JP2010085579A - Method for manufacturing antireflective optical article and siloxane resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflective optical article which is excellent in transparency and abrasion resistance and to provide a siloxane resin composition which is an antireflective laminate. <P>SOLUTION: The antireflective optical article is formed by laminating a high refractive index layer and a low refractive index layer on at least one surface of a transparent film base material directly or via another layer. The high refractive index layer is a coating film which has thickness of 2.5 to 45 μm and is obtained by applying a coating solution consisting essentially of a siloxane resin composition and then curing. The siloxane resin composition is obtained by hydrolyzing an alkoxysilane compound in the presence of metal oxide particles in a solvent by an acid catalyst and then subjecting hydrolyzate to condensation reaction. The low refractive index layer is a coating film which has a refractive index smaller than that of the high refractive index layer by 0.20 or more and is obtained by applying a coating solution consisting essentially of the siloxane low refractive index resin composition containing inorganic particulates and a siloxane compound and then curing. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antireflection optical article used for a flat panel display, a coating material used therefor, and an antireflection film 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. Therefore, such optical components are required to have further low reflectance and high surface hardness.

  For example, Patent Document 1 proposes a method in which a hard coat layer, a high refractive index layer, and a low refractive index layer are provided on the surface of an organic film from the lower layer side. In this method, since the refractive index of the low refractive index layer is not so low, the reflectance is not lowered effectively, the antireflection property is low, and the scratch resistance of the surface is low.

  Patent Document 2 discloses a low-refractive index layer using silica particles having a cavity inside to reduce the refractive index and increase the antireflection property. Such products have good performance in terms of antireflection, but are not suitable for coating layers on film substrates, and are more durable for surface scratches on large flat panels such as home TVs. (Abrasion resistance) is required.

  In Patent Documents 3 to 5, a coating liquid for hard coat in which a polymerizable monomer, an oligomer and high refractive index particles are used in combination in the high refractive index layer is used, but a relatively large amount of silica fine particles are used in the low refractive index layer. An antireflection film in which a siloxane-based material is laminated has insufficient adhesion and is required to have higher scratch resistance.

  In Patent Documents 6 and 7, a coating composition in which a silicone resin and high refractive index particles are used in combination in a matrix of a high refractive index layer is used, but when the coloring in the visible light region or the film thickness of the coating film is increased, Insufficient cracking during curing.

  Patent Document 8 discloses a siloxane-based resin composition comprising metal compound particles and a siloxane compound. This is only a disclosure of a resin composition having a high refractive index layer, which is insufficient as an antireflection film technique for laminating on an organic transparent substrate.

Further, for the purpose of improving scratch resistance, Patent Documents 9 to 11 disclose multilayering and thickening of the hard coat layer, but high hardness in the siloxane-based resin composition has not been achieved. Therefore, further improvement is strongly desired.
JP 2001-350002 A (Claims 1, 9, [0026]) Japanese Patent No. 3272111 (Claim 1, Example 1) JP 2005-172896 A (Claim 1) JP 2007-025078 A (Claims 1 to 8, [0073]) JP 2007-077351 (Claims 1 to 5, [0075]) JP 2001-0814404 A (Claims 1 and 2) JP 2008-094956 A (Claims 1 to 7, [0064]) JP 2007-246877 A (Claims 1 to 10) JP-A-5-008350 (Claims 1 and 2) JP 2008-012926 A (Claims 1 to 7, [0044]) JP 2008-073999 A (Claim 1, [0025])

  An object of the present invention is to provide an antireflection optical article excellent in transparency and scratch resistance, and a siloxane-based resin composition that is an antireflection laminate.

  The present invention provides an antireflective optical article comprising the following high refractive index layer and low refractive index layer laminated on at least one surface on a transparent film substrate directly or via another layer. It is.

  The high refractive index layer is composed mainly of a siloxane-based resin composition obtained by a method in which an alkoxysilane compound is hydrolyzed with an acid catalyst in a solvent in the presence of metal oxide particles, and then the hydrolyzate is subjected to a condensation reaction. It is a film having a thickness of 2.5 μm or more and 45 μm or less, which is obtained by applying and then curing the coating solution containing the low refractive index layer, and the low refractive index layer is a siloxane low refractive index resin composition containing inorganic fine particles and a siloxane compound. It is a film obtained by applying a coating liquid containing as a main component and then curing, and is a film having a refractive index smaller than the refractive index of the high refractive index layer by 0.20 or more.

  The optical article of the present invention can form a cured film laminate having low reflectance, high visible light transmittance, and excellent scratch resistance and crack resistance. In particular, it can be suitably used as a structural member for a visibility improving filter such as a television.

  The optical article of the present invention comprises a high refractive index layer and a low refractive index layer laminated on at least one surface on a transparent film substrate directly or via another layer. In the presence of product particles, the alkoxysilane compound was hydrolyzed with an acid catalyst in a solvent, and then a coating liquid containing a siloxane-based resin composition obtained as a main component by the condensation reaction of the hydrolyzate was applied. A coating liquid obtained by post-curing and having a thickness of 2.5 μm or more and 45 μm or less, and the low refractive index layer containing a siloxane-based low refractive index resin composition containing inorganic fine particles and a siloxane compound as main components Is a film obtained by curing after coating and having a refractive index smaller by 0.20 or more than the refractive index of the high refractive index layer.

  Since the main component of the laminated high refractive index layer and low refractive index layer of the present invention is a siloxane-based composition, a wide range of material designs in terms of coating methods, coating conditions, adhesion, etc. can be studied. Scratch resistance and crack resistance are improved more than those using a composition mainly composed of an acrylic compound in the refractive index layer or the low refractive index layer.

