JP2006103071A - Antireflection laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection laminate to which a coating layer is formed of a resin composition for a low refractive index layer containing a silicate component, which is low in refractive index and can regulate hardness, and a fluorine atom. <P>SOLUTION: The antireflection laminate comprises applying a low refractive index composition having a nanoporous structure which contains an ionizing radiation curable resin composition (A) containing a fluorine atom in its molecule, a silicate compound (B) represented by general formula 1 and/or general formula 2, a monomer (C) having at least three functional groups in one molecule thereof and (D) fine particles with an average particle size of 5-300 nm capable of being dispersed in a liquid medium for use in preparing a coating solution. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an antireflection laminate having a coating film comprising a silicate compound having a low refractive index and a high hardness, and an ionizing radiation hard curable resin composition containing a fluorine atom having a low refractive index and a low hardness and strength. About.

  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 in the resin containing fluorine atoms and the request to increase the strength of the coating film using the resin were incompatible problems.

  Japanese Unexamined Patent Publication No. 2000-66006 (Patent Document 1) discloses a low refractive index layer having a very minute 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. Has been. 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.

  In JP-A-2002-341106 (Patent Document 8), the low refractive index layer is an ionizing radiation curable monomer and / or oligomer having a hydrogen bond-forming group, and the following general formula 1,

(R ¹ represents an alkyl group having 1 to 10 carbon atoms, a vinyl group, a (meth) acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group or a carboxyl group, and R ¹ ′ represents an alkyl group having 1 to 10 carbon atoms. M + n is an integer of 4.)

After forming a coating film with the silicate compound represented by the following, by removing the ionizing radiation curable monomer and / or oligomer of the uncured part by solvent extraction, while forming a minute void at least near the surface, inorganic and A low refractive index composition layer in which an organic network structure intervenes with each other, that is, a so-called IPN structure has been proposed, but an excessive force is applied to the surface of the coating film and the voids inside. If added, the coating will break from it, resulting in damage to the coating.

  In order to impart sufficient scratch resistance to the coating film itself, a metal oxide is chained in an organic binder component having a polymerizable functional group as disclosed in JP 2000-159916 A (Patent Document 9). Although it is ideal to disperse in a connected form, the refractive index of the coating film itself does not decrease, but rather tends to increase.

JP 2000-66006 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 JP 2002-341106 A JP 2000-159916 A

  The present invention has been accomplished in view of the above-mentioned circumstances, and an object of the present invention is to achieve a low refractive index layer resin composition containing a silicate component having a low refractive index and a hardness that can be adjusted to an appropriate hardness and a fluorine atom. An object of the present invention is to provide an antireflection laminate having a coating layer formed thereon.

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 is at least (A) an ionizing radiation curable resin composition containing a fluorine atom in the molecule, and (B) a silicate represented by the following general formula 1 and / or general formula 2. Compound

(R ¹ represents an alkyl group having 1 to 10 carbon atoms, a vinyl group, a (meth) acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group or a carboxyl group, and R ¹ ′ represents an alkyl group having 1 to 10 carbon atoms. M + n is an integer of 4.)

(R ² is an alkyl group having 1 to 10 carbon atoms, R ² ′ and R ² ″ may be the same or different, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, vinyl, Represents a group, a (meth) acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group or a carboxyl group, and l is an integer of 2 to 50).
(C) a monomer that is cured by ionizing radiation having three or more functional groups in one molecule, and (D) an average particle diameter of 5 nm that can be dispersed in a liquid medium for preparing a coating liquid. An antireflective laminate comprising ˜300 nm fine particles.

  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 a 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 the antireflection laminate of the present invention, the refractive index of the low refractive index composition used for forming the low refractive index layer is low, specifically, the refractive index of the low refractive index layer is 1.50 or less, Preferably, it can be made very small as 1.45 or less, and the coating film formed by using the low refractive index composition has hardness and strength that can withstand practical use, and is excellent in adhesion and transparency. Thus, the two properties of a property that can lower the refractive index and a property that can increase the hardness of the coating film can be made compatible.

