WO2007037276A1 - 反射防止膜 - Google Patents
反射防止膜 Download PDFInfo
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- WO2007037276A1 WO2007037276A1 PCT/JP2006/319179 JP2006319179W WO2007037276A1 WO 2007037276 A1 WO2007037276 A1 WO 2007037276A1 JP 2006319179 W JP2006319179 W JP 2006319179W WO 2007037276 A1 WO2007037276 A1 WO 2007037276A1
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- WIPO (PCT)
- Prior art keywords
- layer
- refractive index
- film
- antireflection film
- low refractive
- Prior art date
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249971—Preformed hollow element-containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249971—Preformed hollow element-containing
- Y10T428/249972—Resin or rubber element
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249971—Preformed hollow element-containing
- Y10T428/249974—Metal- or silicon-containing element
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
Definitions
- the present invention relates to an antireflection film, and more specifically, an antireflection film having a low refractive index layer including inorganic fine particles having voids and excellent in low reflectivity and water resistance. It is about.
- LCD liquid crystal display
- CRT cathode ray tube display
- plasma display panel LCD
- the display surface of an image display device such as (PDP) is required to reduce reflection by light emitted from an external light source such as a fluorescent lamp and to improve its visibility. For this reason, by providing an anti-reflection film on the display surface of an image display device that conventionally uses the phenomenon that the reflectance power is reduced by covering the surface of a transparent object with a transparent film having a low refractive index, It has been studied to improve the visibility by reducing the reflectivity of the display surface.
- Patent Document 1 discloses an ionizing radiation curable resin for the purpose of providing an antireflection film having a low refractive index and excellent mechanical strength. At least a part of the surface of the silica fine particles is formed by a silane coupling agent comprising a composition and a silica fine particle having an outer shell layer and being porous or hollow inside, and having an ionizing radiation curable group.
- a silane coupling agent comprising a composition and a silica fine particle having an outer shell layer and being porous or hollow inside, and having an ionizing radiation curable group.
- Patent Document 1 JP 2005-99778 A
- Patent Document 2 Japanese Patent Laid-Open No. 2003-202406
- the low refractive index layer of the antireflection film is usually used on the outermost surface, color change occurs when water is adsorbed to the antireflection film, and thus water resistance is required.
- moisture is taken into the voids over time and the water resistance is immediately inferior.
- moisture is taken into voids and the refractive index of the inorganic fine particles having voids is increased, the reflectance deteriorates over time, the appearance such as water marks is deteriorated, and the scratch resistance is deteriorated over time. The problem arises.
- Patent Document 1 The antireflection film of Patent Document 1 is excellent in mechanical strength, but has not been considered in consideration of water resistance.
- Patent Document 2 water repellent Z oil repellency is applied to the surface of a low refractive index layer using hollow silica fine particles for the purpose of providing an antireflection film having high antireflection performance and antifouling properties with a single antireflection layer. Proposals with an antifouling layer have been made.
- the antifouling layer of such an antireflection film is generally formed of a thin film of less than lOnm that does not affect the refractive index, mainly for the purpose of preventing adhesion of dirt such as fingerprints. Even though it has initial water repellency, it was insufficient to impart water resistance over time to the silica fine particles present near the outermost surface of the low refractive index layer.
- the present invention has been made in view of the above points, and an object thereof is to provide an antireflection film having low reflectivity and excellent water resistance.
- the antireflection film according to the present invention comprises a first layer comprising inorganic fine particles having voids and a cured film containing fluorine atoms, or a first thin film comprising an inorganic thin film having gas barrier properties. It has a low refractive index layer consisting of two layers, a second layer formed on one layer.
- a force comprising a cured film containing fluorine atoms on the first layer containing the inorganic fine particles having the voids and mainly imparting low refractive index properties.
- the second layer of the low refractive index layer in the present invention is fluorine. Since it is made of a hard film containing atoms or an inorganic thin film with gas barrier properties, it is excellent in scratch resistance and prevents reflections over time. The rate stability is also high.
- the water resistance of the antireflection film measured under a condition of 40 ° C. and 90% RH in accordance with JIS K7129 is 50 gZm 2 ′ day or less. Sexual power is also preferable.
- the antireflection film according to the present invention 1 mL of ion-exchanged water is dropped on the surface of the antireflection film and left at 25 ° C for 24 hours.
- the difference in emissivity value and the difference in haze value according to JIS K7361 are both 0.1% or less, and the point of water resistance is also preferable.
- the second layer made of the cured film containing fluorine atoms reacts with ionizing radiation-curable functional groups and Z or thermosetting functional groups. It is also preferable to have a point strength that is excellent in waterproofness, scratch resistance and productivity.
- the inorganic fine particles having voids preferably have a refractive index of 1.45 or less.
- the antireflection film is particularly excellent in antireflection effect.
- the thickness of the second layer in the low refractive index layer is 5 nm to 50 nm.
- the present invention by providing the low refractive index layer containing inorganic fine particles having voids, in which waterproofness and low refractive index properties are integrated, excellent low reflectivity and water resistance are achieved. It is possible to obtain an antireflection film that hardly deteriorates in reflectance, appearance, scratch resistance, etc. over time.
- FIG. 1 schematically shows a cross section of an example of an antireflection film according to the present invention.
- the antireflection film according to the present invention comprises a first layer comprising inorganic fine particles having voids, and a cured film containing fluorine atoms, or an inorganic thin film having gas barrier properties. It has a low refractive index layer consisting of two layers, a second layer formed on one layer.
- a force comprising a cured film containing fluorine atoms on the first layer comprising the inorganic fine particles having the voids and imparting a low refractive index mainly.
- the second layer of the low refractive index layer in the present invention is made of a cured film containing a fluorine atom or an inorganic thin film having gas barrier properties, appearance defects such as water marks are prevented. It has excellent scratch resistance and high stability of reflectance over time.
- the low refractive index layer is formed of inorganic fine particles having voids, it is lower than the low refractive index layer that also has a fluoropolymer isotropic power that does not cause a problem with water resistance. It has the merit that a refractive index can be realized.
- the antireflection film according to the present invention includes at least the low refractive index layer composed of the two specific layers described above, and only the low refractive index layer may be effective, or the low refractive index layer may be used.
- the rate layer may be formed on one or more functional layers and the outermost surface of Z or the light-transmitting substrate.
- FIG. 1 schematically shows a cross section of an example of an antireflection film according to the present invention.
- a low refractive index layer (first layer) 3 and a low refractive index layer (second layer) 4 are provided in this order on one surface side of the light transmissive substrate 2.
- a hard coat layer 5 is provided between the light-transmitting substrate 2 and the low refractive index layer 3 (first layer).
- the overlayer is composed of only two low refractive index layers, another light transmission layer having a different refractive index may be provided.
