JP5076763B2 - Optical laminate manufacturing method, optical laminate, polarizing plate, and image display device - Google Patents

Description

The present invention relates to an optical laminate manufacturing method, an optical laminate, a polarizing plate, and an image display device.

Anti-reflection optics on the outermost surface of image display devices such as cathode ray tube display (CRT), liquid crystal display (LCD), plasma display (PDP), electroluminescence display (ELD), field emission display (FED) A laminate is provided. Such an anti-reflection optical laminate suppresses image reflection or reduces reflectance by scattering or interference of light.

In the anti-reflection optical layered body, as one method for reducing the reflection of light emitted from external light such as fluorescence and improving the visibility of the display surface, layers having different refractive indexes are stacked. Is conventionally performed (Patent Document 1). However, in an antireflection laminate in which layers having a large difference in refractive index are laminated, interface reflection and interference fringes occur at the interface of the layers that overlap each other, resulting in a decrease in image visibility. There was a problem.

As a method for suppressing the occurrence of such interference fringes, a method of forming a hard coat layer on a substrate using a resin composition containing a solvent for dissolving the substrate is known (Patent Documents 2 and 3). ).
In Patent Document 3, a resin having a weight average molecular weight of 200 or more and 10,000 or less and having a functional group of more than 2; a resin having a weight average molecular weight of 200 or more and 1000 or less and having a functional group of 2 or less; An optical laminate that effectively prevents the occurrence of interface reflection and interference fringes is disclosed by forming a hard coat layer on a substrate with a composition comprising a reactive solvent.

However, when a high refractive index resin is added to the hard coat layer in order to form a hard coat layer having a relatively high refractive index, the occurrence of interference fringes is sufficiently suppressed even when formed using a permeable solvent. However, there was a problem that visibility was lowered.
JP 2003-75603 A JP 2003-205563 A JP 2006-299221 A

In view of the above situation, the present invention has an object to provide a manufacturing method for effectively suppressing the occurrence of interface reflection and interference fringes and forming an optical laminate having excellent visibility.

The present invention is a method for producing an optical laminate having a light-transmitting substrate and a hard coat layer, wherein the weight average molecular weight is 200 or more and less than 1000, the high refractive index resin A, the weight average molecular weight is 1000 or more, 10 The total amount of the high-refractive index resin A and the high-refractive index resin B in all the resin components including the high-refractive index resin B, the penetrating solvent, and the binder resin that are 10,000 or less is 10 to 80 mass% (solid content ratio) at which the resin composition was applied onto the light-transmitting substrate have a step of forming the hard coat layer, the high refractive index resin a and a high refractive index resin B A method for producing an optical laminate , wherein the refractive index is 1.55 to 1.65 .
Upper SL content ratio of the high refractive index resin A and the high refractive index resin B (a high refractive index resin A / high refractive index resin B) is in a solid content mass ratio (95/5) - (5/95) Preferably there is.
The permeable solvent is preferably at least one selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone and methylene chloride.
The binder resin has a refractive index of less than 1.55, a resin 1 having a weight average molecular weight of 200 or more and less than 1000, a refractive index of less than 1.55, and a weight average molecular weight of 1000 or more, 10 It is preferable to contain resin 2 that is 10,000 or less.
The resin composition preferably further contains an oxide of at least one element selected from the group consisting of silicon, aluminum, titanium, zinc, germanium, indium, tin and antimony.
The resin composition preferably further has an antistatic agent.
The light-transmitting substrate preferably has an antistatic layer on the surface on which the hard coat layer is formed.
The light transmissive substrate is preferably triacetyl cellulose.

The present invention is also an optical laminate obtained by the above-described method for producing an optical laminate.
The present invention is also a self-luminous image display device including the above-described optical laminate on the outermost surface.
This invention is also a polarizing plate provided with a polarizing element, Comprising: The said polarizing plate is a polarizing plate characterized by providing the above-mentioned optical laminated body on the polarizing element surface.
The present invention is also a non-self-luminous image display device comprising the above-described optical layered body or the above-described polarizing plate on the outermost surface.
Hereinafter, the present invention will be described in detail.

The present invention is a method for producing an optical laminate having a light-transmitting substrate and a hard coat layer, wherein the weight average molecular weight is 200 or more and less than 1000, the high refractive index resin A, the weight average molecular weight is 1000 or more, 10 It has the process of apply | coating the high refractive index resin B which is 10,000 or less, the permeable solvent, and the resin composition containing binder resin on the said transparent base material, and forming the said hard-coat layer, It is characterized by the above-mentioned. It is the manufacturing method of the optical laminated body to do. By having the process of forming the said hard-coat layer, generation | occurrence | production of interface reflection and an interference fringe can be prevented suitably, and the optical laminated body excellent in visibility can be obtained.

In the method for producing an optical layered body of the present invention, when the hard coat layer is formed, a resin composition containing two types of high refractive index resins having different weight average molecular weights is used.
When the resin composition contains two kinds of high-refractive index resins, the hard coat layer formed on the light-transmitting substrate is the light-transmitting substrate or other low-refractive index layers that are laminated as necessary. The difference in refractive index from the above can be increased, and the antireflection property can be improved. In addition, the resin composition contains two kinds of high refractive index resins having different weight average molecular weights and a permeable solvent. Therefore, when the hard coat layer is formed, the low molecular weight part of the resin composition is partially mixed with the permeable solvent. Since a clear interface is not formed by penetrating into the film, generation of interference fringes can be suppressed.
In the present specification, “high refractive index resin” means a resin having a refractive index of 1.55 or more, and “resin” is a concept including resin components such as monomers and oligomers.

The optical laminate produced by the method for producing an optical laminate of the present invention can suitably suppress the occurrence of interface reflection and interference fringes, and therefore has excellent visibility when installed in an image display device. . In addition, since a part of the components of the hard coat layer is formed by penetrating into the light-transmitting substrate, the adhesion between the layers is also excellent.

The method for producing an optical laminate of the present invention includes a high refractive index resin A having a weight average molecular weight of 200 or more and less than 1000, a high refractive index resin B having a weight average molecular weight of 1,000 or more and 100,000 or less, and permeability. It has the process of apply | coating the resin composition containing a solvent to a transparent base material, and forming a hard-coat layer.

When the weight average molecular weight of the high refractive index resin A is less than 200, it is difficult to introduce a component for increasing the refractive index in the molecule, and it is difficult to increase the refractive index of the hard coat layer to be formed. In some cases, the anti-reflection property of the optical laminate produced in this way becomes insufficient. In addition, the volatility may increase and adversely affect the human body, or may volatilize during the drying process and cause contamination. If it is 1000 or more, the effect of partially penetrating the substrate together with the above-mentioned permeable solvent may not be obtained. A preferable lower limit of the weight average molecular weight of the high refractive index resin A is 260.

