JP2008174704A - Coating material and optical article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating material excellent in alkali resistance, scratch resistance, anti-reflecting properties, and antifouling properties and to provide an optical article using the coating material. <P>SOLUTION: The coating material comprises a siloxane resin and a fluorine-containing compound including a structural unit represented by the general formula (1), wherein R<SP>f</SP>represents a group wherein whole or a part of hydrogens is replaced with fluorine; R<SP>1</SP>and R<SP>2</SP>are selected from H, CH<SB>3</SB>, and F; R<SP>3</SP>represents a hydrocarbon group; and Q<SP>1</SP>and Q<SP>2</SP>are each a connection group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a coating material used for an antireflection film and an optical article using the same.

  When an object is viewed through a transparent material, the reflected light becomes strong, so that a reflected image is formed on the surface of the transparent material, and the contents and the display body are unclear due to the reflected light. Particularly in the large display field, for the purpose of improving the visibility, a high-refractive index material and a low-refractive index material have been laminated to form an antireflection film. In recent years, advanced functions of films have advanced, and optical articles with antireflection properties have been devised by taking advantage of lightness, safety, and ease of handling, and providing a thin film on a film base. Further, such optical components are required to be provided with new functions such as low reflectance and high surface hardness. In addition, since such optical components are routinely used at home, functions such as chemical resistance and antifouling properties are also required at the same time.

  Techniques for imparting antifouling properties include a method of forming a fluorine-based organosilicon compound on the outermost layer of an optical article (see Patent Documents 1 and 2), and a method of coating with a fluorine-containing organic silazane copolymer (Patent Document 3). And a method of producing an optical article by laminating a fluorine-containing polymer obtained from a compound having a carbon-carbon unsaturated double bond as an antireflection film (see Patent Documents 4 to 7). However, although the methods disclosed in Patent Documents 1 to 3 improve water repellency and oil repellency, chemical resistance due to alkaline chemicals peculiar to siloxane resins is insufficient. Since the methods shown in Patent Documents 4 to 7 use a fluorine-containing polymer, it is not possible to use a coating liquid mainly composed of a siloxane-based resin as a low refractive index material constituting the antireflection film, Sufficient antireflection could not be performed. There are also methods for providing a photosensitive resin composition excellent in alkali resistance and an antireflection film (see Patent Documents 8 and 9), which are coating materials mainly composed of a siloxane resin exhibiting low refractive index. It is difficult to provide a product at a low cost because it is used as a main material.

In addition, there is a method of providing an antireflection film excellent in scratch resistance with a resin composition using an ethylenically unsaturated group-containing fluoropolymer (see Patent Document 10), but mixing with a siloxane resin is not easy. There wasn't.
Japanese Examined Patent Publication No. 4-61325 (Claim 1) JP-A-7-331115 (Claim 1) Japanese Patent Laid-Open No. 4-314771 (Claim 1) Japanese Patent Laid-Open No. 7-16940 (Claim 1) JP-A-10-104403 (Claims 1 to 4) JP 2002-80784 A (Claims 1 to 6) JP 2006-169375 A (Claims 1 and 2) JP 2006-139259 A (Claim 4) JP 2006-193693 A (Examples 1 to 4) JP 2006-063147 A (Claim 1)

  An object of this invention is to provide the coating material which has as a main component the siloxane type resin which was excellent in low refractive index property, scratch resistance, and slipperiness | lubricant, and was further provided with the chemical resistance by an alkaline chemical.

  That is, the present invention is a coating material containing a siloxane resin and a fluorine-containing compound containing a structural unit represented by the following general formula (1), and has an antireflection property using the coating material as a low refractive index layer. It is an article.

R ^f represents a group selected from the group consisting of an alkyl group having 3 to 14 carbon atoms, an alkenyl group, an aryl group, and an alkyl ether group in which all or part of the hydrogen is substituted with fluorine. R ¹ and R ² may be the same or different and are selected from a hydrogen atom, a methyl group, and a fluorine atom. R ³ represents a hydrocarbon group having 1 to 5 carbon atoms, and a represents an integer of 0 to 2. Q ¹ and Q ^{2 each} represent —CH ₂ —CH ₂ —, —O—, —O—CH ₂ —CH ₂ —, —CH ₂ —CO—, —CO—, —O—CO—, Q ¹ and Q ² may be the same or different from each other. l and m represent the molar ratio of structural units, l is in the range of 71 to 99.5, and m is in the range of 0.5 to 29.

  The coating material of the present invention has scratch resistance, low refractive index property, antifouling property, and chemical resistance against alkaline chemicals. Further, an optical article in which the coating material of the present invention and a high refractive index material are combined has abrasion resistance and antifouling properties, and is excellent in antireflection properties.

  The present invention is a coating material containing a siloxane resin and a fluorine-containing compound containing a structural unit represented by the general formula (1).

  The weight ratio in the molecule of the structural unit represented by the general formula (1) in the fluorine compound molecule is preferably 30% or more, more preferably 50% or more, even if it is 70% or more, It does not matter.

  The siloxane resin used in the present invention is preferably a siloxane compound obtained by hydrolyzing an alkoxysilane compound to form silanol and then subjecting the silanol compound to a condensation reaction. The alkoxysilane compound is preferably at least one selected from alkoxysilane compounds represented by any of the following general formulas (4) to (6).

R ⁴ Si (OR ⁵ ) ₃ (4)
R ⁴ represents hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof. R ⁴ can be selected appropriately depending on the use of the cured film. For example, from the viewpoint of crack resistance of the cured film, it is preferable to use an alkoxysilane compound having a phenyl group as R ⁴ . Further, when it is desired to obtain a cured film having a low refractive index, it is preferable to use an alkoxysilane compound having a methyl group or an alkyl group containing fluorine as R ⁴ . R ⁴ preferably has 1 to 20 carbon atoms. R ⁵ represents a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group, and may be the same or different. R ⁵ is preferably a methyl group or an ethyl group from the viewpoint of easy hydrolysis reaction and availability of raw materials.