  By the way, generally, the coating film formed by the cohesive force and hardness is tightened by dispersing the fine particles in the ionizing radiation curable resin composition, but the coating film is formed by utilizing the refractive index of the fine particles having voids. When lowering the overall refractive index, it is necessary to add a large amount of fine particles to the coating film, so that the strength of the coating film may be significantly reduced. In general, since the resin composition containing fluorine atoms in the molecule is a material having a low refractive index, it may be formed by applying the resin in order to reduce the refractive index of the coating film. The obtained coating film contains a fluorine atom having a small atomic force, and thus has a defect that hardness and strength are likely to be insufficient.

  On the other hand, in the low refractive index layer of the antireflection laminate of the present invention, (D) the fine particles having an average particle diameter of 5 nm to 300 nm as the component and (A) the fluorine atom in the molecule are included. Since the silicate compound as the component (B) is further included in the system containing the low refractive ionizing radiation curable resin composition at the same time, the strength of the coating film is further increased and at the same time the low refractive index is increased. Can do. That is, the silicate compound as the component (B) has excellent affinity for the ionizing radiation curable resin composition of the component (A) and / or for the monomer having a functional group of the component (C), Since a strong siloxane network can be formed by curing, it contributes to improving the hardness and strength of the coating film and lowering the refractive index.

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

Component (A): An ionizing radiation curable resin composition containing fluorine atoms in the molecule (A) is a binder component for imparting film formability (film forming ability) and a low refractive index to a low refractive index composition. And a monomer and / or polymer containing an ionizing radiation curable fluorine atom. 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 a component (D), fine particles, preferably fine particles having voids themselves or forming voids by forming aggregates with inorganic ultrafine particles. 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 a hydroxyl group is easy to introduce into the binder component, contributes to the storage stability of the coating composition, and is present on the surface of fine particles having inorganic voids when the binder component is thermally cured. It is preferable because the fine particles having a covalent bond with a hydroxyl group and having voids act as a cross-linking agent, and the coating film strength can be further improved.

  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), the monomer and / or oligomer containing a fluorine atom in the molecule has a high effect of increasing the crosslinking density of the coating film, and is also a component having high fluidity due to its low molecular weight. There is also an effect of improving.

  On the other hand, among the component (A), the fluorine atom-containing polymer already has a high molecular weight, and therefore has higher film formability than the fluorine atom-containing monomer and / or oligomer. When this fluorine atom-containing polymer is combined with the above fluorine atom-containing monomer and / or oligomer, the fluidity is improved, so that the coating suitability can be improved, and the crosslinking density is also increased. 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 general formula 3 or general formula 4), a fully or partially fluorinated vinyl ether, Examples thereof include fully or partially fluorinated vinyl esters and fully or partially fluorinated vinyl ketones.

  When combining a fluorine atom-containing polymer having a polymerizable functional group capable of polymerizing with each other and a fluorine atom-containing monomer, the film-forming property of the coating composition is improved by the fluorine atom-containing polymer, and the crosslinking density is increased by the fluorine atom-containing monomer. The coating suitability is 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; Polyvinylvinylidene fluoride; (co) polymer of a part of acrylic or methacrylic acid and a fully fluorinated alkyl, alkenyl, aryl ester (for example, a compound represented by the following general formula 3 or 4); Examples include hydrocarbon-based vinyl ether copolymers; fluorine-modified products of resins such as epoxy, polyurethane, cellulose, phenol, polyimide, and silicone.

(Wherein R ³ 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 ⁴ and R ⁵ 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, and R ³ , R ⁴ , R ⁵ and Rf each represent a substituent other than a fluorine atom. And any two or more groups of R ⁴ , R ⁵ and Rf may be bonded to each other to form a ring structure.)

(In the formula, A represents a fully or partially fluorinated n-valent organic group. R ⁶ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a halogen atom. R ⁶ 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 them, in particular, the polyvinyl vinylidene fluoride derivative represented by the following general formula 5 has a low refractive index, can introduce 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 ⁸ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom. R ⁷ is directly or through a fully or partially fluorinated alkyl chain, alkenyl chain, ester chain, or ether chain. And represents a fully 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.)

