Antireflection treatment agent

Abstract

To provide an antireflection treatment agent which has less environmental loads without containing a special solvent, is excellent in production suitability, and enables formation of an antireflection layer that exhibits excellent low reflectivity in a wide light wavelength range and low reflectivity with excellent high adhesion to a base material, while having one layer constitution, and an antireflection laminate manufactured using the antireflection treatment agent.MEANS FOR SOLVING THE PROBLEM: An antireflection treatment agent contains specific colloidal silica (A), a silicate binder (B), and a solvent (C), and forms an antireflection layer on a base material layer.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an antireflection treatment agent for forming an antireflection layer that has a small environmental load, excellent manufacturing suitability, and excellent low reflectivity even in a single-layer configuration and excellent high adhesion to a substrate, and an antireflection laminate produced using the antireflection treatment agent.

Background Art

[0002] For displays for personal computers and the like, an antireflection layer and an antifouling layer are generally provided to prevent light reflection and dirt. The antireflection layer and the antifouling layer are formed by sputtering SiO2 or Nb2O5 in multiple layers after an antiglare treatment such as etching on glass to form the antireflection layer and then forming an antifouling layer by spraying a fluorine-based compound or the like. This is common practice. Since sputtering is performed under vacuum conditions, it requires high equipment costs and has poor productivity. Patent Documents 1 and 2 propose an antireflection layer containing hollow silica, but the surface hardness and light reflectance are insufficient. Patent Document 3 proposes an antifogging and antifouling agent for organic substrates containing organosilica sol and boric acid, but it does not prevent light reflection. Patent Document 4 proposes an acidic sol-gel composition for an antireflection coating layer containing a silane-functional acrylic polymer, an alkoxysilane, a mineral acid, and inorganic fine particles, but the light reflectance is insufficient.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide an antireflection treatment agent capable of forming an antireflection layer that has a small environmental load without containing a special solvent, is excellent in production suitability, has a single-layer structure, exhibits excellent low reflectivity in a wide light wavelength range, and has excellent high adhesion to a substrate, and an antireflection laminate produced using the antireflection treatment agent.

Means for Solving the Problems

[0005] As a result of various studies, the present inventors have found that an antireflection treatment agent containing at least a specific colloidal silica (A), a specific silicate binder (B), and a solvent (C) achieves the above problems.

[0006] That is, the present invention is characterized by the following points. [1] An antireflection treatment agent for forming an antireflection layer on a substrate layer, The antireflection treatment agent contains colloidal silica (A), a silicate binder (B), and a solvent (C), The content of colloidal silica (A) in the solid content of the antireflection treatment agent is 70% by mass or more and 96% by mass or less, 60% by mass or more of the colloidal silica (A) is chain colloidal silica and / or pearl necklace-shaped colloidal silica, The antireflection treatment agent. [2] The silicate binder (B) contains a partial hydrolysis condensate of an alkoxysilane having an epoxy group and an alkoxysilane or silicate oligomer not having an epoxy group, The structural part derived from the alkoxysilane having an epoxy group in the partial hydrolysis condensate is 5 to 50% by mass, The antireflection treatment agent according to [1] above. [3] The antireflection treatment agent according to [1] above, further containing an adherent material (D). [4] The antireflection treatment agent according to [1] or [2] above, further containing a sliding material (E). [5] The antireflection treatment agent according to any one of [1] to [4] above, which can further have an antifouling layer adjacent to the antireflection layer made of the antireflection treatment agent. [6] An antireflection laminate having a single-layer antireflection layer adjacent to a substrate layer, wherein the antireflection layer is a layer made of the antireflection treatment agent according to any one of [1] to [5] above. [7] An antireflection and antifouling laminate having a single-layer antireflection layer and an antifouling layer adjacent to each other in this order on a substrate layer, wherein the antireflection layer is a layer made of the antireflection treatment agent according to any one of [1] to [5] above, and the antifouling layer is the surface layer of the antireflection and antifouling laminate. The antireflection and antifouling laminate.

Advantages of the Invention

[0007] The antireflection treatment agent of the present invention contains no special solvent, has a small environmental load, is excellent in production suitability, and can form an antireflection layer with excellent low reflectivity in a wide range of light wavelengths and excellent low reflectivity with high adhesion to a substrate while having a single-layer structure.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0009] The antireflection treatment agent and antireflection laminate of the present invention will be further described in detail below. Although it will be described with specific examples, the present invention is not limited thereto.

