JP2008183882A - Laminate film for optical use and its production method and anti-reflection film and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a laminate film without causing rainbow irregularity, the film being excellent in anti-scratch property and not causing flow-down of powder and hardly getting scratches. <P>SOLUTION: An easy adhesion layer 12 and a protecting layer 13 in this order from the supporting body 11 is formed at least on one surface of a supporting body 11 made of biaxially stretched polyester to form a laminate film 10. The easy adhesion layer 12 comprises fine powders containing at least one of zinc oxide, indium oxide, zirconium oxide and titanium oxide as the main ingredient and a polyester resin as a binder. The protecting layer 13 comprises a surfactant A, B and carnauba wax and formed in a solid coating amount of 3 to 10 mg/m<SP>2</SP>. By this protecting layer 13 containing no fine powder, peeling-off of the fine powder in the easy adhesion layer 12. Further, anti-scratch property is enhanced by the protecting layer 13, and does not influence upon optical characteristics of the easy adhesion layer 12 because the protecting layer is thin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an optical laminated film and a method for producing the same, an antireflection film comprising the optical laminated film as a constituent member, a liquid crystal display, a plasma display, an organic EL display, a surface electric field display (SED), a CRT display, etc. The present invention relates to an image display device.

  The purpose is to secure these high quality images as the demand for image display devices such as liquid crystal display (LCD), plasma display (PDP), organic EL display, surface electric field display (SED), or CRT display increases. As a result, the demand for optical films as main constituent members has been increasing rapidly. The optical film is a film having various optical functions for preventing reflection of external light, widening the viewing angle, correcting optical unevenness, and the like.

  As the optical film, a multilayer film having a multilayer structure including a support body serving as an axis of the optical film and an upper layer provided so as to be in contact therewith is mainly used. In general, a transparent film mainly composed of a polymer is used as the support. Among them, a support made of a polyester resin is increasing in demand because it has characteristics such as excellent transparency, dimensional stability, chemical resistance, and low hygroscopicity. Further, the upper layer is a layer containing a polymer as a main component and additives for imparting various optical functions such as for the purpose of preventing the reflection of the laminated film. For example, the antireflection layer, the prism layer, the light Examples include a diffusion layer. By appropriately selecting the combination of the support and the upper layer, for example, prism films, antireflection films, light diffusion films used for LCDs, etc., IR absorption films, electromagnetic wave shielding films, and toning films used for PDPs Various optical films such as an antireflection film, an antiglare film, and a hard coat film can be freely formed.

  However, if the adhesive strength at the interface between the support and the upper layer is low, peeling occurs between the upper layer and the support, causing problems such as light leakage and inability to prevent light reflection. Therefore, in optical laminated films, the high adhesive strength at the interface is important, but the adhesive strength at the interface affects the material composition of the support and the upper layer, the unevenness of the contact surface, the formation conditions of each layer, etc. Since it is easy to receive, it is difficult to control it to a desired value. Therefore, for example, Patent Document 1 proposes an optical laminated film in which a polyester film is used as a support, and an easy-adhesion layer containing polyester is provided on the support to improve the adhesive strength at the interface. Yes.

In addition, since the optical laminated film is composed of a plurality of members having different refractive indexes, such as a support, an easy-adhesion layer, and an upper layer, light reflection is likely to occur at each interface. Further, when light is reflected at each interface, the reflected light interferes with each other and rainbow-colored interference unevenness (rainbow unevenness) occurs, so that the display quality of the optical laminated film is significantly deteriorated. At present, the support made of polyester resin, which is mainly used, has a refractive index of about 1.65, which is a relatively high value. In view of this, a method of reducing the refractive index difference between the support and the adjacent layer by increasing the refractive index of the adjacent layer has been studied. For example, Patent Document 2 proposes an optical laminated film having an easy-adhesion layer that contains fine particles that are predetermined metal oxides to increase the refractive index.
JP 2001-294826 A JP 2004-054161 A

  However, when an easy-adhesion layer having a high refractive index containing fine particles of a metal oxide is included, when the functional film such as the next hard coat layer is applied and formed, the powder will fall off due to a decrease in scratch resistance. There are problems such as scratches and scratches, and there is a problem that yield decreases. For this, it is conceivable to form a protective layer. However, simply forming the protective layer causes rainbow unevenness, which causes a new problem that it is not suitable as an optical laminated film. .

  Then, this invention sets it as the 1st objective to provide the laminated film for optics which suppressed generation | occurrence | production of a rainbow nonuniformity, improving a scratch resistance. Furthermore, it is a second object to provide an antireflection plate and an image display device that exhibit an excellent antireflection function and display quality by using this laminated film.

  In order to achieve the above object, the present invention is formed on a support made of polyester and at least one surface of the support, has a refractive index of more than 1.70 and not more than 1.85, and a thickness of 50 nm. An easy adhesion layer having a thickness of 100 nm or less, and a protective layer formed on the easy adhesion layer, having a refractive index of 1.40 to 1.60 and a thickness of 3 nm to 10 nm. And

  The easy-adhesion layer contains fine particles mainly containing any one of tin oxide, zirconium oxide, indium oxide, and titanium oxide, and any one of a polyester resin, a polyurethane resin, and an acrylic resin. Features. The protective layer includes one or more of a polyester resin, a polyurethane resin, and an acrylic resin. Furthermore, the protective layer contains a wax.

  The antireflection film of the present invention includes the optical laminated film, a hard coat layer formed on the protective layer of the optical laminated film, and an antireflective layer formed on the hard coat layer. It is characterized by providing. In the invention, it is preferable that a refractive index of the hard coat layer is 1.75 or more and 2.00 or less. Further, the antireflection layer is a layer having a refractive index of 1.50 or less. The antireflection film is used for an image display device such as a plasma display.

  In the method for producing an optical laminated film of the present invention, an easy-adhesive layer having a refractive index of more than 1.70 and not more than 1.85 and a thickness of not less than 50 nm and not more than 100 nm is applied to at least one surface of a support made of polyester. And a step of forming a protective layer having a refractive index of 1.40 to 1.60 and a thickness of 3 nm to 10 nm on the easy-adhesion layer.