- the layer configuration of the antireflection film according to the present invention is not particularly limited, but specific examples include a single low refractive index layer, a substrate Z low refractive index layer, a substrate Z hard coat layer Z low refractive index. Index layer, base material Z antistatic layer Z hard coat layer Z low refractive index layer, base material Z antistatic layer Z hard coat layer Z high refractive index layer Z low refractive index layer, base material Z antistatic layer Z hard coat layer Z medium refractive index layer Z high refractive index layer Z low refractive index layer, substrate Z hard coat layer Z antistatic layer Z low refractive index layer and the like.
- the low refractive index layer is a low refractive index layer comprising the two specific layers in the present invention.
- the low refractive index layer which is an essential layer in the present invention, will be described in order.
- the low refractive index layer according to the present invention comprises a first layer comprising inorganic fine particles having voids and a cured film containing fluorine atoms, or a first layer comprising an inorganic thin film having gas barrier properties. It is composed of two layers with the second layer formed in the thickness from the viewpoint of low refractive index and transparency
- the low refractive index layer according to the present invention mainly forms the second layer (hereinafter sometimes simply referred to as a waterproof layer) that imparts waterproof properties mainly on the first layer that imparts low refractive index properties.
- a low refractive index layer is realized integrally.
- the refractive index of the low refractive index layer in the present invention is controlled by adjusting the film thickness and refractive index of the first layer and the second layer.
- the refractive index and the layer thickness depending on the constituent material of the waterproof layer of the second layer are considered, and in accordance with this, mainly the low refractive index is considered.
- the amount of inorganic fine particles having voids in the first layer for adjusting the efficiency and the layer thickness are controlled.
- the refractive index of the low refractive index layer in the present invention is preferably 1.40 or less, more preferably 1.35 or less.
- the low refractive index layer preferably satisfies the following formula (I) by integrating the first layer and the second layer from the viewpoint of low reflectance.
- n is the refractive index of the low refractive index layer
- d is the low refractive index
- Thickness layer thickness (nm). Further, ⁇ is a wavelength, which is a value in the range of 380 to 780 nm. Satisfying the above formula (I) means that m (a positive odd number, usually 1) satisfying the formula (I) exists in the above wavelength range.
- the first layer of the low refractive index layer in the present invention contains inorganic fine particles having voids as an essential component, usually further contains a binder component that imparts film-forming properties, and further contains an additive-adding agent as appropriate. May be.
- the inorganic fine particles having voids are a structure in which a gas is filled inside the inorganic fine particles and a porous structure containing Z or gas, and the refractive index in the fine particles is higher than the original refractive index of the inorganic fine particles.
- the present invention also includes fine particles capable of forming a nanoporous structure inside and at least part of the surface or Z depending on the form, structure, aggregation state, and dispersion state of the fine particles inside the film. It is.
- the inorganic fine particles having voids can lower the refractive index while maintaining the layer strength of the low refractive index layer.
- the inorganic fine particles having voids used in the antireflection film according to the present invention include, for example, metals and metal oxides, and specific examples thereof include JP-A-7-133105.
- Examples thereof include composite oxide sols or hollow silica fine particles disclosed in Japanese Unexamined Patent Publication No. 2001-233611.
- hollow silica fine particles prepared using the technique disclosed in Japanese Patent Application Laid-Open No. 2001-233611 are preferred.
- the inorganic fine particles having voids such as the hollow silica fine particles as described above can be produced by the following first to third steps.
- a silica material and an alkaline aqueous solution of an inorganic oxide material other than silica are separately prepared in advance, or a mixed aqueous solution of both is prepared.
- the obtained aqueous solution is gradually added to an alkaline aqueous solution of pHIO or higher with stirring.
- a dispersion containing seed particles in advance can be used as a starting material.
- At least a part of elements other than silicon and oxygen is selectively removed from the colloidal particles made of the composite oxide obtained in the above step.
- the elements in the complex oxide are dissolved and removed using mineral acid or organic acid, or ion exchange is removed by contacting with a cation exchange resin.
- the surface of the colloidal particles is hydrolyzed by adding a hydrolyzable organic key compound or a key acid solution to the colloidal particles of the composite oxide from which some of the elements have been removed. Cover with a decomposable organic key compound or a polymer such as a key acid solution. In this way, the composite oxide sol described in the above publication can be produced.
- the fine particles capable of forming a nanoporous structure in the inside of the film and at least part of Z or the surface are manufactured for the purpose of increasing the specific surface area and are used for filling.
- a collection may be used.
- Such products include a combination of porous silica fine particles from commercial names Nipsil and Nipgel manufactured by Nippon Silica Kogyo Co., Ltd., and silica fine particles manufactured by Nissan Chemical Industries, Ltd. in a chain. From the colloidal silica UP series (trade name) having a structure, it is possible to use those within the preferred particle diameter range of the present invention.
- the inorganic fine particles having voids are preferably those that have been surface-treated with a silane coupling agent having an attailoyl group and Z or methacryloyl group.
- the surface treatment of inorganic fine particles improves the affinity when using a binder consisting mainly of ionizing radiation curable resin composition, and enables uniform dispersion of inorganic fine particles in the coating liquid and coating film.
- the aggregation of inorganic fine particles and the decrease in transparency and coating strength due to the increase in size of the particles can be prevented.
- the inorganic fine particles in the coating are fixed to the binder component, and the silica fine particles are crosslinked in the binder.
- membrane improves, and hardness can be provided, leaving the softness
- Examples of the shape of the fine inorganic particles having voids used in the present invention include a spherical shape and a needle shape.
- the average particle size of the inorganic fine particles having spherical voids is preferably 1 nm or more and lOOnm or less, more preferably the lower limit is lOnm or more and the upper limit is 50 nm or less. If the average particle size of fine particles exceeds lOOnm, transparency may be impaired. On the other hand, when the average particle diameter of the fine particles is less than 1 nm, it may be difficult to disperse the fine particles. 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 refractive index of the inorganic fine particles having voids is preferably 1.45 or less from the viewpoint of sufficiently reducing the refractive index of the low refractive index layer and ensuring the strength of the fine particles themselves. Preferably 1.30 or less.
- the inorganic fine particles having voids are 10% by mass or less with respect to the total mass of the first layer from the viewpoint of obtaining a desired refractive index.
- the fine inorganic particles having the voids are more preferably 15 to 95% by mass, and still more preferably 20 to 70% by mass with respect to the total mass of the first layer. Included in range.
- the first layer of the low refractive index layer in the present invention may be composed of the following materials in addition to the inorganic fine particles having voids.
- the noinder component is blended in the first layer of the low refractive index layer according to the present invention in order to impart film formability and adhesion to the adjacent layer.
- binder component examples include: (i) a reactive binder component that cures in response to light, heat, etc., for example, a binder that cures in response to electromagnetic waves such as visible light, ultraviolet rays, electron beams, or energy particle beams.
- a binder that cures in response to electromagnetic waves such as visible light, ultraviolet rays, electron beams, or energy particle beams.
- Components hereinafter referred to as “photocurable binder components”
- thermosetting binder components binder components that cure in response to heat
- thermoplastic rosin it is possible to use one that has optical transparency when at least solidified or cured to form a coating film.
