compounds, formaldehyde, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime and other oxime-based compounds, these can be used alone or in combination of two or more.

As the isocyanate-based compound, a monomer may be used, or a mixture or a bond with various polymers may be used. In order to improve the dispersibility and crosslinkability of the isocyanate-based compound, a mixture or a bond with a polyester resin or a urethane resin can also be used.

The carbodiimide-based compound refers to a compound having a carbodiimide structure, which may be a compound having one or more carbodiimide structures in a molecule, but in order to obtain better adhesion and the like, it is more preferable to use a compound in the molecule. It has two or more polycarbodiimide compounds.

The carbodiimide compound can be synthesized by a previously known technique, and is generally a condensation reaction using a diisocyanate compound. Diisocyanate The ester compound is not particularly limited, and any of aromatic and aliphatic systems can be used, and specifically, for example, methylenephenyl diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene Diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, dicyclohexyl Methane diisocyanate, etc.

In addition, the effect of the present invention is within a range that does not disappear. In order to improve the water solubility or water dispersibility of the polycarbodiimide-based compound, a surfactant, or a fourth grade of polyepoxide and dialkylamino alcohol can be added. Hydrophilic monomers such as ammonium salts and hydroxyalkyl sulfonates.

The content of the carbodiimide group contained in the carbodiimide-based compound is generally 100 to 1000 at the carbodiimide equivalent (in order to give 1 mol of the carbodiimide compound by weight [g]), The range is preferably 250 to 800, and more preferably 300 to 700. When the above range is used, it is preferable to prevent precipitation of an ester cyclic trimer.

The melamine compound refers to a compound having a melamine skeleton in the compound, and for example, an alkanolated melamine derivative, a compound in which the alkanolated melamine derivative is reacted with an alcohol to partially or completely etherify, or a mixture thereof may be used. From the viewpoint of preventing the precipitation of an ester cyclic trimer, it is preferably a crosslinkable reactive group having more hydroxyl groups and the like, and more preferably having 4 or more. The alcohol used for the etherification is preferably methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol, or the like. The melamine compound may be any one of a monomer or a polymer of a dimer or more, or a mixture of these may be used. Thing. In addition, a part of melamine can be used in combination with urea or the like.

In addition, the cross-linking agents are designed to react in the drying process or the film-forming process to improve the performance of the easy-to-coat layer. It is speculated that the unreacted substances of the cross-linking agents, the reacted compounds, or a mixture of these are presumed to be present in the obtained easy-adhesive coating layer.

As the antistatic coating layer containing a compound having an ammonium group on the (C) layer side of the polyester film, a compound having various ammonium groups previously known can be used. In particular, a polymer type compound having an ammonium group having good heat resistance and moisture and heat resistance is preferred. The ammonium group non-reverse ion is preferably a structure incorporated in the main chain or branch chain of the polymer.

A compound having an ammonium group means a compound containing an ammonium group in the molecule, such as tertiary compounds of alkylamines, quaternary compounds of alkylamines, and those copolymerized with acrylic acid or methacrylic acid, and pyrrolidinium rings , Tertiary or tertiary compounds of N-alkylaminoacrylamide, vinylbenzyltrimethylammonium salt, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt, and the like. It may also be a composition of these, or a copolymerized product with other resins. Examples of the anion for the counter ion (counter ion) of the ammonium group include ions such as a halogen ion, sulfate, phosphite, nitrate, alkyl sulfate, and carboxylate.

Among the compounds having an ammonium group, a polymer having a structure of the following formula (1) is more preferable from the viewpoint of obtaining excellent antistatic properties and moisture and heat stability.

For example, in the above formula, the substituent R ¹ is a hydrocarbon group such as a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R ² is -O- or -NH-; R ³ is an alkylene group having 1 to 20 carbon atoms; For other structures that make the structure of Formula 1, R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen group, a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, or a hydrocarbon group having a functional group such as a hydroxyalkyl group, X -For the various counter ions mentioned above.

Among the above, particularly from the viewpoint of obtaining excellent antistatic properties and moisture and heat stability, the substituent R ¹ in the formula (1) is preferably a hydrogen atom or an alkyl group R ³ having a carbon number of 1 to 6 and preferably a carbon number of 1 to 6 An alkyl group of 6, R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably any one of R ⁴ , R ⁵ , and R ⁶ is a hydrogen atom. Other substituents are alkyl groups having 1 to 4 carbon atoms.

In addition, a compound having an ammonium group is preferably a compound having a pyrrolidinium ring from the viewpoint of obtaining excellent antistatic properties and thermal stability.

In the compound having a pyrrolidinium ring, the two substituents bonded to a nitrogen atom are each independently an alkyl group, a phenyl group, and the like, and these alkyl groups and phenyl groups may be substituted with the following groups. Substitutable groups such as hydroxy, amido, ester, alkoxy, phenoxy, naphthyloxy, thioalkoxy, thiophenoxy, cycloalkyl, trialkylammonium alkyl, cyano ,halogen. The two substituents bonded to the nitrogen atom may be bonded by a chemical formula, 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 -and so on.

The polymer having a pyrrolidinium ring is obtained by cyclizing and polymerizing a diallylamine derivative using a radical polymerization catalyst. During the polymerization, the solvent may be polar water such as water, methanol, ethanol, isopropanol, formamidine, dimethylformamide, dioxane, acetonitrile, etc. Polymerization initiators such as oxides and tertiary butyl peroxides are implemented by known methods, but are not limited thereto. In the present invention, a diallylamine derivative and a polymerizable compound having a carbon-carbon unsaturated bond can be used as a copolymerization component.

The number-average molecular weight of the compound having an ammonium group is generally 1,000 to 500,000, more preferably 2,000 to 100,000, and more preferably 5,000 to 80,000. When the molecular weight is less than 1,000, the strength of the coating film is weakened, and the heat stability is deteriorated. When the molecular weight exceeds 500,000, the viscosity of the coating liquid will be increased, and the handling and coating properties will be deteriorated.

The compound having an ammonium group may be used alone or in combination. In addition, in order to improve the antistatic property, an antistatic agent other than the compound having an ammonium group may be used in combination.

