TW200401707A - Laminated film - Google Patents

Abstract

The objective of the present invention is to provide a laminated film that has excellent impact resistance, transparency and hue, and is reduced with respect to the precipitation of oligomers during the processing thereof. The laminated film of the present invention is characterized by having a substrate layer and, provided at least one surface thereof, a coating layer. The substrate layer is an oriented film comprising polyethylene naphthalene dicarboxylate and having an intrinsic viscosity of 0.45 to 0.70 dl/g. The laminated film has a haze of 0.5% per 100 μ m of the thickness of the film, both of a* and b* values in L*a*b* system are -2.0 to + 2.0 per 100 μ m of the thickness of the film, as measured by the transmission measurement method, and a face orientation coefficient of 0.15 to 0.30.

Description

200401707 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a laminated film made of polyethylene naphthalate. More specifically, it relates to a laminated film made of polyvinyl naphthalate, which has good transparency and hue and rarely generates oligomers when heated. [Previous technology] Advance polyester films, especially biaxially stretched films of polyethylene terephthalate and polyethylene naphthalate, have good mechanical properties, heat resistance, and chemical resistance. Therefore, it is proposed to Tapes, ferromagnetic film tapes, photographic films, packaging films, films for electronic parts, films for electrical insulation, films for metal laminated plastics, films affixed to surfaces such as glass displays, films for protection of various materials, etc. (Patent Document 1). Furthermore, it has been proposed to apply a polyester film to an image display device represented by a liquid crystal display. That is, in the image display device, a user first uses a glass substrate. However, in recent years, image display devices have been required to be thin, lightweight, large screens, shape freedom, and curved display. Therefore, users who use transparent polymer film substrates such as polyester films instead of thick and fragile glass substrates have been criticized. (Patent Documents 2 and 3). Especially in recent years, the self-laser element represented by the organic EL has been actively developed. For image display devices that must use a backlight such as a liquid crystal display and must use a large number of materials, it is extremely desirable to change the glass. The heavy shortcomings have also been strongly requested to be improved. However, as of now, I want to provide an ideal bumper which can improve the shortcomings of glass sufficiently. -5-e; 'e A 疒 ~ (2) (2) 200401707, and a polymer film with transparency and hue close to glass This is still extremely difficult. In addition, the polymer film used for the display application represented by the above note is based on its application. If the gas barrier layer, conductor layer, semiconductor layer, and photobody layer are laminated, the lamination of these layers is performed by evaporation, Ion plating, sputtering, plasma CDV and other methods are used. When this method is applied, there are different temperatures according to different methods. However, if the temperature is too high, it is easy to be exposed, and the oligomers of the low-molecular substances existing in the film are precipitated and the transparency is impaired. Problems with complex steps. (Patent Document 1) JP 2002-27 3 844 (Patent Document 2) JP 200 1 38465 (Patent Document 3) JP 2002-8062 1 [Summary of the Invention] The present invention is to provide a The purpose of solving the problems of this prior art is to have a good impact resistance, transparency, hue, and rarely produce oligomer films during the steps. That is, the present invention is a laminate film formed of a base material layer and a coating layer provided on at least one side thereof. The base material layer is made of polyethylene naphthalate and has an inherent viscosity of 0.45 to 0.70 dl / g. For oriented films, the turbidity of the laminated film is 0.5% or less when the thickness of the film is 100 μm, and a * 値 and b * L in the L * a * b * color system are measured by the transmission method and the film thickness is 100 μm Both are -2.0 ~ + 2.0, and those with a plane orientation coefficient of 0.15 ~ 0.30 are the features of (3) 200401707 laminated films. The present invention includes a laminated film provided with a functional layer on the laminated film. The feature of the functional layer is at least one laminated film selected from the group consisting of a rod coating layer, a gas barrier layer, and a conductive layer. The present invention also includes a substrate for EL displays, a substrate for electrophoretic paper, and a substrate for solar cells formed from the laminated film.

The present invention further includes the use of the laminated film for a substrate for an EL display, a substrate for an electrophoretic paper, or a substrate for a solar cell. In addition, the manufacturing method of the laminated film of the present invention is (1) a step of manufacturing polyethylene naphthalene dicarboxylate by transesterification reaction in the presence of cobalt element, (2) the polyvinyl dicarboxylic acid ester The step of obtaining an unstretched film after pressing on a rotating cooling drum,