Further, if the weight average molecular weight of the high refractive index resin B is less than 1000, the refractive index of the hard coat layer to be formed may not be sufficiently increased. If it exceeds 100,000, the viscosity of the prepared resin composition may increase and coating may not be performed uniformly. The minimum with a preferable weight average molecular weight of the said high refractive index resin B is 1200, and a preferable upper limit is 40,000.
The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) in terms of polystyrene.

The high refractive index resins A and B preferably have a refractive index of 1.55 to 1.65. By including such a high refractive resin, the refractive index of the hard coat layer formed through this step increases, and as a result, when a low refractive index resin is laminated on the hard coat layer, the reflectance is low. An optical laminate can be obtained.

Examples of commercially available products that can be used as the high refractive index resin A include “ALEN10” (monofunctional acrylate having a biphenyl skeleton, refractive index 1.58, weight average molecular weight 268, manufactured by Shin-Nakamura Chemical Co., Ltd.), “EX142 "(Monofunctional epoxy of biphenyl skeleton, refractive index 1.59, weight average molecular weight 226, manufactured by Nagase ChemteX Corporation)", "Z9014" (bromine-containing acrylate, refractive index 1.57, manufactured by JSR Corporation), "Z9009D" ( Bromine-containing acrylate, refractive index 1.57, manufactured by JSR Corporation) and the like.

Examples of commercially available products that can be used as the high refractive index resin B include “R1403M” (urethane acrylate, refractive index 1.58, weight average molecular weight 1500, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), “HRR2” (urethane). Acrylate, refractive index 1.58, weight average molecular weight 1500, manufactured by Showa Ink Co., Ltd.) and the like.

In the resin composition, the content ratio of the high refractive index resin A and the high refractive index resin B (high refractive index resin A / high refractive index resin B) is (5/95) to ( 95/5). If it is less than (5/95), the high refractive index resin A is decreased, interference fringes are generated in the optical laminate to be produced, and the adhesion to the light-transmitting substrate may be deteriorated. If it exceeds (95/5), the high refractive index resin B is decreased, and interference fringes may be generated in the produced optical laminate.

In the resin composition, the total content of the high refractive index resin A and the high refractive index resin B is 10 to 80 among all resin components including a binder resin having a refractive index of less than 1.55, which will be described later. It is mass% (solid content ratio). If it is less than 10% by mass, the hard coat layer to be formed is less likely to have a high refractive index, and the intended effect is reduced. If it exceeds 80% by mass, the hardness of the hard coat layer to be formed is remarkably lowered, and the adhesiveness with the light-transmitting substrate is deteriorated to generate interference fringes. Furthermore, since the high refractive index resins A and B are expensive, the cost increases. The minimum with said preferable total content (solid content ratio) is 20 mass%, and a preferable upper limit is 60 mass%.

The permeable solvent is a solvent that has high permeability to the light transmissive substrate and dissolves or swells the substrate.
By using such a penetrating solvent, interference fringes can be eliminated from the optical laminate to be produced, and the adhesion to the light-transmitting substrate can be improved. This is considered to be due to the following reasons.
That is, in this step, when the resin composition is applied onto the light transmissive substrate and a resin layer is formed, the permeable solvent in the resin layer penetrates near the surface of the light transmissive substrate. When the other components of the resin composition, specifically, the high refractive index resin A (and the binder resin described later) are considered to penetrate into the light-transmitting substrate together with the penetrating solvent. As a result, the manufactured optical laminate has an unclear interface between the light transmissive substrate and the hard coat layer, and the refractive index gradually changes from the light transmissive substrate to the hard coat layer. It is thought that the occurrence of the occurrence can be eliminated. In addition, since a part of the hard coat layer penetrates near the surface of the light transmissive substrate, the produced optical laminate has improved adhesion between the light transmissive substrate and the hard coat layer. it is conceivable that.

Examples of the permeable solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, and diacetone alcohol; esters such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, and ethyl lactate; nitromethane, acetonitrile, Nitrogen-containing compounds such as N-methylpyrrolidone and N, N-dimethylformamide; glycols such as methyl glycol and methyl glycol acetate; ethers such as tetrahydrofuran, 1,4-dioxane, dioxolane and diisopropyl ether; methylene chloride, chloroform, Halogenated hydrocarbons such as tetrachloroethane; glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetate; others, dimethyl sulfoxide, charcoal Propylene, or mixtures thereof. Among these, at least one selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone and methylene chloride is preferable.

The addition amount of the permeable solvent is appropriately adjusted according to the thickness of the hard coat layer to be formed, and is not particularly limited. In the resin composition, the high refractive index resins A and B and the binder resin described later are used. It is preferable that it is about 30-500 mass parts with respect to 100 mass parts of solid content, such as. If it is less than 30 parts by mass, the hard coat layer formed on the light-transmitting substrate does not sufficiently penetrate the light-transmitting substrate, and interference fringes may be generated in the produced optical laminate. In addition, the adhesion of the hard coat layer to be formed to the light-transmitting substrate may be insufficient. When the amount exceeds 500 parts by mass, a hard coat layer having a sufficient thickness may not be formed, and functions such as antireflection properties of the produced optical laminate may be insufficient. A more preferable lower limit is 40 parts by mass, and a more preferable upper limit is 400 parts by mass.

The resin composition for forming the hard coat layer further contains a binder resin.
As the binder resin, a transparent resin having a refractive index of less than 1.55 is preferable. For example, an ionizing radiation curable resin which is a resin curable by ultraviolet rays or an electron beam is suitably used.
The ionizing radiation curable resin preferably includes two types of resins having different molecular weights. By including two kinds of resins having different molecular weights, when the resin composition is applied onto a light-transmitting substrate, a low-molecular resin penetrates the light-transmitting substrate together with the penetrating solvent, and is manufactured. Generation of interface reflection and interference fringes of the laminate can be further suppressed. Moreover, the adhesiveness between layers can be improved. Furthermore, the pencil hardness of the hard coat layer to be formed can be made excellent.

The two types of resins having different molecular weights include a resin 1 having a refractive index of less than 1.55 and a weight average molecular weight of 200 or more and less than 1000, a refractive index of less than 1.55, and a weight. A resin 2 having an average molecular weight of 1,000 or more and 100,000 or less is preferable. The weight average molecular weights of the resins 1 and 2 are values obtained in terms of polystyrene by gel permeation chromatography (GPC).