[0010] 1. Antireflection treatment agent The antireflection treatment agent of the present invention is a treatment agent for forming an antireflection layer on a substrate layer, and contains colloidal silica (A), a silicate binder (B), and a solvent (C). The antireflection treatment agent of the present invention may be a room temperature curing type that can be dried and cured at room temperature (15 to 40 °C, room temperature). The antireflection treatment agent of the present invention may further contain an adhesion promoter (D) to enhance the adhesion to the substrate layer, a lubricant (E) to enhance the slidability of the antireflection layer, or a surfactant (F) to enhance the wettability of the substrate. In addition, the antireflection treatment agent may further contain, as necessary, a wetting agent, a viscous material (thickener), a surface conditioning material, a coloring material (pigment, dye), an antistatic material, a conductivity imparting agent, an antibacterial and antiviral material, various fillers, etc., within a range that does not adversely affect the properties of the antireflection treatment agent or the antireflection and antifouling laminate.

[0011] By containing colloidal silica (A), the antireflection treatment agent of the present invention can reduce the light reflectance in the antireflection layer formed from the antireflection treatment agent, enhance the surface hardness and slidability, and enhance the adhesion to the substrate layer. The content of colloidal silica (A) in the solid content (non-volatile content) of the antireflection treatment agent is preferably 70% by mass or more and 96% by mass or less, and more preferably 75% by mass or more and 90% by mass or less. If it is less than the above range, antireflection tends to be insufficient, and if it is more than the above range, the hardness tends to be weak.

[0012] By containing a silicate binder (B), the antireflection treatment agent of the present invention can coat and connect colloidal silica (A), enhance the surface hardness of the antireflection layer, and enhance the adhesion between the antireflection layer and the substrate layer.

[0013] The antireflection treatment agent of the present invention can be applied to a substrate layer for use. Examples of materials constituting the base material layer include inorganic materials and / or organic materials. Examples of inorganic materials include ceramics, glass, etc. As examples of base materials using glass, glass plates, glass cloths, etc. can also be used. Further, examples of organic materials include resins, and specific examples of resins include, but are not limited to, PMMA (polymethyl methacrylate), PC (polycarbonate), PET (polyethylene terephthalate), etc. Among these, PMMA is preferred.

[0014] The thickness of the antireflection layer formed from the antireflection treatment agent of the present invention is preferably 50 to 500 nm, more preferably 100 to 300 nm. If it is thinner than the above range, the light reflectance tends to be high and the surface hardness tends to be low. Even if it is thicker than the above range, the light reflectance and surface hardness do not change much.

[0015] The antireflection layer formed from the antireflection treatment agent of the present invention can exhibit a low light reflectance in a wide wavelength range of light wavelengths from 380 nm to 780 nm. The minimum light reflectance of the antireflection layer is preferably 0.3% or more and 1.5% or less, more preferably 0.4% or more and 1.2% or less, still more preferably 0.5% or more and 1.0% or less. It is difficult to obtain a minimum light reflectance smaller than the above range, and if the minimum light reflectance is larger than the above range, the antireflection property tends to be inferior. And the light reflectance of light with a wavelength of 430 nm is preferably 3% or less, the light reflectance of light with a wavelength of 580 nm is preferably 0.3% or more and 1.5% or less, and the light reflectance of light with a wavelength of 780 nm is preferably 0.3% or more and 3% or less. More preferably, the light reflectance of light with a wavelength of 430 nm is 0.3% or more and 1.2% or less, the light reflectance of light with a wavelength of 580 nm is 0.3% or more and 1% or less, and the light reflectance of light with a wavelength of 780 nm is 0.3% or more and 2% or less. It is difficult to obtain a light reflectance smaller than the above range, and if the light reflectance is larger than the above range, the antireflection property tends to be inferior.

[0016] The surface hardness of the antireflection layer is preferably H or more in terms of the surface hardness measured in accordance with JIS K5600-5-4 "Scratch hardness (pencil method)".

[0017] The surface roughness Ra of the antireflection layer is preferably 0.5 to 20 nm, more preferably 0.5 to 15 nm. It is difficult to obtain Ra smaller than the above range, and when it is larger than the above range, haze is likely to occur.

