JP2014128978A - Optical laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical laminate that exhibits antistatic properties and antifouling property even in the case where it has a constitution of a single layer of an optical functional layer laminated on a light-transmitting substrate (a single layer constitution) and has little possibility of reducing antistatic properties and antifouling property even in the case where it is subjected to saponification treatment, and to provide a polarizer and a display device using the same.SOLUTION: The optical laminate has a light-transmitting substrate and an optical function layer produced by curing a composition containing at least an ionizing radiation-curable fluoride acrylate and an electroconductive metal oxide. The ionizing radiation-curable fluoride acrylate has a molecular weight of 1,000 or more and contains three or more acryloyl groups.

Description

  An image display surface in an image display device such as a liquid crystal display, a CRT (CRT) display, a projection display, a plasma display, or an electroluminescence display is required to be provided with scratch resistance so as not to be damaged when handled. Therefore, an optical laminate is disposed on the display surface. This optical laminate has a structure in which an optical functional layer is laminated on a translucent substrate such as polyethylene terephthalate (hereinafter referred to as “PET”) or triacetylcellulose (hereinafter referred to as “TAC”). It is.

  The optical functional layer has desired properties. For example, an optical laminate in which the optical functional layer has a hard coat property can be used as a hard coat film provided with a hard coat layer. Moreover, the optical laminated body in which the fine concavo-convex structure is formed on the surface of the optical functional layer can be used as a hard coat film and also as an antiglare film having an antiglare layer. Furthermore, a light diffusion layer or a low refractive index layer can be used as the optical functional layer. Development of an optical laminate having a desired function has been promoted by using these optical functional layers such as a hard coat layer and an antiglare layer as a single layer or by combining a plurality of layers.

  On the outermost surface (observation surface side) of the display, there are problems such as dust adhesion due to static electricity and defects in liquid crystal display operation, and an optical laminate having an antistatic function is required. In particular, with the increase in contrast of displays, the adhesion of dust has become more conspicuous, and therefore an optical laminate having an antistatic function is required.

  In addition, the display surface (observation surface side) is expected to be handled harshly (load due to physical, mechanical, chemical stimulation, etc.). Wiping with a rag soaked with a cleaner (surfactant, organic solvent, etc.) is expected. For this reason, the antifouling property improvement is calculated | required about the hard coat film surface mounted in the display.

  As an antistatic antiglare film having an antistatic function, a film in which a transparent conductive layer and an antiglare layer are sequentially laminated on a transparent base film has been proposed (for example, see Patent Document 1).

  In addition, by adding a resin layer containing a quaternary ammonium salt compound for imparting antistatic properties and adding light-transmitting fine particles for imparting antiglare properties, the antistatic preventive agent having a single layer structure is provided. A dazzling film can be obtained (see, for example, Patent Documents 2 and 3).

  In addition, on a substrate made of a triacetyl cellulose film, a metal oxide such as antimony oxide having a particle size of 100 nm or less, a compound having three or more acrylic groups in the molecule, and an acrylic compound containing fluorine atoms in the molecule An antistatic hard coat film is disclosed in which a hard coat layer containing is directly provided (see, for example, Patent Document 4).

JP 2002-254573 A WO2007 / 032170 Publication JP 2009-66891 A Japanese Patent No. 4221990

  An optical laminate used for a display is required to have antistatic performance and antifouling properties. Moreover, the protective film (hard coat film) of the polarizing plate used for the display is subjected to a treatment such as saponification when the polarizer and the triacetyl cellulose-based protective film are bonded, and the adhesive property between the polarizer and the protective film. It is usually done to improve. For this reason, the optical functional layer and the optical laminate laminated on the triacetyl cellulose-based protective film are required to have saponification resistance that does not change the antistatic performance and the antifouling property.

  As in Patent Document 1, an antistatic antiglare film having an antistatic function has been proposed in which a transparent conductive layer and an antiglare layer are sequentially laminated on a transparent substrate film. Although it is excellent in antistatic property, anti-glare property, etc., there is a problem that the cost increases due to the constitution in which two layers are laminated on the transparent substrate film.

  As in Patent Documents 2 and 3, by applying a resin layer containing a quaternary ammonium salt compound for imparting antistatic properties and adding translucent fine particles for imparting antiglare properties, Although an optical laminate having a structure in which one layer is laminated on a transparent substrate film can be obtained, problems such as a decrease in conductivity due to a saponification treatment occur in this configuration.

  The antistatic hard coat film described in Patent Document 4 is excellent in antistatic properties and scratch resistance. However, a fluorine material is added to this antistatic hard coat film for controlling the refractive index. However, sufficient antifouling property cannot be obtained, and when saponification is applied, the fluorine material in the hard coat layer is not obtained. It has a problem that the antifouling property decreases due to elution. That is, improvement of antifouling property after saponification treatment has been demanded.

  In view of the above-described situation, the present invention exhibits antistatic properties and antifouling properties and performs saponification treatment even in a configuration (one-layer configuration) in which an optical functional layer is laminated on a translucent substrate. However, it is an object of the present invention to provide an optical laminate that is less likely to decrease the antistatic property and antifouling property, and a polarizing plate and a display device using the same.

The present invention (1) is an optical laminate having a translucent substrate and an optical functional layer obtained by curing a composition containing at least an ionizing radiation curable fluorinated acrylate and a conductive metal oxide. Yes,
The ionizing radiation curable fluorinated acrylate has a molecular weight of 1000 or more and contains 3 or more acryloyl groups.

  The present invention (2) is the optical laminate according to the invention (1), wherein the ionizing radiation curable fluorinated acrylate contains a perfluoroalkyl group.

  The present invention (3) is the optical laminate according to the invention (1) or (2), wherein the ionizing radiation-curable fluorinated acrylate has a fluorine atom content of 20% or more.

（ここで、Ｃｙはその水素の一部が上記式の置換基及び任意でメチル基又はエチル基により置換される５又は６員環のシクロアルキル部位であり、ａは１〜３の整数であり、Ｘはメチレン基又は直接結合であり、Ｒ_Ｆは炭素数４〜９のパーフルオロアルキル基であり、ｎは１〜３の整数である。但し、前記ａが２以上である場合には前記Ｘ、Ｒ_Ｆ、ｎは互いに独立に選択される。） The optical laminate according to any one of the inventions (1) to (3), wherein the ionizing radiation curable fluorinated acrylate is a compound represented by the following formula (A): It is.

(Wherein Cy is a 5- or 6-membered cycloalkyl moiety in which part of the hydrogen is substituted with a substituent of the above formula and optionally a methyl or ethyl group, and a is an integer of 1 to 3. , X is a methylene group or a direct bond, R _F is a perfluoroalkyl group having 4 to 9 carbon atoms, and n is an integer of 1 to 3. However, when a is 2 or more, X, R _F and n are selected independently of each other.)

  The present invention (5) is the optical laminate according to any one of the inventions (1) to (4), wherein the ionizing radiation curable fluorinated acrylate is urethane acrylate.

  The present invention (6) is the optical layered body according to any one of the inventions (1) to (5), wherein the optical functional layer further contains translucent fine particles.

  The present invention (7) is a polarizing plate having the optical laminate of any one of the inventions (1) to (6).

  The present invention (8) is a display device comprising the optical laminate according to any one of the inventions (1) to (6).

