JP5628357B2 - 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 resin, acrylic resin, and urethane resin 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 urethane resin has been proposed, and improvement in adhesion has been achieved. However, even with such a coating layer, adhesion has not always been sufficient for solventless resins. (Patent Document 4).

  In order to improve adhesion to a solvent-free resin, a coating layer mainly composed of a urethane resin and an oxazoline compound has been proposed (Patent Document 5). However, there is a case where the adhesiveness to the prism resin corresponding to the increase in the brightness of the prism derived from the decrease in the number of backlights and the demand for reduction in power consumption, that is, the prism resin having a higher refractive index, 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, on at least one surface of the polyester film, containing a (meth) acrylate compound, as a percentage of total non volatile components in the coating solution for forming the coating layer, from 10 to 40 wt% oxazoline compound The present invention resides in a laminated polyester film having a coating layer formed from a coating solution.

  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 for various prisms and microlens resins, 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 of 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.

  Although the thickness of the polyester film in this invention will not be specifically limited if it is a range which can be formed into a film as a film, Usually, 10-350 micrometers, Preferably it is the range of 50-300 micrometers.

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. Since the coating can be performed simultaneously with the film formation, the production can be handled at a low cost, and therefore in-line coating is preferably used.

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

  In the present invention, it is an essential requirement to have a coating layer formed from a coating solution containing a (meth) acrylate compound and an oxazoline compound on at least one side of a polyester film. In addition, the notation of “(meth) acrylate compound” in this specification represents “acrylate compound and methacrylate compound”.

  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 that the (meth) acrylate compound (CH ₂ = CH-COO-R or CH ₂ ) contained in the coating layer of the film of the present invention is irradiated with ultraviolet rays irradiated when forming the prism layer or the microlens layer. A carbon-carbon double bond in CH ₂ ═C (CH ₃ ) —COO—R) is reacted with a carbon-carbon double bond of a compound used for forming a prism layer or a microlens layer to form a covalent bond. It is to form.

  As the carbon-carbon double bond of the (meth) acrylate compound, a conventionally known material may be used as long as it can react with the carbon-carbon double bond contained in the compound forming the prism layer or the microlens layer. Although not particularly limited, for example, monofunctional (meth) acrylate, bifunctional (meth) acrylate, polyfunctional (meth) acrylate, and the like can be given.

  Although it does not specifically limit as monofunctional (meth) acrylate, For example, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meta) ) Acrylate, cyclohexyl (meth) acrylate, alkyl (meth) acrylate such as isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate such as hydroxyalkyl (meth) acrylate, Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, etc. Relate, aromatic (meth) acrylates such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, amino group-containing (meth) acrylates such as diaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methoxyethylene glycol ( (Meth) acrylate, phenoxypolyethyleneglycol (meth) acrylate, ethylene oxide modified (meth) acrylate such as phenylphenol ethylene oxide modified (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic An acid etc. are mentioned.

  Although it does not specifically limit as bifunctional (meth) acrylate, For example, 1, 4- butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) Alkanediol di (meth) acrylate such as acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, bisphenol F ethylene oxide modified Bisphenol-modified di (meth) acrylate such as di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, urethane di (meth) acrylate, epoxy di (meth) acrylate Examples include chlorate.

  The polyfunctional (meth) acrylate is not particularly limited. For example, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) ) Isocyanurates such as acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethaneethylene oxide modified tetra (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate Acid-modified tri (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol Triacrylate toluene diisocyanate urethane prepolymer, urethane acrylates such as dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, and the like.

  These compounds may be used alone or in combination as a mixture. Moreover, from a viewpoint of adhesive improvement, Preferably bifunctional (meth) acrylate and polyfunctional (meth) acrylate, More preferably, polyfunctional (meth) acrylate is good.

  Further, the ratio of the carbon-carbon double bond part to the (meth) acrylate compound is preferably 3% 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. More preferably, it is 5% by weight or more. The upper limit is usually 40% by weight.

  The oxazoline compound used in the formation of the coating layer of the film of the present invention is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferred, and an addition polymerizable oxazoline group-containing monomer alone or other Can be made by polymerization with monomers. 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.

  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 them, polyurethane resin and 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 polycarbonate 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 more preferable in order to improve adhesion to various topcoat layers.

  Examples of the polyisocyanate compound used for obtaining the urethane resin include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, α, α, α ′, α ′. -Aliphatic diisocyanates having aromatic rings such as tetramethylxylylene diisocyanate, aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl Methanzi Cyanate, alicyclic diisocyanates such as isopropylidene dicyclohexyl diisocyanates. These may be used alone or in combination. These polyisocyanate compounds may be a dimer, a trimer represented by an isocyanuric ring, or a higher polymer.