  In the optical article of the present invention, it is important that the thickness of the high refractive index layer is 2.5 μm or more and 45 μm or less. When the thickness of the high refractive index layer is less than 2.5 μm, the pencil hardness decreases. If the thickness exceeds 45 μm, cracks are generated in the coating obtained by curing after coating, and crack resistance is also lowered. A preferable thickness is 2.5 μm or more and 35 μm or less, and 2.5 μm or more and 20 μm or less is more preferable in terms of productivity for winding the film.

  In addition, the thickness of the high refractive index layer in this invention says the value measured with the following measuring methods. A sample for observing the cross section of the high refractive index layer is cut from the substrate side into a substrate with a high refractive index layer obtained by coating on a PET film, which is a transparent substrate, and cut to tear. create. This sample is observed with a scanning electron microscope, and the distance from the interface with the transparent substrate to the surface of the high refractive index layer can be determined using a scale. Sampling is performed at 3 cm intervals, and is shown as an average of measured values (read to the second decimal place, unit: μm).

  The siloxane-based resin composition (hereinafter referred to as “siloxane-based high refractive index resin composition”) used for the material for the high refractive index layer of the present invention is homogenized by the reaction of the metal compound particles and the siloxane compound. In addition, because the condensation shrinkage is suppressed by the condensation reaction, cracks are unlikely to occur, and even if the cured film is formed by increasing the film thickness, the curl of the film can be reduced. Become.

  The metal oxide particles used in the material for the high refractive index layer of the present invention preferably have a refractive index of 1.45 to 2.8, and include silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, and An oxide of at least one element selected from the group consisting of cerium can be preferably used. Examples thereof include titanium oxide, zirconium oxide, zinc oxide, indium oxide, antimony pentoxide, tin oxide, cerium oxide, silicon oxide, ITO (tin-containing indium oxide), and ATO (tin-containing antimony oxide). In order to further increase the refractive index of the high refractive index layer, titanium oxide and zirconium oxide are preferably used, and in order to have conductivity, tin oxide, zinc oxide, antimony pentoxide, and ATO can be preferably used. Moreover, in order to make it easy to react with the siloxane compound of a matrix, the metal oxide particle which has a reactive group which can react with siloxane compounds, such as a hydroxyl group, on the particle | grain surface is preferable. The metal oxide particles can be used in powder form, but are preferably used in a form dispersed in water or an organic solvent from the viewpoint of stability of the particles and ease of mixing with alkoxysilane.

  The number average particle diameter of the metal oxide particles is preferably 1 nm to 200 nm. By making the number average particle diameter 1 nm or more, the crack resistance is further improved. Moreover, a film | membrane more transparent with respect to visible light is obtained by setting it as a number average particle diameter of 200 nm or less. In order to satisfy both crack resistance and transparency of the cured film, the number average particle diameter is more preferably 1 nm to 70 nm. Here, the number 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 using a transmission electron microscope or a scanning electron microscope, and the like. be able to.

  The content of the metal compound particles in the siloxane-based high refractive index resin composition is preferably 10% by weight to 90% by weight with respect to all the resin composition components excluding the solvent. Within this range, a film with better transmittance and crack resistance can be obtained. More preferably, it is 20 to 70% by weight.

  As an example of the metal oxide particles, commercially available inorganic particles include tin oxide-titanium oxide composite particles “OPTRAIK TR-502”, “OPTRAIK TR-504”, “OPTRAIK TR-520”, "Optlake TR-513", silicon oxide-titanium oxide composite particles "Optlake TR-503", "Optlake TR-527", "Optlake TR-528", "Optrake TR-529", titanium oxide “OPTRAIK TR-505” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.), “Selnax” of antimony oxide particles, tin oxide-zirconium oxide composite particles, “Sun” of zirconium oxide-antimony oxide particles Colloid ”(trade name, manufactured by Nissan Chemical Industries, Ltd.), zirconium oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.), acid Examples include tin oxide-zirconium oxide composite particles (manufactured by Catalyst Chemical Industry Co., Ltd.), tin oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.), and the like.

  The siloxane compound used in the siloxane-based high refractive index resin composition can be obtained by hydrolyzing an alkoxysilane compound in a solvent with an acid catalyst to form a silanol compound and then subjecting the silanol compound to a condensation reaction. it can. As the alkoxysilane compound, one or more alkoxysilane compounds selected from the alkoxysilane compounds represented by the following general formulas (1) to (3) are preferable.

R ¹ Si (OR ⁴ ) ₃ (1)
R ¹ represents hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof. From the viewpoint of crack resistance, it is preferable to use an alkoxysilane compound having a phenyl group as R ¹ . R ⁴ 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 ⁴ is more preferably a methyl group or an ethyl group.

R ² R ³ Si (OR ⁵ ) ₂ (2)
R ² and R ³ each represent hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof. 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 more preferably a methyl group or an ethyl group.

Si (OR ⁶ ) ₄ (3)
R ⁶ represents a methyl group or an ethyl group, and may be the same or different.

  Specific examples of the alkoxysilane compound represented by the general formulas (1) to (3) are shown below. Examples of the trifunctional alkoxysilane compound represented by the general formula (1) include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, and methyltributoxy. Silane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, 3-aminopropyltriethoxysilane N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimeth Sisilane, 3-glycidoxy propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3 -Acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-acryloxypropyltriisopropoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) ) -Γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxy Silane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxy Silane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxy Sisilane, γ-glycidoxypropyl triisopropoxy silane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycid Xibutyltriethoxysila , Β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane , Δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltributoxysilane, 2- (3,4- Epoxycyclohexyl) ethylto Limethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, trifluoromethyltrimethoxy Examples thereof include silane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, and trifluoropropyltriethoxysilane. Of these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable from the viewpoint of crack resistance of the obtained coating film. In addition, from the viewpoint of improving adhesion with the low refractive index layer and thus improving surface hardness, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, vinyltrimethoxysilane Vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane are preferably used.