  According to the present invention (1), (7), (8), an optical laminate that exhibits antistatic properties and antifouling properties and has a low risk of lowering the antistatic properties and antifouling properties even when subjected to a saponification treatment. Body, a polarizing plate using the same, and a display device can be obtained.

  According to the present invention (2) and (3), it is possible to sufficiently introduce fluorine atoms.

According to the present invention (4), since the number of n in the perfluoroalkyl group (—C _n F _{2n + 1} ) is 4 to 9, the molecular chain containing fluorine gathers to form a crystal structure. Thus, there is a portion where the conductive metal oxide is exposed, and the function of the conductive metal oxide is hardly hindered.

  According to this invention (5), there exists an effect that film forming property becomes favorable and also the scratch resistance, elongation and flexibility of the cured product are improved.

  According to the present invention (6), the translucent fine particles can be used as an antiglare film by forming irregularities on the surface and scattering light or scattering light inside the optical functional layer.

  The optical laminate according to the best mode includes an optical functional layer obtained by curing a composition containing an ionizing radiation curable fluorinated acrylate and a conductive metal oxide, and a translucent substrate. Here, the optical functional layer may be laminated on one side of the translucent substrate or on both sides. Furthermore, the optical layered body may have other layers. Here, examples of the other layer include a polarizing substrate and other function-imparting layers (for example, near infrared (NIR), absorption layer, neon cut layer, electromagnetic wave shielding layer). The position of the other layer is, for example, on the light-transmitting substrate opposite to the optical function layer in the case of a polarizing substrate, and on the optical function layer in the case of another functional layer. The lower layer. However, the optical laminate is preferably composed of a translucent substrate and an optical functional layer directly provided on the translucent substrate in order to reduce the number of layers. According to the product, even with the optical layered body having such a configuration, it is possible to obtain an optical layered body having properties sufficiently satisfying characteristics required when applied to an image display device such as a liquid crystal display. Hereafter, each component (an optical function layer, a translucent base | substrate, etc.) of the optical laminated body which concerns on this best form is explained in full detail.

(Optical function layer)
The optical functional layer according to the best mode contains an ionizing radiation curable fluorinated acrylate and a conductive metal oxide. The optical functional layer may further contain an ionizing radiation curable resin. Hereinafter, solid contents in the optical functional layer such as ionizing radiation curable resin, ionizing radiation curable fluorinated acrylate, and conductive metal oxide are collectively referred to as “resin composition”. In addition, translucent fine particles may optionally be included.

The conductive metal oxide is not particularly limited, and examples thereof include indium tin oxide, antimony-doped tin oxide (ATO), zinc antimonate, and antimony oxide. One of these may be selected as the conductive metal oxide, or two or more of these may be used in combination. Among these, antimony-doped tin oxide is particularly preferable. Although the average particle diameter of a metal oxide is not specifically limited, For example, 2-30 nm is suitable and 5-25 nm is more suitable. The average particle size is obtained as an average value obtained by taking a transmission electron microscope (TEM), measuring the particle size of primary particles for 100 particles, and measuring the average particle size. By using the conductive metal oxide having such a particle size, an effect of suppressing coloring by the conductive metal oxide can be obtained. Although the ratio of the conductive metal oxide contained in the optical functional layer is not particularly limited, 1 to 40% by mass is preferable and 3 to 35% by mass is more preferable in 100 parts by mass of the resin composition. -20% by weight is more preferred. If it is less than 1% by mass, the antistatic property tends to be insufficient. If it exceeds 40% by mass, the optical functional layer is colored and the transparency of the optical functional layer tends to decrease, such being undesirable.

Translucent fine particles The translucent fine particles have a certain diameter and have a refractive index difference from the matrix in the optical functional layer, form irregularities on the surface and scatter light, or the optical functional layer It has a role of scattering light inside. An optical laminate comprising an optical functional layer containing translucent fine particles can be used as an antiglare film. Here, the average particle diameter of the translucent fine particles is preferably 0.3 to 10 μm, and more preferably 1 to 8 μm. When the particle size is smaller than 0.3 μm, the antiglare property is lowered. When the particle size is larger than 10 μm, it is not preferable because glare occurs and the surface unevenness becomes too large and the surface becomes whitish. The refractive index of the translucent fine particles is preferably 1.40 to 1.75. When the refractive index is less than 1.40 or greater than 1.75, the difference in refractive index from the translucent substrate or the resin matrix becomes large. Too much, the total light transmittance decreases. Further, the difference in refractive index between the translucent fine particles and the resin component is preferably 0.2 or less. The ratio of the light-transmitting fine particles contained in the optical functional layer is not particularly limited, but it is preferably 1 to 20% by mass in 100 mass of the resin composition in order to satisfy the antiglare function, glare and other characteristics. It is easy to control the fine irregular shape and haze value on the surface of the optical functional layer. Here, “refractive index” refers to a measured value according to JIS K-7142. Further, “average particle diameter” refers to an average value of the diameters of 100 particles actually measured with an electron microscope.

Ionizing radiation curable fluorinated acrylate The ionizing radiation curable fluorinated acrylate according to the present best mode has a molecular weight of 1000 or more. As the ionizing radiation curable fluorinated acrylate, it is preferable to use a fluorinated acrylate having a molecular weight of 1000 to 4000. When the molecular weight is 1000 or more, even when the saponification treatment is performed, the antistatic property and the antifouling property are hardly lowered. When the molecular weight is less than 1000, it is not preferable because a sufficient amount of fluorine atoms cannot be introduced and sufficient leveling properties cannot be obtained. When the molecular weight is larger than 4000, the crosslinking density is lowered and sufficient hardness cannot be obtained, which is not preferable.

  By adding the ionizing radiation curable fluorinated acrylate, the optical functional layer has excellent chemical resistance and can exhibit sufficient antifouling property even after saponification treatment. In addition, ionizing radiation curable fluorinated acrylates are superior in chemical resistance because they are cross-linked between molecules because they are ionizing radiation curable compared to other non-ionizing radiation curable types. In addition, the effect of exhibiting sufficient antifouling property is exhibited. The fluorinated acrylate component is preferably unevenly distributed near the surface layer of the optical functional layer, and the fluorine component in the fluorinated acrylate molecule is preferably unevenly distributed near the surface layer of the optical functional layer. As a result, problems such as detachment of the conductive metal oxide due to the saponification treatment are less likely to occur. For example, the fact that the fluorinated acrylate is unevenly distributed on the surface side from the translucent substrate side means that the fluorine element ratio existing in the range from the optical functional layer surface containing the fluorinated acrylate to a depth of 5 nm is 10% or more. That means. The fluorine element ratio is measured by X-ray photoelectron spectroscopy (hereinafter referred to as “ESCA”). In ESCA, the abundance ratio of fluorine is calculated from the peak areas of fluorine, carbon, oxygen, silicon and the like obtained at a depth of 5 nm. Further, when the range from the surface of the optical functional layer to the depth of 200 nm is measured by ESCA in increments of 5 nm, fluorine present at every depth of 5 nm obtained by measuring from the surface of the optical functional layer to the depth of 5 nm in increments of 5 nm. The value obtained by dividing the element ratio by the average value of the ratio of fluorine elements existing from the depth of 5 nm to the depth of 200 nm on the surface of the optical functional layer is preferably 10 or more, and more preferably 20 or more. Although an upper limit is not specifically limited, For example, it is 1000 or less. By setting the value to 10 or more, fluorine atoms can be efficiently present on the surface of the optical functional layer. Therefore, even when an expensive fluorine material is used, an optical laminate excellent in economic efficiency is provided. can do.