R ⁶ R ⁷ Si (OR ⁸ ) ₂ (5)
R ⁶ and R ⁷ each represent hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituent thereof, and may be the same or different. R ⁶ and R ⁷ preferably have 1 to 20 carbon atoms. R ⁸ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and may be the same or different. R ⁸ is preferably a methyl group or an ethyl group from the viewpoint of easy hydrolysis reaction and availability of raw materials.

Si (OR ⁹ ) ₄ (6)
R ⁹ represents a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group, and may be the same or different. R ⁹ is preferably a methyl group or an ethyl group from the viewpoint of easy hydrolysis reaction and availability of raw materials.

  The alkoxysilane compound represented by any one of these general formulas (4) to (6) may be used alone or in combination of two or more.

  Specific examples of the alkoxysilane compound represented by the general formulas (4) to (6) are shown below. Examples of the trifunctional silane compound represented by the general formula (4) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane. Ethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysila , Vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- ( Aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxy Ethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxyp Pyrtrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxy Propyltriisopropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycid Xylbutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycid Xibutyltriethoxysilane (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxy Cyclohexyl ) Butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, par Fluoropropylethyltrimethoxysilane, perfluoropropylethyltriethoxysilane, perfluoropentylethyltrimethoxysilane, perfluoropentylethyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluoro Octyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, hepta Such as perfluoro decyl triethoxy silane.

  Examples of the bifunctional silane compound represented by the general formula (5) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane. , Γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, γ-methacryloxypropyl Methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxy Silane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropyl Methyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycyl Sidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxy Silane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldi Ethoxysilane, trifluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, 3- Examples include methacryloxypropylmethyldimethoxysilane and octadecylmethyldimethoxysilane. Of these, dimethyl dialkoxysilane is preferably used for the purpose of imparting flexibility to the resulting coating film.

Examples of the tetrafunctional silane compound represented by the general formula (6) include tetramethoxysilane and tetraethoxysilane.
When reducing the refractive index of the coating material of the present invention or imparting water repellency, it is preferable to include an alkoxysiloxane compound containing an organic group having fluorine. Examples of the organic group containing fluorine include a trifluoromethyl group, a trifluoropropyl group, a perfluoropropyl group, a perfluoropentyl group, and a tridecafluorooctyl group. Since a film having a low refractive index can be obtained by increasing the fluorine content, it is preferable to contain 10% by mass or more, more preferably 15% by mass or more of fluorine with respect to the total solid content of the siloxane resin composition. In order to further lower the refractive index, it is preferable to use an alkoxysilane compound containing an organic group containing fluorine and not containing an aromatic ring.

As for the siloxane resin used by this invention, it is preferable that solid content contained in coating material is 10 mass% or more. More preferably, it is 20 mass% or more.
The hydrolysis reaction of the silane compound is preferably performed in the presence of an acid catalyst. Examples of the acid catalyst include acid catalysts such as formic acid, oxalic acid, hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins. In particular, from the viewpoint of the stability of the coating agent, an acidic aqueous solution containing formic acid, acetic acid or phosphoric acid is preferred. The content of these acid catalysts is preferably 0.05 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass of the total silane compounds used during the hydrolysis reaction. is there. If the amount of the acid catalyst is less than 0.05 parts by mass, the hydrolysis reaction may not proceed sufficiently. If the amount exceeds 10 parts by mass, the hydrolysis reaction may not be controlled well. In addition, it is also possible to use the residual acid in the silanol reaction solution obtained by hydrolyzing one of the silane compounds, and mix the remaining silane compound and water and hydrolyze them under an arbitrary reaction condition. There is no problem in efficiently synthesizing using the difference in decomposability.

  The solvent used for the hydrolysis reaction is preferably an organic solvent, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol, propylene glycol, etc. Glycols: ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethyl ether and other ethers, methyl isobutyl ketone, diisobutyl ketone and other ketones, dimethyl Amides such as formamide and dimethylacetamide, ethyl acetate, ethyl cellosolve acetate, 3-methyl-3-methoxy-1 Acetates such as butanol acetate, toluene, xylene, hexane, other aromatic or aliphatic hydrocarbons such as cyclohexane, .gamma.-butyrolactone, N- methyl-2-pyrrolidone, and dimethyl sulfoxide. In addition, the quantity of the solvent used when producing a copolymer from 2 or more types of silane compounds chosen from the silane compound represented by General formula (4)-(6) is with respect to the total silane compound content. It is preferable to add in the range of 50 mass%-500 mass%, Most preferably, it is the range of 80 mass%-200 mass%. If the amount is less than 50% by mass, the reaction cannot be controlled and gelation may occur. On the other hand, if it exceeds 500 mass%, hydrolysis may not proceed. Although the reaction temperature at the time of hydrolysis is determined at an arbitrary temperature depending on the compound to be used, it is preferably 1 to 130 ° C. from the viewpoint of promptly advancing the hydrolysis reaction and suppressing the reaction. If it is lower than 1 ° C, the unhydrolyzed product may be the main component, and if it exceeds 130 ° C, the gelated product may be the main component. Moreover, it is more preferable to carry out in the range of room temperature to 70 ° C.

  The water used for the hydrolysis reaction is preferably ion exchange water. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1 to 4 mol with respect to 1 mol of the alkoxysilane compound.

Furthermore, the conditions for the condensation reaction of the silane hydrolyzate for obtaining the siloxane resin are preferably performed after the hydrolysis by using the reaction solution as it is for 1 to 100 hours under reflux.
In the present invention, inorganic particles may be contained in the siloxane resin. In this case, a condensate composed of two or more types selected from silane compounds and inorganic particles having a reactive group are added in the coating material. It is desirable to improve the dispersion stability of the inorganic particles. The inorganic particles referred to here are preferably metal compound particles having a number average particle diameter of 1 nm to 200 nm constituting the inorganic material in the coating material. In order to obtain a cured film having a high transmittance, the number average particle diameter is more preferably 1 nm to 70 nm. Here, the average particle size of the metal compound particles is measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a method of directly measuring the particle size by a transmission electron microscope or a scanning electron microscope, and the like. Can do. The number average particle diameter in the present invention refers to a value measured by a dynamic light scattering method.