  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: Silicate Compound In the coating composition used for forming the low refractive index layer of the antireflective laminate of the present invention, the silicate compound forms an inorganic network in the coating film, and is a fluororesin component, ionizing radiation curing. It is necessary to form a cross-linking bond between the mold binder component and the fine particles having voids. Therefore, in this invention, the silicate compound shown by the said General formula 1 and / or General formula 2 is used as (B) component.

  These two compounds have an organic group having an affinity for the organic binder component in any molecule, and can form a strong inorganic network by thermosetting. In addition, when the fine particles having voids are inorganic fine particles, these silicate compounds having an inorganic and organic bond can prevent the aggregation of the fine particles having voids in the coating composition in order to mediate the affinity between the two, and the coating film In this case, there is an effect of uniformly dispersing fine particles having voids.

  Specific examples of the silicate compound represented by the general formula 1 include tetramethoxysilane, tetraethoxysilane, tetraiso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-ter. -Butoxysilane, tetrapentaethoxysilane, tetrapenteriso-propoxysilane, tetrapenter n-propoxysilane, tetrapenter n-butoxysilane, tetrapenter sec-butoxysilane, tetrapenter tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyl Tripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmeth Sisilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexyltrimethoxysilane, vinyltriethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-(-2-aminoethylaminopropyl) trimethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycid Xylpropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γaminopropyltriethoxysilane, N-phenyl-γaminopropyltrimethoxysilane, γ- Examples include, but are not limited to, mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, and the like.

  Specific examples of the silicate compound represented by the general formula 2 are obtained by hydrolysis and polycondensation of the silicate compound represented by the general formula 1. Specifically, arbitrarily selected water of the above general formula 1 is added in an amount of water necessary for hydrolysis, and the temperature is 15 ° C. to 90 ° C., preferably 20 ° C. to 40 ° C., for 1 to 30 hours. Preferably, stirring is performed for 2 to 10 hours.

  It is preferable to use a catalyst in the hydrolysis, and as these catalysts, acids such as hydrochloric acid, nitric acid, sulfuric acid or acetic acid are preferable, and these acids are about 0.001 to 20.0 N, preferably about 0.005 to 10 N. As an aqueous solution, water in the aqueous solution can be used as water for hydrolysis.

  Usually, the silicate compound of the general formula 2 produced by a general hydrolysis and condensation method usually has a value of n of 10 or less. For example, technical report of IEICE.O ME97-4,19 (1997) The value of n can be increased to 10 or more by controlling the reaction using the method described in.

  The silicate compound of the general formula 1 or the general formula 2 can be appropriately changed depending on the kind and amount of fine particles having an organic binder component and voids. In particular, the silicate compound of the general formula 1 is preferably used when it is necessary to improve the affinity between the two or when it is desired to form a cross-linked bond. The silicate compound of the general formula 2 is added to the performance of the general formula 1. Since it has viscosity by increasing the molecular weight, it can be preferably used when it is desired to provide good adhesion to the base film.

  The silicate compound represented by the general formula 2 can also be purchased as a commercial product such as a trade name “MS silicate 51” manufactured by Mitsubishi Chemical and a trade name “siloxane alkoxy oligomer X-40 series” manufactured by Shin-Etsu Chemical. .

  Fluoropolymers and silicate compounds belonging to the above components (A) and (B) and monomers, oligomers and polymers not belonging to components (A) and (B) are appropriately combined to form a film, suitability for coating, and ionizing radiation. Various properties such as the crosslinking density of curing and the content of polar groups having thermosetting properties 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.