  Examples of the bifunctional alkoxysilane compound represented by the general formula (2) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, and methylvinyl. Diethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxye Rumethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidyl Sidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypro Ruethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, tri Fluoropropylethyldiethoxysilane, trifluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxy Examples thereof include silane and octadecylmethyldimethoxysilane. Among these, dimethyl dialkoxysilane is preferably used for the purpose of imparting flexibility to the resulting coating film.

  Examples of the tetrafunctional alkoxysilane compound represented by the general formula (3) include tetramethoxysilane and tetraethoxysilane.

  These alkoxysilane compounds represented by the general formulas (1) to (3) may be used alone or in combination of two or more.

  The content of the siloxane compound in the siloxane-based high refractive index resin composition is preferably 10% by weight to 90% by weight with respect to all components of the resin composition excluding the solvent. By containing the siloxane compound within this range, the transmittance and crack resistance of the coating film can be further improved. More preferably, it is 20 to 80% by weight.

  The hydrolysis reaction is preferably carried out at 5 to 110 ° C. for 1 to 180 minutes after an acid catalyst and water are added to the above alkoxysilane compound in a solvent over 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 15 to 70 ° C.

  Moreover, after obtaining a silanol compound by a hydrolysis reaction, the reaction solution is preferably heated as it is at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours to perform a condensation reaction. In order to increase the degree of polymerization of the siloxane compound, it is possible to reheat or add a base catalyst.

  Various conditions in the hydrolysis can be obtained by considering the reaction scale, reaction vessel size, shape, etc., for example, by setting the acid concentration, reaction temperature, reaction time, etc., and obtaining physical properties suitable for the intended application. Can do.

  Examples of the acid catalyst used in the hydrolysis reaction include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins. In particular, an acidic aqueous solution using formic acid, acetic acid or phosphoric acid is preferred.

  The preferred content of these acid catalysts is preferably 0.05 parts by weight to 10 parts by weight, particularly preferably 0.1 parts by weight with respect to 100 parts by weight of the total alkoxysilane compound used during the hydrolysis reaction. ~ 5 parts by weight. Here, the total amount of the alkoxysilane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate, and the same shall apply hereinafter. When the amount of the acid catalyst is 0.05 parts by weight or more, hydrolysis proceeds smoothly, and when the amount is 10 parts by weight or less, the hydrolysis reaction is easily controlled.

  The solvent is not particularly limited, but is appropriately selected in consideration of the stability, wettability, volatility, etc. of the siloxane-based resin composition. The solvent can be used not only as one type but also as a mixture of two or more types. Specific examples of the solvent include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl- Alcohols such as 3-methoxy-1-butanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, Ethers such as lenglycol diethyl ether, ethylene glycol dibutyl ether and diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and 2-heptanone; Amides such as dimethylformamide and dimethylacetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , Acetates such as methyl lactate, ethyl lactate and butyl lactate; Ren, hexane, other aromatic or aliphatic hydrocarbons such as cyclohexane, .gamma.-butyrolactone, N- methyl-2-pyrrolidone, dimethyl sulfoxide and the like. Of these, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol in terms of cured film transmittance, crack resistance, etc. Mono-t-butyl ether, γ-butyrolactone and the like are preferably used. Moreover, it is also preferable to adjust to a suitable density | concentration as a resin composition by adding a solvent after completion | finish of a hydrolysis reaction. Moreover, after hydrolysis according to the purpose, it is also possible to distill and remove a suitable amount of the produced alcohol under heating and / or reduced pressure, and then add a suitable solvent.

  The amount of the solvent used during the hydrolysis reaction is preferably in the range of 50 to 500 parts by weight, particularly preferably in the range of 80 to 200 parts by weight, based on 100 parts by weight of the total alkoxysilane compound. . The production | generation of a gel can be suppressed by making the quantity of a solvent into 50 weight part or more. Moreover, a hydrolysis reaction advances rapidly by setting it as 500 parts weight or less.

  Moreover, as water used for a hydrolysis reaction, ion-exchange water is preferable. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of the alkoxysilane compound.

  Examples of the inorganic fine particles used in the low refractive index layer of the present invention include hollow silica particles, porous silica particles, and magnesium fluoride particles. 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 siloxane-based low refractive index resin composition, not only can the refractive index of the low refractive index film obtained from the siloxane-based low refractive index resin composition be 1.38 or less, The hardness of the low refractive index 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 commercially available such as those disclosed in JP-A-2001-233611 and those disclosed in Japanese Patent No. 3272111.

  The introduction amount of the inorganic fine particles 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 of the siloxane-based low refractive index resin composition. 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 low refractive index film obtained due to particle aggregation is not uniform and low. It may cause a decrease in the hardness of the refractive index film and non-uniformity of the refractive index.

  The siloxane-based low refractive index resin composition used for the low refractive index layer of the present invention is obtained by hydrolyzing an alkoxysilane compound in the presence of inorganic fine particles to form silanol and then subjecting the silanol compound to a condensation reaction. A siloxane-based resin composition is preferable.

  The alkoxysilane compound is preferably at least one selected from alkoxysilane compounds represented by any of the following general formulas (4) to (6).

R ⁷ Si (OR ¹⁰ ) ₃ (4)
R ⁷ represents hydrogen, an alkyl group, an alkenyl group, an aryl group or a substituted product thereof. R ⁷ 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 ⁷ . Further, when it is desired to obtain a low refractive index cured film, it is preferable to use an alkoxysilane compound having an alkyl group containing a methyl group or fluorine as R ^7. Further, R ⁷ preferably has 1 to 20 carbon atoms. R ¹⁰ 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 ¹⁰ is preferably a methyl group or an ethyl group from the viewpoint of ease of hydrolysis reaction and availability of raw materials.