In order to improve the coating appearance and transparency when forming the antistatic coating layer, the polymer and the cross-linking agent used to form the easy-adhesion coating layer may be used in combination. Especially from the viewpoint of improving the appearance and transparency of the coating, it is preferable that In addition, an acrylic resin is used in combination, and a melamine compound or an oxazoline compound is preferably used in combination in order to enhance the strength of the coating film. In particular, a melamine compound is more preferable in terms of obtaining excellent moisture and heat stability.

Moreover, when forming an antistatic coating layer, in order to improve abrasion resistance and sliding property, it is preferable to use a mold release agent together. Examples of release agents include waxes, fluorine compounds, long-chain alkyl compounds, and polysiloxanes. When the mold release agent is used in combination, it is suitable for applications where various functional layers are not provided on the antistatic coating layer.

Wax refers to waxes selected from natural waxes, synthetic waxes, or those added waxes. Natural wax refers to plant wax, animal wax, mineral wax, petroleum wax, plant wax such as water candle resin, carnauba wax, rice wax, wood wax, jojoba oil and the like. Animal waxes, such as dense wax, lanolin, whale wax, etc. Mineral waxes such as montan wax, natural earth wax, pure earth wax, etc. Petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum, etc. Synthetic waxes such as synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, ammonium acid, amines, amines, esters, ketones, and the like. Synthetic hydrocarbons such as Fischer-Tropsch wax (also known as Longer tile wax), polyethylene wax, and other polymers such as low molecular weight polymers (specifically polymers with viscosity number average molecular weight of 500 to 20,000), namely polypropylene , Ethylene-acrylic acid copolymer, polyethylene glycol, polypropylene glycol, block or plate bond of polyethylene glycol and polypropylene glycol. Modified waxes such as montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives and the like. The derivative at this time refers to a compound obtained by any one of purification, oxidation, esterification, and ketization, or a combination of these treatments. Hydrogenated waxes such as hardened ramie oil and hardened ramie oil derivatives.

From the viewpoint of stable properties, synthetic wax is preferable. Polyethylene wax is preferred, and oxidized polyethylene wax is more preferred. The molecular weight of the synthetic wax is from the viewpoint of the stability and handling properties of the barrier and other characteristics, preferably from 500 to 30,000, more preferably from 1,000 to 15,000, and more preferably from 2000 to 8000.

The fluorine compound is preferably a compound containing a fluorine atom in the compound. From the viewpoint of coating the surface, it is preferable to use an organic fluorine compound such as a perfluoroalkyl compound, a polymer containing a fluorine atom olefin compound, an aromatic fluorine compound such as fluorobenzene, and the like. However, when considering heat resistance and contamination, molecular compounds are preferred.

The long-chain alkyl-containing compound refers to a compound having a linear or branched alkyl group having 6 or more carbon atoms, particularly 8 or more carbon atoms. Specific examples are not particularly limited, such as a polyethylene resin containing a long-chain alkyl group, an acrylic resin containing a long-chain alkyl group, a polyester resin containing a long-chain alkyl group, an amine compound containing a long-chain alkyl group, and a long-chain alkyl group Ether compounds, quaternary ammonium salts containing long-chain alkyl groups, and the like. However, when considering heat resistance and contamination properties, polymer compounds are preferred.

Polysiloxane refers to compounds with a polysiloxane structure within the molecule, such as polysiloxane latex, acrylic grafted polysiloxane, polysiloxane grafted acrylic ester, amino modified polysiloxane, perfluoroalkyl modified Modified polysiloxane, alkyl modified polysiloxane and so on. However, when considering heat resistance and stain resistance, it is preferable to contain a hardened silicone resin.

These release agents can be used individually or in combination. Among these mold release agents, waxes, fluorine compounds, and long-chain alkyl compounds are preferred from the viewpoint of less contamination, and more preferably, a small amount can be imparted with good sliding properties. wax.

In addition, in order to improve the sliding properties and barrier properties of the easy-adhesion coating layer and the antistatic coating layer, it is preferred to use particles in combination when forming the coating layer.

The average particle diameter of the particles used when forming the coating layer is preferably 1.0 μm or less, more preferably 0.5 μm or less, and particularly preferably in a range of 0.2 μm or less from the viewpoint of film transparency.

The particles used include, for example, inorganic particles such as silicon dioxide, aluminum oxide, and metal oxides, or organic particles such as crosslinked polymer particles. Especially from the viewpoint of the dispersibility with respect to the coating layer and the transparency of the obtained coating film, silicon dioxide particles are preferred.

In addition, within the range that does not impair the gist of the present invention, when a coating layer is formed as necessary, a defoamer, a coating property improver, a tackifier, an ultraviolet absorbent, an antioxidant, a foaming agent, a pigment, a dye, and the like may be used in combination.

The content of the polymer in the coating liquid that forms the easy-to-adhere layer is generally 20 to 90% by weight, preferably 30 to 85% by weight, and more preferably 45 to 80% by weight, relative to the total non-volatile content. range. When it exceeds the above range, the adhesion with the fluorene layer and the microlens layer will be insufficient.

In addition, the content of the cross-linking agent in the coating liquid that forms the easy-to-adhere layer is generally 80% by weight or less, preferably 10 to 60% by weight, and more preferably 15 to 50% by weight relative to the total non-volatile content % Range. When the above range is used, sufficient moisture and heat resistance and adhesion can be obtained.

The content of particles in the coating liquid that forms the easy-to-adhesive layer, the ratio of the total non-volatile content to the total non-volatile content will vary due to the particle size and the characteristics of the polyester film, so sliding properties and barrier properties cannot be generalized, but preferably 25 weight The amount is less than or equal to 3%, more preferably 3 to 15% by weight, and more preferably 5 to 10% by weight. When it exceeds 25% by weight, the transparency and adhesiveness of the coating layer are reduced.

The content of the compound having an ammonium group in the coating liquid forming the antistatic coating layer is generally 3 to 90% by weight, preferably 5 to 70% by weight, and 10 to 60% by weight relative to the total non-volatile content. % Is better, more preferably in the range of 15 to 40% by weight. If it is less than 3% by weight, the antistatic property will be insufficient, dust adhesion will occur, and the sheets will adhere to each other, resulting in poor handleability. When it exceeds 90% by weight, sufficient coating appearance and transparency cannot be obtained.