  Examples of the metal compound particles include silicon compound particles, aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles, and the like, and an appropriate one can be selected depending on the application. For example, titanium compound particles such as titanium oxide particles and zirconium compound particles such as zirconium oxide particles are preferably used to obtain a cured film having a high refractive index. In addition, silica particles are preferably used for improving scratch resistance, and hollow silica particles, porous silica particles, and magnesium fluoride particles are preferably contained for lowering the refractive index. Among these, the compatibility with the siloxane resin is good, and hollow silica particles are most preferable for improving scratch resistance and low refractive index. The silica particles used are preferably porous silica and / or hollow silica particles. When these silica-based particles are introduced into the coating material, not only the refractive index of the coating film obtained from the coating material can be reduced to 1.38 or less, but also the hardness of the coating film can be increased. The refractive index of the silica particles themselves is 1.2 to 1.4, and 1.2 to 1.35 is more preferable in terms of low refractive index. The fine particles can be produced by the method disclosed in Japanese Patent No. 3272111 or the method disclosed in Japanese Patent Laid-Open No. 2001-233611, and the refractive index is disclosed in Japanese Patent Laid-Open No. 2001-233611. It can be measured by the method. Examples of such silica-based fine particles include those disclosed in Japanese Patent Application Laid-Open No. 2001-233611 and those commercially available such as Japanese Patent No. 3272111.

When inorganic particles are used, the amount introduced is preferably 20% by mass to 70% by mass, and more preferably 30% by mass to 60% by mass with respect to the total solid matter in the coating material. When the amount introduced is less than 20% by mass, the effect of lowering the refractive index due to the voids of the particles is small, and when it exceeds 70% by mass, the resulting coating film is not uniform due to particle aggregation and the like. It may cause a decrease in hardness and non-uniformity of refractive index.
The water used for the hydrolysis reaction is preferably ion exchange water. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1 to 4 mol with respect to 1 mol of the alkoxysilane compound.

  The coating material of the present invention may contain various curing agents that accelerate the curing of the resin composition or facilitate the curing. Specific examples of the curing agent 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 contained. Of these, metal chelate compounds are preferably used in view of the stability of the curing agent and the processability of the obtained coating film.

  Examples of the metal chelate compound include a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound, and a magnesium chelate compound. These metal chelate compounds can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of chelating agents include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane; β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate. Preferable specific examples of the metal chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris ( Examples include aluminum chelate compounds such as acetylacetonate), magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkylacetoacetate magnesium monoisopropylate, and magnesium bis (acetylacetonate).

  The content of the curing agent is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the siloxane resin in the coating material, while preferably 20 parts by mass or less, More preferably, it is 10 parts by mass or less.

  Moreover, since hardening is accelerated | stimulated by an acid for a siloxane resin, it is also preferable to contain hardening catalysts, such as a thermal acid generator. Examples of the thermal acid generator include various onium salt compounds such as sulfonium salts, aromatic diazonium salts, diaryliodonium salts, triarylsulfonium salts, and triarylselenium salts, sulfonate esters, and halogen compounds.

  The coating material of this invention contains the fluorine-containing compound containing the structural unit represented by following General formula (1).

R ^f represents a group selected from the group consisting of an alkyl group having 3 to 14 carbon atoms, an alkenyl group, an aryl group, and an alkyl ether group in which all or part of the hydrogen is substituted with fluorine. R ¹ and R ² may be the same or different and are selected from a hydrogen atom, a methyl group, and a fluorine atom. R ³ represents a hydrocarbon group having 1 to 5 carbon atoms, and a represents an integer of 0 to 2. Q ¹ and Q ^{2 each} represent —CH ₂ —CH ₂ —, —O—, —O—CH ₂ —CH ₂ —, —CH ₂ —CO—, —CO—, —O—CO—, Q ¹ and Q ² may be the same or different from each other. l and m represent the molar ratio of structural units, l is in the range of 71 to 99.5, and m is in the range of 0.5 to 29.

  The fluorine-containing compound containing the structural unit represented by the general formula (1) is used as an additive in the coating material. It is preferable to use an addition amount of 0.5 to 30% by mass with respect to the siloxane resin solid content. More preferably, it is 1 mass%-15 mass%. When the amount is less than 0.5% by mass, the improvement in alkali resistance is small. When the amount is more than 30% by mass, the low refractive index property and the steel wool resistance of the coating material may be impaired.

  The fluorine-containing compound containing the structural unit represented by the general formula (1) has an unsaturated double bond which is a polymerizable group and has a carbon having at least one fluorine bonded thereto. It can obtain by hydrolyzing the alkoxy part of the copolymer of a body compound and the silane compound which has a polymerizable unsaturated double bond.

  Specific examples of the monomer compound having an unsaturated double bond which is a polymerizable group and having carbon bonded to at least one fluorine include 2- (perfluorobutyl) ethyl ( (Meth) acrylate, 2- (perfluoropentyl) ethyl (meth) acrylate, 2- (perfluoropentyl) propyl (meth) acrylate, 2- (perfluoropentyl) butyl (meth) acrylate, 2- (perfluorohexyl) Ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorooctyl) butyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro -5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyl) Oxyl) ethyl (meth) acrylate, 2- (perfluoro-5-methyldecyl) ethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3, -pentafluoropropyl Fluorine-containing (meth) acrylates such as (meth) acrylates, 1H, 1H, 5H-octafluoropentyl (meth) acrylates and α-fluoroacrylates thereof, or unsaturated double bonds are vinyl groups (Fluoroalkyl) vinyl ether, (fluoroalkoxyalkyl) vinyl ether, perfluoro (alkoxyalkyl vinyl ether), and the like can be mentioned. Among these, 2- (perfluorooctyl) ethyl (meth) acrylate and 2- (perfluorooctyl) ethyl acrylate are preferably used in terms of availability of raw materials and improvement in alkali resistance. These monomers having fluorine may be used alone or in combination of two or more.

  As an example of the silane compound having a polymerizable unsaturated double bond, a compound represented by the following general formula (7) is preferably used.