R ⁸ R ⁹ Si (OR ¹¹ ) ₂ (5)
R ⁸ and R ⁹ each represent hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituent thereof, and may be the same or different. R ⁸ and R ⁹ preferably have 1 to 20 carbon atoms. R ¹¹ 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 ¹¹ is preferably a methyl group or an ethyl group from the viewpoint of easy hydrolysis reaction and availability of raw materials.

Si (OR ¹² ) ₄ (6)
R ¹² 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 ¹² is preferably a methyl group or an ethyl group from the viewpoint of ease of 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 lowering the refractive index of the siloxane-based low refractive index resin composition 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 contains 10% by mass or more, more preferably 15% by mass or more of fluorine with respect to the total solid content of the siloxane-based low refractive index resin composition. It is preferable. 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.

The siloxane-based low refractive index resin composition used in the present invention is preferably 20% by mass or more based on the total solid content. More preferably, it is 30 mass% or more.
The hydrolysis reaction of the alkoxysilane 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 utilize the residual acid in the silanol reaction solution obtained by hydrolyzing one alkoxysilane compound and to mix the remaining alkoxysilane compound and water and hydrolyze them under any reaction conditions. There is no problem in terms of efficient synthesis utilizing the difference in hydrolyzability.

  The solvent is not particularly limited, but is appropriately selected in consideration of the stability, wettability, volatility, etc. of the siloxane-based low refractive index resin composition. The solvent can be used not only as one type but also as a mixture of two or more types. Specific examples of the solvent include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl- Alcohols such as 3-methoxy-1-butanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, Ethers such as lenglycol diethyl ether, ethylene glycol dibutyl ether and diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and 2-heptanone; Amides such as dimethylformamide and dimethylacetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , Acetates such as methyl lactate, ethyl lactate and butyl lactate; Ren, hexane, other aromatic or aliphatic hydrocarbons such as cyclohexane, .gamma.-butyrolactone, N- methyl-2-pyrrolidone, dimethyl sulfoxide, and the like fluorine-based solvent. Of these, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol in terms of cured film transmittance, crack resistance, etc. Mono-t-butyl ether, γ-butyrolactone and the like are preferably used. Moreover, it is also preferable to adjust to a suitable density | concentration as a resin composition by adding a solvent after completion | finish of a hydrolysis reaction. Moreover, after hydrolysis according to the purpose, it is also possible to distill and remove a suitable amount of the produced alcohol under heating and / or reduced pressure, and then add a suitable solvent.

  The amount of the solvent used during the hydrolysis reaction is preferably in the range of 50 to 500 parts by weight, particularly preferably in the range of 80 to 200 parts by weight, based on 100 parts by weight of the total alkoxysilane compound. . The production | generation of a gel can be suppressed by making the quantity of a solvent into 50 weight part or more. Moreover, a hydrolysis reaction advances rapidly by setting it as 500 parts weight or less. 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. 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.

  Moreover, as water used for a hydrolysis reaction, ion-exchange water is preferable. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of the alkoxysilane compound.

  The conditions for the condensation reaction of the alkoxysilane hydrolyzate for obtaining the siloxane-based low refractive index resin composition of the present invention are as follows. After hydrolysis, the reaction solution is used as it is, and the condensation reaction is performed for 1 to 100 hours under reflux. Is preferred. In order to increase the degree of polymerization of the siloxane compound, reheating or addition of a base catalyst can be performed.

  Various conditions in the hydrolysis and condensation reactions take into consideration the reaction scale, reaction vessel size, shape, etc., for example, by setting the acid concentration, reaction temperature, reaction time, etc., the physical properties suitable for the intended application Can be obtained.

  The coating material for the high refractive index layer and the low refractive index layer 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 used 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), and magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monosopropylate, and magnesium bis (acetylacetonate). . The amount of the curing agent contained is preferably from 0.1 to 20 parts by weight, particularly preferably from 3 to 15 parts by weight, based on 100 parts by weight of the total alkoxysilane compound in the siloxane-based resin composition. Parts by weight.

  The coating material for the high refractive index layer and the low refractive index layer of the present invention may contain various surfactants in order to improve flowability and film thickness uniformity during application. There is no restriction | limiting in particular in the kind of surfactant, For example, a fluorine-type surfactant, a silicone type surfactant, a polyalkylene oxide type surfactant, a poly (meth) acrylate type surfactant etc. can be used. Among these, a fluorine-based surfactant is used from the viewpoint of flowability and film thickness uniformity, and a silicone-based surfactant is preferably used from the viewpoint of improving adhesion with the low refractive index layer, and thus improving hardness. .

  Examples of commercially available silicone surfactants include SH28PA, SH7PA, SH21PA, SH30PA, ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd.), BYK-333 (manufactured by Big Chemie Japan Co., Ltd.), and the like. It is done. Examples of other surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene distearate and the like.

  Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl. Hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 , 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2 , 8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (Perful Looctanesulfonamido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-par) phosphate Fluorosurfactant comprising a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain, such as fluorooctylsulfonyl-N-ethylaminoethyl) and monoperfluoroalkylethyl phosphate ester An agent can be mentioned. Commercially available products include MegaFuck F142D, F172, F173, and F183 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Ftop EF301, 303, and 352 (made by Shin-Akita Kasei Co., Ltd.). ), FLORARD FC-430, FC-431 (manufactured by Sumitomo 3M)), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, Fluorine such as SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15, FTX-218 (manufactured by Neos Co., Ltd.) There may be mentioned system surfactants. Among these, the above-mentioned Megafac F172, BM-1000, BM-1100, NBX-15, and FTX-218 are particularly preferable from the viewpoints of flowability and film thickness uniformity.