- a photocurable binder component particularly an ionizing radiation curable binder component, can prepare a coating composition excellent in coating suitability, and forms a uniform large-area coating film. It's easy to do. Moreover, a relatively high strength coating film can be obtained by curing the binder component in the coating film by photopolymerization after coating.
- ionizing radiation curable binder component a polymerization that causes a reaction that causes a large molecule such as polymerization or dimerization to proceed directly when irradiated with ionizing radiation or indirectly by the action of an initiator.
- Monomers, oligomers and polymers having a functional functional group can be used.
- radically polymerizable monomers and oligomers having an ethylenically unsaturated bond such as an acryl group, a bur group, and a allyl group can be used, and a photopolymerization initiator is combined as necessary. .
- the binder component is a polyfunctional binder component having two or more polymerizable functional groups in one molecule so that a cross-linking bond occurs between the molecules of the one-node component.
- Monomers and oligomers having an ethylenically unsaturated bond that are preferably used include di (meth) acrylates such as ethylene glycol di (meth) acrylate and pentaerythritol di (meth) acrylate monostearate; trimethylol Multifunctional (such as propane tri (meth) acrylate, penta (erythritol) tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Examples thereof include meta) acrylate, derivatives thereof such as these EO-modified products, and oligomers obtained by polymerizing the above radical polymerizable monomers.
- di (meth) acrylates such as ethylene glycol di (meth) acrylate and pentaerythritol di (meth) acrylate monostearate
- trimethylol Multifunctional such as propane tri (
- epoxy acrylate resin (“Epoxy ester” manufactured by Kyoeisha Chemical Co., Ltd., “Epoxy” manufactured by Showa Polymer Co., Ltd.) and various isocyanates and monomers having hydroxyl groups are bonded via urethane bonds.
- Urethane talylate resin obtained from heavy weight kettle (Nippon Synthetic Chemical Industry) “Suriko” manufactured by Kyoeisha Chemical Co., Ltd. and “Urethane Atylate” manufactured by Kyoeisha Chemical Co., Ltd.), and oligomers having a number average molecular weight (number average molecular weight in terms of polystyrene measured by GPC method) of 20,000 or less are also preferably used.
- These monomers and oligomers have a high effect of increasing the cross-linking density of the coating film, and since the force average molecular weight is as small as 20,000 or less, it is a highly fluid component and improves the coating suitability of the coating composition. There is also an effect.
- a reactive polymer having a (meth) acrylate group in the main chain or side chain and having a number average molecular weight of 20,000 or more can be preferably used.
- These reactive polymers can be purchased as commercial products such as “macromonomer” manufactured by Toagosei Co., Ltd., or a copolymer of methyl (meth) acrylate and glycidyl methacrylate is used.
- a reactive polymer having a (meth) acrylate group can be obtained by condensing the glycidyl group of the copolymer and the carboxyl group of (meth) acrylic acid later.
- the ionizing radiation curable binder component includes a non-reactive polymer, a polymerizable monomer, oligomer, or polymer of another reaction type such as a thermosetting binder component typified by epoxy resin. You may combine as a binder component.
- the binder component itself is not reactive, and as a binder component, a non-polymerization reactive transparent resin conventionally used to form an optical thin film, such as polyacrylic acid, polymethacrylic acid, polyacrylate, polymer, etc. Examples include tartrate, polyolefin, polystyrene, polyamide, polyimide, polyvinyl chloride, polybutyl alcohol, polybutyl butyral, polycarbonate, and the like.
- thermosetting binder component examples include a monomer having a curable functional group that can be cured by heating to proceed with a large molecular weight reaction such as polymerization or crosslinking with the same functional group or another functional group, Oligomers and polymers can be used.
- thermosetting resin examples include monomers and oligomers having an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a hydrogen bond forming group, and the like.
- Specific examples of thermosetting resins include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino acid.
- thermosetting resin Alkyd resin, melamine urea co-condensed resin, key resin, polysiloxane ⁇ ⁇ etc. are used. If necessary, these thermosetting resins are added with a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, and a viscosity modifier.
- a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, and a viscosity modifier.
- the first layer constituting the low refractive index layer in the present invention Te you, the first layer constituting the low refractive index layer in the present invention, the binder component, 5 to 85 weight 0/0 relative to the total weight of the first layer, further 30 to 50 mass% Force included in the range Forces such as film formability and film strength are also preferable.
- the binder component used in the present invention is ionizing radiation curable
- a photopolymerization initiator is appropriately selected from a photoradical initiator or a photopower thione initiator according to the ionizing radiation curable reaction mode of the binder component.
- the photopolymerization initiator is not particularly limited, and examples thereof include acetophenones, benzophenones, ketals, anthraquinones, disulfide compounds, thiuram compounds, and fluoroamine compounds.
- 1-hydroxy monocyclohexyl monophenol monoketone and 2 methyl 1 [4 (methylthio) phenol] 2 morpholinopropane 1-one are polymerized by irradiation with ionizing radiation even in a small amount.
- 1-hydroxy monocyclohexyl-luketone can be obtained from Ciba Specialty Chemicals Co., Ltd. under the trade name Irgacure 184.
- the photopolymerization initiator When using a photopolymerization initiator, it is preferable to blend the photopolymerization initiator in a proportion of usually 3 to 8 parts by mass with respect to 100 parts by mass of the ionizing radiation curable binder component.
- the first layer of the low refractive index layer in the present invention includes an ultraviolet blocking agent and an ultraviolet absorber.
- a surface conditioner (leveling agent), or other components may be contained. Further, even in the first layer, in addition to inorganic fine particles having voids, fine particles having no voids inside may be contained.
- the thickness of the first layer of the low refractive index layer is appropriately adjusted in consideration of the refractive index and thickness with the second layer. Preferably it is 0-80nm! /.
- the second layer of the low-refractive index layer in the present invention mainly functions as a waterproof layer for the first layer while constituting the low-refractive index layer integrally with the first layer, and contains fluorine atoms. It consists of an inorganic thin film having a gas barrier property or a mold made of a cured film.
- a case of a cured film containing fluorine atoms and a case of an inorganic thin film having gas barrier properties will be described in order.
- the cured film containing a fluorine atom can reduce the refractive index of the coating film as the second layer, and can have water repellency and water resistance higher than that.
- the cured film containing fluorine atoms includes: (i) a film obtained by curing a fluorine-containing curable monomer, oligomer, and Z or polymer containing a fluorine atom and a curable functional group in the molecule; and (ii) a fluorine atom.
- Fluorine-containing non-curable monomer, oligomer, or polymer that contains in the molecule but no curable functional group in the molecule, and fluorine-free curing that does not contain a fluorine atom but contains a curable functional group in the molecule A film obtained by curing a composition containing a polymerizable monomer, oligomer, and / or polymer, (iii) the fluorine-containing curable monomer, oligomer, and Z or polymer, and the fluorine-free curable monomer, oligomer, and Z Or a film obtained by curing a composition containing a polymer, (iv) containing fluorine-containing inorganic fine particles and the above fluorine-free curable monomer, oligomer, and / or polymer.
