JP6052845B2 - Laminated polyester film - Google Patents

Description

  The present invention relates to a laminated polyester film, and in particular, a laminated polyester that is suitably used as a prism sheet or a microlens member used in a backlight unit of a liquid crystal display and has good adhesion to various functional layers. It relates to film.

  In recent years, liquid crystal displays have been widely used as display devices for televisions, personal computers, digital cameras, mobile phones and the like. Since these liquid crystal displays do not have a light emitting function by a liquid crystal display unit alone, a method of displaying by irradiating light using a backlight from the back side is widespread.

  The backlight system has a structure called an edge light type or a direct type. Recently, there is a tendency to reduce the thickness of liquid crystal displays, and an edge light type is increasingly used. The edge light type is generally configured in the order of a reflection sheet, a light guide plate, a light diffusion sheet, and a prism sheet. As the flow of light, the light incident on the light guide plate from the backlight is reflected by the reflection sheet and emitted from the surface of the light guide plate. The light beam emitted from the light guide plate enters the light diffusion sheet, is diffused and emitted by the light diffusion sheet, and then enters the next existing prism sheet. The light beam is condensed in the normal direction by the prism sheet and emitted toward the liquid crystal layer.

  The prism sheet used in this configuration is for improving luminance by improving the optical efficiency of the backlight. As the transparent base film, a polyester film is generally used in consideration of transparency and mechanical properties. In order to improve the adhesion between the base polyester film and the prism layer, these intermediate layers are easily bonded. In general, a conductive coating layer is provided. As an easily adhesive coating layer, for example, polyester resins, acrylic resins, and polyurethane resins are known (Patent Documents 1 to 3).

  As a method for forming the prism layer, for example, an active energy ray-curable coating material is introduced into a prism type, irradiated with active energy rays while being sandwiched between polyester films, the resin is cured, and the prism type is removed to remove polyester. The method of forming on a film is mentioned. In the case of such a method, it is necessary to use a solventless active energy ray-curable resin in order to form the prism type with precision. However, solventless resins are less permeable and swellable to the easy-adhesion layer laminated on the polyester film than solvent-based resins, and the adhesion tends to be insufficient. A coating layer made of a specific polyurethane resin has been proposed to improve adhesion, but for solventless resins, even such a coating layer does not necessarily have sufficient adhesion. (Patent Document 4).

  In order to improve adhesion to a solvent-free resin, a coating layer mainly composed of a polyurethane resin and an oxazoline compound has been proposed (Patent Document 5). However, there are cases where the adhesiveness to the prism layer corresponding to the increase in the brightness of the prism, that is, the prism layer having a higher refractive index, which is derived from the current decrease in the number of backlights or the reduction in power consumption, is not sufficient.

JP-A-8-281890 Japanese Patent Laid-Open No. 11-286092 JP 2000-229395 A JP-A-2-158633 JP 2010-13550 A

  The present invention has been made in view of the above circumstances, and the problem to be solved is a prism sheet that has good adhesion to various solvent-free resins, such as a backlight unit of a liquid crystal display. Another object of the present invention is to provide a laminated polyester film that can be suitably used as a member for microlenses.

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

That is, the gist of the present invention is a urethane (meth) acrylate compound containing a difunctional or polyfunctional (meth) acrylate structure (excluding a polymer compound having a urethane structure in the molecule), an isocyanate compound, and an oxazoline. The present invention resides in a laminated polyester film having a coating layer formed from a coating solution containing a compound, a carbodiimide-based compound, or an epoxy compound on at least one surface of the polyester film.

  According to the laminated polyester film of the present invention, it is possible to provide a laminated polyester film excellent in adhesion and heat-and-moisture resistance to surface functional layers such as various prism layers and microlens layers, and its industrial value is high.

  The polyester film constituting the laminated polyester film in the present invention may have a single layer structure or a multilayer structure, and may have four or more layers as long as it does not exceed the gist of the present invention other than a two-layer or three-layer structure. It may be a multilayer, and is not particularly limited.

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

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

  The polyester film of the present invention may contain an ultraviolet absorber for improving the weather resistance of the film and preventing deterioration of the liquid crystal and the like. The ultraviolet absorber is not particularly limited as long as it is a compound that absorbs ultraviolet rays and can withstand the heat applied in the production process of the polyester film.