  According to the present invention, on at least one surface of a support made of polyester, an easily adhesive layer having a refractive index of more than 1.70 and not more than 1.85 and a thickness of not less than 50 nm and not more than 100 nm; Is 1.40 or more and 1.60 or less, and a protective layer having a thickness of 3 nm or more and 10 nm or less can be formed, so that scratch resistance can be improved, and rainbow unevenness is eliminated while suppressing occurrence of powder falling and scratches. Can do. Moreover, the antireflection film and image display apparatus which have the outstanding display quality are obtained by making these laminated films into a structural member.

  Hereinafter, the present invention will be described in detail with reference to embodiments. However, the following embodiment is one of preferred examples of application of the present invention, and does not limit the present invention.

  First, an embodiment according to the present invention will be described. As shown in FIG. 1, an optical laminated film 10 of the present invention includes a film-like support 11 formed from a polyester resin, an easy-adhesion layer 12 and a protective layer that are sequentially laminated from the side close to the support 11. 13, a hard coat layer 14, and an antireflection layer 15. The easy-adhesion layer 12 and the protective layer 13 may be provided not only on one side of the support 11 but also on both sides. For example, as shown in FIG. 2, an easy-adhesion layer 16 and a protective layer 17 are provided on the back surface of the support 11 with respect to the optical laminated film 10 shown in FIG. 1, and a NIRA (near infrared blocking) coating layer is provided thereon. When 18 is formed, the NIRA coating layer 18 can be provided on the back surface of the support 11 with good easy adhesion, and such an optical laminated film 20 can be suitably used as an antireflection film for PDP. it can.

[Support]
The polyester used as the support 11 is not particularly limited, and a known polyester can be used. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate. Among these, it is particularly preferable to use polyethylene terephthalate from the viewpoint of cost and mechanical strength.

  The support 11 of the present invention is preferably biaxially stretched. Biaxial stretching refers to stretching in both directions, assuming that the width direction and the longitudinal direction of the support 11 are each uniaxial. Thus, the biaxially stretched support 11 has a very excellent mechanical strength because the biaxial molecular orientation is sufficiently controlled. The draw ratio is not particularly limited, but the draw ratio in one direction is preferably 1.5 to 7 times, more preferably 2 to 5 times. In particular, the support 11 that has been biaxially stretched at a stretching ratio of 2 to 5 times per uniaxial direction has a very excellent mechanical strength because the molecular orientation is controlled more efficiently and effectively, It is suitable as the support 11. By setting the draw ratio of the support 11 to 1.5 times or more, sufficient mechanical strength can be obtained as compared with the case of less than 1.5 times. Further, by setting the draw ratio to 7 times or less, a uniform thickness can be obtained as compared with the case where the draw ratio exceeds 7 times.

  The thickness of the support 11 is preferably 30 μm or more and 400 μm or less. More preferably, it is 35 μm or more and 350 μm or less. The thickness of the support 11 can be easily adjusted by controlling the draw ratio. Such a support 11 is lightweight and excellent in handleability while having transparency and various optical properties. The support 11 having a thickness of 30 μm or more is not too thin and is easy to handle. Further, the support 11 having a thickness of 400 μm or less has an appropriate thickness, which makes it easy to reduce the size and weight of the image display device, and does not cause an increase in manufacturing cost. The support 11 of the present invention may contain an ultraviolet absorber and an antioxidant. In particular, when used for an antireflection film for PDP, it is preferable to contain an ultraviolet absorber.

[Easily adhesive layer]
The easy adhesion layer 12 is composed of a layer containing one or more of a polyester resin, a polyurethane resin, and an acrylic resin. The refractive index of the easy adhesion 12 is preferably more than 1.70 and not more than 1.85, more preferably not less than 1.71 and not more than 1.80. The thickness is preferably 50 nm to 100 nm, more preferably 55 nm to 90 nm. By making the refractive index exceed 1.7, interference unevenness is reduced compared to the case where the refractive index is 1.7 or less. Further, by setting the refractive index to 1.85 or less, the film strength becomes stronger than when the refractive index exceeds 1.85. By setting the thickness to 50 nm or more, interference unevenness is reduced as compared with the case of less than 50 nm. Further, by setting the thickness to 100 nm or less, the interference unevenness is reduced as compared with the case where the thickness exceeds 100 nm. If necessary for adjusting the refractive index, fine particles mainly containing any one of tin oxide, indium oxide, zirconium oxide, and titanium oxide may be contained. The easy adhesion layer 12 is provided on the support 11.

  The polyester resin is a general term for polymers having an ester bond in the main chain, and is usually obtained by a reaction between a polycarboxylic acid and a polyol. Examples of the polycarboxylic acid include fumaric acid, itaconic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and the like. Of these, terephthalic acid and naphthalenedicarboxylic acid are preferably used. A copolymer obtained by copolymerizing sodium sulfoisophthalate or the like is preferable because it can be used as a water-soluble or water-dispersible polyester resin.

  Examples of polyols include ethylene glycol, propylene glycol, 1,4 butanediol, 1,6 hexanediol, glycerin, hexanetriol, neopentyl glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and bisphenol A ethylene oxide addition. Product (NC-1900, manufactured by Nippon Emulsifier Co., Ltd.), polyester polyol and the like. Commercially available products include polyester-based aqueous dispersions Finetex ES650 and ES2200 (trade name: manufactured by Dainippon Ink & Chemicals, Inc.), Bironal MD1400, MD1480 (trade name: manufactured by Toyobo Co., Ltd.), and polyester-based water-soluble products. Examples include plus coats Z-221, Z-561, Z-730, RZ-142 (trade name: manufactured by Kyoyo Chemical Co., Ltd.) and the like, which are functional polymers.

  The polyurethane resin is a general term for polymers having a urethane bond in the main chain, and is usually obtained by a reaction between a polyisocyanate and a polyol. Examples of the polyisocyanate include TDI, MDI, NDI, TODI, HDI, and IPDI. Examples of the polyol include ethylene glycol, propylene glycol, glycerin, and hexanetriol. As the isocyanate of the present invention, a polymer obtained by subjecting a polyurethane polymer obtained by the reaction of polyisocyanate and polyol to a chain extension treatment to increase the molecular weight can also be used. The polyisocyanate, polyol and chain extension treatment described above are described in, for example, “Polyurethane Resin Handbook” (edited by Keiji Iwata, Nikkan Kogyo Shimbun, published in 1987). As commercially available products, Superflex 830, 460, 870, 420, 420NS (trade names: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Bondick 1370NS, 1320NS, Hydran AP-40F (trade names: Dainippon Ink & Chemicals, Inc.).