- Examples include a film obtained by curing the composition, (V) a film obtained by curing a composition containing fluorine-containing inorganic fine particles and the fluorine-containing curable mono
- a composition comprising a combination force of a fluorine-containing curable polymer, a fluorine-containing curable monomer, an oligomer and Z or a fluorine-free curable monomer, and an oligomer
- a fluorine-containing curable polymer, a fluorine-containing curable monomer having two or more curable functional groups in one molecule, an oligomer and Z or two in one molecule is preferable.
- the film-forming property of the coating composition is improved by the fluorine-containing curable polymer, and the crosslinking density is increased by the fluorine-containing curable monomer, oligomer and Z or fluorine-free curable monomer, oligomer.
- the coating suitability can be improved and excellent hardness and strength can be imparted to the coating film by the balance of both components.
- Examples of the curable functional group include radical polymerizability having an ethylenically unsaturated bond such as an acryl group, a bur group, and an aryl group as described in the binder of the first layer, and an epoxy group.
- the fluorine-free curable monomer, oligomer, or polymer ionizing radiation curable and Z or thermosetting resin as described in the binder component of the first layer can be appropriately selected and used.
- the affinity between the first layer and the second layer is improved and it is possible to react with each other. It is possible to improve the adhesion between the first layer and the second layer by applying and curing the second layer after the first layer is half-cured.
- fluorine-containing curable monomer those having a hydrocarbon skeleton are preferably used.
- Fluoroolefins for example, fluoroethylene, bi-lidene fluoride, tetrafluoroethylene, Oxaphnoleo-propylene, perfnoreo-butadiene, / monofluoro-2,2-dimethyl-1,3-dioxole
- acrylic or Methacrylic acid moieties and fully fluorinated alkyl, alkyl, aryl esters (for example, compounds represented by the following formula (1) or formula (2)), fully or partially fluorinated vinyl ethers , Fully or partially fluorinated butyl esters, fully or partially fluorinated vinyl ketones, and the like.
- R 1 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom
- R 2 and R 3 each independently represents a hydrogen atom, an alkyl group, a alkenyl group, a hetero group, A ring, an aryl group or a group defined by Rf, wherein Rf represents a fully or partially fluorinated alkyl group, an alkyl group, a heterocyclic ring or an aryl group
- R 2 , R 3, and Rf each may have a substituent other than a fluorine atom
- R 2 , R 3, and Rf are a ring formed by bonding two or more of them together.
- a structure may be formed.
- A represents a fully or partially fluorinated n-valent organic group
- R 4 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom
- R 4 Can have a substituent other than a fluorine atom
- q is an integer of 2 to 8.
- Examples of the compound represented by the above formula (2) include, for example, completely or partially fluorinated pentaerythritol tritalylate, ethylene glycol ditalylate, pentaerythritol.
- Diatalylates such as triethylolate monostearate;
- Tri (meth) acrylates such as trimethylolpropane tritalate, pentaerythritol tritalate, pentaerythritol tetraatalylate derivatives or dipentaerythritol pentaatalylate
- Multifunctional (meth) acrylate or oligomer obtained by polymerizing these radical polymerizable monomers can be mentioned.
- the fluorine-containing polymer containing fluorine in the molecule is not particularly limited, but preferable examples include those having a hydrocarbon skeleton, and the fluorine-containing monomer power as described above is arbitrarily selected.
- a homopolymer or copolymer of one or more fluorine-containing curable monomers, or a copolymer of one or more fluorine-containing curable monomers and one or more fluorine-free curable monomers Can be used.
- Examples of such examples include polytetrafluoroethylene 1, 4 fluoroethylene 6, fluoropropylene copolymer, 4 fluoroethylene perfluoroalkyl butyl ether copolymer, 4 fluoroethylene ethylene copolymer, polybulufluoride, (Polyvinylidene fluoride, acrylic or methacrylic acid moiety and fully fluorinated alkyl, alkenyl, aryl ester (for example, a compound represented by the above formula (1) or the above formula (2)) ) Polymer, fluoroethylene hydrocarbon-based butyl ether copolymer, epoxy, polyurethane, cellulose, phenol, polyimide, silicone, and other fluorine-modified products of each resin.
- CYTOP trade name: manufactured by Asahi Glass Co., Ltd.
- CYTOP can be mentioned as a commercial product.
- the polyvinylidene fluoride derivative represented by the following formula (3) is capable of introducing a curable functional group having a low refractive index, and other This is particularly preferable because of excellent compatibility with the binder.
- R 5 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom
- R 6 is a direct or fully or partially fluorinated alkyl chain, an alkenyl chain, an ester chain, a fully or partially fluorinated vinyl group via an ether chain, a (meth) acrylate group.
- p is 100,000 to 100,000.
- polyvinylidene fluoride derivatives represented by the above formula (3) include alkyl chains, alkenyl chains, ester chains, ethers in which R 6 is directly or completely or partially fluorinated. Fully or partially fluorinated pentaerythritol di (meth) acrylate, ethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, etc. via chain Rate: trimethylolpropane tri (meth) atalylate, pentaerythritol tri (meth) acrylate, etc.
- the fluorine-containing curable polymer in which R 6 contains a (meth) acrylate group is represented by the formula
- the fluorine-containing curable monomer represented by (1) or formula (2), and the ionizing radiation-curable monomer, oligomer, which does not contain fluorine atoms as described above in the binder component of Z or the first layer is particularly preferred.
- the fluorine-containing curable polymer, the fluorine-containing curable monomer, and the ionizing radiation-curable monomer not containing a fluorine atom can be used alone or in combination of two or more.
- the above-mentioned monomers and oligomers improve the crosslinking density and cacheability, and the above-mentioned polymer improves the film-forming properties of the composition. Therefore, the film-forming properties and coating suitability can be adjusted by appropriately adjusting the amount of each compound. It adjusts various properties such as ionizing radiation curing crosslinking density, fluorine atom content, and content of thermosetting polar groups.
- the film is a cured composition of (ii) a fluorine-containing non-curable monomer, oligomer, or polymer and a fluorine-free non-curable monomer, oligomer, and Z or polymer.
- a fluorine-containing non-curable monomer, oligomer, or polymer The compound used is not particularly limited as long as it contains a fluorine atom, and CF (d is 1 to 2 d 2d + l
- Perfluoroalkyl group represented by (integer of 1), — (CF CF) one (
- It may be a fluorine-based additive having a perfluoroalkyl group exemplified by the first class, and further contains a key compound in the molecule. Fluorosilane compounds may also be used.
