JPWO2008032722A1 - Coating material, optical article using the same, and method for producing optical article - Google Patents

Abstract

An object of the present invention is to uniformly disperse inorganic particles, and to obtain a coating film having good surface hardness and antireflective property due to low refractive index, and is hardened by photocuring, so that heat shrinkage easily occurs. An excellent coating material that can be applied to a substrate, a method of forming a coating film using the same, and an optical article using the same are provided. A polymer containing a hydrolyzed condensate of at least three kinds of silane compounds and bound to inorganic particles having a reactive group, and a coating material having a thermal and / or photopolymerization initiator and Optical article used. [Selection figure] None

Description

  The present invention relates to a coating material used for an antireflection film suitable for various displays, an optical article using the same, and a method for producing the optical article.

  When an object is viewed through a transparent material, it is troublesome that the reflected light is strong and the reflected image is clear, and sometimes a reflected image called a ghost, flare, etc. is generated and uncomfortable. In addition, because of the reflected light, there arises a problem that the contents and the display body are unclear.

  Conventionally, for the purpose of improving visibility, a method of forming a plurality of layers of a coating film of a high refractive index material and a low refractive index material by a vacuum deposition method, a sputtering method, or the like has been performed (see Patent Documents 1 and 2). .

  Especially in recent years, high functionalization of films has progressed, taking advantage of light weight, safety, ease of handling, etc., and taking advantage of the film as a base material, and providing a thin film thereon, an optical article having antireflection properties Has been devised and put into practical use. However, the thin film provided on the film needs to have a low reflectance, and in particular, the layer existing on the outermost layer is required to have a low refractive index. In order to reduce the refractive index of the layer, it is conceivable to reduce the number of cross-linking points in the resin forming the layer, but there is a problem that the surface hardness decreases with the decrease in the cross-linking points in the resin. . In addition, in the case of a flexible substrate such as a film, conditions such as curing temperature and time are limited, and it is a problem how to quickly cure and form a suitable material for each layer Become. In particular, when the layer formed on the film is a thermosetting material that requires a temperature higher than the heat resistance of the film, there is a problem that the film undergoes heat shrinkage during the drying and curing processes. .

  As a method for solving the above-described problem, there is a method in which a thermal radical polymerization initiator is added to a resin forming a layer to generate radicals to advance polymerization and cure at low temperature to form a layer. As an example, there is a method in which a coating paint using an acrylic resin and a thermal radical polymerization initiator is applied on a film to generate radicals at a low temperature. In addition, there is a method in which a transparent coating layer added with a photo radical polymerization initiator is provided on a film, the surface of the transparent coating layer is irradiated with an electromagnetic wave having a high energy such as an ultraviolet ray or an electron beam, and the layer is formed by photocuring. . As an example, ultraviolet rays are irradiated under an oxygen-inhibiting condition such as in a nitrogen or carbon dioxide atmosphere to generate radicals to advance polymerization to form a film. This method is preferable for production because the film can be cured without solvent. Alternatively, even if a solvent is contained, the solvent can be removed at a low temperature. As a specific composition used when this method is applied to the formation of a low refractive index layer, a composition containing a fluorinated alkyl group-containing (meth) acrylate and a polymerization initiator (see Patent Document 3), Examples include a composition containing a fluorine (meth) acrylate compound and a photopolymerization initiator in a copolymer of a perfluoroolefin-containing compound and an alkyl vinyl ether (see Patent Document 4).

  However, since these compositions contain a large amount of fluorine in the resin for the purpose of imparting water repellency and surface slipperiness, the mechanical strength of the cured film is insufficient. In addition, since there is no inorganic component and the resin is composed only of resin, film shrinkage may occur during curing by ultraviolet irradiation.

  In order to solve the above problems, the following compositions are disclosed. (1) A coating composition to which polyfunctional (meth) acrylate, silica fine particles, and a radical photopolymerization initiator are added (see Patent Document 5). (2) A coating composition in which a fluoropolymer, a polyfunctional (meth) acrylate, and silica fine particles are blended with a polymerization initiator (see Patent Document 6). (3) A coating composition to which a fluorine-containing acrylate, silica fine particles, and a polymerization initiator are added (see Patent Document 7). These use low-refractive-index hollow silica fine particles as inorganic components without using a large amount of fluorine as in the past, and achieve both high surface hardness and low refractive index by introducing the fine particles into the resin. Yes. However, if the inorganic fine particles are not uniformly dispersed, aggregation and precipitation occur, and the appearance and surface hardness of the coating film decrease. Further, when the crosslinking between the inorganic component and the resin component is insufficient, the surface hardness of the coating film is liable to decrease. Therefore, there is a method for improving the coating film properties such as storage stability in the coating material, surface hardness, and antifouling property by introducing a modifying group on the particle surface. In Patent Documents 5 and 6, dispersibility is improved by using inorganic fine particles that have been surface-treated with a (meth) acryl group-containing and fluorine-containing silane coupling agent. Moreover, in patent document 7, the dispersibility of particle | grains is aimed at by synthesize | combining the fluorine-containing (meth) acrylate of a resin component with an inorganic fine particle with a (meth) acryl group-containing silane coupling agent. Yes.

Furthermore, a coating material having a silane compound, inorganic particles, and a curing agent is known (see Patent Document 8), and the hardness of the coating film is obtained by bonding a fluorine-containing silane compound and hollow silica fine particles. And a low refractive index.
JP-B-2-36921 (Claims, page 2) Japanese Patent Publication No. 6-5324 (Claims, page 2-3) Japanese Patent Laying-Open No. 2005-171238 (Claims, pages 2-4) JP-A-2005-290133 (Claims, page 2) Japanese Patent Laying-Open No. 2005-181543 (Claims, pages 2-4) JP-A-2005-307176 (Claims, pages 2-5) JP 2006-182937 A (Claims, page 1-2) WO05 / 121265 pamphlet (Claims, pages 2-3)

  In Patent Documents 5 and 6, since the bonding between the modifying group of the particles and the reactive group in the resin component is not made in the state before curing, the amount is not sufficient even when bonded at the time of curing, The hardness of the resulting coating film is not sufficient. Furthermore, when a (meth) acrylic group-containing silane coupling agent is used for surface modification of inorganic fine particles, the refractive index of the inorganic fine particles themselves increases, making it difficult to obtain the desired antireflection property. In addition, when a fluorine group-containing silane coupling agent is used for surface modification of inorganic fine particles for surface modification such as imparting antifouling properties, the radical polymerizability is lowered, and thus the surface hardness of the resulting coating film is further lowered. . As described above, low refractive index materials capable of low temperature curing and photocuring are known, but the hardness of the coating film obtained is low due to insufficient bonding between the resin component and the inorganic component.

  Further, the low-temperature curable coating material described in Patent Document 7 does not have excellent antireflection properties because the fluorine-containing acrylate itself has a high refractive index. The coating material described in Patent Document 8 is cured by a thermal crosslinking reaction by high-temperature heating, and cannot be applied to a substrate that easily causes thermal shrinkage, and is about 60 ° C. considering the heat resistance of the substrate. Curing by low-temperature heating does not sufficiently proceed with crosslinking. Therefore, the surface hardness inherent to the coating material cannot be sufficiently exhibited.

  That is, an object of the present invention is to provide a coating material having a high surface hardness, a low refractive index, excellent antireflection properties, and capable of forming a coating film that can be cured at a low temperature.

  That is, the present invention has the following configuration in order to solve the above problems. (I) 1 to 50% by mass of the silane compound represented by the general formula (1), 5 to 50% by mass of the silane compound represented by the general formula (2) and the general formula (1) with respect to the total solid content in the coating material 3) A coating material comprising a hydrolysis condensate of 5 to 50% by mass of a silane compound represented by formula (3) and bonded to inorganic particles having a reactive group, and (II) a coating material having heat and / or a photopolymerization initiator. is there.

R ¹ Si (R ² ) _a (OR ⁶ ) _3-a (1)
(R ¹ represents a hydrocarbon group having a vinyl group, an allyl group, an alkenyl group, a (meth) acryl group, a mercapto group, or an epoxy group, and R ² represents a hydrocarbon group having 1 to 5 carbon atoms. R ⁶ Represents a hydrocarbon group having 1 to 3 carbon atoms, and a plurality of R ⁶ may be the same or different, and a is 0 or 1.)
R ³ Si (R ⁴ ) _b (OR ⁷ ) _3-b (2)
(R ³ represents a hydrocarbon group having a fluoroalkyl group having 3 to 17 fluorine atoms, R ⁴ represents a hydrocarbon group having 1 to 5 carbon atoms, and R ⁷ represents a carbon atom having 1 to 3 carbon atoms. Represents a hydrogen group, a plurality of R ⁷ may be the same or different, and b is 0 or 1.)
(R ⁵ ) _c Si (OR ⁸ ) _4-c (3)
(R ⁵ represents hydrogen, an alkyl group having 1 to 12 carbon atoms, and a substituent thereof. R ⁸ represents a hydrocarbon group having 1 to 3 carbon atoms, and a plurality of R ⁸ may be the same or different. Well, c is 0, 1, or 2.)

  The film formed using the coating material of the present invention has inorganic particles uniformly dispersed, and has antireflection properties due to good surface hardness and low refractive index. Moreover, since the coating material of this invention can be hardened | cured by light or low temperature, it can be applied also to the base material which is easy to produce heat shrink.

The present invention will be specifically described below.
The coating material of the present invention comprises (I) 1 to 50% by mass of the silane compound represented by the general formula (1) and 5 to 5 of the silane compound represented by the general formula (2) with respect to the total solid content in the coating material. A polymer composed of a hydrolytic condensate of 50% by mass and 5-50% by mass of the silane compound represented by the general formula (3), and bonded to inorganic particles having a reactive group; and (II) thermal and / or photopolymerization Has an initiator. Here, the solid content in the coating material means the total (mass) of the solid content of the inorganic particles and the organic component contained in the coating material, and the solid content is measured by weighing the coating material on an aluminum dish and measuring at 130 ° C. It is a component after heating in an oven for 2 hours.

R ¹ Si (R ² ) _a (OR ⁶ ) _3-a (1)
R ¹ represents a hydrocarbon group having a vinyl group, an allyl group, an alkenyl group, a (meth) acryl group, a mercapto group or an epoxy group, and R ² represents a hydrocarbon group having 1 to 5 carbon atoms. R ⁶ represents a hydrocarbon group having 1 to 3 carbon atoms, and a plurality of R ⁶ may be the same or different, and a is 0 or 1.