It is preferable that the ionizing radiation curable fluorinated acrylate contains an acrylate containing a perfluoroalkyl group, the perfluoroalkyl group is represented by —C _n F _{2n + 1} , and the number of n is 4 to 9. When n is 3 or less, fluorine atoms cannot be sufficiently introduced, which is not preferable. When n is 10 or more, the crosslinking density is lowered and sufficient hardness cannot be obtained, which is not preferable. When the fluorinated acrylate is applied, it is predicted that the fluorine-containing layer is unevenly distributed on the outermost surface to form a film. For this reason, when it uses together with a conductive metal oxide, there exists a possibility that a fluorine-containing layer may be formed in the upper layer of a conductive metal oxide, and a surface resistivity may rise. When the number of n in the perfluoroalkyl group (—C _n F _{2n + 1} ) is 4 to 9, a molecular chain containing fluorine gathers to form a crystal structure, so that a conductive metal oxide appears locally. This is preferable in that a portion is formed and the function of the conductive metal oxide as described above is not hindered. Compared with a perfluoroalkylene group (—C _n F _2n —) present in the middle of the molecule, it has a substituent having a fluorine atom present at the end of the molecule such as a perfluoroalkyl group (—C _n F _{2n + 1} ). Thus, before the optical functional layer is formed, the fluorine component in the molecule is likely to be unevenly distributed in the vicinity of the surface layer of the optical functional layer, which is preferable because it is easy to improve the antifouling property.

The ionizing radiation curable fluorinated acrylate preferably has a fluorine atom content of 20% or more. The fluorine atom content is a ratio of the fluorine atom weight to the molecular weight of the fluorinated acrylate, and is obtained by the following formula.
Fluorine atom content = [(the amount of fluorine atoms contained in the molecule) / (molecular weight)] × 100
When a fluorine atom content of less than 20% is used, it is necessary to increase the amount of fluorinated acrylate in order to develop sufficient antifouling properties. There arises a problem that a detailed blending ratio must be determined after thoroughly examining the compatibility with other materials when added.

  The ionizing radiation curable fluorinated acrylate contains three or more acryloyl groups. Since three or more acryloyl groups are contained, it is possible to improve the hardness of the optical functional layer. In addition, when mixed with conductive metal oxide, the conductive metal oxide is fixed in the highly cross-linked molecular chain. Defects such as falling off are less likely to occur, and the effect of preventing the deterioration of antifouling property and conductivity due to the saponification treatment is exhibited.

  The ionizing radiation curable fluorinated acrylate is preferably urethane acrylate. Since the fluorinated acrylate is urethane acrylate, the viscosity is high. For this reason, film forming property becomes favorable. Since fluorinated acrylate is urethane acrylate, it is preferable from the viewpoint of scratch resistance, elongation and flexibility of the cured product.

  As the ionizing radiation curable fluorinated acrylate, the following compounds (i) to (vii) can be used. The following compounds all show the case of acrylate, and any acryloyl group in the formula can be changed to a methacryloyl group.

  These can be used alone or in combination. Of the fluorinated acrylates, a fluorinated alkyl group-containing urethane acrylate having a urethane bond is preferred from the viewpoint of scratch resistance, elongation and flexibility of the cured product. Of the fluorinated acrylates, polyfunctional fluorinated acrylates are preferred. Here, the polyfunctional fluorinated acrylate means one having 3 or more, more preferably 4 or more (meth) acryloyloxy groups.

（ここで、Ｃｙはその水素の一部が上記式の置換基及び任意でメチル基又はエチル基により置換される５又は６員環のシクロアルキル部位であり、ａは１〜３の整数であり、Ｘはメチレン基又は直接結合であり、Ｒ_Ｆは炭素数４〜９のパーフルオロアルキル基であり、ｎは１〜３の整数である。但し、前記ａが２以上である場合には前記Ｘ、Ｒ_Ｆ、ｎは互いに独立に選択される。） Preferred examples of the ionizing radiation curable fluorinated acrylate include compounds represented by the following formula (A).

(Wherein Cy is a 5- or 6-membered cycloalkyl moiety in which part of the hydrogen is substituted with a substituent of the above formula and optionally a methyl or ethyl group, and a is an integer of 1 to 3. , X is a methylene group or a direct bond, R _F is a perfluoroalkyl group having 4 to 9 carbon atoms, and n is an integer of 1 to 3. However, when a is 2 or more, X, R _F and n are selected independently of each other.)

（ここで、Ｒ_Ｆは炭素数４〜９のパーフルオロアルキル基であり、ｎは１〜３の整数であり、ｍは０又は１〜３の整数であり、ｎ＋ｍが３以下の整数である。） Among the compounds represented by the above formula (A), a compound represented by the following formula (B) is particularly suitable.

(Wherein R _F is a C 4-9 perfluoroalkyl group, n is an integer of 1-3, m is an integer of 0 or 1-3, and n + m is an integer of 3 or less. .)

  More specifically, the following compounds (1) or (2) are preferred.

  The proportion of ionizing radiation curable fluorinated acrylate contained in the optical functional layer is not particularly limited, but is preferably 0.05 to 50% by mass, more preferably 0.2 to 20% by mass in 100% by mass of the resin composition. Is preferred. When the blending amount of the ionizing radiation curable fluorinated acrylate is less than 0.05% by mass, the water repellent effect and the slipping property are lowered, and the scratch resistance, antifouling property and chemical resistance are deteriorated. When the blending amount of the ionizing radiation curable fluorinated acrylate is more than 50% by mass, the film forming property may be deteriorated.

Ionizing radiation curable resins Ionizing radiation curable resins are polymerized and dimerized directly when irradiated with ionizing radiation such as ultraviolet rays, visible rays, infrared rays, and electron beams, or indirectly by the action of initiators. Monomers, oligomers, polymers, and the like having a curing reactive functional group that causes a reaction that causes a large molecule to progress. Specifically, monomers, oligomers, and prepolymers having radical polymerizable functional groups such as acryloyl group, methacryloyl group, acryloyloxy group, and methacryloyloxy group, and cationic polymerizable functional groups such as epoxy group, vinyl ether group, and oxetane group Are used alone, or a composition obtained by appropriately mixing them. Examples of monomers include methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and the like. it can. As oligomers and prepolymers, polyester acrylate, polyurethane acrylate, polyfunctional urethane acrylate, epoxy acrylate, polyether acrylate, acrylate compounds such as alkit acrylate, melamine acrylate, silicone acrylate, unsaturated polyester, tetramethylene glycol diglycidyl ether, Epoxy compounds such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether and various alicyclic epoxies, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[((3- Oxeta such as ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether Mention may be made of the compound. These can be used alone or in combination. Among these ionizing radiation curable resins, a polyfunctional monomer having three or more (meth) acryloyloxy groups or a polyfunctional urethane acrylate can increase the curing speed and improve the hardness of the cured product. In addition, when mixed with conductive metal oxide, the conductive metal oxide is fixed in the highly cross-linked molecular chain, so that the conductive metal oxide is removed by saponification treatment or light resistance test. Thus, there is an effect that it is difficult for problems such as these to occur and the decrease in conductivity due to the saponification treatment is less likely to occur. In addition, when polyfunctional urethane acrylate is used, the hardness and flexibility of the cured product can be imparted, and further, the effect of increasing the viscosity when formed into a paint can be imparted. Can be improved. Although the ratio of the ionizing radiation curable resin contained in the optical functional layer is not particularly limited, 20 to 80% by mass is preferable and 30 to 70% by mass is more preferable in 100 parts by mass of the resin composition.