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

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

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

  The average particle diameter of the particles is usually 5 μm or less, preferably 0.01 to 3 μm. When the average particle diameter exceeds 5 μm, the surface roughness of the film becomes too rough, and a problem may occur when various surface functional layers are provided in the subsequent process.

  Furthermore, the content of particles in the polyester layer is usually 5% by weight or less, preferably 0.0003 to 3% by weight. When there are no or few particles, the transparency of the film becomes high and the film becomes a good film, but the slipperiness may be insufficient. There are cases where improvement is required. Further, when the particle content exceeds 5% by weight, the transparency of the film may be insufficient.

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

  In the polyester film of the present invention, conventionally known antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments and the like are added to the polyester film in the present invention, if necessary, in addition to the above-described particles and ultraviolet absorbers. be able to.

  The thickness of the polyester film in the present invention is not particularly limited as long as it can be formed as a film, but is usually 10 to 350 μm, preferably 25 to 300 μm.

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

  In the present invention, the simultaneous biaxial stretching method can be adopted for the production of the polyester film constituting the laminated polyester film. The simultaneous biaxial stretching method is a method in which the above-mentioned unstretched sheet is usually stretched and oriented in the machine direction and the width direction at a temperature controlled normally at 70 to 120 ° C., preferably 80 to 110 ° C. Is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times in terms of area magnification. Subsequently, heat treatment is performed at a temperature of 170 to 250 ° C. under tension or under relaxation within 30% to obtain a stretched oriented film. With respect to the simultaneous biaxial stretching apparatus that employs the above-described stretching method, a conventionally known stretching method such as a screw method, a pantograph method, or a linear driving method can be employed.

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

  In-line coating is a method of coating within the process of manufacturing a polyester film, and specifically, a method of coating at any stage from melt extrusion of a polyester to heat setting after stretching and winding up. Usually, it is coated on any of an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, and a film after heat setting and before winding. Although not limited to the following, for example, in sequential biaxial stretching, a method of stretching in the transverse direction after coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) is particularly excellent. According to such a method, film formation and coating layer formation can be performed at the same time, so there is an advantage in manufacturing cost. In addition, in order to perform stretching after coating, the thickness of the coating layer can be changed by the stretching ratio. Compared to offline coating, thin film coating can be performed more easily. Further, by providing the coating layer on the film before stretching, the coating layer can be stretched together with the base film, whereby the coating layer can be firmly adhered to the base film. Furthermore, in the production of a biaxially stretched polyester film, the film can be restrained in the longitudinal and lateral directions by stretching while gripping the film end with a clip, etc. High temperature can be applied while maintaining the properties. Therefore, since the heat treatment performed after coating can be performed at a high temperature that cannot be achieved by other methods, the film forming property of the coating layer can be improved, and the coating layer and the base film can be more firmly adhered to each other. Furthermore, it can be set as a firm coating layer, and performances such as adhesion to various functional layers that can be formed on the coating layer and wet heat resistance can be improved.

  In the present invention, it is an essential requirement to have a coating layer formed from a coating solution containing a urethane (meth) acrylate compound and an isocyanate compound on at least one surface of the polyester film.

  The coating layer in the present invention can particularly improve the adhesion to the solventless active energy ray-curable layer, and for example, a prism layer or a microlens layer can be formed. In particular, aiming at a high-luminance prism, the adhesiveness to the coating layer tends to be reduced, and the adhesiveness to the prism layer and the microlens layer having a high refractive index can be dealt with.

  The presumed mechanism for improving the adhesion is the carbon-carbon double bond in the urethane (meth) acrylate compound contained in the coating layer of the film of the present invention by ultraviolet rays irradiated when forming the prism layer and the microlens layer. In this method, a carbon-carbon double bond of a compound used for forming a prism layer or a microlens layer is reacted to form a covalent bond.

  The ratio of the carbon-carbon double bond to the urethane (meth) acrylate compound is preferably 5% by weight or more in consideration of adhesion to the prism layer and the microlens layer, particularly adhesion to a resin having a high refractive index. Preferably it is 10 weight% or more.