Component (C): Monomer curable with ionizing radiation having 3 or more functional groups in the molecule The binder component in the low refractive index composition used in the present invention has 3 or more functional groups in one molecule. A monomer that is cured by ionizing radiation is included as an essential component. The monomer having a functional group that is cured by ionizing radiation (sometimes referred to simply as “ionizing radiation curable group”) used in the present invention has a functional group that is cured by heat in addition to having an ionizing radiation curable functional group. (Simply referred to as “thermosetting group”), the coating liquid containing the resin composition is applied to the surface of the object to be coated, dried, irradiated with ionizing radiation, or ionized. When irradiation and heating are performed, chemical bonds such as crosslinks are formed in the coating film, and the coating film can be efficiently cured.

  The “ionizing radiation curable group” of the monomer component is a functional group capable of curing a coating film by proceeding with a large molecular weight reaction such as polymerization or crosslinking by irradiation with ionizing radiation, for example, photo radical polymerization. , Polymerization reaction such as photocationic polymerization and photoanion polymerization, and those in which the reaction proceeds by a reaction mode such as addition polymerization or condensation polymerization that proceeds through photodimerization. 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.

  The “thermosetting group” that may be contained in the monomer component is cured by heating to cause a large molecular weight reaction such as polymerization or crosslinking between the same functional groups or between other functional groups. Examples of functional groups that can be used include alkoxy groups, hydroxyl groups, carboxyl groups, amino groups, and epoxy groups.

  Among these functional groups, the hydrogen bond-forming group is a silicate compound as the component (B) or a fine particle having an average particle size of 5 nm to 300 nm as the component (C) is an inorganic ultrafine particle. Or the fine particles having voids by forming aggregates are inorganic ultrafine particles, they are also excellent in affinity with the component (B), in the binder of the inorganic ultrafine particles and aggregates thereof. This is preferable because it improves dispersibility. Of the hydrogen bond-forming groups, particularly hydroxyl groups are easy to introduce into the binder component, and are covalently bonded to hydroxyl groups present on the surface of fine particles having silicate compounds and inorganic voids due to the storage stability and thermal curing of the coating composition. In particular, the fine particles having voids act as a crosslinking agent and can further improve the coating strength.

  In order to sufficiently reduce the refractive index of the coating film, the refractive index of the monomer component is preferably 1.65 or less.

  As a binder component of the coating composition used for forming the low refractive index layer of the antireflection laminate of the present invention, a monomer component having three or more ionizing radiation curable groups in one molecule improves the crosslinking density of the coating film. It is preferable for improving the film strength and hardness.

Component (D): “Fine particle having voids” is preferably used as the fine particle as the fine particle (D) component. 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 component (D) 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.

Other components The low refractive index layer of the antireflective laminate according to the present invention further comprises a fluorine-based and / or compatible with both ionizing radiation-curable resin compositions containing fluorine atoms in the molecule and fine particles. It preferably comprises a silicon 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, it is further preferable that at least a part of the fluorine-based and / or silicon compound is fixed to the outermost surface of the coating film by forming a covalent bond by a chemical reaction with the ionizing radiation curable resin composition. As a result, it is possible to stably maintain the slipperiness required to improve 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 6,

(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.)
It is preferable to have the structure shown by these.

  Polydimethylsilicone having a basic skeleton such as the above general formula 6 is generally known to have low surface tension and excellent water repellency and releasability, but various functional groups are present on the side chain or terminal. By introducing it, further effects can be imparted. 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 is represented by the following general formula 7,
Rc _n SiX _4-n (formula 7)
(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.)
The structure shown by may be sufficient.

  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 mass, preferably 0.1 to 3.3%, based on the total mass of the ionizing radiation curable resin composition containing fluorine atoms in the molecule and fine particles. The content is preferably 0% by mass. When the content is less than 0.01% by mass, sufficient antifouling property and slipperiness cannot be imparted to the antireflection laminate, and when it exceeds 10% by mass, 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 fluorine atom-containing (A) component, the (D) component of fine particles having voids, and the ionizing radiation curable group of the (C) component may not easily cause a direct polymerization reaction by ionizing radiation irradiation. 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 are also present 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 at a ratio of 3 to 15 parts by mass with respect to a total of 100 parts by mass 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, an aluminum compound represented by the following general formula 8 is particularly preferable. And its derivatives have good compatibility with hydroxyl groups and are particularly preferably used.

