JP4404337B2 - Anti-reflection laminate - Google Patents

Description

  The present invention relates to an antireflection laminate obtained from a coating film having a low refractive index and high hardness and containing fluorine atoms in the molecule.

  A display surface of an image display device such as a liquid crystal display (LCD) or a cathode ray tube display device (CRT) is required to reflect less light emitted from an external light source such as a fluorescent lamp in order to improve its visibility. .

  It has been known that the reflectance is reduced by coating the surface of a transparent object with a transparent film having a low refractive index, and an antireflection film using such a phenomenon is provided on the display surface of the image display device. It is possible to improve visibility. The antireflection film is a single layer structure in which a low refractive index layer having a low refractive index is provided on the display surface, or a medium to high refractive index layer is provided on the display surface to further improve the antireflection effect. Or a multi-layer structure in which a low refractive index layer for reducing the refractive index of the outermost surface is provided on the middle to high refractive index layer.

  The single-layer type antireflection film has a simple layer structure as compared with the multilayer type, and is excellent in productivity and cost performance. On the other hand, the multilayer type antireflection film can improve the antireflection performance by combining the layer structures, and can easily achieve higher performance than the single layer type.

  The method of forming a low refractive index layer contained in such an antireflection film is generally roughly divided into a vapor phase method and a coating method. The vapor phase method includes a physical method such as a vacuum deposition method and a sputtering method, and a CVD method. The coating method includes a roll coating method, a gravure coating method, a slide coating method, a spray method, a dipping method, a screen printing method, and the like.

  In the case of the vapor phase method, it is possible to form a high-performance and high-quality transparent thin film, but it is necessary to precisely control the atmosphere in a high vacuum system, and a special heating device or ion generation acceleration device Therefore, there is a problem that the manufacturing cost is inevitably increased because the manufacturing apparatus is complicated and large. Further, in the case of the vapor phase method, it is difficult to increase the area of the transparent thin film or to form the transparent thin film with a uniform thickness on the surface of a film having a complicated shape.

  On the other hand, in the case of the spray method among the application methods, there are problems such as poor utilization efficiency of the coating liquid and difficulty in controlling the film forming conditions. In the case of roll coating method, gravure coating method, slide coating method, dipping method, screen printing method, etc., the utilization efficiency of film forming raw material is good, and there are advantages in mass production and equipment cost, but generally The transparent thin film obtained by the coating method has a problem that its function and quality are inferior to those obtained by the vapor phase method.

  As a coating method, a coating solution containing a polymer containing a fluorine atom in its molecular structure (fluorine-containing polymer) is applied to the surface of the support and dried, or a monomer containing a fluorine atom in its molecular structure (fluorine) It is known to form a low refractive index layer by applying a coating solution containing a monomer) on the surface of a support and drying it, followed by curing by UV irradiation or the like. A coating film made of a binder containing fluorine atoms has a low refractive index, and the refractive index decreases as the fluorine content increases. Further, when the fluorine content of the coating film is increased, there is an effect that dirt is difficult to adhere and the antifouling property is improved. However, since the intermolecular force of fluorine itself is small, molecules containing fluorine atoms tend to be soft, and there is a problem that the hardness and strength of the coating film decrease when the fluorine atom content in the coating film increases.

  In principle, the low refractive index layer is often provided on or near the outermost surface of the antireflection film. Therefore, the low refractive index layer is inherently susceptible to attacks such as contact, collision or friction with any article, and increases the refractive index of the coating film. For this reason, if the fluorine content is too high, the hardness will be significantly reduced and the film will be easily damaged, and it may be damaged even if it is rubbed strongly to wipe off dust and dirt.

  In addition, when the low refractive index layer is provided as an intermediate layer near the surface, it is slightly damaged against external attack, but the fluorine content is increased to lower the refractive index of the coating film. If it is too high, the stress is concentrated, so that peeling tends to occur at the interface between the low refractive index layer and the layer adjacent to the low refractive index layer. Thus, the request to lower the refractive index of the resin containing fluorine atoms and the request to increase the strength of the coating film using the resin were incompatible problems.

  Using a binder resin composition obtained by mixing a low refractive index resin composition having a high fluorine atom content in a molecular structure and a resin composition not containing a fluorine atom in the molecular structure and having a high hardness or strength. By forming the low refractive index layer, it is possible to improve the hardness and strength of the low refractive index layer. However, in this case, a resin having a high refractive index that does not contain a fluorine atom is included, and the content of fluorine atoms in the entire low refractive index layer is low. The lowering effect is impaired, and the refractive index cannot be lowered sufficiently.

Patent Document 1 discloses a low refractive index layer having a very fine porous structure formed by forming microvoids having an average diameter of 200 nm or less in a coating film made of a fluorine-containing polymer. The low refractive index layer disclosed in this publication can make the refractive index of the coating film close to the refractive index of air (ie, refractive index 1) by forming a large number of microvoids in the coating film. The refractive index can be lowered without increasing the fluorine content of the polymer. However, even in this case, if the amount of microvoids is excessively increased in order to lower the refractive index of the coating film, the hardness and strength of the coating film are reduced as in the case of increasing the fluorine content.
JP 2000-64601 A JP-A-6-3501 JP 2002-311210 A JP 2002-317152 A JP 7-133105 A JP 2002-256004 A JP 2000-267708 A

  The present invention has been achieved in view of the above-mentioned actual situation, and the object thereof is an antireflection laminate having a low refractive index layer formed by coating a fluorine-containing low refractive index composition having a low refractive index and a high hardness. Is to provide.

In order to solve the above problems, the antireflection laminate of the present invention has a low refractive index having a nanoporous structure directly on at least one side of a light-transmitting substrate or inside and / or on the surface via another layer. An antireflection laminate having a low refractive index layer formed by coating a refractive index composition,
The low refractive index composition having the nanoporous structure includes at least the following (A) to (C):
(A) ionizing radiation curable resin composition comprising a fluorine atom in the molecule,
(B) Fine particles that can be dispersed in a liquid medium for preparing a coating liquid and have an average particle diameter of 5 nm to 300 nm , and
(C) a fluorine-based and / or silicon-based compound having compatibility with both the ionizing radiation curable composition containing fluorine atoms in the molecule and the fine particles, and the fluorine-based and / or silicon A fluorine-based and / or silicon-based compound that forms a covalent bond by chemical reaction with an ionizing radiation curable resin composition in which at least a part of the compound includes a fluorine atom in the molecule, A compound in which the system compound is represented by the following general formula .

(In the formula, Ra represents an alkyl group having 1 to 20 carbon atoms, Rb is unsubstituted, or an amino group, an epoxy group, a carboxyl group, a hydroxyl group, a perfluoroalkyl group, a perfluoroalkylene group, a perfluoroalkyl ether group, Or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a polyether-modified group substituted with a (meth) acryloyl group, and each Ra and Rb may be the same or different from each other. M is an integer from 0 to 200, and n is an integer from 0 to 200.)

In addition, the antireflection laminate of another aspect of the present invention has a low refractive index having a nanoporous structure directly on at least one side of a light-transmitting substrate or inside and / or on the surface via another layer. An antireflection laminate having a low refractive index layer formed by coating a composition,
The low refractive index composition having the nanoporous structure contains at least the following (A), (B) and (D):
(A) an ionizing radiation curable resin composition containing fluorine atoms in the molecule;
(B) Fine particles that can be dispersed in a liquid medium for preparing a coating liquid and have an average particle diameter of 5 nm to 300 nm, and
(D) a fluorine-based and / or silicon-based compound having compatibility with both the ionizing radiation curable composition containing fluorine atoms in the molecule and the fine particles, and the fluorine-based and / or silicon A fluorine-based and / or silicon-based compound that forms a covalent bond by chemical reaction with an ionizing radiation curable resin composition in which at least a part of the compound includes a fluorine atom in the molecule, A compound in which the system compound is represented by the following general formula .

  Rc _n SiX _4-n
(Here, Rc represents a hydrocarbon group having 3 to 1000 carbon atoms including a perfluoroalkyl group, a perfluoroalkylene group and a perfluoroalkyl ether group, and X represents an alkoxy group having 1 to 3 carbon atoms and an oxyalkoxy group. , Represents a halogen group, and n represents an integer of 1 to 3)

  In the low refractive index layer formed by coating the low refractive index composition having a nanoporous structure in the antireflection laminate of the present invention, the nanoporous structure results from the formation of aggregates of fine particles having an average particle diameter of 5 nm to 300 nm. The structure which is the independent and / or continuous hole containing the air whose average hole diameter is 0.01-100 nm is mentioned.

  Alternatively, in the low refractive index layer formed by coating the low refractive index composition having a nanoporous structure, the nanoporous structure has pores containing air having an average pore diameter of 0.01 nm to 100 nm of the fine particles themselves having an average particle diameter of 5 nm to 300 nm. The structure formed by having is mentioned.

  In the present invention, nanoporous refers to the pores of the particles themselves, the voids formed by the particles forming an aggregate, or the air taken into the porous particles having a large specific surface area in the process of forming the coating film. It refers to air holes that are generated by diffusing from particles into the coating, and may be independent or continuous as long as they are within a desired size range.