  The content of the surfactant is usually 0.001 to 10 parts by weight with respect to 100 parts by weight of the total alkoxysilane compound content in the siloxane-based resin composition. These may be used alone or in combination of two or more.

  The coating material for the high refractive index layer and the low refractive index layer of the present invention can contain a viscosity modifier, a stabilizer, a colorant, a vitreous forming agent, and the like, if necessary.

  Further, the high refractive index layer and the low refractive index layer of the present invention are preferably cured and formed at a low temperature and / or ultraviolet rays and an electron beam by selecting a reactive group of the siloxane compound. Therefore, it is preferable to use various heat and / or photoinitiators. 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.

  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. .

  As azo compounds, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobis (2-methylpropionate) ) 2,2′-azobisisobutyronitrile, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2-azobis (2,4-dimethylvaleronitrile), Examples include 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2-azobis (4-methoxy2,4-dimethylvaleronitrile).

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

  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. For example, 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 (above, trade name, manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate Is mentioned. 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 (trade name) (651, 184, 754, 819, 907, 1870, 500, 369) manufactured by Ciba Specialty Chemicals. , 1173, 2959, 4265, 4263), 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.

  Examples of photoacid generators include onium salt compounds, halogen-containing compounds, diazoketone compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and sulfonimide compounds.

  Specific examples of the onium salt compounds include diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphonium salts, oxonium salts and the like. Preferred onium salts include diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate Etc.

  Specific examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2-naphthyl-4,6. -Bis (trichloromethyl) -s-triazine and the like can be mentioned.

  Specific examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. Preferred diazo ketone compounds are esters of 1,2-naphthoquinonediazido-4-sulfonic acid and 2,2,3,4,4′-tetrahydroxybenzophenone, 1,2-naphthoquinonediazide-4-sulfonic acid and 1,1, Examples thereof include esters with 1-tris (4-hydroxyphenyl) ethane.

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylyl). Sulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl ( And benzoyl) diazomethane.

  Specific examples of the sulfone compound include β-ketosulfone compounds and β-sulfonylsulfone compounds. Preferred compounds include 4-trisphenacyl sulfone, mesityl phenacyl sulfone, bis (phenylsulfonyl) methane, and the like.

  Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like. Specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and the like.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethyl). Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 Ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (camphorsulfur Nyloxy) succinimide, N- (camphorsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl Imido, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) Phthalimide, N- (4-methylpheny Sulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7 -Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-trifluoromethylphenylsulfonyloxy) diphe Nilmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy)- 7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6 -Oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (2-fluorophenylsulfonyloxy) Phthalimide, N- (4-fluorophenylsulfonyloxy) diphenylmale N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3- Examples thereof include dicarboxylimide and N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide.

  In addition, 5-norbornene-2,3-dicarboxyimidyl triflate (trade name “NDI-105” manufactured by Midori Chemical Co., Ltd.), 5-norbornene-2,3-dicarboxyimidyl tosylate (trade name “NDI”) -101 "Midori Chemical Co., Ltd.), 4-methylphenylsulfonyloxyimino-α- (4-methoxyphenyl) acetonitrile (trade name" PAI-101 "Midori Chemical Co., Ltd.), trifluoromethylsulfonyloxyimino -Α- (4-Methoxyphenyl) acetonitrile (trade name “PAI-105” manufactured by Midori Chemical Co., Ltd.), 9-camphorsulfonyloxyimino α-4-methoxyphenylacetonitrile (trade name “PAI-106” Midori Chemical ( 1,8-naphthalimidyl butane sulfonate (trade) Product name “NAI-1004” manufactured by Midori Chemical Co., Ltd.), 1,8-naphthalimidyl tosylate (trade name “NAI-101” manufactured by Midori Chemical Co., Ltd.), 1,8-naphthalimidyl triflate (trade name “NAI-105”) “Midori Chemical Co., Ltd.”, 1,8-naphthalimidyl nonafluorobutane sulfonate (trade name “NAI-109” Midori Chemical Co., Ltd.) and the like can also be mentioned as examples.

  These photoacid generators can be used alone or in combination of two or more. The content of the photoacid generator is generally 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the siloxane compound. If the amount is less than 0.01 parts by weight, pattern formation becomes difficult. If the amount is more than 20 parts by weight, poor development due to a decrease in affinity with the developer or precipitation of the photoacid generator itself may occur.

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%, crack resistance may fall.

  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 coating material of the high refractive index layer and the low refractive index layer of the present invention may be adjusted in concentration 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 high refractive index layer and the low refractive index layer of the present invention is preferably 30 parts by mass or more and 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 of the low refractive index layer used in the present invention is preferably 1.25 to 1.45. More preferably, it is 1.28-1.37. Moreover, it is necessary to be 0.20 or more smaller than the refractive index of the high refractive index layer. The luminous reflectance can be effectively reduced by setting the refractive index difference between the high refractive index layer and the low refractive index layer to 0.20 or more. In order to set the refractive index of the low refractive index layer to 1.25 to 1.45, for example, the addition amount of inorganic particles having a porous and / or hollow interior in the siloxane-based low refractive index resin composition is 20 mass. The target refractive index can be obtained by adjusting the content to from% to 70% 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.

  By forming the low refractive index layer used in 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 low refractive index layer used in 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.