(3) After the coating layer is set on the unstretched film, it is stretched in the continuous film-forming direction (MD direction), or after the unstretched film is stretched in the MD direction, after the coating layer is set, the laminated uniaxial extension is obtained. The step of film, (4) the step of obtaining the biaxially stretched film after the laminated uniaxially stretched film is extended in the vertical direction (TD direction) for the continuous film making direction, and (5) the biaxially stretched film is obtained for thermal fixation Step, the method of manufacturing the laminated film. [Embodiment] [The best form of implementation of the invention] (Polyvinylnaphthalene dicarboxylate) -7- (4) (4) 200401707 The polyethylene naphthalate dicarboxylate constituting the laminated film in the present invention is mainly dicarboxylic Those whose acid component is naphthalenedicarboxylic acid and whose main diol component is ethylene glycol. Examples of naphthalenedicarboxylic acids are: 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. For the better. The "mainly" means that the total repeating unit in the polymer constituents of the film component of the present invention is at least 90 mol%, preferably at least 95 mol%. In the case of a copolymer, as a copolymer component constituting the copolymer, a compound having two ester-forming functional groups can be used in the molecule, such as oxalic acid, adipic acid, phthalic acid, sebacic acid, and dodecane. Dicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4, diphenyl dicarboxylic acid, phenylindane dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, Dicarboxylic acids such as naphthalene dicarboxylic acid, decalin dicarboxylic acid, diphenyl ether dicarboxylic acid, p-oxybenzoic acid, p-oxyethoxybenzoic acid, or propylene glycol , Trimethylene glycol 'tetramethylene glycol, hexamethylene glycol' cyclohexylene glycol, neopentyl glycol, bisphenol milled ethylene oxide addition, bisphenol A ring Ethylene oxide additives, diethylene glycol, polyethylene oxide glycol divalent alcohols are ideal users. These compounds may be used singly or in combination of two or more kinds. In addition, the ideal acid component is isophthalic acid, terephthalic acid, 4,4f-diphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and p-oxybenzoic acid as the diol component. Examples include: trimethylene glycol, hexamethylene glycol, neopentyl glycol, and bisphenol milled ethylene oxide additives. Polyethylene naphthalene dicarboxylic acid esters can be partially or fully blocked by monofunctional compounds such as benzoic acid, methoxy polyalkylene, and diols at the terminal. It is also possible to obtain a copolymer of substantially linear polymers in a small amount of (5) (5) 200401707 triglyceride-like ester-forming compounds such as glycerol and pentaerythritol. The polyester of the present invention can obtain a direct low-polymer polyester under the reaction of a dicarboxylic acid and a diol. After the lower alkyl ester of the dicarboxylic acid and the diol are reacted by using a transesterification catalyst, it is in the presence of a polymerization catalyst. Obtained by a method of performing melt polymerization. Examples of catalysts used in the transesterification reaction include compounds containing sodium, potassium, magnesium, calcium, zinc, hafnium, titanium, chromium, manganese, and cobalt, among which one or two types of cobalt are used. Compounds of the above elements are more likely to achieve ideal hue when used as a thin film. Examples of cobalt compounds are oxides, chlorides, carbonates, carboxylates, and the like, and carboxylates, especially acetates are more preferred. The amount of the cobalt compound to be added is preferably polyethylene naphthalene dicarboxylate with respect to the cobalt element, and 2 to 80 ppm at the weight fraction is preferable, more preferably 4 to 60 ppm, and particularly 8 to 40 ppm. When the amount of cobalt is less than 2 ppm, the hue tends to be yellowish; conversely, when it exceeds 80 p p m, the transparency is liable to decrease. Examples of compounds that are ideally used in combination with cobalt compounds are: Examples of compounds such as magnesium, calcium, and manganese. Among them, manganese can maintain a good compound hue and promote transesterification as an ideal catalyst. By. Examples of manganese compounds are oxides, chlorides, carbonates, carboxylates, and the like, and carboxylates, especially acetates are the most preferable. The ideal amount of added manganese compound is 20 ~ 120ppm, preferably 30 ~ 100ppm, especially 40 ~ 80ppm. When the elemental film has a weight fraction of less than 20 ppm (6) (6) 200401707, the transesterification reaction tends to be insufficient. On the other hand, if it exceeds 120 ppm, the transparency is not compromised. When polymerization is carried out through a transesterification reaction, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, orthophosphoric acid, etc. are usually added for the purpose of deactivating the transesterification catalyst before the polymerization reaction. Phosphorus compounds. Polyethylene naphthalene dicarboxylate as the phosphorus element has an ideal polyester having good thermal stability if the content is 20 to 100 ppm. More preferable addition amounts are 30 to 90 ppm, and 40 to 80 ppm are the best. In addition, the amount of phosphorus compound is preferably 0.7 to 2.0 based on the total amount of the transesterification catalyst added. When the molar ratio is less than 0.7, the inactivation effect of the transesterification catalyst is likely to be insufficient. On the other hand, when it exceeds 2.0, the thermal stability is easily deteriorated. The molar ratio is preferably 0.8 to 1.9, more preferably 0.9 to 1.8, and most preferably 1.0 to 1.7. Examples of polymerization catalysts include antimony trioxide, antimony pentoxide antimony compounds, germanium compounds represented by germanium dioxide, tetraethyl titanate, tetrapropyl phthalate, and tetraphenyl phthalate. Or some of these hydrolysates, titanium oxalate oxalate phthalate, potassium titanyl oxalate, titanium triacetamyl acetate, etc. Examples of titanium compounds are suitable for obtaining a good hue, especially trioxide Antimony is the best. The ideal amount of antimony compound is for the thin film of antimony element. In the weight fraction, it is preferably 50 ~ 400ppm, more preferably 60 ~ 300ppm, especially 70 ~ 200ppm. When the amount of antimony is less than 50ppm When it is too high, the polymerization rate will be extremely delayed, while if it exceeds 400 ppm, the transparency will be reduced. Regarding the adding time of the aforementioned catalyst and stabilizer, the transesterification catalyst was added at the beginning of the transesterification reaction, and the stabilizer was essentially terminated at the transesterification reaction. The polymerization catalyst was added in 10 minutes after adding the female tincture. Anyone should. -10- (7) (7) 200401707 In addition, after the polyester is melt-polymerized, it is crushed, and then solid-phase polymerization is performed under heating or reduced pressure, or in an inert gas stream such as nitrogen, and then thermally deteriorates during polymerization. Prevents coloring from being ideal. In particular, after the melt-polymerized polymer having an intrinsic viscosity of 0.40 to 0.60 dl / g is further reduced, its solid state polymerization can maintain a good hue when the intrinsic viscosity is 0.46 to 0.75 dl / g, and the temperature can be suppressed in this processing step. The appearance of oligomers is ideal. The polyethylene naphthalene dicarboxylate of the present invention may also contain a colorant, an antistatic agent, an oxidation inhibitor, an organic lubricant, and the like. The laminated film of the present invention is obtained by extruding the polymer through thermal dissolution, pressing a metal drum rotated by a joint, etc., and then quenching the obtained unstretched film such as: a continuous film forming direction described later ( MD direction) and the continuous film forming direction is extended to the vertical direction (TD direction), which can be manufactured after heat fixing treatment. (Intrinsic viscosity) The intrinsic viscosity of the oriented film constituting the base material layer is 0.45 to 0.70 dl / g. When the intrinsic viscosity of the thin film is less than 0.45 dl / g, it is easy to crystallize during the film formation step. Therefore, microcrystals are easily formed in the thin film, which scatters light and causes hue deterioration. In addition, a thin film having an intrinsic viscosity of less than 0.45 dl / g is prone to breakage during the film forming step, lowering the impact resistance, and is liable to crack when made into a thin film. Conversely, when a film with an inherent viscosity exceeding 0.70 dl / g is produced, its polymer has a high melt viscosity, resulting in melt extrusion: it is not easy, reduces productivity, and increases costs. 1 Intrinsic viscosity of the oriented film After removing the coating layer and the like from the laminated film, 0.3 g of the substrate layer was dissolved in 25 ml of o-chlorophenol solution, and the temperature was at 35 ° C -11-(8) (8) 2 The measurement was performed at 407,007,7. The coating layer, etc. can be removed by shaving, filing, etc. (Haze) The turbidity of the laminated film of the present invention at a thickness of 100 μm is 0.5% or less. When it exceeds 0.5%, the transparency becomes poor, the visibility is poor when used as a display, and the photoelectric conversion efficiency is reduced when used as a solar cell. The turbidity per 100 μm is more preferably 0.45% or less, particularly 0.4% or less. (L * a * b * a * 値 and b * 値 of the color rendering system) The laminated film of the present invention is directed to a film having a thickness of 100 μm, and the a * 値 and b * 显 of the L * a * b * color rendering system are transmitted When measured by the measurement method, all were -2 to +2. When this value is less than -2, or exceeds +2, the color tone of the film will change from no color to a greatly different tone, and the color will be worse when used as a display. In this case, -1.8 to +1.8 is more preferable, and -1.6 to +1.6 is particularly preferable. In addition, when the laminated film of the present invention is directed to a film having a thickness of 100 μm, when a * 値 and b * 値 are -0.5 to +0.5 by reflection measurement method, the color reappearance is better when exposed to external light, so it is ideal. . In this case, -0.4 ~ + 0.4 is preferable, -0.3 ~ + 0.3 is more preferable, and the most preferable is -0.2 ~ + 0.2. After these transparency-controlled hue-related parameters are obtained, a film of good quality can be obtained by optimizing the types of catalysts, stabilizers, addition amounts, and polymerization degrees as used in the aforementioned polyester polymerization. Reached. (Face Alignment Coefficient) The laminated film of the present invention has a surface orientation coefficient of 0.15 to 0.30. When the surface orientation?-*. * Rv rr 'ih〇-12- 200401707 〇) When the coefficient is less than 0.15, sufficient impact resistance cannot be obtained. Conversely, when it is greater than 0.30, it is easy to break when manufacturing thin films, and Unable to obtain a stable film. The more ideal surface orientation coefficient is 0.18 ~ 0.29, the more preferred is 0.21 ~ 0.28, and the most preferred is 0.24 ~ 0.27. (Size conversion rate)

In the laminated film of the present invention, the size conversion rate of the continuous film forming direction (MD direction) of the film is preferably at a temperature of 200 ° C and a load of i40g / mm2 of -2 to + 2%. Therefore, in the process of providing a functional layer such as a rod coating layer, a gas barrier layer, a transparent conductive layer, a semiconductor layer, a light emitting layer, and a metal electrode layer in the thin film, the size change of the thin film is reduced, and cracks are unlikely to occur in the functional layer. The more ideal size conversion rate is -1 · 5 ~ + 1.5%, the more ideal is -1 · 〇 ~ + 1 · 〇%, and especially _ 〇0.5 ~ + 0.5% is the most ideal. The surface alignment coefficient and size conversion rate are such that the polymerization degree of the polymer is as described above, and the predetermined range can be made by adjusting the stretching temperature, stretching ratio, and heat-fixing temperature of the film.