R ³ Si (R ⁴ ) _b (OR ⁷ ) _3-b (2)
R ³ represents a hydrocarbon group having a fluoroalkyl group having 3 to 17 fluorine atoms, and R ⁴ represents a hydrocarbon group having 1 to 5 carbon atoms. R ⁷ represents a hydrocarbon group having 1 to 3 carbon atoms, and a plurality of R ⁷ may be the same or different, and b is 0 or 1.

(R ⁵ ) _c Si (OR ⁸ ) _4-c (3)
R ⁵ represents hydrogen, an alkyl group having 1 to 12 carbon atoms, or a substituted product thereof. R ⁸ represents a hydrocarbon group having 1 to 3 carbon atoms, a plurality of R ⁸ may be the same or different, and c is 0, 1, or 2.

  The addition amount of the silane compound represented by the general formula (1) is 1 to 50% by mass. If it is less than 1% by mass, it is difficult to perform low-temperature heating for forming a film from the coating material or curing by light irradiation. On the other hand, if it exceeds 50% by mass, the refractive index of the coating film exceeds 1.38. In that case, the minimum reflectance of light exceeds 1.0%, or cracks occur due to shrinkage of the coating film during curing. In some cases, the coating film warps. Here, the light reflectance is the reflectance of light measured in the visible light wavelength region of 380 nm to 800 nm on the coating film surface. The minimum value of the reflectance in this range is defined as the minimum reflectance. In addition, when seeing an object through the transparent base material with a coating film, the reflected light which enters into the visual field is reduced, and the reflectance range giving good visibility is 1.0% or less. In the present invention, when the refractive index of the coating film is 1.38 or less, incident light and reflected light at the layer interface are effectively interfered with each other, and the reflectance can be 1.0% or less. Moreover, when it is 25 mass% or less, the refractive index of a coating film can be made into 1.38 or less, and light ray minimum reflectance can be made into 1.0% or less, and it is preferable. From the point of low refractive index property, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

  Among the silane compounds represented by the general formula (1), trifunctional silane compounds in which a = 0 are vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, methylvinyltri Methoxysilane, methylvinyltriethoxysilane, methylvinyltripropoxysilane, methylvinyltriisopropoxysilane, octylvinyltrimethoxysilane, octylvinyltriethoxysilane, octylvinyltripropoxysilane, octylvinyltriisopropoxysilane, 3-methacrylic Loxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, 3-methacryloxypropyltriisopropoxysilane, 3- Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-acryloxypropyltriisopropoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltri Propoxysilane, mercaptomethyltriisopropoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyltriisopropoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyl Lysopropoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) methyltripropoxysilane, β- (3,4-epoxycyclohexyl) methyltriisopropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, allyltriisopropoxysilane, vinyltris (trimethylsiloxy) silane, and the like. Among these, from the point of hardness and refractive index of the obtained coating film, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane are preferred.

  Among the silane compounds represented by the general formula (1), a bifunctional silane compound in which a = 1 is methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldipropoxysilane, methylvinyldiisopropoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldipropoxysilane, 3-methacryloxypropylmethyldiisopropoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3 -Acryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldipropoxysilane, 3-acryloxypropylmethyldiisopropoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methyl Captopropylmethyldiethoxysilane, 3-mercaptopropylmethyldipropoxysilane, 3-mercaptopropylmethyldiisopropoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidyl Sidoxypropylmethyldipropoxysilane, 3-glycidoxypropylmethyldipropoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldipropoxysilane, allylmethyldiisopropoxysilane, dimethoxydivinylsilane, diethoxydi Examples include vinyl silane. These are preferably used because the resulting coating film can be more flexible.

  The addition amount of the silane compound represented by the general formula (2) is 5 to 50% by mass. When it is less than 5% by mass, the surface slipperiness of the film formed from the coating material is lowered. On the other hand, if it exceeds 50% by mass, the hardness of the film formed from the coating material decreases. Preferably, it is 20% by mass or more, and in this case, the surface slipperiness is good. More preferably, it is 30% by mass or more and less than 40% by mass. In this case, both good hardness and surface slipperiness can be achieved.

  Among the silane compounds represented by the general formula (2), trifunctional silane compounds in which b = 0 are trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltripropoxysilane, and trifluoropropyl. Triisopropoxysilane, perfluoropropylethyltrimethoxysilane, perfluoropropylethyltriethoxysilane, perfluoropropylethyltripropoxysilane, perfluoropropylethyltriisopropoxysilane, perfluorobutylethyltrimethoxysilane, perfluorobutylethyl Triethoxysilane, perfluorobutylethyltripropoxysilane, perfluorobutylethyltriisopropoxysilane, tridecafluorooctyltrimethoxysilane, Decafluorooctyltriethoxysilane, Tridecafluorooctyltriisopropoxysilane, Tridecafluorooctyltriisopropoxysilane, Heptadecafluorodecyltrimethoxysilane, Heptadecafluorodecyltriethoxysilane, Heptadecafluorodecyltripropoxysilane, Hepta Examples include decafluorodecyltriisopropoxysilane. Of these, trifluoropropyltrimethoxysilane and trifluoropropyltriethoxysilane are preferred from the viewpoint of the hardness of the resulting coating film.

  Among the silane compounds represented by the general formula (2), the bifunctional silane compound in which b = 1 is trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylmethyldipropoxysilane, tri Fluoropropylmethyldiisopropoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluorooctylmethyldiethoxysilane, tridecafluorooctylmethyldipropoxysilane, tridecafluorooctylmethyldiisopropoxysilane, heptadecafluorodecylmethyldimethoxy Silane, heptadecafluorodecylmethyldiethoxysilane, heptadecafluorodecylmethyldipropoxysilane, heptadecafluorodecylmethyldiisopropoxysilane, etc. It is below. These are preferably used because the resulting coating film can be more flexible.

  Among the silane compounds represented by the general formula (3), examples of the tetrafunctional silane compound in which c = 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane. Among these, tetramethoxysilane and tetraethoxysilane are preferably used from the viewpoint that the obtained coating film can further increase the hardness.

  The addition amount of the silane compound represented by the general formula (3) is 5 to 50% by mass. If it is less than 5% by mass, cracks occur when a film is formed and cured from the coating material, and it is difficult to form the coating material uniformly. On the other hand, if it exceeds 50% by mass, the refractive index of the coating film exceeds 1.38, and the minimum light ray reflectance in that case exceeds 1.0%. Preferably it is 15 mass% or more, and in this case, good coatability is obtained. More preferably, the content is 20% by mass or more and 35% by mass or less. In this case, both good applicability and low refractive index can be achieved.

Among the silane compounds represented by the general formula (3), trifunctional silane compounds where c = 1 are trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltrimethoxysilane. Ethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, Propyltriisopropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltripropoxysilane, isopropyltriisopropoxysilane, butyltrimethoxysilane , Butyltriethoxysilane, butyltripropoxysilane, butyltriisopropoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, isobutyltriisopropoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyl Examples include trimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane. Of these, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane are preferable from the viewpoint of the hardness of the obtained coating film. When R ⁵ is an alkyl group having 6 or less carbon atoms, the resulting coating film is preferable because the hardness can be further increased.

  Among the silane compounds represented by the general formula (3), bifunctional silane compounds where c = 2 are dimethoxysilane, diethoxysilane, dipropoxysilane, diisopropoxysilane, dimethoxymethylsilane, diethoxymethylsilane. , Dipropoxymethylsilane, diisopropoxymethylsilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiisopropoxy Silane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane, dipropyldiisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane , Diisopropyldipropoxysilane, diisopropyldiisopropoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxysilane, dibutyldiisopropoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, diisobutyldipropoxysilane, diisobutyldiisopropoxy Silane, dipentyldimethoxysilane, dipentyldiethoxysilane, dipentyldipropoxysilane, dipentyldiisopropoxysilane, dihexyldimethoxysilane, dihexyldiethoxysilane, dihexyldipropoxysilane, dihexyldiisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane , Diphenyldipropoxysilane, diphenyldiisopropoxy Silane and the like. These are preferably used because the resulting coating film can be more flexible.

  In the present invention, the silane compound represented by the general formula (1) represents the low-temperature curability and ultraviolet curability of the film formed from the coating material, and the silane compound represented by the general formula (2) represents the surface of the film. The silane compound represented by the general formula (3) for slipperiness imparts low refractive index properties, hardness, and good coatability of the film.

  These copolymers can be obtained through the hydrolysis reaction and polycondensation reaction described in the present invention. The silane compound used is the silane compound represented by the general formula (3). In particular, trifunctional silanes are preferably used from the viewpoints of hydrolysis and polycondensation reactivity and good coating film. For tetrafunctional silanes, gelated products are generated in the copolymer over time, and it may be difficult to obtain a coating film having a uniform surface film thickness. Moreover, about bifunctional silane, the coating film obtained may become flexible and surface hardness may fall.

  Moreover, it is preferable that the fluorine-containing rate contained in these copolymers is 20 mass%-70 mass%. Here, the fluorine content represents the ratio of fluorine atoms to the total solid content in the copolymer used as the surfactant. This is obtained from a formula of solid content mass of fluorine atom (F atomic weight: 18.9984) ÷ total solid content mass in the copolymer × 100 (mass%). When it is less than 20% by mass, fluorine does not localize on the surface layer, and surface slipperiness and antifouling properties are difficult to obtain. If it exceeds 70% by mass, incompatibility with the polymer may cause insufficient crosslinking with the polymer, resulting in non-uniform film thickness of the resulting coating film or reduced surface hardness.

  Acid catalysts used for the hydrolysis reaction of silane compounds include formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, ion exchange resins, etc. Of the acid catalyst. In particular, formic acid and acetic acid are preferably used as catalysts from the viewpoint of improving the hardness of the coating film.

  The addition amount of the acid catalyst is preferably 0.05% by mass to 10% by mass with respect to the total amount of the silane compound used. More preferably, it is 0.1 mass%-5 mass%. If the amount of the acid catalyst is less than 0.05% by mass, the hydrolysis reaction may not proceed sufficiently. If the amount exceeds 10% by mass, the hydrolysis reaction may not be controlled.

  The water used for hydrolysis is preferably distilled water or purified water. The amount of water can be arbitrarily selected, but it is preferable to use water in the range of 1 to 4 moles with respect to 1 mole of silane. Most preferably, an amount of water equivalent to the hydrolyzable group is used. If the amount is less than 1 mol, sufficient hydrolysis reaction may not be performed. On the other hand, if it exceeds 4 moles, gelation proceeds or the remaining water causes layer separation from the organic component, so that the crosslinkability of the polymer becomes insufficient and the hardness of the coating film may be lowered.