  As the urethane (meth) acrylate compound used for forming the coating layer in the present invention, a conventionally known compound can be used, and is not particularly limited. For example, an isocyanate compound and a (meth) acrylate compound having a hydroxyl group and The compound obtained by reaction of these is mentioned.

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

  Examples of the (meth) acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone or alkylene oxide adduct of each acrylate, glycerin mono ( (Meth) acrylate, glycerin di (meth) acrylate, glycidyl methacrylate-acrylic acid adduct, trimethylolpropane mono (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, ditrimethylolpropane tri (meth) acrylate, trimethylolpropane-alkylene oxide adduct-di (meth) acrylate, etc. That. These may be used alone or in combination. Also, from the viewpoint of improving adhesion, bifunctional (meth) acrylates and polyfunctional (meth) acrylates are preferable, and polyfunctional (meth) acrylates are more preferable.

  Examples of the isocyanate compound used for forming the coating layer in the present invention include compounds similar to the isocyanate compound constituting the urethane (meth) acrylate described above.

  When used in the form of blocked isocyanate, the blocking agent includes, for example, dimethyl malonate, diethyl malonate, methyl isobutanoyl acetate, ethyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, acetylacetone and the like, bisulfite Salts, phenolic compounds such as phenol, cresol, ethylphenol, alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, ethanol, mercaptan compounds such as butyl mercaptan, dodecyl mercaptan, ε-caprolactam, δ -Lactam compounds such as valerolactam, amine compounds such as diphenylaniline, aniline, and ethyleneimine, acetanilide, acetic acid acetate Examples include amide acid amide compounds, formaldehyde, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, oxime compounds such as cyclohexanone oxime, and these may be used alone or in combination of two or more. Among these, active methylene compounds are preferred from the viewpoint of improving adhesion.

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

  In forming the coating layer in the film of the present invention, various polymers can be used in combination for improving the coating appearance, transparency and adhesion.

  Specific examples of the polymer include polyurethane resin, acrylic resin, polyester resin, polyvinyl (polyvinyl alcohol, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches and the like. Among these, a polyurethane resin and an acrylic resin are preferable from the viewpoint of improving adhesion.

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

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

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

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

  Among the above polyols, polyester polyols and polycarbonate polyols are preferable in order to improve the adhesion with various surface functional layers.

  Examples of the polyisocyanate compound used for obtaining the polyurethane resin include isocyanate compounds constituting the urethane (meth) acrylate described above.

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

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

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

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

  In forming the coating layer in the film of the present invention, a crosslinking agent other than the isocyanate compound can be used in combination for improving the coating appearance, transparency, strength of the coating layer, and the like.

  Examples of the crosslinking agent include oxazoline compounds, carbodiimide compounds, epoxy compounds, melamine compounds, silane coupling compounds, and the like. Among the above crosslinking agents, oxazoline compounds, carbodiimide compounds, and epoxy compounds are preferable from the viewpoint of improving adhesion.

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

  A carbodiimide-based compound is a compound having a carbodiimide structure, and is a compound having one or more carbodiimide structures in the molecule, but for better adhesion, etc., the polycarbodiimide having two or more in the molecule More preferred are system compounds.

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

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

  The content of the carbodiimide group contained in the carbodiimide-based compound is a carbodiimide equivalent (weight of the carbodiimide compound to give 1 mol of carbodiimide group [g]) and is usually 100 to 1000, preferably 250 to 800, more preferably 300. It is -700, More preferably, it is the range of 350-650. By using in the above range, adhesion to the prism layer and the microlens layer is improved.

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

  As an epoxy compound, the compound containing an epoxy group in a molecule | numerator, its prepolymer, and hardened | cured material are mentioned, for example. Examples include condensates of epichlorohydrin with hydroxyl groups and amino groups such as ethylene glycol, polyethylene glycol, glycerin, polyglycerin, and bisphenol A, and polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, and the like. is there. Examples of the polyepoxy compound include sorbitol, polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylol. Examples of the propane polyglycidyl ether and diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether. Ether, polypropylene glycol diglycidyl ether, Ritetramethylene glycol diglycidyl ether and monoepoxy compounds include, for example, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N ′,-tetraglycidyl-m. -Xylylenediamine, 1,3-bis (N, N-diglycidylamino) cyclohexane and the like.