  An acrylic resin is a polymer containing acrylic acid, methacrylic acid and derivatives thereof as components. Examples of such acrylic resins include acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylamide, acrylonitrile, hydroxyl acrylate, and the like, and monomers copolymerizable therewith. Examples thereof include a copolymerized polymer. Examples of this monomer include styrene and divinylbenzene. Examples of commercially available products include Jurimer ET325, ET410, SEK301 (trade name: manufactured by Nippon Pure Chemical Co., Ltd.), Boncourt AN117, AN226 (trade name: manufactured by Dainippon Ink & Chemicals, Inc.), which are acrylic water dispersions. Can be mentioned.

  If fine particles are used for the purpose of adjusting the refractive index as described above, the fine particles aggregate to form a huge foreign substance, which may reduce the light transmittance of the easy-adhesion layer 12. In this case, aggregation can be suppressed by suitably selecting and using the particle size and type of the fine particles. In order to effectively suppress the aggregation of the fine particles, the average particle size of the fine particles is preferably 5 nm or more and 200 nm or less. More preferably, the average particle size is 10 nm or more and 100 nm or less, and particularly preferably 15 nm or more and 70 nm or less. When fine particles having an average particle diameter of 200 nm or less are used, there is no possibility that the transparency of the first easy-adhesion layer 12 and the second easy-adhesion layer 13 that can be visually confirmed is lowered or the light transmittance is lowered. . Further, by using fine particles having an average particle diameter of 5 nm or more, it is possible to obtain them at a lower price than fine particles having a smaller average particle diameter, which is advantageous in terms of production cost. In addition, since fine particles of 5 nm or more are used, there is less risk of becoming a giant foreign material due to aggregation of the fine particles compared to the case of using fine particles of less than that, and no decrease in transparency is caused. The average particle size of the fine particles in the present invention is the particle size obtained for any 50 fine particles when the fine particles taken with a scanning electron microscope are taken as the diameter of a circle having the same area. The average value of

  As the fine particles used for the easy-adhesion layer 12, it is preferable to use tin oxide, zirconium oxide, and titanium oxide among the fine particles listed above because they are easily available and are relatively inexpensive.

As the tin oxide, tin (IV) oxide having a SnO ₂ composition is preferable. Further, it is preferable to use a tin oxide doped with antimony or the like as a doping agent. Since the tin oxide doped in this manner has conductivity, it can reduce the surface resistivity of the laminated film and prevent impurities such as dust from adhering. Examples of tin oxide doped with antimony include FS-10D, SN-38F, SN-88F, SN-100F, TDL-S, and TDL-1 (all manufactured by Ishihara Sangyo Co., Ltd.). Can be preferably used in the present invention. Note that tin oxide using phosphorus as a doping agent can also be suitably used.

Zirconium oxide (IV) having a composition of ZrO ₂ is preferably used as the zirconium oxide. For example, NZS-20A, NZS-30A (both manufactured by Nissan Chemical Co., Ltd.) and the like can be mentioned. As the titanium oxide, titanium (IV) oxide having a composition of TiO ₂ is preferably used. Titanium oxide includes a rutile type which is a tetragonal high-temperature type and an anatase type which is a tetragonal low-temperature type depending on the crystal structure, but is not particularly limited. Further, titanium oxide subjected to surface treatment can also be used. Examples of titanium oxide that can be suitably used include IT-S, IT-O, and IT-W (all manufactured by Idemitsu Kosan Co., Ltd.) and TTO-W-5 (produced by Ishihara Sangyo Co., Ltd.). Can be mentioned.

  The molecular weight of the polymer used for the easy-adhesion layer 12 is not particularly limited, but a polymer having a weight average molecular weight of 3000 to 1,000,000 is usually used for the purpose of forming a layer having excellent handling properties and a good plane. Is preferred. When the weight average molecular weight of the polymer is 3000 or more, there is no possibility that the strength of the first easy-adhesion layer 12 and the second easy-adhesion layer 13 is insufficient as compared with the case of less than 3000. In addition, when the weight average molecular weight of the polymer is 1,000,000 or less, the ease of application due to the decrease in fluidity is not impaired as compared with the case where the weight average molecular weight exceeds 1,000,000. Deterioration of the surface state of the adhesive layer 13 is suppressed.

  The easy adhesion layer 12 preferably contains a compound having a plurality of carbodiimide structures in the molecule. When the easy-adhesion layer 12 is formed by including such a compound, when the fine particles are contained, the peeling is prevented. The carbodiimide-based compound is not particularly limited as long as it has a plurality of carbodiimide groups, and the number of carbodiimide groups is not limited. Polycarbodiimide is usually synthesized by a condensation reaction of organic diisocyanate. The organic group of the organic diisocyanate used in this synthesis is not particularly limited, and either aromatic or aliphatic, or a mixture thereof can be used. An aliphatic system is particularly preferred from the viewpoint of reactivity. As the synthetic raw material, organic isocyanate, organic diisocyanate, organic triisocyanate and the like are used.

  As examples of organic isocyanates, aromatic isocyanates, aliphatic isocyanates, and mixtures thereof can be used. Specifically, 4,4'-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane Diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate and the like are used. As the organic monoisocyanate, isophorone isocyanate, phenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like are used. Moreover, as a carbodiimide type compound which can be used for this invention, it can also obtain as commercial items, such as carbodilite V-02-L2 (brand name: Nisshinbo Co., Ltd. product).

  It is preferable to add the carbodiimide type compound of this invention in 1-200 mass% with respect to a binder. More preferably, it is adding in 5-100 mass%. By making the addition amount of the carbodiimide-based compound 1% by mass or more, the first easy-adhesion layer 12 and the second easy-adhesion layer 13 peel off the fine particles when compared with the case of less than 1%. It can be sufficiently prevented. Moreover, by making the addition amount 200% by mass or less, deterioration of the planar shape of the first easy-adhesive layer 12 and the second easy-adhesive layer 13 can be suppressed as compared with the case where the amount exceeds 200% by mass.