The ionizing radiation that cures the resin composition may be any of ultraviolet rays, visible rays, infrared rays, and electron beams. Further, these radiations may be polarized or non-polarized. In particular, ultraviolet rays are suitable from the viewpoints of equipment cost, safety, running cost, and the like. As the ultraviolet energy beam source, for example, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a nitrogen laser, an electron beam accelerator, a radioactive element, and the like are preferable. The amount of irradiation with the energy radiation source of accumulative exposure at an ultraviolet wavelength of 365 nm, preferably in the range of ^{100~5,000mJ / cm 2, 300~3,000mJ / cm} 2 irradiation amount, of less than 100 mJ / cm ² Since the curing becomes insufficient, the hardness of the optical functional layer may be lowered. Moreover, when it exceeds 5,000 mJ / cm < ² >, an optical function layer will color and transparency will fall. When curing by ultraviolet irradiation, it is necessary to add a photopolymerization initiator. A conventionally well-known thing can be used as a photoinitiator. For example, benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, N, N, N, N-tetramethyl-4,4′-diaminobenzophenone, benzylmethyl ketal; acetophenone, 3 -Acetophenones such as methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone; methylanthraquinone, 2-ethylanthraquinone Anthraquinones such as 2-amylanthraquinone; xanthone; thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; Ketals such as tophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; and others, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- ON etc. can be illustrated. These can be used alone or as a mixture of two or more. The use amount of the photopolymerization initiator is preferably about 5% or less, more preferably 1 to 4% in terms of the total solid content ratio with respect to the radiation curable resin composition.

  A polymer resin can be added to the resin composition system as long as the polymerization and curing are not hindered. This polymer resin is a thermoplastic resin that is soluble in an organic solvent used in the optical functional layer coating described later, and specifically includes acrylic resins, alkyd resins, polyester resins, cellulose derivatives, and the like. The resin preferably has an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group.

  In addition, additives such as a leveling agent, a thickener, an antistatic agent, a filler, and an extender can be used. The leveling agent has a function of uniforming the tension on the surface of the coating film and repairing defects before forming the coating film, and a substance having lower interfacial tension and surface tension than the resin composition is used.

  The thickness of the optical functional layer needs to be in the range of 3 to 50 μm, more preferably in the range of 5 to 30 μm, and still more preferably in the range of 7 to 20 μm. When the optical functional layer is thinner than 3 μm, the scratch resistance is deteriorated and interference unevenness appears remarkably, which is not preferable. When it is thicker than 50 μm, curling occurs due to curing shrinkage of the optical functional layer, micro cracks occur on the surface of the optical functional layer, adhesion to the translucent substrate is reduced, and light transmittance is further reduced. Or drop. And it becomes a cause of the cost increase by the increase in the amount of required coating materials accompanying the increase in film thickness.

(Translucent substrate)
The translucent substrate according to the best mode is not particularly limited as long as it is translucent, and glass such as quartz glass and soda glass can also be used. Polyethylene terephthalate (PET), triacetyl cellulose (TAC) , Polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin Various resin films such as copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, and aromatic polyamide can be suitably used. These films can be unstretched or stretched. In particular, a biaxially stretched polyethylene terephthalate film is preferable from the viewpoint of excellent mechanical strength and dimensional stability, and unstretched triacetyl cellulose (TAC) is preferable from the viewpoint of very little in-plane retardation. In addition, when using for PDP and LCD, these PET and TAC films are more preferable.

  The higher the transparency of these translucent substrates, the better. However, the total light transmittance (JIS K7105) is 80% or more, more preferably 90% or more. Further, the thickness of the translucent substrate is preferably thinner from the viewpoint of weight reduction, but considering the productivity and handling properties, the thickness of the translucent substrate is in the range of 1 to 700 μm, preferably 20 to 250 μm. Is preferred. When the optical laminate of the present invention is used for LCD applications, it is preferable to use TAC having a thickness of 20 to 80 μm as the translucent substrate. In the optical layered body of the present invention, curling can be prevented particularly when 20 to 80 μm TAC is used as a light-transmitting substrate, so that it is suitably used for LCD applications that are required to be thin and lightweight. be able to.

  In addition, surface treatment such as alkali treatment, corona treatment, plasma treatment, sputtering treatment, saponification treatment, application of surfactant, silane coupling agent, etc., or surface modification treatment such as Si deposition on the translucent substrate. By performing this, the adhesion between the translucent substrate and the optical functional layer can be improved. By performing these treatments, the adhesion between the translucent substrate and the optical functional layer is improved, so that the scratch resistance, surface hardness and chemical resistance in the optical functional layer are improved.

(Polarizing substrate)
In the present invention, a polarizing substrate may be laminated on a light transmitting substrate opposite to the optical functional layer. By laminating the optical functional layer, the translucent substrate, and the polarizing substrate, a polarizing plate can be obtained. These layers may be laminated directly or via other layers such as an adhesive layer. Here, the polarizing substrate uses a light-absorbing polarizing film that transmits only specific polarized light and absorbs other light, or a light reflective polarizing film that transmits only specific polarized light and reflects other light. I can do it. As the light-absorbing polarizing film, a film obtained by stretching polyvinyl alcohol, polyvinylene or the like can be used. For example, it can be obtained by uniaxially stretching polyvinyl alcohol adsorbed with iodine or a dye as a dichroic element. Polyvinyl alcohol (PVA) film. As the light reflection type polarizing film, for example, two kinds of polyester resins (PEN and PEN copolymer) having different refractive indexes in the stretching direction when stretched are alternately laminated and stretched by several hundreds of extrusion techniques. "DBEF" manufactured by 3M, or a cholesteric liquid crystal polymer layer and a quarter-wave plate are laminated, and light incident from the cholesteric liquid crystal polymer layer side is separated into two circularly polarized light beams that are opposite to each other. Nitto Denko's “Nipox” and Merck's “Transmax”, which are configured to convert circularly polarized light that is transmitted through the cholesteric liquid crystal polymer layer and converted into linearly polarized light by a quarter-wave plate, and the like. .

(Properties of optical laminate)
<Haze>
The total haze of the optical layered body according to the best mode is preferably 3 to 13, more preferably 4 to 10.5, and still more preferably 5 to 9. .

<Total light transmittance>
The total light transmittance of the optical layered body is preferably 90% or more, more preferably 90.5% or more, and further preferably 91% or more.

<Image clarity>
The image clarity before the saponification treatment of the optical laminate is preferably 0 to 80% at an optical comb width of 0.5 mm, more preferably 10 to 77.5%, and 20 to 20%. More preferably, it is 75%.

<Glitter>
The glare of the optical laminate is bonded to the surface of several liquid crystal displays with different resolutions through a colorless and transparent adhesive layer on the surface opposite to the surface on which the optical laminate is formed, photographed with a CCD camera, and variations in image brightness. Can be judged by the presence or absence. It is preferable that the glare cannot be confirmed on a display with a higher resolution, and it is preferable that the liquid crystal display with a resolution of 101 to 140 ppi has no glare.