[0018] In addition, the antireflection treatment agent of the present invention can be used in combination with an antifouling treatment agent. An antifouling layer can be formed adjacent thereto by further applying an antifouling treatment agent on the antireflection layer formed from the antireflection treatment agent of the present invention. By forming an antifouling layer, the surface hardness of the laminate having an antireflection layer can be increased, and the water repellency (hydrophobicity) or hydrophilicity can be increased, but it is preferable to increase the water repellency (hydrophobicity).

[0019] <Colloidal silica (A)> Colloidal silica (A) is silica particles in a solid content in a colloidal state and is dispersed in a solvent. A mixture of colloidal silica and a solvent is a colloidal silica sol. Colloidal silica (A) is preferably nanosilica. The average particle diameter of colloidal silica (A) is preferably 2 to 500 nm, more preferably 5 to 50 nm, and still more preferably 8 to 20 nm. When using colloidal silica with an average particle diameter smaller than the above range, secondary aggregation is likely to occur, and when the average particle diameter is larger than the above range, it becomes difficult to balance light reflectance, surface hardness, slidability, transparency, and adhesion to the base material layer.

[0020] Colloidal silica (A) preferably contains chain-like colloidal silica and / or pearl necklace-like colloidal silica. When colloidal silica (A) is chain-like colloidal silica and / or pearl necklace-like colloidal silica, the scattering of incident light increases, and the effect of reducing the light reflectance is enhanced. In addition, the surface hardness and slidability of the antireflection layer can be increased, and the adhesion to the base material layer can be increased. The content of chain colloidal silica and / or pearl necklace-shaped colloidal silica in the colloidal silica (A) is preferably 60% by mass or more and 100% by mass or less, and more preferably 70% by mass or more and 95% by mass or less. If it is less than the above range, the effect of reducing the light reflectance is likely to be insufficient, and even if it is more than the above range, the effect of reducing the light reflectance will not be improved much.

[0021] <Silicate binder (B)> The silicate binder (B) contains an alkyl silicate partially hydrolyzed and condensed oligomer. And the silicate binder (B) may further contain an alkoxysilane monomer and a catalyst as required. The content rate of the alkyl silicate partially hydrolyzed and condensed oligomer in the antireflection treatment agent is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass.

[0022] [Alkyl silicate partially hydrolyzed and condensed oligomer, alkyl silicate] The alkyl silicate partially hydrolyzed and condensed oligomer is an oligomer formed by partial hydrolysis and dehydration condensation of an alkyl silicate (alkoxysilane) and is soluble in the solvent (C). The alkyl silicate is a silane compound having one or more alkoxys, and may have one or more alkyl groups. Also, the alkyl silicate may be an alkyl silicate having a functional group, an amino group-containing alkyl silicate, or an epoxy group-containing alkyl silicate. In the present invention, the alkyl silicate partially hydrolyzed and condensed oligomer can be used alone or in combination of two or more.

[0023] Specific examples of the alkyl silicate include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, butyltributoxysilane, and the like. In the present invention, as the alkyl silicate, the above compound can be used alone or in combination of two or more kinds.

[0024] Specific examples of the amino group-containing alkyl silicate include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldiethylethoxysilane, 8-aminooctyltrimethoxysilane, and the like. Among these, 3-aminopropyltrimethoxysilane is preferred. In the present invention, as the amino group-containing alkyl silicate, the above compound can be used alone or in combination of two or more kinds.

[0025] Specific examples of the epoxy group-containing alkyl silicate include, but are not limited to, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropyldiethylethoxysilane, 8-glycidoxyoctyltrimethoxysilane, and the like. Among these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane are preferred. In the present invention, as the epoxy group-containing alkyl silicate, the above compound can be used alone or in combination of two or more kinds.

[0026] The partially hydrolyzed and condensed oligomer of alkyl silicate is more preferable because, in addition to the hardness and durability of the silicate, it has excellent adhesion to the substrate and the substrate in the subsequent process. It is obtained by partially hydrolyzing and condensing an epoxy group-containing alkyl silicate (epoxy group-containing alkoxysilane) and an alkoxysilane or silicate oligomer without an epoxy group such as tetramethoxysilane and tetraethoxysilane, with the epoxy group-containing alkyl silicate being 5% to 50% by mass. That is, the silicate binder (B) contains a partial hydrolyzate condensate of an alkoxysilane having an epoxy group and an alkoxysilane or silicate oligomer having no epoxy group, and the structural part derived from the alkoxysilane having an epoxy group in the partial hydrolyzate condensate is 5 to 50% by mass. This is more preferable because, in addition to the hardness and durability of the antireflection layer, it has excellent adhesion to the substrate and the substrate in the subsequent process.