The content of the polymer in the coating solution for forming the antistatic coating layer is preferably 90% by weight or less with respect to the total nonvolatile components, more preferably 10 to 80% by weight, and more preferably 20 to 70% by weight. Range. The use of the above range can improve the appearance of the coating layer.

The content of the cross-linking agent in the coating liquid forming the antistatic coating layer is preferably 90% by weight or less relative to the total non-volatile content, and more preferably 5 to 50% by weight, and more preferably 10 to 40% by weight. % Range. The use of the above range can improve the strength of the coating layer, and improve the scratch resistance and moisture and heat stability.

The content of the mold release agent in the coating solution forming the antistatic coating layer is preferably 50% by weight or less relative to the total non-volatile content, more preferably 1 to 40% by weight, and more preferably 3 to 30% by weight. %. Use of the above range can improve sliding properties and abrasion resistance.

The content of particles in the coating liquid forming the antistatic coating layer, The ratio to all non-volatile components will vary due to the particle size and the characteristics of the polyester film, so sliding properties and barrier properties cannot be generalized, but it is preferably 50% by weight or less, and preferably 1 to 30% by weight. More preferably, it is in the range of 1 to 10% by weight. Using the above range can improve the sliding property.

When analyzing the components in the coating layer, for example, TOF-SIMS, ESCA, fluorescent X-rays, NMR, and the like can be performed.

When the coating layer is provided by in-line coating, it is preferable that the above-mentioned series of compounds be in the form of an aqueous solution or an aqueous dispersion. The method is to apply a coating solution having a solid content concentration of 0.1 to 50% by weight to a polyester. Film to make laminated polyester film. In addition, the coating liquid may contain a small amount of an organic solvent in order to improve the dispersibility with respect to water, the film-forming property, and the like within the scope of the gist of the present invention. The organic solvent may be a single type, or two or more types may be appropriately used.

The film thickness of the easy-adhesion coating layer is preferably 0.002 to 1.0 μm, more preferably 0.005 to 0.5 μm, more preferably 0.01 to 0.2 μm, and particularly preferably 0.01 to 0.1 μm. When the film thickness exceeds the above range, adhesion, coating appearance, and barrier properties are deteriorated.

The film thickness of the antistatic coating layer is preferably 0.002 to 1.0 μm, more preferably 0.01 to 0.5 μm, more preferably 0.03 to 0.3 μm, and particularly preferably 0.05 to 0.12 μm. When the film thickness is out of the above range, antistatic properties, coating appearance, barrier properties, and moisture and heat stability are deteriorated. In addition, when it is easy to prepare a coating layer or a microlens layer on the coating layer to improve the brightness, the thickness of the coating layer is preferably adjusted to 0.04 to 0.2 μm, and most preferably adjusted to 0.05 to The range is 0.15 μm.

The method for forming the coating layer is, for example, using gravure coating, reverse roll coating, mold coating, pneumatic blade coating, blade coating, rod coating, rod coating, curtain coating, knife coating, and conveying rollers. Coating methods such as coating, extrusion coating, impregnation coating, contact coating, spray coating, calendar coating, extrusion coating, and the like are previously known.

The drying and hardening conditions when forming the coating layer are not particularly limited. For example, when the coating layer is set by offline coating, the general standard can be performed at 80 to 200 ° C for 3 to 40 seconds, and preferably 100 to 180 ° C. 3 to 40 seconds of heat treatment.

In addition, when a coating layer is provided by in-line coating, the general standard is heat treatment at 70 to 280 ° C for 3 to 200 seconds.

When a coating layer is formed on the film, a surface treatment such as corona treatment or plasma treatment may be performed if necessary.

The surface resistance value of the antistatic coating layer is preferably 1 × 10 ¹³ Ω or less, more preferably 1 × 10 ¹² Ω or less, more preferably 5 × 10 ¹¹ Ω or less, and particularly preferably 1 × 10 ¹¹ Ω or less. range. When the surface resistance value exceeds 1 × 10 ¹³ Ω, the antistatic property will be insufficient, and the sheets will adhere to each other and dust will adhere.

From the viewpoint of humidity and heat stability, it is required that the appearance of the film does not change even under high temperature and high humidity conditions in various optical applications. In general, when the antistatic layer is a coating layer derived from an ion conductive material, the antistatic layer itself will deteriorate under high temperature and high humidity conditions due to weak water, and the surface will be deteriorated due to high turbidity. By providing the antistatic layer with the above-mentioned structure, the present invention can reduce turbidity change and suppress appearance deterioration even under high temperature and high humidity conditions. The film of the present invention is treated at 60 ° C and 95% RH for 12 hours. Subsequent changes in turbidity are preferably 1.0% or less, more preferably 0.5% or less, and more preferably 0.3% or less. When the amount of change in turbidity is within the above range, the apparent change is small, and it has good transparency and is suitable for various applications.

The easy-to-adhere coating layer of the coating film of the present invention is generally provided with a hafnium layer or a microlens layer for improving brightness. In particular, in recent years, a resin layer having a relatively high refractive index for high brightness has been provided.

The refractive index of the gadolinium layer and the microlens layer is preferred to increase the brightness, and when the refractive index of the general polyester film is near 1.65, it is preferably 1.57 to 1.65, and more preferably 1.58 to 1.64. Especially good range is 1.59 ~ 1.63. When using the above range, high brightness can be obtained.

In recent years, in order to effectively improve the brightness of the base layer, various shapes have been proposed, but they are generally parallel objects with a triangular shape in cross section. In addition, various shapes of the microlens layer have been proposed, but generally, a hemispherical convex lens is provided on the film. Also, any of the above layers can be made into a previously known shape.