  In general, since a resin composition containing fluorine atoms in the molecule is a material having a low refractive index, it has an advantage of being able to form a coating film having a low refractive index, but the coating film formed by applying the resin composition is In addition, since it contains a fluorine atom having a small atomic force, it has a drawback that its hardness and strength are likely to be insufficient. On the other hand, the antireflection laminate of the present invention contains fine particles having an average particle diameter of 5 nm to 300 nm, which have a void in the coating film and / or have a void by forming an aggregate. Therefore, despite the use of a resin composition containing fluorine atoms in the molecule, the coating film formed by the cohesive strength and hardness of fine particles having voids dispersed in the cured resin composition Is tightened. Therefore, even when the content of fluorine atoms is very large, a significant decrease in the hardness and strength of the coating film can be avoided.

  In particular, fine particles having voids themselves have fine voids on the outside and inside, and are filled with gas, for example, air having a refractive index of 1, and thus have a low refractive index. Even when dispersed uniformly without forming an aggregate in the coating film, the refractive index of the coating film can be lowered, which is preferable. Preferable examples of the fine particles having voids include porous silica fine particles and hollow silica fine particles. That is, for example, when silica is taken as an example, the refractive index of fine particles having voids in silica is 1.20 to 1 compared to ordinary colloidal silica particles having no gas inside (refractive index n = 1.46 or so). .45 and low. Alternatively, other preferable examples of the fine particles having voids include porous polymer fine particles and hollow polymer fine particles.

  From the above, fine particles having voids with a selected refractive index and / or addition amount, preferably fine particles having a refractive index of 1.20 to 1.45 having pores containing air having an average pore diameter of 0.01 nm to 100 nm, Alternatively, independent and / or continuous containing air having an average pore size of 0.01 nm to 100 nm and a refractive index of 1.20 to 1.45 resulting from the formation of aggregates of fine particles having an average particle size of 5 nm to 300 nm A low refractive index composition obtained by adding fine particle aggregates having pores to an ionizing radiation curable resin composition containing fluorine atoms is an ionizing radiation curable resin composition containing fluorine atoms characterized by a low refractive index. The refractive index is not affected at all or only slightly, but rather, the refractive index can be lowered, and the addition of fine particles having voids as described above. The effect of increasing the strength of the coating film as result. In particular, in the case of fine particles having silica voids, the coating film can be given a hardness comparable to or higher than that when colloidal silica is added.

  Moreover, since the average particle diameter of the fine particles having voids is 5 nm to 300 nm, the transparency of the coating film is also excellent. In addition, these fine particles are aggregated in the coating film, and in particular, by forming fine irregularities on the outermost surface of the coating film with a wavelength of less than or equal to the wavelength of visible light, the air is less than that of a resin that becomes a normal flat film. Since the structure to be incorporated is realized, the refractive index of the coating film can be expected to be lower than the effect of the refractive index of fine particles.

  The low refractive index composition used in the present invention contains fine particles having voids having an average particle diameter of 5 nm to 300 nm in a coating film made of an ionizing radiation curable resin containing fluorine atoms and cured by cross-linking. Has a distributed structure.

The low refractive index layer of the antireflection laminate according to the present invention further comprises a fluorine-based and / or silicon-based compound that is compatible with both ionizing radiation curable resin compositions having fluorine atoms in the molecule and fine particles. It is characterized by including . By including a fluorine-based compound or the like in this way, it imparts slipperiness that is effective in improving the antifouling property and scratch resistance required for the flattening of the coating surface used on the outermost surface and the antireflection laminate. be able to. "Compatibility" means the effect of addition to ionizing radiation curable resin compositions containing fluorine atoms in the molecule in which the fluorine-based and / or silicon compound has fluorine atoms in the molecule and the coating film containing fine particles. Even when an amount that can be confirmed is added, it means that the film has an affinity to the extent that a decrease in transparency due to cloudiness of the coating film or an increase in haze cannot be confirmed.

In the present invention, furthermore, at least a part of the fluorine-based and / or silicon compound forms a covalent bond by chemical reaction with the ionizing radiation curable resin composition having a fluorine atom in the molecule to form the coating film on the outermost surface. It is characterized by being fixed, and it can stably maintain slipperiness that is effective for improving antifouling properties and scratch resistance over the long term, which is necessary after commercialization of the antireflection laminate. It becomes possible.

  The low refractive index layer used in the antireflective laminate of the present invention contains fine particles that themselves have voids or voids by forming an aggregate. The content of fluorine atoms in the binder resin to be used can be increased, and the refractive index of the low refractive index layer can be made very low, 1.50 or less, preferably 1.45 or less. In addition, it has hardness and strength that can withstand practical use, and has excellent adhesion and transparency.

  Specifically, when the surface of the low refractive index layer is rubbed 10 times with # 0000 steel wool, the minimum load amount at which the change in haze value of the low refractive index layer is recognized is 200 g or more. It is possible to obtain a certain high hardness antireflection laminate.

  Preferably, the addition amount of fine particles having an average particle diameter of 5 nm to 300 nm is 1 to 400 parts by weight, more preferably 5 to 200 parts by weight, most preferably 100 parts by weight of ionizing radiation curable resin composition containing fluorine atoms. The range of 10 to 100 parts by weight is desirable.

  Therefore, the antireflection laminate of the present invention can be used for an antireflection film, and is suitably applied for antireflection of display surfaces such as liquid crystal display devices and CRTs.

  That is, the antireflective laminate of the present invention that solves the above-described problems has a low porous structure having a nanoporous structure inside and / or on the surface, directly or via another layer, on at least one side of a light-transmitting substrate. It is an antireflection laminate in which a low refractive index layer formed by coating a refractive index composition is formed.

  The layer structure of the antireflective laminate according to the present invention includes a low refractive index layer alone, a high refractive index layer / low refractive index layer, and a medium refractive index layer in order to obtain a desired antireflection effect with the low refractive index layer as the outermost layer. / High refractive index layer / low refractive index layer. The film thickness of all these layers is in the range of 0.05 to 0.15 μm, preferably in the range of 0.07 to 0.12 μm. When the film thickness is 0.05 or less or 0.15 μm or more, a sufficient antireflection effect cannot be obtained.

  According to the antireflective laminate of the present invention, the low refractive index layer itself contains fine particles having voids or voids by forming an aggregate, so that the strength of the coating film is ensured. Therefore, the content of fluorine atoms in the binder resin to be used can be increased, and the refractive index of the low refractive index layer should be very small, 1.50 or less, preferably 1.45 or less. In addition, it has hardness and strength that can withstand practical use, and has excellent adhesion and transparency. In particular, the low refractive index layer in the antireflection laminate of the present invention can satisfy both of the properties of reducing the refractive index and the property of increasing the hardness of the coating film.

  The present invention is described in detail below.

(A) component:
The binder component in the low refractive index composition used in the present invention is effective with ionizing radiation containing fluorine atoms and having a number average molecular weight of 20,000 or more, and three or more ionizing radiations per molecule. Desirably, fluorine-containing and / or non-containing monomers having functional groups are included. The resin composition includes a monomer and / or polymer containing an ionizing radiation curable fluorine atom, which is a binder component for imparting a film forming property (film forming ability) and a low refractive index to the low refractive index composition. . The fluorine atom-containing ionizing radiation curable resin composition used in the present invention has a functional group that is cured by ionizing radiation (sometimes referred to simply as “ionizing radiation curable group”), or has an ionizing radiation curable functional group. In addition to having a group, it also has a functional group that is cured by heat (sometimes referred to simply as a “thermosetting group”), so that the coating liquid containing the resin composition is applied to the surface of the object to be coated. When applied, dried, irradiated with ionizing radiation, or irradiated with ionizing radiation and heated, chemical bonds such as crosslinks are formed in the coating film, and the coating film can be cured efficiently.

  The “ionizing radiation curable group” contained in the fluorine atom-containing ionizing radiation curable resin composition of the component (A) is a coating film by causing a large molecular weight reaction such as polymerization or crosslinking by irradiation with ionizing radiation. The functional group can be cured by, for example, a polymerization reaction such as photo radical polymerization, photo cation polymerization, or photo anion polymerization, or a reaction mode such as addition polymerization or condensation polymerization that proceeds via photodimerization. One that progresses. Among them, in particular, ethylenically unsaturated bonds such as acrylic group, vinyl group, and allyl group are directly photoradically polymerized by irradiation with ionizing radiation such as ultraviolet rays and electron beams, or indirectly by the action of an initiator. It is preferable because it causes a reaction and is relatively easy to handle including the photocuring step.

  In the component (A), the “thermosetting group” that may be contained in the fluorine atom-containing ionizing radiation curable resin composition is polymerized or crosslinked between the same functional groups or other functional groups by heating. It is a functional group that can be cured by advancing a large molecular weight reaction such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and the like.

  Among these functional groups, the hydrogen bond-forming group is the component (B). When the fine particles having voids themselves or forming voids by forming aggregates are inorganic ultrafine particles, the component (B) It is also preferable because the dispersibility of the inorganic ultrafine particles and aggregates in the binder is improved. Among the hydrogen bond-forming groups, particularly hydroxyl groups are easy to introduce into the binder component, and form covalent bonds with hydroxyl groups present on the surface of fine particles having inorganic voids due to the storage stability of the coating composition or heat curing. The fine particles having voids act as a cross-linking agent and can further improve the coating film strength, which is particularly preferable.

  In order to sufficiently reduce the refractive index of the coating film, the refractive index of the fluorine atom-containing (A) component is preferably 1.50 or less.

  Among the components (A), a monomer and / or oligomer containing and / or not containing a fluorine atom in the molecule has a high effect of increasing the crosslinking density of the coating film, and is a component having a high fluidity because of its low molecular weight. There is also an effect of improving the applicability of the object.