(Number of oligomers) The number of oligomers in the area of the surface of the laminated film of the present invention after being heated at 200 ° C for 30 minutes is preferably 0.24 mm2 or less, and more preferably 100 or less. The oligomer number is obtained by heating the film in a 200-art oven for 30 minutes, removing the surface, and vapor-depositing aluminum, and then observing the area of 0 · 2 4 m 2 with a differential interference microscope at 640 times. Number of oligomers. -13- (10) (10) 200401707 (coating layer) The laminated film of the present invention is for the purpose of improving the easy adhesion of the functional layer as described later, and improving the sliding property of the film itself, at least on one side of the film. Coating layer. The coating layer is preferably made of at least one kind of water-soluble or water-dispersible polymer resin selected from the group consisting of polyester resins, urethane resins, acrylic resins, and ethylene-based resins. In particular, the coating layer contains a polymer Both ester resins and acrylic resins are more preferred. The polyester resin of the coating layer preferably has a glass transition point (Tg) of 0 to 100 ° C, and more preferably 10 to 90 ° C. The polyester resin is preferably a water-soluble or dispersible polyester which is soluble in water, and may also contain some organic solvents. Examples of the polyester resin include those formed from the following polybasic acid or its ester-forming derivative and a polyalcohol or its ester-forming derivative. That is, examples of the polybasic acid component include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and adipic acid. Examples include acids, sebacic acid, trimellitic acid, pyroic acid, dimer acid, and sodium 5-sulfoisophthalate. After using two or more of these acids, a synthetic copolymer polyester resin is carried out. Also, a small amount of an unsaturated polybasic acid component, such as maleic acid, itaconic acid, and the like, and hydroxycarboxylic acids such as p-hydroxybenzoic acid, can be used. In addition, as examples of the polyol component, ethylene glycol, 1, butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and xylene Examples of alcohols, dimethylolpropane, poly (ethylene oxide) glycol, poly (tetraalkylene poison) glycol, bisphenol A, bisphenol A, ethylene oxide, or propylene oxide additions. In addition, these monomer examples are not limited to these. -14- (11) (11) 200401707 The acrylic resin of the coating layer used in the present invention preferably has a glass transition point (Tg) of -50 to 50 ° C, more preferably -50 to. The propylene resin is preferably water-soluble or dispersible propylene, and may contain some organic solvents. As the propylene resin, the following propylene monomers can be copolymerized. Examples of such propylene monomers are: alkyl acrylates and alkyl methacrylates (as alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Group, tert-butyl, 2-ethylhexyl, cyclohexyl, etc.); 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2.hydroxypropyl Hydroxyl-containing monomers such as methacrylate; epoxy-containing monomers such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether; acrylic acid, methacrylic acid, itaconic acid, Maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) and other carboxyl groups or monomers containing the salts; acrylamide, methacrylic acid Amine, N-alkyl propylene amide, N-alkyl methacrylamide, N, N-dialkyl propylene amide, N, N-dialkyl methacrylate (for alkyl Group, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, etc.), N-alkoxyacrylamide, N ·alkyl Methyl methacrylamide, N, N-dialkoxyacrylamide, N, N-dialkoxymethacrylamide (as alkoxy groups such as: methoxy, ethoxy, butane (Oxy, isobutoxy, etc.), acrylamidomorpholine, N-methylol acrylamide, N-methylol acrylamide, N-phenylacrylamide, N-phenylmethyl Acrylamidine-containing monomers such as fluorenamine; monomers of anhydrides such as maleic anhydride and itaconic anhydride; ethylene isocyanate, allyl isocyanate, styrene, α-methylstyrene, and vinyl methyl ether , Ethylene ethyl ether, ethylene trialkoxy silane, alkyl maleic acid monoester, alkyl extended (12) (12) 200401707 humic acid monoester, alkyl itaconic acid monoester, acrylonitrile, methyl Examples of monomers are acrylonitrile, vinylidene chloride, ethylene, propylene, vinyl chloride, vinyl acetate, and butadiene. Moreover, these individual examples are not limited to these. The composition used in the present invention is suitable for users to form a coating, and to perform it in the form of an aqueous solution such as an aqueous solution, an aqueous dispersion, or an emulsion. In order to form the coating, if necessary, in addition to the composition, other resins can be added, such as: polymers with oxazoline groups, melamine, epoxy groups, azacyclopropane, etc. With preventive agents, colorants, surfactants, UV absorbers, lubricants (economy, wax), surfactants, etc. In particular, by adding a lubricant, the lubricity and the adhesion resistance can be improved. The solid content concentration of the aqueous coating liquid is usually less than 20% by weight, and more preferably 1 to 10% by weight. When the ratio is less than 1% by weight, the coating property to the polyester film will be insufficient, otherwise, If it exceeds 20% by weight, the stability and coating appearance of the coating agent will be poor. The thickness of the coating layer is preferably from 0.01 to 0.2 μm. A more desirable thickness of the coating layer is 0.01 to 0. Ιμιη, and the best is 0.02 to 〇. Ϊ́μπι. (Thickness of laminated film) The thickness of laminated film is used as a thin film for liquid crystal display, anti-reflection film, touch panel, plasma display, electromagnetic wave protective film for distribution panel (PDP), organic EL, electrophoretic paper, When a support such as a solar cell is used, it is preferably 12 to 500 μm in order to obtain necessary strength and a certain degree of free refraction. More preferably, the thickness of the laminated film is 16 to 400 μm, more preferably 25 to 350 μm, and most preferably 50 to 250 μm. -16- (13) (13) 200401707 (Manufacturing method of laminated film) The ideal laminated film of the present invention can be used to produce polyethylene naphthalene dicarboxylate by (1) using transesterification reaction in the presence of element Ming. (2) the step of obtaining the unstretched film after extruding the polyethylene naphthalene dicarboxylate on a rotary cooling drum, (3) setting the coating layer on the unstretched film, and continuing After the film forming direction (Md direction) is extended, or the unstretched film is extended in the MD direction, a coating layer is provided to obtain a step of laminating a uniaxially stretched film. (4) The continuous film forming direction is directed to the vertical direction ( TD direction) performing the steps of stretching and laminating a uniaxially stretched film to obtain a biaxially stretched film, and (5) a step of thermally fixing the obtained biaxially stretched film, and a transesterification reaction that can be manufactured is directed to polyethylene naphthalene dicarboxylate In the case of acid esters and weight fractions, 2 to 80 ppm, more preferably 4 to 60 ppm, and particularly 8 to 40 ppm of the element in the presence of the element is the most desirable. In the step of producing polyethylene naphthalene dicarboxylate, after the transesterification reaction, the melt viscosity reaction is performed until the intrinsic viscosity is 0.40 to 0.60 dl / g, and after the crushing, the solid viscosity is reduced to 0.46 to 0.75 dl / g. Phase polymerization is preferred. The adjustment of the intrinsic viscosity is performed after the small pieces obtained by the melt polymerization are vacuum-dried, and can be heated at a temperature of 200 to 250 ° C to the intended, inherent viscosity under vacuum or in the presence of an inert gas. After the small pieces are melt-formed into a thin film, the inherent viscosity is slightly reduced. The ideal film extension temperature is made by the glass transition temperature of the polymer