The shape of the concrete layer is, for example, a cross-sectional triangular shape with a thickness of 10 to 500 μm, an interval of 10 to 500 μm, and an apex angle of 40 ° to 100 °. The material used for the base layer may be a previously known material, such as an active energy ray-curable resin coating, for example, a (meth) acrylate resin. The compounds constituting the resin generally include, for example, polyhydric alcohol components such as ethylene glycol, propylene glycol, tetramethylene glycol, and hexamethylene glycol, bisphenol A structure, urethane structure, polyester structure, and epoxy structure. Group) an acrylate-based compound.

The prescription of high refractive index used for high brightness is as follows, In addition to the general compounds, a method having a large amount of aromatic compounds, sulfur atoms, halogen atoms, and metal compounds is used. Among them, a method using a compound having a large number of aromatic structures or a sulfur atom is particularly preferable from the viewpoints of uniformizing the refractive indexes of the hafnium layer and the microlens layer and the environment.

Compounds with a large number of aromatic structures such as naphthalene, anthracene, phenanthrene, Ding, benzo [a] anthracene, benzo [a] phenanthrene, pyrene, benzo [c] phenanthrene, pyrene, etc. Compounds having a family structure, compounds having a biphenyl structure, compounds having a fluorene structure, and the like.

The shape of the microlens layer is, for example, a hemispherical object having a thickness of 10 to 500 μm and a diameter of 10 to 500 μm, and it may have a conical, polygonal pyramid-like shape. The material of the microlens layer may be the same as that of the hafnium layer, and a previously known material may be used.

The above-mentioned hafnium layer and microlens layer generally use a resin component as a main material, and the content of the organic solvent is small. The content of the organic solvent is preferably 5% by weight or less, preferably 3% by weight or less, and more preferably 1 It is particularly preferably not more than% by weight, that is, a non-solvent-based ultraviolet curable resin.

The coating film of the present invention is particularly volatile and has excellent effects when used for optics. The specific components are, for example, microlens sheets and trowels for backlight optical sheets for LCDs in response to the drastic cost reduction requirements in recent years. Suitable for substrates requiring high optical performance and cost.

Examples

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to the following examples without exceeding the gist thereof. The measurement method used in the present invention is as follows.

(1) Determine the limiting viscosity of polyester:

After finely weighing 1 g of polyester, 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) was added, and the solution was measured at 30 ° C. after being dissolved.

(2) Determine the average particle size of the particles:

The particles were observed with an electron microscope, the maximum diameter and the minimum diameter were determined, and the average value was used as the particle size of one particle. The particle size of 10 particles was measured, and the average value was used as the average particle size.

(3) Full light transmittance and turbidity:

The total light transmittance is based on JIS-K-7361, and the turbidity is based on JIS-K-7136. The total light transmittance and turbidity are measured with an integrating sphere turbidimeter "NDH 2000" manufactured by Nippon Denshoku Industries. .

(4) Heat shrinkage:

The sample was placed in an oven maintained at 150 ° C for 30 minutes under no tension, and the length of the sample before and after the treatment was measured, and then the heat shrinkage was calculated by the following formula.

Heat shrinkage (%) = ((L0-L1) / L0) × 100

(In the above formula, L0 is the length of the sample before heat treatment, and L1 is the length of the sample after heat treatment)

The length direction (MD) and width direction (TD) of the film were measured at five points, and the average values were calculated.

(5) Hue (reflection method y value)

The hue reflection method y value was measured with a spectrophotometer "CM-3700d" manufactured by Minota based on JIS-Z-5722. When measuring, for example, the thickness of the film is 10 when the thickness is 100 μm, 5 when the thickness is 188 μm, and 4 when 250 μm, so that the total thickness is approximately 1000 μm, and the measurement is performed in the range of 900 μm to 1000 μm.

(6) Plane orientation (△ P)

The Abbe-type refractive index manufactured by Atago Optical Co., Ltd. was used to measure the maximum refractive index nγ in the plane of the film, the refractive index nβ in the orthogonal direction, and the refractive index nα in the thickness direction of the film, and the plane alignment was calculated as follows. The refractive index was measured at 23 ° C using a sodium D line. In the measurement, the two sides of the film with respect to each sample were n = 3, and the average value was calculated.

Plane orientation (△ P) = {(nγ + nβ) / 2} -nα

(7) Method for measuring film thickness of coating layer:

The surface of the coating layer was dyed with RuO ₂ and embedded in epoxy resin. Thereafter, sections were prepared by the ultra-thin sectioning method and then stained with RuO _{4. The} cross-section of the coating layer was measured using TEM (H-7650, manufactured by Hitachi High-Technologies Corporation, acceleration voltage 100V), and the average value of 10 points was used as the coating The film thickness of the layer.

(8) Weight of carbon-carbon bond in polyurethane resin:

After the polyurethane resin was dried under reduced pressure, it was summarized using NMR (AVANCEIII 600 manufactured by Bruker Biospin Corporation), and each peak of 1H and 13C was calculated and obtained.

(9) Method for measuring the refractive index of the resin layer:

The ultraviolet curable resin compound was flatly arranged on the coating layer side with a film thickness of 10 μm, and after being cured by ultraviolet rays, a flattened ultraviolet curable resin layer was formed. The refractive index of the ultraviolet-curable resin layer side was measured using a refractometer (SL-NA-B manufactured by Atago Co., Ltd.).

(10) Evaluation method of tightness:

In order to form a fluorene layer system, 50 parts by weight of bisphenol A acrylate (ethylene glycol chain = 8) modified with ethylene glycol, 4,4 '-(9-fluorenylene) bis (2-phenoxyethyl) Acrylate) 27 parts by weight, 2-biphenoxyethyl acrylate 20 parts by weight, and diphenyl (2,4,6-trimethylphenylphosphonium) phosphine oxide 3 parts by weight are arranged in a composition Most of the mold members obtained by lining up at a distance of 50 μm in parallel and a top angle of 65 ° are laminated on top of each other so that the coating layer can easily contact the resin, and then the polyester film is uniformly extended by a roller. UV The linear irradiation device irradiates ultraviolet rays to harden the resin (the refractive index of the resin layer is 1.60). Then, the film is peeled from the mold member to obtain a thin film. After processing the obtained film under the environment of 60 ° C and 90% RH for 24 hours, a 10 × 10 cross cut was formed on the grate layer, and an 18 mm wide tape (celluloid (registered trademark of Nijiban Co., Ltd.) was applied on the top. CT-18), and then quickly peel off at a peeling angle of 180 degrees and observe the peeling surface. The peeling area is less than 5% as A, more than 5% and less than 20% as B, and more than 20% and less than 50% as C. More than 50% is D.

