JP2007264277A - Optical laminate provided with low refractive index layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical laminate provided with both of antifouling property and a lubricating property in a low refractive index layer. <P>SOLUTION: The optical laminate is provided with at least a low refractive index layer on a light transmission substrate, wherein the low refractive index layer contains an antifouling agent and/or a lubricity giving agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an optical laminate comprising at least a low refractive index layer.

  An image display surface in an image display device such as a liquid crystal display (LCD) or a cathode ray tube display device (CRT) is required to reduce reflection due to light rays emitted from an external light source and to improve its visibility. On the other hand, by using an optical laminate (for example, an antireflection laminate) in which an antireflection layer is formed on a light transmissive substrate, reflection on the image display surface of the image display device is reduced and visibility is improved. It is generally made to improve.

  Conventionally, it has been pointed out that the outermost surface of an optical layered body is exposed to various use environments, is easily scratched, and easily adheres to dirt. On the other hand, Japanese Patent Application Laid-Open No. 10-104403 (Patent Document 1) proposes an optical laminate in which a hard coat layer is added with a stain proofing agent in order to improve the scratch resistance and contamination prevention of the image display surface. Has been.

  However, as a result of confirmation by the present inventors, an optical layered body having both antifouling properties and slipperiness in a low refractive index layer formed on a light-transmitting substrate has not been proposed yet.

Japanese Patent Laid-Open No. 10-104403

  The inventors obtained knowledge that, at the time of the present invention, a low refractive index layer having both antifouling property and slipperiness can be formed by including a specific component in the low refractive index layer. It was. Accordingly, an object of the present invention is to provide an optical layered body in which antifouling properties and slip properties are imparted to a low refractive index layer.

Therefore, the optical laminate according to the present invention is
Comprising at least a low refractive index layer on the light transmissive substrate;
The low refractive index layer comprises a stainproofing agent and / or a slipperiness imparting agent.

Optical laminate 1. Low refractive index layer
Antifouling agent and / or slipperiness imparting agent Examples of the antifouling agent and / or slipperiness imparting agent include silicon compounds, fluorine compounds, and mixed compounds thereof.

（上記式中、
Ｒは、疎水基として、メチル基、フッ素原子、アクリル基、又はメタクリル基であり、親水基として、水酸基、カルボキシル基、ポリエーテル基、又はエポキシ基であり、或いはこれらの混合基であってよく、
Ｒ^１はアルキル基、好ましくは炭素数１〜２０のアルキル基、より好ましくは炭素数１〜１０のアルキル基であり、
Ｘは０〜１２００であり、
Ｙは０〜１２００である。）
で表されるものが挙げられる。 In the present invention, the silicon compound is preferably a compound in which the terminal or side chain of the compound is modified. Examples of such silicon compounds include the following general formulas (I) to (III) or (IV):

(In the above formula,
R may be a methyl group, a fluorine atom, an acrylic group, or a methacryl group as a hydrophobic group, and may be a hydroxyl group, a carboxyl group, a polyether group, or an epoxy group as a hydrophilic group, or a mixed group thereof. ,
R ¹ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms,
X is 0 to 1200,
Y is 0-1200. )
The thing represented by is mentioned.

In the present invention, the fluorine compound is
Specific examples of the fluorine-based compound include a general formula:
(A) w- (B) x- (D) y-CF ₃
(In the above formula,
A represents one or more groups selected from the group consisting of CF ₂ , CFCF ₂ , and C (CF ₂ ) ₂ ;
B is OCF ₂ CF ₂ , OCF ₂ CF (CF ₂ ), OCF ₂ C (CF ₂ ) ₂ ,
OCF (CF ₂ ) CF (CF ₂ ), OCF (CF ₂ ) C (CF ₂ ) ₂ ,
Represents one or more groups selected from the group consisting of OC (CF ₂ ) ₂ CF (CF ₂ ), OC (CF ₂ ) ₂ C (CF ₂ ) ₂ ;
D represents one or more groups selected from the group consisting of OCH ₂ CH ₂ , OCH ₂ CH ₂ CH ₂ , OC (O) (CH ₂ ) z;
w, x, y, and z represent numbers greater than 0 and less than or equal to 50. )
The thing represented by is mentioned.