-17- (14) (14) 200401707

Tg (° c) is preferably Tg -20 ° C ~ Tg + 60 ° C, Tg -i0 ° c ~ Tg + 50 ° c is more preferred, more preferably Tg ~ Tg + 40 ° C, especially Tg + 5 ° C ~ Tg + 30 ° C is the best. The ideal stretch ratio is 2.0 to 5.0 times in the continuous film formation direction (MD direction) and vertical direction (TD direction) in the continuous film formation. And, the difference in extension magnification is less than 1.0 time. The ideal stretch ratio is 2.5 to 4.5 times, the more preferred is 2.8 to 4.3 times, and the most preferred is 3.0 to 4.0 times. The ideal heat-fixing temperature is that when the melting point of the polymer is Tm (° C), it is preferably Tm-100 ° C ~ Tm-5 ° C. The ideal heat-fixing temperature is dm_80 ～ Tm-10 ° C, more preferably dm-60 ° C ～ Tm-lOt :, especially τχ · 4〇Τ: dm-10 ° C is the most good. After the laminated film of the present invention can be heat-fixed, it can be manufactured after heat treatment. At this time, the heat treatment is performed at a temperature of (X-80) ~ X ° c of the film. The continuous film formation direction or its vertical direction may also relax. Where X stands for heat-fixing temperature. As a method of relaxing the film in the continuous film-forming direction of the continuous film-forming film, for example, after the heat-fixing is performed, the cylinder is wound up, and both ends of the film are cut in the middle of the heat-fixing area, and then the film is pulled out according to the film supply speed Method of speed deceleration 'Method of heating between different speed rollers by an IR heater, a method of decelerating the speed of the rollers after heating and transporting the film on the heating and transportation rollers, thermosetting After deposition, while the hot air is conveying the film on the spray nozzle, the method of decelerating the pull-out speed from the supply speed, or after being wound by a film making machine, the film is conveyed on a heating conveying roller. -18 -(15) (15) 200401707 The method of decelerating the roller speed, or by heating the heating area in the oven and IR heater, and decelerating the light speed after the heating area by the speed of the roller before the heating area. The methods are all ideal methods. For the speed on the supply side, the deceleration rate of the speed on the pull-out side is made 0.1 to 10%, and it is appropriate to perform a relaxation treatment. In addition, when the relaxation process in the vertical direction of the continuous film-forming direction is performed, the result that the force is not applied in the vertical direction can be achieved, and, independently, when heat-fixing the film, the heat-fixation is achieved. Outlet tenter width can be achieved by reducing the width of the heat-fixed inlet from 0.01 to 10%. The coating layer is one that is coated with an aqueous coating solution on an unstretched film or a uniaxially stretched film, and then stretched and fixed in two directions or in one direction, and then set firmly on the film. As a coating method, a roll coating method, a photocopying coating method, a roll washing method, a spray method, an air-scraping coating method, a soaking method, a curtain coating method, etc. may be used alone or in combination. (Hard-coating layer) It is preferable that at least one side of the laminated film of the present invention is a hard-coating layer which is set as a functional layer. The hard coating layer is preferably provided on the coating layer side. Thereby, a person who can prevent the film from being scratched can be promoted. Therefore, the hard coating layer is not particularly limited as long as it is a hardening resin having strong chemical resistance and damage resistance. This hardening resin is, for example, ionizing radiation-hardening resin, thermosetting resin, thermoplastic resin, etc. The ionizing radiation-hardening resin is easy to form a film for a transparent substrate film, and it is easy to improve the hardness of a pencil. Logic -19- (16) (16) 200401707 thinkers. Examples of the ionizing radiation-curable resin used for the formation of the hard coating layer are those having an acrylate-based functional group, and particularly preferably polyester acrylate or urethane acrylate. The polyester acrylate is composed of an acrylate and / or a methacrylate (hereinafter referred to as (meth) acrylate containing acrylate and methacrylate) of an oligomer of a polyester polyol. In addition, the urethane acrylate is constituted by acrylate-forming an oligomer formed of a polyol compound and a diisocyanate compound. In addition, as a single body constituting an acrylate, for example, meth (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2ethylhexyl (meth) acrylate Examples include esters, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, and phenyl (meth) acrylate. When it is desired to increase the hardness of the hard coating layer, a polyfunctional monomer may be used. Specific polyfunctional monomers such as: trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) Examples include acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like. As the polyester-based oligomer used for hard coating layer formation, such as adipic acid and glycols (ethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, polybutanediol, etc.), triols (Glycerin, trimethylolpropane, etc.), polyadipate triol, polysebacate polyalcohol, etc., which are the condensation products of sebacic acid, diol 'and triol, etc. In addition, part or all of the aliphatic dicarboxylic acid may be replaced by other organic acids. When this -20- (17) (17) 200401707, as examples of other organic acids, such as: isophthalic acid, terephthalic acid, or acid anhydride, etc., can have high hardness in the hard coating layer, which is ideal. The polyurethane-based oligomer used for the formation of the hard coating layer can be obtained from a polycondensation product of polyisocyanate and polyol. Examples of its polyisocyanate are: methylene, bis (p-phenylenediisocyanate), hexamethylene diisocyanate-hexane triol, hexamethylene diisocyanate, tolyl diisocyanate Adducts of isocyanate, tolyl diisocyanate trihydroxypropane, 1,5-naphthalene diisocyanate, thiopropyl diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4_ tolyl diisocyanate Examples of acid vinegar dimers, hydrogenated xylyl diisocyanate, tris (4-phenylisocyanate) phosphorothioate, etc., and specific examples of polyalcohol are: polyoxytetramethylene glycol Examples include polyester polyols such as polyether polyols, polyadipate polyols, and polycarbonate polyols, and copolymers of acrylates and hydroxyethyl methylpropionate. As examples of the ionizing radiation-curable resin, when an ultraviolet-curable resin is used, acetophenones, benzophenones, mifedibenzyl benzoate, and α-pentyl are used in these resins. Oxime esters or thioxanthones are used as photopolymerization heuristics, and n-butylamine, triethylamine, tri-n-butylphosphine and the like are used as photosensitizers for mixing. In addition, urethane acrylate has good elasticity, bendability, and good workability (reflexibility), but the surface hardness is insufficient, and it is difficult to obtain a pencil hardness of 2Η or more. Conversely, polyester acrylate can form a hard coating layer with extremely high hardness by selecting the constituent components of polyester. Therefore, it is easy to establish a combination of high hardness and flexibility. Therefore, the hard coating of 60 to 90 parts by weight of urethane acrylate and 40 to 10 parts by weight of polyester acrylate is the most ideal -21 -