  On the other hand, among the component (A), the fluorine atom-containing polymer has a high molecular weight, and therefore has higher film-forming properties than fluorine atom-containing and / or non-containing monomers and / or oligomers. When this fluorine atom-containing polymer is combined with the above-mentioned fluorine atom-containing and / or non-containing monomer and / or oligomer, the fluidity is improved, so that the coating suitability can be improved and the crosslinking density is also increased. The hardness and strength can be improved.

  Examples of the fluorine atom-containing monomer having an ethylenically unsaturated bond include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1). , 3-dioxole, etc.), a part of acrylic or methacrylic acid and a fully fluorinated alkyl, alkenyl, aryl ester (for example, a compound represented by the following formula 1 or formula 2), a complete or partially fluorinated vinyl ether, Examples thereof include partially fluorinated vinyl esters, fully or partially fluorinated vinyl ketones, and the like.

  Examples of fluorine atom-free monomers having an ethylenically unsaturated bond include diacrylates such as pentaerythritol triacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate monostearate; trimethylolpropane triacrylate, pentaerythritol triacrylate, and the like. Examples thereof include polyfunctional (meth) acrylates such as tri (meth) acrylate, pentaerythritol tetraacrylate derivative and dipentaerythritol pentaacrylate, and oligomers obtained by polymerizing these radical polymerizable monomers. These fluorine-free monomers and / or oligomers may be used in combination of two or more.

  When combining a fluorine atom-containing polymer having a polymerizable functional group capable of polymerizing with each other and a fluorine atom-containing and / or non-containing monomer, the film-forming property of the coating composition is improved by the fluorine atom-containing polymer, and The contained and / or non-containing monomers are preferable because the crosslinking density and coating suitability are improved, and excellent hardness and strength can be imparted to the coating film by the balance of both components. In this case, by using a combination of a fluorine atom-containing polymer having a number average molecular weight of 20,000 to 500,000 and a fluorine atom-containing and / or non-containing monomer having a number average molecular weight of 20,000 or less, It is preferable because various physical properties including film properties, film hardness, film strength and the like are easily balanced.

  As the polymer containing fluorine in the molecule, a homopolymer or copolymer of one or two or more fluorine atom-containing monomers arbitrarily selected from the fluorine atom-containing monomers as described above, or one or two or more A copolymer of a fluorine atom-containing monomer and one or more fluorine-free monomers can be used.

  Specifically, polytetrafluoroethylene; 4-fluoroethylene-6-fluoropropylene copolymer; 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer; 4-fluoroethylene-ethylene copolymer; polyvinyl fluoride; Polyvinylidene fluoride; (co) polymers of acrylic or methacrylic acid moieties and fully fluorinated alkyl, alkenyl, aryl esters (eg, compounds represented by Formula 1 or Formula 2); fluoroethylene-hydrocarbons Examples of such vinyl ether copolymers include fluorine-modified products of resins such as epoxy, polyurethane, cellulose, phenol, polyimide, and silicone.

(Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom. Rf represents a fully or partially fluorinated alkyl group, alkenyl group, heterocycle or aryl group. R ² and R ³ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a heterocyclic ring, an aryl group or a group defined by the above Rf, wherein R ¹ , R ² , R ³ and Rf each represent a substituent other than a fluorine atom. And any two or more groups of R ² , R ³ and Rf may be bonded to each other to form a ring structure.)

(In the formula, A represents a completely 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 represents a substituent other than a fluorine atom. (N represents an integer of 2 to 8.)
In addition, a commercial product such as a trade name Cytop manufactured by Asahi Glass Co., Ltd. can be exemplified.

  Among these, in particular, the polyvinylidene fluoride derivative represented by the following general formula 3 has a low refractive index, allows introduction of a curable functional group, and is excellent in compatibility with other binder components and fine particles having voids. Therefore, it is particularly preferable.

(In the formula, R ¹ is directly .R ² represents a hydrogen atom, an alkyl group or a halogen atom having 1 to 3 carbon atoms. Or fully or partially fluorinated alkyl chains, alkenyl chains, ester chains, via an ether chain And represents a completely or partially fluorinated vinyl group, (meth) acrylate group, epoxy group, oxetane group, aryl group, maleimide group, hydroxyl group, carboxyl group, amino group, amide group, and alkoxy group.)
Specifically, diacrylates such as pentaerythritol triacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate monostearate; tri (meth) acrylates such as trimethylolpropane triacrylate and pentaerythritol triacrylate, pentaerythritol tetraacrylate derivatives And polyfunctional (meth) acrylates such as dipentaerythritol pentaacrylate, or oligomers obtained by polymerizing these radical polymerizable monomers. These fluorine-free monomers and / or oligomers may be used in combination of two or more.

  Monomer, oligomer, polymer belonging to component (A) and monomer, oligomer, polymer not belonging to component (A) are appropriately combined to form a film, coating suitability, ionizing radiation curing crosslinking density, fluorine atom Various properties such as the content and the content of a thermosetting polar group can be adjusted. For example, the crosslinking density and processability are improved by monomers and oligomers, and the film forming property of the coating composition is improved by polymers.

  In the present invention, among the components (A), a monomer having a number average molecular weight (polystyrene equivalent number average molecular weight measured by GPC method) of 20,000 or less and a polymer having a number average molecular weight of 20,000 or more are appropriately combined and coated. Various properties of the membrane can be easily adjusted.

(B) Component: Fine Particles “Fine particles having voids” are preferably used as the fine particles as component (B). The term “fine particles having voids” means a result of taking a structure in which fine particles are filled with gas and / or a porous structure containing gas, or as a result of fine particles forming an aggregate, so that the gas has a refractive index of 1.0. In the case of air, the fine particles whose refractive index is decreased in inverse proportion to the occupancy ratio of the air in the fine particles compared to the original refractive index of the fine particles and the aggregate thereof. For example, it is manufactured for the purpose of increasing the specific surface area, and is used as a column for packing, a controlled release material that adsorbs various chemical substances to the porous portion of the surface, porous fine particles used for catalyst fixation, a heat insulating material, Of the hollow fine particles intended to be incorporated into a low dielectric material, those having an average particle diameter in the range of the present invention can be preferably used.

  As inorganic porous fine particles, for example, those within the range of particle diameters that can be preferably used in the present invention from the trade names Nipsil and Nipgel manufactured by Nippon Silica Kogyo Co., Ltd. as commercially available products, and as inorganic hollow particles The hollow silica fine particles prepared by using the technique disclosed in JP-A-2001-233611 are preferably used.

  Examples of the inorganic fine particles forming the aggregate include aggregates of porous silica fine particles and silica fine particles manufactured by Nissan Chemical Industries, Ltd. from the product names Nippon and Nippon manufactured by Nippon Silica Kogyo Co., Ltd. as commercial products. Among the colloidal silica UP series (trade name) having a chain-like structure, those within the range of the particle diameter that can be preferably used in the present invention can be used. The fine particles having an average particle diameter of 5 nm to 300 nm used in the present invention may be formed by connecting fine particles having a primary particle diameter of 5 nm to 100 nm in a chain.

  The organic fine particles having voids themselves are, for example, porous particles having a polymer layer and a pore-filling layer as shown in JP-A No. 2002-256004, wherein the pore-filling layer is a fugitive substance, Examples thereof include a substitution gas, or a combination thereof, and porous particles having a glass transition temperature of 10 ° C. to 50 ° C. of the polymer layer.

  The organic fine particles forming the aggregate are, for example, commercially available functional fine particle aggregate MP-300F manufactured by Soken Chemical Co., Ltd. (commercially available as 0.1 μm acrylic aggregate particles). Etc. can be preferably used.

  Among the fine particles having voids themselves or forming voids by forming aggregates, the fine particles having voids of inorganic components, particularly silica, are easy to manufacture and hard themselves, The film strength when combined is improved, and a refractive index of 1.20 to 1.45 can be achieved, so that it can be preferably used.

  The primary particle size of the fine particles having voids as the component (B) is preferably in the range of an average particle size of 5 nm to 300 nm in order to impart excellent transparency to the coating film.

Component (C), Component (D) The low refractive index layer of the antireflective laminate according to the present invention is compatible with both ionizing radiation curable resin compositions containing fluorine atoms in the molecule and fine particles. It is characterized by containing a fluorine-based and / or silicon-based compound. By including a fluorine-based compound or the like in this way, it imparts slipperiness that is effective in improving the antifouling property and scratch resistance required for the flattening of the coating surface used on the outermost surface and the antireflection laminate. be able to.

In the present invention, furthermore, at least part of the fluorine-based and / or silicon compound, and ionizing radiation-curable resin composition is fixed to the coated film outermost surface to form a covalent bond by a chemical reaction, thereby In addition, it is possible to stably maintain the slipperiness required for improving the antifouling property and scratch resistance over a long period of time required after the antireflection laminate is commercialized.

Examples of the fluorine-based compound include a perfluoroalkyl group represented by C _d F _{2d + 1} (d is an integer of ₁ to 21), and — (CF ₂ CF ₂ ) _g — (g is an integer of 1 to 50). perfluoroalkylene group represented or F, - (- CF (CF 3) CF 2 O-) e -CF (CF 3) ( where, e is an integer of 1 to 50) perfluoroalkyl ether represented by Group, CF ₂ = CFCF ₂ CF _2- , (CF ₃ ) ₂ C = C (C ₂ F ₅ )-, and ((CF ₃ ) ₂ CF) ₂ C = C (CF ₃ )- It is preferable to have a perfluoroalkenyl group.