The resin 1 is not particularly limited as long as it satisfies the above-described refractive index and weight average molecular weight. For example, a trifunctional or higher functional (meth) acrylate compound is preferably used.
Examples of the trifunctional or higher functional (meth) acrylate compound include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, and isocyanuric acid-modified triacrylate. Is mentioned. These acrylates may be modified in part of the molecular skeleton, such as those modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, etc. be able to.

The (meth) acrylate may be an oligomer such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polybutadiene (meth) acrylate, or silicon (meth) acrylate. Two or more of these may be used in combination.

When the molecular weight of the (meth) acrylate compound exceeds 1000, not only the adhesion to the substrate is deteriorated but also the interference fringes may not disappear. The molecular weight is more preferably 700 or less, and further preferably 280 to 600.
By containing such a resin 1, it is possible to suppress the generation of interference fringes in the optical laminate to be manufactured, and to improve the adhesion between the layers.

The resin 2 is not particularly limited as long as it satisfies the above-described refractive index and weight average molecular weight. For example, a hexafunctional or higher functional urethane (meth) acrylate compound is preferably used.
As a commercial item of the said urethane (meth) acrylate type-compound, for example, the Nihon Gosei Co., Ltd. purple light series, UV1700B, UV6300B, UV765B, UV7640B, UV7600B etc. are mentioned; Art resin series, Art resin HDP by Negami Kogyo Art Resin UN3320HSBA, UN9000H, Artresin UN3320HA, Artresin UN3320HB, Artresin UN3320HC, Artresin UN3320HS, Artresin UN901M, Artresin UN902MS, Artresin UN903, UA made by H4 Shin 100, U4 made by H4, 100 , U6H, U6HA, U15HA, UA32P, U6LPA, U324A, U9HAMI, etc .; manufactured by Daicel UCB Ebecryl series, 1290, 5129, 254, 264, 265, 1259, 1264, 4866, 9260, 8210, 204, 205, 6602, 220, 4450, etc .; Beam set series made by Arakawa Chemical Co., Ltd., 371, 577, etc. RQ series manufactured by Mitsubishi Rayon Co., Ltd., Unidic series manufactured by Dainippon Ink Co., Ltd., and the like; DPHA40H (manufactured by Nippon Kayaku Co., Ltd.), CN9006 (manufactured by Thermar Corporation), CN968 and the like. Of these, UV1700B (manufactured by Nippon Gohsei Co., Ltd.), DPHA40H (manufactured by Nippon Kayaku Co., Ltd.), Art Resin HDP (manufactured by Negami Kogyo Co., Ltd.), beam set 371 (manufactured by Arakawa Chemical Co., Ltd.), beam set 577 (Arakawa Chemical Co., Ltd.) And U15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.).

When the weight average molecular weight of the urethane (meth) acrylate compound is less than 1000, the permeability to the substrate is increased, and sufficient hardness may not be obtained for the optical laminate to be produced. If it exceeds 100,000, the viscosity is too high, and there is a possibility that suitable coating cannot be performed.
By containing such resin 2, sufficient pencil hardness can be imparted to the optical laminate to be produced.

In addition, relatively low molecular weight polyester resins having unsaturated double bonds, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, etc. are also used in the ionizing radiation curable type. It can be used as a resin.

In addition, as the binder resin, an ionizing radiation curable resin and a solvent-drying resin (a resin that forms a film by simply drying a solvent added to adjust the solid content during coating, such as a thermoplastic resin) And a thermosetting resin.

The ionizing radiation curable resin can be used in combination with a solvent-drying resin. By using the solvent-drying resin in combination, it is possible to effectively prevent coating defects on the coated surface, thereby obtaining a more excellent glossy blackness. In general, a thermoplastic resin can be used as the solvent-drying resin that can be used in combination with the ionizing radiation curable resin.

The thermoplastic resin is not particularly limited. For example, a styrene resin, a (meth) acrylic resin, a vinyl acetate resin, a vinyl ether resin, a halogen-containing resin, an alicyclic olefin resin, a polycarbonate resin, or a polyester resin. Examples thereof include resins, polyamide-based resins, cellulose derivatives, silicone-based resins, rubbers, and elastomers. The thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds). In particular, styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) are preferable from the viewpoint of excellent film forming properties, transparency and weather resistance. .

When the material of the light-transmitting substrate on which the resin composition is applied in this step is a cellulose resin such as triacetyl cellulose (TAC), a preferable specific example of the thermoplastic resin is a cellulose resin such as nitrocellulose. , Cellulose derivatives such as acetylcellulose, cellulose acetate propionate, ethylhydroxyethylcellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose. By using a cellulose-based resin as the thermoplastic resin, it is possible to improve adhesion and transparency with a light-transmitting substrate. Furthermore, as the thermoplastic resin, in addition to the above-mentioned cellulose resin, vinyl acetate and its copolymer, vinyl chloride and its copolymer, vinyl resin such as vinylidene chloride and its copolymer, polyvinyl formal, Acetal resins such as polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, polycarbonate resins, and the like can also be used.

Examples of the thermosetting resin that can be used as the binder resin include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-urea. A condensation resin, a silicon resin, a polysiloxane resin, etc. can be mentioned.

The resin composition further includes an oxide of at least one element selected from the group consisting of silicon, aluminum, titanium, zinc, germanium, indium, tin and antimony (hereinafter, these are collectively referred to as a metal oxide). It is preferable to contain. By having the said metal oxide, the pencil hardness of the optical laminated body to manufacture can be improved.

As the metal oxide, colloidal silica having a photoreactive group on the surface is particularly preferable. The pencil hardness of the optical laminate to be manufactured can be made extremely excellent.
The photoreactive group is not particularly limited, and examples thereof include an acrylate group, a methacrylate group, and an epoxy group.
Colloidal silica having such a photoreactive group on the surface includes, for example, a method of reacting the surface of silica fine particles with the silane coupling agent having the photoreactive group.

The compounding amount of the metal oxide in the resin composition is not particularly limited, and the effect of improving the pencil hardness by having the metal oxide can be sufficiently enjoyed, and the optical laminate produced by the present invention described above can be used. It is preferable that the resin composition is appropriately blended as long as the effect is not impaired.

Moreover, it is preferable that the said resin composition has an antistatic agent further.
When the resin composition contains an antistatic agent, antistatic properties can be imparted to the hard coat layer to be formed.