Uod (18) (18) 200401707 In the coating liquid used to form the hard coating layer, while adjusting the gloss, the inactive fine particles with a secondary particle diameter of 20 μηι or less are adjusted for the purpose of attaching a surface lubricant to 100 weight It is preferable to add 0.3 to 3 parts by weight of the resin component. When it is less than 0.3 parts by weight, the effect of improving lubricity will be reduced. On the other hand, when it exceeds 3 parts by weight, the pencil hardness of the hard coating layer is reduced. Examples of inactive fine particles other than the coating fluid include inorganic fine particles such as silicon dioxide, magnesium carbonate, aluminum hydroxide, and barium sulfate, and polycarbonate, acrylic resin, polyimide, polyimide, and polyethylene. Examples of fine particles of organic polymers such as naphthalate and melamine resin. The hard coat layer may contain an ultraviolet absorber. As a result, it is possible to prevent UV degradation of the base material layer and the coloring agent (especially dyes), and to maintain visibility and explosion-proof properties for a long period of time. The type of the ultraviolet absorber is not specific, but it is preferable to select the specific cyclic imide as described above. The addition amount is preferably 0.1 to 10% by weight based on the resin forming the hard coating layer. When it is less than 0.1% by weight, the effect of preventing UV deterioration is reduced, while when it exceeds 10% by weight, the abrasion resistance and scratch resistance are reduced. The method of addition is preferably used after being dispersed in a solvent. The coating method for forming the hard coating layer is appropriately selected from roller coating, photocopying coating, rod coating, extrusion coating, etc., and according to the characteristics of the coating liquid and the amount of coating, an appropriate prior self-knowledge is selected. Method. The thickness of the hard coating layer is preferably in the range of 1 to 15 μm. The solid content concentration of the coating liquid is 30 to 70% by weight, and more preferably 40 to 60% by weight. The hard coating layer is preferably provided on one side or both sides of the laminated film. In addition, a functional layer such as a gas barrier layer and a conductive layer may be provided on the opposite side of the hard coating layer or on the hard coating layer. -22-0868 (19) (19) 200401707. (Gas Isolation Layer) When the laminated film of the present invention is used as a support film of an organic EL, it is advisable to provide a gas isolation layer as a functional layer at least on one side, and the gas isolation layer can also be arbitrarily disposed on the substrate layer. On, on the coating layer, on the hard coating layer. As the gas barrier layer, such as those of organic materials and inorganic materials. As the gas barrier layer of organic materials, polyvinyl alcohol, ethyl alcohol-ethyl alcohol copolymer, vinyl alcohol copolymer, polyacrylonitrile, propionitrile-methyl acrylate copolymer, acrylonitrile- A layer made of an acrylonitrile copolymer such as a styrene copolymer or an organic polymer material such as polyvinyl chloride. These materials can be used to form a gas barrier layer by a wet coating method using a photolithographic coating and reverse coating on the polyester of the present invention. When using a polyethylene-based insulation layer, it is advisable to reduce the oxygen insulation properties suddenly after absorbing moisture to form another water vapor insulation. As an example of the gas barrier layer of the inorganic material system, one or two or more kinds of metals selected from the group consisting of silicon, aluminum, magnesium, and zinc as the metal oxide and metal nitride as the main component can be used. These are known as ideal gas barrier materials. These oxide layers can be formed by a vapor deposition method in which a material is deposited in a gas phase such as a sputtering method, a vacuum evaporation method, an ion plating method, and a plasma CVD method, and then a film is formed.

Among them, the metal oxide is mainly composed of silicon oxide whose silicon atom has an oxygen atomic ratio of 1.5 to 2.0. Its gas barrier properties, transparency, smoothness of the surface, flexibility, film stress, cost, etc. For the ideal. The proportion of silicon atoms in silicon oxide and the number of oxygen atoms is determined after analysis by X-ray photoelectron spectroscopy, X (20) (20) 200401707 line differential spectroscopy, Auger electron spectroscopy, and Rutherford backscattering. Its oxygen atomic ratio. When the ratio is less than 1.5, flexibility and transparency are reduced, and therefore, 1.5 to 2.0 is preferable. The thickness of the inorganic gas barrier layer made of metal oxide is preferably 5 to 200 nm. If it is less than 5nm, it is difficult to form a uniform film, and a part where no film is formed is generated. As a result, the part penetrates into the gas, and the gas barrier property is deteriorated. In addition, beyond 200 nm, not only the transparency is poor, but the bendability is also poor, and the gas barrier properties are damaged after cracking. In addition, according to the method of forming a metal oxide film, the characteristics are different. Generally, the film thickness of the metal oxide becomes thicker, and the residual stress of the metal oxide layer becomes larger. Therefore, the metal oxide layer of the transparent conductive polymer substrate of the present invention After the formation of the concave becomes larger, it is not ideal. For the requirement of high transparency, the silicon oxide is preferably 5 to 30% by weight based on the total weight of magnesium fluoride. At this time, from the viewpoint of gas barrier properties, a thickness of 60 to 200 nm is preferable. These gas barrier layers can be used as a single layer or a combination of multiple layers. Especially when organic and inorganic gas barrier layers are used, the good resistance of the cracked organic gas barrier layer to the gas barrier layer and the good resistance of the inorganic gas barrier layer to water vapor are multiplied. , So it is the ideal combination. (Fixed layer) In order to strengthen the adhesion between the laminated film and the gas barrier layer, various fixed layers can also be formed between these layers. The fixed layer must be resistant, transparent, Good interlayer adhesion, such as: silicone resin

-24- (21) (21) 200401707, thermosetting resins such as epoxy resins, radiation curable resins such as ultraviolet curable acrylic resins, melamine resins, urethane resins, alkyd resins, and the like. The structure of the laminated film with an isolation layer is not particularly limited. Generally, the structure of the laminated film is laminated on one or both sides of the laminated film, and the structure of the laminated film is laminated on the hard-coated surface of the laminated film. Or the structure of lamination on the reverse side. In addition, those who include functional layers such as conductive layers and fixed layers (conductive layers) can be used as substrates for EL displays, substrates for electrophoretic paper, and substrates for solar cells. It is suitable to set the conductive layer as the functional layer on the cloth layer, the hard coating layer, and the gas barrier layer. The conductive layer is not particularly limited as long as it has good transparency and conductive materials. Examples of this conductive layer include metal oxide films such as tin, tellurium, cadmium, molybdenum, tungsten, fluorine, etc. as impurities indium oxide, cadmium oxide, tin oxide, zinc oxide, titanium oxide, etc. as impurities . Among them, an indium tin oxide (ITO) film containing 2 to 15% by weight of tin oxide is preferable because it has good transparency and electrical conductivity. The film thickness of the conductive layer is set according to its intended surface resistance. The surface resistance of the conductive layer is set from 300 Ω / □ ~ 1 Ω / □ according to its purpose, and its film thickness is usually made from 10nm to 400nm. However, when making a conductive polymer substrate with a flexible polymer substrate, in order to prevent the conductive layer from being cracked against the substrate bending stress, it is preferable to thin the conductive layer, and the thickness of the conductive layer is 30 ~ 140nm, which is particularly desirable -25- (22 ) (22) 200401707. In order to obtain low resistance, it is advisable to perform heat treatment at a temperature of 130 to 200 ° C. The structure of the electrode layer is not particularly limited. Generally, the structure is laminated on at least one side of the base material layer, the laminated film with hard coating is laminated on at least one side, and the laminated film with gas barrier layer is at least Examples of the structure of lamination on one side. Moreover, a structure including other functional layers may be used. The laminated film of the present invention, a laminated film with a hard coat layer, a laminated film with a gas barrier layer, and a laminated film with a conductive layer use its good hue, transparency, and non-breakability, and can be used as, for example, a liquid crystal display. Film for diffusion plate, anti-reflection film, organic EL, electrophoretic paper, touch switchboard, electromagnetic wave protective film for PDP, substrate for solar cell, and window-sticker. [Examples] In addition, various physical properties and properties in the present invention were measured and defined as follows. (1) Film thickness The thickness of the sample film was measured using an electric micrometer (trade name "K-312A model" manufactured by Anlitu (stock)) and a needle pressure of 30 g. (2) Turbidity and total light transmittance The total light transmittance Tt (%) and diffusion transmittance Td (%) of the sample were measured according to the IS standard and K-7 1 05- 1 98 1 as a reference. The turbidity Hz (%) of the sample film is calculated from Hz = (Td / Tt) x 100. When the sample film with a thickness of 100 μΉ is ► ►26- (23) 200401707 The turbidity Hzm (%) is calculated from the thickness ϋ (μΐΉ) and turbidity Hz of the sample film in Hzm = Hz x (D / 100). (3) Hue