AlR ⁹ (Formula 8)
(The above general formula 8 can be selected from aluminum compounds and / or oligomers and / or complexes derived therefrom and aluminum salts of inorganic or organic acids, wherein the residues R ⁹ are the same. However, it may be different, and is halogen, alkyl having 10 or less carbon atoms, preferably 4 or less, alkyl, alkoxy, or acyloxy, or hydroxy, and these groups may be entirely or partially replaced by chelating ligands. )

  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 mass parts with respect to a total of 100 mass parts of a binder component.

When a relatively large amount of liquid monomer and / or oligomer is used as the solvent binder component, the monomer and / or oligomer can also function as a liquid medium for preparing a coating liquid, so that no solvent is used. In some cases, the solid component of the coating composition can be dissolved, dispersed, or diluted 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.

  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 mass or more, particularly 80% by mass or more of the solvent is occupied by one 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 mass, the solvent is 50 to 95.5 parts by mass with respect to the total solids of 0.5 to 50 parts by mass, and more preferably the total solid content is 10 to 30 parts by mass. By using the solvent in a proportion of 70 to 90 parts by mass 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, it comprises (A), (B), (C), (D) components, and other components as required. A coating containing a low refractive index composition on the surface of the object to be coated, dried, and cured by ionizing radiation and / or heating, and containing mainly the component (A) and the component (B) The cured product.

  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.

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 of a liquid crystal display device in which a display surface is covered with a multilayer antireflection film including 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 backlight-side glass substrate 6, the backlight-side glass substrate 6 and the color filter 4, and the transparent electrode layers 5 and 7 are Opposing each other with a predetermined gap therebetween, and adhering the periphery with a sealant 8, enclosing liquid crystal L in the gap, forming an alignment film 9 on the outer surface of the glass substrate 6 on the back side, The polarizing film 10 which laminated | stacked the antireflection laminated body of this invention was affixed on the outer surface of the glass substrate 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 or the like, the hard coat layer 16 is formed by forming the surface of the hard coat layer 16 in an uneven shape or the hard coat layer 16. An antiglare layer (antiglare layer) may be used in which an inorganic or organic filler is dispersed inside the coat layer 16 to have a function of scattering light inside the hard coat layer 16. The hard coat layer 16 may be composed of two or more layers, and the hard coat layer 16 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 a coating composition for forming a low refractive index layer on the high refractive index layer 19, drying and photocuring, and having a refractive index of 1.45 or less. Preferably, it can be set to 1.41 or less, and can be lowered to about 1.20. Further, the medium refractive index layer 18 and the high refractive index layer 19 are made of 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). 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 16. The same properties can also be obtained by using conductive particles for the inorganic oxide fine particles having a high refractive index dispersed in the medium refractive index layer 18 and the high refractive index layer 19. Further, 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 20, or an antistatic layer is added to the outermost surface of the low refractive index layer 20 to improve the performance of the antireflection film. Similar properties can be obtained by providing the film thickness within a range of 30 nm or less which does not affect the film thickness.

  FIG. 3 schematically shows a cross section of an example of an antireflection film in which a high refractive index layer 22 is formed on a transparent base film 21 and a low refractive index layer 23 is further formed thereon.

  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 the alignment plate is not attached to the display surface of the CRT, it is necessary to directly provide the antireflection laminate of the present invention. However, applying the coating composition to the display surface of the CRT is a cumbersome 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.

  In the following Examples 1 and 2, and Comparative Examples 1 to 3, the reflectance measurement, the scratch resistance evaluation, and the steel wool test were performed as follows.

Reflectance Measurement The absolute reflectance was measured using a spectrophotometer (UV-3100PC: trade name) 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.

Evaluation of Scratch Resistance Nail Scratch Test Evaluation of nail scratch resistance was performed by rubbing the surface of the obtained material with a nail and visually confirming whether the silica thin film was peeled off from the base material (hard coat layer). The case of peeling was marked with x, the case where scratches were confirmed on the surface but not peeling was marked with Δ, and the case where no scratches were observed was marked with ○.