  Examples of the antifouling agent and / or slipperiness-imparting agent include polyfunctional acrylates containing two or more functional groups containing polyorganosiloxane groups, polyorganosiloxane-containing graft polymers, polyorganosiloxane-containing block polymers, fluorinated alkyl groups, and the like. Those comprising are preferred. Examples of the polyfunctional acrylate include tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 1,3-butane. Diol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, neopentyl glycol di (meth) acrylate, pro Xylated neopentyl glycol di (meth) acrylate, pentaerythritol diacrylate monostearate, isocyanuric acid ethoxy modified di (meth) acrylate (isocyanuric acid EO modified di (meth) acrylate), bifunctional urethane acrylate, bifunctional polyester acrylate, etc. Is mentioned. Trifunctional acrylates include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, ethoxylated trimethylolpropane tri Examples include (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, and trifunctional polyester acrylate. Examples of the tetrafunctional acrylate include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and ethoxylated pentaerythritol tetra (meth) acrylate. Examples of the pentafunctional or higher acrylate include dipentaerythritol hydroxypenta (meth) acrylate and dipentaerythritol hexaacrylate. Moreover, urethane acrylates of 9, 10, 12, 15 functional groups and the like can be mentioned.

Antifouling agents and / or slipperiness-imparting agents are available as commercial products. For example, as silicon compounds, X22176F, X22164E, X223710, X22162C, X223710E, X22160AS, X224015, X22170DX, X22176DX, KF8001, X22163A, X22173DX, X22163C, X22164A, X248201, X22174DX, X22164C, X222426, X222445, X222457, X22259, X222458, X221602, X221603 (manufactured by Shin-Etsu Chemical Co., Ltd.). Also, FS1265, BY16750, BY16880, BY16848, SF8427, SF8411, SF8413, SF8421, BY16152D, BY16152, BY16152C, 8388A, (manufactured by Toray Dow Corning Co., Ltd.), FM0425, FM4421, M7725, M7725 , FM7727 (manufactured by Chisso Corporation). SUA1900L10 (weight average molecular weight 4200; manufactured by Shin-Nakamura Chemical Co., Ltd.), SUA1900L6 (weight average molecular weight 2470; manufactured by Shin-Nakamura Chemical Co., Ltd.), Ebecryl 1360 (manufactured by Daicel UCB), UT3971 (manufactured by Nippon Gosei Co., Ltd.), Daifensa TF3001 (Dainippon) Ink Co., Ltd.), Difensa TF3000 (Dainippon Ink Co., Ltd.), Difensa TF3028 (Dainippon Ink Co., Ltd.), KRM7039 (Daicel UCB Co., Ltd.), and Light Procoat AFC3000 (Kyoeisha Chemical Co., Ltd.).
In the present invention, another reactive antifouling agent and / or slipperiness imparting agent that is reactive is available as a commercial product, for example, KNS5300 (manufactured by Shin-Etsu Silicone), UVHC1105 (manufactured by GE Toshiba Silicone) UVHC8550 (manufactured by GE Toshiba Silicone), Ebecryl350 (manufactured by Daicel UCB), and ACS-1122 (manufactured by Nippon Paint Co., Ltd.).

  The antifouling agent and / or slipperiness imparting agent has a number average molecular weight of 500 or more and 200,000 or less, preferably a lower limit of 2500 or more, more preferably 5000 or more, and preferably an upper limit of 20,000 or less. Yes, more preferably 10,000 or less.

  The addition amount of the antifouling agent and / or slipperiness imparting agent is 0.1% by weight or more and 20% by weight or less with respect to the total weight of the composition forming the low refractive index layer, preferably the lower limit is 2% by weight. Or more, more preferably 3% by weight or more, preferably the upper limit is 5% by weight or less, more preferably 4% by weight or less.

Low refractive index agent The low refractive index agent has a lower refractive index than the antiglare layer. According to a preferred embodiment of the present invention, the refractive index of the antiglare layer is 1.5 or more, and the refractive index of the low refractive index agent is less than 1.5, preferably 1.45 or less. Is preferred.

  Specific examples of the low refractive index agent include a silicone-containing vinylidene fluoride copolymer, and examples thereof include a monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene. Examples thereof include a composition comprising 100 parts by weight of a fluorine-containing copolymer having a fluorine content ratio of 60 to 70% by weight and 80 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group.