  For the easy-adhesion layer 12, fine particles having an action as a matting agent may be used for the purpose of improving slipperiness. As the matting agent, either organic or inorganic fine particles can be used. Examples thereof include polymer fine particles such as polystyrene, polymethyl methacrylate, silicone resin, and benzoguanamine resin, and inorganic fine particles such as silica, calcium carbonate, magnesium oxide, and magnesium carbonate. Among these, polystyrene, polymethyl methacrylate, and silica are preferable because of improved slipperiness and low cost.

In order to impart good slipperiness, it is preferable to use a matting agent having an average particle size of 0.01 μm or more and 12 μm or less. More preferably, a matting agent having an average particle size of 0.03 μm or more and 9 μm or less is used. By setting the average particle size of the matting agent to 0.01 μm or more, better slipperiness can be obtained as compared to the case of less than 0.01 μm. Further, by setting the average particle size to 12 μm or less, there is no possibility that the display quality of the image display device is deteriorated as compared with the case of exceeding 12 μm. Further, the amount of the matting agent added varies depending on the average particle diameter, but it is excellent in the effect of improving the slipperiness and does not deteriorate the display quality of the image display device, so that it is 0.1 mg / m ² or more and 30 mg / m. It is preferably ² or less, more preferably 0.5 mg / m ² or more and 20 mg / m ² or less. When the addition amount of the matting agent is 0.1 mg / m ² or more, an effect of improving slipperiness can be obtained. Moreover, the fall of the display quality of an image display apparatus can be suppressed by setting it as 30 mg / m < ² > or less. The average particle size of the matting agent in the present invention is a value measured by the same method as the average particle size of the fine particles described above.

Various additives such as a surfactant can be used for the easy-adhesion layer 12. Examples of the surfactant include known anionic, nonionic, and cationic surfactants. Surfactants that can be used in the present invention are described in, for example, “Surfactant Handbook” (Nishi Ichiro, Imai Sachiichiro, Sho Kasai edited by Sangyo Kasai Co., Ltd., 1960). When using a surfactant, the addition amount is preferably 0.1 mg / m ² or more and 30 mg / m ² or less, more preferably 0.2 mg / m ² or more and 10 mg / m ² or less. By making the addition amount of the surfactant 0.1 mg / m ² or more, the effect by the surfactant can be obtained compared to the case of making it less than 0.1 mg / m ² , and the first easy-adhesion layer 12 and the second Occurrence of cissing in the easy-adhesion layer 13 is suppressed. Moreover, by making the addition amount 30 mg / m ² or less, it is possible to suppress deterioration of the surface states of the first easy-adhesion layer 12 and the second easy-adhesion layer 13 as compared with the case where the amount exceeds 30 mg / m ^2. .

An antistatic agent can also be used for the easy adhesion layer 12 for the purpose of antistatic. The type of the antistatic agent is not particularly limited. For example, an electron conductive polymer such as polyaniline and polypyrrole, an ion conductive polymer having a carboxyl group or a sulfonic acid group in the molecular chain, conductive fine particles, etc. Is mentioned. The conductive fine particles may be fine particles that are the same as the fine particles mainly containing tin oxide and indium oxide. For example, the conductive tin oxide fine particles described in JP-A-61-020033 can be preferably used from the viewpoints of conductivity and transparency. When the antistatic agent is used, the addition amount thereof is such that the surface resistance of the easy adhesion layer 12 and the protective layer 13 measured in an atmosphere of 25 ° C. and 30% RH is 1 × 10 ⁵ Ω or more and 1 × 10 ¹³ Ω or less. It is preferable to adjust to. By making the surface resistance of the easy-adhesion layer 12 1 × 10 ⁵ Ω or more, compared with the case of less than 1 × 10 ⁵ Ω, a large amount of antistatic agent is avoided and the transparency of the easy-adhesion layer 12 is improved. Reduction is suppressed. Further, by making the surface resistance 1 × 10 ¹³ Ω or less, an antistatic effect can be secured as compared with the case where the surface resistance exceeds 1 × 10 ¹³ Ω, and impurities such as dust are present on the surface of the easy adhesion layer 12. There is no risk of adhesion.

[Protective layer]
The protective layer 13 is a layer including any one or more of a polyester resin, a polyurethane resin, and an acrylic resin, and is formed on the easy adhesion layer 12. The polyester resin, polyurethane resin, and acrylic resin are the same as those used for the easy-adhesion layer 12. The refractive index of the protective layer 13 is preferably 1.40 or more and 1.60 or less, more preferably 1.45 or more and 1.55 or less. The thickness is preferably 3 nm or more and 10 nm or less, more preferably 6 nm or more and 8 nm or less. In order to set the thickness to 3 nm or more and 10 nm or less, although depending on the specific gravity of the coating layer, for example, the fixed coating amount during coating is about 3 to 10 mg / m ² . By setting the refractive index to 1.4 or more, interference unevenness is reduced as compared with the case where the refractive index is less than 1.4. Further, by setting the refractive index to 1.60 or less, the interference unevenness is reduced as compared with the case where the refractive index exceeds 1.60. By setting the thickness to 3 nm or more, the scratch resistance is excellent compared to the case of less than 3 nm. Further, by setting the thickness to 10 nm or less, the interference unevenness is reduced as compared with the case where the thickness exceeds 10 nm.

  The molecular weight of the polymer used for the protective layer 13 is not particularly limited, but a polymer having a weight average molecular weight of 3,000 to 1,000,000 is usually used for the purpose of forming a layer having excellent handleability and a good plane. preferable. When a material within this range is used, it is possible to suppress the deterioration of the surface shape while maintaining the strength of the protective layer 13.

  Various additives such as a surfactant similar to the above-mentioned easy-adhesion layer 12 can also be used for the protective layer 13. In addition, the protective layer 13 may be made of the same antistatic agent as that of the easy-adhesion layer 12 for the purpose of preventing static charge.