Steel wool of steel wool test # 0000 was used to visually check the flaws of the scratches when reciprocating 5 times and 20 times with a load of 200 g. The case of peeling was marked with x, the case where scratches were confirmed on the surface but not peeling was marked with Δ, and the case where no scratches were observed was marked with ○. The evaluation results are shown in Table 1 below.
[Example 1]

Preparation of Fluorine Atom-Containing Resin A polymer having a hydroxyl group of 1,1,2-trifluoroallyloxy monomer represented by the following formula 9 is reacted with an a-F acryloyl group as a reactive group. A compound represented by the following formula 10 was prepared. The resulting compound had a molecular weight of 150,000 and the hydroxyl group ratio was 15:85.

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

Hollow silica sol (20% methyl isobutyl ketone solution) 13.71 parts by mass Dipentaerythritol hexaacrylate (DPHA) 0.91 parts by mass Fluorine atom-containing resin obtained in the above step 0.91 parts by mass γ-methacryloxypropyltrimethoxy Silane 0.92 parts by mass Photopolymerization initiator (Irgacure 907: trade name, manufactured by Ciba Specialty Chemicals)
0.05 parts by mass Photopolymerization initiator (Irgacure 184: trade name, manufactured by Ciba Specialty Chemicals)
0.02 parts by mass EFKA3239 (trade name, manufactured by Ciba Specialty Chemicals) 0.23 parts by mass Methyl isobutyl ketone 84.17 parts by mass

Formation of hard coat layer The following components were mixed to prepare a hard coat layer forming coating composition, and the obtained hard coat layer forming coating composition was bar coated on a transparent substrate, and the solvent was removed by drying. After that, using an ultraviolet irradiation device (manufactured by Fusion UV System Japan Co., Ltd., light source H bulb), ultraviolet irradiation was performed at an irradiation dose of 108 mJ / cm ² to cure the hard coat layer. A material / 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 composition for forming a hard coat layer having the above composition, and the solvent is removed by drying, and then an ultraviolet irradiation device (Fusion UV System Japan ( From a substrate / hard coat layer having a hard coat layer with a film thickness of about 5 μm by irradiating with ultraviolet rays at an irradiation dose of 100 mJ / cm ² using a light source H pulp) A laminated film was obtained.

On the obtained laminated film composed of the substrate / hard coat layer, the coating composition for forming a low refractive index layer obtained in the above step is bar-coated and dried to remove the solvent, and then an ultraviolet irradiation device (fusion) Using UV System Japan Co., Ltd., light source H pulp), UV irradiation is performed at an irradiation dose of 200 mJ / cm ² , the coating film is cured, and a laminated film consisting of a base material / hard coat layer / low refractive index layer Got. Table 1 below shows the test results of the minimum reflectance, haze value, nail scratch resistance, and steel wool resistance of the obtained laminated film.
[Example 2]

Preparation of silicate compound Polymethoxysiloxane (MS-51: trade name, manufactured by Mitsubishi Chemical Corporation, average molecular weight 500 to 700) 10.0 g and γ-acryloxypropyltrimethoxysilane 2.5 g, 0.01 N hydrochloric acid 0 By adding 0.3 g and stirring at room temperature for 5 hours, a silicate oligomer having an acryloyl group introduced into a part of the methoxy group of polymethoxysiloxane was obtained.

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

Hollow silica sol (20% methyl isobutyl ketone solution) 13.71 parts by mass Dipentaerythritol hexaacrylate (DPHA) 0.91 parts by mass Fluorine-containing resin obtained in the above step of Example 1 0.91 parts by mass 0.92 parts by mass of silicate oligomer obtained in the above-mentioned step 2 0.05 parts by mass of Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals) 0.02 parts by mass of Irgacure 184 (trade name, manufactured by Ciba Specialty Chemicals) EFKA3239 (Product name, manufactured by Ciba Specialty Chemicals) 0.23 parts by mass Methyl isobutyl ketone 84.17 parts by mass

Formation of Hard Coat Layer A hard coat layer was formed on a triacetate cellulose (TAC) film in the same manner as in Example 1.