(11) Method for measuring surface resistance:

Using a high-resistance measuring device: HP4339B and measuring electrode: HP16008B manufactured by Japan Hewlett-Bart Co., Ltd. After the polyester film is fully humidified under the measurement environment of 23 ° C and 50% RH, the antistatic property is measured after applying a voltage of 100V for 1 minute. Surface resistance value of the coating layer.

(12) Evaluation method of dust adhesion of antistatic coating layer:

After the polyester film was sufficiently humidified in a measurement environment at 23 ° C and 50% RH, the second coating layer was wiped back and forth with a cotton cloth 10 times. Keep it quietly close to the finely divided soot, and then evaluate the soot adhesion status based on the following criteria.

A: The film does not adhere even when it comes in contact with ash.

B: The film adheres slightly when it comes in contact with ash.

C: The film is adhered to the ash only in a large amount.

(13) Evaluation method of humidity and heat stability (turbidity change):

After processing the film at 60 ° C and 95% RH for 12 hours, the turbidity was measured by the method described in (3), and the value obtained by subtracting the turbidity value before retreatment from the turbidity value after retreatment was taken as the turbidity change Quantity.

(14) Optical characteristics (brightness):

The characteristics when used as a thin sheet of an optical member were evaluated. That is, an acrylic-based adhesive is applied to the A-layer side of the film to form a hafnium layer, and the obtained hafnium sheet and one light source are used to form an LED edge-type backlight unit. The quality of surface light. Brightness standard: It was evaluated using a brightness meter and compared with the case where the film of Example 4 was used.

A: Increase the brightness and find improvement.

B: It was confirmed that the brightness was not lowered.

C: Reduce the brightness.

(15) Optical properties (shielding properties)

Assemble 2 pieces of holmium flakes obtained in the above (14), and use the light source to form an LED edge type backlight unit, and evaluate the quality of the obtained planar light emission from the following viewpoints.

A: No light image appears, and improvement is observed.

B: Partial faint light image appears.

C: A light image with clear and comprehensive appearance appears.

(16) Optical characteristics (wear resistance):

The cymbal sheet obtained in the above (14) was cut into a size of 150 mm in the longitudinal direction (MD) and 50 mm in the width direction (TD) of the polyester film for the substrate, and then it was set on an acrylic plate so that After the opposite surface side is the acrylic surface side, a weight of 500 g is placed on the concrete sheet, and the concrete sheet is moved 100 mm at a speed of 3.0 m / min. After 5 times, it is evaluated relative to the acrylic sheet from the following viewpoints Accompanying injuries.

A: No scar was confirmed and improvement was found.

B: Some faint scars were confirmed.

C: Confirmation of comprehensive and clear scars.

The following are examples / comparative examples, and the manufacturing method of the polyester film used in the other examples is as follows.

<Made polyester> <Manufacturing method of polyester (a)>

Using 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol as starting materials, using a reactor weigher to obtain 0.09 parts by weight of magnesium acetate osmium tetrahydrate salt for the catalyst, and set the reaction start temperature to 150 ° C. While distilling off the methanol, the reaction temperature was gradually increased, and after 3 hours, it was 230 ° C. After 4 hours, the transesterification reaction was substantially completed. After 0.04 parts of ethyl acid phosphate was added to the reaction mixture, 0.03 parts of antimony trioxide was added to perform a polycondensation reaction for 4 hours. That is, the temperature was gradually raised from 230 ° C to 280 ° C. In addition, the pressure was gradually reduced from normal pressure to finally 0.3 mmHg. After starting the reaction, by changing the stirring power of the reaction tank, the reaction was stopped when the limiting viscosity was equal to 0.67 dl / g, and the polymer was discharged under nitrogen pressure. The limiting viscosity of the obtained polyester (a) is 0.67dl / g.

<Production method of polyester (b)>

In the production process of the polyester (a), the polyester (b) is produced such that the cross-linked styrene-acrylic copolymer resin particles having an average particle diameter of 3.8 μm are 10% by weight. The limiting viscosity of the obtained polyester (b) was 0.65 dl / g.

<Production method of polyester (c)>

A polyester was obtained by the same method as the method for producing the polyester (b), except that the cross-linked styrene-acrylic copolymer particles having an average particle size of 6.1 μm were used in the method for producing the polyester (b) (c). The limiting viscosity of the obtained polyester (c) was 0.65 dl / g.

<Manufacturing method of polyester (d)>

The polyester was obtained by the same method as the method for producing the polyester (b), except that the cross-linked styrene-acrylic copolymer particles having an average particle diameter of 1.2 μm were used in the method for producing the polyester (b). (d). The limiting viscosity of the obtained polyester (d) was 0.64 dl / g.

<Manufacturing method of polyester (e)>

The polyester was obtained by the same method as the method for producing the polyester (b), except that the cross-linked styrene-acrylic copolymer particles having an average particle diameter of 9.1 μm were used in the method for producing the polyester (b). (e). The limiting viscosity of the obtained polyester (e) was 0.65 dl / g.

<Manufacturing method of polyester (f)>

The polyester (f) was obtained by the same method as the method for producing the polyester (b), except that the silica particles having an average particle diameter of 1.9 μm were 0.4% by weight. The limiting viscosity of the obtained polyester (f) was 0.66 dl / g.

<Manufacturing method of polyester (g)>

The polyester (g) was obtained by the same method as the method for producing the polyester (b), except that the silica particles having an average particle diameter of 3.5 μm were used in the method for producing the polyester (b). The limiting viscosity of the obtained polyester (g) was 0.64 dl / g.

<Manufacturing method of polyester (h)>

Except for the production method of polyester (a), the starting materials are 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, and 2 parts by weight of diethylene glycol, and the polymerization catalyst uses germanium oxide. A polyester (h) was obtained by the same method as the method for producing the polyester (a). The method for adding germanium oxide is a known method, and the amount of germanium oxide is 100 ppm based on the weight of the raw material. The inherent viscosity of the obtained polyester (h) was 0.69 dl / g.