According to JIS standard Z 87 29, L * 値, a * 値 (a * T), b * 値 (b * T) in the L * a * b * color rendering system of the film are measured by transmission and reflection, respectively. Determine it by the measurement method. At this time, a transmission and reflection spectrum of a film for standard light was measured using a color difference meter (trade name "SZS-Σ 90" manufactured by Nippon Denshoku Industries). When a sample film with a thickness of 100 μm is used, a * 値 (a * 1 () ()) and b * 値 (b * 1G ()) can be determined by the sample film thickness D (pm) a * 1Q () = a * TX (D / 100) b * i〇〇 = b * T x (D / 100). (4) refractive index of thin film

The film thickness direction was measured using a 稜鏡 coupling (trade name "M ode 1 2 0 1 0" manufactured by Metricon Corporation) with the film formation direction of the continuous film formation, and the film formation direction within the film plane was perpendicular. Refractive index (nMD, nTD, nZ). This measurement was performed at a wavelength of 4 7 3 nm, 6 3 3 nm, 8 3 Onm. The obtained measurement 値 is equivalent to the following formula of Koch's dispersion. Where λ i represents the measurement wavelength and ni represents the refractive index measured at the wavelength λ i = a + [b / (A i) 2] + [C / (A i) 4] -27- (24) ( 24) 200401707 Find the constants a, b, and c by solving the simultaneous equations. Based on the obtained a, b, and c, the refractive index at a wavelength of 589 nm (the wavelength of the Na D line) was calculated, and the refractive index of the thin film was obtained. (5) Number of plane orientations Using the refractive index of the obtained thin film, the plane orientation coefficient n S 0 is calculated by the following formula.

nS = (nMD + nTD) / 2-nZ (6) The oligomer was heated in a 200 ° C oven for 30 minutes and then removed. After the aluminum was vapor-deposited on the surface, it was observed under a differential interference microscope at 640 times. The area of 0.24 mm2 was determined by calculating the number of precipitated oligomers based on the following criteria: ○ (excellent): 0 to 100; (good): 101 to 2,000 x (defective): 2,001 or more. (7) Dimensional stability

Using the brand name "TMA / SS 1 2 0 C" of Seko insturments (shares), under a load of 140 g / mm 2 at a temperature rising rate of 20 ° C / min from 3 0 T: Measure the dimensional change at 250 ° C. Obtained by the following formula as the dimensional change rate at 200 ° C. -28- (25) (25) 200401707 Dimensional change rate (%) = (20 (size in TC-original length) / original length xl 00 (8) Melting point and glass transfer point (Tg) Samples were measured for glass transition and melting point using a differential scanning calorimeter (manufactured by τα Instruments, trade name "DSC 2920") at a temperature rise rate of 20 ° C / minute. (9) Inherent viscosity polymer Viscosity ("7?" Dl / g) was measured with an o-chlorophenol solution at 35 ° C. The inherent viscosity of the alignment film of the substrate layer was measured in the same way after removing the coating layer. (10) In the coating layer The average particle size of the particles was embedded in a thin film piece in epoxy resin (trade name "epomount" made by retaintec (stock)).

Microtome 2 050 was cut to a thickness of 50 nm per embedded resin, and 100 particles were observed in a transmission electron microscope (LEM-2000) at an acceleration voltage of 100 κν and a magnification of 100,000 times. (11) Impact resistance According to JIS standard K721K 1 976, the 50% breaking energy E50 of the sample film was calculated. In this case, the measurement device is the one shown in Fig. 1. In the first figure, 1 represents 5 yards (mass is 3 0 g or 5 0 g), 2 represents U-shaped perforation (diameter of the top part 4 mm -29- (26) (26) 200401707, mass 142g), 3 stands for sample film fixing frame, 4 stands for sample film. Also, in the evaluation method of the present invention, the 50% breaking energy E5 is shown in JIS standard K7211. In the calculation formula, m 値 uses only 1 mass% of the weight in the first figure. < Polymerization of polyethylene naphthalate >

Polymer A 100 parts by weight of dimethyl naphthalene-2,6-dicarboxylic acid and 60 parts by weight of ethylene glycol are used as the transesterification catalyst with 0.001 parts by weight of cobalt acetate 4 molybdenum and 0.02 parts by weight of manganese acetate. After carrying out the transesterification reaction according to the usual method, add 1.2 parts by weight of a 1% solution of antimony trioxide in ethylene glycol, and then add 0.029 parts by weight of trimethyl phosphate to terminate the transesterification reaction. Table 1 represents the amount of catalyst added to the polyethylene naphthalate. Hereinafter, the polycondensation reaction is performed under a high temperature and high vacuum according to a conventional method. Monofilament pieces were then made. The inherent viscosity of this polymer is 0.49dl / g

Polymers B and C After polymer A was subjected to solid phase polymerization, polymer B having an intrinsic viscosity of 0.62 dl / g and polymer C of 0.79 dl / g were obtained.

Polymers D and E changed the amount of catalyst added to those different from A to C as shown in Table 1, and then polymerized with Polymer A in the same manner to obtain polymer chips with an inherent viscosity of 0.50 dl / g. The obtained pellets were subjected to solid-phase polymerization to obtain a polymer D having an intrinsic viscosity of 0.64 dl / g and a polymer E having 0.71 dl / g. ^ -30- (27) (27) 200401707