The solvent used for the hydrolysis reaction is preferably an organic solvent, and alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, 3-methyl-3-methoxy-1-butanol; ethylene glycol, propylene glycol Glycols such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monotertiary butyl ether, propylene glycol diethyl ether, and the like; methyl isobutyl Ketones such as ketone and diisobutyl ketone; Amides such as dimethylformamide and dimethylacetamide; Acetates such as rubacetate, ethyl cellosolve acetate, 3-methyl-3-methoxy-1-butanol acetate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane, γ-butyrolactone, N-methyl -2-pyrrolidone, dimethyl sulfoxide and the like.
The amount of the solvent used for the hydrolysis reaction is preferably added in the range of 5% by mass to 500% by mass, more preferably 80% by mass to 200%, with respect to the total amount of the silane compound used during the hydrolysis reaction. It is the range of mass%. When the amount is less than 5% by mass, the reaction cannot be controlled and gelation may occur. On the other hand, if it exceeds 500 mass%, hydrolysis may not proceed.

  The hydrolysis reaction is performed by adding the acid catalyst and water to the silane compound represented by the general formulas (1) to (3) in a solvent. Although reaction temperature is determined by arbitrary compounds by the compound to be used, 1-100 degreeC is preferable from the point which can advance a hydrolysis reaction rapidly and can control progress of reaction. If it is lower than 1 ° C., the unhydrolyzed product becomes the main component, and if it exceeds 100 ° C., the gelled product becomes the main component. The range of room temperature to 70 ° C. is more preferable.

  In addition, by utilizing the difference in hydrolyzability of three or more different silane compounds and efficiently synthesizing, the remaining acid in the silanol reaction solution obtained by hydrolyzing one silane compound first is used, and the remaining It is no problem to mix the silane compound with water and hydrolyze it under an arbitrary reaction condition. In the present invention, the silane compound represented by the general formula (1) or the general formula (2) having relatively low hydrolyzability is first hydrolyzed, and the solution is represented by the general formula (3) in the solution. It is preferable to hydrolyze a highly hydrolyzable silane compound, but the order of addition should be appropriately selected depending on the silane compound used, and is not limited thereto.

  The conditions for the condensation reaction for obtaining the siloxane polymer in which the silane compounds represented by the general formulas (1) to (3) are polymerized are hydrolyzed to obtain a silanol compound, and then the reaction solution is refluxed as it is. The condensation reaction is preferably carried out for 1 to 100 hours underneath. Different silanol compounds may be hydrolyzed and polycondensed at an arbitrary temperature, and then further mixed to carry out copolymerization under conditions of an arbitrary temperature, reaction time, acid catalyst concentration, and polymerization solution concentration.

  In addition, various curing agents, three-dimensional crosslinking agents, and the like can be added to the coating material for the purpose of accelerating curing or facilitating curing. Specific examples of these additives include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, melamine resins, polyfunctional acrylic resins, urea resins, and the like. One kind or two or more kinds may be added.

  In addition, in order to increase the polymerization degree of the siloxane polymer obtained from the hydrolysis reaction of the silane compounds represented by the general formulas (1) to (3), it is possible to perform reheating or addition of a base catalyst. Further, in consideration of storage stability, it may be diluted to an arbitrary solid content concentration using a solvent after the condensation reaction.

  The silane compound used in the present invention improves the dispersibility of the inorganic particles in the coating material and the hardness of the coating film by bonding with the inorganic particles having a reactive group in advance. A silanol compound is once formed by a hydrolysis reaction using an acid catalyst in a solvent, and then the aforementioned curable polymer is obtained by utilizing a known condensation reaction in the presence of inorganic particles having a reactive group. Can do.

  The inorganic particles used in the present invention have a reactive group. Specific examples of the reactive group include a silanol group in the case of a polycondensable group, and a vinyl group, a (meth) acryl group, an alkenyl group, an aryl group, a mercapto group, and an epoxy group in the case of a radical polymerizable group. Is mentioned. Particularly preferably, a silanol group is preferable because of its high binding property during condensation polymerization with a hydrolyzate of a silane compound. The reactive group only needs to be present on the surface of the inorganic particles, and the modification method is not particularly limited. However, when the reactive group to be imparted is a polycondensable group, various reactions with water and alcohols are possible. And a method using a surface modifier. The surface modifier is preferably a tetrafunctional alkoxysilane, and is applied to the particle surface using an acid catalyst or a metal chelate catalyst. In the case where the reactive group to be imparted is a radically polymerizable group, a method using a surface modifier may be used. Preferably, a vinyl group, a (meth) acryl group, an alkenyl group, an aryl group, a mercapto group, an epoxy group are used. The silane coupling agent is applied to the particle surface using an acid catalyst or a metal chelate catalyst.

  The inorganic particles only have to have a size of several nanometers to several hundred nanometers of crystals constituting the inorganic material in the coating material. The average particle size is preferably 5 nm to 120 nm, and more preferably the average particle size is 5 nm to 70 nm. The particle diameter is measured as follows. Using a film with a coating film as a sample, a cross section is prepared using an ultrathin section method. The cross section is observed under a condition of an acceleration voltage of 100 kV using a transmission electron microscope (H-7100FA type manufactured by Hitachi, Ltd.), and the diameter of the particle is measured from the obtained image. In the present invention, the particle diameter of each single particle is measured from an image obtained by observing a coating film cross section having a thickness of 100 nm at an observation magnification of 200,000 times, and the average value thereof is taken as the average particle diameter. The number of particles used for the measurement is several hundred to several thousand.

  The inorganic particles used in the present invention are preferably silicon oxide, zirconium oxide, titanium oxide, aluminum oxide, indium oxide, zinc oxide, tin oxide, and antimony oxide. In particular, silica particles made of silicon dioxide are more preferable because they can impart excellent hardness and low refractive index.

  When silica particles are used, silica particles having a porous interior and / or voids are preferred from the viewpoint of lowering the refractive index of the coating film. The silica particles that are not porous inside or have no cavities have a small refractive index reduction effect that is expected because the refractive index of the particles themselves is 1.45 to 1.5. On the other hand, silica particles having a porous interior and / or voids have a large refractive index reduction effect because the refractive index of the particles themselves is 1.2 to 1.4.

  In addition, introducing silica particles having a porous and / or void inside into the coating material can not only reduce the refractive index of the film obtained from the coating material to 1.38 or less, but also increase the hardness of the film. Can be increased. Examples of the silica particles having an internal porous and / or hollow space used in the present invention include silica particles having a hollow portion surrounded by an outer shell, porous silica particles having a large number of hollow portions, and the like. Among these, when considering the hardness of the transparent coating, silica particles having a cavity with high strength of the particles themselves are preferable. The refractive index of the particles themselves is 1.2 to 1.4, more preferably 1.2 to 1.35. These silica particles can be produced by the methods disclosed in Japanese Patent No. 3272111 and Japanese Patent Laid-Open No. 2001-233611. Examples of such silica particles include those disclosed in Japanese Patent Application Laid-Open No. 2001-233611, and those commercially available as disclosed in Japanese Patent No. 3272111.

  Silica particles that are not porous inside or have no cavities include, for example, IPA-ST using 2-propanol with a particle size of 12 nm as a dispersant, MIBK-ST using methyl isobutyl ketone with a particle size of 12 nm as a dispersant, IPA-ST-L using 2-propanol with a particle diameter of 45 nm as a dispersant, IPA-ST-ZL using 2-propanol with a particle diameter of 100 nm as a dispersant (trade name, manufactured by Nissan Chemical Industries, Ltd.), Oscar 101 using γ-butyrolactone having a particle diameter of 12 nm as a dispersant, Oscar 105 using γ-butyrolactone having a particle diameter of 60 nm as a dispersant, Oscar 106 using diacetone alcohol having a particle diameter of 120 nm as a dispersant (trade names, Catalyst Chemical Industry Co., Ltd.). The presence or absence of cavities can be confirmed by a particle cross-sectional image by a TEM (scanning electron microscope) photograph.

The refractive index of the particles is measured by the following method. A mixed solution sample of a matrix resin and particles having a solid content concentration of 30% prepared so that the particle content is 0% by mass, 20% by mass, 30% by mass, 40% by mass, and 50% by mass is prepared. These are each coated on a silicon wafer by using a spin coater so as to have a thickness of 1.5 to 4 μm, and then heated and dried in an oven at 130 ° C. for 2 hours to obtain a coating film. Thereafter, the sample is passed through a conveyor type ultraviolet irradiation device equipped with a single high pressure mercury lamp (120 w) at a speed of 5 m / min and irradiated with ultraviolet rays (about 300 mJ / cm ² when converted to ultraviolet rays) to obtain a measurement sample. About the obtained sample, the refractive index in wavelength 633nm of a coating film is calculated | required with a prism coupler (Mettronic Co., Ltd. product: MODEL2010), and it calculates | requires by extrapolating the value of 100 mass% of particle | grains.

  The refractive index of the cured coating film obtained from the coating material of the present invention is preferably 1.25 to 1.45. More preferably, it is 1.28-1.38. In this range, in the case where the high refractive index layer having a refractive index of 1.5 to 2.0 is the lower layer, incident light and reflected light at the layer surface and the layer interface effectively interfere with each other, Reflected light entering the field of view can be reduced. The thickness of the coating film is usually 50 to 200 nm, more preferably 70 to 150 nm.

  In the present invention, the inorganic particles are preferably contained in an amount of 30% by mass to 60% by mass. If it is less than 30% by mass, the effect of lowering the refractive index due to the voids of the particles is small, and if it exceeds 60% by mass, the resulting coating film surface is not uniform due to particle aggregation and the like. It may cause a decrease, a decrease in transmittance due to whitening, and a non-uniform refractive index.

  In order to set the refractive index of the coating film after curing to 1.25 to 1.45, the amount of inorganic particles having porous and / or cavities inside is set to 30% by mass to the total solid content in the coating material. The target refractive index can be obtained by adjusting the amount of the silane compound represented by the general formulas (1) to (3) to 60% by mass. If it exceeds 1.45, the refractive index difference with the high refractive index layer is small, and good antireflection properties may not be obtained. If it is less than 1.25, the difference from the high refractive index layer is large, and the wavelength dependency of the reflectance may be increased.

  Further, the hardness of the coating film of the present invention is preferably less than 30 scratches after steel wool test, preferably 10 or less. In the steel wool test, a load of 250 mPa is applied to the surface of the coating film of each sample using # 0000 steel wool, and the number of scratches after 10 reciprocations is observed.

  In order to reduce the number of scratches after steel wool test of the coating film to less than 30, the addition amount of inorganic particles is 30% by mass to 60% by mass with respect to the total solid content in the coating material, and the general formulas (1) to ( The desired hardness can be obtained by adjusting each amount of the silane compound represented by 3) and using a polymerization initiator. When the number of scratches is 30 or more, there is a possibility that it is not practical when used on the outermost surface of the display, for example.