The compounds constituting the coating layer are as follows

<Compound Example> 胺 Urethane resin with carbon-carbon double bond: (IA)

By hydroxyethyl acrylate unit: dicyclohexylmethane diisocyanate unit: hexamethylidene diisocyanate terpolymer unit: caprolactone unit: ethyl A urethane resin having a diol unit: dimethylolpropanoic acid unit = 18: 12: 22: 26: 18: 4 (mol%) and a carbon-carbon double bond portion weight of 2.0% by weight.

胺 Urethane resin without carbon-carbon double bond: (IB)

80 parts by weight of a polycarbonate polyol with a number average molecular weight of 2000 formed from 1,6-hexanediol and diethyl carbonate, 4 parts by weight of a polyethylene glycol with a number average molecular weight of 400, and methylidene bis ( 4-cyclohexyl isocyanate) 12 parts by weight of urethane resin formed by 4 parts by weight of dimethylolbutyric acid, and then neutralized with triethylamine to obtain an aqueous dispersion.

˙Acrylic resin: (IC)

Ethyl acrylate / n-butyl acrylate / N-hydroxymethacrylamide / acrylic acid = 88/10/1/1 (% by weight) emulsifying polymer (emulsifier: non-ionic surfactant)

Oxazoline compound: (IIA)

Acrylic polymer with oxazoline group and polyepoxide chain, Yeboku (oxazoline group amount = 4.5mmol / g, made by Japan Catalyst Corporation)

˙Epoxy compounds: (IIB)

Polyglycerol polyglycidyl ether

˙Melamine compound: (IIC)

Hexamethoxymethylol melamine

˙ Compounds with ammonium group (IIIA)

A polymer compound having a number-average molecular weight of 50,000 as a counter ion, which is a constituent unit of the following formula 2 and is a methanesulfonic acid ion.

化合物 Compounds with ammonium groups: (IIIB)

Polymer obtained by polymerizing the following composition having a pyrrolidinium ring in the main chain

Diallyl dimethyl ammonium chloride / dimethyl acrylamide / N-hydroxymethyl acrylamide = 90/5/5 (mol%). The number average molecular weight is 30,000.

˙Releasing agent: (IV)

300 g of oxidized polyethylene wax with a melting point of 105 ° C, an acid value of 16 mg KOH / g, a density of 0.93 g / mL, an average molecular weight of 5000, 650 g of ion-exchanged water, 50 g of deca glycerol monooleate surfactant, and 48% by weight potassium hydroxide 10 g of the aqueous solution was added to an emulsification device equipped with a stirrer, a thermometer and a temperature controller, and the content was 1.5 L. It was sealed with nitrogen and then stirred at 150 ° C at high speed. After 1 hour, it was cooled to 130 ° C, and a wax latex cooled to 40 ° C was obtained through a high-pressure homogenizer at 400 atmospheres.

˙ Particles (V)

Silica dioxide with an average particle diameter of 0.07 μm

Example 1:

A mixed raw material obtained by mixing the aforementioned polyesters (h) and (f) at a ratio of 90% by weight and 10% by weight is used as a raw material of the layer (A), and 100% by weight of the polyester (h) is used as a material of the (B) layer. As raw materials, the mixed raw materials obtained by mixing polyesters (h) and (b) at a ratio of 95% by weight and 5% by weight as raw materials of the layer (C), each of which is supplied to three vented biaxial extruder Then, each layer was melted at 285 ° C, and then the three layers (A / B / C) of the three layers (A / B / C) of the layer (A) and (C) as the outermost layer (surface layer) and (B) as the middle layer were formed by the nozzle It was extruded, and then it was cooled and solidified on a cooling roll with a surface temperature set to 40 ° C using an electrostatic application densification method to obtain an unstretched sheet. Next, the film was stretched 3.0 times in the longitudinal direction at a film temperature of 85 ° C. using a roll speed difference, and then the water-based coating liquid A1 shown in Table 2 below was applied to the (A) plane side of the longitudinally stretched film (easy adhesion formation). Coating layer), and the water-based coating solution B3 shown in Table 3 below is applied on the side of the (C) layer (forming an antistatic coating layer), and then introduced into the tenter, and the horizontal direction is 120 ° C. After stretching for 4.1 times, heat treatment was performed at 225 ° C to relax 2% in the transverse direction. The thickness of the coating layer (after drying) was 250 μm with an easy-to-adhere coating layer of 0.03 μm and an antistatic coating layer of 0.06 μm. Each layer has a laminated polyester film having a thickness of 10/230/10 μm. The structure of the obtained film 1 is shown in the table 1 is shown. The obtained polyester film had good optical characteristics, good adhesion to the easy-to-adhere coating layer, and good surface resistance of the antistatic coating layer.

In addition, various optical characteristics such as a change in turbidity and brightness are also good. The characteristics of the film are shown in Tables 4, 6, and 8 below.

Example 2:

Except that the mixed raw materials obtained by mixing the polyesters (h) and (b) at a ratio of 96.5 wt% and 3.5 wt% as raw materials of the C layer, 75 wt% of the polyester (h) and polymer from Production Example 1 were used. The mixed raw material obtained by mixing the flange portion, the flange portion of the main roll, and the regenerating portion of the lower roll portion of the main roll at the time of ester was used as the raw material of the B layer. Layer (A / B / C) is a polyester film with a thickness of 250 μm and a thickness of 10/230/10 μm for each layer. The structure of the obtained film 2 is shown in Table 1, and various characteristics are shown in Tables 4, 6, and 8.

Example 3:

Except that the mixed raw materials obtained by mixing the polyesters (h) and (c) at a ratio of 95% by weight and 5% by weight as raw materials for the C layer, the layer structure obtained in Example 1 was three three layers (A / B / C) A polyester film having a thickness of 250 μm and a thickness of 10/230/10 μm each. The structure of the obtained film 3 is shown in Table 1, and various characteristics are shown in Tables 4, 6, and 8.