<Surface resistivity>
The surface resistivity measured from the surface of the optical functional layer of the optical laminate is required to be 1.0 × 10 ¹² Ω / □ or less. If it exceeds 1.0 × 10 ¹² Ω / □, sufficient antistatic performance may not be obtained. Although the surface resistivity is in the range of 1.0 × 10 ¹² Ω / □ to 1.0 × 10 ¹⁰ Ω / □, the electrostatic charge exhibits a property of decaying immediately but is preferably less charged 1 0.0 × 10 ¹⁰ Ω / □ or less. The lower limit value is not limited, but is, for example, 1.0 × 10 ⁶ Ω / □ or more.
The surface resistivity after the saponification treatment of the optical layered body needs to be 1.0 × 10 ¹² Ω / □ or less. If it exceeds 1.0 × 10 ¹² Ω / □, sufficient antistatic performance may not be obtained. Although the surface resistivity is in the range of 1.0 × 10 ¹² Ω / □ to 1.0 × 10 ¹⁰ Ω / □, the electrostatic charge exhibits a property of decaying immediately but is preferably less charged 1 0.0 × 10 ¹⁰ Ω / □ or less. The lower limit value is not limited, but is, for example, 1.0 × 10 ⁶ Ω / □ or more.

<Contact angle>
The contact angle of the optical laminate before saponification treatment is preferably 100 ° or more, more preferably 105 ° or more, with water. Although an upper limit is not specifically limited, For example, it is 150 degrees or less. The contact angle after the saponification treatment of the optical laminate is preferably 90 ° or more, more preferably 95 ° or more, with water. Although an upper limit is not specifically limited, For example, it is 150 degrees or less.

<Average tilt angle>
The optical layered body of the present invention has a fine uneven shape on the surface of the optical functional layer. Here, the fine concavo-convex shape preferably has an average inclination angle calculated from an average inclination obtained according to ASME 95 in the range of 0.2 to 1.4, more preferably 0.25 to 1.2. More preferably, it is 0.25 to 1.0. When the average inclination angle is less than 0.2, the antiglare property is deteriorated, and when the average inclination angle exceeds 1.4, the contrast is deteriorated, so that it is not suitable for the optical laminate used for the display surface.

<Surface roughness>
In the optical layered body of the present invention, the surface roughness Ra is preferably 0.05 to 0.2 μm, and more preferably 0.05 to 0.15 μm, as the fine uneven shape of the optical functional layer. Preferably, it is 0.05-0.10 micrometer. When the surface roughness Ra is less than 0.05 μm, the antiglare property of the optical laminate is insufficient. If the surface roughness Ra is more than 0.2 μm, the contrast of the optical laminate is deteriorated.

<Anti-fouling>
The antifouling property can be evaluated by the ease of wiping off the ink when a line is drawn on the optical functional layer with an oil-based pen (trade name; Mackey (registered trademark), manufactured by ZEBRA). It can be evaluated by a method of wiping with a clean wiper (product number; FF-390C, manufactured by Clarek Laurex Co., Ltd.). It is preferable to completely wipe off after reciprocating 20 times with a load of 500 g / cm ² .

<Macbeth concentration>
The Macbeth reflection density of the optical layered body of the present invention indicates that the larger the value measured in a state where the surface of the light-transmitting substrate of the optical film opposite to the resin layer is black, the black. The Macbeth reflection density value is preferably 3.2 or more. When an optical film is used on the surface of a display or the like, a large difference in white display is rarely seen. Therefore, in order to increase the contrast, it is necessary to emphasize blackness during black display. When the Macbeth reflection density is less than 3.2, high contrast is insufficient.

<Glossiness>
The 60 ° glossiness of the optical laminate of the present invention is preferably in the range of 100 to 130. When the 60 ° gloss is greater than 130, the antiglare property is lowered, which is not preferable. On the other hand, when the 60 ° glossiness is less than 100, the antiglare property is good, but it is not preferable because the light room contrast becomes low due to strong light scattering on the surface.

(Method for producing optical laminate)
As a method for forming the optical functional layer according to the best mode, for example, in the above-described components, and together with water or an organic solvent, a paint shaker, a sand mill, a pearl mill, a ball mill, an attritor, a roll mill, a high-speed impeller disperser, Paint or ink dispersed by jet mill, high-speed impact mill, ultrasonic disperser, etc., air doctor coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, Slot orifice coating, calendar coating, electrodeposition coating, dip coating, die coating, etc., relief printing such as flexographic printing, direct printing Single layer or multiple layers on one or both sides of the transparent substrate directly or via other layers by printing such as gravure printing, intaglio printing such as offset gravure printing, flat printing such as offset printing, stencil printing such as screen printing, etc. If it contains a solvent and contains a solvent, it is formed by curing the coating layer or printing layer by ultraviolet drying (in the case of ultraviolet rays, an initiator is required) or electron beam irradiation through a heat drying step, etc. Is mentioned. In the case of using an electron beam, energy of 50 to 1000 KeV emitted from various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type is used. In the case of ultraviolet rays, ultraviolet rays emitted from a light source such as an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not restrict | limited to these.

分子量；２２５９
フッ素原子含有率；４２．９％ (Production Example 1) Synthesis of ionizing radiation curable fluorinated acrylate solution A In a 500 ml reaction flask, air bubbling was performed on 100 ml of MIBK (methyl isobutyl ketone) in 22.2 g (0.1 mol) of isophorone diisocyanate. Then, a solution of 59.6 g (0.20 mol) of pentaerythritol triacrylate in 50 ml of MIBK was added dropwise at 25 ° C. After completion of dropping, 0.3 g of dibutyltin dilaurate was added, and the mixture was further stirred with heating at 70 ° C. for 4 hours. After completion of the reaction, the reaction solution was washed with 100 ml of 5% hydrochloric acid. After separating the organic layer, the solvent was distilled off under reduced pressure at 40 ° C. or less to obtain 80.5 g of a colorless transparent viscous liquid urethane acrylate. Into a 200 ml reaction flask, 40.8 g (0.05 mol) of the prepared urethane acrylate, 71.9 g (0.15 mol) of perfluorooctylethyl mercaptan, and 60 g of MIBK were added to make uniform. To this mixed solution, 1.0 g of triethylamine was gradually added at 25 ° C. After the addition was completed, the mixture was further stirred at 50 ° C. for 3 hours. After completion of the reaction, triethylamine is distilled off under reduced pressure using an evaporator under conditions of 50 ° C. or lower, and further dried with a vacuum pump, thereby containing a fluorinated alkyl group-containing urethane acrylate represented by Structural Formula 1, and an acryloyl group. An ionizing radiation curable fluorinated acrylate A liquid comprising a mixture further containing a compound different from the structural formula 1 in the position of the addition reaction between and perfluorooctylethyl mercaptan was obtained.