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

Moreover, in order to improve slipperiness and blocking, it is preferable to use particles together in forming the coating layer.

The average particle diameter of the particles is preferably in the range of 1.0 μm or less, more preferably 0.5 μm or less, and particularly preferably 0.2 μm or less from the viewpoint of film transparency. Moreover, when it is necessary to further improve the slipperiness and the blocking improving effect, it is preferable to use particles having an average particle size larger than the film thickness of the coating layer.

  Examples of the particles used include inorganic particles such as silica, alumina and metal oxide, or organic particles such as crosslinked polymer particles. In particular, silica particles are preferred from the viewpoint of dispersibility in the coating layer and transparency of the resulting coating film.

  Further, in the range not impairing the gist of the present invention, an antifoaming agent, a coating property improver, a thickener, an organic lubricant, an antistatic agent, an ultraviolet absorber, and an antioxidant are formed as necessary for forming the coating layer. , Foaming agents, dyes, pigments and the like may be used in combination.

  As a ratio with respect to all the non-volatile components in the coating liquid which forms the coating layer in the film of the present invention, the urethane (meth) acrylate compound is usually 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 15 to 85%. It is in the range of wt%. When it is out of the above range, the adhesion after the heat-resistant heat treatment with the prism layer or the microlens layer may not be sufficient.

  As a ratio with respect to all the non-volatile components in the coating liquid which forms the coating layer in the film of the present invention, the carbon-carbon double bond part of the urethane (meth) acrylate compound is preferably 0.75 wt% or more, more preferably 1 0.0% by weight or more, more preferably 1.5% by weight or more. When it is out of the above range, the adhesion after the heat-resistant heat treatment with the prism layer or the microlens layer may not be sufficient.

  As a ratio with respect to all the non-volatile components in the coating liquid which forms the coating layer in the film of the present invention, the isocyanate compound is usually 5 to 90% by weight, preferably 5 to 85% by weight, more preferably 10 to 80% by weight. It is a range. When it is out of the above range, the adhesion after the heat-resistant heat treatment with the prism layer or the microlens layer may not be sufficient.

  As a ratio with respect to the total nonvolatile components in the coating solution for forming the coating layer in the film of the present invention, the particles cannot be said unconditionally because the slipperiness and blocking characteristics change depending on the particle size and the characteristics of the polyester film, but preferably Is more preferably in the range of 25% or less, more preferably 3 to 15%, still more preferably 3 to 10%. When it exceeds 25%, the transparency of the coating layer may be lowered or the adhesion may be lowered.

  In the polyester film of the present invention, a coating layer can also be provided on the surface opposite to the surface on which the coating layer is provided. For example, when a functional layer such as an anti-sticking layer, a light diffusion layer, or a hard coat layer is formed on the opposite side of the prism layer or the microlens layer, it is possible to improve the adhesion with the functional layer. . A conventionally well-known thing can be used as a component of the coating layer formed in the surface on the opposite side. Examples thereof include polymers such as polyester resins, acrylic resins, polyurethane resins, cross-linking agents such as oxazoline compounds, epoxy compounds, melamine compounds, isocyanate compounds, carbodiimide compounds, etc., and these materials may be used alone. A plurality of types may be used in combination. Further, it may be a coating layer (a coating layer having the same surface on both sides of a polyester film) formed from a coating solution containing a urethane (meth) acrylate compound and an isocyanate compound as described above.

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

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

  Regarding the laminated polyester film in the present invention, the thickness of the coating layer provided on the polyester film is usually 0.002 to 1.0 μm, preferably 0.005 to 0.5 μm, more preferably 0.01 to 0.2 μm. Range. The coating layer of the present invention is characterized by excellent adhesion even when the film thickness is small. When the film thickness is out of the above range, adhesion, coating appearance, and blocking characteristics may be deteriorated.

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

  In the present invention, the drying and curing conditions for forming the coating layer on the polyester film are not particularly limited. For example, when the coating layer is provided by off-line coating, it is usually 3 to 40 at 80 to 200 ° C. The heat treatment may be performed for 2 seconds, preferably 100 to 180 ° C. for 3 to 40 seconds.