  Examples of the fluorine-containing copolymer include a copolymer obtained by copolymerizing a monomer composition containing vinylidene fluoride and hexafluoropropylene. The proportion of each component in the monomer composition is 30 to 90% by weight of vinylidene fluoride, preferably 40 to 80% by weight, particularly preferably 40 to 70% by weight, or 5 to 50% by weight of hexafluoropropylene. , Preferably 10 to 50% by weight, particularly preferably 15 to 45% by weight. This monomer composition may further contain 0 to 40% by weight, preferably 0 to 35% by weight, particularly preferably 10 to 30% by weight of tetrafluoroethylene.

  The monomer composition for obtaining this fluorine-containing copolymer contains other copolymer components in an amount of, for example, 20% by weight or less, preferably 10% by weight or less as required. May be. Specific examples of this copolymer include fluoroethylene, trifluoroethylene, chlorotrifluoroethylene, 1, 2-dichloro-1, 2-difluoroethylene, 2-bromo-3, 3, 3-trifluoroethylene, 3- Polymerization having fluorine atoms such as bromo-3, 3-difluoropropylene, 3, 3, 3-trifluoropropylene, 1, 1, 2-trichloro-3, 3, 3-trifluoropropylene, α-trifluoromethacrylic acid, etc. Mention may be made of monomers.

  The fluorine content of the fluorine-containing copolymer obtained from such a monomer composition is preferably 60 to 70% by weight, more preferably 62 to 70% by weight, and particularly preferably 64 to 68% by weight. When the addition ratio is in such a range, it has good solubility in the solvent. Alternatively, by including a fluorine-containing copolymer as a component, it is possible to form an optical laminate having excellent adhesion, high transparency, low refractive index, and excellent mechanical strength. It becomes.

  The molecular weight of the fluorine-containing copolymer is preferably 5,000 to 200,000, particularly 10,000 to 100,000, in terms of polystyrene-equivalent number average molecular weight. By using a fluorine-containing copolymer having such a molecular weight, the viscosity of the resulting fluorine-based resin composition becomes a suitable size, and therefore surely has a suitable coating property. It can be.

  The refractive index of the fluorine-containing copolymer itself is 1.45 or less, preferably 1.42 or less, more preferably 1.40 or less. When the refractive index is in this range, the antireflection effect of the formed optical laminate is preferable.

  The amount of the resin added is 30 to 150 parts by weight, preferably 35 to 100 parts by weight, particularly preferably 40 to 70 parts by weight, based on 100 parts by weight of the fluorine-containing copolymer. Moreover, it is preferable that the fluorine content rate in the total amount of the polymer formation component containing a fluorine-containing copolymer and resin is 30 to 55 weight%, Preferably it is 35 to 50 weight%. When the addition amount or the fluorine content is in the above-described range, the adhesion of the surface adjustment layer to the base material becomes good, and a high antireflective effect with a high refractive index can be obtained.

  According to a preferred embodiment of the present invention, it is preferable to use “fine particles having voids” as the low refractive index agent. The “fine particles having voids” can reduce the refractive index while maintaining the layer strength of the surface adjustment 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, aggregation state, and dispersion state of the fine particles inside the coating film. It is. Further, according to a preferred embodiment of the present invention, “fine particles having voids” can be preferably used after being treated with a solvent. For example, fine particles having voids treated by applying a 20% methyl isobutyl ketone solution can be used.

  As specific examples of the inorganic fine particles having voids, silica fine particles prepared by using the technique disclosed in Japanese Patent Application Laid-Open No. 2001-233611 are preferably exemplified. Since silica fine particles having voids are easy to manufacture and have high hardness, when a low refractive index layer is formed by mixing with a binder, the layer strength is improved and the refractive index is 1.20-1. It is possible to prepare within the range of about 45. In particular, as specific examples of the organic fine particles having voids, hollow polymer fine particles prepared by using the technique disclosed in JP-A-2002-80503 are preferably exemplified.

  The fine particles capable of forming a nanoporous structure inside and / or at least part of the surface of the coating film are manufactured for the purpose of increasing the specific surface area in addition to the silica fine particles, and the packing column and the surface porosity Examples include controlled release materials that adsorb various chemical substances in the mass part, porous fine particles used for catalyst fixation, or dispersions and aggregates of hollow fine particles intended to be incorporated into heat insulating materials and low dielectric materials. it can. As such a specific example, an aggregate of porous silica fine particles and a silica fine particle manufactured by Nissan Chemical Industries, Ltd. were linked in a chain form from the product names Nippon and Nippon manufactured by Nippon Silica Kogyo Co., Ltd. as commercial products. From the colloidal silica UP series (trade name) having a structure, those within the range of the preferable particle diameter of the present invention can be used.