Molecular weight; 2259
Fluorine atom content: 42.9%

(Production Example 2) Synthesis of ionizing radiation curable fluorinated acrylate solution B In a 500 ml reaction flask, air bubbling was performed on 100 ml of MIBK (methyl isobutyl ketone) in 22.2 g (0.1 mol) of isophorone diisocyanate in a 500 ml reaction flask. Then, a solution of 59.6 g (0.20 mol) of pentaerythritol triacrylate in 50 ml of MIBK was added dropwise at 25 ° C. After completion of dropping, 0.3 g of dibutyltin dilaurate was added, and the mixture was further stirred with heating at 70 ° C. for 4 hours. After completion of the reaction, the reaction solution was washed with 100 ml of 5% hydrochloric acid. After separating the organic layer, the solvent was distilled off under reduced pressure at 40 ° C. or less to obtain 80.5 g of a colorless transparent viscous liquid urethane acrylate. The prepared urethane acrylate (40.8 g, 0.05 mol), perfluorobutylethyl mercaptan (42 g, 0.15 mol), and MIBK (60 g) were charged uniformly into a 200 ml reaction flask. To this mixed solution, 1.0 g of triethylamine was gradually added at 25 ° C. After the addition was completed, the mixture was further stirred at 50 ° C. for 3 hours. After completion of the reaction, triethylamine is distilled off under reduced pressure using an evaporator at 50 ° C. or lower, and further dried with a vacuum pump to contain the fluorinated alkyl group-containing urethane acrylate represented by the structural formula 2, and an acryloyl group An ionizing radiation curable fluorinated acrylate B liquid comprising a mixture further containing a compound in which the position of the addition reaction between and perfluorobutylethyl mercaptan further differs from the structural formula 2 was obtained.

分子量；１６５９
フッ素原子含有率；３０．９％

Molecular weight; 1659
Fluorine atom content: 30.9%

(Production Example 3) Synthesis of ionizing radiation curable fluorinated acrylate C solution Perfluorohexyl ethyl mercaptan 150.0 g, thiomalic acid 30.0 g, concentrated sulfuric acid 1.5 g in a 500 ml flask equipped with a stirrer and a Dean-stark trap Then, 200 ml of toluene was charged and heated under reflux until the theoretical amount of water (7.1 g) could be removed. After cooling to 60 ° C., 20 g of slaked lime was added and stirred at the same temperature for 30 minutes. After separation by filtration, toluene was distilled off under reduced pressure to obtain 168.0 g of thiomalic acid di- (perfluorohexylethyl ester) as a yellow transparent viscous liquid.
In a 200 ml reaction flask, 17.6 g (0.05 mol) of pentaerythritol tetraacrylate (Aronix M-450 manufactured by Toagosei Co., Ltd.), 43.7 g (0.05 mol) of thiomalic acid di- (perfluorohexylethyl ester) Then, 10 g of ethyl acetate was added, and 1.0 g of triethylamine was gradually added with stirring at 50 ° C. After the addition was completed, the mixture was further stirred at 50 ° C. for 3 hours. After completion of the reaction, ethyl acetate and triethylamine were distilled off under reduced pressure at 50 ° C. or lower, and further dried with a vacuum pump to obtain 25.0 g of a fluorinated alkyl group-containing acrylate C liquid represented by the following structural formula 3. It was.

分子量；１１６２
フッ素原子含有率；４２．５％

Molecular weight; 1162
Fluorine atom content: 42.5%

(Production Example 4) Fluorosurfactant Synthesis of Liquid D 19 parts by weight of fluorinated alkyl group-containing (meth) acrylate monomer (Structural Formula 4) in a glass flask equipped with a stirrer, a condenser and a thermometer 30 parts by weight of an ethylenically unsaturated monomer having a branched aliphatic hydrocarbon group (Structural Formula 5), 39 parts by weight of a monoacrylate compound having a copolymer of ethylene oxide and propylene oxide having a molecular weight of 400 in the side chain 4 parts by weight of a compound in which both ends of tetraethylene glycol were methacrylated, 8 parts by weight of methyl methacrylate, and 350 parts by weight of isopropyl alcohol (hereinafter abbreviated as IPA) were charged with nitrogen gas. 1 part by weight of azobisisobutyronitrile (hereinafter abbreviated as AIBN) as a polymerization initiator and lauryl mercaptan as a continuous transfer agent under reflux in an air stream After addition of 0 parts by weight to obtain a fluorine-containing oligomer to complete the refluxing was polymerized for 7 hours at 85 ° C.. The molecular weight of this polymer in terms of polystyrene by gel permeation chromatograph (hereinafter abbreviated as GPC) was Mn = 5,500. The fluorine atom content was 11.8%. This copolymer is referred to as a fluorosurfactant D solution.

Production Example 5 Synthesis of ATO-containing UV-curable resin E solution A mixed solution was prepared by dissolving 130 g of potassium stannate and 30 g of potassium antimonyl tartrate in 400 g of pure water. This prepared solution was added to 1000 g of pure water in which 1.0 g of ammonium nitrate and 12 g of 15% ammonia water were dissolved at 60 ° C. over 12 hours for hydrolysis. At this time, a 10% nitric acid solution was simultaneously added so as to keep the pH at 9.0. The generated precipitate was washed by filtration and then dispersed again in water to prepare a metal oxide precursor hydroxide dispersion having a solid concentration of 20% by weight. This dispersion was spray-dried at a temperature of 100 ° C. to prepare a metal oxide precursor hydroxide powder. This powder was heat-treated at 550 ° C. for 2 hours in an air atmosphere to obtain Sb-doped tin oxide (ATO) powder.
60 g of this powder was dispersed in 140 g of an aqueous potassium hydroxide solution having a concentration of 4.3% by weight, and the dispersion was pulverized with a sand mill for 3 hours while maintaining the temperature at 30 ° C. to prepare a sol. Next, this sol was subjected to dealkalization ion treatment with an ion exchange resin until the pH became 3.0, and then pure water was added to prepare an ATO dispersion having a solid content concentration of 20% by weight. The PH of this ATO dispersion was 3.3. The average particle diameter of the ATO fine particles was 10 nm.
Next, 100 g of ATO dispersion was adjusted to 25 ° C., 4.0 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: normal ethyl silicate, SiO 2 concentration 28.8 wt%) was added in 3 minutes, and then stirred for 30 minutes. Went. Thereafter, 100 g of ethanol was added over 1 minute, the temperature was raised to 50 ° C. over 30 minutes, and a heat treatment was performed for 15 hours. The solid concentration at this time was 10% by weight.
Subsequently, water and ethanol as a dispersion medium were replaced with ethanol by an ultrafiltration membrane, and an ATO dispersion liquid surface-treated with an organosilicon compound having a solid content concentration of 30% by weight was prepared.
13.1 g of ATO dispersion surface-treated with this organosilicon compound, 25.6 g of pentaerythritol triacrylate (PE-3A manufactured by Kyoeisha Chemical Co., Ltd.), 17.1 g of urethane acrylate (UA306I manufactured by Kyoeisha Chemical Co., Ltd.), photopolymerization initiator (Ciba Japan Irgacure 184) 2.5 g, ethanol 34.2 g, and toluene 7.5 g were mixed and mixed in a paint shaker for 30 minutes to obtain an ATO-containing UV curable resin E solution having a solid content concentration of 49% by weight. .