It is preferable to use a slipping agent for the protective layer 13 in order to improve its slipperiness. As such a slipping agent, an aliphatic wax is preferably used, and the amount added is preferably 0.1 mg / m ² or more and 8 mg / m ² or less. More preferably, the addition amount is 0.5 mg / m ² or more and 6 mg / m ² or less. By making the addition amount of the slip agent 0.1 mg / m ² or more, the slipperiness can be sufficiently exhibited. Further, by setting the addition amount to 8 mg / m ² or less, it is possible to sufficiently secure the adhesive strength at the interface between the protective layer 13 and the hard coat layer 14. The aliphatic wax that can be used in the present invention is described in detail in JP-A No. 2004-054161.

  A method for forming the easy adhesion layer 12 and the protective layer 13 will be described. In this embodiment, after applying a coating solution in which a polymer resin, fine particles, additives, and the like and a solvent are mixed in advance to the surface of the support 11 (biaxially stretched polyethylene terephthalate film) to form a coating layer, The easy adhesion layer 12 and the protective layer 13 are sequentially formed by a coating method for drying the coating layer. As said solvent, ie, a coating solvent, water, toluene, methyl alcohol, isopropyl alcohol, methyl ethyl ketone, etc., and mixtures thereof can be used. Water can also be used as the coating solvent. In this case, water acts as a coating solvent. Thus, when water is used as a coating solvent, it is preferable because manufacturing cost and manufacturing can be simplified.

  The coating liquid is preferably applied to the biaxially stretched support 11, but after providing the easy-adhesion layer 12 on the uniaxially stretched support 11, the support 11 is different from the previous one. Biaxial stretching can be performed by uniaxial stretching in the direction to produce the support 11 on which the easy-adhesion layer 12 is coated, and the protective layer 13 can be further coated off-line. Here, uniaxial means either the width direction or the longitudinal direction of the support 11, and when biaxial stretching is performed, the order of the stretching direction is not limited.

  The formation method of the easily bonding layer 12 and the protective layer 13 will not be specifically limited if the layer of desired thickness can be formed. Therefore, the coating method is not limited, and a known method used when forming a thin film can be used. Examples of the method include a dipping method, a spinner method, a spray method, a roll coater method, a gravure method, a wire bar method, a slot extrusion coater method (single layer and multilayer), and a slide coater method. The first and second easy-adhesion layers 12 and 13 may be applied individually off-line in addition to on-line sequential application. The above method can be used as a method for forming the layer according to the present invention, that is, the easy adhesion layer 12, the protective layer 13, the hard coat layer 14, and the antireflection layer 15.

  When the easy-adhesion layer 12 and the protective layer 13 are formed on the support 11, the laminated film is once wound up in a roll shape by a film winding device and sent to the next hard coat layer coating step. Moreover, a laminated | multilayer film is sent online to the following hard-coat layer application | coating process, without winding up in roll shape with a film winding apparatus.

[Hard coat layer]
The hard coat layer 14 is preferably formed using an energy curable resin or a thermosetting resin. Among these, it is preferable to use an energy curable resin. Since the energy curable resin is cured by irradiating active energy rays, the resin is not damaged as compared with a heat energy curable resin that uses heat as energy during curing. Therefore, it has the feature that a highly transparent layer can be formed.

  The energy curable resin used when forming the hard coat layer 14 will be described. The energy curable resin is preferably a curable resin having two or more acrylic groups in the same molecule. For example, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol-A diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Polyol polyacrylates such as dipentaerythritol hexaacrylate, polyfunctional urethane acrylate obtained by reaction of polyisocyanate curable resin and hydroxyl group-containing acrylate such as hydroxyethyl acrylate, polyepoxy curable resin and hydroxyethyl acrylate, etc. Polyfunctional ester obtained by reaction with hydroxyl group-containing acrylate (methacrylate) Carboxymethyl acrylate, and the like. It is also possible to use a polymer having an ethylenically unsaturated group in the side chain.

  When using an energy curable resin, it is preferable to irradiate the coating layer with ionizing radiation such as radiation, gamma rays, alpha rays, electron rays, ultraviolet rays, which are active energies. As a result, the resin can be cured efficiently and effectively, so that a coating layer having a sufficient hardness, that is, the hard coat layer 14 can be formed. In addition, when forming the hard-coat layer 14, after apply | coating the coating liquid for forming the hard-coat layer 14 to the protective layer 13 and forming a coating layer, this coating layer may be irradiated with an ultraviolet-ray. preferable. Thereby, the hard coat layer 14 having a uniform film thickness and uniform optical characteristics can be obtained within a short time. In addition, it is preferable to use a solution obtained by diluting a desired energy curable resin, a polymerization initiator, or the like with a solvent in advance, because a coating layer having a uniform film thickness can be easily formed.

  In the present invention, the polymerization initiators may be used alone or in combination, and are not particularly limited. Further, the addition amount of the polymerization initiator is not particularly limited, but the sum of the ethylenically unsaturated group-containing curable resin and the ring-opening polymerizable group-containing curable resin contained in the curable resin composition. And 0.1 to 15% by mass is preferable. More preferably, the addition amount with respect to the above-mentioned total is 1 to 10% by mass.

  The refractive index of the hard coat layer 14 is preferably 1.75 or more and 2.00 or less, for example, by adding inorganic fine particles to the binder used for forming the hard coat layer 14. In general, since inorganic fine particles have a high refractive index of 1.8 to 2.7, the refractive index of the layer to be formed can be adjusted within the range of the high refractive index as described above. By setting the refractive index of the hard coat layer 14 to 1.75 or more, it becomes easy to reduce the reflectance as compared with the case of less than 1.75. Further, by setting the refractive index to 2.00 or less, the hard coat layer 14 does not become brittle compared to the case where the refractive index exceeds 2.00, and deterioration of scratch resistance can be suppressed.

  As an example of a composition capable of forming a hard coat layer 14 exhibiting a high refractive index, a polyfunctional acrylate monomer is used as a resin component, which contains inorganic fine particles such as alumina and titanium oxide. And the composition disclosed in Japanese Patent No. 1815116. In addition, there is a detailed description in Japanese Patent No. 1416240 as a photopolymerizable compound composition containing inorganic fine particles made of alumina, and these descriptions can also be applied to the present invention. However, the hard coat layer 14 used in the present invention is not limited to the above example.