  The coating material of the present invention contains (II) heat and / or photoinitiator. Therefore, the film can be cured and formed by a polymerization reaction by acting on the polymerizable group of the (I) siloxane polymer by irradiation with low temperature and / or ultraviolet rays, electron beams or the like. In the case of thermal curing at a low temperature, a thermal radical polymerization initiator, a thermal acid generator, and a thermal base generator are exemplified. In the case of photocuring, a photoradical polymerization initiator, a photoacid generator, and a photobase generator can be used. In the present invention, one or a combination of these may be used, but the hydrolysis condensate of the silane compound having a polymerizable group represented by the general formula (1) is represented by 1 Since it is formed by containing ˜50 mass%, a light and / or thermal radical polymerization initiator is preferred.

  As a thermal radical polymerization initiator, as a peroxide, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide, inorganic peroxide, Examples include hydrogen peroxide, ammonium persulfate, and potassium persulfate. Examples of the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, and examples of the diazo compound include diazoaminobenzene and p-nitrobenzenediazonium. .

  The thermal radical polymerization initiator in the coating material used in the present invention preferably has a 10-hour half-life temperature of 30 ° C. or higher and lower than 90 ° C. When the 10-hour half-life temperature is lower than 30 ° C., curing starts at room temperature and it is difficult to obtain a coating film having a uniform film thickness. On the other hand, if it is 90 ° C. or higher, it becomes hard to cure and it is difficult to obtain a coating film having a high surface hardness. The 10-hour half-life temperature of the thermal radical polymerization initiator refers to a temperature at which the concentration is halved after 10 hours when the thermal radical polymerization initiator is dissolved in a radically inert solvent (benzene, toluene, etc.). . Specifically, it is obtained by the following method. A thermal radical polymerization initiator is dissolved in a radical inert solvent (benzene, toluene, etc.), and the concentration is adjusted to 0.1 mol / L. The obtained solution is sealed in a glass tube substituted with nitrogen, immersed in a constant temperature bath at a predetermined temperature, and thermally decomposed. The concentration of the thermal radical polymerization initiator after decomposition is measured by an iodometric titration method or the like. The decomposition reaction can be treated approximately as a primary reaction, and the half-life can be known based on a half-life calculation method in the primary reaction. The half-life is calculated at various temperatures, a graph relating to temperature and half-life is plotted, and the temperature at which the half-life is 10 hours is obtained from the graph.

  There are various methods for setting the 10-hour half-life temperature of the thermal radical polymerization initiator to 30 ° C. or more and less than 90 ° C. Among them, the type of decomposition site and the decomposition site of the thermal radical polymerization initiator due to thermal decomposition It can control by the substituent of. For example, since the decomposition site of the —N═N— bond has a lower half-life temperature than the —O—O— bond, the thermal radical polymerization initiator used in the present invention is preferably an azo compound rather than a peroxide. .

  As an azo compound preferably used in the coating material of the present invention, 1,1′-azobis (cyclohexane-1-carbonitrile) having a 10-hour half-life temperature of 88 ° C., and 2,2′-, having 67 ° C. Azobis (2-methylbutyronitrile), dimethyl 2,2′-azobis (2-methylpropionate) at 66 ° C., 2,2′-azobisisobutyronitrile at 65 ° C., 61 ° C. 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2-azobis (2,4-dimethylvaleronitrile) at 51 ° C., 2,2′- at 45 ° C. Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), which is 30 ° C.

  In order to promote the polycondensation of silanol groups in the polymer, a thermal acid generator or a thermal base generator may be used.

  As a thermal acid generator, SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L SI-150L, SI-160L, SI-180L (all manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxy Phenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, their methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluene Examples include sulfonates. Among these, when the layer forming material is cured and dried at a low temperature from 60 ° C. to 130 ° C. to a medium temperature, SI-15, SI-20, SI-25, SI-40, SI-45, SI-47, SI- 60, SI-80, and SI-100 are preferably used.

  Examples of thermal base generators include carbamate derivatives such as 1-methyl-1- (4-biphenylyl) ethyl carbamate and 1,1-dimethyl-2-cyanoethyl carbamate, urea, N, N-dimethyl-N′-methyl urea, etc. Urea derivatives, dihydropyridine derivatives such as 1,4-dihydronicotinamide, quaternized ammonium salts of organic silane and organic borane, dicyandiamide and the like.

  Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, thioxanthones, mercaptos, glycines, oximes, benzylidenes, coumarins, anthraquinones, etc. Examples of acetophenones 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone, 2-hydroxy-2 -Methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone 4-phenoxy dichloroacetophenone, 4-t-butyl - include dichloroacetophenone. Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is. Examples of benzophenones include benzophenone, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4 '-Bis (dimethylamino) benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone is included. Examples of the thioxanthones include thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-isopropylthioxanthone. Examples of mercaptos include ethylene glycol di (3-mercaptopropionate), 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole. Examples of glycines include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- (p-chlorophenyl) glycine, and N- (4-cyanophenyl) glycine. Examples of oximes include 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1- Phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (α-isonitrosopropiophenone oxime) Isophthal, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) is included. Examples of benzylidenes include 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone and 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone. Examples of coumarins include 7-diethylamino-3-thenonylcoumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1 -Methylmethylbenzimidazolyl) coumarin, 3-anthraquinone (2-benzothiazolyl) -7-diethylaminocoumarin. 2-t-butylanthraquinone, 2-ethylanthraquinone, 1,2-benzanthraquinone are included. These initiators may be used alone or in combination.

  Among them, the photocleavage type and hydrogen abstraction type photo radical polymerization initiators preferably used include IRGACURE (registered trademark) (651, 127, 184, 819, 907, 1870, 500, 369, 1173, manufactured by Ciba Co., Ltd. 2959, 4265, 4263, etc. Trade name), KAYACURE (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC manufactured by Nippon Kayaku Co., Ltd. , MCA, etc., all of which are trade names). These radical photopolymerization initiators may be used alone or in combination of two or more according to the desired performance.

  In order to promote polycondensation of silanol groups in the polymer, a photoacid generator or a photobase generator may be used.

  Photoacid generators include ionic compounds and nonionic compounds. As the ionic compound, those containing no heavy metal or halogen ion are preferable. Specifically, triphenylphosphonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylphosphonium trifluoromethanesulfonate, (4-phenylthiophenyl) -diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl)- Diphenylsulfonium hexafluorophosphate, (4-phenylthiophenyl) -diphenylsulfonium trifluoromethanesulfonate, (4-chlorophenyl) -diphenylsulfonium hexafluorophosphate, (4-chlorophenyl) -diphenylsulfonium hexafluoroantimonate, (4-chlorophenyl) -Diphenylsulfonium trifluoromethanesulfonate, (4-methylpheny ) - diphenyl sulfonium hexafluorophosphate, (4-methylphenyl) - diphenyl sulfonium hexafluoroantimonate, (4-methylphenyl) - diphenyl sulfonium trifluoromethanesulfonate, and the like. Examples of nonionic acid generators include diazomethane compounds, sulfonimide compounds, sulfonebenzotriazole compounds, bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, N- Hydroxy naphthalimide trifluoromethane sulfonate, N-hydroxy phthalimide trifluoromethane sulfonate, etc. are mentioned.

Examples of photobase generators include those that generate amines such as benzyl carbamates, benzoin carbamates, O-carbamoylhydroxyamines, O-carbamoyl oximes, and R ^x R ^y —N—CO—OR ^z. (Wherein R ^x and R ^y are hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and R ^z is nitrobenzyl or α-methylnitrobenzyl).

  The addition amount of the heat and / or photopolymerization initiator is preferably used in the range of 0.1 to 15% by mass, more preferably in the range of 1 to 10% by mass, based on the total solid content in the coating material. It is. When it is less than 0.1% by mass, curing becomes poor and it is difficult to obtain a coating film having high surface hardness. Moreover, when it exceeds 15 mass%, since hardening will be accelerated | stimulated more than needed, a crack may generate | occur | produce in a coating film.

  In the present invention, a photosensitizer may be further used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination. Examples of the photosensitizer include KAYACURE (DMBI, EPA, both trade names) manufactured by Nippon Kayaku Co., Ltd.

  The solvent used in the coating material of the present invention includes at least one kind each of an organic solvent having a boiling point of less than 100 ° C. and an organic solvent having a boiling point of from 100 ° C. to less than 150 ° C. from the viewpoint of adjusting the evaporation rate. Preferably it is. When the above organic solvent is used, the film having the coating material applied is evaporated in the order of the solvent having the lowest boiling point to the solvent having the higher boiling point.

  Specific examples of the solvent having a boiling point of less than 100 ° C. under atmospheric pressure include alcohols such as methanol, ethanol, 1-propanol, and 2-propanol, methyl ether, ethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether. Ethers such as acetone, isobutyl formate, methyl formate, propyl formate, ethyl acetate and isopropyl acetate, ketones such as diethyl ketone and methyl ethyl ketone, and chlorine-containing hydrocarbons such as ethylidene chloride, butyl chloride and methylene chloride , Hydrocarbons such as benzene and cyclohexane. Among these, a hydrophilic alcohol solvent having good dispersion stability of fine particles having a reactive group is preferable, specifically, methanol or isopropyl alcohol is particularly preferable, and one or two kinds may be used.

  Specific examples of the solvent having a boiling point of 100 ° C. or more and less than 150 ° C. under atmospheric pressure include ethers such as butyl cellosolve, methyl carbitol, carbitol, n-butyl acetate, isobutyl acetate, n-amyl acetate, cellosolve acetate, Esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, ketones such as acetylacetone, methylpropylketone, methylbutylketone, methylisobutylketone, cyclopentanone, 2-pentanone, 2-heptanone, butyl alcohol, isobutyl Alcohols such as alcohol, pentaanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol, toluene, m-xylene, etc. Aromatic hydrocarbons. Among these, methyl isobutyl ketone and propylene glycol monoethyl ether are preferable from the viewpoint of coatability with the substrate, drying, and surface uniformity of the film, and one or two of them may be used.

  When the drying temperature is set to a higher temperature, the evaporation rate may be adjusted using a solvent having a boiling point of 150 ° C. or higher and lower than 300 ° C. under atmospheric pressure. Specific solvents include ethylene glycol butyl ether, propylene glycol propyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether and other ethers, ethylene glycol monoethyl ether Acetates, ethylene glycol monopropyl acetate, ethylene glycol monobutyl ether acetate, acetates such as ethyl lactate, butyl lactate and butyl butyrate, ketones such as diisobutyl ketone, diisopropyl ketone and γ-butyrolactone, 2-ethylhexyl alcohol, benzyl alcohol, cyclohexane Alcohols such as SANOL like.