(Production Example 6) Quaternary ammonium base-containing copolymer Synthesis of solution F In a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, and a reflux condenser, n-butyl methacrylate 40 g, light ester DQ-100 (Kyoei Chemical Co., Ltd.) 50 g, 5 g of N, N-dimethylaminoethyl methacrylate, 5 g of acrylic acid, 60 g of methanol, and 60 g of methyl cellosolve were charged, and the mixture was stirred for 30 minutes while introducing nitrogen gas into the flask. Was heated to 75 ° C. Next, 0.5 g of AIBN (azobisisobutyronitrile) was added into the flask. While maintaining the contents in the flask at 75 ° C., 0.5 g of AIBN was added twice every hour. 9 hours after the first AIBN addition, the mixture was cooled to room temperature to obtain a copolymer F solution containing a quaternary ammonium base having a polymer concentration of 45%. When the obtained copolymer was measured by GPC, the mass average molecular weight was 100,000. Moreover, it was 12.15 when SP value of the polymer was measured.

  A coating for forming an optical functional layer obtained by stirring the predetermined mixture shown in Table 1 containing the ionizing radiation curable fluorinated acrylate A liquid and the ATO-containing ultraviolet curable resin E liquid with a disper for 30 minutes. The film was applied on one side of a transparent TAC film (manufactured by FUJIFILM; TD80UL) having a film thickness of 80 μm and a total light transmittance of 92% by a roll coating method (line speed; 20 m / min), and 30 to 50 ° C. After 20 seconds of preliminary drying at 100 ° C. for 1 minute, irradiation with ultraviolet rays in a nitrogen atmosphere (nitrogen gas replacement) (lamp; condensing high-pressure mercury lamp, lamp output: 120 W / cm, number of lamps: 4 lamps, The coating film was cured by performing an irradiation distance of 20 cm. Thus, the optical laminated body of Example 1 which has an optical function layer with a thickness of 7.3 micrometers was obtained.

  The optical functional layer-forming coating material was changed in the same manner as in Example 1 except that the ionizing radiation curable fluorinated acrylate A liquid and the ATO-containing ultraviolet curable resin E liquid were changed to the predetermined mixed liquid described in Table 1. An optical layered body of Example 2 having an optical functional layer with a thickness of 7.2 μm was obtained.

  The optical functional layer-forming coating material was changed in the same manner as in Example 1 except that the ionizing radiation curable fluorinated acrylate B liquid and the ATO-containing ultraviolet curable resin E liquid were changed to the predetermined mixed liquid described in Table 1. An optical laminate of Example 3 having an optical functional layer with a thickness of 7.3 μm was obtained.

  Except for changing the coating material for forming an optical functional layer to the predetermined mixed solution shown in Table 1 containing the ionizing radiation curable fluorinated acrylate C solution and the ATO-containing ultraviolet curable resin E solution, the same procedure as in Example 1 was performed. The optical layered body of Example 4 having an optical functional layer with a thickness of 7.2 μm was obtained.

[Comparative Example 1]
Example except that the coating material for forming the optical functional layer was changed to the predetermined mixed solution described in Table 1 containing LINC-3A manufactured by Kyoeisha Chemical Co., Ltd. as ionizing radiation curable fluorinated acrylate, and ATO-containing ultraviolet curable resin E solution In the same manner as in Example 1, an optical laminate of Comparative Example 1 having an optical functional layer having a thickness of 7.2 μm was obtained. The structural formula of LINC-3A is shown below. LINC-3A is a mixture of Structural Formula 6 and Structural Formula 7, and (Structural Formula 6) :( Structural Formula 7) = 65: 35 (weight ratio).

トリアクリロイルーヘプタデカフルオロノネニルペンタエリスリトール
分子量；７２８
フッ素原子含有率；４４．３％

Triacrylloy heptadecafluorononenyl pentaerythritol
Molecular weight; 728
Fluorine atom content: 44.3%

ペンタエリスリトールテトラアクリレート

Pentaerythritol tetraacrylate

[Comparative Example 2]
Implementation was carried out except that the coating for forming the optical functional layer was changed to a predetermined mixed solution described in Table 1 containing a fluorosurfactant D solution and an ATO-containing UV curable resin E solution as a non-ionizing radiation curable fluorinated acrylate. In the same manner as in Example 1, an optical laminate of Comparative Example 2 having an optical functional layer having a thickness of 7.3 μm was obtained.

[Comparative Example 3]
The coating for forming an optical functional layer includes 2- (perfluorooctyl) -ethyl acrylate (product name: Light acrylate FA-108 manufactured by Kyoeisha Chemical Co., Ltd.) as an ionizing radiation curable fluorinated acrylate, and an ATO-containing UV curable resin E liquid. An optical layered body of Comparative Example 3 having an optical functional layer having a thickness of 7.4 μm was obtained in the same manner as in Example 1 except that the liquid mixture was changed to the predetermined mixed liquid described in Table 1. The structural formula of 2- (perfluorooctyl) -ethyl acrylate is shown below (Structural Formula 8).

分子量；５１８
フッ素原子含有率；６２．４％

Molecular weight; 518
Fluorine atom content: 62.4%

[Comparative Example 4]
The optical functional layer-forming coating material was changed to the predetermined mixed solution described in Table 1 that did not contain ionizing radiation curable fluorinated acrylate but contained ATO-containing ultraviolet curable resin E solution, and was the same as in Example 1. The optical laminated body of the comparative example 4 which has an optical functional layer with a thickness of 7.3 micrometers was obtained.

[Comparative Example 5]
Except for changing the coating material for forming the optical functional layer to the predetermined mixed solution described in Table 1 containing the ionizing radiation curable fluorinated acrylate A solution and the quaternary ammonium base-containing copolymer F solution, the same procedure as in Example 1 was performed. The optical laminated body of the comparative example 5 which has an optical function layer with a thickness of 7.3 micrometers was obtained.

[Comparative Example 6]
An optical functional layer having a thickness of 7.3 μm was obtained in the same manner as in Example 1 except that the coating material for forming the optical functional layer was changed to the predetermined liquid mixture shown in Table 1 containing the ionizing radiation curable fluorinated acrylate A liquid. The optical laminated body of the comparative example 6 which has this was obtained.

<Evaluation method>
Next, the following items were evaluated for the optical laminates of Examples and Comparative Examples.

(Contact angle)
The contact angle of water on the surface of the optical functional layer was measured. Next, the contact angle of water on the surface of the saponified optical functional layer was measured. The contact angle of water was measured using a contact angle meter (trade name; Elma G-1 type contact angle meter, manufactured by Elma) in accordance with JIS R3257 (method for testing the wettability of the substrate glass surface).

(Saponification treatment)
The saponification process of an optical laminated body follows the following procedures. When the contact angle of water on the surface of the TAC film constituting the optical laminate was measured, it was 55 ° or more before the saponification treatment and was 20 ° or less after the saponification treatment. Confirmed that it was done.
(1) Immerse in a 6% sodium hydroxide aqueous solution at 55 ° C. for 2 minutes.
(2) Wash with water for 30 seconds.
(3) Immerse in 0.1 N sulfuric acid at 35 ° C. for 30 seconds.
(4) Wash with water for 30 seconds.
(5) Hot air drying at 120 ° C. for 1 minute.

(Total light transmittance)
The total light transmittance was measured using a haze meter (trade name: NDH2000, manufactured by Nippon Denshoku) in accordance with JIS K7105.

(Haze value)
The haze value was measured according to JIS K7105 using a haze meter (trade name: NDH2000, manufactured by Nippon Denshoku). In addition, the haze in a table | surface is a value of all haze.