  On the other hand, when the coating layer is provided by in-line coating, heat treatment is usually performed at 70 to 280 ° C. for 3 to 200 seconds as a guide.

  Moreover, you may give surface treatments, such as a corona treatment and a plasma treatment, to the polyester film which comprises the laminated polyester film in this invention previously.

  On the coated layer of the laminated polyester film of the present invention, it is common to provide a prism layer, a microlens layer, or the like in order to improve the luminance. It is possible to provide a resin layer having a high refractive index necessary for the above. In recent years, various shapes have been proposed for the prism layer in order to improve the luminance efficiently. Generally, prism layers are formed by arranging prism rows having a triangular cross section in parallel. Similarly, various shapes of the microlens layer have been proposed, but in general, a large number of hemispherical convex lenses are provided on the film. Any layer can have a conventionally known shape.

  Examples of the shape of the microlens layer include a hemispherical shape having a thickness of 10 to 500 μm and a diameter of 10 to 500 μm, but may have a shape like a cone or a polygonal pyramid.

  As materials used for the prism layer and the microlens layer, conventionally known materials can be used, for example, those made of an active energy ray-curable resin, and (meth) acrylate resins are representative examples. is there. As a constituent compound of the resin, generally, for example, it has a polyhydric alcohol component such as ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, bisphenol A structure, urethane structure, polyester structure, epoxy structure, etc. ( Examples include meth) acrylate compounds.

  The higher the refractive index of the active energy ray-curable resin layer is, the higher the luminance tends to improve, and it is usually 1.56 to 1.65, preferably 1.57 to 1.64, more preferably 1.58. It is in the range of ~ 1.63. If it is out of the above range, the luminance may not be sufficiently increased.

  Examples of the prescription for increasing the refractive index for increasing the brightness include a method using a compound having a large aromatic structure, a sulfur atom, a halogen atom, and a metal compound in addition to the above general compound. Among them, a method using a compound having a large aromatic structure or a sulfur atom is particularly preferable from the viewpoint of the environment because the refractive index of the prism layer and the microlens layer can be made uniform.

  Examples of the compound having a large aromatic structure include condensed polycyclic aromatic structures such as naphthalene, anthracene, phenanthrene, naphthacene, benzo [a] anthracene, benzo [a] phenanthrene, pyrene, benzo [c] phenanthrene, and perylene. , A compound having a biphenyl structure, a compound having a fluorene structure, and the like.

  Various substituents may be introduced into the biphenyl structure, fluorene structure, and condensed polycyclic aromatic structure, and those having a benzene ring-containing substituent such as a phenyl group have a refractive index. Since it can be made higher, it is preferable. It is also possible to introduce atoms that increase the refractive index, such as sulfur atoms and halogen atoms. Furthermore, various functional groups such as an ester group, an amide group, a hydroxyl group, an amino group, and an ether group can be introduced in order to improve the adhesion with the coating layer.

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

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

(2) Measuring method of average particle diameter The coating layer was observed using TEM (H-7650 manufactured by Hitachi High-Technologies Corporation, acceleration voltage 100V), and the average value of the particle diameters of 10 particles was defined as the average particle diameter. .

(3) Weight of carbon-carbon double bond part in urethane (meth) acrylate compound Calculation from molecular weight and number of carbon-carbon double bonds, or each peak of ¹ HNMR and ¹³ CNMR was assigned and obtained by calculation. . NMR measurement was performed using NMR (AVANCE III600 manufactured by Bruker Biospin) after drying the compound under reduced pressure.

(4) Method for measuring film thickness of coating layer The surface of the coating layer was dyed with RuO ₄ and embedded in an epoxy resin. Thereafter, the section prepared by the ultrathin section method is stained with RuO ₄ , and the cross section of the coating layer is measured using TEM (H-7650 manufactured by Hitachi High-Technologies Corporation, acceleration voltage 100V), and the average value of 10 places is applied. It was set as the film thickness of the layer.