  The amount of solvent contained in the coating material is appropriately determined depending on heating, drying, and curing conditions. The optimum amount of each solvent suitable for the curing conditions used in the present invention is 20 to 90% by mass, more preferably 40 to 70% by mass with respect to the total organic solvent in the coating material in the case of a solvent having a boiling point of less than 100 ° C. is there. If it exceeds 90% by mass, uneven coating may occur. In the case of a solvent having a boiling point of 100 ° C. or higher and lower than 150 ° C., it is 5 to 70% by mass, more preferably 10 to 40% by mass, based on the total organic solvent in the coating material. When it exceeds 70 mass%, a residual solution exists in a cured film, and hardness may be impaired.

  The coating material of the present invention is formed as a film on at least one surface of a transparent substrate, and an optical article can be produced. Although it does not specifically limit as an aspect of an optical article, The refractive index higher than the refractive index of a coating film in which the film | membrane which has the coating material of this invention was formed directly on the transparent substrate, and between a transparent substrate and a coating film And the like in which a layer having high refractive index (high refractive index layer) is formed.

  When forming a high refractive index layer in an optical article, the refractive index of the high refractive index layer is preferably 1.5 to 2.0. If it is less than 1.5, the refractive index difference with the low refractive index layer is small, and the antireflection property may be poor. If it exceeds 2.0, the wavelength dependency of the reflectance increases at a wavelength of 400 to 700 nm. Specifically, when the wavelength region is in the vicinity of the wavelength 400 or 700 nm, the reflectance increases, and it may be difficult to reduce the average reflectance over the entire wavelength range of 400 to 700 nm.

  Although the material which forms a high refractive index layer will not be specifically limited if it is a material which has a refractive index 1.5-2.0, It is more preferable to contain the resin component which has ultraviolet curing property. The ultraviolet curing property is preferable in that the cost required for the curing process is lower than that in heat curing, and the heat shrinkage of the substrate is less likely to occur, and the range of applicable substrates is wide. Furthermore, when hardening the coating material of this invention on a high refractive index layer, it is preferable also from the point which adhesiveness improves because the polymeric group of both layers couple | bond together. Specific examples of the resin include polyfunctional (meth) acrylic compounds containing at least two (meth) acryloyl groups in the molecule. Specific examples of these compounds include monoethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, or triethylene glycol di (meth) acrylate, monopropylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate. Or tripropylene glycol di (meth) acrylate, glycerin di (meth) acrylate, or glycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, or trimethylolpropane tri (meth) acrylate, tetramethylolmethane di ( (Meth) acrylate, tetramethylol methane tri (meth) acrylate or tetra (meth) acrylate, pentaerythritol (meth) acrylate, pen Erythritol di (meth) acrylate or pentaerythritol tri (meth) acrylate, neopentyl glycol di (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, or sorbitol hepta (meta ) Aliphatic polyfunctional (meth) acrylate compounds such as acrylate, and further aromatic ring-containing polyfunctional (meth) such as bisphenol A-ethylene oxide adduct, bisphenol F-ethylene oxide adduct, or phenyl group-containing (meth) acrylate An acrylate compound is mentioned. Further, in order to improve the adhesion to the coating material of the present invention, a polymerizable group-containing silane compound, an alkyl group-containing silane compound, a tetrafunctional silane compound monomer, a hydrolysis condensate and a copolymer are added in the high refractive index layer. It is also possible to add. In order to perform the polymerization reaction more efficiently, it is preferable to add various polymerization initiators and / or photosensitizers in the high refractive index layer.

  In addition, the high refractive index layer may contain a metal oxide or a conductive polymer for the purpose of increasing the refractive index and preventing static charge. Examples of the metal oxide include metal oxides selected from the group consisting of zirconium, indium, antimony, zinc, tin, cerium, and titanium having a particle diameter of 5 nm to 100 nm, and composite oxides thereof. Among them, a composite oxide (ITO) made of indium and tin, or a composite oxide (ATO) made of tin and antimony can impart conductivity and provide antistatic properties in addition to increasing the refractive index. Examples of the conductive polymer include polyacetylene, polythiophene, poly (3-alkyl) thiophene, polypyrrole, polyisothiaphthalene, polyethylenedioxythiophene, poly (2,5-dialkoxy) paraphenylene vinylene, polyparaphenylene, Examples include polyheptadiyne, poly (3-hexyl) thiophene, and polyaniline.

The surface resistance of the high refractive index layer is 1 × 10 ¹² (Ω / □) or less, more preferably 1 × 10 ¹⁰ (Ω / □) or less in that antistatic performance can be exhibited and transparency is not impaired. It is preferable. If the surface resistance value exceeds 1 × 10 ¹² (Ω / □), the antistatic property is impaired, dust adhesion may occur due to static electricity, and visibility may be reduced.

  Furthermore, the film thickness of the high refractive index layer is preferably 40 nm to 200 nm, more preferably 60 nm to 150 nm, from the viewpoint of the antireflection effect. Further, when the high refractive index layer also serves as a hard coat film performance, the thickness may be 0.5 μm to 10 μm, and further 1 to 6 μm. With this thickness, the surface hardness can be increased and the elasticity can be increased, and at the same time, an inexpensive article can be provided by reducing the number of coatings and thus reducing the cost.

  The optical article of the present invention may further be provided with a near-infrared absorbing layer and / or a layer containing a dye in addition to the above embodiment. These layers may be provided on at least one surface of the transparent substrate, and may be provided on both surfaces. The near-infrared absorbing layer and the layer having a dye are formed between the high refractive index layer and the low refractive index layer, the refractive index difference between the two layers becomes small, and the low reflectance layer does not function effectively, The reflectance characteristics are poor, which is not preferable.

  An optical article provided with a near-infrared absorbing layer and / or a layer containing a dye is used as, for example, a front plate of various displays as an optical film having antireflection properties. It is particularly suitable for an antireflection film for a plasma display panel (PDP). PDP emits near-infrared rays due to plasma discharge. This near-infrared rays affect peripheral electronic equipment, and the PDP itself may cause malfunction of the remote control. By using the above optical article, it is possible to shield light in a specific wavelength region and suppress the influence of plasma discharge on peripheral electronic devices.

  As a compound that forms a near infrared absorption layer (near infrared absorption compound), anthraquinone compound, phthalocyanine compound, naphthalocyanine compound, metal oxide fine powder, imonium compound, diimonium compound, aminium salt compound, thiourea Compounds, bisthiourea compounds, square acid compounds, and metal complex compounds. Cyanine dyes, merocyanine dyes, (thio) pyrylium dyes, naphtholactam dyes, pentacene dyes, oxyindolizine dyes, quinoid dyes, aminium dyes, diimmonium dyes, indoaniline dyes, nickel thio complex dyes.

  When using a dye, it is preferable to select a dye that absorbs less light of the three primary colors of the display. In particular, by cutting a wavelength around 595 nm, which is called neon light, it is possible to improve red color purity and color reproducibility. Examples of the dye used in the present invention include cyanine compounds, oxonol compounds, triphenylmethane compounds, diphenylmethane compounds, xanthene compounds, thiazine compounds, and the like. Also, the contrast can be improved by using various dyes to achieve neutral gray. Examples of the dye having little absorption of the three luminescent primary colors include squarylium, cyanine, azo, azomethine, oxonol, benzylidene, xanthene, and metrocyanine.

  As an aspect using the near-infrared absorbing layer and / or the layer containing a dye in the optical article of the present invention, a transparent molded body in which a layer containing a near-infrared absorbing compound or a dye (NIR layer) is laminated on a transparent substrate is used. The method of sticking together through the adhesive layer to the transparent molded object which prepared beforehand and prepared the low refractive index layer of this invention prepared separately is mentioned. In addition, a pressure-sensitive adhesive layer may be provided on the surface of the transparent molded article having a low refractive index layer on which the low refractive index layer is not laminated, and the pressure-sensitive adhesive layer may serve as an NIR layer. Other functions of low refractive index layer (LR) / high refractive index layer (HR) / transparent substrate / NIR layer, LR / HR / NIR layer / transparent substrate, LR / high refractive index and near infrared absorption Layer / transparent substrate, LR / HR / transparent substrate / bonding adhesive layer / transparent substrate / NIR layer, and the like. In general, near-infrared absorbing compounds are unstable with respect to heat, and when formed on a transparent substrate, they may be altered by heating. When forming a near-infrared absorbing layer, it is preferable to use a near-infrared absorbing compound in a hard coat agent or an adhesive layer.

  Next, an example is given and demonstrated about the manufacturing method of the optical article of this invention. A coating material is applied to the transparent substrate to form a coating film. Application methods include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, flow coating, etc., but from the viewpoint of uniform antireflection properties, that is, prevention of unevenness in reflected light color. In particular, microgravure coating is preferably used.

  The transparent substrate used in the present invention is not particularly limited as long as it is transparent, but preferably has a haze (index indicating haze) of 40% or less, more preferably 20% or less. Specific materials include glass and plastics. Moreover, if haze value is 40% or less, you may color with dye, a pigment, etc. Among these, plastic materials are particularly preferably used in view of various physical properties such as transparency, refractive index, optical properties such as dispersion, impact resistance, heat resistance, durability, mechanical strength, chemical resistance, and moldability. Specifically, polyester, especially polyethylene terephthalate, and unsaturated polyester, acrylonitrile-styrene copolymer, polyvinyl chloride, polyurethane, epoxy resin, triacetyl cellulose, polymethyl methacrylate, and triacetyl cellulose and polymethyl methacrylate Resins such as coalescence and polycarbonate are preferred. In addition, since various physical properties such as adhesion to a high refractive index layer, hardness, chemical resistance, heat resistance, and durability can be improved, a transparent substrate with a hard coat film formed thereon may be used. Since the coating material of the present invention can be cured at light or low temperature and does not require heating at high temperature, it is selected from triacetyl cellulose, polymethyl methacrylate, and a copolymer of triacetyl cellulose and polymethyl methacrylate having low heat resistance. It is also preferable to use a substrate.

  Moreover, it is preferable that the surface of the transparent base material used by this invention is wash | cleaned. As the cleaning method, there are a method of removing dirt with a surfactant, further degreasing with an organic solvent, steam cleaning, and spraying air spray to clean.