The structure of the fluorine compound is not particularly limited as long as it is a compound containing the above functional group. For example, a polymer of a fluorine-containing monomer or a copolymer of a fluorine-containing monomer and a non-fluorine monomer is used. You can also. Among them, in particular, a fluorine-containing polymer segment composed of either a homopolymer of a fluorine-containing monomer or a copolymer of a fluorine-containing monomer and a non-fluorine monomer, and a non-fluorine polymer segment, A block copolymer or graft copolymer consisting of is preferably used. In such a copolymer, the fluorine-containing polymer segment mainly has a function of improving antifouling properties and water / oil repellency, while the non-fluorine polymer segment is compatible with the binder component. Since it is high, it has an anchor function. Therefore, in the antireflection laminate using such a copolymer, even when the surface is repeatedly rubbed, it is difficult to remove these fluorine-based compounds, and various performances such as antifouling properties over a long period of time. Can be maintained.
The said fluorine-type compound can be obtained as a commercial product, for example, Nippon Oil & Fats Modiper F series (brand name), Dainippon Ink & Chemicals, Inc. defender MCF series (brand name) etc. are used preferably.

The fluorine-based or / and silicon-based compound has the following general formula:

(In the formula, Ra represents an alkyl group having 1 to 20 carbon atoms such as a methyl group, and Rb is unsubstituted, or an amino group, an epoxy group, a carboxyl group, a hydroxyl group, a perfluoroalkyl group, a perfluoroalkylene group, a perfluoro group. An alkyl ether group or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a polyether-modified group substituted with a (meth) acryloyl group, wherein each Ra and Rb are the same or different from each other. M is an integer from 0 to 200, and n is an integer from 0 to 200.)
(C) component) .

Polydimethylsilicone having a basic skeleton like the above general formula is generally known to have low surface tension and excellent water repellency and releasability, but various functional groups are introduced into the side chain or terminal. By doing so, a further effect can be provided. For example, reactivity can be imparted by introducing an amino group, an epoxy group, a carboxyl group, a hydroxyl group, a (meth) acryloyl group, an alkoxy group, etc., and an ionizing radiation curable resin composition containing a fluorine atom in the molecule. A covalent bond can be formed by a chemical reaction. In addition, by introducing perfluoroalkyl groups, perfluoroalkylene groups, and perfluoroalkyl ether groups, oil resistance and lubricity can be imparted, and by introducing polyether-modified groups, leveling properties and lubricity can be provided. Can be improved.
Such a compound can be obtained as a commercial product. For example, silicone oil FL100 having a fluoroalkyl group (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) or polyether-modified silicone oil TSF4460 (trade name, GE Toshiba) Various modified silicone oils can be obtained according to the purpose.

In a preferred embodiment of the present invention, the fluorine-based and / or silicon-based compound has the following general formula:
Rc _n SiX _4-n
(In the formula, Rc represents a hydrocarbon group having 3 to 1000 carbon atoms including a perfluoroalkyl group, a perfluoroalkylene group, or a perfluoroalkyl ether group, and X represents a carbon such as a methoxy group, an ethoxy group, or a propoxy group. A hydrolyzable group such as an alkoxy group of formulas 1 to 3, an oxyalkoxy group such as a methoxymethoxy group or a methoxyethoxy group, or a halogen group such as a chloro group, a bromo group or an iodo group, which may be the same or different; And n represents an integer of 1 to 3.)
It may be the structure shown by ((D) component) .
By including such a hydrolyzable group, particularly when inorganic fine particles are used, it is easy to form a covalent bond or a hydrogen bond with the hydroxyl group on the surface of the fine particles, and the adhesiveness can be maintained.
Specific examples of such a compound include fluoroalkylsilanes such as TSL8257 (trade name: manufactured by GE Toshiba Silicone).

  The fluorine-based and / or silicon-based compound is 0.01 to 10% by weight, preferably 0.1 to 3.3% by weight based on the total weight of the ionizing radiation curable resin composition containing fluorine atoms in the molecule and fine particles. The content is preferably 0% by weight. When the content is less than 0.01% by weight, sufficient antifouling property and slipperiness cannot be imparted to the antireflection laminate, and when it exceeds 10% by weight, the strength of the coating film is extremely lowered. .

  These fluorine-based compounds and silicon-based compounds may be used alone or in combination of two or more depending on the expected effect. By appropriately combining these compounds, various properties such as antifouling property, water and oil repellency, slipping property, scratch resistance, durability, and leveling property can be adjusted to achieve the intended function.

  The low refractive index layer constituting the antireflection laminate according to the present invention comprises, as an essential component, an ionizing radiation curable resin composition component containing a fluorine atom in the molecule, the fine particle component, and the fluorine-based and / or silicon compound. However, if necessary, a binder component other than the ionizing radiation curable resin composition component containing a fluorine atom in the molecule as described above may be contained, and further, a coating for forming a low refractive index layer may be included. The working liquid may contain a solvent, a polymerization initiator, a curing agent, a crosslinking agent, an ultraviolet blocking agent, an ultraviolet absorber, a surface conditioner (leveling agent), or other components.

  A polymerization initiator is not necessarily required in the present invention. However, the ionizing radiation curable groups of the fluorine atom-containing (A) component, the (B) component of fine particles having voids, and other optional binder components may not easily cause a direct polymerization reaction upon irradiation with ionizing radiation. is there. In such a case, it is preferable to use an appropriate initiator in accordance with the reaction mode of the binder component and the inorganic ultrafine particles.

  For example, when the ionizing radiation curable group of the fluorine atom-containing (A) component is an ethylenically unsaturated bond, a photo radical polymerization initiator is used. Examples of photo radical polymerization initiators include acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoro An amine compound or the like is used. More specifically, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzyldimethylketone, 1- (4-dodecyl) Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane Examples thereof include -1-one and benzophenone. Among these, 1-hydroxy-cyclohexyl-phenyl-ketone and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one are polymerized by irradiation with ionizing radiation even in a small amount. Since it initiates and accelerates the reaction, it is preferably used in the present invention. These can be used either alone or in combination. These also exist in commercial products. For example, 1-hydroxy-cyclohexyl-phenyl-ketone can be obtained from Ciba Specialty Chemicals Co., Ltd. under the trade name Irgacure 184.

  When using a radical photopolymerization initiator, the radical photopolymerization initiator is usually blended in a proportion of 3 to 15 parts by weight with respect to a total of 100 parts by weight of the binder component mainly composed of a fluorine atom-containing component.

  A hardening | curing agent is mix | blended in order to accelerate | stimulate the thermosetting reaction of the thermosetting polar group of a fluorine atom containing (A) component. When the thermosetting polar group is a hydroxyl group, a compound having a basic group such as methylol melamine, a compound having a hydrolyzable group that generates a hydroxyl group by hydrolysis of a metal alkoxide, etc. Is done. As the basic group, an amine, nitrile, amide, or isocyanate group is preferably used, and as the hydrolyzable group, an alkoxy group is preferably used. In the latter case, in particular, an aluminum compound represented by the following general formula: The derivative has good compatibility with a hydroxyl group and is particularly preferably used.

AlR ₃ Formula (4)
(The above general formula (4) can be selected from aluminum compounds and / or oligomers and / or complexes derived therefrom and aluminum salts of inorganic or organic acids, wherein the residue R is These may be the same or different, and are halogen, alkyl having 10 or less carbon atoms, preferably 4 or less, alkyl, alkoxy, or acyloxy, or hydroxy, and these groups may be replaced in whole or in part by chelating ligands Good.)
Specific examples include aluminum-sec-butoxide, aluminum-iso-propoxide, and complexes thereof with acetylacetone, ethyl acetoacetate, alkanolamines, glycols, and derivatives thereof.

  When the thermosetting polar group of the component (A) is an epoxy group, a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid is usually used as a curing agent in the coating composition.

  Specific examples of polyhydric carboxylic acid anhydrides include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride; fats such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride Aromatic polycarboxylic dianhydrides; aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ester groups such as ethylene glycol bistrimellitate and glycerin tristrimitate Containing acid anhydrides, particularly preferably aromatic poly It may be mentioned carboxylic acid anhydrides. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably.

  Specific examples of the polyvalent carboxylic acid used in the present invention include aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid, Aliphatic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, Aromatic polyvalent carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid can be mentioned, and aromatic polyvalent carboxylic acids can be mentioned preferably.

  When using a hardening | curing agent, a hardening | curing agent is normally mix | blended in the ratio of 0.05-30.0 weight part with respect to a total of 100 weight part of the binder components which have a fluorine atom containing component as a main component.

When a relatively large amount of a liquid fluorine atom-containing monomer and / or oligomer is used as a solvent fluorine atom-containing binder component, the fluorine atom-containing monomer and / or oligomer also functions as a liquid medium for preparing a coating liquid. Therefore, in some cases, the solid component of the coating composition can be dissolved, dispersed, or diluted without using a solvent to prepare a coating solution. Accordingly, in the present invention, a solvent is not always necessary, but in many cases, a solvent is used to dissolve and disperse solid components, adjust the concentration, and prepare a coating solution having excellent coating suitability.

  The solvent used for dissolving and dispersing the solid component of the low refractive index composition used in the present invention is not particularly limited, and various organic solvents, for example, alcohols such as isopropyl alcohol, methanol, and ethanol; methyl ethyl ketone, methyl isobutyl ketone Ketones such as cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; aromatic hydrocarbons such as toluene and xylene; or a mixture thereof.