  The high refractive index hard coat layer 14 can also be formed by using a polymer having a high refractive index. Examples of the polymer having a high refractive index include a polymer having a cyclic group, a polymer containing a halogen atom other than fluorine, and a polymer containing both a cyclic group and a halogen atom other than fluorine. The cyclic group includes an aromatic group, a heterocyclic group, an aliphatic ring group, and the like.

  The thickness of the hard coat layer 14 is not particularly limited, but is preferably 0.5 μm or more and 10 μm or less. More preferably, they are 1 micrometer or more and 5 micrometers or less. Thereby, it has a desired optical function and a physical function such as excellent scratch resistance, and furthermore, a high adhesive strength at the interface between the second easy-adhesive layer 13 and the hard coat layer 14 can be secured. When the film thickness of the hard coat layer 14 is 0.5 μm or more, the physical function can be sufficiently expressed and the scratch resistance is excellent. In the case of 10 μm or less, it is possible to secure a high adhesive strength at the interface between the second easy-adhesive layer 13 and the hard coat layer 14 by reducing the influence of curing and absorption of the hard coat layer 14.

(Antireflection layer)
In order to provide an antireflection effect, the antireflection layer 15 is a layer having a lower refractive index than the hard coat layer 14. In order to form a low refractive index layer, adjustment is performed by using a low refractive index material such as a fluorine-based material or a silicone-based material as a binder. The refractive index of the antireflection layer 15 is preferably 1.50 or less. In this case, the antireflection performance is ensured as compared with the case of exceeding 1.50. When forming the antireflection layer 15, a commercially available coating material for an antireflection film can be used. As such a coating material, when a low refractive index layer is formed, commercially available low refractive index materials such as TT1148, TU2111, and TU2153 (all manufactured by JSR Corporation) and the like can be mentioned.

  The laminated film obtained as described above has high adhesive strength at each interface, and light interference at each interface is suppressed, so that the occurrence of rainbow unevenness is reduced. Such a laminated film excellent in optical function can be used in various image display devices as an antireflection film excellent in display quality.

    The laminated film of the present invention can be used as an optical film for use in liquid crystal displays, plasma displays, organic EL displays, SED (surface electric field) displays, and CRT displays. For these image display devices, for example, “Display Advanced Technology” (published by Tanizuka, Kyoritsu Publishing Co., Ltd. 1998), “EL, PDP, LCD Display” (Toray Research Center, Inc. 2001) And “Color LCD” (Shunsuke Kobayashi, Sangyo Tosho Publishing Co., Ltd., published in 1990).

  The laminated film of the present invention can be suitably used as an antireflection film, an IR absorption film, an electromagnetic wave shielding film, an optical film such as a toning film, and a film filter in which these films are integrated, which are used for PDP. These films are described, for example, on page 74 of the August 2002 issue of Electric Journal, in addition to the above-mentioned documents.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, each Example and a comparative example are examples of this invention, and do not limit this invention. Therefore, the following types of materials, ratios of the respective materials, prescriptions, and the like may be appropriately changed without departing from the spirit of the present invention. In the following description, the manufacturing method, conditions, and the like will be described in detail in the first embodiment, and the description will be omitted when the other embodiments and comparative examples are the same as the first embodiment.

[Example 1]
In this example, the laminated film shown in FIG. 1 was produced according to the following procedure.

[Support]
First, after a polyethylene terephthalate (hereinafter referred to as PET) resin having an intrinsic viscosity of 0.66 polycondensed with antimony trioxide as a catalyst is dried to a moisture content of 50 ppm or less, extrusion is performed at a heater temperature set at 280 to 300 ° C. It was melted in the machine. Next, the melted PET resin was discharged from a die part onto a chill roll electrostatically applied to obtain an amorphous film. Subsequently, the amorphous film was stretched 2.9 times in the longitudinal direction of the film, and then stretched 4.0 times in the width direction of the film to give a biaxially stretched thickness of 150 μm. A support 11 was produced. The completed support 11 had a refractive index η1 of 1.65.

[Easily adhesive layer, protective layer]
While the roll-shaped support 11 having a width of 2 m and a length of 2000 m was transported at a transport speed of 70 m / min, the surface thereof was subjected to a corona discharge treatment under the condition of 730 J / m ² . Thereafter, the coating solution A was applied to both surfaces of the support 11 by a bar coating method and dried at 180 ° C. for 1 minute to form the easy adhesion layer 12. Subsequently, after performing a corona discharge treatment under the condition of 730 J / m ^2, the coating liquid B was applied to the surface of the easy-adhesion layer 12 by a bar coating method, and dried at 165 ° C. for 1 minute to provide the protective layer 13. The wet coating amounts of the coating liquids A and B were 4.4 ml / m ^{2 on} both sides.

[Coating solution]
In order to obtain the solid coating amount (mg / m ² ) shown in Table 1 and Table 2, various raw materials were mixed to prepare coating liquids A to C for easy adhesion layer and coating liquids D to N for protective layer. The raw materials in Tables 1 and 2 are as follows.
・ Polyester resin Z-561, manufactured by Kyodo Chemical Industry Co., Ltd., 25% solid content
・ Surfactant A
Nippon Oil & Fats Co., Ltd., Lapisol B-90, 1% solids aqueous solution, anionic and surfactant B
SANYO KASEI KOGYO Co., Ltd., NAROACTY NH-100, 5% solid content aqueous solution, nonionic carbodiimide compound, Nisshinbo Co., Ltd., Carbodilite V-02-L2, 10% solid content aqueous solution (carbodiimide equivalent 385)
-Titanium oxide dispersion manufactured by Ishihara Sangyo Co., Ltd., TTO-W-5 30% solid content aqueous solution (average particle size 70 nm)
・ Silica dispersion manufactured by Nippon Aerosil Co., Ltd., OX-50 aqueous dispersion, 10% solids aqueous solution ・ Carbana wax liquid, manufactured by Chukyo Yushi Co., Ltd., Cerosol 524 3% solids aqueous solution

  The thicknesses of the easy-adhesion layer 12 and the protective layer 13 after drying were measured at a magnification of 200000 times using a transmission electron microscope (JEM2010 (manufactured by JEOL Ltd.). Specifically, a 10-point film at 20 nm intervals. The thickness was measured and the average value excluding the maximum and minimum values was taken as the thickness, and the results are shown in Tables 1 and 2. The refractive indexes of the easy-adhesion layer 12 and the protective layer 13 were determined by the following method. The measurement results are shown in Tables 1 and 2.