The antistatic agent is not particularly limited, and examples thereof include cationic compounds such as quaternary ammonium salts, pyridinium salts, and primary to tertiary amino groups; sulfonate groups, sulfate ester bases, phosphate ester bases, and phosphonic acids. Anionic compounds such as bases; amphoteric compounds such as amino acids and aminosulfate esters; nonionic compounds such as amino alcohols, glycerin and polyethylene glycol; organometallic compounds such as tin and titanium alkoxides; Examples thereof include metal chelate compounds such as acetylacetonate salts of compounds. Compounds obtained by increasing the molecular weight of the compounds listed above can also be used. Also, polymerizability of organometallic compounds such as coupling agents having a tertiary amino group, a quaternary ammonium group or a metal chelate moiety and having a monomer, oligomer or functional group that can be polymerized by ionizing radiation. Compounds can also be used as antistatic agents.

Examples of the antistatic agent include conductive polymers. The conductive polymer is not particularly limited. For example, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing polyaniline, mixed type Conjugated poly (phenylene vinylene), a double chain conjugated system that has a plurality of conjugated chains in the molecule, and a conductive polymer that is a polymer obtained by grafting or block-copolymerizing the conjugated polymer chain to a saturated polymer. And the like.

The antistatic agent may be conductive metal oxide fine particles. The conductive metal oxide fine particles are not particularly limited. For example, ZnO (refractive index 1.90, hereinafter, all values in parentheses indicate refractive index), Sb ₂ O ₂ (1.71). ), SnO ₂ (1.997), CeO ₂ (1.95), indium tin oxide (abbreviated as ITO; 1.95), In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), Antimony-doped tin oxide (abbreviation ATO; 2.0), aluminum-doped zinc oxide (abbreviation AZO; 2.0), and the like can be given.

As the content of the antistatic agent, the resin can be used as long as the effect of containing the antistatic agent can be fully enjoyed and the effect obtained in the optical laminate produced according to the present invention is not impaired. It is preferable to be appropriately blended in the composition.

The resin composition for forming the hard coat layer may contain other components as necessary in addition to the components described above. Examples of the other components include a photopolymerization initiator, a leveling agent, a crosslinking agent, a curing agent, a polymerization accelerator, and a viscosity modifier.

Examples of the photopolymerization initiator include acetophenones (for example, trade name Irgacure 184, 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by Ciba Specialty Chemicals, trade name Irgacure 907, 2 manufactured by Ciba Specialty Chemicals). -Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one), benzophenones, thioxanthones, benzoin, benzoin methyl ether, aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium Examples thereof include salts, metathelone compounds, and benzoin sulfonic acid esters. These may be used alone or in combination of two or more.
The addition amount of the photopolymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin solid content.
Known leveling agents, crosslinking agents, curing agents, polymerization accelerators, and viscosity modifiers may be used.

The resin composition can be obtained by mixing and dispersing the above-described high refractive index resin A, high refractive index resin B, permeable solvent, binder resin and other components. For mixing and dispersing, a paint shaker or a bead mill may be used.

In this step, the resin composition is applied onto a light transmissive substrate to form a hard coat layer.
The light-transmitting substrate preferably has transparency, smoothness, heat resistance, and excellent mechanical strength. Specific examples of the material forming the light-transmitting substrate include cellulose compounds such as triacetyl cellulose (TAC), cellulose diacetate, and cellulose acetate butyrate. Especially, it is more preferable that it is a triacetyl cellulose (TAC) from a viewpoint that it is easy to exhibit the effect of invention.

The thickness of the light transmissive substrate is preferably 20 to 300 μm, a more preferable lower limit is 30 μm, and a more preferable upper limit is 200 μm.

Furthermore, the light-transmitting substrate is called an anchor agent or primer in addition to physical treatment such as corona discharge treatment and oxidation treatment for improving adhesion when a hard coat layer is formed thereon. Application of the paint may be performed in advance. Moreover, when the said light-transmitting base material is a triacetyl cellulose, you may perform a saponification process previously. The saponification treatment may be performed by a known method / condition.

Examples of a method for applying the resin composition on the light-transmitting substrate include known coating methods such as a roll coating method, a Miya bar coating method, and a gravure coating method.
The coating amount of the resin composition is appropriately determined in consideration of the film thickness of the target hard coat layer, etc., but is preferably 0.1 to 30 g / m ² . If it is less than 0.1 g / m ² , the hardness of the hard coat layer to be formed may be lowered. In addition, it may be difficult to control the film thickness, resulting in large variations in performance. If it exceeds 30 g / m ² , cracks are likely to occur when the produced optical laminate is bent, which may be a problem. Moreover, it is not preferable because the cost increases. A more preferred lower limit is 1 g / m ² and a more preferred upper limit is 20 g / m ² .

As the method for forming the hard coat layer, the resin composition is applied to the light-transmitting substrate to form a resin layer, and then the resin layer is heated as necessary, and cured by irradiation with active energy rays. The method of making it form is mentioned.
Examples of the active energy ray irradiation include irradiation with ultraviolet rays or electron beams. Specific examples of the ultraviolet light source include light sources such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp. As the wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type.

The hard coat layer formed through this step preferably exhibits a hardness of “H” or higher in a pencil hardness test specified by JIS K5600-5-4 (1999). By having the above-mentioned hardness, an optical laminate that can realize desired scratch resistance and the like can be manufactured.

The method for producing an optical laminate of the present invention preferably includes a step of forming an antistatic layer.
The antistatic layer can be formed of, for example, a composition containing the above-described antistatic agent and a resin. It does not specifically limit as said resin, For example, the binder resin etc. which were illustrated with the above-mentioned resin composition are mentioned.
The step of forming the antistatic layer may be performed before the step of forming the hard coat layer on the light transmissive substrate, or the step of forming the hard coat layer on the light transmissive substrate. You may go after. In the former case, the produced optical laminate has a structure in which an antistatic layer is formed on a light-transmitting substrate and a hard coat layer is formed on the antistatic layer. On the other hand, in the latter case, the optical laminate to be produced has a structure in which a hard coat layer is formed on a light-transmitting substrate and an antistatic layer is formed on the hard coat layer.

Moreover, it is preferable that the manufacturing method of the optical laminated body of this invention has the process of forming a low refractive index layer further on the hard-coat layer formed through the process mentioned above.
By forming a low refractive index layer on the hard coat layer containing the high refractive index resin A and the high refractive index resin B, a plurality of layers having different refractive indexes can be formed to further improve the antireflection performance. . The low refractive index layer preferably has a refractive index of less than 1.50, more preferably 1.45 or less.

The low refractive index layer is composed of 1) a resin containing silica or magnesium fluoride, 2) a fluorine resin which is a low refractive index resin, 3) a fluorine resin containing silica or magnesium fluoride, 4) silica or fluorine. You may be comprised with either of the thin films of magnesium halide.