  Preferably, a ketone organic solvent is used. The reason is that when the low refractive index composition used in the present invention is prepared using a ketone solvent, it can be easily and uniformly applied to the substrate surface, and the evaporation rate of the solvent after coating is high. This is because it is moderate and hardly causes uneven drying, and a large-area coating film having a uniform thickness can be easily obtained.

  In order to impart a function as an antiglare layer to the hard coat layer that is the support layer of the antireflection film, the surface of the hard coat layer is formed with fine irregularities, and then, a medium refractive index layer or a high refractive index layer is interposed therebetween. In some cases, the low refractive index layer is formed by applying the coating composition of the present invention with or without intervention. When the coating composition of the present invention is prepared using a ketone solvent, it can be applied evenly on the surface of such fine irregularities, and uneven coating can be prevented.

  As a ketone solvent, it contains a single solvent composed of one kind of ketone, a mixed solvent composed of two or more kinds of ketones, and other solvents together with one or more kinds of ketones, and has lost its properties as a ketone solvent. Those that are not can be used. Preferably, a ketone solvent in which 70% by weight or more, particularly 80% by weight or more of the solvent is occupied by one or two or more ketones is used.

  The amount of the solvent is appropriately adjusted so that each component can be uniformly dissolved and dispersed, does not cause aggregation during storage after preparation, and does not become too dilute during coating. Prepare a low-refractive-index composition for high-concentration coating by reducing the amount of solvent used within the range that satisfies this condition, store it in a state that does not take up any volume, and take out the necessary amount at the time of use. It is preferable to dilute to a concentration suitable for the work. When the total amount of the solid content and the solvent is 100 parts by weight, the solvent is 50 to 95.5 parts by weight, more preferably 10 to 30 parts by weight based on the total solids of 0.5 to 50 parts by weight. By using the solvent in a proportion of 70 to 90 parts by weight with respect to parts, a low refractive index composition that is particularly excellent in dispersion stability and suitable for long-term storage can be obtained.

Preparation of Low Refractive Index Composition for Coating In order to prepare a low refractive index composition for a coating used in the present invention using each of the above components, a dispersion treatment is performed according to a general method for preparing a coating liquid. That's fine. For example, each essential component and each desired component are mixed in an arbitrary order, and a medium such as beads is added to the obtained mixture, and appropriately dispersed with a paint shaker or a bead mill to reduce the refractive index for coating. Rate composition is obtained.

Formation of Coating Film In order to form a coating film using the low refractive index composition used in the present invention, a coating solution containing (A) (B) component and (C) component or (D) component Is coated on the surface of the object to be coated, dried, and cured by ionizing radiation and / or heating to obtain a cured product of a film mainly containing the component (A) and the component (B).

  Examples of the coating method of the low refractive index composition used in the present invention include spin coating, dipping, spraying, slide coating, bar coating, roll coater, meniscus coater, flexographic printing, and screen printing. It can apply | coat on support bodies, such as a base material, by various methods, such as a method and a bead coater method.

  The support on which the low refractive index composition is applied is not particularly limited. Preferred substrates include, for example, a glass plate; triacetate cellulose (TAC), polyethylene terephthalate (PET), diacetyl cellulose, acetate butyrate cellulose, polyethersulfone, acrylic resin; polyurethane resin; polyester; polycarbonate; Examples thereof include films formed of various resins such as polyether; trimethylpentene; polyether ketone; (meth) acrylonitrile. The thickness of a base material is about 30 micrometers-200 micrometers normally, Preferably it is 50 micrometers-200 micrometers.

  Applying the coating solution of the low refractive index composition directly on the surface of an object to be coated such as a base material or through another layer such as a hard coat layer or a light-transmitting anti-glare layer, and drying. Thus, a coating film having excellent adhesion to the surface of the object to be coated can be obtained by the action of the polar group having thermosetting properties.

Antireflection stack will now be described a specific example of the anti-reflection laminate of the present invention. The antireflection laminate of the present invention is a layer (light transmissive layer) having a light transmissive property and a refractive index different from each other directly or via another layer on at least one surface side of a light transmissive substrate. At least one layer of a single layer type or multilayer type antireflection film formed by laminating one or more layers is a low refractive index layer. The antireflection laminate can be used as an antireflection film. In the present invention, in the multilayer antireflection film, the layer having the highest refractive index is referred to as a high refractive index layer, the layer having the lowest refractive index is referred to as a low refractive index layer, and other intermediate refractions. A layer having a refractive index is referred to as a medium refractive index layer. The base material and the light transmission layer need to have light transmittance that can be used as a material for the antireflection film, and are preferably as transparent as possible.

  In the antireflection laminate obtained in the present invention, as the other layer, a hard coat layer may be provided for the purpose of imparting hard performance such as scratch resistance and strength to the antireflection laminate. Alternatively, an antiglare layer may be provided as another layer for the purpose of imparting antiglare properties to the antireflection laminate.

Hard coat layer The hard coat layer in the antireflection laminate of the present invention is preferably formed using an ionizing radiation curable resin composition. In the present specification, the “hard coat layer” means a layer having a hardness of H or higher in a pencil hardness test shown in JIS 5600-5-4: 1999.

  The ionizing radiation curable resin composition suitable for forming the hard coat layer is preferably one having an acrylate functional group, such as a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin. , Urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyether resins, polyhydric alcohols, di (meth) acrylates such as ethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate; Tri (meth) acrylates such as methylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate derivatives and dipentaerythritol penta (meth) acrylate Etc. may be used polyfunctional (meth) oligomer, such as monomers, epoxy acrylates and urethane acrylates such as multifunctional compounds such as acrylates rates.

  The hard coat layer in the antireflection laminate of the present invention has a cured film thickness of 0.1 to 100 μm, preferably 0.8 to 20 μm. When the film thickness is 0.1 μm or less, sufficient hard coat performance cannot be obtained, and when the film thickness is 100 μm or more, it is not preferable because it easily breaks against an external impact.

  When the refractive index of the hard coat layer in the antireflection laminate of the present invention is 1.57 to 1.70, the antireflection laminate can have the function of a medium refractive index layer or a high refractive index layer. Preferred for sex.

Antiglare layer The hard coat layer in the antireflection laminate of the present invention may have antiglare properties described below, and an antiglare layer may be provided separately from the hard coat layer.

  The antiglare layer of the present invention can be constituted using an ionizing radiation curable resin composition and resin beads having a refractive index of 1.40 to 1.60. By including resin beads, in addition to hard coat properties, antiglare properties can be imparted. The ionizing radiation curable resin composition can be appropriately selected from those preferably used for the hard coat layer.

  The reason why the refractive index of the resin beads is in such a range is that the ionizing radiation curable resin, in particular, the refractive index of the acrylate or methacrylate resin is usually 1.45 to 1.55. This is because if resin beads having a refractive index as close as possible to the refractive index are selected, the transparency of the coating film is not impaired and the antiglare property can be increased. Examples of resin beads having a refractive index close to that of ionizing radiation curable resin include polymethyl methacrylate beads (1.49), polycarbonate beads (1.58), polystyrene beads (1.50), and polyacrylstyrene beads. (1.57), polyvinyl chloride beads (1.54), etc., but those within the above range can be used.

  The particle diameter of these resin beads is preferably 3 to 8 μm, and 2 to 10 parts by weight, usually about 4 parts by weight, is used with respect to 100 parts by weight of the resin. When resin beads such as paint are mixed, it is necessary to agitate and disperse the resin beads precipitated on the bottom of the container when using the paint. In order to eliminate such inconvenience, silica beads having a particle diameter of 0.5 μm or less, preferably 0.1 to 0.25 μm may be included in the coating material as an anti-settling agent for resin beads. Note that the more silica beads are added, the more effective the prevention of sedimentation of the organic filler is, but it adversely affects the transparency of the coating film. Therefore, it is preferable that the amount is less than 0.1 parts by weight, which is a range in which sedimentation can be prevented with respect to 100 parts by weight of the resin without impairing the transparency of the coating film.

  The antiglare layer in the antireflection laminate of the present invention desirably has a film thickness after curing of 0.1 to 100 μm, preferably 0.8 to 20 μm. When the film thickness is 0.1 μm or less, sufficient hard coat performance cannot be obtained, and when the film thickness is 100 μm or more, it is not preferable because it easily breaks against an external impact.

Antistatic layer The antireflective laminate of the present invention has no need to generate static electricity and prevent dust from adhering to it, or when it is incorporated into a liquid crystal display, etc. An antistatic layer may be formed. In this case, the antistatic layer preferably has a surface resistance of 1012 Ω / □ or less after the formation of the antireflection laminate. However, even if it is 10 12 Ω / □ or more, dust adhesion can be prevented as compared with the case where no antistatic layer is provided.

  Examples of the antistatic agent contained in the antistatic resin composition include various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and first to third amino groups, and a sulfonate group. , Anionic antistatic agents having anionic groups such as sulfate ester base, phosphate ester base, phosphonate base, amphoteric antistatic agents such as amino acid and aminosulfate esters, amino alcohols, glycerols, polyethylene glycols Nonionic antistatic agents such as, various surfactant type antistatic agents such as metal chelate compounds such as organometallic compounds such as alkoxides of tin and titanium, and acetylacetonate salts thereof, and charging as described above High molecular weight antistatic agent having a high molecular weight, and tertiary amino groups and quaternary amines. Sulfonium groups, polymerizable antistatic agents such as an organic metal compound such as a coupling agent having polymerizable monomer or oligomer by ionizing radiation has a metal chelate portion, the same polymerizable functional groups by ionizing radiation may also be used.