Example 4:

Except for the ratios of 90% by weight and 10% by weight of polyesters (a) and (f), respectively For example, the mixed raw material obtained by mixing is used as the raw material of the layer A, 100% of the polyester (a) is used as the raw material of the layer B, and the polyester (a) and (b) are each 95% by weight and 5% by weight. Except that the mixed raw material was used as the raw material of the C layer, the same layer as in Example 1 was used to obtain three three-layer (A / B / C) polyester films each having a thickness of 250 μm and each layer having a thickness of 10/230/10 μm. The structure of the obtained film 4 is shown in Table 1, and various characteristics are shown in Tables 4, 6, and 8. The film surface has a small amount of ash.

Example 5:

Except that the polyester (h) and (b) were mixed at a ratio of 96% by weight and 4% by weight as the raw material of the C layer, 35% by weight of the polyester (h) and the polymer from Production Example 1 were used. The mixed raw material obtained by mixing 65% by weight of the flange portion, the flange portion of the main roll, and the rebirth of the lower roll portion of the main roll during esterification was used as the raw material of the B layer. The thickness of each layer (A / B / C) is 250 μm, and each layer is a polyester film having a thickness of 10/230/10 μm. The structure of the obtained film 5 is shown in Table 1, and various characteristics are shown in Tables 4, 6, and 8.

Example 6:

Except that the mixed raw materials obtained by mixing the polyesters (h) and (f) at a ratio of 25% by weight and 75% by weight as raw materials of the A layer, the layer structure obtained in Example 1 was three three layers (A / B / C) A polyester film having a thickness of 250 μm and each layer having a thickness of 10/230/10 μm. The structure of the obtained film 6 is shown in Table 1, and various characteristics are shown in Tables 4, 6, and 8.

Example 7

Except that the mixed raw materials obtained by mixing polyesters (h) and (b) at a proportion of 85% by weight and 15% by weight as raw materials for the C layer, the layer structure obtained in Example 1 was three three layers (A / B / C) A polyester film having a thickness of 250 μm and each layer having a thickness of 4/242/4 μm. The structure of the obtained film 7 is shown in Table 1, and various characteristics are shown in Tables 4, 6, and 8.

Example 8:

Except that the roll speed difference is used to extend the longitudinal direction to 2.5 times at a film temperature of 82 ° C, the tenter is used to extend the transverse direction to 3.4 times at 120 ° C, and then heat treatment is performed at 208 ° C, and the transverse direction is relaxed by 25%. In the same manner as in Example 1, a three-layer (A / B / C) three-layer (A / B / C) polyester film having a thickness of 250 μm and a layer thickness of 10/230/10 μm was obtained. The structure of the obtained film 8 is shown in Table 1, and various characteristics are shown in Tables 4, 6, and 8.

Examples 9 to 25:

A polyester film was obtained in the same manner as in Example 1 except that the coating agent composition of Example 1 was changed to the coating agent composition shown in Tables 2 to 4. As shown in Tables 4, 6, and 8, the obtained polyester film had good optical properties such as adhesion of the coating layer, dust adhesion, change in turbidity, and brightness.

Comparative Example 1:

Except for polyester (h) and (d), which are 81% by weight and 19% by weight, respectively Except that the mixed raw material obtained by mixing the examples is used as the raw material of the C layer, a polyester film having a three-layer (A / B / C) layer thickness of 250 μm and a layer thickness of 10/230/10 μm was obtained in the same manner as in Example 1. The structure of the available film 9 is shown in Table 1. In addition, as shown in Tables 5, 7, and 9, the film characteristics are inferior in optical characteristics such as brightness.

Comparative Example 2:

Except that the mixed raw materials obtained by mixing the polyesters (h) and (d) at a proportion of 95% by weight and 5% by weight as raw materials for the C layer, the layer structure obtained in Example 1 was three three layers (A / B / C) A polyester film having a thickness of 250 μm and each layer having a thickness of 10/230/10 μm. The structure of the available film 10 is shown in Table 1. In addition, as shown in Tables 5, 7, and 9, the film characteristics are inferior in optical characteristics such as brightness.

Comparative Example 3:

Except that the mixed raw materials obtained by mixing the polyesters (h) and (e) at a ratio of 98% by weight and 3% by weight as raw materials for the C layer, the layer structure obtained in Example 1 was three three layers (A / B / C) A polyester film having a thickness of 250 μm and a thickness of 10/230/10 μm. The structure of the available thin film 11 is shown in Table 1, and various characteristics are shown in Tables 5, 7, and 9.

Comparative Example 4:

Except that the mixed raw materials obtained by mixing the polyesters (h) and (g) at a ratio of 92% by weight and 8% by weight, respectively, were used as the raw material of the C layer, the same as in Example 1 was obtained. The layer structure is three types of three-layer (A / B / C) polyester films with a thickness of 250 μm and a thickness of 10/230/10 μm. The structure of the available thin film 12 is shown in Table 1, and various characteristics are shown in Tables 5, 7, and 9.

Comparative Example 5:

Except that the easy-adhesive coating layer was not provided in Example 1, the polyester film was produced in the same manner as in Example 1. The properties of the obtained film are shown in Tables 5, 7, and 9, and were poor adhesion properties.

Comparative Example 6:

A polyester film was obtained in the same manner as in Example 1 except that the antistatic coating layer was not provided in Example 1. The characteristics of the available films are shown in Tables 5, 7 and 9, which are high surface resistance, poor dust adhesion, and poor abrasion resistance.

Comparative Examples 7, 8:

A polyester film was obtained in the same manner as in Example 1 except that the coating agent composition of Example 1 was changed to the coating agent compositions shown in Tables 3 and 5. The available polyester films are shown in Tables 5, 7, and 9, which are those with high surface resistance, poor dust adhesion, or those with poor abrasion resistance.

* In the above Table 1 is silicon dioxide particles.

Industrial use possibility

The coating film of the present invention is suitable as a basic film for microlenses and thin films of backlights for LCDs, which are required for drastic cost reduction in recent years.