- a film obtained by curing a composition containing fluorine-containing inorganic fine particles and the fluorine-free curable monomer, oligomer, and Z or polymer, and (V) fluorine-containing inorganic fine particles and the fluorine-containing composition fluorine-containing inorganic fine particles used in a film obtained by curing a composition containing a curable monomer, an oligomer, and Z or a polymer include metal fluorides such as magnesium fluoride, calcium fluoride, lithium fluoride, and aluminum fluoride. Fluoride fine particles are listed.
- the thickness is preferably 5 to 50 nm, more preferably 10 to 50 nm, and still more preferably 10 to 30 nm.
- the refractive index of the second layer is 1.40 to L 47, which is a low refractive index while imparting water resistance. It is preferable from the viewpoint of realizing efficiency.
- the second layer of the low refractive index layer may further contain other components in addition to the components described above.
- a curing agent for example, a crosslinking agent, an ultraviolet shielding agent, an ultraviolet absorber, a surface conditioner (leveling agent) and the like can be used as necessary.
- a surface conditioner for example, a surface conditioner (leveling agent) and the like can be used as necessary.
- the second layer preferably has a gas barrier property.
- Thickness 80 Water vapor gas permeability measurement device (PERMATRAN-W3 / 31, Modern Control) under the condition of 90 ° RH at 40 ° C, when formed on ⁇ m Triacetino Resenellose (TAC) Finolem) according to JIS K7129
- TAC Triacetino Resenellose
- the water vapor permeability of the laminate having the light-transmitting base material and the second layer force is 50 gZm 2 ′ day or less, measured using More preferably, it is 10 g / m 2 'day or less.
- the gas barrier property in the inorganic thin film having gas barrier property used as the second layer of the low refractive index layer of the present invention is a property that the film can block oxygen and water vapor, and is used as the second layer.
- a light-transmitting substrate for example, 80m thick triacetylcellulose (TAC) film
- TAC triacetylcellulose
- the water vapor transmission rate of the laminate composed of the light transmissive substrate and the second layer measured using a water vapor gas transmission rate measurement device (PERMATRAN-W3 / 31, manufactured by Modern Control Co., Ltd.) under the conditions is 50 gZm 2 ' It can be a guideline that it will be less than day.
- the gas-noble inorganic thin film used for the second layer needs to maintain visibility and therefore needs to be further transparent.
- the gas-noreal inorganic thin film used for the second layer uses, for example, silicon oxide, aluminum oxide, silicon nitride, silicon oxide silicon nitride, etc., for example, electron beam evaporation, sputtering, plasma CVD, etc. (CVD is Chemical Vapor
- an abbreviation for Deposition which may be called chemical vapor deposition or chemical vapor deposition
- an atmospheric pressure plasma discharge treatment method Among these, an oxide silicon film is preferable from the viewpoint of transparency. From the viewpoint of noria, acid aluminum is also preferable.
- the thickness of the second layer is preferably 5 to 50 nm, more preferably 10 to 30 nm from the viewpoint of water resistance.
- the first layer and the second layer composed of a cured film containing fluorine atoms are usually prepared by dissolving each of the above-described components in a solvent and performing a dispersion treatment according to a general preparation method. It can be formed by preparing a working liquid and coating, drying and curing the coating liquid on a light-transmitting substrate, one or a plurality of functional layers, or the first layer. Fluorine on the first layer In the case of forming a second layer made of a cured film containing atoms, the first layer is formed as a semi-cured film that is half-cured, and a cured film of the second layer is formed thereon to form the first layer. It is also possible to improve the adhesion between the layer and the second layer.
- a gas barrier inorganic thin film is formed as the second layer, it is formed by using an electron beam evaporation method, a sputtering method, or a plasma CVD method as described above.
- an antireflection film comprising only the two low refractive index layers is formed, it may be formed on a release sheet.
- the method for forming the low refractive index layer is not particularly limited.
- a solvent for dissolving and dispersing the solid component is essential, and the type thereof is not particularly limited.
- ketones For example, ketones; acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, diacetone alcohol, esters; methyl formate, methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, nitrogen-containing compounds; nitromethane, Acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, glycols; methyl glycol, methyl darlicol acetate, ethers; tetrahydrofuran, 1,4-dioxane, dioxolane, diisopropyl ether, halogenated hydrocarbons; methylene chloride , Chlorophonolem, Tetrachloroethane, Glycol ethers; Methyl cereal solve
- the amount of the solvent is such that each component can be uniformly dissolved and dispersed, and the inorganic fine particles having voids do not aggregate even after being prepared, and do not become too dilute during coating. Adjust as appropriate. It is preferable to prepare a high-concentration coating solution by reducing the amount of solvent added within the range where this condition is satisfied. By doing so, it can be stored without taking up any capacity, and can be used after diluting to an appropriate concentration during coating. When the total weight of the solid content and the solvent is 100 parts by mass, the solvent is preferably used for 0.5 to 50 parts by mass of the total solid content.
- a coating solution for forming a low refractive index layer is obtained.
- a layer forming coating solution can be obtained by adding a medium such as beads to the obtained mixture and appropriately dispersing it with a paint shaker or a bead mill.
- the coating solution for forming the first layer or the second layer is applied to the light-transmitting substrate, one or a plurality of functional layers, or the first layer, dried, and then subjected to ionizing radiation as necessary. Curing by irradiation and Z or heating.
- various methods such as a spin coating method, a dip method, a spray method, a die coating method, a bar coating method, a roll coater method, a meniscus coater method, a flexographic printing method, a screen printing method, and a pea coater method are used. be able to.
- the low refractive index layer of the antireflection film according to the present invention preferably has a minimum reflectance that can be lowered to 2.5% or less, more preferably 2% or less.
- the low refractive index layer of the antireflection film according to the present invention has, as water resistance, 1 mL of ion-exchanged water dropped, left to stand at 25 ° C. for 24 hours, wiped off the water drops, and the minimum reflectance before dropping.
- the difference in the values is preferably 0.1% or less.
- the difference here is 0.1% or less.
- the minimum reflectance value before dropping is 2.5%
- the minimum reflectance value after dropping is 2.4% to 2%. It means within 6%.
- the low refractive index layer of the antireflective film according to the present invention has water resistance such that 1 mL of ion-exchanged water is dropped and left at 25 ° C. for 24 hours. Preferably not.
- the low refractive index layer of the antireflection film according to the present invention is made of ion-exchanged water as water resistance. It is preferable that the difference in haze value in accordance with JIS-K73 61 after the dropwise addition of mL and leaving for 24 hours at 25 ° C after wiping off the water droplets is 0.1% or less. The difference here is 0.1% or less as described above, for example, when the haze value before dropping is 0.3%, the haze value after dropping is 0.2% to 0. It means within 4%.
- the low refractive index layer of the antireflection film according to the present invention has, as scratch resistance, lmL of ion-exchanged water dropped on the surface of the low refractive index layer, left at 25 ° C. for 24 hours, and then wiped off the water drops.
- the minimum load is no more than 200g when scratching 10 times with # 0000 steel wool.
- the base material and the functional layer included in the form in which the antireflection film according to the present invention has a plurality of layers other than the low refractive index layer single layer will be sequentially described.