  Various surfactants can be used to improve the flowability during coating. In particular, the addition of a fluorosurfactant is preferred from the standpoint of improving the anti-staining properties of the antireflection film in addition to the flow properties. A more preferable surfactant is a copolymer of the silane compound represented by the general formula (2) used in the present invention and the silane compound represented by the general formula (3). Moreover, it is a copolymer of the silane compound represented by General formula (1), the silane compound represented by (2), and the silane compound represented by General formula (3). When these copolymers are added to the polymer and form a coating film, the fluoroalkyl group is localized in the surface layer portion of the coating film that is closest to the air. The anti-fouling property becomes good. In addition, since these copolymers have silanol groups, there is no change such as surface peeling due to friction even after curing due to bonding with the silanol groups of the polymer in the coating material of the present invention. Further, when the copolymer has a silane compound containing a polymerizable group represented by the general formula (1), thermal curing at a low temperature and photocuring with ultraviolet rays and electron beams are possible, Since it also binds to the polymerizable group of the polymer in the coating material of the present invention, the surface slipperiness is good and the surface hardness is higher.

  Moreover, it is preferable that 0.5-30 mass parts is added as an amount with which the surfactant used by this invention is added with respect to the solid content whole quantity in a coating material. If the amount is less than 0.5 parts by mass, an effective antifouling property cannot be obtained. If the amount exceeds 30 parts by mass, the coatability is impaired and the surface hardness is reduced.

  In addition, in order to improve adhesion and durability, it is also effective to perform various pretreatments on the substrate surface before applying the coating material, such as activated gas treatment, chemical treatment with acid, alkali, etc. Can be given.

  Moreover, since the coating material should just be apply | coated to the at least one surface on a transparent base material, apply | coating a coating material on the surface of what laminated | stacked the high refractive index layer, the NIR layer, etc. suitably on the transparent base material. Also good.

  The coating material applied on the substrate using the above method is dried and cured by heating under conditions according to circumstances. The drying and curing method by heating is determined depending on the applied base material and the components of the coating material, but the treatment is usually performed at a temperature of room temperature to 300 ° C. for usually 0.5 minutes to 240 minutes. . When the coating material of the present invention uses a thermal polymerization initiator, it can be further dried and cured by heating at a low to medium temperature of 60 ° C to 130 ° C. In particular, when dried and cured by heating at 60 ° C. to 90 ° C., on a substrate having low heat resistance, such as a substrate selected from triacetyl cellulose, polymethyl methacrylate, and a copolymer of triacetyl cellulose and polymethyl methacrylate. Even in the case where is used, the substrate does not curl due to heat shrinkage, which is more preferable. When the coating material of the present invention uses a photopolymerization initiator, a film is formed while irradiating ultraviolet rays having a wavelength shorter than the visible region at the time of drying and curing by heating after coating the coating material on a substrate. Alternatively, the film may be formed by irradiating ultraviolet rays having a wavelength shorter than the visible region before or after drying or curing by heating or simultaneously. In the case of curing by ultraviolet irradiation, the heating step can be omitted, but for the purpose of further activating the curing reaction, heating at 50 ° C. to 100 ° C., more preferably 60 ° C. to 90 ° C., promotes curing and heat resistance. It is preferable at the point which can be used for a low base material. Examples of lamps used for ultraviolet irradiation include high-pressure mercury lamps, ultrahigh-pressure mercury lamps, low-pressure mercury lamps, halogen lamps, microwave lamps, and the like. It is preferable to use a light intensity of 40 W or more, and not only one lamp. Two or more lamps may be used at the same time.

  Further, in order to prevent curing failure due to the influence of oxygen, ultraviolet irradiation may be performed in a nitrogen or carbon dioxide atmosphere.

  The optical article obtained by the production method of the present invention is a coating film having good surface slipperiness and high surface hardness despite the fact that the coating film on the substrate surface is cured at a low temperature of 60 ° C. to 90 ° C. Have

  The optical article of the present invention is used in front of various displays such as optical elements such as cathode ray tubes (CRT), liquid crystal displays (LCD), PDPs, electroluminescence (EL), field emission displays (FED) as optical films having antireflection properties. Used for face plates.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The characteristics measurement method and performance evaluation method of the optical article obtained in each example and comparative example are shown below.

[Measurement of light reflectance]
Measurement was performed using a spectrophotometer 3410 of Hitachi Instrument Service (manufactured by Co., Ltd.). Optical article is # 320-400 water-resistant sandpaper, and the surface opposite to the coating film surface is uniformly scratched, black paint (black magic ink (registered trademark) liquid) is applied, and the coating film surface is The measurement was performed by completely eliminating reflection from the opposite surface and pressing the surface to be measured against an integrating sphere. The incident angle was 10 °, and the inspection wavelength region was 380 nm to 800 nm. The scan speed was 600 nm / min. The light reflectance is good when the minimum reflectance is 1.0% or less. Here, the light reflectance is the reflectance of light measured in the visible light wavelength region of 380 nm to 800 nm, and the minimum reflectance in this range is defined as the minimum reflectance.

[Evaluation of steel wool test]
Using a 1 cm × 1 cm area portion of # 0000 steel wool, a load of 250 mPa was applied to the coating film surface of each optical article, and the number of scratches after 10 reciprocations was observed.

[Evaluation of surface slipperiness]
The degree of catch when the coated film surface of each optical article was scratched with a fingernail was evaluated. Five testers each tested and evaluated according to the following criteria. The evaluation results of 5 people were averaged with 5 points, 3 points, and 1 point. If the average value is 5 points, it is good, if the average value is 3 points, it is a little bad, and the average value is 1 point is bad.
○: Not caught at all.
(Triangle | delta): If it strengthens, it will catch.
X: It is caught even if weak.

[Evaluation of coating properties]
The coating film surface of each optical article was observed with the naked eye, and the film surface uniformity, coating unevenness, and presence of cracks were evaluated.

[Measurement of refractive index of coating material]
The coating material is adjusted to a solid content concentration of 30%, applied onto a silicon wafer using a spin coater so that the thickness is 1.5 to 4 μm, and then heated and dried in an oven at 130 ° C. for 2 hours. To obtain a coating film. After that, the sample for measurement was obtained by passing it once through a conveyor type ultraviolet irradiation device equipped with a high pressure mercury lamp (120w) at a speed of 5 m / min and irradiating with ultraviolet rays (about 300 mJ / cm ² when converted to ultraviolet rays). It was. The refractive index at a wavelength of 633 nm of the coating film was measured with a prism coupler (Mettronic Co., Ltd .: MODEL2010).

[Measurement of surface resistance]
The surface of the laminate was measured using a surface resistance measuring machine (Dia Instruments Inc .: Hiresta UP) and a dedicated probe (Dia Instruments Inc .: Resistive URS probe), voltage: 100 V, measurement time: 60 seconds. Measured under conditions.

Example 1
"OPSTAR" Z7528 (trade name, manufactured by JSR Corp.) Coating a 50% -concentrated paint on a PET film (thickness 100 μm, manufactured by Toray Industries, Inc.) by hand coating using a metal ring bar did. Using a No. 8 metering bar, hang a 1.5 cc coating solution on an A4 size base material and take care to prevent bubbles from entering. A coat layer was formed. Immediately after the hard coat layer was formed, heat treatment was performed for 1 minute in an oven set at 90 ° C. After that, using a conveyor type UV irradiation device equipped with a high pressure mercury lamp (120w), it is passed once at a speed of 5m / min and irradiated with UV (approx. 300mJ / cm ² when converted to UV intensity), with a hard coat layer A substrate was obtained. The film thickness after drying was about 5 μm.

After adding 12 g of “KAYANOVA” HRA-196 (trade name, manufactured by Nippon Kayaku Co., Ltd.) having a solid content of 10% to a 50 ml screw tube, add 8 g of 2-propanol at room temperature (about 23-25 ° C.) The mixture was stirred for about 1 minute and diluted to a solid content concentration of 6% to prepare a coating for a high refractive index layer. The prepared coating material for 6% high refractive index layer was applied to the hard coat layer side of the base material with a hard coat layer by hand coating using a metal ring bar with a number of 5. A 1.5 cc coating solution was dropped on an A4 size base material, and while taking care not to enter bubbles, the metallizing bar was pulled to spread the coating film to form a high refractive index layer. After the high refractive index layer was formed, it was immediately put into an oven at 90 ° C. for heat treatment for 1 minute. After that, a high-pressure mercury lamp (120w) equipped with a high-pressure mercury lamp (120w) was passed through a conveyor-type ultraviolet irradiation device at a rate of 5 m / min for ultraviolet irradiation (approximately 300 mJ / cm ² when converted to ultraviolet light). A substrate with a refractive index layer was obtained. The film thickness of the high refractive index layer after drying was about 100 nm. As a result of measuring the surface resistance value of the obtained base material with a hard coat layer and a high refractive index layer, it was 1 × 10 ⁸ (Ω / □). The refractive index of only the high refractive index layer was 1.67.

  Next, a siloxane polymer having inorganic particles was produced. In a 2 L three-necked flask, 72.73 g (0.33 mol) of 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 156.56 g of propylene glycol monoethyl ether (Wako Pure Chemical Industries, Ltd.) (Made by Co., Ltd.), the temperature is set to 40 to 42 ° C. in an oil bath, about 19.70 g of a formic acid aqueous solution prepared to 3 N using a stirrer over about 10 minutes is dropped at about 270 rpm at the same temperature. And stirred. After stirring for about 1 hour after completion of dropping, 68.1 g (0.5 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 11.42 g (0.05 mol), 119.5 g of propylene glycol monoethyl ether, and isopropyl alcohol (IPA) -dispersed silanol group-containing hollow silica sol having a solid content concentration of 20.4% by mass (manufactured by Catalyst Chemical Industry Co., Ltd.) After adding 400 g to make a solution with a solid content of 20%, 29.48 g of water was added dropwise over about 20 minutes, and after completion of the addition, the oil bath was heated from about 40 to 70 ° C. over about 30 minutes, The mixture was stirred at 270 rpm for about 2 hours from the time when the temperature reached 70 ° C. Then it was cooled to room temperature. When the solid content rate of the obtained polymer was measured, the solid content rate was 20 mass%. In addition, 5% by mass of 3-methacryloxypropyltrimethoxysilane, 30% by mass of 3,3,3-trifluoropropyltrimethoxysilane, 20% by mass of methyltrimethoxysilane, and 45% by mass of hollow silica with respect to the total solid content. It is.