  In the case of an antireflection film in which the low refractive index layer is a single layer, when the optical film thickness nd of the low refractive index layer is ¼ of the wavelength λ of visible light, that is, nd = 1 / 4λ ( In the equation, when the condition of λ is the central wavelength for antireflection is satisfied, the reflectance becomes the lowest at the wavelength of λ, so that the thickness of the low refractive index layer can be set. For example, when the refractive index n = 1.35 and λ = 550 nm, it can be said that the thickness of the low refractive index layer is preferably about 100 nm. When the low refractive index paint has fine particles, it is preferably formed with a film thickness larger than the particle diameter. 40 nm or more and 200 nm or less are preferable, and 80 nm or more and 130 nm or less are more preferable in terms of surface hardness and reflectance control.

  In addition, the high refractive index layer may further 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.

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, 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 can be wound into a film and is not particularly limited as long as it is transparent. However, in the case of a plastic film, the thickness is preferably 30 to 250 μm. 30 μm or more is preferable from the viewpoint of productivity, and 250 μm or less is preferable from the viewpoint of winding property as a film. In the case where the film is bonded via an adhesive, the film thickness is preferably 100 μm or more from the viewpoint of productivity, and in the case of forming an antireflection substrate of 0.4 mm or more and 1 mm or less, the film thickness is set to More preferably, they are 180 micrometers or more and 250 micrometers or less. The haze (index indicating haze) is 40% or less, more preferably 20% or less. If the haze value is 40% or less, it may be colored with a dye, a pigment or the like. 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. 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.

  Hereinafter, the present invention will be described with reference to examples and techniques, but the present invention is not limited to these examples.

Preparation and lamination of cured film Each film thickness after curing was determined by hand coating using a metal ring bar with a siloxane-based resin composition on a PET film (thickness 100 μm, manufactured by Toray Industries, Inc.) which is a transparent substrate. It apply | coated so that it might become the value of an Example and a comparative example, Then, it dried for 2 minutes at 90 degreeC using the hot air dryer. Thereafter, a UV-irradiation treatment (about 450 mJ / cm ² when converted to ultraviolet rays) was performed on a conveyor-type UV irradiation apparatus equipped with one high-pressure mercury lamp (120 W) at a speed of 3 m / min. Obtained. Further, the siloxane-based low refractive index resin composition was applied by hand coating using a metalling bar so that the film thickness after curing was 100 to 110 nm, and then using a hot air dryer at 130 ° C. for 5 minutes. Dried. After that, UV irradiation treatment (about 450 mJ / cm ² when converted to ultraviolet rays) was performed on a conveyor type UV irradiation device equipped with one high-pressure mercury lamp (120 W) at a speed of 3 m / min. An optical article having an index layer was obtained.

Measurement of the thickness of the high refractive index layer A substrate with a high refractive index layer obtained by coating on a PET film, which is a transparent substrate, is cut from the substrate side and cut so as to tear the high refractive index layer. Make a sample to observe the cross section. This sample can be observed with a scanning electron microscope, and the distance from the interface with the transparent substrate to the surface of the high refractive index layer can be observed (about 3,000 to 30,000 times) and obtained using a scale. Sampling was carried out at 4 points at intervals of 3 cm, and indicated by the average of the measured values (read to the second decimal place, unit: μm).

Crack resistance The obtained optical article was wound around a stainless steel rod having a diameter of 20 mm and tested, and the presence or absence of cracks was visually confirmed. In addition, what has already cracked before a test was represented by "x".

Scratch resistance: Steel wool hardness evaluation Using a steel wool of # 0000, a load of 500 mPa was applied to the coating film surface of each sample, 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 4 or 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 Scratch resistance: Pencil hardness evaluation Pencil scratch value manufactured by Dazai Equipment Co., Ltd. Using a testing machine, five tests were performed under a load of 500 g ± 5 g, and the presence or absence of scratches was observed. The result was expressed as the hardness of a pencil that was not damaged more than 3 times.

Measurement of total light transmittance Based on JIS K 7105, measurement was performed using a turbidimeter NDH 2000 manufactured by Nippon Denshoku Industries Co., Ltd. The total light transmittance is desirably 85% or more.

Reflectance measurement The surface opposite to the measurement surface (the surface on which the low refractive index layer is provided) is uniformly made of 320-400 water resistant sandpaper so that the 60 ° C. gloss (JIS Z 8741) is 10 or less. After roughening, a black paint was applied and colored so that the visible light transmittance was 5% or less.

  The absolute reflectance spectrum in the wavelength region of 380 nm to 780 nm was measured with a spectrophotometer (UV-3150) manufactured by Shimadzu Corporation at an incident angle of 5 degrees from the measurement surface, and expressed as a minimum value (%). . In the case where the reflection spectrum has undulations, an intermediate point between adjacent undulation peaks (maximum points) and valleys (minimum points) is connected to obtain a reflectance spectrum.

Refractive Index Measurement About a cured film prepared by applying and drying on a 6-inch silicon wafer, a film surface at 633 nm (using a He—Ne laser) at 22 ° C. using a prism coupler MODEL 2010 (manufactured by Metricon). The refractive index (TE) in the vertical direction was measured.

Example 1
Methyltrimethoxysilane 38.2 g (0.28 mol), phenyltrimethoxysilane 23.81 g (0.12 mol), number-average particle diameter 15 nm “OPTRAIK TR-527” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) (Composition: 20% by weight of titanium oxide particles, 80% by weight of methanol) 250.18 g was placed in a reaction vessel, and 21.62 g of water and 0.31 g of phosphoric acid were stirred into this solution while the reaction temperature exceeded 40 ° C. It was dripped so that there was no. After the dropping, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 90 ° C. for 2.5 hours, and reacted while distilling off methanol generated by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C. for 2 hours and then cooled to room temperature to obtain a polymer solution A1. To the obtained polymer solution A, 2.5 g of aluminum tris (ethyl acetoacetate) (trade name: ALCH-TR, manufactured by Kawaken Fine Chemical Co., Ltd.) and 85 g of propylene glycol mono-t-butyl ether were used as the aluminum-based curing agent. By addition, a siloxane-based resin composition solution “H1” was obtained.