- the material of the light-transmitting substrate is not particularly limited, and general materials used for the antireflection film can be used.
- polyester polyethylene terephthalate, polyethylene naphthalate
- cenorelose triacetate cenorelose diacetate.
- Cellulose acetate butyrate Polyester, Polyethersulfone, Polysulfone, Polypropylene, Polymethylpentene, Polyvinyl chloride, Polyvinylacetal, Polyetherketone, Polymethyl methacrylate, Polycarbonate, Polyurethane, etc.
- a resin substrate such as a film formed of various resins such as polyester (polyethylene terephthalate, polyethylene naphthalate) and cellulose triacetate. That.
- amorphous olefin polymer (COP) film with an alicyclic structure there is also an amorphous olefin polymer (COP) film with an alicyclic structure.
- This is a norbornene polymer, a monocyclic olefin-based polymer.
- Polymers, cyclic conjugation polymers, vinyl alicyclic hydrocarbon polymer resins, etc. are used.
- ZEONEX YAZENOA Neorbornene-based resin
- Aton modified norbornene-based resin manufactured by JSR Co., Ltd.
- Abel (cyclic olefin copolymer) manufactured by Mitsui Chemicals, Inc. Topas manufactured by Ticona Co., Ltd.
- OPTTREX OZ-1000 series (alicyclic acrylic resin) manufactured by Hitachi Chemical Co., Ltd.
- FV series low birefringence, low photoelastic modulus film manufactured by Asahi Kasei Chemicals Corporation is also preferable as an alternative base material for triacetyl cellulose.
- the thickness of the substrate is usually about 25 ⁇ m to 1000 ⁇ m, but is not particularly limited, and may be about 1 to 5 mm.
- the hard coat layer may be provided on the antireflection film for the purpose of improving performance such as scratch resistance and strength.
- “Hard coat layer” means a layer having a hardness of “H” or higher in the pencil hardness test specified in JIS K5600-5-4: 1999.
- the hard coat layer is preferably formed using an ionizing radiation curable resin composition, and more preferably has a (meth) acrylate functional group, such as a polyester resin resin having a relatively low molecular weight.
- Polyether resin acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, polythiol polyether resin, polyhydric alcohol, ethylene glycol di (meth) acrylate, penta Di (meth) acrylates such as erythritol di (meth) acrylate monostearate; (Meta) Atalylate derivative, dipentaerythritol Monomers as polyfunctional compounds such as tantalum (meth) acrylate, or oligomers such as epoxy acrylate or urethane acrylate can be used.
- the photopolymerization initiator to be contained in the ionizing radiation curable resin composition is appropriately selected from those exemplified above and used.
- the hard coat layer has a film thickness after curing of 0.1 to: LOO m, preferably 0.8 to 20 m.
- LOO m film thickness after curing
- the film thickness is 0 .: L m or less, sufficient hard coat performance cannot be obtained, and when it is 100 m or more, it is easy to crack against external impact.
- the hard coat layer made of the ionizing radiation curable resin composition may have a function of a medium refractive index layer or a high refractive index layer as described below.
- Anti-reflection film suppresses the generation of static electricity, eliminates adhesion of dust, and external static electricity
- An antistatic layer may be provided to suppress air damage. It is preferable that the antistatic layer has a function of reducing the surface resistance of the antireflection film to 10 12 ⁇ or less, but on the other hand, even if the surface resistance is 10 12 ⁇ or more, it suppresses the generation of static electricity. As long as the above functions such as the above can be exhibited.
- the antistatic material is not particularly limited, and is not particularly limited, such as an ion conductive material, an electronic conductive material, and inorganic fine particles.
- Examples of the antistatic agent contained in the resin composition for forming an antistatic layer include various types of cattle having cationic groups such as quaternary ammonium salts, pyridinium salts, and primary to tertiary amino groups.
- antistatic agents non-ionic antistatic agents such as amino alcohols, glycerin and polyethylene glycols, organometallic compounds such as tin tantalum alkoxides and their acetyl cetate salts
- examples thereof include various surfactant-type antistatic agents such as metal chelate compounds, and polymer-type antistatic agents in which the above-described antistatic agents have a high molecular weight.
- surfactant-type antistatic agents such as metal chelate compounds
- polymer-type antistatic agents in which the above-described antistatic agents have a high molecular weight.
- tertiary amino groups, quaternary ammonium groups, monomers and oligomers that have a metal chelate moiety and can be polymerized by ionizing radiation and organometallic compounds such as coupling agents having functional groups that can be polymerized by ionizing radiation.
- a polymerizable antistatic agent such as a compound can also be used.
- the antistatic agent include conductive polymers, and specific examples thereof include aliphatic conjugated polyacetylene, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, and the like. Other examples include heteroatom-conjugated polyarines and mixed conjugated poly (phenolene-bylene). Besides these, double-chain conjugated, which is a conjugated system with multiple conjugated chains in the molecule. And conductive composites that are polymers obtained by grafting or block-copolymerizing the above-described conjugated polymer chains onto saturated polymers.
- antistatic agents contained in the resin composition for forming an antistatic layer include inorganic oxide ultrafine particles having a particle diameter of ⁇ m or less, such as tin oxide, tin-doped indium oxide (ITO), antimony dope Tin oxide ( ⁇ ), indium-doped zinc oxide ( ⁇ ), antimony oxide, indium oxide, or the like can be used.
- the particle diameter is less than the wavelength of visible light.
- the antistatic layer may be provided directly on the light-transmitting substrate, but the same effect can be obtained by dispersing the antistatic agent in the hard coat layer. Furthermore, if the desired refractive index is within the range, an antistatic agent with organic component power is added directly to the low refractive index layer, or the antistatic layer is applied to the outermost surface of the low refractive index layer, affecting the performance of the antireflection film. It is also possible to provide the film thickness within a range of 30 ⁇ m or less.
- other refractive index layers are provided in order to further improve the antireflection property.
- the refractive index of these refractive index layers can be arbitrarily set within the range of 1.46 to 2.00.
- the medium refractive index layer means at least a refractive index higher than that of the low refractive index layer and a refractive index in the range of 1.46 to L80.
- the middle refractive index layer When used in combination with the middle refractive index layer, it means that the refractive index is at least higher than that of the middle refractive index layer and the refractive index is in the range of 1.65-2.00.
- These refractive index layers may be formed of a binder and ultrafine particles having a particle diameter of lOOnm or less and having a predetermined refractive index.
- Such fine particles include zinc oxide (1.90), titanium yua (2.3 to 2.7), ceria (1.95), tin-doped indium oxide ( 1.95), antimony tin oxide (1.80), yttria (1.87), and zircoyu (2.0).