  Other antistatic agents contained in the antistatic resin composition include ultrafine particles having a particle diameter of 100 nm or less, such as tin oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and indium-doped zinc oxide (AZO). Antimony oxide, indium oxide, or the like can be used. In particular, it is preferable that the particle diameter is 100 nm or less, which is equal to or less than the wavelength of visible light, since it becomes transparent after film formation and the transparency of the antireflection film is not impaired.

  By mixing the antistatic agent in the coating material for forming the hard coat layer and the antiglare layer, two properties of antistatic performance and hard coat property, and similarly two properties of antistatic performance and antiglare property. It becomes possible to obtain a coating film that improves the above simultaneously.

High refractive index layer to medium refractive index layer (refractive index layer in the range of refractive index 1.46 to 2.00)
Between the hard coat layer and the low refractive index layer, a refractive index in the range of 1.46 to 2.00 and a film thickness in the range of 0.05 to 0.15 μm to a high refractive index layer, It is desirable in terms of antireflection properties that at least one layer is provided.

  The middle to high refractive index layer in the antireflection laminate of the present invention can be constituted mainly by containing ionizing radiation curable resin and medium to high refractive index ultrafine particles having a particle diameter of 100 nm or less. Examples of ultrafine particles with medium to high refractive index include zinc oxide (refractive index 1.90, the following numerical values indicate refractive index), titania (2.3-2.7), ceria (1.95), tin-doped Examples include indium oxide (1.95), antimony-doped tin oxide (1.80), yttria (1.87), and zirconia (2.0). The ultrafine particles preferably have a higher refractive index than the ionizing radiation curable resin binder. The refractive index is determined by the content of the fine particles in the refractive index layer, that is, the refractive index increases as the content of the fine particles increases. Therefore, the refractive index is set to 1 by controlling the composition ratio of the ionizing radiation curable resin and the fine particles. It can be freely controlled in the range of .46 to 2.00.

  If these ultrafine particles have conductivity, the high refractive index layer and the medium refractive index layer formed using the ultrafine particles have antistatic properties.

  The medium refractive index layer and the high refractive index layer are formed by depositing an inorganic oxide having a high refractive index such as titanium oxide or zirconium oxide formed by a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD). It can be formed into a film or a coating film in which inorganic oxide fine particles having a high refractive index such as titanium oxide are dispersed. As the medium refractive index layer, a light transmissive layer having a refractive index of 1.46 to 1.80 can be used, and as the high refractive index layer, a light transmissive layer having a refractive index of 1.65 or more can be used. .

An antifouling layer may be provided on the surface of the low refractive index layer opposite to the substrate side for the purpose of antifouling the surface of the low refractive index layer. Although the antifouling layer is provided on the surface opposite to the substrate side of the low refractive index layer, it has an effect on antifouling properties and scratch resistance of the antireflection film, but ionizing radiation having fluorine atoms in the molecule Fluorine-based and / or silicon compounds that have low compatibility with the curable resin composition and cannot be added to the low refractive index layer, and ionizing radiation curable resin compositions and fine particles having fluorine atoms in the molecule Alternatively, compatible fluorine-based and / or silicon-based compounds may be used. By providing the low refractive index layer on the surface opposite to the substrate side, the anti-reflection laminate required for the antireflection laminate is required. Further improvement in dirtiness and scratch resistance can be expected.

  FIG. 3 schematically shows a cross section of an example of the antireflection laminate of the present invention as an antireflection film. The antireflection film 102 is formed by forming a high refractive index layer 22 on one surface side of a base film 21 having optical transparency, and further applying a low refractive index composition used in the present invention on the high refractive index layer. Thus, the low refractive index layer 23 is provided. In this example, there are only two light transmissive layers having different refractive indexes, a high refractive index layer and a low refractive index layer, but three or more light transmissive layers may be provided. In that case, not only the low refractive index layer but also the middle refractive index layer can be formed by applying the low refractive index composition used in the present invention.

Image Display Device The antireflective laminate of the present invention is a display surface of an image display device such as a liquid crystal display device (LCD), a cathode ray tube display device (CRT), a plasma display panel (PDP), or an electroluminescence display (ELD). It is suitably used for forming at least one of the multilayer antireflection coatings, particularly the low refractive index layer.

  FIG. 1 schematically shows a cross section of an example (101) of a liquid crystal display device in which a display surface is covered with a multilayer antireflection film containing the antireflection laminate of the present invention as a light transmission layer. The liquid crystal display device 101 prepares a color filter 4 in which an RGB pixel portion 2 (2R, 2G, 2B) and a black matrix layer 3 are formed on one surface of a glass substrate 1 on the display surface side, and the pixel of the color filter. The transparent electrode layer 5 is provided on the part 2, the transparent electrode layer 7 is provided on one surface of the glass substrate 6 on the backlight side, and the transparent electrode layers 5 and 7 face each other with the glass substrate on the backlight side and the color filter. Then, a predetermined gap is left facing each other, the periphery is adhered with a sealing material 8, liquid crystal L is sealed in the gap, an alignment film 9 is formed on the outer surface of the glass substrate 6 on the back side, and the glass substrate on the display surface side The polarizing film 10 is affixed on the outer surface of 1, and the backlight unit 11 is arrange | positioned back.

  FIG. 2 schematically shows a cross section of the polarizing film 10 attached to the outer surface of the glass substrate 1 on the display surface side. The polarizing film 10 on the display surface side covers both surfaces of a polarizing element 12 made of polyvinyl alcohol (PVA) or the like with protective films (light-transmitting base films) 13 and 14 made of triacetyl cellulose (TAC) or the like. An adhesive layer 15 is provided on the back side, and a hard coat layer 16 and a multilayer antireflection film 17 are sequentially formed on the viewing side. The adhesive layer 15 is provided on the glass substrate 1 on the display surface side. It is stuck.

  Here, in order to reduce the glare by diffusing the light emitted from the inside as in a liquid crystal display device, the hard coat layer 16 is formed by forming the surface of the hard coat layer in a concavo-convex shape or the hard coat layer. It is good also as an anti-glare layer (anti-glare layer) which gave the function to disperse | distribute light inside a hard-coat layer by disperse | distributing an inorganic or organic filler inside the layer. The hard coat layer may be composed of two or more layers, and the hard coat layers can be used in appropriate combination.

  The multilayer antireflection film 17 has a three-layer structure in which a middle refractive index layer 18, a high refractive index layer 19, and a low refractive index layer 20 are sequentially laminated from the backlight side to the viewing side. The multilayer antireflection film 17 may have a two-layer structure in which a high refractive index layer 19 or a medium refractive index layer 18 and a low refractive index layer 20 are sequentially stacked. When the surface of the hard coat layer 16 is formed in an uneven shape, the multilayer antireflection film 17 formed thereon also has an uneven shape as shown in the drawing.

  The low refractive index layer 20 is a coating film formed by applying the coating composition of the present invention on the high refractive index layer 19, drying, and photocuring, and has a refractive index of 1.45 or less, preferably 1. .41 or less, and can be lowered to about 1.20. The medium refractive index layer 18 and the high refractive index layer 19 are inorganic oxides having a high refractive index such as titanium oxide and zirconium oxide formed by a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD). Or a coating film in which inorganic oxide fine particles having a high refractive index such as titanium oxide are dispersed. The medium refractive index layer 18 has a refractive index of 1.46 to 1.80. A light transmissive layer having a refractive index of 1.65 or more is used for the light transmissive layer in the range and the high refractive index layer 19.

  Furthermore, when it is necessary to impart antistatic properties or electrostatic properties, a conductive layer may be provided on the base film, or conductive particles may be included in the hard coat layer. The same properties can also be obtained by using a conductive material for the inorganic oxide fine particles having a high refractive index dispersed in the medium refractive index layer or the high refractive index layer. Furthermore, if the desired refractive index is within the range, an antistatic agent composed of an organic component is added directly to the low refractive index layer, or an antistatic layer is applied to the outermost surface of the low refractive index layer, affecting the performance of the antireflection film. Similar properties can be obtained by providing the film thickness within a range of 30 nm or less.

  Due to the action of the antireflection film, the reflectance of light emitted from the external light source is reduced, so that the reflection of scenery and fluorescent light is reduced and the visibility of the display is improved. Moreover, the reflected light of external light is reduced by the light scattering effect by the unevenness | corrugation of the hard-coat layer 16, and the visibility of a display improves further that external light is reflected on the display surface, or is a dazzling state. .

  In the case of the liquid crystal display device 101, the intermediate refractive index layer 18 having a refractive index adjusted in the range of 1.46 to 1.80 and a refractive index of 1.65 are provided on the laminate including the polarizing element 12 and the protective films 13 and 14. The low refractive index layer 20 can be provided by forming the high refractive index layer 19 adjusted as described above and further applying the low refractive index composition used in the present invention. Then, the polarizing film 10 including the antireflection film 17 can be stuck on the glass substrate 1 on the viewing side through the adhesive layer 15.

  On the other hand, since an orientation plate is not attached to the display surface of the CRT, it is necessary to directly provide an antireflection laminate. However, applying the coating composition of the present invention to the display surface of the CRT is a complicated operation. In such a case, an antireflection film containing the antireflection laminate of the present invention is prepared, and the antireflection film is formed by sticking it to the display surface. It is not necessary to apply the low refractive index composition.

  Examples and Comparative Examples of the present invention are shown below, but the scope of the present invention is not limited thereto.

Preparation of coating composition for low refractive index layer A coating composition for low refractive index layer was prepared by blending the components of the following composition.