  A surfactant was prepared as follows. In a 100 ml eggplant flask, a rotor and tridecafluorooctyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) 14.04 g (0.03 mol) and vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) 1.96 g (0 .01 mol) and 7.48 g of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) were added, the temperature was adjusted to 50 to 55 ° C., and 2.67 g of a formic acid aqueous solution prepared to 3N over about 10 minutes was added dropwise. Stir at ~ 200 rpm. After stirring for about 2 hours, the reaction solution was cooled to room temperature, 6.13 g of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 45.77 g of 2-propanol were added, and the solid content was 20 mass concentration. After that, 2.43 g of water was added dropwise at 20 to 25 ° C. over about 10 minutes, and then stirred at room temperature (about 20 to 23 ° C.) for about 1 hour at 100 to 200 rpm. Thereafter, the reaction temperature was raised to 60 ° C., and the mixture was stirred for about 2 hours and then cooled to room temperature. Then, when the solid content rate of the solution was measured, the solid content rate was 20 mass%. On the other hand, 80.48 g of 2-propanol was added and diluted to a solid content concentration of 10%, and this was designated as Surfactant-1. The copolymerization ratio of the obtained surfactant-1 solution was 5.1 / 3.4 / 1.5 mol ratio of methyltrimethoxysilane / tridecafluorooctyltrimethoxysilane / vinyltrimethoxysilane. Moreover, the fluorine content rate in surfactant-1 is 46.23 mass%.

  2 g of a siloxane polymer having inorganic particles prepared in advance was added to the sample bottle, 0.82 g of a methanol solution was added to this solution, and then 16.8 mg of aluminum trisacetylacetonate was added. Further, 9 g of 2-propanol was added, and then 2.9 g of methyl isobutyl ketone was added. Finally, 12 mg of IRGACURE (registered trademark) 184 (trade name, manufactured by Ciba Co., Ltd.) and 0.2 g of surfactant-1 were added as a radical photopolymerization initiator. The solid content concentration of the obtained coating material is 3% by mass. Moreover, the used radical photopolymerization initiator was 3 mass% with respect to the total solid of the coating material, and the organic solvent used was 10 mass% methanol, 70 mass% 2-propanol, methyl isobutyl with respect to the total organic solvent. The ketone is 20% by mass. The refractive index of the obtained coating material was measured.

  The prepared coating material was applied to the surface of the high refractive index layer of the base material with a hard coat layer and a high refractive index layer prepared in advance by hand coating using a No. 6 metal ring bar. A coating material (low refractive index layer) was formed by hanging a coating material of 1.5 cc and spreading the coating material by pulling a metalling bar so that bubbles do not enter. The thickness of the low refractive index layer was about 100 nm.

After the coating material was applied, it was immediately placed in an oven at 60 ° C. and heat-treated for 2 minutes. Thereafter, UV irradiation (about 300 mJ / cm ² when converted to UV intensity) was performed once through a conveyor type UV irradiation device equipped with a high pressure mercury lamp (120 w) at a speed of 5 m / min. Thus, an optical article was obtained in which a hard coat layer, a high refractive index layer, and a low refractive index layer were provided in this order on the substrate. The resulting optical article was evaluated for light reflectance, steel wool resistance, surface slipperiness, and coatability.

  Further, heat treatment and ultraviolet irradiation were performed in the same manner as above except that 60 ° C. was changed to 90 ° C. and 130 ° C., optical components were prepared, and steel wool resistance was evaluated.

Example 2
In the siloxane polymer, 10% by mass of 3-methacryloxypropyltrimethoxysilane, 40% by mass of 3,3,3-trifluoropropyltrimethoxysilane, 15% by mass of methyltrimethoxysilane, and 35% by mass of hollow silica with respect to the total solid content. %, 2,2-azobis (2,4-dimethylvaleronitrile) as a thermal radical polymerization initiator from IRGACURE (registered trademark) 184 (manufactured by Wako Pure Chemical Industries, Ltd., 10 hour half-life temperature 51 ° C. in toluene) ), Changed to catalog value manufactured by Wako Pure Chemical Industries, Ltd.), implemented except that 3% by mass of thermal radical polymerization initiator was added to the total solid content in the coating material, and the UV irradiation process was not performed. Performed as in Example 1.

Example 3
A surfactant was prepared as follows. A rotor, perfluorobutylethyltrimethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) 4.53 g (0.012 mol) and 2-propanol 2.1 g (made by Wako Pure Chemical Industries, Ltd.) are put into a 30 ml eggplant flask. The mixture was stirred at 100 to 200 rpm while dropping 0.76 g of an aqueous formic acid solution adjusted to 3N over about 10 minutes. After stirring for about 2 hours, the reaction solution was cooled to room temperature, and 3.91 g (0.029 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 15.2 g of 2-propanol were added. After making a solution with a solid content of 20% by mass, 1.55 g of water was added dropwise at 20 to 25 ° C. over about 10 minutes, and then stirred at 100 to 200 rpm for about 1 hour at room temperature (about 20 to 23 ° C.). Thereafter, the reaction temperature was raised to 60 ° C., and the mixture was stirred for about 2 hours and then cooled to room temperature. Then, when the solid content rate of the solution was measured, the solid content rate was 20 mass%. On the other hand, 28.04 g of 2-propanol was added and diluted to a solid content concentration of 10%, and this was designated as Surfactant-2. The copolymerization ratio of the obtained surfactant-2 solution was methyltrimethoxysilane / perfluorobutylethyltrimethoxysilane in a 7/3 mol ratio. Moreover, the fluorine content rate in surfactant-2 is 38.48 mass%.

  In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane is changed to 5% by mass of 3-acryloxypropyltrimethoxysilane, 5% by mass of 3,3,3-trifluoropropyltrimethoxysilane, The same procedure as in Example 1 was carried out except that 35% by mass of methoxysilane and 55% by mass of hollow silica were used and the surfactant-1 was changed to the surfactant-2.

Example 4
In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane is 15% by mass of 3-acryloxypropyltrimethoxysilane, 20% by mass of 3,3,3-trifluoropropyltrimethoxysilane, The thermal radical polymerization initiator was changed from IRGACURE (registered trademark) 184 to 2,2-azobis (2,4-dimethylvaleronitrile) as a thermal radical polymerization initiator by changing methoxysilane to 20% by mass and hollow silica to 45% by mass. Was added in an amount of 5% by mass based on the total solid content in the coating material, and the same procedure as in Example 1 was performed except that the ultraviolet irradiation step was not performed.

Example 5
In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane is changed to 5% by mass of vinyltrimethoxysilane, 40% by mass of 3,3,3-trifluoropropyltrimethoxysilane, and 20% by mass of methyltrimethoxysilane with respect to the total solid content. %, Hollow silica 35 mass%, 2,2′-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd., 10 hours half-life temperature 65) as a thermal radical polymerization initiator from IRGACURE (registered trademark) 184 Changed to ° C (in toluene), catalog value manufactured by Wako Pure Chemical Industries, Ltd., and added 8% by mass of thermal radical polymerization initiator based on the total solid content in the coating material, and did not perform the UV irradiation step The procedure was the same as in Example 1 except that.

Example 6
In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane is changed to 5% by mass of vinyltrimethoxysilane, 5% by mass of 3,3,3-trifluoropropyltrimethoxysilane, and 35% by weight of methyltrimethoxysilane with respect to the total solid content. %, Hollow silica 55 mass%, and 2,2′-azobisisobutyronitrile as a thermal radical polymerization initiator was added in an amount of 3 mass% based on the total solid content in the coating material. The same was done.

Example 7
In the siloxane polymer, 30% by mass of 3-methacryloxypropyltrimethoxysilane with respect to the total solid content, 5% by mass of 3,3,3-trifluoropropyltrimethoxysilane, 10% by mass of methyltrimethoxysilane, hollow silica The same operation as in Example 1 was performed except that the content was changed to 55% by mass.

Example 8
In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane is 5% by mass of vinyltrimethoxysilane, 5% by mass of 3,3,3-trifluoropropyltrimethoxysilane, and 40% by mass of methyltrimethoxysilane with respect to the total solid content. % And hollow silica 50% by mass. Further, an optical article was produced in the same manner as in Example 1 except that the heat treatment time after the application of the low refractive index layer was changed from 2 minutes to 5 minutes under the respective conditions of 60 ° C., 90 ° C. and 130 ° C. The applicability was evaluated. The optical article was placed on a flat desk, and the presence or absence of curling of the substrate was visually confirmed.

Example 9
In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane is changed to 35% by mass of 3-acryloxypropyltrimethoxysilane, 5% by mass of 3,3,3-trifluoropropyltrimethoxysilane, The same procedure as in Example 1 was performed except that 5% by mass of methoxysilane and 55% by mass of hollow silica were used.

Example 10
The same procedure as in Example 8 was performed except that the transparent substrate was changed from a PET film to a polymethyl methacrylate film (thickness 250 μm).

Example 11
The same procedure as in Example 8 was performed except that the transparent substrate was changed from a PET film to a triacetylcellulose film (thickness 80 μm).

Comparative Example 1
In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane is not used with respect to the total solid content, but 3,3,3-trifluoropropyltrimethoxysilane is 30% by mass, methyltrimethoxysilane is 25% by mass, and hollow silica is 45% by mass. The same procedure as in Example 1 was performed except that the content was changed to%.

Comparative Example 2
In the siloxane polymer, the total amount of solid content is 28% by mass of 3-methacryloxypropyltrimethoxysilane, 2% by mass of 3,3,3-trifluoropropyltrimethoxysilane, 35% by mass of methyltrimethoxysilane, and 35% by mass of hollow silica. The same procedure as in Example 1 was performed except that the percentage was changed to%.

Comparative Example 3
In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane is changed to 20% by mass of 3-acryloxypropyltrimethoxysilane, 23% by mass of 3,3,3-trifluoropropyltrimethoxysilane, The same procedure as in Example 1 was performed except that 2% by mass of methoxysilane and 55% by mass of hollow silica were used.

Comparative Example 4
In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane is changed to 3-acryloxypropyltrimethoxysilane, and 38% by mass of 3, acryloxypropyltrimethoxysilane, 3,3,3- The composition was changed from Surfactant-1 to Surfactant-2 to 2% by mass of trifluoropropyltrimethoxysilane, 40% by mass of methyltrimethoxysilane, and 20% by mass of hollow silica, and IRGACURE (registered trademark) 184 The polymerization initiator is changed to 2,2-azobis (2,4-dimethylvaleronitrile), and a thermal radical polymerization initiator is added in an amount of 5% by mass with respect to the total solid content in the coating material, and an ultraviolet irradiation process is performed. Except for the absence, the same procedure as in Example 1 was performed.

Comparative Example 5
In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane is not used with respect to the total amount of solids, 3,3,3-trifluoropropyltrimethoxysilane 5 mass%, methyltrimethoxysilane 25 mass%, hollow silica 70 mass %, And IRGACURE (registered trademark) 184 was changed to 2,2-azobis (2,4-dimethylvaleronitrile) as a thermal radical polymerization initiator, and the thermal radical polymerization initiator was changed to the total solid content in the coating material. 3% by mass was added, and the same procedure as in Example 1 was performed except that the ultraviolet irradiation step was not performed.