Formation of Low Refractive Index Layer On the laminated film composed of the substrate / hard coat obtained in the above step, the coating composition for low refractive index layer prepared above is applied, and the substrate / hard coat layer / low refractive index is applied. A laminated film consisting of layers was obtained. Table 1 below shows the test results of the minimum reflectance, haze value, nail scratch resistance, and steel wool resistance of the obtained laminated film.

[Comparative Example 1]
A hard coat layer and a low refractive index layer were formed in the same manner as in Example 1 except that the hollow silica fine particles were not used in Example 1 to obtain a laminated film of Comparative Example 1. Table 1 below shows the test results of the minimum reflectance, haze value, nail scratch resistance, and steel wool resistance of the obtained laminated film.

[Comparative Example 2]
In Example 1, instead of a 20% methyl isobutyl ketone solution of hollow silica fine particles, colloidal silica having a particle diameter of about 30 nm (MEK-ST: trade name, manufactured by Nissan Chemical Industries, Ltd., refractive index: 1.45, solid A layer consisting of a base material / hard coat layer / low refractive index layer was formed by forming a low refractive index layer in the same manner as in Example 1 except that 9.14 parts by weight of 30% methyl ethyl ketone solution) was added. A film was obtained. Table 1 below shows the test results of the minimum reflectance, haze value, nail scratch resistance, and steel wool resistance of the obtained laminated film.

[Comparative Example 3]
A hard coat layer and a low refractive index layer were formed in the same manner as in Example 1 except that the silicate compound (γ-methacryloxypropyltrimethoxysilane) was not used in Example 1, and the laminated film of Comparative Example 1 was formed. Got. Table 1 below shows the test results of the minimum reflectance, haze value, nail scratch resistance, and steel wool resistance of the obtained laminated film.

  The reflectance of the TAC film itself, which is the substrate used in Examples 1 and 2 and Comparative Examples 1 to 3, was about 4%. According to Table 1, the reflectances of Examples 1 and 2 are all about 1% or less, have a low refractive index that can be used as an antireflection film, have high transparency, and have nail scratch resistance. The steel wool resistance was excellent.

  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 low refractive index layer of this invention as a light transmissive layer. It is the figure which showed typically the cross section of the polarizing film affixed on the outer surface of the glass substrate of the display surface side. It is the figure which showed typically the cross section of an example of the antireflection film containing the coating film of this invention.

Explanation of symbols

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 DESCRIPTION OF SYMBOLS 17 Multilayer type antireflection film 18 Medium refractive index layer 19 High refractive index layer 20 Low refractive index layer 21 Transparent base film 22 High refractive index layer 23 Low refractive index layer 101 Liquid crystal display device 102 Antireflection film

Claims (26)