  Separately, 60 g of methyltrimethoxysilane, 41.2 g of 3,3,3-trifluoropropyltrimethoxysilane, 300 g of 2-propanol, 2-propanol-dispersed hollow silica sol (refractive index 1.30, solid content 20.5% by mass) ) 188 g was placed in a reaction vessel, and 34.84 g of a 1N formic acid aqueous solution was added dropwise to the solution so that the reaction temperature did not exceed 40 ° C. Stirring was continued for about 1 hour, and then the temperature was raised using an oil bath set at 70 ° C., and the temperature of the reaction solution was stirred at 70 ° C. for 2 hours, and then cooled to room temperature to obtain polymer solution B1. 356 g of methanol is added to the obtained polymer solution B1, and then 5 g of aluminum trisacetylacetonate, 1890 g of 2-propanol, 720 g of methyl isobutyl ketone, and 10 g of a fluorosiloxane-based surface modifier are added to obtain a siloxane-based low refractive index resin composition. A product solution “L1” was obtained.

  A cured film was prepared using the obtained solutions “H1” and “L1”, and the film thickness, transmittance, reflectance, crack resistance, scratch resistance, and refractive index were evaluated.

Example 2
Methyltrimethoxysilane 17.6 g (0.13 mol), phenyltrimethoxysilane 10.98 g (0.06 mol), “Sun Colloid HZ-307M6” (trade name, manufactured by Nissan Chemical Industries, Ltd.) Composition: zirconium oxide composite 78.4 g of particles (70% by weight of particles, 70% by weight of methanol) were put in a reaction vessel, and 9.97 g of water and 0.7 g of formic acid were added dropwise to this solution with stirring so that the reaction temperature did not exceed 40 ° C. . After the dropping, a distillation apparatus was attached to the flask, and the resulting solution was reacted by heating and stirring at an internal temperature of 70 ° C. for 2 hours. Then, it cooled to room temperature and obtained polymer solution A2. To the obtained polymer solution A2, 2.0 g of aluminum tris (ethyl acetoacetate) (trade name ALCH-TR, manufactured by Kawaken Fine Chemical Co., Ltd.) and 60 g of propylene glycol monoethyl ether are added as an aluminum-based curing agent. Thus, a siloxane-based resin composition solution “H2” was obtained.
Separately, 60 g of methyltrimethoxysilane, 41.2 g of 3,3,3-trifluoropropyltrimethoxysilane, 300 g of 2-propanol, 2-propanol-dispersed hollow silica sol (refractive index 1.30, solid content 20.5% by mass) ) 235 g was placed in a reaction vessel, and 34.84 g of a 1N formic acid aqueous solution was added dropwise to this solution so that the reaction temperature did not exceed 40 ° C. The mixture was stirred as it was for about 1 hour, and then heated using an oil bath set at 70 ° C., and the temperature of the reaction solution was stirred at 70 ° C. for 2 hours, and then cooled to room temperature to obtain a polymer solution B2. 356 g of methanol is added to the obtained polymer solution B2, and then 5 g of aluminum trisacetylacetonate, 1890 g of 2-propanol, 720 g of methyl isobutyl ketone, and 10 g of a fluorosiloxane-based surface modifier are added to obtain a siloxane-based low refractive index resin composition. A product solution “L2” was obtained.

  A cured film was prepared using the obtained solutions “H2” and “L2”, and the film thickness, transmittance, reflectance, crack resistance, scratch resistance, and refractive index were evaluated.

Example 3
Methyltrimethoxysilane 27.8 g (0.20 mol), phenyltrimethoxysilane 17.3 g (0.09 mol), “CELNAX CX-Z210IP-F2” (trade name, manufactured by Nissan Chemical Industries, Ltd. Composition: antimony oxidation 180.3 g (21% by weight of product particles, 79% by weight of 2-propanol) are put in a reaction vessel, and 15.74 g of water and 1.11 g of formic acid are added to this solution while stirring so that the reaction temperature does not exceed 40 ° C. It was dripped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was reacted by heating and stirring at an internal temperature of 75 ° C. for 2 hours. Then, it cooled to room temperature and obtained polymer solution A3. To the obtained polymer solution A3, 2.5 g of aluminum tris (ethyl acetoacetate) (trade name ALCH-TR, manufactured by Kawaken Fine Chemical Co., Ltd.) and 60 g of propylene glycol monoethyl ether are added as an aluminum curing agent. Thus, a siloxane-based resin composition solution “H3” was obtained.
Separately, 60 g of methyltrimethoxysilane, 41.2 g of 3,3,3-trifluoropropyltrimethoxysilane, 300 g of 2-propanol, 2-propanol-dispersed hollow silica sol (refractive index 1.30, solid content 20.5% by mass) ) 212 g was placed in a reaction vessel, and 34.84 g of 1N formic acid aqueous solution was added dropwise to this solution so that the reaction temperature did not exceed 40 ° C. The mixture was stirred as it was for about 1 hour, and then heated using an oil bath set at 70 ° C., and the temperature of the reaction solution was stirred at 70 ° C. for 2 hours, and then cooled to room temperature to obtain a polymer solution B2. 356 g of methanol is added to the obtained polymer solution B2, and then 5 g of aluminum trisacetylacetonate, 1890 g of 2-propanol, 720 g of methyl isobutyl ketone, and 10 g of a fluorosiloxane-based surface modifier are added to obtain a siloxane-based low refractive index resin composition. A product solution “L3” was obtained.