Polymer F was added without a cobalt compound. Polymerization was performed by the catalyst in Table 1 to obtain polymer F with an intrinsic viscosity of 0.64 dl / g by melt polymerization. < Adjustment of coating layer > The coating agents used for the coating layers of Examples 1 to 4 and Comparative Examples 1 and 3 were adjusted as follows. Composition: It is composed of polyester resin, acrylic resin, wetting agent and concrete. The weight ratio of each component is polyester resin: acrylic resin: humectant: binder = 45: 40: 5: 1 0 ° Polyester resin: It is based on the method described in Example 1 of JP 6-1 16487. Manufactured as follows. That is, 42.2 parts of dimethyl terephthalate, 7.9 parts of dimethyl isophthalate, 4 parts of sodium 5-sulfoisophthalate, and 36.8 parts of 1,4- Butylene glycol, 27.5 parts of ethylene oxide add-on to bisphenol A. Here, 0.05 part of titanium tetrabutoxide was added, and the temperature was adjusted to 230 ° C under a nitrogen atmosphere, followed by heating to distill off the generated methanol. A transesterification reaction is performed. Then, the temperature of the reaction system was gradually raised to 255 ° C, and the pressure in the system was reduced to ImmHg, and then a polycondensation reaction was performed to obtain a polyester. Acrylic resin: 60 mol methyl methacrylate / 30 mol% ethylene acrylate / 5 mol% 2-hydroxyethyl methacrylate / 5 mol% N-hydroxymethyl acrylamide . The acrylic resin is manufactured in the following methods based on the methods described in Production Examples 1 to 3 of JP-A-63-37-67. That is, put 302 parts of ion-exchanged water in a four-necked flask, raise the temperature to 60 ° C in a nitrogen flow, and then add 0.5 parts of ammonium persulfate as a polymerization-31-(28) (28) 200401707 heuristic. , 0.2 parts of sodium hydrogen nitrite, and then adjust the liquid temperature to 60 ~ 70 ° C within 3 hours while dripping 59.9 parts of methyl methacrylate, 30 parts of ethyl acrylate, 5.8 parts A mixture of 2-hydroxyethylene methacrylate and 4.3 parts of N-hydroxymethacrylamide. After dripping, it was maintained at the same temperature for 2 hours. The reaction was continued while stirring. After cooling, a 25% propylene aqueous dispersion was obtained. Wetting agent (surfactant): Polyethylene oxide (n = 7) lauryl ether (manufactured by Sanyo Kasei Co., Ltd., trade name "Naloacty N-70"). Material: Silicon dioxide material (average particle size: 60nm). The trade name "Snowtex" made by Nissan Chemical Co., Ltd. [Example 1] After polymer B was dried at 170 ° C for 6 hours, it was fed into a hopper extruder, melted at a melting temperature of 30 ° C, and performed in a stainless steel thin wire filter with an average opening of 10 μm. Filter, pass through a 3mm slit-shaped mold, squeeze on a rotating cooling roller with a surface temperature of 60 ° C, and obtain an unstretched thin film after rapid cooling. Preheat the unstretched film at 120 ° C. After heating between the low-speed and high-speed rollers with an IR heater, the film temperature is 140 ° C, and it extends 3.3 times in the continuous film-forming direction (MD direction). After the film was extended in the MD direction on one side, the coating thickness after the coating agent was dried was 0.03 μπ, and the coating was performed on a roll coater. After being fed into the fixed-frame dryer, it was extended to a continuous film forming direction and a vertical direction (TD direction) at 1 45 ° C by 3.5 times. Obtain the biaxially oriented film after heat-fixing at 24 (TC-32- (29) (29) 200401707 degrees) to obtain a 100 μm thick laminated film. Tables 2 and 3 represent the film manufacturing conditions and the characteristics of the obtained film. A film with good transparency, hue, and few oligomers when heated, and good impact resistance. Also, the dimensional stability is good when the tension 'temperature is applied. [Examples 2 to 4] Polymers used Except for the stretching ratio and heat-fixing temperature shown in Table 2, laminated films of various thicknesses were obtained in the same manner as in Example 1. Tables 2 and 3 represent the manufacturing conditions of the films and the characteristics of the obtained films. [Comparative Example 1] Except Except for polymer A, a laminate film having a thickness of 100 μm was obtained in the same manner as in Example 1. Table 2 and Table 3 represent the manufacturing conditions of the film and the characteristics of the obtained film. The obtained film had poor transparency and hue. It is easy to produce oligomers when heated, and it is a film with poor impact resistance. [Comparative Example 2] Using polymer C to make an unstretched film with a thickness of 200 μm. Table 2 and Table 3 represent the manufacturing conditions of the film and the characteristics of the obtained film. ,through The properties are all good, but oligomers are easily generated when heated, and the impact resistance is also poor. Moreover, they are stretched under tension and temperature conditions, and the dimensional stability cannot be measured. [Comparative Example 3] -33- (30) 200401707 Using polymer F, the stretching ratio and heat-fixing temperature are made as shown in Table 2 to obtain a laminated film with a thickness of 100 μL. Table 2 and Table 3 represent the manufacturing conditions of the film and the characteristics of the obtained film. The film has poor transparency and hue, and is easy to generate oligomers when heated. In addition, under the conditions of tension and temperature, the film shrinks greatly. [Example 5]

On the side of the laminated film coating layer obtained in Example 1, a hard coating agent (trade name "PETD-31" manufactured by Daiichi SEIKO Kogyo Co., Ltd.) and a 1-hydroxycyclobenzene will be used to form a hard coating layer. After the ketone is added together for stirring and defoaming, the coater is dried to a thickness of 5 μm by a roll coating method. After drying, the electron beam is irradiated under the conditions of 175 Kv and 10 OMrad to form a hard coat coating. In addition, as a gas barrier layer, on the reverse side of the hard coating layer, a vapor deposition material formed by heating a mixture of Si and SiO2 by an electron beam in a vacuum evaporation device is evaporated to form Si having a thickness of 20 nm. 〇 > Film.

Then, an Ar · 〇2 mixed gas (〇2 concentration! · 4νο1%) was introduced by a sputtering device, the pressure was adjusted to 0.27Pa, and an IT ◦ target (SnO2 concentration 5wt%) was used to input power density TW / cm2. DC sputtering was performed next, and a thickness of 130 nm was laminated on the gas barrier layer, and then a heat treatment was performed at 150 ° C for 2 hours to obtain a transparent conductive film made of an ITO film. It means those who obtain the characteristics of a thin film and obtain a thin structure with good impact resistance. [Example 6] The thin film obtained in Example 2 was used to obtain a transparent conductive film made of a hard-coated -34 «(31) 200401707 layer, a gas barrier layer, and an IT0 film in the same manner as in Example 5. Table 4 shows the characteristics of the obtained film. Obtain a thin structure with good impact resistance. [Comparative Example 4] Using the film of Comparative Example 2, a transparent conductive film made of a hard coat layer, a gas barrier layer, and ITO was obtained in the same manner as in Example 5. Table 4 shows the characteristics of the obtained film. The obtained film was one with poor impact resistance.

[Comparative Example 5] A 200 μm thick polyether film (made by Sumitomo Beclite Co., Ltd. "trade name" FS-1300 ") was used in the same manner as in Example 5 to obtain a hard coating layer, a gas barrier layer, and an ITO film. Transparent conductive film. Table 4 shows the characteristics of the obtained film. The obtained film had poor impact resistance. [Comparative Example 6;]

Table 4 shows characteristics obtained with ITO glass (trade name "Mu?" Manufactured by Koning Corporation). -35- (32) 200401707 Table 1 \ Catalyst amount (weight p P m) Intrinsic viscosity polymerization method Co Mn Sb dl / g A 24 45 100 0.49 Melt B 24 45 100 0.62 Melt + solid phase C 24 45 100 0.79 Melt + Solid phase D 12 68 300 0.64 Melt + Solid phase E 6 1 68 300 0.7 1 Melt + Solid phase F 0 68 300 0.64 Melt Table 2 \ Polymer type elongation rate Heat fixing temperature MD direction TD direction ° c Real 1 B 3.3 3.5 235 Application 2 B 3.1 3.2 245 Example 3 D 3.2 3.7 230 4 E 3.2 3.7 230 than 1 A 3.3 3.5 235 than 2 C 1.0 1.0 Example 3 F 4.0 3.0 225 -36- r IH ^ rj (33) 200401707