The fluororesin is a polymerizable compound containing at least a fluorine atom in the molecule or a polymer thereof. Although it does not specifically limit as a polymeric compound, For example, what has hardening reactive groups, such as a functional group (ionizing radiation hardening group) hardened by ionizing radiation, and a polar group (thermosetting polar group) hardened by heat preferable. Moreover, the compound which has these reactive groups simultaneously may be sufficient.

As the polymerizable compound having an ionizing radiation curable group containing a fluorine atom, fluorine-containing monomers having an ethylenically unsaturated bond can be widely used. More specifically, exemplify fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) Can do. As having a (meth) acryloyloxy group, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) Ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, α-trifluoromethacryl (Meth) acrylate compounds having fluorine atoms in the molecule, such as methyl acrylate and ethyl α-trifluoromethacrylate; C 1-14 fluoroalkyl groups having at least 3 fluorine atoms in the molecule, fluorocyclo An alkyl group or a fluoroalkylene group and at least two (meta And fluorine-containing polyfunctional (meth) acrylic acid ester compounds having an acryloyloxy group.

Examples of the polymerizable compound having a thermosetting polar group containing a fluorine atom include 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer; fluoroethylene-hydrocarbon vinyl ether copolymer; epoxy, polyurethane, cellulose, Examples include fluorine-modified products of resins such as phenol and polyimide. As said thermosetting polar group, hydrogen bond forming groups, such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, are mentioned preferably, for example. These are excellent not only in adhesion to the coating film but also in affinity with inorganic ultrafine particles such as silica.

Polymerizable compounds having both ionizing radiation curable groups and thermosetting polar groups (fluorinated resins) include acrylic or methacrylic acid moieties and fully fluorinated alkyl, alkenyl, aryl esters, fully or partially fluorinated vinyl ethers. Examples thereof include fully or partially fluorinated vinyl esters, fully or partially fluorinated vinyl ketones, and the like.

Examples of the polymer of the polymerizable compound containing a fluorine atom include a polymer of a monomer or a monomer mixture containing at least one fluorine-containing (meth) acrylate compound of the polymerizable compound having the ionizing radiation curable group; At least one fluorine (meth) acrylate compound and a fluorine atom in a molecule such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Copolymers with (meth) acrylate compounds not containing; fluoroethylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3, 3,3-trifluoropropylene, hex Homopolymers and copolymers of fluorine-containing monomers such as hexafluoropropylene; and the like.

Moreover, the silicone containing vinylidene fluoride copolymer which made these copolymers contain a silicone component can also be used as a polymer of the said polymeric compound. Examples of silicone components in this case include (poly) dimethylsiloxane, (poly) diethylsiloxane, (poly) diphenylsiloxane, (poly) methylphenylsiloxane, alkyl-modified (poly) dimethylsiloxane, azo group-containing (poly) dimethylsiloxane, , Dimethyl silicone, phenylmethyl silicone, alkyl aralkyl modified silicone, fluorosilicone, polyether modified silicone, fatty acid ester modified silicone, methyl hydrogen silicone, silanol group containing silicone, alkoxy group containing silicone, phenol group containing silicone, methacryl modified silicone, Acrylic modified silicone, amino modified silicone, carboxylic acid modified silicone, carbinol modified silicone, epoxy modified silicone, mercapto modified silicone Corn, fluorine-modified silicones, polyether-modified silicones and the like. Among them, those having a dimethylsiloxane structure are preferable.

In addition to the above, a fluorine-containing compound having at least one isocyanato group in the molecule, and a compound having at least one functional group in the molecule that reacts with an isocyanato group such as an amino group, a hydroxyl group, or a carboxyl group A compound obtained by reacting a fluorine-containing polyether polyol, a fluorine-containing alkyl polyol, a fluorine-containing polyester polyol, a fluorine-containing polyol such as a fluorine-containing ε-caprolactone-modified polyol, and a compound having an isocyanato group. Compounds; etc. can also be used as the fluororesin.

In forming the low refractive index layer, for example, it can be formed using a composition containing a raw material component (a composition for forming a low refractive index layer). More specifically, a raw material component (resin, etc.) and, if necessary, an additive (for example, “fine particles having voids” described later, a polymerization initiator, an antistatic agent, an antiglare agent, etc.) are dissolved or dispersed in a solvent The resulting solution or dispersion is used as a composition for forming a low refractive index layer, a coating film is formed from the composition on the hard coat layer, and the coating film is cured to obtain a low refractive index layer. be able to. In addition, as additives, such as a polymerization initiator, the thing similar to what is used by a hard-coat layer can be used, for example. As the antistatic agent and the antiglare agent, those known in the technical field of optical laminates can be used.

Examples of the solvent include water, alcohol (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone). , Heptanone, diisobutyl ketone, diethyl ketone), esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate, PGMEA), aliphatic hydrocarbons (eg, hexane, Cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n -Methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol) and the like. Of these, methyl isobutyl ketone, methyl ethyl ketone, isopropyl alcohol (IPA), n-butanol, s-butanol, t-butanol, PGME, and PGMEA are preferable.

In the low refractive index layer, it is preferable to use “fine particles having voids” as the low refractive index agent. The “fine particles having voids” can lower the refractive index while maintaining the layer strength of the low refractive index layer. In the present invention, the term “fine particles having voids” refers to a structure in which a gas is filled with gas and / or a porous structure containing gas, and the gas in the fine particle is compared with the original refractive index of the fine particle. It means fine particles whose refractive index decreases in inverse proportion to the occupation ratio. The present invention also includes fine particles capable of forming a nanoporous structure inside and / or at least part of the surface depending on the form, structure, aggregated state, and dispersed state of the fine particles inside the coating. . The low refractive index layer using these fine particles can adjust the refractive index to 1.30 to 1.45.

Examples of the inorganic fine particles having voids include the production methods described in JP-A-2001-233611, JP-A-7-133105, JP-A-2002-79616, JP-A-2006-106714, and the like. Examples thereof include silica fine particles to be obtained. Since the silica fine particles having voids are easy to manufacture and have high hardness itself, when mixed with a binder to form a low refractive index layer, the layer strength is improved and the refractive index is 1.20 to 1. It can be adjusted within a range of about .45.
Specific examples of the organic fine particles having voids include hollow polymer fine particles prepared by using the technique disclosed in JP-A-2002-80503.