  A cured film was prepared using the obtained solutions “H3” and “L3”, and the film thickness, transmittance, reflectance, crack resistance, scratch resistance, and refractive index were evaluated.

Example 4
A cured film was prepared using the solution “H1” obtained in Example 1 and the solution “L2” obtained in Example 2, and the film thickness, transmittance, reflectance, crack resistance, scratch resistance, refraction, The rate was evaluated.

Example 5
In the production of the high refractive index layer cured film of Example 1, a laminated cured film was produced in the same manner except that the thickness of the high refractive index layer after curing was changed to 15.20 μm using a thick coating metal ring bar. The film thickness, transmittance, reflectance, crack resistance, scratch resistance, and refractive index were evaluated.

Example 6
The high refractive index layer cured film of Example 5 was prepared in the same manner except that a 50 μm film spacer was applied, a thick coating metal ring bar was used, and the high refractive index layer was cured to 40.85 μm. A laminated cured film was produced. The film thickness, transmittance, reflectance, crack resistance, scratch resistance, and refractive index were evaluated.

Comparative Example 1
As in Example 1, except that the acrylate paint “SEICA BEAM PET-HC15NS” (trade name, manufactured by Dainichi Seika Kogyo Co., Ltd., tin oxide / antimony pentoxide particles) was used as the high refractive index layer forming material. A cured film was prepared and evaluated for film thickness, transmittance, reflectance, crack resistance, scratch resistance, and refractive index. The scratch resistance was poor.

Comparative Example 2
38.2 g (0.28 mol) of methyltrimethoxysilane, 23.81 g (0.12 mol) of phenyltrimethoxysilane and 85 g of propylene glycol mono-t-butyl ether were placed in a reaction vessel, and 21.62 g of water and phosphorus were added to this solution. While stirring, 0.31 g of acid was added dropwise so that the reaction temperature did not exceed 40 ° C. After the dropping, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 90 ° C. for 2.5 hours, and reacted while distilling off methanol generated by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C. for 2 hours and then cooled to room temperature to obtain a polymer solution C1. To the obtained polymer solution C1, “Optlake TR-527” having a number average particle size of 15 nm (trade name, manufactured by Catalyst Chemical Industries, Ltd., composition: titanium oxide particles 20% by weight, methanol 80% by weight) 250.18 g, As an aluminum-based curing agent, 2.5 g of aluminum tris (ethyl acetoacetate) (trade name: ALCH-TR, manufactured by Kawaken Fine Chemical Co., Ltd.) was added to obtain a high refractive index polymer solution “E1”.

  A cured film was prepared using the obtained polymer solution “E1” and the solution “L1”, and the film thickness, transmittance, reflectance, crack resistance, scratch resistance, and refractive index were evaluated. Scratch resistance and crack resistance were poor.

Comparative Example 3
A laminated cured film was produced in the same manner as in the production of the high refractive index layer cured film of Example 5 except that a 70 μm film spacer was applied and a thick coating metal ring bar was used. The film thickness, transmittance, reflectance, crack resistance, scratch resistance, and refractive index were evaluated. The film thickness of the high refractive index layer was 50.30 μm, and the crack resistance was poor.

Comparative Example 4
In the production of the high refractive index layer cured film of Example 5, a laminated cured film was produced in the same manner except that a thin coating metal ring bar was used. The film thickness, transmittance, reflectance, crack resistance, scratch resistance, and refractive index were evaluated. The film thickness of the high refractive index layer was 1.50 μm and the scratch resistance was poor. The results of Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Table 1.

Claims (9)

1. An antireflection optical article comprising a high refractive index layer and a low refractive index layer which are laminated on at least one surface on a transparent film substrate directly or via another layer.
High refractive index layer: Mainly a siloxane-based resin composition obtained by a method in which an alkoxysilane compound is hydrolyzed with an acid catalyst in a solvent in the presence of metal oxide particles, and then the hydrolyzate is subjected to a condensation reaction. A film having a thickness of 2.5 μm or more and 45 μm or less, which is obtained by applying and then curing a coating solution to be contained.
Low refractive index layer: a coating obtained by applying a coating liquid containing a siloxane-based low refractive index resin composition containing inorganic fine particles and a siloxane compound as a main component, followed by curing, and having a refractive index of the high refractive index layer A film having a refractive index smaller than 0.20. The optical article according to claim 1, wherein the alkoxysilane compound is at least one selected from the following general formulas (1) to (3).
R ¹ Si (OR ⁴ ) ₃ (1)
(R ¹ represents hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof. R ⁴ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, which may be the same or different. .)
R ² R ³ Si (OR ⁵ ) ₂ (2)
(R ² and R ³ each represent hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituent thereof. R ⁵ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, May be different.)
Si (OR ⁶ ) ₄ (3)
(R ⁶ represents a methyl group or an ethyl group, and may be the same or different.) The optical article according to claim 1 or 2, wherein the metal compound particles have a number average particle diameter of 1 nm to 200 nm. The metal compound particles are mainly composed of an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, germanium, and cerium. 4. The optical article according to any one of 3. The optical article according to any one of claims 1 to 4, wherein the inorganic fine particles of the low refractive index layer have a refractive index of 1.46 or less. The optical article according to any one of claims 1 to 5, wherein the metal compound particles contain zirconium oxide and / or titanium oxide particles. The optical article according to any one of claims 1 to 6, wherein the transparent substrate is an antireflection film substrate used for a flat panel display. The optical article according to claim 1, further comprising a photopolymerization initiator as the coating liquid for high refractive index. The optical article according to claim 1, wherein the high refractive index layer coating liquid contains a silicone-based surfactant.