(Impact resistance) 50% destruction energy S CD 6 rH rH CO O in d 00 d rH d CD d (Dimensional stability) Dimensional change rate ① 6 1 CM 6 rH i —1.2 _1 Inch 6 is greater than 9_3. 5 〇〇〇 ◎ XXX (thickness 100 "m conversion) m reflection measurement method 8 cC tH d rH d LO 6 CSl d CO d ο d -0 · 4 〇1 -0. 1 i-0 · 1 rH 6 odod CSl d LO 6 transmission measurement 〇 * cd CO d 1-0 · 3 CO 6 1 inch d 1 LO d 1 〇d -0. 6 〇CO rH inch i-Η LO r—i rH rH inch 03 CO d 03 < N turbidity Hz100 CO 6 inch 6 CO 6 inch d; 〇dr-id CD 6 plane alignment coefficient in c 0. 259 0. 251 0. 261 0. 261 0. 256 0. 006 0. 260 refractive index N) C 1. 498 ΙΟ g rH a inch τ—1 BU inch τΗ 1. 498 CO inch CD rH 1. 498 rH CD BU rH 1. 755 00 CO rH 00 CO IN rH 00 LO rH I 1. 648 < N rH RH nMD 1. 753 1 1. 756 00 inch rH 1. 748 1_ o 10 rH 1. 649 1. 803 intrinsic viscosity dl / g 0. 55 0. 55 0. 58 0. 65 rH inch 6 0. 71 0 58 lit ε a. Oo rH ο g LO oo rH oo CN oo tH rH Cv3 CO inch rH CO CO -37-(34) (34) 200401707 Table 4 \ Substrate layer thickness (impact resistance 50% failure energy — μΐΏ J-Example 5 Film 100 of Example 1 0.6 0.6 Example 6 Film of Example 2 1.1 _ Comparative Example 4 Film of Example 2 200 0.1-Comparative Example 5 Commercial PES film 0.4- Comparative Example 6 Market glass 720 0.07 _ PES: Polyether (Inventive Effect) The present invention can obtain polyethylene with good transparency and hue, and rarely generates oligomers when heated, and has a thin film with good impact resistance. Laminated film of naphthalene dicarboxylate film. [Industrial Applicability] In addition, the present invention obtains a laminated film and uses it as a hard coat film, a gas barrier film, and a transparent conductive film to take advantage of these good characteristics, particularly for liquid crystal displays, antireflection films, and organic EL It is extremely useful for displays, electrophoretic paper, solar batteries, touch switchboards, and electromagnetic wave prevention films for i_DP. -38- (35) (35) 200401707 [Brief description of the diagram] Figure 1 represents the diagram of the impact resistance test device. In the figure, 1 represents the weight, 2 represents the perforation, and 3 represents the film fixing frame, which represents the sample film. Comparison table of main components 1 Weight 2 U-shaped perforation 3 Sample film fixing machine 4 Sample film -39-

Claims (1)

(1) (1) 200401707 Pickup and patent application scope 1. A laminated film characterized by a laminated film formed of a substrate layer and a coating layer provided on at least one side of the substrate layer, the substrate layer is Oriented film made of polyethylene naphthalate and having an inherent viscosity of 0.45 to 0.70 dl / g. The turbidity of the laminated film is 0.5% or less per 100 μm thickness, L * a * b In the color development system, a * 中 and b * 値 are both measured by transmission, and the thickness of the film 100 μm is -2.0 ~ + 2.0, and the plane orientation coefficient is 0.15 ~ 0.30. 2. If the laminated film according to item 1 of the scope of patent application, wherein the polyethylene naphthalene dicarboxylic acid ester is used to obtain a polyester after transesterification reaction in the presence of cobalt element. 3 If the layer is applied to the second scope of patent application Composite film, in which the weight fraction of cobalt is 2 to 80 ppm of polyethylene naphthalate. 4. The laminated film according to item 1 of the scope of patent application, wherein the dimensional change rate in the continuous film forming direction is -2 to + 2% at 200 ° C and a load of 140 g / mm2. 5. The laminated film according to item 1 of the scope of patent application, wherein the a * 値 and b * 値 in the L * a * b * color rendering system are 100 μm thick films, and the reflection measurement method is used to obtain -0.5 ~ + 0.5 range. 6. The laminated film according to item 1 of the scope of patent application, wherein the film has a number of oligomers of less than 100 within 0.24 mm2 of the surface after heating at 200 ° C for 30 minutes. 7. The laminated film according to item 1 of the scope of patent application, wherein the 蝥 coating layer is at least one kind of water-soluble or water group selected from the group consisting of polyester resin, urethane resin, acrylic resin, and vinyl resin. Made of dispersible polymer resin. -40- (2) (2) 200401707 8. The laminated film according to item 1 of the scope of patent application, wherein the thickness is 12 to 50 μm. 9. A laminated film, characterized in that a functional film is provided on a laminated film such as the laminated film in item 1 of the scope of patent application, the functional layer is at least one selected from a hard coating layer, a gas barrier layer, and Those in a group of conductive layers. 10. The laminated film according to item 9 of the scope of patent application, wherein the hard coating layer is made of polyester acrylate or urethane. 1 1. The laminated film according to item 9 of the scope of patent application, wherein the gas barrier layer is made of a metal oxide containing silicon oxide containing 1.5 to 2.0 in proportion to the number of silicon atoms and the number of oxygen atoms. 12. For example, the laminated film according to item 9 of the scope of the patent application, wherein the conductive layer is a thin film of tin oxide (ITO) containing 2 to 15% by weight of tin oxide. 13. A substrate for an EL display, characterized in that it is formed of a laminated film as described in the first patent application. 14. A substrate for electrophoretic paper, characterized by being formed of a laminated film such as the first item in the scope of patent application. 1 5 · A substrate for a solar cell, characterized by being formed of a laminated film as described in the first patent application. 16. The use of the laminated film according to item 1 of the scope of patent application, wherein the use is for users of substrates for EL displays, substrates for electrophoretic paper, or substrates for solar cells. 1 7 · A manufacturing method, characterized in that it is a method for manufacturing a laminated film such as the one in the scope of patent application, and (1) uses a transesterification reaction to produce polyethylene naphthalene-41-( 3) (3) 200401707 step of dicarboxylic acid ester, (2) step of obtaining unstretched film after extruding the polyethylene naphthalene dicarboxylic acid ester in a rotary cooling drum, (3) setting a coating layer on the After the film is stretched, it is stretched in the direction of continuous film formation (MD), or after the unstretched film is stretched in the MD direction, a coating layer is provided to obtain a step of laminating a uniaxially stretched film. (4) The lamination The uniaxially stretched film is a step of obtaining a biaxially stretched film after stretching in a vertical direction (TD direction) for the continuous film forming direction, and (5) a step of obtaining a biaxially stretched film for thermal fixation. 18. The manufacturing method according to item 17 of the application for a patent, wherein the method is to perform the melt polymerization reaction until the intrinsic viscosity is 0.40 to 0.60 dl / g after the transesterification reaction, and then to perform the solid-phase polymerization reaction after fragmentation. Those with an inherent viscosity of 0.46 to 0.75 dl / g.