The fine particles capable of forming a nanoporous structure inside and / or at least a part of the surface of the coating are manufactured for the purpose of increasing the specific surface area in addition to the silica fine particles, and the packing column and the porous surface Examples include a release material that adsorbs various chemical substances on the part, a porous fine particle used for catalyst fixation, a dispersion or aggregate of hollow fine particles intended to be incorporated into a heat insulating material or a low dielectric material. Specifically, as a commercial product, an assembly of porous silica fine particles from the product names Nippil and Nipgel manufactured by Nippon Silica Industry Co., Ltd., and a structure in which silica fine particles manufactured by Nissan Chemical Industries, Ltd. are connected in a chain form. From the colloidal silica UP series (trade name), it is possible to use those within the preferred particle diameter range of the present invention.

The average particle diameter of the “fine particles having voids” is preferably 5 nm to 300 nm, more preferably 8 nm to 100 nm, and still more preferably 10 nm to 80 nm. When the average particle diameter of the fine particles is within this range, it is possible to impart excellent transparency to the hard coat layer. The average particle diameter is a value measured by a dynamic light scattering method. The “fine particles having voids” are usually about 0.1 to 500 parts by mass, preferably about 10 to 200 parts by mass with respect to 100 parts by mass of the matrix resin in the low refractive index layer.

The preparation method of the said composition for low refractive index layer formation should just be able to mix the above-mentioned component uniformly, and should just implement it according to a well-known method. For example, it can mix using the well-known apparatus mentioned above in formation of the said hard-coat layer.

In the formation of the low refractive index layer, the viscosity of the low refractive index layer forming composition is preferably in the range of 0.5 to 5 cps (25 ° C.) at which preferable coatability is obtained. An antireflection film excellent in visible light can be realized, a uniform thin film with no coating unevenness can be formed, and a low refractive index layer particularly excellent in adhesion to a substrate can be formed. The viscosity is more preferably 0.7 to 3 cps (25 ° C.).

As a method for forming the coating film by applying the composition for forming a low refractive index layer on the hard coat layer, a known method may be followed. For example, various methods similar to the coating method of the resin composition in forming the hard coat layer can be used.

Examples of the method for curing the coating film include the same method as the method for curing the resin composition in the formation of the hard coat layer. When a heating means is used for the curing treatment, it is preferable to add a thermal polymerization initiator that generates, for example, a radical by heating to start polymerization of the polymerizable compound, to the fluororesin composition.

The film thickness (nm) d _A of the low refractive index layer is expressed by the following formula (I):
d _A = mλ / (4n _A ) (I)
(In the above formula,
n _A represents the refractive index of the low refractive index layer;
m represents a positive odd number, preferably 1;
λ is a wavelength, preferably a value in the range of 480 to 580 nm)
Those satisfying these conditions are preferred.

In the present invention, the low refractive index layer has the following formula (II):
_{120 <n A d A <145} (II)
It is preferable from the viewpoint of low reflectivity.

The optical laminate obtained by the method for producing an optical laminate of the present invention has a hard coat layer on an optically transparent substrate, and optionally an antistatic layer or a low refractive index layer. An arbitrary layer may be provided with an antifouling layer, an antiglare layer, a medium refractive index layer and the like. The antifouling layer, the antiglare layer, and the medium refractive index layer are prepared by adding a commonly used antifouling agent, antiglare agent, medium refractive index agent, resin, or the like, and preparing each layer by a known method. It is good to form by.

The total light transmittance of the optical layered body is preferably 90% or more. If it is less than 90%, color reproducibility and visibility may be impaired when it is mounted on the display surface. The total light transmittance is more preferably 92% or more, and still more preferably 94% or more.

The haze value of the optical layered body is preferably 10% or less. If it exceeds 10%, color reproducibility and visibility may be impaired when mounted on the display surface. The haze value is more preferably 5% or less. 1% or less is more preferable.

One mode of the optical layered body will be described with reference to the drawings. FIG. 1 shows an optical laminate including a low refractive index layer 1, a hard coat layer 2, and a light-transmitting substrate 3 in order from the top. An optical laminate obtained by such a method for producing an optical laminate of the present invention is also one aspect of the present invention. In addition to such an aspect, the optical layered body may be composed of any layer depending on the purpose, and is not limited to the above-described aspect.

A polarizing plate can be obtained by providing the optical layered body on the surface of the polarizing element on the surface opposite to the surface where the hard coat layer is present in the optical layered body. Such a polarizing plate is also one aspect of the present invention.

The polarizing element is not particularly limited, and for example, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, etc. dyed and stretched with iodine or the like can be used. In the laminating process of the polarizing element and the optical laminate of the present invention, it is preferable to saponify the light-transmitting substrate (preferably a triacetyl cellulose film). By the saponification treatment, the adhesiveness is improved and an antistatic effect can be obtained.

The present invention is also an image display device including the optical laminate or the polarizing plate on the outermost surface. The image display device may be a non-self-luminous image display device such as an LCD, or a self-luminous image display device such as a PDP, FED, ELD (organic EL, inorganic EL), or CRT.

An LCD that is a typical example of the non-self-luminous type includes a transmissive display and a light source device that irradiates the transmissive display from the back. When the image display device of the present invention is an LCD, the optical laminate of the present invention or the polarizing plate of the present invention is formed on the surface of this transmissive display.

In the case where the present invention is a liquid crystal display device having the optical laminate, the light source of the light source device is irradiated from the lower side of the optical laminate. Note that in the STN liquid crystal display device, a retardation plate may be inserted between the liquid crystal display element and the polarizing plate. An adhesive layer may be provided between the layers of the liquid crystal display device as necessary.

The PDP, which is the self-luminous image display device, has a front glass substrate (electrodes are formed on the surface) and a rear glass substrate (electrodes and minute electrodes) disposed with a discharge gas sealed between the front glass substrate and the front glass substrate. Are formed on the surface, and red, green, and blue phosphor layers are formed in the groove). When the image display device of the present invention is a PDP, the above-mentioned optical laminate is provided on the surface of the surface glass substrate or the front plate (glass substrate or film substrate).

The self-luminous image display device is an ELD device that emits light when a voltage is applied, such as zinc sulfide or a diamine substance: a phosphor is deposited on a glass substrate, and the voltage applied to the substrate is controlled. It may be an image display device such as a CRT that converts light into light and generates an image visible to the human eye. In this case, the optical laminated body described above is provided on the outermost surface of each display device as described above or the surface of the front plate.

In any case, the image display apparatus of the present invention can be used for display display of a television, a computer, a word processor, or the like. In particular, it can be suitably used for the surface of high-definition image displays such as CRT, liquid crystal panel, PDP, ELD, FED and the like.