[Measurement of refractive index of easy-bonding layer]
Using a refractive index measuring machine (SPA-4000 (manufactured by Sairon Technology, Inc.)), the refractive index at wavelengths of 660 nm and 850 nm of the sample provided with the coating layer was measured by the prism coupler method. Next, the refractive index at 550 nm was calculated from the measured value of the refractive index at each wavelength and the following Cermeier equation, and this was taken as the refractive index η1 in the first layer. The Selmeier equation is an equation represented by η ² −1 = Aλ ² / (λ ² −B). Here, λ is a measurement wavelength (nm), η is a refractive index at the measurement wavelength, and A and B are constants. After the constants A and B are obtained by substituting the measurement wavelength and the refractive index into the above formula, the refractive index at 550 nm can be obtained by substituting the wavelength = 550 nm. The above sample is prepared by applying a coating solution on a commercially available silicon wafer so that the film thickness after drying is 3 to 4 μm to provide a coating layer, and then drying it at 105 ° C. for 10 minutes. did.

[Hard coat layer]
Titanium oxide TTO-55B (Ishihara Sangyo Co., Ltd.) 30 mass% cyclohexanone dispersion was prepared. MEK is added to 2 parts by mass of TTO-55B dispersion 177 parts by mass, DPHA (dipentaerythritol hexaacrylate: Nippon Kayaku Co., Ltd.) 20 parts by mass, Irgacure 184 (Ciba Specialty Chemicals), and solid content 8% by mass. A hard coat layer coating solution was prepared. A hard coat layer coating solution is applied to one surface of the formed easy-adhesion layers on both sides so as to have a film thickness of about 35 μm, and then the coating layer is dried at 80 ° C. for 1 minute. I let you. Next, the resin was cured by irradiating the dried coating layer with ultraviolet rays using a high-pressure mercury lamp to form a 3 μm hard coat layer 14. In addition, the irradiation amount of the ultraviolet-ray with respect to a coating layer was 1000 mj / cm < ² >. Moreover, it was 1.83 when (eta) 4 which is the refractive index of the hard-coat layer 14 was measured similarly to the refractive index measuring method of the easily bonding layer 12. FIG.

(Antireflection layer)
On the hard coat layer 14, TU2111 manufactured by JSR Co., Ltd. was applied and dried, followed by UV irradiation (1000 mj / cm ² ) to provide a low refractive index layer having a thickness of 0.1 μm (refractive index 1.39). .
Since the hard coat layer 14 has a high refractive index of 1.83, the low-refractive index layer functions as the antireflection layer 15.

[Examples 2-7, Comparative Examples 1-3]
Examples 2 to 7 and Comparative Examples 1 to 3 were constituted by a combination of an easy-adhesion layer and a protective layer as shown in Table 2, and experiments were conducted in the same manner as in Example 1.

  With respect to the laminated films produced in each of the above Examples 1 to 7 and Comparative Examples 1 to 3, the following five items related to adhesiveness and optical characteristics were evaluated. Evaluation 1 is the adhesion between the support 11 and the easy-adhesion layer 12, evaluation 2 is the adhesion between the protective layer 13 and the hard coat layer 14, evaluation 3 is the coated surface of the laminated film, and evaluation 4 is the rainbow unevenness of the laminated film. Presence or absence, evaluation 5 is scratch resistance. Below, the detail of each evaluation method is shown.

[1. Adhesiveness between support and easy-adhesion layer)
First, the coating liquid used for forming the easy-adhesion layer 12 in each of the examples and the comparative examples was applied to the surface of the support 11, and then the sample was immersed in distilled water at 60 ° C. for 16 hours. Next, the sample after immersion is taken out of the distilled water, and water droplets adhering to the surface of the sample are lightly wiped with paper (Kimwipe S-200, manufactured by Crecia Co., Ltd.), and immediately, the surface of the sample is immediately removed. Was scratched with a 0.1 R diamond needle using a scratch strength tester (HEIDON-18, manufactured by Shinto Kagaku Co., Ltd.). Then, after observing the rubbed portion with a microscope magnification of 100, the substrate 11 and the easy-adhesion layer are further observed by visual observation and judging the degree of peeling of the easy-adhesion layer 12 according to the following criteria. The adhesive strength with No. 12, that is, the adhesiveness was evaluated in five stages. The load applied to the diamond needle was 200 g. In the following evaluation, the rank B or higher is a level with no problem in terms of products.
Rank A: When there is no peeling Rank B: When the peeled area is less than 30% of the area rubbed with the diamond needle Rank C: With respect to the area of the peeled area rubbed with the diamond needle 30% or more and less than 70% D rank: When the peeled area is 70% or more and 100% or less of the area of the portion rubbed with the diamond needle E rank: In addition to the portion rubbed with the diamond needle, its peripheral portion When peeling occurs to the coating layer

[2. Adhesiveness between protective layer and hard coat layer)
The film on which the hard coat layer 14 was laminated was conditioned for 24 hours in an atmosphere of 25 ° C. and 60% RH to prepare a sample. Next, using a single-blade razor, the surface to be used as an evaluation surface of this sample was made with 25 scratches by making 6 vertical and horizontal scratches, and then cellophane tape (405 manufactured by Nichiban Co., Ltd.) was formed thereon. No., 24 mm width). Then, after the cellophane tape is rubbed with poppy rubber and completely adhered, the adhesive strength of the protective layer 13 and the hard coat layer 14 is determined by obtaining the number of cells peeled by peeling in the direction of 90 degrees with respect to the horizontal plane. Height, that is, adhesiveness was evaluated in five stages. In the case of partial peeling within the squares, the peeled parts were integrated and converted to the number of squares. In the following evaluation, rank B or higher is a level with no problem in terms of product. The width of the scratch was 3 mm both vertically and horizontally.
Rank A: No peeling B rank: When the number of peeled squares is less than 1 Rank C: When the number of peeled squares is 1 or more and less than 3 D rank: When the number of peeled squares is 3 or more and less than 20, E rank : When the number of peeled cells is 20 or more

[3. (Apply surface of easy-adhesive film)
First, an easy adhesion layer 12 and a protective layer 13 were formed on the surface of the support 11 to prepare a sample. Next, the sample was placed on a desk on which a black doskin cloth was bonded, and then the diffused light of a fluorescent lamp passed through a milky white acrylic plate was applied to the coating layer. And the reflected light which generate | occur | produces here was observed visually and the coating nonuniformity was judged by the following reference | standard, and it evaluated in three steps as a coating surface shape. In the following evaluation, the rank B or higher is a level with no problem in terms of products.
Rank A: Coating unevenness is not visually confirmed in both the blackened sample and the untreated sample.
Rank B: Coating unevenness is visually confirmed in the sample after the blackening treatment, but is not confirmed in the untreated sample.
C rank: Coating unevenness is visually confirmed in both the sample after the blackening treatment and the untreated sample.