Claims (21)

A coating film, characterized in that a biaxially stretched layer formed by a three-layer structure each comprising a polyester layer (A) and a polyester layer (C) as a surface layer and a polyester layer (B) as an intermediate layer is polymerized The (A) layer of the ester film has an easy-adhesion coating layer containing a polymer, the (C) layer has an antistatic coating layer containing a compound having an ammonium group, and the (C) layer contains an average particle diameter of 2.0 ~ Organic particles of 9.0 μm, the antistatic coating layer contains particles, and the content of the particles in the coating solution forming the antistatic coating layer is 50% by weight or less with respect to the total non-volatile components. A coating film, characterized in that a biaxially stretched layer formed by a three-layer structure each comprising a polyester layer (A) and a polyester layer (C) as a surface layer and a polyester layer (B) as an intermediate layer is polymerized The (A) layer of the ester film has an easy-adhesion coating layer containing a polymer, the (C) layer has an antistatic coating layer containing a compound having an ammonium group, and the (C) layer contains an average particle diameter of 2.0 ~ The organic particles of 9.0 μm include a self-emulsifying urethane resin obtained as a polymer contained in the easy-adhesion coating layer by introducing an ionic group and polymerizing an ionic bond. A coating film, characterized in that a biaxially stretched layer formed by a three-layer structure each comprising a polyester layer (A) and a polyester layer (C) as a surface layer and a polyester layer (B) as an intermediate layer is polymerized The (A) layer of the ester film has an easy-adhesion coating layer containing a polymer, the (C) layer has an antistatic coating layer containing a compound having an ammonium group, and the (C) layer contains an average particle diameter of 2.0 ~ The organic particles of 9.0 μm, as a polymer contained in the easily-adhesive coating layer, contain a compound for forming an optical functional layer formed on the surface of the easily-adhesive coating layer. Carbon-carbon double bond reaction urethane resin contained in the material. For example, the coating film of any one of claims 1 to 3, wherein the content of the polymer in the coating liquid forming the easy-to-adhere layer is 20 to 90% by weight relative to the total non-volatile components, forming an antistatic coating. The content of the compound having an ammonium group in the coating liquid of the cloth layer is 3 to 90% by weight relative to the total non-volatile content. The coating film according to any one of claims 1 to 3, wherein the antistatic coating layer contains a polymer, and the content of the polymer in the coating liquid forming the antistatic coating layer with respect to the total non-volatile content is 90 % By weight or less. The coating film according to any one of claims 1 to 3, wherein the easy-adhesive coating layer contains a cross-linking agent, and the content of the cross-linking agent in the coating liquid forming the easy-adhesive coating layer with respect to the total non-volatile content It is 80% by weight or less. The coating film according to any one of claims 1 to 3, wherein the antistatic coating layer contains a crosslinking agent, and the content of the crosslinking agent in the coating liquid forming the antistatic coating layer is relative to the total non-volatile component It is 80% by weight or less. The coating film according to any one of claims 1 to 3, wherein the easy-adhesive coating layer contains particles, and the content of the particles in the coating liquid forming the easy-adhesive coating layer is 25% by weight relative to the total non-volatile content. the following. The coating film according to any one of claims 1 to 3, wherein the antistatic coating layer contains a mold release agent, and the mold is released from the coating liquid forming the antistatic coating layer. The ratio of the content of the agent to the total non-volatile components is 50% by weight or less. A coating film characterized by having an active energy ray hardening paint formed from a compound having a carbon-carbon double bond on the surface of an easy-adhesive coating layer of the coating film according to any one of claims 1 to 9 An optical functional layer having a refractive index of 1.57 or more. A coating film, characterized in that a biaxially stretched layer formed by a three-layer structure each comprising a polyester layer (A) and a polyester layer (C) as a surface layer and a polyester layer (B) as an intermediate layer is polymerized The (A) layer of the ester film has an easy-adhesion coating layer containing a polymer, the (C) layer has an antistatic coating layer containing a compound having an ammonium group, and the (C) layer contains an average particle diameter of 2.0 ~ The organic particles of 9.0 μm use an active energy ray-curable coating material formed from a compound having a carbon-carbon double bond to form a functional layer on the surface of the easy-adhesive coating layer. For example, the coating film of claim 11, wherein the content of the polymer in the coating liquid that forms the easy-to-adhere layer is 20 to 90% by weight relative to the total non-volatile components, and the coating liquid that forms the antistatic coating layer The content of the compound having an ammonium group in the total non-volatile component is 3 to 90% by weight. For example, the coating film of claim 11, wherein the antistatic coating layer contains a polymer, and the content of the polymer in the coating liquid forming the antistatic coating layer is 90% by weight or less with respect to the total non-volatile components. For example, the coating film of claim 11, wherein the easy-adhesive coating layer contains a cross-linking agent, and the content of the cross-linking agent in the coating liquid forming the easy-adhesive coating layer with respect to the total non-volatile components is 80% by weight or less. For example, the coating film of claim 11, wherein the antistatic coating layer contains a crosslinking agent, and the content of the crosslinking agent in the coating solution forming the antistatic coating layer is 80% by weight or less with respect to the total non-volatile components. For example, the coating film of claim 11, wherein the easy-adhesive coating layer contains particles, and the content of the particles in the coating liquid forming the easy-adhesive coating layer with respect to the total non-volatile content is 25% by weight or less. For example, the coating film of claim 11, wherein the antistatic coating layer contains particles, and the content of the particles in the coating solution forming the antistatic coating layer is 50% by weight or less with respect to the total non-volatile components. For example, the coating film of claim 11, wherein the antistatic coating layer contains a mold release agent, and the content of the mold release agent in the coating liquid forming the antistatic coating layer is 50% by weight or less with respect to the total non-volatile components. For example, the coating film of claim 11, wherein the polymer that is easy to adhere to the coating layer is any one or more of urethane resin, acrylic resin, and polyester resin. The coating film according to claim 19, wherein the urethane resin is a self-emulsifying urethane resin obtained by introducing an ionic group and polymerizing an ionic bond. The coating film according to claim 19, wherein the urethane resin contains a carbon-carbon double bond that reacts with a carbon-carbon double bond contained in a compound for forming an optical functional layer formed on the surface of the easy-adhesive coating layer. Carbon double bond urethane resin.