  The average particle diameter of the “fine particles having voids” is 5 nm or more and 300 nm or less, preferably the lower limit is 8 nm or more and the upper limit is 100 nm or less, more preferably the lower limit is 10 nm or more and the upper limit is 80 nm or less. When the average particle diameter of the fine particles is within this range, excellent transparency can be imparted to the low refractive index layer.

The resin resin is preferably transparent, and specific examples thereof include an ionizing radiation curable resin that is a resin curable by ultraviolet rays or an electron beam, a mixture of an ionizing radiation curable resin and a solvent-drying resin, or a heat There are three types of curable resins, preferably ionizing radiation curable resins.

  Specific examples of the ionizing radiation curable resin include those having an acrylate functional group, for example, a polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene having a relatively low molecular weight. Resins, polythiol polyene resins, oligomers or prepolymers such as (meth) allylates of polyfunctional compounds such as polyhydric alcohols, and reactive diluents, and specific examples thereof include ethyl (meth) acrylate, ethylhexyl (meta ) Monofunctional monomers such as acrylate, styrene, methylstyrene, N-vinylpyrrolidone and polyfunctional monomers such as polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) Acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. .

When using an ionizing radiation curable resin as an ultraviolet curable resin, it is preferable to use a photopolymerization initiator. Specific examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime esters, and thioxanthones. Further, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine and the like.
Moreover, when using ionizing radiation curable resin as an ultraviolet curable resin, a photoinitiator or a photoinitiator can be added. As the photopolymerization initiator, in the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like are used alone or in combination. In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metatheron compound, a benzoin sulfonic acid ester or the like is used alone or as a mixture as a photopolymerization initiator. . The addition amount of a photoinitiator is 0.1-10 weight part with respect to 100 weight part of ionizing radiation-curable compositions.

  The solvent-drying resin used by mixing with the ionizing radiation curable resin mainly includes a thermoplastic resin. As the thermoplastic resin, those generally exemplified are used. By adding the solvent-drying resin, coating film defects on the coated surface can be effectively prevented. According to a preferred embodiment of the present invention, when the material of the light-transmitting substrate is a cellulose resin such as TAC, preferred specific examples of the thermoplastic resin include cellulose resins such as nitrocellulose, acetylcellulose, and cellulose acetate propio. Nate, ethyl hydroxyethyl cellulose and the like.

  Specific examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin. And polysiloxane resin. When a thermosetting resin is used, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like can be further added as necessary.

When forming the polymerization initiator low refractive index layer, a photopolymerization initiator can be used, and specific examples thereof include 1-hydroxy-cyclohexyl-phenyl-ketone. This compound is commercially available, and examples thereof include trade names Irgacure 184, Irgacure 907, Irgacure 369, Irgacure 819, DAROCUR TPO (manufactured by Ciba Specialty Chemicals).

In order to form the solvent low refractive index layer, a composition in which a solvent is mixed with the above components can be used. Specific examples of the solvent include alcohols such as isopropyl alcohol, methanol and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; toluene, xylene and the like Aromatic hydrocarbons; or a mixture thereof, preferably ketones and esters.

Light-transmitting substrate The light-transmitting substrate may be transparent, translucent, colorless, or colored as long as it transmits light, but is preferably colorless and transparent. Specific examples of the light-transmitting substrate include a glass plate; triacetate cellulose (TAC), polyethylene terephthalate (PET), diacetyl cellulose, acetate butyrate cellulose, polyethersulfone, acrylic resin; polyurethane resin; polyester; polycarbonate Polysulfone; polyether; trimethylpentene; polyether ketone; thin film formed of (meth) acrylonitrile, norbornene resin, and the like. According to a preferred embodiment of the present invention, triacetate cellulose (TAC) is preferably mentioned. The thickness of the light-transmitting substrate is about 30 μm to 200 μm, preferably 40 μm to 200 μm.