  In the above evaluation 3, in the visual judgment, blackening treatment was performed on a predetermined surface of the sample in order to prevent reflection from the back surface, and the transmittance of 550 nm light was adjusted to 1% or less. In the above blackening treatment, magic ink (artline oil-based marker supplement ink KR-20 black, manufactured by shachihata Co., Ltd.) was applied to the surface of the sample opposite to the surface to be observed, and then dried.

[4. (With or without rainbow unevenness)
First, a sample was prepared by conditioning the finished laminated film (provided up to the antireflection layer 15) in an atmosphere of 25 ° C. and 60% RH for 24 hours. Next, after rubbing an appropriate amount of the surface of this sample without the hard coat layer 14 with sandpaper, the same black magic as that used in the evaluation 3 was applied to prevent back surface reflection. . Then, this sample is placed on a desk, and interference spots (rainbow unevenness) generated by illuminating with a three-wavelength fluorescent lamp (trade name: National Parook fluorescent lamp FL20SS / EX-D / 18) from 30 cm above are obtained. It was observed visually. The interference spots observed in this observation were regarded as rainbow unevenness and evaluated in five stages according to the following criteria. In the evaluation described later, the rank C or higher is a level that does not cause a problem in terms of products.
A rank: The rainbow nonuniformity cannot be seen at all.
B rank: The rainbow nonuniformity is hardly visible.
C rank: Some rainbow unevenness is visible.
D rank: Rainbow unevenness looks strong.
E rank: Rainbow unevenness looks very strong.

[5. (Scratch resistance)
First, an easy-adhesion layer was formed on the surface of the support 11 to produce a laminated film. Using a continuous load type scratch strength tester TYPE-HEIDON-18 (Shinto Kagaku Co., Ltd., detection needle: sapphire needle 0.1R scratching speed: 600 mm / min, weight used: 200 g weight), scratches are generated on the laminated film. The load at the time was determined.
Rank A: Load at the time of scratch generation ≧ 30 g Good scratch resistance.
Rank B: 30 g> load at the time of scratch generation ≧ 20 g No problem in practical use.
Rank C: 20 g> Load at the time of scratch ≧ 20 g Problem D rank: 10 g> Load at the time of scratch occurrence Problem

  The evaluation results in each example and comparative example are summarized in Table 3.

  As shown in Table 3, in each Example, good results were shown for use as products for all evaluations. On the other hand, in Comparative Examples 1 and 3, the scratch resistance was evaluated as D, and scratches were confirmed. Further, in Comparative Example 2, the rainbow unevenness was evaluated as D, and the rainbow unevenness causing a problem as a product was confirmed.

  When the prepared anti-reflection film is placed on the part where the optical filter of the commercially available PDP (Hitachi Co., Ltd. W37P-H9000) is removed, the occurrence of rainbow unevenness is suppressed and the optical properties such as anti-reflection are excellent. Confirmed that.

It is general | schematic sectional drawing which shows an example of the laminated | multilayer film concerning this invention. It is general | schematic sectional drawing which shows an example of the laminated | multilayer film in other embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10, 20 Laminated film 11 Support body 12,16 Easy-adhesion layer 13, 17 Protective layer 14 Hard-coat layer 15 Antireflection layer

Claims (12)

A support made of polyester;
An easy-adhesion layer formed on at least one surface of the support, having a refractive index of more than 1.70 and not more than 1.85, and a thickness of not less than 50 nm and not more than 100 nm;
An optical laminated film comprising: a protective layer formed on the easy-adhesion layer, having a refractive index of 1.40 to 1.60 and a thickness of 3 nm to 10 nm.   The easy-adhesion layer contains fine particles mainly composed of any one of tin oxide, zirconium oxide, indium oxide, and titanium oxide, and any one of a polyester resin, a polyurethane resin, and an acrylic resin. The optical laminated film according to claim 1.   3. The optical laminated film according to claim 1, wherein the protective layer includes one or more of a polyester resin, a polyurethane resin, and an acrylic resin.   4. The optical laminated film according to claim 1, wherein the protective layer contains a wax. 5. An optical laminated film according to any one of claims 1 to 4,
A hard coat layer formed on the protective layer of the laminated optical film;
An antireflection film comprising an antireflection layer formed on the hard coat layer.   6. The antireflection film according to claim 5, wherein the refractive index of the hard coat layer is 1.75 or more and 2.00 or less.   The antireflection film according to claim 5 or 6, wherein the antireflection layer is a layer having a refractive index of 1.50 or less.   An image display device comprising the antireflection film according to claim 5. Forming an easy-adhesion layer having a refractive index of more than 1.70 and a thickness of 1.85 or less and a thickness of 50 nm or more and 100 nm or less on at least one surface of a support made of polyester;
Forming a protective layer having a refractive index of 1.40 to 1.60 and a thickness of 3 nm to 10 nm on the easy-adhesion layer. .   The easy-adhesion layer contains fine particles mainly composed of any one of tin oxide, zirconium oxide, indium oxide, and titanium oxide, and any one of a polyester resin, a polyurethane resin, and an acrylic resin. The method for producing an optical laminated film according to claim 9.   The method for producing an optical laminated film according to claim 9 or 10, wherein the protective layer includes one or more of a polyester resin, a polyurethane resin, and an acrylic resin.   The method for producing an optical laminated film according to any one of claims 9 to 11, wherein the protective layer contains a wax.

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