Since the method for producing an optical laminate of the present invention includes a step of forming a hard coat layer on the above-described light-transmitting substrate, an optical laminate having excellent visibility, in which interface reflection and interference fringes are suppressed. Can be manufactured. The optical laminate manufactured by the present invention is suitably applied to a cathode ray tube display (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED) and the like. be able to.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, the content of this invention is limited to these embodiments and is not interpreted.

(Production Example 1 Preparation of Resin Composition 1)
The composition shown below was mixed and the resin composition 1 was prepared.
Urethane acrylate (UV1700B, manufactured by Nihon Gosei) 5 parts by mass high refractive index resin A (A-REN-10, manufactured by Shin-Nakamura Chemical Co., Ltd., Mw268) 2.5 parts by mass high refractive index resin B (R1403, manufactured by Daiichi Kogyo Seiyaku, Mw1500) 2.5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 2 Preparation of Resin Composition 2)
The composition shown below was mixed and the resin composition 2 was prepared.
Dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku) 5 parts by mass high refractive index resin A (A-REN-10, Shin-Nakamura Chemical, Mw268) 2.5 parts by mass high refractive index resin B (R1403, Daiichi Mw 1500, manufactured by Kogyo Seiyaku Co., Ltd. 2.5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 3 Preparation of Resin Composition 3)
The composition shown below was mixed and the resin composition 3 was prepared.
Urethane acrylate (UV1700B, manufactured by Nippon Gosei Co., Ltd.) 2.5 parts by mass Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 2.5 parts by mass high refractive index resin A (A-REN-10, manufactured by Shin-Nakamura Chemical, Mw268 ) 2.5 parts by mass high refractive index resin B (R1403, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Mw 1500) 2.5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 4 Preparation of Resin Composition 4)
The composition shown below was mixed and the resin composition 4 was prepared.
Urethane acrylate (BS577, manufactured by Arakawa Chemical) 2.5 parts by mass pentaerythritol tetraacrylate (PET30, manufactured by Nippon Kayaku) 2.5 parts by mass high refractive index resin A (A-REN-10, manufactured by Shin-Nakamura Chemical Co., Mw268) 2.5 parts by mass high refractive index resin B (R1403, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Mw 1500) 2.5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 5 Preparation of Resin Composition 5)
The composition shown below was mixed and the resin composition 5 was prepared.
Urethane acrylate (UV1700B, manufactured by Nihon Gosei) 5 parts by mass High refractive index resin A (EX142, manufactured by Nagase ChemteX, Mw226) 2.5 parts by mass High refractive index resin B (HRR2, Showa Ink, Mw1500) 2.5 parts by mass Polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 6 Preparation of Resin Composition 6)
The composition shown below was mixed and the resin composition 6 was prepared.
Urethane acrylate (UV1700B, Nippon Synthetic 7 mass parts high refractive index resin A (A-REN-10, Shin-Nakamura Chemical, Mw268) 1.5 mass parts high refractive index resin B (R1403, Daiichi Kogyo Seiyaku, Mw1500) ) 1.5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 7 Preparation of Resin Composition 7)
The composition shown below was mixed and the resin composition 7 was prepared.
Dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku) 3 parts by mass high refractive index resin A (A-REN-10, Shin-Nakamura Chemical, Mw268) 3.5 parts by mass high refractive index resin B (R1403, Daiichi Kogyo Seiyaku, Mw 1500) 3.5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 8 Preparation of Resin Composition 1 ′)
The composition shown below was mixed to prepare a resin composition 1 ′.
Urethane acrylate (UV1700B, manufactured by Nippon Gosei Co., Ltd.) 5 parts by mass high refractive index resin B (R1403, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Mw 1500) 5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 9 Preparation of Resin Composition 2 ′)
The composition shown below was mixed to prepare a resin composition 2 ′.
Dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku) 5 parts by mass high refractive index resin B (R1403, Daiichi Kogyo Seiyaku, Mw 1500) 5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 10 Preparation of Resin Composition 3 ′)
The composition shown below was mixed to prepare a resin composition 3 ′.
Urethane acrylate (UV1700B, manufactured by Nippon Gosei Co., Ltd.) 5 parts by mass high refractive index resin A (A-REN-10, manufactured by Shin-Nakamura Chemical Co., Ltd., Mw268) 5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 11 Preparation of Resin Composition 4 ′)
The composition shown below was mixed to prepare a resin composition 4 ′.
Dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku) 5 parts by mass high refractive index resin A (A-REN-10, Shin-Nakamura Chemical, Mw268) 5 parts by mass polymerization initiator (Irgacure 184; Ciba Specialty Chemicals) (Made by company)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 12 Preparation of Resin Composition 5 ′)
The composition shown below was mixed to prepare a resin composition 5 ′.
Urethane acrylate (UV1700B, manufactured by Nihon Gosei) 2.5 parts by mass Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku) 2.5 parts by mass High refractive index resin B (R1403, Daiichi Kogyo Seiyaku, Mw1500) 5 masses Partial polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 13 Preparation of Resin Composition 6 ′)
The composition shown below was mixed to prepare a resin composition 6 ′.
Urethane acrylate (UV1700B, manufactured by Nippon Gosei Co., Ltd.) 2.5 parts by mass Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 2.5 parts by mass high refractive index resin A (A-REN-10, manufactured by Shin-Nakamura Chemical, Mw268 ) 5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 14 Preparation of Resin Composition 7 ′)
The composition shown below was mixed to prepare a resin composition 7 ′.
Urethane acrylate (UV1700B, manufactured by Nippon Gosei Co., Ltd.) 0.5 parts by mass Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 0.5 parts by mass High refractive index resin A (A-REN-10, manufactured by Shin-Nakamura Chemical Co., Mw268) ) 4.5 parts by mass high refractive index resin B (R1403, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Mw 1500) 4.5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFuck MCF350-5) 0.2 parts by weight methyl ethyl ketone 10 parts by weight

(Production Example 15 Preparation of Resin Composition 8 ′)
The composition shown below was mixed to prepare a resin composition 8 ′.
Urethane acrylate (UV1700B, manufactured by Nippon Gosei Co., Ltd.) 2.5 parts by mass Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 2.5 parts by mass high refractive index resin B (R1403, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Mw1500) 5 parts by mass high refractive index resin A (A-REN-10, Shin-Nakamura Chemical, Mw268) 2.5 parts by mass polymerization initiator (Irgacure 184; manufactured by Ciba Specialty Chemicals)
0.4 parts by weight leveling agent (Dainippon Ink, MegaFac MCF350-5) 0.2 parts by weight Toluene 10 parts by weight

Example 1
A triacetylcellulose (TAC) film (manufactured by Fuji Photo Film, TF80UL, thickness 80 microns) is prepared as a light-transmitting substrate, and the resin composition 1 prepared on the surface of this film has a wet weight of 26 g / m ^2. A resin layer was formed by coating (bar coating) at a dry weight of 13 g / m ² , and then the solvent was removed by drying at 50 ° C. Thereafter, the resin layer formed using the resin composition 1 is cured by irradiating with ultraviolet rays at an irradiation dose of 50 mJ / cm ² using an ultraviolet irradiation device (manufactured by Fusion UV System Japan Co., Ltd.). And an optical laminate was produced. The film thickness was formed so that the minimum value of the reflectance was around a wavelength of 550 nm (film thickness of 0.10 μm).