(5) Adhesion evaluation method In order to form a prism layer, a mold member in which a large number of prism rows having a pitch of 50 μm and an apex angle of 65 ° are arranged in parallel, 40 parts by weight of 2-biphenoxyethyl acrylate, 4,4′- 10 parts by weight of (9-fluorenylidene) bis (2-phenoxyethyl acrylate), 37 parts by weight of ethylene glycol-modified bisphenol A acrylate (ethylene glycol chain = 8), 10 parts by weight of trimethylolpropane triacrylate, diphenyl (2, 4, 6 -A composition comprising 3 parts by weight of trimethylbenzoyl) phosphine oxide is placed, and a laminated polyester film is laminated thereon in such a direction that the coating layer is in contact with the resin. The composition is uniformly stretched by a roller, and ultraviolet rays are emitted from an ultraviolet irradiation device. Irradiated to cure the resin. Subsequently, the film was peeled off from the mold member to obtain a film on which a prism layer (refractive index of 1.58) was formed. Immediately thereafter (adhesion 1) and after being treated for 48 hours in an environment of 80 ° C. and 90% RH (adhesion 2), the prism layer of the film was scratched with a cutter knife at intervals of 5 mm, and the width of 24 mm A tape (Cello Tape (registered trademark) CT-24 manufactured by Nichiban Co., Ltd.) was applied and peeled off rapidly at a peeling angle of 180 degrees. When the peeled surface was observed, if the peeled area was 5% or less, ◎ if it exceeded 5% and 15% or less, ○, if it exceeded 15% and 25% or less, Δ, and if it exceeded 25%, it was ×.

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

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

<Method for producing polyester (C)>
In the production method of polyester (A), polyester (C) is obtained using the same method as the production method of polyester (A), except that 0.3 part by weight of silica particles having an average particle diameter of 2 μm is added before melt polymerization. It was.

Examples of compounds constituting the coating layer are as follows.
(Example compounds)
・ Urethane (meth) acrylate compounds: (IA)
Dicyclohexylmethane diisocyanate unit: isophthalic acid unit: adipic acid unit: dipentaerythritol pentaacrylate unit: bisphenol A ethylene oxide adduct unit (ethylene oxide chain: n = 2): neopentyl glycol unit: dimethylolpropanoic acid unit = 32: An aqueous dispersion of urethane acrylate formed from 6: 6: 22: 8: 21: 5 (mol%). Contains 10% by weight of carbon-carbon double bond.

・ Urethane (meth) acrylate compounds: (IB)
3-6 functional polyester polyurethane acrylate. Number average molecular weight = 1500 (g / mol) 7% by weight of carbon-carbon double content.

Active methylene block polyisocyanate: (IIA)
(I) Block polyisocyanate synthesized by the following method: 1000 parts by weight of hexamethylene diisocyanate was stirred at 60 ° C., and 0.1 part by weight of tetramethylammonium capryate was added as a catalyst. Four hours later, 0.2 parts by weight of phosphoric acid was added to stop the reaction, and an isocyanurate type polyisocyanate composition was obtained. 100 parts by weight of the obtained isocyanurate-type polyisocyanate composition, 42.3 parts by weight of methoxypolyethylene glycol having a number average molecular weight of 400, and 29.5 parts by weight of propylene glycol monomethyl ether acetate were charged and maintained at 80 ° C. for 7 hours. Thereafter, the temperature of the reaction solution was maintained at 60 ° C., 35.8 parts by weight of methyl isobutanoyl acetate, 32.2 parts by weight of diethyl malonate, and 0.88 parts by weight of 28% methanol solution of sodium methoxide were added and maintained for 4 hours. . Block polyisocyanate obtained by adding 58.9 parts by weight of n-butanol, maintaining the reaction solution temperature at 80 ° C. for 2 hours, and then adding 0.86 parts by weight of 2-ethylhexyl acid phosphate.

・ Isocyanate compounds: (IIB)
Hexamethylene diisocyanate trimer unit: methoxypolyethylene glycol unit having a number average molecular weight of 1400: methyl ethyl ketone oxime unit = 30: 2: 68 (mol%), a number consisting of 1,6-hexanediol and diethyl carbonate Polyethylene polyol unit having an average molecular weight of 2000: isophorone diisocyanate unit: trimethylolpropane unit: dimethylolpropionic acid unit = 24: 55: 3: 18 (mol%) neutralized with triethylamine to diethylenetriamine An aqueous blocked isocyanate compound containing a urethane resin obtained by chain extension at

・ Isocyanate compounds: (IIC)
Trimethylolpropane adduct unit of tolylene diisocyanate (tolylene diisocyanate: trimethylolpropane = 3: 1 (mol%)): methoxypolyethylene glycol unit having a number average molecular weight of 2000: N, N, N ′, N′-tetrakis An aqueous block polyisocyanate compound formed from (2-hydroxyethyl) ethylenediamine unit: methyl ethyl ketone oxime unit = 33: 2: 55: 10 (mol%).