- the refractive index of the ultrafine particles is preferably higher than that of Noinda. Since the refractive index of the refractive index layer is generally determined by the content of ultrafine particles, the refractive index of the refractive index layer increases as the amount of ultrafine particles added increases. Therefore, by adjusting the addition ratio of the binder and the ultrafine particles, a high refractive index layer or a medium refractive index layer having a refractive index in the range of 1.46 to L80 is formed. Is possible. If the ultrafine particles have conductivity, the other refractive index layer (high refractive index layer or medium refractive index layer) formed using such ultrafine particles also has antistatic properties.
- the high refractive index layer or medium refractive index layer is a high refractive index inorganic oxide such as titanium or zirconium formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD). Or a refraction like a titer. A film in which inorganic oxide fine particles having a high rate are dispersed can be obtained.
- the thickness of these other refractive index layers is preferably in the range of 10 to 300 nm, more preferably 30 to 200 nm.
- the other refractive index layers may be provided directly on the light transmissive substrate.
- a hard coat layer is provided on the light transmissive substrate, and the hard coat layer and the low refractive index layer are provided. It is preferably provided between the rate layer.
- the antireflection film according to the present invention obtained as described above has a haze value specified in JIS-K73 61 that is different from the haze value of the light-transmitting substrate only after coating all the layers. It is preferable that the difference from the haze value of only the light transmissive substrate is within 1.5%.
- the antireflection film according to the present invention was measured using a water vapor gas permeability measurement device (PERMATRAN-W3 / 31, manufactured by Modern Control Co., Ltd.) under the condition of 40 ° C. and 90% RH in accordance with JIS K7129.
- the water vapor permeability is preferably 50 g / m 2 'day or less.
- the water vapor transmission rate is more preferably 10 gZm 2 'day or less.
- the antireflection film according to the present invention has a minimum reflectance value after 1 mL of ion-exchanged water is dropped on the surface of the antireflection film, left at 25 ° C for 24 hours and then wiped off the water droplets, and before dropping.
- the difference in haze and the difference in haze values according to JIS K7361 are both 0.1% or less.
- the antireflection film according to the present invention has scratch resistance, so that lmL of ion-exchanged water is dropped on the surface of the antireflection film, left at 25 ° C for 24 hours, wipes off the water droplets, and then has # 0000 steel wool.
- the minimum load amount at which no scratch is observed is 200 g or more.
- the present invention is not limited to the above embodiment.
- the above embodiment is an exemplification, and any device that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operational effects can be used. It is included in the technical scope.
- composition of the following composition was mixed and the composition for hard-coat layer formation was prepared.
- PET-30 trade name, manufactured by Nippon Kayaku
- 'Irgacure 907 (trade name, manufactured by Ciba' Specialty 'Chemicals); 1.5 parts by mass • methyl isobutyl ketone; 73.5 parts by mass
- the hard coat layer-forming composition prepared above is bar-coated on a 80 ⁇ m thick triacetylcellulose (TAC) film, the solvent is removed by drying, and then the irradiation dose is reduced using an ultraviolet irradiation device.
- TAC triacetylcellulose
- the film was cured by irradiating with ultraviolet rays at 20 mjZcm 2 to obtain a laminated film having a hard coat layer with a film thickness of 10 / zm and having a substrate Z hard coat layer strength.
- composition of the following composition was mixed and the composition for 1st layer formation was prepared.
- Hollow silica fine particle dispersion (hollow silica methylisobutylketone sol; average particle size 50 ⁇ m, solid content 20%, manufactured by Catalytic Chemical Industry Co., Ltd.); 16. 64 parts by mass
- PET-30 trade name, manufactured by Nippon Kayaku
- 'Irgacure 369 (trade name, manufactured by Chinoku' Specialty 'Chemicals); 0.06 parts by weight' Methyl isobutyl ketone; 81.44 parts by weight
- composition of the following composition was mixed and the composition for 2nd layer formation was prepared.
- Fluorine atom-containing curable binder resin OSTAR JM5010: trade name, manufactured by GSJAL Co., Ltd., refractive index 1.41, solid content 10% by mass, methyl ethyl ketone solution); 20 parts by mass' Irgacure 369 ( Product name, Ciba 'Specialty'Chemicals); 0.1 parts by weight • Methyl isobutyl ketone; 21.9 parts by mass
- the substrate obtained in (1) is bar-coated with the composition for forming the first layer prepared on the laminated film composed of the Z hard coat layer and dried to remove the solvent.
- the composition for forming the first layer prepared on the laminated film composed of the Z hard coat layer and dried to remove the solvent (Fusion UV System Japan Co., Ltd., light source H bulb) was used to irradiate with ultraviolet rays at an irradiation dose of 80mi / C m 2 , and the coating film was cured to produce a first layer with a film thickness of about 60 nm.
- the composition for forming the second layer prepared above is bar-coated and dried to remove the solvent, and then an ultraviolet irradiation device (Fusion UV System Japan Co., Ltd., light source H bulb) is used.
- UV irradiation was performed at an irradiation dose of 200 mjZcm 2 , and the coating film was cured to produce a second layer having a thickness of about 30 nm, and a low refractive index layer having a thickness of about 90 ⁇ m was formed as a whole.
- the obtained antireflection film was evaluated for refractive index, minimum reflectance, haze value, scratch resistance, and water vapor transmission rate as follows. Furthermore, after adding ImL of ion-exchanged water to the surface of the obtained antireflection film, it was allowed to stand at room temperature for 24 hours, and the appearance change, refractive index, minimum reflectance, haze value, scratch resistance after the water resistance test. Evaluated. These results are shown in Table 1 below.
- the absolute reflectance was measured using a spectrophotometer (UV-3100PC) manufactured by Shimadzu Corporation. Table 1 shows the minimum reflectance.
- the film thickness of the low refractive index layer was set so that the minimum value of the reflectance was around 550 nm.
- the refractive index of the low refractive index layer was obtained using simulation.
- the haze was measured using a turbidimeter NDH2000 (Nippon Denshoku Industries Co., Ltd.) in accordance with JIS-K7361.
- the water vapor transmission rate was measured using a water vapor gas transmission rate measuring device (PERMATRAN-W3Z31 manufactured by Modern Control Co., Ltd.) under the condition of 40 ° C. and 90% RH in accordance with JIS K7129.
- a water vapor gas transmission rate measuring device PERMATRAN-W3Z31 manufactured by Modern Control Co., Ltd.
- the thickness of the first layer of the low refractive index layer in Example 1 is 50 nm
- the composition for forming the second layer is as follows, the thickness of the second layer is changed to 45 nm, and the total thickness is 95 nm.
- An antireflection film was produced in the same manner as in Example 1 except that the low refractive index layer was formed.
- composition of the following composition was mixed and the composition for 2nd layer formation was prepared.
- PET-30 trade name, manufactured by Nippon Kayaku
- Irgacure 369 trade name, manufactured by Ciba 'Specialty' Chemicals
- An antireflection film was produced in the same manner as in Example 1 except that the second layer of the low refractive index layer was an oxide silicon film.
- TAC substrate Z hard coat layer Z first layer (hollow silica under the same production conditions as in Example 1 Composition layer) was formed.