Other layers
Hard Coat Layer In the present invention, it is preferable to form a hard coat layer between the light transmissive substrate and the low refractive index layer. The “hard coat layer” refers to a layer having a hardness of “H” or higher in a pencil hardness test specified by JIS 5600-5-4 (1999). The thickness of the hard coat layer (during curing) is in the range of 0.1 to 100 μm, preferably 0.8 to 20 μm. The hard coat layer is formed of a resin and an optional component.

The resin resin is preferably transparent, and specific examples thereof include an ionizing radiation curable resin that is a resin curable by ultraviolet rays or an electron beam, a mixture of an ionizing radiation curable resin and a solvent-drying resin, or a heat There are three types of curable resins, preferably ionizing radiation curable resins.

  Specific examples of the ionizing radiation curable resin include those having an acrylate functional group, for example, a polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene having a relatively low molecular weight. Examples thereof include oligomers or prepolymers such as resins, polythiol polyene resins, (meth) allylates of polyfunctional compounds such as polyhydric alcohols, and reactive diluents.

  When using an ionizing radiation curable resin as an ultraviolet curable resin, it is preferable to use a photopolymerization initiator. Specific examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylchuram monosulfide, and thioxanthones. Further, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine and the like.

  The solvent-drying resin used by mixing with the ionizing radiation curable resin mainly includes a thermoplastic resin. As the thermoplastic resin, those generally exemplified are used. By adding the solvent-drying resin, coating film defects on the coated surface can be effectively prevented. According to a preferred embodiment of the present invention, when the material of the transparent substrate is a cellulose resin such as TAC, as a preferred specific example of the thermoplastic resin, a cellulose resin such as nitrocellulose, acetylcellulose, cellulose acetate propionate, Examples thereof include ethyl hydroxyethyl cellulose.

  Specific examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin. And polysiloxane resin. When a thermosetting resin is used, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like can be further added as necessary.

2. Method for producing optical laminate
Adjustment of Composition Each liquid composition for a low refractive index layer, a hard coat layer and the like may be adjusted by mixing and dispersing the components described above according to a general preparation method. For mixing and dispersing, it is possible to appropriately disperse with a paint shaker or a bead mill.

Specific examples of the method of forming (coating) each coating composition include spin coating, dipping, spraying, die coating, bar coating, roll coater, meniscus coater, flexographic printing, screen printing, Various methods such as a peade coater method can be used.

Use of Optical Laminate The optical laminate produced by the production method according to the present invention is used as an antireflection laminate, and further has the following uses.
According to another aspect of the polarizing plate present invention, it is possible to provide a polarizing element, a polarizing plate formed and an optical laminate according to the present invention. Specifically, it is possible to provide a polarizing plate comprising the optical layered body according to the present invention on the surface of the polarizing element opposite to the surface where the low refractive index layer is present in the optical layered body.

  As the polarizing element, for example, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, which is dyed with iodine or a dye and stretched can be used. In the laminating process, it is preferable to saponify the light-transmitting substrate (preferably a triacetyl cellulose film) in order to increase adhesion or prevent electricity.

According to yet another aspect of the image display device the present invention, it is possible to provide an image display device, the image display device includes a transmissive display body, a light source device for irradiating the transparent display member from the back The optical laminated body according to the present invention or the polarizing plate according to the present invention is formed on the surface of the transmissive display body. The image display device according to the present invention may basically be composed of a light source device (backlight), a display element, and an optical laminate according to the present invention. The image display device is used for a transmissive display device, and is particularly used for display display of a television, a computer, a word processor, or the like. In particular, it is used on the surface of high-definition image displays such as CRTs and liquid crystal panels.

  When the image display device according to the present invention is a liquid crystal display device, the light source of the light source device is irradiated from the lower side of the optical laminate according to the present invention. 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.

Mode of implementation

The contents of the present invention will be described in detail with reference to the following examples, but the scope of the present invention should not be construed as being limited to these examples.
Preparation of composition for hard coat layer The components in the following composition table were sufficiently mixed in a mixer, and then filtered through a polypropylene filter having a pore size of 30 μm to prepare a composition for hard coat layer.
Composition urethane acrylate resin 5 parts by weight (Nippon Gosei Co., Ltd., UV1700B, 10 functional)
5 parts by weight of polyester acrylate resin (manufactured by Toagosei Co., Ltd., M9050, trifunctional)
Polymerization initiator: IRGACURE 184 0.5 part by weight (manufactured by Ciba Specialty Chemicals)
10 parts by weight of methyl ethyl ketone

Preparation of composition for low refractive index layer The components of the following composition tables (compositions 1 to 13 and compositions I to IV) were sufficiently mixed in a mixer, and then filtered through a polypropylene filter having a pore diameter of 30 μm. A composition was prepared.