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 is at least:
(A) an ionizing radiation curable resin composition containing fluorine atoms in the molecule;
(B) A silicate compound represented by the following general formula 1 and / or general formula 2
(R ¹ represents an alkyl group having 1 to 10 carbon atoms, a vinyl group, a (meth) acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group or a carboxyl group, and R ¹ ′ represents an alkyl group having 1 to 10 carbon atoms. M + n is an integer of 4.)
(R ² is an alkyl group having 1 to 10 carbon atoms, R ² ′ and R ² ″ may be the same or different, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, vinyl, Represents a group, a (meth) acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group or a carboxyl group, and l is an integer of 2 to 50).
(C) a monomer that is cured by ionizing radiation having three or more functional groups in one molecule, and
(D) Fine particles that can be dispersed in a liquid medium for preparing a coating liquid and have an average particle size of 5 nm to 300 nm,
An antireflective laminate comprising: The nanoporous structure is an independent and / or continuous pore containing air having an average pore size of 0.01 nm to 100 nm, which is formed as a result of formation of aggregates of fine particles having an average particle size of 5 nm to 300 nm. The antireflection laminate of claim 1. The antireflection according to claim 1, wherein the nanoporous structure is formed by having 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. Laminated body. The antireflection laminate according to claim 3, wherein the fine particles having pores containing air having an average pore diameter of 0.01 nm to 100 nm have a refractive index of 1.20 to 1.45. The antireflection laminate according to any one of claims 1 to 4, wherein the ionizing radiation curable resin composition containing fluorine atoms in the molecule is curable by heat. 6. The antireflection laminate according to any one of claims 1 to 5, wherein at least a part of the functional groups contained in the ionizing radiation curable resin composition containing fluorine atoms in the molecule is a hydroxyl group. . The antireflective laminate according to any one of claims 1 to 6, wherein the monomer curable with ionizing radiation having three or more functional groups in one molecule is curable by heat. 8. The reflection according to claim 7, wherein at least a part of the functional group contained in the monomer having a functional group that is cured by three or more ionizing radiations in one molecule that can be cured by heat is a hydroxyl group. Prevention laminate. The antireflective laminate according to any one of claims 1 to 8, wherein the silicate compound has a refractive index of 1.53 or less. The addition amount of the fine particles having an average particle diameter of 5 nm to 300 nm is in the range of 1 to 400 parts by weight with respect to 100 parts by weight of the binder component composed of (A), (B) and (C). Item 9. The antireflection laminate according to any one of Items 1 to 8. The low refractive index layer comprises a fluorine-based and / or silicon-based compound having compatibility with any of the binder component composed of (A), (B) and (C) and the fine particles. The antireflection laminate according to any one of claims 1 to 10. The antireflection laminate according to claim 11, wherein at least a part of the fluorine-based and / or silicon-based compound forms a covalent bond with the binder component by a chemical reaction. The fluorine-based compound is selected from the group consisting of a compound having at least one of a perfluoroalkyl group, a perfluoroalkylene group, a perfluoroalkyl ether group, and a perfluoroalkenyl group, and a mixture of these compounds. The antireflection laminate according to claim 11 or 12, wherein there is an antireflection laminate. The fluorine-based and / or silicon-based compound has the following general formula 6,
(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 as or different from each other. M is an integer from 0 to 200, and n is an integer from 0 to 200.)
The antireflection laminate according to claim 11, comprising a compound represented by the formula: The fluorine-based and / or silicon-based compound is represented by the following general formula 4,
Rc _n SiX _4-n-type 4
(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)
The antireflection laminate according to claim 11, comprising a compound represented by the formula: The fluorine-based and / or silicon-based compound is contained in an amount of 0.01 to 10% by weight based on the total weight of the binder component consisting of the (A), (B) and (C), and the fine particles. The antireflection laminate according to any one of claims 11 to 15. The antireflection laminate according to any one of claims 1 to 16, wherein a refractive index of the low refractive index layer is 1.45 or less. The antireflection laminate according to any one of claims 1 to 16, wherein the other layer is a hard coat layer. The antireflection laminate according to claim 18, wherein the refractive index of the hard coat layer is in the range of 1.57 to 1.70. The antireflection laminate according to claim 18, wherein the hard coat layer has an antiglare performance. 21. The antireflection laminate according to any one of claims 1 to 20, wherein an antifouling layer is provided on a surface of the low refractive index layer opposite to the substrate side. A medium to high refractive index layer having 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 between the hard coat layer and the low refractive index layer. The antireflection laminate according to any one of claims 18 to 21, wherein at least one layer is provided. The reflection according to any one of claims 18 to 22, wherein at least one layer selected from the group consisting of the hard coat layer, the medium to high refractive index layer, and the low refractive index layer has antistatic performance. Prevention laminate. The antireflection laminate according to any one of claims 18 to 23, wherein an antistatic layer is provided between the substrate and the hard coat layer. The antireflection laminate according to any one of Claims 1 to 24, wherein the low refractive index layer has a thickness in the range of 0.05 to 0.15 µm. The minimum load amount at which a change in haze value of the low refractive index layer is recognized when the surface of the low refractive index layer is rubbed 10 times with # 0000 steel wool is 200 g or more. 26. The antireflection laminate according to any one of 1 to 25.