Comparative Example 6
In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane is changed to 5% by mass of vinyltrimethoxysilane, 55% by mass of 3,3,3-trifluoropropyltrimethoxysilane, and 5% by mass of methyltrimethoxysilane with respect to the total solid content. %, Hollow silica 35% by mass, changed from surfactant-1 to surfactant-2, and IRGACURE (registered trademark) 184 as a radical photopolymerization initiator is 8% by mass with respect to the total solid content in the coating material. The same procedure as in Example 1 was performed except for the addition.

Comparative Example 7
In the siloxane polymer, 3% by mass of 3-methacryloxypropyltrimethoxysilane, 5% by mass of 3,3,3-trifluoropropyltrimethoxysilane, 55% by mass of methyltrimethoxysilane, and 35% by mass of hollow silica with respect to the total solid content. The same procedure as in Example 1 was performed except that the content was changed to%.

Comparative Example 8
In the siloxane polymer, 3-methacryloxypropyltrimethoxysilane 55% by mass, 3,3,3-trifluoropropyltrimethoxysilane 5% by mass, methyltrimethoxysilane 5% by mass, and hollow silica 35% by mass with respect to the total solid content. The same procedure as in Example 1 was performed except that the content was changed to%.

Comparative Example 9
The same procedure as in Example 1 was performed except that IRGACURE (registered trademark) 184 was not added to the coating material for the low refractive index layer.

Comparative Example 10
To a 1 L three-necked flask A, 11.42 g (0.05 mol) of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and isopropyl alcohol (IPA dispersion having a solid content concentration of 20.4% by mass) Type) 400 g of silanol group-containing hollow silica sol (manufactured by Catalytic Chemical Industry Co., Ltd.) and 2.48 g of formic acid aqueous solution prepared to 0.5 N were added, and 35.35 g of propylene glycol monoethyl ether (Wako Pure Chemical Industries, Ltd.) )) To make a solution with a solid content concentration of 20% by mass, and then set the temperature in the oil bath to 70 to 72 ° C. and stirring at about 270 rpm at the same temperature using an agitator for about 2 hours. Stir. Thereafter, the mixture was cooled to room temperature to obtain a solution of silica particles whose surface was modified with silanol groups. When the solid content was measured, the solid content rate was 20% by mass.

  Next, in another 1 L three-necked flask B, 68.1 g (0.5 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 3,3,3-trifluoropropyltrimethoxysilane (Shin-Etsu) at room temperature. Chemical Industry Co., Ltd.) 72.73 g (0.33 mol) and propylene glycol monoethyl ether 230.5 g were added. 46.09 g of 2N formic acid aqueous solution was added dropwise over about 20 minutes to form a solution having a solid content of 20% by mass, and then stirred at room temperature for about 1 hour. Thereafter, the temperature of the oil bath was raised to about 70 ° C. over about 30 minutes, and when the temperature reached 70 ° C., the mixture was stirred at 270 rpm for about 2 hours from that point. Thereafter, the mixture was cooled to room temperature to obtain a siloxane polymer solution. When solid content was measured, the solid content rate was 20 mass%.

  When the solid content was measured by mixing 446.77 g of the obtained siloxane polymer solution and 417.42 g of a silica particle solution whose surface was modified with silanol groups at room temperature, the solid content was 20% by mass. Further, 3-methacryloxypropyltrimethoxysilane 5% by mass, 3,3,3-trifluoropropyltrimethoxysilane 30% by mass, methyltrimethoxysilane 20% by mass, and hollow silica 45% by mass with respect to the total solid content. .

  2 g of the prepared mixed solution of siloxane polymer and silica particles was added to a sample bottle, 0.82 g of a methanol solution was added to this solution, and then 16.8 mg of aluminum trisacetylacetonate was added. Further, 0.2 g of Surfactant-1 was added, 9 g of 2-propanol was added, and then 2.9 g of methyl isobutyl ketone was added. Finally, 12 mg of IRGACURE (registered trademark) 184 was added as a radical photopolymerization initiator. The solid content concentration of the obtained coating material is 3% by mass. The added radical photopolymerization initiator is 3% by mass with respect to the total solid content of the coating material, and the organic solvent used is 10% by mass of methanol, 70% by mass of 2-propanol, It is 20 mass% of methyl isobutyl ketone. The refractive index of the obtained coating material was measured. Further, using the obtained coating material for the low refractive index layer, an optical component was prepared and evaluated in the same manner as in Example 1.

Comparative Example 11
A siloxane polymer was prepared as follows. Perfluorooctylethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) 100 g (0.24 mol) and 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 59.38 g (0. 24 mol) and 554.22 g of propylene glycol monoethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), and a isopropyl alcohol (IPA) -dispersed silanol group-containing hollow silica sol having a solid content concentration of 20.4% by mass (catalyst conversion) Kogyo Co., Ltd.) (70.28 g) and 2,2′-azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd.) as a thermal polymerization catalyst (3.43 g) were added, and a solid content 20% concentration solution After that, 14.69 g of a formic acid aqueous solution prepared to 3N was added dropwise at 40 ° C., and the mixture was stirred at 40 ° C. at about 270 rpm. After stirring for about 1 hour, the oil bath was heated from about 40 ° C. to 80 ° C. over about 30 minutes, and stirred at 270 rpm for about 4 hours after reaching 80 ° C. Then it was cooled to room temperature. When the solid content rate of the obtained polymer was measured, the solid content rate was 20 mass%. Moreover, perfluoro octyl ethyl methacrylate 35 mass%, 3-methacryloxypropyl trimethoxysilane 15 mass%, and hollow silica 50 mass% are contained with respect to solid content whole quantity.

  2 g of the resulting polymer solution was added to the sample bottle, 0.82 g of methanol solution was added to this solution, and then 16.8 mg of aluminum trisacetylacetonate was added. Further, 0.2 g of Surfactant-1 was added, 9 g of 2-propanol was added, and then 2.9 g of methyl isobutyl ketone was added. Finally, 12 mg of IRGACURE (registered trademark) 907 (trade name, manufactured by Ciba Co., Ltd.) was added as a radical photopolymerization initiator. The solid content concentration of the obtained coating material is 3% by mass. The added radical photopolymerization initiator was 3% by mass with respect to the total solid content of the coating material, and the organic solvent used was 10% by mass of methanol, 70% by mass of 2-propanol, and methyl with respect to the total organic solvent. Isobutyl ketone is 20% by mass. The refractive index of the obtained coating material was measured. Further, using the obtained coating material for the low refractive index layer, an optical component was prepared and evaluated in the same manner as in Example 1.

  Tables 1 and 2 show the compositions of the coating materials used in the examples and comparative examples. Moreover, the evaluation result of each Example and a comparative example is shown to Tables 3-5.

The meaning of each symbol in Tables 1 and 2 is as follows.
KBM-503: 3-methacryloxypropyltrimethoxysilane KBM-5103: 3-acryloxypropyltrimethoxysilane KBM-1003: vinyltrimethoxysilane MTM: methyltrimethoxysilane TFM: 3,3,3-trifluoropropyltri Methoxysilane PMMA: Polymethylmethacrylate TAC: Triacetylcellulose

    The coating formed by the coating material of the present invention includes a low refractive index layer used for antireflection, a buffer coating for a semiconductor device, a planarizing agent, a protective film for a liquid crystal display, an interlayer insulating film, and a waveguide forming material. , Phase shifter materials, and various protective films.

    The optical article of the present invention is suitably used for an antireflection film, an antireflection film, an antireflection plate, an optical filter, an optical lens, a display, and the like. In particular, an antireflection sheet and an antireflection film used for display surfaces of display devices (CRT, LCD, PDP, EL, FED, etc.), front filters, window glass, show window glass, instrument covers, watch cover glasses, etc. Is preferably used.

Claims (9)

(I) 1 to 50% by mass of the silane compound represented by the general formula (1), 5 to 50% by mass of the silane compound represented by the general formula (2) and the general formula (1) based on the total solid content in the coating material 3) A coating material comprising a hydrolyzed condensate of 5 to 50% by mass of the silane compound represented by 3) and bound to inorganic particles having a reactive group, and (II) a heat and / or photopolymerization initiator.
R ¹ Si (R ² ) _a (OR ⁶ ) _3-a (1)
(R ¹ represents a hydrocarbon group having a vinyl group, an allyl group, an alkenyl group, a (meth) acryl group, a mercapto group or an epoxy group, and R ² represents a hydrocarbon group having 1 to 5 carbon atoms. R ⁶ Represents a hydrocarbon group having 1 to 3 carbon atoms, and a plurality of R ⁶ may be the same or different, and a is 0 or 1.)
R ³ Si (R ⁴ ) _b (OR ⁷ ) _3-b (2)
(R ³ represents a hydrocarbon group having a fluoroalkyl group having 3 to 17 fluorine atoms, R ⁴ represents a hydrocarbon group having 1 to 5 carbon atoms, and R ⁷ represents a carbon atom having 1 to 3 carbon atoms. Represents a hydrogen group, a plurality of R ⁷ may be the same or different, and b is 0 or 1.)
(R ⁵ ) _c Si (OR ⁸ ) _4-c (3)
(R ⁵ represents hydrogen, an alkyl group having 1 to 12 carbon atoms, and a substituent thereof. R ⁸ represents a hydrocarbon group having 1 to 3 carbon atoms, and a plurality of R ⁸ may be the same or different. Well, c is 0, 1, or 2.) The coating material according to claim 1, wherein the inorganic particles are silica having an average particle diameter of 5 nm to 120 nm, and the inside is porous and / or hollow. The coating material according to claim 1, wherein the inorganic particles are contained in an amount of 30 to 60% by mass based on the total solid content of the inorganic particles and the matrix resin component in the coating material. The optical article in which the coating material in any one of Claims 1-3 is formed in the at least one surface on a transparent base material. A layer having a refractive index of 1.5 to 2.0 and a surface resistance of 1 × 10 ¹² (Ω / □) or less is formed on at least one surface of the transparent substrate. An optical article in which the coating material according to any one of the above is formed. The optical article according to claim 4 or 5, wherein a layer containing a near-infrared absorbing layer and / or a dye is formed on at least one surface of the transparent substrate. The optical article according to any one of claims 4 to 6, wherein the transparent substrate is a substrate selected from triacetyl cellulose, polymethyl methacrylate, and a copolymer of triacetyl cellulose and polymethyl methacrylate. The process of apply | coating the coating material in any one of Claims 1-3 to at least one surface on a transparent base material, and forming the coating film, and the process of hardening the formed coating film at 60 to 90 degreeC The manufacturing method of the optical article which has this. The method for producing an optical article according to claim 8, wherein the transparent substrate is a substrate selected from triacetyl cellulose, polymethyl methacrylate, and a copolymer of triacetyl cellulose and polymethyl methacrylate.