R ¹⁰ Si (R ¹¹ ) _b (OR ¹² ) _3-b (7)
R ¹⁰ represents a vinyl group, an allyl group, an alkenyl group, a (meth) acryl group, a mercapto group, an epoxy group or a substituted product thereof, and R ¹¹ represents a hydrocarbon group having 1 to 5 carbon atoms. R ¹² represents a hydrocarbon group having 1 to 3 carbon atoms, a plurality of R ¹² may be the same or different, and b is 0 or 1.

  The copolymerization ratio when producing the fluorine-containing compound containing the structural unit represented by the general formula (1) in the present invention has an unsaturated double bond which is a polymerizable group in a molar ratio, and is at least 1 Monomer compound having carbon bonded to one fluorine / silane compound having unsaturated double bond = 99.5 to 71 / 0.5 to 29 is preferable. More preferably, it is the range of 99-90 / 1-10. When the number of silane compounds having an unsaturated double bond is less than 0.5, the scratch resistance of the coating material may be lowered, and when the number of silane compounds having an unsaturated double bond is more than 29, the alkali resistance is lowered.

  The hydrolysis of the alkoxy moiety of the copolymer is preferably performed in the presence of an acid catalyst. Examples of the acid catalyst include acid catalysts such as formic acid, oxalic acid, hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins. In particular, from the viewpoint of the stability of the copolymer compound, an acidic aqueous solution containing formic acid, acetic acid or phosphoric acid is preferred. If the copolymer is not hydrolyzed and does not have silanol groups, a synergistic effect with the siloxane resin cannot be obtained, resulting in a decrease in alkali resistance and scratch resistance, and a significant decrease in antifouling properties. .

  Among the silane compounds represented by the general formula (7), trifunctional silane compounds in which b = 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, in terms of the hardness and refractive index of the obtained coating film, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxy Propyltrimethoxysilane and 3-acryloxypropyltriethoxysilane are preferred.

  Among the silane compounds represented by the general formula (7), the bifunctional silane compound in which b = 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 fluorine-containing compound containing the structural unit represented by the general formula (1) of the present invention is further selected from the group consisting of the structural units represented by the general formula (2) and the general formula (3). It preferably contains a structural unit.

Here, R ¹³ , R ¹⁴ and R ¹⁵ in the general formula (2) and the general formula (3) may be the same or different and are selected from a hydrogen atom, a methyl group and a fluorine atom. R ¹⁶ is a group having 1 to 20 carbon atoms and has at least one group selected from the group consisting of an alkyl group, an alkenyl group, an aryl group, and an alkyl ether group. Q ³ , Q ⁴ , and Q ⁵ are at least selected from the group consisting of —C ₂ H ₄ —, —O—, —O—C ₂ H ₄ —, —CH ₂ —CO—, —CO—, —O—CO—. One is selected, and Q ³ , Q ⁴ , and Q ⁵ may be the same or different. Z is selected from the group consisting of —C ₂ H ₄ —O—, —CH ₂ —CH (CH ₃ ) —O—, —C ₂ H ₄ —, —C (R ¹⁷ ) ₂ —, a benzene ring, and tricyclodecane. It represents an organic group having 2 to 30 carbon atoms selected from at least one. R ¹⁷ represents an alkyl group having 1 to 4 carbon atoms. n and o represent the molar ratio of the structural units. When l + m + n + o is 100, when the fluorine-containing compound includes any one of the structural units represented by the general formula (2) and the general formula (3), l is 22 to 99.4, m is 0.5 to 29, n or o is 0.1 to 49, and includes both structural units represented by the general formula (2) and the general formula (3). Is 22 to 99.4, m is 0.5 to 29, n is 0.05 to 48.95, o is 0.05 to 48.95, and n + o is 0.1 to 49.

In order that the fluorine-containing compound containing the structural unit represented by the general formula (1) further includes the structural unit represented by the general formula (2), it is a polymerizable group that gives the structural unit. It can be obtained by copolymerizing a compound having two unsaturated double bonds in the molecule.
Specific examples of the bifunctional monomer that is a compound having two unsaturated double bonds in the molecule include triethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, and 1,6-hexanediol diester. Acrylate, 1,9-nanonediol diacrylate, dimethylol tricyclodecane diacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, pentaerythritol diacrylate monostearate , Polypropylene glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, polytetramethylene glycol diacrylate, bisphenol F Oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4- Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, glycerin dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2 -Hydroxy-3-acryloyloxypropyl methacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate Rate, polypropylene glycol dimethacrylate, and neopentyl glycol dimethacrylate. These bifunctional monomers may be used alone or in combination of two or more. These can improve the storage stability of the obtained fluorine-containing compound and increase the surface slipperiness of the coating film.

  In order that the fluorine-containing compound containing the structural unit represented by the general formula (1) further includes the structural unit represented by the general formula (3), it is a polymerizable group that gives the structural unit. It can be obtained by copolymerizing a compound having one unsaturated double bond in the molecule.

  Specific examples of the compound having one unsaturated double bond in the molecule include isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, isooctyl acrylate, isomyristyl acrylate, isostearyl acrylate, 2-ethylhexyl di Glycol acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, methoxydipropylene glycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxy Ethyl ak 2-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, methoxydiethylene glycol methacrylate, methoxy Polyethylene glycol methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, t-butyl methacrylate, isostearyl methacrylate, methoxytriethylene glycol methacrylate, n-butoxyethyl methacrylate, 2 Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate. These compounds having one unsaturated double bond in the molecule may be used alone or in combination of two or more. These can improve the storage stability of the obtained fluorine-containing compound and increase the surface slipperiness of the coating film.

  The fluorine-containing compound containing the structural unit represented by the general formula (1) further includes the structural unit represented by the general formula (2) and the structural unit represented by the general formula (3). Is a compound having two unsaturated double bonds in the molecule, which is a polymerizable group that gives a structural unit represented by the general formula (2), and an unsaturated group that gives a structural unit represented by the general formula (3) It can be obtained by copolymerizing a compound having one bond in the molecule. In this case, a compound having two unsaturated double bonds in the molecule that give the structural unit represented by the general formula (2), and an unsaturated double bond that gives the structural unit represented by the general formula (3) One compound or two or more compounds each may be used in the molecule.