- the first layer of the silica silica composition side was mounted on the lower electrode in the chamber of the sputtering apparatus with the upper side (film formation side).
- the inside of the chamber was depressurized to an ultimate vacuum of 0.0005 Pa with an oil rotary pump and a turbo molecular pump.
- the sputtering apparatus described above was equipped with a chamber, a power source, an exhaust valve, an exhaust device, and a gas inlet.
- silicon and oxygen gas manufactured by Taiyo Toyo Oxygen Co., Ltd. (purity 99.9999% or more) were prepared as targets.
- the resulting antireflection film was evaluated in the same manner as in Example 1 for appearance change before and after the water resistance test, refractive index, minimum reflectance, transparency of the coating film, and scratch resistance. The results are shown in Table 1 below.
- Example 3 the low refractive index layer was changed to the first hollow silica composition layer thickness of 80 nm, and the second oxide silicon film thickness was changed to 10 nm.
- An antireflection film was produced in the same manner as in Example 3 except that the rate layer was formed.
- the thickness of the hollow silica composition layer of the first low refractive index layer in Example 3 is 70 nm, the second layer is an acid-aluminum film, and the film thickness is changed to 20 nm.
- An antireflection film was produced in the same manner as in Example 3 except that the refractive index layer was formed.
- the target was aluminum and oxygen gas (manufactured by Taiyo Toyo Oxygen Co., Ltd. (purity 99. 9999% or more)).
- An inorganic thin film layer made of a silicon oxide film was formed.
- a fluorine-based additive generally used as an antifouling agent was added to the low refractive index layer containing hollow silica fine particles to produce an antireflection film.
- compositions having the following composition were mixed to prepare a composition for forming a low refractive index layer.
- PET-30 trade name, manufactured by Nippon Kayaku
- 'Irgacure 369 (trade name, manufactured by Ciba' Specialty 'Chemicals); 0.07 parts by mass' Anti-fouling agent (fluorine additive, trade name Modiper FS720, made by Nippon Oil &Fats); 0.66 parts by mass
- Example 1 Example 2 Example 3 Example 4 Example 5 Comparison J1 Water resistance Refractive index 1.37 1.38 1.38 1.36 1.39 1.37 Minimum reflectance
- the antireflective coating according to the present invention obtained in Examples 1 to 5 having a low refractive index layer composed of two layers according to the present invention has a water vapor transmission rate of 50 gZm 2 ′ day or less.
- All of the antireflection films according to the present invention have low reflectivity, the difference in the minimum reflectance value before and after the water resistance test is 0%, and the difference in haze value is 0%. Thus, the water resistance, which is difficult to deteriorate the reflectivity, appearance, scratch resistance and the like, was good.
- Comparative Example 1 in which a fluorine-based additive that has been used as an antifouling agent was added to a low refractive index layer containing organic fine particles having voids has a large water vapor transmission rate. there were.
- Such Comparative Example 1 deteriorated in appearance such as water marks after the water resistance test, and further, the difference in minimum reflectance value was 0.6%, and the difference in haze value was 0.2%. Water resistance was insufficient, such as deterioration of optical characteristics and mechanical properties.
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Abstract
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Cited By (6)
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JP2010084054A (ja) * | 2008-10-01 | 2010-04-15 | Dainippon Printing Co Ltd | 耐熱層形成用塗布液、ガスバリア性シートの製造方法、ガスバリア性シート、及び製品 |
JP2011108887A (ja) * | 2009-11-18 | 2011-06-02 | Asahi Kasei Corp | 感光性樹脂積層体 |
JP2013521533A (ja) * | 2010-03-03 | 2013-06-10 | スリーエム イノベイティブ プロパティズ カンパニー | ナノ構造化表面を有する複合多層構造 |
JP2014205271A (ja) * | 2013-04-11 | 2014-10-30 | 日本カーバイド工業株式会社 | 積層シート |
JP2015004753A (ja) * | 2013-06-19 | 2015-01-08 | キヤノン株式会社 | 光学素子、光学系および光学機器 |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003202406A (ja) * | 2001-10-25 | 2003-07-18 | Matsushita Electric Works Ltd | 反射防止フィルム及びディスプレイ装置 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5747152A (en) * | 1993-12-02 | 1998-05-05 | Dai Nippon Printing Co., Ltd. | Transparent functional membrane containing functional ultrafine particles, transparent functional film, and process for producing the same |
EP1089093B1 (en) * | 1999-09-28 | 2008-04-02 | FUJIFILM Corporation | Anti-reflection film, polarizing plate comprising the same, and image display device using the anti-reflection film or the polarizing plate |
KR20070011650A (ko) * | 2001-10-25 | 2007-01-24 | 마츠시다 덴코 가부시키가이샤 | 코팅재 조성물 및 그것에 의해 형성된 피막을 가지는 물품 |
AU2002360000A1 (en) * | 2001-12-26 | 2003-07-15 | Tdk Corporation | Article having composite hard coat layer and method for forming composite hard coat layer |
-
2006
- 2006-09-27 US US12/064,356 patent/US20080292866A1/en not_active Abandoned
- 2006-09-27 KR KR1020087010182A patent/KR20080059262A/ko not_active Application Discontinuation
- 2006-09-27 JP JP2007537643A patent/JPWO2007037276A1/ja active Pending
- 2006-09-27 WO PCT/JP2006/319179 patent/WO2007037276A1/ja active Application Filing
- 2006-09-29 TW TW095136218A patent/TW200718974A/zh unknown
-
2010
- 2010-05-06 US US12/774,948 patent/US20100215943A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003202406A (ja) * | 2001-10-25 | 2003-07-18 | Matsushita Electric Works Ltd | 反射防止フィルム及びディスプレイ装置 |
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JP2010084054A (ja) * | 2008-10-01 | 2010-04-15 | Dainippon Printing Co Ltd | 耐熱層形成用塗布液、ガスバリア性シートの製造方法、ガスバリア性シート、及び製品 |
JP2011108887A (ja) * | 2009-11-18 | 2011-06-02 | Asahi Kasei Corp | 感光性樹脂積層体 |
JP2013521533A (ja) * | 2010-03-03 | 2013-06-10 | スリーエム イノベイティブ プロパティズ カンパニー | ナノ構造化表面を有する複合多層構造 |
JP2014205271A (ja) * | 2013-04-11 | 2014-10-30 | 日本カーバイド工業株式会社 | 積層シート |
JP2015004753A (ja) * | 2013-06-19 | 2015-01-08 | キヤノン株式会社 | 光学素子、光学系および光学機器 |
JP2017518521A (ja) * | 2014-04-09 | 2017-07-06 | ダウ コーニング コーポレーションDow Corning Corporation | 光学素子 |
Also Published As
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TW200718974A (en) | 2007-05-16 |
JPWO2007037276A1 (ja) | 2009-04-09 |
US20080292866A1 (en) | 2008-11-27 |
US20100215943A1 (en) | 2010-08-26 |
KR20080059262A (ko) | 2008-06-26 |
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