  A chain extender may be used when synthesizing the urethane 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, isoprobilitincyclohexyl-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 addition, in the formation of the coating layer in the film of the present invention, a crosslinking agent other than the oxazoline compound can be used in combination for improving the coating appearance, transparency and adhesion.

  Examples of the crosslinking agent include melamine compounds, isocyanate compounds, carbodiimide compounds, silane coupling compounds, and the like.

  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.

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

  When used in the state of blocked isocyanate, the blocking agent includes, for example, bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, and alcohols such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol. Compounds, active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, lactam compounds such as ε-caprolactam and δ-valerolactam , Amine compounds such as diphenylaniline, aniline, ethyleneimine, acetanilide, acid amide compounds of acetic acid amide, formaldehyde, acetoald Examples include oxime compounds such as oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, and these may be used alone or in combination of two or more.

  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.

  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.

  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 (meth) acrylate compound is usually 5 to 95% by weight, preferably 10 to 80% by weight, more preferably 20 to 70% by weight. % 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.

  The ratio of the carbon-carbon double bond part of the (meth) acrylate compound is preferably 0.1% by weight or more, more preferably 0.8% as a ratio with respect to the total nonvolatile components in the coating liquid forming the coating layer in the film of the present invention. It is 3% by weight or more, more preferably 1.0% 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. The upper limit is usually 28% by weight.

  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 oxazoline compound is usually in the range of 5 to 95% by weight, preferably 10 to 60% by weight, more preferably 10 to 40% by weight. It is. 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 wt% or less, more preferably 3 to 15 wt%, and even more preferably 3 to 10 wt%. When it exceeds 25% by weight, 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 and urethane resins, cross-linking agents such as oxazoline compounds, epoxy compounds, melamine compounds, isocyanate compounds and carbodiimide compounds, 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 (meth) acrylate compound and an oxazoline 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. When the film thickness is out of the above range, adhesion, coating appearance, and blocking characteristics may be deteriorated.

  In the film of the present invention, as a method for providing the coating layer, a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating or the like 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. The heat treatment should 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, it is usually preferable to perform heat treatment 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 prism layer include a triangular cross section having a thickness of 10 to 500 μm, a pitch of prism rows of 10 to 500 μm, and an apex angle of 40 ° to 100 °. As the material used for the prism layer, conventionally known materials can be used, and examples thereof include materials made of an active energy ray-curable resin, and (meth) acrylate-based resins are typical examples.
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.

  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 and 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.

  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 such as a cone or a polygonal pyramid. As a material used for the microlens layer, a conventionally known material can be used as in the prism 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 (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 was formed. Immediately thereafter (adhesion 1) and after being treated for 24 hours in an environment of 60 ° C. and 90% RH (adhesion 2), the prism layer of the film was scratched with a cutter knife at intervals of 5 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. The peeled surface was observed. If the peeled area was 10% or less, it was evaluated as ◯ if it exceeded 10% and 25% or less, and × if it exceeded 25%.

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. 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)
・ (Meth) acrylate compounds: (IA)
Tetramethylol methane ethylene oxide modified tetraacrylate (total ethylene glycol chain = 35). A tetrafunctional acrylate having a carbon-carbon double bond ratio of 5% by weight based on the whole.

・ (Meth) acrylate compounds: (IB)
Biscoat # 1000 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), which is a hyper-branched polymer having dipentaerythritol as a core and a polyfunctional acrylate having a carbon-carbon double bond ratio of 5% by weight or more based on the whole.

・ Polyurethane resin: (IIA)
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: (IIB)
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: (IIC)
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: (IIIA)
Acrylic polymer having an oxazoline group and a polyalkylene oxide chain Epocros WS-500 (manufactured by Nippon Shokubai Co., Ltd., containing about 38% by weight of 1-methoxy-2-propanol solvent)

・ Epoxy compounds: (IIIB)
Denacol EX-521 (manufactured by Nagase ChemteX), a polyglycerol polyglycidyl ether

Particles: (IV) 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 in which the film is stretched 4.0 times at 120 ° C. in the transverse direction and heat-treated at 225 ° C. and then relaxed by 2% in the transverse direction and the coating layer thickness (after drying) is 0.13 μm. 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 2-6:
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. The finished polyester film was as shown in Table 2 and had good adhesion.

Comparative Examples 1-5:
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 surface functions such as prism layers and microlens layers and good adhesion, for example, backlight units for liquid crystal displays.

Claims (1)

On at least one surface of the polyester film, (meth) acrylate compound, as a percentage of total non volatile components in the coating solution for forming the coating layer, the coating formed from the coating solution containing a 10 to 40 wt% oxazoline compound A laminated polyester film comprising a layer.