  The proportion of copolymerizing the general formula (2) and / or the general formula (3) with the fluorine-containing compound containing the structural unit represented by the general formula (1) is such that the selected structural unit is the general formula (2) or When the structural unit is represented by the general formula (3), l in the general formula (1) is 22 to 99.4, m is 0.5 to 29, n in the general formula (2) is 0.1 to 49, Or o of general formula (3) is 0.1-49. More preferably, l in the general formula (1) is in the range of 46 to 99, m is in the range of 0.5 to 29, n in the general formula (2) is in the range of 0.5 to 25, or o in the general formula (3) is 0.5-25. If n or o is less than 0.1, the storage stability of the coating material is poor, and scratch resistance may be reduced, film thickness unevenness during coating, and defects due to undissolved polymer may occur. If it exceeds 49, the alkali resistance and antifouling properties may decrease.

  When the structural unit selected is a structural unit represented by general formula (2) and general formula (3), l in general formula (1) is 22 to 99.4, m is 0.5 to 29, In the general formula (2), n is 0.05 to 48.95, o is 0.05 to 48.95, and n + o is 0.1 to 49. When n + o is less than 0.1, the storage stability of the coating material is poor, and the scratch resistance is deteriorated and defects in the coating film may occur. When n + o is more than 49, alkali resistance and antifouling properties decrease. In general formula (1), l is 22 to 92.5, m is 3 to 45, n is 3 to 45, o is 4 to 46, and n + o is preferably 7 to 49.

  The concentration of the coating material of the present invention may be adjusted using a solvent so that the solid content has an appropriate concentration. Although there is no restriction | limiting in particular in a density | concentration, For example, when apply | coating to a film, it is common that a solid content density | concentration shall be 1.5-50 mass%. Two or more kinds of solvents may be contained. Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether. , Ethers such as ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate , Acetates such as ethyl lactate and butyl lactate , Ketones such as acetylacetone, methylpropylketone, methylbutylketone, methylisobutylketone, cyclopentanone, 2-heptanone, methanol, ethanol, propanol, 2-propanol, butanol, isobutyl alcohol, pentanol, 4-methyl Alcohols such as 2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, γ-butyrolactone, N -Methylpyrrolidinone and the like. Among these, examples of particularly preferable solvents are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methanol, 2-propanol, methyl isobutyl ketone, and the like. is there.

The content of the total solvent in the coating material of the present invention is preferably 30 parts by mass or more and more preferably 50 parts by mass or more with respect to 100 parts by mass of the total solid. On the other hand, 9900 mass parts or less are preferable, and 5000 mass parts or less are more preferable.
The refractive index after curing of the coating material of the present invention is preferably 1.25 to 1.45. More preferably, it is 1.28-1.37. The thickness of the coating film is usually 50 to 200 nm, more preferably 70 to 150 nm.

  In order to set the refractive index after curing of the coating material to 1.25 to 1.45, for example, the addition amount of inorganic particles having porous and / or voids in the coating material is 20% by mass to 70% by mass. Thus, the target refractive index can be obtained. 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.

  The coating material of the present invention is formed as a film on at least one surface of a transparent substrate and can be provided as an optical article. Although it does not specifically limit as an aspect of an optical article, The coating film of this invention is applied between the transparent substrate and the film (coating film) comprising the coating material of the present invention. Examples include a layer in which a layer having a refractive index higher than the refractive index (high refractive index layer) is formed.

  By forming the coating material of the present invention on the surface of the high refractive index layer as described above, an optical article having excellent antireflection properties can be obtained. In this case, the smaller the refractive index of the coating material of the present invention, the lower the reflectance of the optical article. That is, low refractive index can be exhibited by the minimum reflectance in the visible light region (380 to 780 nm), and antireflection properties as an optical article are also exhibited.

  When the high refractive index layer is formed on the optical article, the high refractive index layer preferably has a refractive index of 1.5 to 2.3. 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. When 2.3 is exceeded, the wavelength dependency of the reflectance is high at a wavelength of 380 to 780 nm. On the other hand, the reflectance increases when the wavelength is in the vicinity of 400 or 700 nm other than the wavelength of 500 to 600 nm, and covers the entire wavelength range of 380 to 780 nm. It may be difficult to reduce the average reflectance. Moreover, as a high refractive index material used in the present invention, an ultraviolet curable resin component is used from the viewpoint of adhesion to a coating film (in this case, a low refractive index layer), productivity, workability, and the like. It is preferable to use it.

  As a preferable resin component having ultraviolet curability, a polyfunctional (meth) acrylic compound containing at least two (meth) acryloyl groups in the molecule can be exemplified. 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, tetramethylolmethane tri (meth) acrylate or tetra- (meth) acrylate, pentaerythritol (meth) acrylate, Taerythritol 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 ( Aliphatic polyfunctional (meth) acrylate compounds such as meth) acrylate, and further aromatic ring-containing polyfunctional (meth) such as bisphenol A-ethylene oxide adduct, bisphenol F-ethylene oxide adduct, or di- (meth) acrylate An acrylate compound is mentioned. Furthermore, it is also possible to add a compound having a polymerizable unsaturated group and an alkoxysilane group in the molecule.

  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. If formed between the high refractive index layer and the low refractive index layer, the difference in refractive index between the two layers becomes small, the low reflectance layer does not function effectively, and the reflectance characteristics become poor. 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 absorbing layer (near-infrared absorbing compound), anthraquinone compounds, phthalocyanine compounds, naphthalocyanine compounds, metal oxide fine powders, imonium compounds, diimonium compounds, aminium salt compounds, 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.

  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, and flow coating. A microgravure coating is particularly 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, resins such as polyester, particularly polyethylene terephthalate, unsaturated polyester, acrylonitrile-styrene copolymer, polyvinyl chloride, polyurethane, epoxy resin, and polycarbonate are preferable. 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 coated with a hard coat film may be used.

  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. 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.