Composition 1
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: X22164E 0.15 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.)
Methyl isobutyl ketone 83.5 parts by weight

Composition 2
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: X22176F 0.15 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.)
Methyl isobutyl ketone 83.5 parts by weight

Composition 3
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: FM7725 0.15 parts by weight (manufactured by Chisso)
Methyl isobutyl ketone 83.5 parts by weight

Composition 4
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: BY16152C 0.15 parts by weight (manufactured by Toray Dow Corning)
Methyl isobutyl ketone 83.5 parts by weight (using 20% methyl isobutyl ketone solution)

Composition 5
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: X22-164C 0.15 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.)
Methyl isobutyl ketone 83.5 parts by weight

Composition 6
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: FM0725 0.15 parts by weight (manufactured by Chisso)
Methyl isobutyl ketone 83.5 parts by weight

Composition 7
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: 0.177 parts by weight of FM7726 (manufactured by Chisso)
Methyl isobutyl ketone 83.5 parts by weight

Composition 8
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: 0.12 parts by weight of X-22-176DX (manufactured by Shin-Etsu Chemical Co., Ltd.)
Methyl isobutyl ketone 83.5 parts by weight

Composition 9
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: 0.12 parts by weight of X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.)
Methyl isobutyl ketone 83.5 parts by weight

Composition 10
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: X-22-2426 0.15 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.)
Methyl isobutyl ketone 83.5 parts by weight

Composition 11
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: X-22-3701E 0.15 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.)
Methyl isobutyl ketone 83.5 parts by weight

Composition 12
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: X-22-164E 0.1 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.)
Modified silicone oil: 0.1 part by weight of X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.)
Methyl isobutyl ketone 83.5 parts by weight

Composition 13
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: X-22-164E 0.1 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.)
Modified silicone oil: FM7726 0.1 part by weight (manufactured by Chisso Corporation)
Methyl isobutyl ketone 83.5 parts by weight

Composition 14
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: X-22-2000 0.0005 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.)
Methyl isobutyl ketone 83.6 parts by weight

Composition 15
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: SH3746 0.15 parts by weight (Toray Dow Corning)
Methyl isobutyl ketone 83.6 parts by weight

Composition 16
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: 0.15 parts by weight of TSF4460 (manufactured by GE Toshiba Silicone)
Methyl isobutyl ketone 83.6 parts by weight

Composition 17
Treated silica sol (fine particles with voids) 14.3 parts by weight (treated with 20% methyl isobutyl ketone solution)
Pentaerythritol triacrylate (PETA) 1.95 parts by weight Irgacure 369 (manufactured by Ciba Specialty Chemicals) 0.1 part by weight Modified silicone oil: SH3749 0.15 parts by weight (manufactured by Toray Dow Corning)
Methyl isobutyl ketone 83.6 parts by weight

Preparation of optical laminate
Example 1
A wet weight 30 g / m ² (dry weight 15 g / m ² ) of the composition for a hard coat layer was applied to one side of a cellulose triacetate film (thickness 80 μm). The film was dried at 50 ° C. for 30 seconds, and irradiated with ultraviolet light 50 mJ / cm ² to prepare a high refractive index hard coat layer. Next, the composition for low refractive index layer having composition 1 is dried on one surface (coating surface) of the optical laminate having a hard coat layer so that the film thickness after drying (40 ° C. × 1 minute) becomes 0.1 μm. It was applied to. Then, using an ultraviolet irradiation device (Fusion UV System Japan Co., Ltd., light source H bulb), an ultraviolet ray was irradiated at an irradiation dose of 192 mJ / m ² and cured to obtain an optical laminate. The film thickness was adjusted so that the minimum value of reflectivity was around 550 nm.

Examples 2-13
An optical laminate was prepared in the same manner as in Example 1 except that the low refractive index layer composition was replaced with the composition 1 with the composition 2 to 13, respectively.

Examples 1-4
An optical laminate was prepared in the same manner as in Example 1 except that the low refractive index layer composition was replaced with the composition 1 except that the compositions 14 to 17 were used.