Fluorine atom-containing binder resin (OPSTAR JM5010: trade name, manufactured by JSR Corporation, refractive index 1.41, solid content 10% by weight, methyl ethyl ketone solution) 14. 3 parts by mass photopolymerization initiator (Irgacure 907: trade name, 0.1 parts by mass of porous silica fine particles (Nipsil SS50F: trade name, manufactured by Nippon Silica Kogyo Co., Ltd., primary particle diameter 20 nm, refractive index 1.38, specific surface area 82 m ² / g) 1.43 Mass part F3035 (trade name, manufactured by NOF Corporation) 0.4 parts by mass
Formation of hard coat layer The following components were mixed to prepare a coating composition for forming a hard coat layer. The resulting hard coat layer forming coating composition was bar-coated on a transparent substrate, and the solvent was removed by drying. Then, using a UV irradiation device (Fusion UV System Japan Co., Ltd., light source H bulb), UV irradiation was performed at an irradiation dose of 108 mJ / cm ² to harden the hard coat layer, and the substrate having a film thickness of 2 to 5 μm / A hard coat film was obtained.

Pentaerythritol triacrylate (PETA) 5 parts by mass Photopolymerization initiator (Irgacure 184: trade name, manufactured by Ciba Specialty Chemicals) 0.25 parts by mass Methyl isobutyl ketone 94.75 parts by mass
Formation of a low refractive index layer A triacetate cellulose (TAC) film having a thickness of 80 μm is bar-coated with a hard coat layer-forming composition having the above composition, and after drying, the solvent is removed, and then an ultraviolet irradiation device (Fusion UV System Japan ( A substrate / hard coat layer film having a hard coat layer with a film thickness of about 5 μm by irradiating ultraviolet rays at an irradiation dose of 100 mJ / cm ² using a light source H pulp). Obtained.

On the obtained base material / hard coat layer film, the above-mentioned composition for forming a low refractive index layer is bar-coated, and after removing the solvent by drying, an ultraviolet irradiation device (Fusion UV System Japan Co., Ltd., Using a light source H bulb), ultraviolet rays were irradiated at an irradiation dose of 200 mJ / cm ² , and the coating film was cured to obtain a laminate of base material / hard coat layer / low refractive index layer.

Preparation of Coating Composition for Low Refractive Index Layer 2-1 Atomization Treatment of Aggregated Particles Components having the following composition were mixed and the agglomerated silica particles were pulverized with a three roll until the average particle size became 100 nm. The refractive index of the aggregated silica particles after pulverization was 1.36.
Pentaerythritol triacrylate (PETA) 0.72 parts by mass Aggregated silica fine particles (Nipsil E220A: trade name, manufactured by Nippon Silica Kogyo Co., Ltd., primary particle size 20 nm, particle size 1.5 μm, specific surface area 150 m 2 / g) 1.43 mass Part 2-2 Preparation of coating composition for low refractive index layer The following components were mixed with the monomer solution in which the aggregated silica obtained in the above step was dispersed to prepare a coating composition for the low refractive index layer.

Fluorine atom-containing binder resin (OPSTAR JM5010: trade name, manufactured by JSR Corp., refractive index 1.41, solid content 10%, methyl ethyl ketone solution) 7.2 parts by mass photopolymerization initiator (Irgacure 907: trade name, Ciba Specialty Chemicals) 0.1 parts by mass F3035 (trade name, manufactured by NOF Corporation) 0.4 parts by mass
Formation of Hard Coat Layer A hard coat layer was formed on the transparent substrate in the same manner as in Example 1.

Formation of Low Refractive Index Layer On the transparent substrate / hard coat film obtained in the above step, the coating composition for low refractive index layer prepared above was applied, and the substrate / hard substrate was prepared in the same manner as in Example 1. A coating layer / low refractive index layer film was obtained.

  A hard coat layer and a low refractive index layer were formed in the same manner as in Example 1 except that the composition for forming a low refractive index layer in Example 1 was changed as follows. Obtained.

Fluorine atom-containing binder resin (OPSTAR JM5010: trade name, manufactured by JSR Corporation, refractive index 1.41, solid content 10% by weight, methyl ethyl ketone solution) 14.3 parts by mass photopolymerization initiator (Irgacure 907: trade name, 0.1 parts by mass porous silica fine particles (Nipsil SS50F: trade name, manufactured by Nippon Silica Kogyo Co., Ltd., primary particle diameter 20 nm, refractive index 1.38, specific surface area 82 m ² / g) 1.43 Mass part F3035 (trade name, manufactured by NOF Corporation) 0.4 part by mass TSF4460 (trade name, manufactured by GE Toshiba Silicone Co., Ltd.) 0.12 parts by mass

Preparation of Antistatic Layer Forming Composition An antistatic layer forming composition was prepared by mixing the following components.

Antimony-doped tin oxide dispersion (solid content 45%, Pertron C-4456S-7: trade name, manufactured by Nippon Pernox) 25 parts by mass HDDA (KS-HDDA: trade name, manufactured by Nippon Kayaku) 10.5 parts by mass Irgacure 184 (Product name, manufactured by Ciba Specialty Chemicals) 0.84 parts by mass Butyl acetate 76.5 parts by mass Cyclohexanone 32.8 parts by mass
Preparation of laminate (base material / antistatic layer / hard coat layer / low refractive index layer) The antistatic layer forming composition having the above composition is bar-coated on a TAC film, the solvent is removed by drying, and then UV irradiation is performed. The apparatus was used to irradiate ultraviolet rays at an irradiation dose of about 20 mJ / cm ² to cure the antistatic layer to produce an antistatic layer having a thickness of about 1 μm.

  Next, a hard coat layer and a low refractive index layer were formed on the obtained base material / antistatic layer film in the same manner as in Example 1 to obtain the laminate of Example 4.

Evaluation of antistatic performance (1) Dust wiping test When the surface of the obtained laminate 5 was sprinkled with dust from a tissue paper and the surface was lightly wiped with Bencot, the dust was easily wiped off.

(2) Charge decay measurement The charge decay of the laminate 5 obtained above and the base material / hard coat layer film not provided with the antistatic layer was measured using an Honest meter (manufactured by Sindh Static Co., Ltd.). The measurement conditions are shown below.

Applied voltage: + 10kV
Probe position: 20 cm
Measurement time: 5 minutes The results are shown below. The effect of the antistatic layer was confirmed.

Preparation of composition for forming anti-glare layer A composition for forming an anti-glare layer was prepared by mixing the following components.

Dipentaerythritol hexaacrylate (DPHA) 25 parts by mass Styrene beads (particle size 3.5 μm) 6 parts by mass Toluene 50 parts by mass Irgacure 184 (trade name, manufactured by Ciba Specialty Chemicals) 2 parts by mass
Preparation of Laminate (Base Material / Anti-Glare Layer / Low Refractive Index Layer) The anti-glare layer forming composition having the above composition is bar-coated on a TAC film, and after removing the solvent by drying, an ultraviolet irradiation device is used. The antiglare layer was cured by irradiating with an ultraviolet ray at an irradiation dose of 100 mJ / cm ² to obtain a substrate / antiglare layer film having an antiglare layer having a thickness of about 4 μm.

  Next, a low refractive index layer was formed on the obtained base material / antiglare layer film in the same manner as in Example 1 to obtain a laminate of Example 5.

Preparation of composition for forming medium refractive index hard coat layer A composition for forming a medium refractive index hard coat layer was prepared by mixing components having the following composition.

KZ7973 (trade name, manufactured by JSR) 47 parts by weight pentaerythritol triacrylate (PETA) 5 parts by weight Irgacure 184 (trade name, manufactured by Ciba Specialty Chemicals) 1 part by weight cyclohexanone 12 parts by weight
Preparation of Laminate (Base Material / Medium Refractive Index Hard Coat Layer / Low Refractive Index Layer) After medium-refractive index hard coat layer forming composition of the above composition was bar coated on TAC film and solvent was removed by drying, using an ultraviolet irradiation apparatus, to cure the coating film dose 100 mJ / cm ^2, to obtain a substrate / medium refractive index hard coat layer film having a refractive index hard coat layer in a thickness of about 5 [mu] m.

  Next, a low refractive index layer was formed on the obtained base material / medium refractive index hard coat layer film in the same manner as in Example 2 to obtain a laminate of Example 6.

Preparation of antifouling layer forming composition The components of the following composition were mixed to prepare an antifouling layer forming composition.

KP-801M (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 6.7 parts by mass FC-40 (trade name, manufactured by Sumitomo 3M Ltd.) 93.3 parts by mass
Preparation of Laminate (Base Material / Hard Coat Layer / Low Refractive Index Layer / Antifouling Layer) In the same manner as in Example 1, a hard coat layer and a low refractive index layer were formed on a substrate. Thereafter, the antifouling layer forming composition having the above composition was bar-coated and thermally cured at 70 ° C. for 4 minutes to obtain a laminate of Example 7.

Preparation of high refractive index layer forming composition A high refractive index layer forming composition having a refractive index of 1.90 was prepared by mixing the following components.

Rutile-type titanium oxide (trade name: MT-500HDM, manufactured by Teica) 10 parts by weight Disperbyk163 (trade name, manufactured by Big Chemie Japan) 2 parts by weight pentaerythritol triacrylate (PETA) 4 parts by weight Irgacure 184 (trade name, Ciba Specialty) Chemicals) 0.2 parts by weight Methyl isobutyl ketone 37.3 parts by weight
Preparation of medium refractive index layer forming composition 2.5 parts by mass of dipentaerythritol pentaacryl paste (SR399E: trade name, manufactured by Nippon Kayaku Co., Ltd.) with respect to 10 parts by mass of the titania dispersion having a refractive index of 1.90. In addition, a composition for forming a medium refractive index layer having a refractive index of 1.76 was prepared.