  It apply | coats on a base material using said method, and it heats, dries, and hardens | cures as needed. The heating and drying method is determined by the applied substrate and membrane components, but the film substrate is usually treated at a temperature of room temperature to 200 ° C., usually for 0.5 to 240 minutes. . In addition, when using a polymer having a photopolymerizable group, a film may be formed while irradiating ultraviolet rays having a wavelength shorter than that in the visible region at the time of heating, drying and curing after the formation of the coating film. You may form a film | membrane by irradiating the ultraviolet-ray whose wavelength is shorter than visible region after drying and hardening.

  The optical article of the present invention is used as a front plate of various displays such as a cathode ray tube (CRT), a liquid crystal display (LCD), a PDP, and a field emission display (FED) as an optical element or an optical film having antireflection properties.

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

[Evaluation of alkali resistance]
About 0.5 ml of each is dripped on the coating film surface kept horizontal using 1 mass% and 3 mass% sodium hydroxide aqueous solution. Every 5 minutes after the dropping, the droplets were wiped off with “Kimwipe” (trade name, Crecia Wiper S-200), and the state of the wiping traces was visually confirmed. The alkali resistance was expressed by the time when the wiping trace was not observed at all after 30 minutes.

[Measurement of refractive index]
Using a prism coupler (manufactured by Metricon), a coating film formed at 633 nm (using a He-Ne laser) at 20 ° C. for a coating film formed on each silicon wafer with a coating thickness of 1.5 μm. The refractive index in the direction perpendicular to the surface was measured.

[Scratch resistance evaluation]
A load of 250 mPa was applied to the surface of the coating film of each sample using # 0000 steel wool, and the number of scratches after 10 reciprocations was observed and evaluated according to the following criteria. Scratch resistance is good if it is grade 3, 4, 5.
5th grade: No scratch 4th grade: 1-5 scratches 3rd grade: 6-10 scratches 2nd grade: 11 or more scratches 1st grade: Full scratches

[Evaluation of antifouling properties (wipe off fingerprints)]
Fingerprints were attached by pressing sebum or sweat on the finger against the coating film surface of each sample for 3 seconds, and then the attached fingerprint was used with “Kimwipe” (trade name, Crecia Wiper S-200). It was wiped off by 5 rotations and 10 rotations, and the removability was visually evaluated.
○: After 5 rotations, fingerprint marks are not noticeable and can be easily wiped off. Δ: After 10 rotations, traces remain and are difficult to wipe off.
X: Remarks remain after 10 rotations and cannot be wiped off at all.

[Evaluation of applicability]
The coating film surface of each sample was observed with the naked eye, and the film surface uniformity, coating unevenness, and the presence of repellency were evaluated.

[Measurement of light reflectance]
Measurement was performed using a spectrophotometer 3410 of Hitachi Instrument Service Co., Ltd. The sample is # 320-400 water-resistant sandpaper, the surface opposite to the coating film surface is evenly scratched, black paint (black magic ink (registered trademark) liquid) is applied, and it is opposite to the coating film surface The measurement was performed by completely eliminating reflection from the side 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 780 nm. The scan rate was 600 nm / min, and the measured value was recorded every 1 nm. The maximum value and the minimum value in the above wavelength range were taken as the reflectance of each sample.

[Measurement of surface resistance]
The surface of each sample was measured using a surface resistance measuring machine (Mitsubishi Chemical Corporation: Hiresta UP) and a dedicated probe (Mitsubishi Chemical Corporation: Resistive URS probe), voltage: 100 V, measurement time: 60 seconds. It measured on condition of this.

[Evaluation of surface slipperiness of coating film]
The surface of each sample was rubbed with 10 reciprocating hands under a load of 1000 gf / cm ² using “Kimwipe” (trade name, Crecia Wiper S-200), and the degree of sliding was evaluated according to the following criteria.

  ○: Even after 10 reciprocations, the sliding did not decrease, and it rubbed easily.

  (Triangle | delta): Resistance becomes large by 5 reciprocations and it is hard to rub.

  ×: Resistance is strong from the second round and does not rub.

Example 1
Preparation of coating material for high refractive index layer X-41 manufactured by Shin-Etsu Chemical Co., Ltd. as an additive to AS-41 (manufactured by Dainichi Seika Co., Ltd.) having a solid content concentration of 30% in a screw tube. -1056 alkoxysilane oligomer was added in an amount of 10 parts by mass with respect to 100 parts by mass of the solid content of AS-41, and then stirred at room temperature (23-25 ° C) for 10 minutes. The conductive oxide (ATO) contained in AS-41 is 25 mass% in the solid content contained in the coating material.

Formation of a high refractive index layer The high refractive index layer was applied to a PET film (thickness 100 μm, manufactured by Toray Industries, Inc.), which is a transparent base material, by coating the coating material prepared by the above method with a metal ring bar. . The film thickness after drying and curing was about 3 μm.
After forming the high refractive index layer, it was placed in an oven at a temperature of 80 ° C. and heat-treated for 1 minute. After that, it passes through a conveyor type UV irradiation device equipped with one high-pressure mercury lamp (120 W) at a speed of 5 m / min, and UV irradiation treatment (approx. 300 mJ / cm ² when converted to ultraviolet light) is performed, with a high refractive index layer. A substrate was obtained. As a result of measuring the surface resistance value, it was 1 × 10 ⁸ (Ω / □). The refractive index was 1.64.

Preparation of coating material Preparation of fluorine-containing compound represented by general formula (1) 300 g (0.58 mol) of perfluorooctylethyl acrylate, 7.6 g (0.03 mol) of 3-methacryloxypropyltrimethoxysilane, 2-propanol 460 g was weighed in a reaction vessel, and 3.1 g of mercaptopropyltrimethoxysilane and 9.2 g as a polymerization initiator were added to the vessel and mixed with stirring. Then, it was made to react by heating and stirring at a bath temperature of 60 ° C. for 2 hours. Thereafter, the bath temperature was set to 40 ° C., 1.7 g of a 1N formic acid aqueous solution was dropped over 10 minutes, and after dropping, the mixture was heated and stirred at 40 ° C. for 1 hour to cause a hydrolysis reaction. Then, it cooled to room temperature and obtained the 40 mass% solution of fluorine-containing compounds. The copolymerization molar ratio of perfluorooctylethyl acrylate / methacryloxypropyltrimethoxysilane was 95/5.