(Surface roughness, average interval of unevenness)
The surface roughness Ra and the average interval Sm of the unevenness were measured using a surface roughness measuring instrument (trade name: Surfcorder SE1700α, manufactured by Kosaka Laboratory) according to JIS B0601-1994.

(Average tilt angle)
The average inclination angle was determined according to ASME95 using a surface roughness measuring instrument (trade name: Surfcorder SE1700α, manufactured by Kosaka Laboratories), and the average inclination angle was calculated according to the following formula.
Average inclination angle = tan ⁻¹ (average inclination)

(Image clarity)
According to JIS K7105, a measuring device (trade name: ICM-1DP, manufactured by Suga Test Instruments Co., Ltd.) was used, and the measuring device was set to a transmission mode, and measurement was performed at an optical comb width of 0.5 mm.

(Anti-glare)
The antiglare property was set to ○ when the value of image clarity was 0 to 80, and × when 81 to 100.

(Surface resistivity)
The surface resistivity was measured using a high resistivity meter (trade name: Hiresta-UP, manufactured by Mitsubishi Chemical Corporation) according to JIS K6911. The measurement was carried out under conditions of 20 ° C. and 65% RH after conditioning the sample for 1 hour in an environment of 20 ° C. and 65% RH. The surface resistivity was measured from the surface side of the optical functional layer of the optical laminate with an applied voltage of 250 V and an application time of 10 seconds.

(Glitter)
The glare is a liquid crystal display (trade name: LC-32GD4, manufactured by Sharp Corporation) with a resolution of 50 ppi on the surface opposite to the optical laminate-forming surface of each example and each comparative example via a colorless and transparent adhesive layer. Liquid crystal display (trade name: LL-T1620-B, manufactured by Sharp), liquid crystal display with resolution of 120 ppi (trade name: LC-37GX1W, manufactured by Sharp), and liquid crystal display with resolution of 140 ppi (trade name) : VGN-TX72B (manufactured by Sony), liquid crystal display with a resolution of 150 ppi (trade name: nw8240-PM780, manufactured by Hewlett-Packard Japan), and liquid crystal display with a resolution of 200 ppi (trade name: PC-CV50FW, manufactured by Sharp) ) Are attached to the screen surface, and the LCD After the play is displayed in green, the resolution value when the brightness variation is not confirmed in an image taken with a CCD camera (CV-200C, manufactured by Keyence Corporation) with a resolution of 200 ppi from the normal direction of each liquid crystal TV is 0. When it was ˜50 ppi, it was marked as Δ when it was 51 to 100 ppi, ◯ when 101 to 140 ppi, and ◎ when 141 to 200 ppi.

(Light room contrast)
Bright room contrast is a liquid crystal display device (trade name: LC-37GX1W, manufactured by Sharp Corporation) through a colorless and transparent adhesive layer on the surface opposite to the surface on which the optical functional layer is formed in the optical laminates of Examples and Comparative Examples. Pasted on the screen surface of the liquid crystal display device, the liquid crystal display surface was illuminated with a fluorescent lamp (trade name: HH4125GL, manufactured by National Corporation) from the direction 60 ° above the front of the liquid crystal display device screen, and then the liquid crystal display The luminance when the device is in white display and black display is measured with a color luminance meter (trade name: BM-5A, manufactured by Topcon Corporation), and the resulting luminance (cd / m ² ) and white display in black display are obtained. When the luminance (cd / m ² ) at the time was calculated by the following formula, the value was 800 when the value was 800 or less, and when the value was 801 or more, the result was ○.
Contrast = Brightness of white display / Brightness of black display

(Dark room contrast)
The dark room contrast is that of the liquid crystal display device (trade name: LC-37GX1W, manufactured by Sharp Corporation) through a colorless and transparent adhesive layer on the surface opposite to the surface on which the optical functional layer is formed in the optical laminates of Examples and Comparative Examples. The black display was obtained by measuring the luminance when the liquid crystal display device was set to white display and black display under dark room conditions with a color luminance meter (trade name: BM-5A, manufactured by Topcon Corporation). value when calculated in the luminance (cd / ^{m 2)} and the white display of the luminance (cd / ^{m 2)} the following equation when there is, × when 900-1100, when 1,101 to 1300 △, 1301 to In the case of 1500, it was rated as “good”.
Contrast = Brightness of white display / Brightness of black display

(Anti-fouling Mackey (registered trademark) test)
A 3 cm long line is drawn on the optical functional layer of the produced optical laminate with an oil-based pen (trade name; Mackey (registered trademark), manufactured by ZEBRA), and left for 1 minute, and then a clean wiper (product number: FF-390C Kuraraykura) is used. Evaluation was carried out by a method of wiping by Flex Corporation. After rubbing 20 times with a load of 500 g / cm 2, the case where it was completely wiped was indicated as “◯”.

(Macbeth concentration)
The Macbeth reflection density is in accordance with JIS K 7654, using a Macbeth reflection densitometer (trade name: RD-914, manufactured by Sakata Engineering Co., Ltd.) and the resin layer of the translucent substrate of the optical laminates of Examples and Comparative Examples The opposite surface was black-coated with magic ink (registered trademark), and then Macbeth reflection density on the surface of the resin layer was measured.
(Glossiness)
The glossiness was 60 ° specular glossiness measured using a gloss meter (trade name: VG2000, Nippon Denshoku Co., Ltd.) according to JIS Z8741.

  The obtained results are shown in Table 2. In addition, the data in a table | surface are the results of measuring the optical laminated body before performing saponification unless there is particular description.

  As described above, according to the present invention, an optical laminate having excellent antistatic performance and excellent saponification resistance, and a display device using the same can be provided.

The present invention (1) is an optical laminate having a translucent substrate and an optical functional layer obtained by curing a composition containing at least an ionizing radiation curable fluorinated acrylate and a conductive metal oxide. Yes,
The thickness of the optical function layer is 3 to 50 μm,
The ionizing radiation curable fluorinated acrylate has a molecular weight of 1000 or more and contains 3 or more acryloyl groups.

Claims (8)

An optical laminate having a translucent substrate and an optical functional layer obtained by curing a composition containing at least an ionizing radiation curable fluorinated acrylate and a conductive metal oxide,
An optical laminate having a molecular weight of 1000 or more, and containing 3 or more acryloyl groups.   The optical laminate according to claim 1, wherein the ionizing radiation curable fluorinated acrylate contains a perfluoroalkyl group.   The optical laminate according to claim 1 or 2, wherein the ionizing radiation curable fluorinated acrylate has a fluorine atom content of 20% or more. The optical laminate according to any one of claims 1 to 3, wherein the ionizing radiation curable fluorinated acrylate is a compound represented by the following formula (A).

(Wherein Cy is a 5- or 6-membered cycloalkyl moiety in which part of the hydrogen is substituted with a substituent of the above formula and optionally a methyl or ethyl group, and a is an integer of 1 to 3. , X is a methylene group or a direct bond, R _F is a perfluoroalkyl group having 4 to 9 carbon atoms, and n is an integer of 1 to 3. However, when a is 2 or more, X, R _F and n are selected independently of each other.)   The optical laminate according to claim 1, wherein the ionizing radiation curable fluorinated acrylate is urethane acrylate.   The optical layered product according to any one of claims 1 to 5, wherein the optical functional layer further contains translucent fine particles.   A polarizing plate comprising the optical layered body according to claim 1.   A display device comprising the optical laminate according to claim 1.