Preparation of Laminate (Base Material / Hard Coat Layer / Medium Refractive Index Layer / High Refractive Index Layer / Low Refractive Index Layer) On the substrate / hard coat layer film prepared in the same manner as in Example 1, After the refractive index layer forming composition is bar-coated and the solvent is removed by drying, UV irradiation is performed with an irradiation dose of 100 mJ / cm ² using an UV irradiation device, the coating is cured, and the film thickness is about 80 nm. A refractive index layer was obtained.

  Furthermore, the composition for forming a high refractive index layer having the above composition was applied under the same conditions to obtain a high refractive index layer having a thickness of about 60 nm.

  On the obtained laminate (base material / hard coat layer / medium refractive index layer / high refractive index layer), a low refractive index layer was formed in the same manner as in Example 1 to obtain the laminate of Example 8. .

Preparation of composition for forming a high refractive index layer A composition for forming a high refractive index layer having a refractive index of 1.70 was prepared by mixing the following components.

Rutile-type titanium oxide (trade name: MT-500HDM, manufactured by Teica) 10 parts by weight Disperbyk163 (trade name, manufactured by Big Chemie Japan) 2 parts by weight pentaerythritol triacrylate (PETA) 7.5 parts by weight Irgacure 184 (trade name, Ciba Specialty Chemicals 0.2 parts by mass Methyl isobutyl ketone 37.3 parts by mass
Preparation of Laminate (Base Material / Hard Coat Layer / High Refractive Index Layer / Low Refractive Index Layer) For forming a high refractive index layer having the above composition on a substrate / hard coat layer film prepared in the same manner as in Example 1. After coating the composition with a bar and removing the solvent by drying, an ultraviolet irradiation device is used to irradiate with ultraviolet rays at an irradiation dose of 100 mJ / cm ² to cure the coating film to obtain a high refractive index layer having a thickness of about 80 nm. It was.

  A low refractive index layer was formed on the obtained laminate (base material / hard coat layer / high refractive index layer) in the same manner as in Example 1 to obtain a laminate of Example 9.

Comparative Example 1

Preparation of coating composition for low refractive index layer The components of the following composition were mixed to prepare a coating composition for low refractive index layer.

Fluorine atom-containing binder resin (OPSTAR JM5010: trade name, manufactured by JSR Corporation, refractive index 1.41, solid content 10% by weight, methyl ethyl ketone solution) 14.3 parts by mass photopolymerization initiator (Irgacure 907: trade name, Ciba Specialty Chemicals) 0.1 parts by mass
Formation of hard coat layer The following components were mixed to prepare a coating composition for forming a hard coat layer. The resulting hard coat layer forming coating composition was bar-coated on a transparent substrate, and the solvent was removed by drying. Then, using a UV irradiation device (Fusion UV System Japan Co., Ltd., light source H bulb), UV irradiation was performed at an irradiation dose of 108 mJ / cm ² to harden the hard coat layer, and the substrate having a film thickness of 2 to 5 μm / A hard coat film was obtained.

Pentaerythritol triacrylate (PETA) 5 parts by mass Photopolymerization initiator (Irgacure 184: trade name, manufactured by Ciba Specialty Chemicals) 0.25 parts by mass Methyl isobutyl ketone 94.75 parts by mass
Formation of Low Refractive Index Layer The above-described coating composition for low refractive index layer was applied on the above substrate / hard coat film to obtain a substrate / hard coat layer / low refractive index layer film.

Comparative Example 2

  In Example 1, colloidal silica having a particle diameter of 30 nm (MEK-ST: trade name, manufactured by Nissan Chemical Industries, Ltd., refractive index 1.45, solid content 30% methyl ethyl ketone solution) instead of porous silica particles as silica fine particles A base material / hard coat layer / low refractive index layer film was obtained by forming a low refractive index layer in the same manner as in Example 1 except that 2.34 parts by mass of was added.

  Each laminate obtained in this manner was subjected to a test evaluation of reflectivity, scratch resistance, and antifouling property.

Reflectance measurement The absolute reflectance was measured using a spectrophotometer (UV-3100PC) manufactured by Shimadzu Corporation. The film thickness of the low refractive index layer was set so that the minimum value of the reflectivity was around 550 nm. The reflectance of the TAC film itself, which is the base material used, is about 4%, and all the reflectances of the examples are about 1% or less, and have a low refractive index that can be used as an antireflection film. It was.

Evaluation of scratch resistance Nail scratch test For evaluation of nail scratch resistance, the surface of the obtained sample was rubbed with a nail, and it was visually confirmed whether the silica thin film was peeled off from the base material (hard coat layer). . The exfoliation was marked with ×, the surface with scratches but not exfoliating was marked with Δ, and the sample with no flaws was marked with ○.

Using steel wool of steel wool test # 0000, the presence or absence of scratches was confirmed by visual inspection at 10 and 20 reciprocations at a load of 200 g. The exfoliation was marked with ×, the surface with scratches but not exfoliating was marked with Δ, and the sample with no flaws was marked with ○.

  These evaluation results are shown in Table 2 below.

  From the above evaluation results, the antireflection laminate having the low refractive index layer formed by coating the low refractive index composition having the nanoporous structure of the present invention is compared with the conventional fluororesin composition alone. The minimum reflectance was lower, the optical performance was excellent, and the scratch resistance was such that it could be used on the outermost surface.

  The antireflection laminate of the present invention is coated with a fluorine-containing low refractive index composition having a low refractive index and a high altitude, which can be applied to an image display device such as a liquid crystal display (LCD) or a cathode ring display device (CRT). It is useful as an antireflection laminate such as an antireflection film having a low refractive index layer formed thereon.

It is the figure which showed typically the cross section of an example of the liquid crystal display device which coat | covered the display surface with the multilayer type antireflection film containing the coating film of this invention as a light transmissive layer. It is the figure which showed typically the cross section of the polarizing film of this invention affixed on the outer surface of the glass substrate by the side of a display surface. It is the figure which showed typically the cross section of an example of the antireflection film containing the coating film of this invention.

DESCRIPTION OF SYMBOLS 1,6 Glass substrate 2 Pixel part 3 Black matrix layer 4 Color filter 5, 7 Transparent electrode layer 8 Sealing material 9 Orientation film 10 Polarizing film 11 Backlight unit 12 Polarizing element 13, 14 Protective film 15 Adhesive layer 16 Hard coat layer 17 Multi-layer type antireflection film 18 Middle refractive index layer 19 High refractive index layer 20 Low refractive index layer 21 Base film 22 High refractive index layer 23 Low refractive index layer 101 Liquid crystal display device 102 Antireflection film

Claims (2)

A low refractive index layer formed by coating a low refractive index composition having a nanoporous structure on the inside and / or on the surface directly or through another layer on at least one surface side of a light-transmitting substrate was formed. An anti-reflection laminate,
The low refractive index composition having the nanoporous structure contains at least the following (A)-(C):
(A) an ionizing radiation curable resin composition containing fluorine atoms in the molecule ;
(B) Fine particles that can be dispersed in a liquid medium for preparing a coating liquid and have an average particle diameter of 5 nm to 300 nm , and
(C) a fluorine-based and / or silicon-based compound having compatibility with both the ionizing radiation curable composition containing fluorine atoms in the molecule and the fine particles, and the fluorine-based and / or silicon A fluorine-based and / or silicon-based compound that forms a covalent bond by chemical reaction with an ionizing radiation curable resin composition in which at least a part of the compound includes a fluorine atom in the molecule, A compound in which the system compound is represented by the following general formula .

(In the formula, Ra represents an alkyl group having 1 to 20 carbon atoms, Rb is unsubstituted, or an amino group, an epoxy group, a carboxyl group, a hydroxyl group, a perfluoroalkyl group, a perfluoroalkylene group, a perfluoroalkyl ether group, Or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a polyether-modified group substituted with a (meth) acryloyl group, and each Ra and Rb may be the same or different from each other. M is an integer from 0 to 200, and n is an integer from 0 to 200.) A low refractive index layer formed by coating a low refractive index composition having a nanoporous structure on the inside and / or on the surface directly or through another layer on at least one surface side of a light-transmitting substrate was formed. An anti-reflection laminate,
The low refractive index composition having the nanoporous structure contains at least the following (A), (B) and (D):
(A) an ionizing radiation curable resin composition containing fluorine atoms in the molecule ;
(B) coating liquid can be dispersed in a liquid medium for preparing the a and fine particles having an average particle diameter of 5 nm to 300 nm, and,
(D) a fluorine-based and / or silicon-based compound having compatibility with both the ionizing radiation curable composition containing fluorine atoms in the molecule and the fine particles, and the fluorine-based and / or silicon A fluorine-based and / or silicon-based compound that forms a covalent bond by chemical reaction with an ionizing radiation curable resin composition in which at least a part of the compound includes a fluorine atom in the molecule, A compound in which the system compound is represented by the following general formula .
Rc _n SiX _4-n
(Here, Rc represents a hydrocarbon group having 3 to 1000 carbon atoms including a perfluoroalkyl group, a perfluoroalkylene group and a perfluoroalkyl ether group, and X represents an alkoxy group having 1 to 3 carbon atoms and an oxyalkoxy group. , Represents a halogen group, and n represents an integer of 1 to 3)

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