Preparation of siloxane resin In a separable flask, 60 g of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 41.2 g of 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) are placed. After charging 300 g of 2-propanol as a solvent, 2-propanol-dispersed hollow silica sol (refractive index 1.30, solid content 20.5% by mass) produced by the method disclosed in JP-A-2001-233611 is used. Add 188 g. Thereafter, the temperature was set to about 20 ° C., and 34.84 g of a 1N aqueous formic acid solution was added over about 20 minutes while stirring with a stirring blade at a rotational speed of about 270 rpm. When the addition of the formic acid aqueous solution is completed, the mixture is stirred for about 1 hour at the same set temperature and rotation speed, and then heated using an oil bath set at 60 ° C., and the temperature of the reaction solution is kept at 60 ° C. for 3 hours. Stir. Thereafter, the reaction solution was cooled to room temperature or lower and stored in a refrigerator (about 7 to 8 ° C.) to obtain 622 g of a silica particle-dispersed polymer solution (solid content 20% by mass). To this polymer solution, 356 g of methanol was added, then 5 g of aluminum trisacetylacetonate was added and 1890 g of 2-propanol was added with stirring, and further 720 g of methyl isobutyl ketone was added to obtain a siloxane resin solution. The ratio of the siloxane resin to the hollow silica particles was 60/40 by mass ratio.

Coating Film Formation A coating material was obtained by mixing and stirring 100 g of the obtained siloxane resin solution and 0.7 g of the fluorine compound represented by the general formula (1) obtained as described above. The mass ratio of the solid of the siloxane resin solution and the solid of the fluorine compound was 92.5 / 7.5. The obtained coating material was applied to the surface of the high refractive index layer of the substrate with the high refractive index layer film using a metal ring bar, and was subjected to heat treatment for 2 minutes in an oven set at a temperature of 130 ° C. 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 in which a high refractive index layer and a low refractive index layer were provided in this order on the substrate was obtained. The obtained optical article was subjected to alkali resistance, refractive index, scratch resistance, antifouling property (fingerprint wiping property), light reflectance measurement, surface resistance value of optical article, and applicability evaluation. The results are shown in Tables 1 and 2.

Example 2
In preparation of the fluorine-containing compound represented by the general formula (1), 7.6 g (0.03 mol) of 3-methacryloxypropyltrimethoxysilane was replaced with 7.02 g (0.03 mol) of acryloxypropyltrimethoxysilane. Except for this, the same procedure as in Example 1 was performed.

Example 3
Example 1 except that 40 g of methyltrimethoxysilane, 27.5 g of 3,3,3-trifluoropropyltrimethoxysilane, 240 g of 2-propanol, and 282 g of 2-propanol-dispersed hollow silica sol were used in the siloxane resin solution. went.

Example 4
In the fluorine-containing compound represented by the general formula (1), except that 237 g of perfluorooctylethyl acrylate, 38 g of 3-methacryloxypropyltrimethoxysilane, 379.6 g of 2-propanol, and 8.3 g of 1N aqueous formic acid were used. Performed as in Example 1.

Example 5
The same procedure as in Example 1 was performed except that the coating material was replaced with 0.22 g of the fluorine compound represented by the general formula (1) obtained in Example 1.

Example 6
The same procedure as in Example 1 was performed except that the coating material was replaced with 2.2 g of the fluorine compound represented by the general formula (1) obtained in Example 1.

Example 7
In the fluorine-containing compound represented by the general formula (1), 300 g (0.58 mol) of perfluorooctylethyl acrylate is changed to 210 g (0.41 mol) of perfluorooctylethyl acrylate and 28 g (0.17 mol) of trifluoroethyl methacrylate. Instead, the same procedure as in Example 1 was performed except that 28 g of 3-methacryloxypropyltrimethoxysilane, 334.5 g of 2-propanol, and 6.1 g of a 1N formic acid aqueous solution were used.

Example 8
In the fluorine-containing compound represented by the general formula (1), 300 g (0.58 mol) of perfluorooctylethyl acrylate was added to 116 g (0.58 mol) of 2,2,3,3-tetrafluoropropyl methacrylate and 2-propanol. Was carried out in the same manner as in Example 1 except that 187 g was replaced.

Example 9
The siloxane resin solution was replaced with 100 g of methyltrimethoxysilane, 68.7 g of 3,3,3-trifluoropropyltrimethoxysilane, 398 g of 2-propanol, 0 g of 2-propanol-dispersed hollow silica sol, and 56.7 g of 1N formic acid aqueous solution. Was carried out in the same manner as in Example 1.

Example 10
In preparation of the fluorine-containing compound of Example 1, 293 g (0.57 mol) of perfluorooctylethyl acrylate 300 g (0.57 mol) and 7.6 g of 3-methacryloxypropyltrimethoxysilane (0.03 mol) were 7.7 g. A fluorine-containing compound was produced in the same manner as in Example 1 except that 3.6 g (0.012 mol) of dimethylol tricyclodecane diacrylate was added in place of (0.03 mol). Next, 30 days after the preparation of the fluorine-containing compound, the siloxane resin solution of Example 1 was prepared, and a coating material was prepared and evaluated. The results are shown in Tables 3 and 4.

Example 11
In the preparation of the fluorine-containing compound of Example 1, 287 g (0.56 mol) of perfluorooctylethyl acrylate 300 g (0.58 mol) and 7.6 g of 3-methacryloxypropyltrimethoxysilane (0.03 mol) were 7.7 g. (0.03 mol), respectively, except that 3.6 g (0.012 mol) of dimethylol tricyclodecane diacrylate and 1.7 g (0.012 mol) of isoamyl acrylate were added. A containing compound was prepared. Next, 30 days after the preparation of the fluorine-containing compound, the siloxane resin solution of Example 1 was prepared, and a coating material was prepared and evaluated. The results are shown in Tables 3 and 4.