(Examples 2-7, Comparative Examples 1-8)
Except having changed the resin composition 1 into the resin compositions 2-7 and 1'-8 ', it manufactured the optical laminated body which concerns on Examples 2-7 and Comparative Examples 1-8 similarly to Example 1. .

(Evaluation)
The following evaluation was performed about each optical laminated body obtained by Examples 1-7 and Comparative Examples 1-8. The results are shown in Table 1.

(With or without interference fringes)
A black tape for preventing back surface reflection is applied to the surface opposite to the hard coat layer of each optical laminate obtained in Examples 1 to 7 and Comparative Examples 1 to 8, and each optical laminate is formed from the surface of the hard coat layer. The body was visually observed with a three-wavelength fluorescent lamp, and the presence or absence of interference fringes was evaluated according to the following criteria.
○: No interference fringes were generated.
X: Interference fringes were generated.

(Evaluation of antireflection effect)
First, on the hard coat layer of the optical laminate produced in Examples 1 to 7 and Comparative Examples 1 to 8, using a low refractive index resin composition having the following composition, a thickness (Dry) of 0.10 microns It laminated | stacked so that it might become.
<Low refractive index resin composition>
Treated silica fine particles “having voids” (solid content of the silica fine particles is 20% by mass solution; methyl isobutyl ketone, particle size 50 nanometers) 11.5 parts by mass Pentaerythritol triacrylate (PETA) 1.58 parts by mass polymerization start Agent (Irgacure 127; manufactured by Ciba Specialty Chemicals)
0.1 parts by mass silicone oil (X22164E; manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 parts by mass methyl isobutyl ketone 32 parts by mass PGME 20 parts by mass

<Measurement of reflectance>
The reflection Y value is calculated with software (built-in MPC3100) that measures 5 ° specular reflectance in the wavelength range from 380 to 780 nm with an MPC3100 spectrophotometer manufactured by Shimadzu Corp. This is a value indicating the luminous reflectance. In addition, when measuring 5 degree regular reflectance, in order to prevent the back surface reflection of the film which is an optical laminated body, it measured by sticking a black tape (made by Teraoka) on the opposite side to a measurement film surface. Evaluation was performed according to the following criteria.
A: Reflectance was less than 1.2% B: Reflectance was 1.2% or more

(Pencil hardness test)
Each optical laminate having the low refractive index layer formed by the above-described method is conditioned for 2 hours under conditions of a temperature of 25 ° C. and a relative humidity of 60%, and then a test pencil (hardness H) specified by JIS-S-6006 is used. Using, according to the pencil hardness evaluation method prescribed | regulated by JISK5600-5-4 (1999), it implemented by the load of 4.9N and evaluated by the following evaluation criteria.
Evaluation ○: No scratch / number of measurements = 4/5, 5/5
Evaluation x: No scratch / number of measurements = 0/5, 1/5, 2/5, 3/5

From Table 1, the optical laminated body of the example did not generate interference fringes, and the pencil strength antireflection performance was good, whereas the optical laminated body of the comparative example had interference fringes. Some were generated and had poor pencil hardness.

The optical laminate obtained by the method for producing an optical laminate of the present invention includes a cathode ray tube display (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), and a field emission display (FED). It can apply suitably to.

It is an example of the schematic diagram of the optical laminated body of this invention.

Explanation of symbols

1 Low refractive index layer 2 Hard coat layer 3 Light transmissive substrate

Claims (12)

A method for producing an optical laminate having a light-transmitting substrate and a hard coat layer,
A high refractive index resin A having a weight average molecular weight of 200 or more and less than 1,000, a high refractive index resin B having a weight average molecular weight of 1,000 or more and less than 100,000, a penetrating solvent, and a binder resin. A resin composition in which the total amount of the high refractive index resin A and the high refractive index resin B in the resin component is 10 to 80% by mass (solid content ratio) is applied onto the light-transmitting substrate, and It has a step of forming a hard coat layer,
The method for manufacturing an optical laminate, wherein the high refractive index resin A and the high refractive index resin B have a refractive index of 1.55 to 1.65 . The content ratio of the high refractive index resin A and the high refractive index resin B (high refractive index resin A / high refractive index resin B) is (95/5) to (5/95) in terms of solid content mass ratio. A method for producing an optical laminate according to 1 . 3. The optical laminate according to claim 1, wherein the permeable solvent is at least one selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone, and methylene chloride. Method. The binder resin has a refractive index of less than 1.55 and a weight average molecular weight of 200 or more and less than 1000, a resin 1 having a refractive index of less than 1.55 and a weight average molecular weight of 1,000 or more and 100,000. The manufacturing method of the optical laminated body of Claim 1, 2 or 3 containing the resin 2 which is the following. 5. The resin composition according to claim 1, 2, 3 or 4 , further comprising an oxide of at least one element selected from the group consisting of silicon, aluminum, titanium, zinc, germanium, indium, tin and antimony. Manufacturing method of optical laminated body. The method for producing an optical laminate according to claim 1, 2, 3, 4, or 5 , wherein the resin composition further comprises an antistatic agent. Light transmitting substrate, a manufacturing method of claim 1, 2, 3, 4, 5 or 6 optical laminate according with an antistatic layer on the surface to form a hard coat layer. Light transmitting substrate, according to claim 1,2,3,4,5 triacetyl cellulose, 6 or 7 method of producing an optical laminate according. An optical laminate obtained by the method for producing an optical laminate according to claim 1, 2, 3, 4, 5, 6, 7 or 8 . A self-luminous image display device comprising the optical laminate according to claim 9 on an outermost surface. A polarizing plate comprising a polarizing element,
The said polarizing plate is equipped with the optical laminated body of Claim 9 on a polarizing element surface, The polarizing plate characterized by the above-mentioned. A non-self-luminous image display device comprising the optical laminate according to claim 9 or the polarizing plate according to claim 11 on an outermost surface.

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