・ Polyurethane resin: (IIIA)
Tolylene diisocyanate unit: terephthalic acid unit: isophthalic acid unit: ethylene glycol unit: neopentyl glycol unit: dimethylolpropanoic acid unit = 14: 17: 17: 23: 24: 5 (mol%) polyester-based polyurethane Water dispersion of resin.

・ Polyurethane resin: (IIIB)
Polycarbonate polyol unit comprising 1,6-hexanediol and diethyl carbonate having a number average molecular weight of 2000: Polycarbonate formed from methylenebis (4-cyclohexylisocyanate) unit: dimethylolpropanoic acid unit = 45: 50: 5 (mol%) An aqueous dispersion of polyurethane resin.

・ Acrylic resin: (IIIC)
Aqueous dispersion of acrylic resin formed from ethyl acrylate unit: n-butyl acrylate unit: methyl methacrylate unit: N-methylol acrylamide unit: acrylic acid unit = 67: 17: 10: 2: 4 (mol%) (emulsifier: Anionic surfactant)
・ Oxazoline compounds: (IVA)
An acrylic polymer having an oxazoline group and a polyalkylene oxide chain. Oxazoline group amount = 4.5 mmol / g

・ Carbodiimide compounds: (IVB)
Carbodiimide equivalent: 430 g / mol polycarbodiimide compound.

Melamine compound: (IVC) hexamethoxymethylol melamine

・ Epoxy compounds: (IVD)
Polyglycerol polyglycidyl ether.
-Particles: (V) Silica sol with an average particle size of 0.07 μm

Example 1:
A mixed raw material in which polyesters (A), (B), and (C) are mixed at a ratio of 89%, 5%, and 6%, respectively, is used as a raw material for the outermost layer (surface layer), and polyesters (A) and (B) are each 95 %, 5% mixed raw materials were used as intermediate layer raw materials, each was supplied to two extruders, melted at 285 ° C., and then on a cooling roll set at 40 ° C. Coextruded with a layer structure of layers (surface layer / intermediate layer / surface layer = 1: 18: 1 discharge amount) and cooled and solidified to obtain an unstretched sheet.
Next, the film was stretched 3.4 times in the longitudinal direction at a film temperature of 85 ° C. using the difference in peripheral speed of the roll, and then the coating liquid 1 shown in Table 1 below was applied to both sides of the longitudinally stretched film, and led to a tenter. Thickness having a coating layer having a coating layer thickness of 0.01 μm, stretched 4.0 times at 120 ° C. in the transverse direction, heat-treated at 225 ° C. and then relaxed by 2% in the transverse direction. A 125 μm polyester film was obtained. When the obtained polyester film was evaluated, the adhesion with the prism layer was good. The properties of this film are shown in Table 2 below.

Examples 2-17:
In Example 1, it manufactured similarly to Example 1 except having changed the coating agent composition into the coating agent composition shown in Table 1, and obtained the polyester film. The finished polyester film was as shown in Table 2 and had good adhesion.

Comparative Examples 1-6:
In Example 1, it manufactured similarly to Example 1 except having changed the coating agent composition into the coating agent composition shown in Table 1, and obtained the polyester film. When the completed laminated polyester film was evaluated, it was as shown in Table 2 and had poor adhesion.

  The film of the present invention can be suitably used for applications that require good adhesion to surface functional layers such as prism layers and microlens layers, such as backlight units for liquid crystal displays.

Claims (1)

Urethane (meth) acrylate compounds containing a bifunctional or polyfunctional (meth) acrylate structure (excluding polymer compounds having a urethane structure in the molecule) and isocyanate compounds, and oxazoline compounds, carbodiimide compounds, or epoxies A laminated polyester film having a coating layer formed from a coating solution containing a compound on at least one surface of the polyester film.