Example 12
In the preparation of the fluorine-containing compound of Example 1, 174 g (0.34 mol) of perfluorooctylethyl acrylate 300 g (0.58 mol) and 7.6 g (0.03 mol) 3-methacryloxypropyltrimethoxysilane 15.2 g A fluorine-containing compound was prepared in the same manner as in Example 1 except that 66 g (0.22 mol) of dimethylol tricyclodecane diacrylate was added in place of (0.06 mol). Next, 30 days after the preparation of the fluorine-containing compound, the siloxane resin solution of Example 1 was prepared, and a coating material was prepared and evaluated. The results are shown in Tables 3 and 4.

Example 13
After 30 days had passed since the preparation of the fluorine-containing compound of Example 2, the siloxane resin solution of Example 2 was prepared, and a coating material was prepared and evaluated. The results are shown in Tables 3 and 4.

Comparative Example 1
The same procedure as in Example 1 was performed except that the fluorine-containing compound represented by the general formula (1) was not used in the coating material.

Comparative Example 2
In the fluorine-containing compound represented by the general formula (1) prepared in Example 1, 300 g (0.58 mol) of perfluorooctylethyl acrylate was changed to 92.8 g (0.58 mol) of butoxyethyl acrylate, and 552 g of 2-propanol was changed. It was made to react instead of and the additive was produced. The additive is a compound having no fluorine-containing group, and is different from the compound represented by the general formula (1). The same procedure as in Example 1 was performed except that the compound represented by the general formula (1) was replaced with the additive prepared in Comparative Example 2.

Comparative Example 3
In the fluorine-containing compound represented by the general formula (1) prepared in Example 1, in place of 300 g (0.58 mol) of perfluorooctylethyl acrylate and 7.6 g (0.03 mol) of 3-methacryloxypropyltrimethoxysilane In addition, only 316 g (0.61 mol) of perfluorooctylethyl acrylate was reacted in place of 483 g of 2-propanol to prepare an additive. The additive is a compound that does not contain an alkylsilane monomer, and is different from the compound represented by the general formula (1). The same procedure as in Example 1 was performed except that the compound represented by the general formula (1) was replaced with the additive prepared in Comparative Example 3.

Comparative Example 4
In the fluorine-containing compound represented by the general formula (1) prepared in Example 1, 1.7 g of 1N formic acid aqueous solution was not dropped and mixed to prepare a fluorine-containing compound having an alkoxysilane that was not hydrolyzed. The compound is different from the compound represented by the general formula (1). The same operation as in Example 1 was performed except that the compound represented by the general formula (1) was replaced with the compound prepared in Comparative Example 4.

Comparative Example 5
The same procedure as in Example 9 was conducted except that the fluorine-containing compound represented by the general formula (1) was not used in the coating material.

The meaning of each symbol in the table is as follows.
FA108: perfluorooctylethyl acrylate FM3: trifluoroethyl methacrylate FM4: 2,2,3,3-tetrafluoropropyl methacrylate MPS: 3-methacryloxypropyltrimethoxysilane APS: 3-acryloxypropyltrimethoxysilane DCPA : Dimethylol tricyclodecane diacrylate IAA: Isoamyl acrylate DPHA: Dipentaerythritol hexaacrylate

Claims (5)

A coating material comprising a siloxane resin and a fluorine-containing compound containing a structural unit represented by the following general formula (1).

(R ^f represents a group selected from the group consisting of a C 3-14 alkyl group, an alkenyl group, an aryl group, and an alkyl ether group in which all or part of the hydrogen is substituted with fluorine. R ¹ , R ² Each may be the same or different and is selected from a hydrogen atom, a methyl group and a fluorine atom, R ³ represents a hydrocarbon group having 1 to 5 carbon atoms, a represents an integer of 0 to 2. Q ¹ and Q ² are —CH ₂ —CH ₂ —, —O—, —O—CH ₂ —CH ₂ —, —CH ₂ —CO—, —CO—, —O—CO— is represented, and Q ¹ and Q ² are Each may be the same or different, l and m represent the molar ratio of structural units, l is 71 to 99.5, and m is in the range 0.5 to 29.) A fluorine-containing compound containing a structural unit represented by the general formula (1) and at least one structural unit selected from the group consisting of the structural units represented by the general formula (2) and the general formula (3) A coating material according to claim 1 comprising.

(R ¹³ , R ¹⁴ , and R ¹⁵ may be the same or different and are selected from a hydrogen atom, a methyl group, and a fluorine atom. R ¹⁶ is a group having 1 to 20 carbon atoms, and includes an alkyl group, an alkenyl group, and an aryl group. And at least one group selected from the group consisting of alkyl ether groups, Q ³ , Q ⁴ , and Q ⁵ are —C ₂ H ₄ —, —O—, —O—C ₂ H ₄ —, —CH _2. At least one selected from the group consisting of —CO—, —CO—, and —O—CO—, and Q ³ , Q ⁴ , and Q ⁵ may be the same or different, and Z is —C ₂ H ₄ —O. ₂ selected from the group consisting of —, —CH ₂ —CH (CH ₃ ) —O—, —C ₂ H ₄ —, —C (R ¹⁷ ) ₂ —, a benzene ring and tricyclodecane. Represents an organic group of ˜30, and R ¹⁷ represents an alkyl group having 1 to 4 carbon atoms. N, o represents a molar ratio of structural units, and when l + m + n + o is 100, the fluorine-containing compound represents either one of the structural units represented by the general formula (2) or the general formula (3). In the case of inclusion, l is 22 to 99.4, m is 0.5 to 29, n or o is 0.1 to 49, and both structural units represented by general formula (2) and general formula (3) Is 1 to 22-99.4, m is 0.5 to 29, n is 0.05 to 48.95, o is 0.05 to 48.95, and n + o is 0.1. ~ 49.) The coating material according to claim 1 or 2, wherein the fluorine-containing compound is contained in an amount of 0.1 to 30% by mass with respect to the solid content in the coating material. An optical article in which the coating material according to claim 1 or 2 is formed on at least one surface on a transparent substrate. An optical article in which a layer having a refractive index of 1.5 to 2.3 is formed on at least one surface of a transparent substrate, and the coating material according to claim 1 or 2 is formed on the surface of the layer.