The following tests were conducted on the optical laminates prepared in the evaluation test examples and comparative examples, and the results are shown in Table 1 below.
Evaluation 1: Antifouling property evaluation test Magic (trade name: Mackey: manufactured by ZEBRA) or artificial fingerprint liquid (JIS K2246) was attached to the surface of the optical laminate, and after wiping with a commercially available tissue, it was visually observed. And evaluated according to the following evaluation criteria. The artificial fingerprint liquid (JIS K2246) was a solution in which water (500 ml), methanol (500 ml), sodium chloride (7 g), urea (1 g), and lactic acid (4 g) were mixed.
Evaluation criteria Evaluation A: Magic and fingerprints were easily wiped off.
Evaluation X: Magic and fingerprint wiping were considerably difficult.

Evaluation 2: Sliding property evaluation test Water was dropped on the surface of the optical laminate, the contact angle was measured, and the presence or absence of sliding property was evaluated according to the following evaluation criteria.
Evaluation standard evaluation A: Contact angle of 90 ° or more, and smoothness was good.
Evaluation x: The contact angle was less than 90 °, and the smoothness was poor.

Example / Evaluation Evaluation 1 Evaluation 2
Example 1 ◎ ◎
Example 2 ◎ ◎
Example 3 ◎ ◎
Example 4
Example 5
Example 6
Example 7
Example 8
Example 9
Example 10
Example 11
Example 12
Example 13
Example 1 × ×
Example 2 ◎ ×
Example 3 ◎ ×
Example 4 × ×

Claims (10)

An optical laminate comprising at least a low refractive index layer on a light transmissive substrate,
The optical layered body, wherein the low refractive index layer comprises an antifouling agent and / or a slipperiness imparting agent.   The optical laminate according to claim 1, wherein the antifouling agent and / or slipperiness imparting agent is a silicon compound, a fluorine compound, or a mixture thereof. The silicon compound is represented by the following general formulas (I) to (III) or (IV):

(In the above formula,
R is a methyl group, a fluorine atom, an acrylic group, a methacryl group, a hydroxyl group, a carboxyl group, a polyether group, or an epoxy group;
R ¹ is an alkyl group;
X is 0 to 1200,
Y is 0-1200. )
The optical laminated body of Claim 1 or 2 which is represented by these. The fluorine-based compound has the following general formula:
(A) w- (B) x- (D) y-CF ₃
(In the above formula,
A represents one or more groups selected from the group consisting of CF ₂ , CFCF ₂ , and C (CF ₂ ) ₂ ;
B is OCF ₂ CF ₂ , OCF ₂ CF (CF ₂ ), OCF ₂ C (CF ₂ ) ₂ ,
OCF (CF ₂ ) CF (CF ₂ ), OCF (CF ₂ ) C (CF ₂ ) ₂ ,
Represents one or more groups selected from the group consisting of OC (CF ₂ ) ₂ CF (CF ₂ ), OC (CF ₂ ) ₂ C (CF ₂ ) ₂ ;
D represents one or more groups selected from the group consisting of OCH ₂ CH ₂ , OCH ₂ CH ₂ CH ₂ , OC (O) (CH ₂ ) z;
w, x, y, and z represent numbers greater than 0 and less than or equal to 50. )
The optical laminated body according to any one of claims 1 to 3, which is represented by:   The addition amount of the antifouling agent and / or slipperiness imparting agent is 0.1 wt% or more and 10 wt% or less with respect to the total weight of the composition forming the low refractive index layer. 5. The optical laminate according to any one of 4 above.   The optical laminated body according to any one of claims 1 to 5, wherein the low refractive index layer uses fine particles having voids as a low refractive index agent.   The optical laminate according to any one of claims 1 to 6, comprising a hard coat layer between the light transmissive substrate and the low refractive index layer.   The optical laminated body as described in any one of Claims 1-7 utilized as an antireflection laminated body. A polarizing plate comprising a polarizing element,
A polarizing plate comprising, on the surface of the polarizing element, the optical laminate according to any one of claims 1 to 8 on a surface opposite to the surface on which the low refractive index layer is present in the optical laminate. An image display device comprising a transmissive display and a light source device that irradiates the transmissive display from the back,
The image display apparatus which comprises the optical laminated body as described in any one of Claims 1-8, or the polarizing plate as described in Claim 9 on the surface of the said image display body.