[0027] [Catalyst] The catalyst can promote the hydrolysis reaction and dehydration condensation reaction of the partially hydrolyzed and condensed oligomer of alkyl silicate, alkoxysilane monomer, and colloidal silica (A). Therefore, the catalyst can be used as a catalyst when synthesizing the partially hydrolyzed and condensed oligomer of alkyl silicate in the silicate binder (B) and / or when curing the antireflection layer formed from the antireflection treatment agent.

[0028] The content of the catalyst in the silicate binder (B) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5.0% by mass. If it is less than the above range, the effect of promoting the formation of the partially hydrolyzed and condensed oligomer of alkyl silicate tends to be insufficient, and if it is more than the above range, the formation of the partially hydrolyzed and condensed oligomer of alkyl silicate tends to be non-uniform. When the content of the catalyst in the antireflection treatment agent is preferably 0.05 to 10% by mass, 0.1 to 5...

[0029] % by mass is more preferable. 0 mass % is more preferable. If it is less than the above range, the promoting effect of enhancing the surface hardness of the antireflection layer tends to be insufficient, and if it is more than the above range, the surface hardness of the antireflection layer tends to be non-uniform.

[0030] As the catalyst, an acid catalyst or a base catalyst can be used. Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzenesulfonic acid, 10-camphorsulfonic acid, formic acid, oxalic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, lactic acid, etc. Specific examples of the base catalyst include triethylenediamine, dimethylaminoethanol, aqueous ammonia, etc. Among these, nitric acid as the acid catalyst is preferable. In the present invention, as the catalyst, the above compound can be used alone or in combination of two or more.

[0031] <Solvent (C)> The solvent (C) is not particularly limited as long as it can dissolve or disperse the colloidal silica (A) and the silicate binder (B), but it is preferable to contain an alcohol-based solvent and / or a glycol-based solvent. In addition, when the antireflection treatment agent of the present invention is cured at a low temperature, it is preferable to use a solvent with a low boiling point in order to dry it at a low temperature. When the antireflection treatment agent of the present invention is dried and cured, for example, at 40 °C or lower within 1 hour, it is preferable to use a solvent having 10 or less carbon atoms and a boiling point of 50 to 90 °C. Solvents with a lower boiling point than the above range are difficult to handle, and solvents with a larger number of carbon atoms and a higher boiling point than the above range will require high temperature and long time for drying the antireflection layer formed from the antireflection treatment agent. When drying at 80 °C or higher, the appearance can be made smoother by using a high boiling point solvent having a boiling point of 120 °C to 220 °C in combination.

[0032] Specific examples of alcohol solvents include methanol (carbon number 1, boiling point 65°C), ethanol (carbon number 2, boiling point 78°C), normal propanol (carbon number 3, boiling point 97°C), isopropyl alcohol (carbon number 3, boiling point 82°C), tertiary butanol (carbon number 4, boiling point 82°C), normal butanol (carbon number 4, boiling point 118°C), isobutanol (carbon number 4, boiling point 108°C), secondary butanol (carbon number 4, boiling point 100°C), 1-pentanol (carbon number 5, boiling point 138°C), 2-methyl-1-butanol (carbon number 5, boiling point 128°C), 3-methyl-1-butanol (carbon number 5, boiling point 131°C), 2-pentanol (carbon number 5, boiling point 119°C), 1-ethyl-1-propanol (carbon number 5, boiling point 116°C), 2-methyl-2-butanol (carbon number 5, boiling point 102°C), etc., but are not limited thereto. Among these, ethanol and normal butanol are preferred.

[0033] Specific examples of glycol solvents include alkylene glycols and alkylene glycol ethers. Specific alkylene glycols include ethylene glycol (carbon number 2, boiling point 197°C), propylene glycol (carbon number 3, boiling point 189°C), butylene glycol (carbon number 4, boiling point 207°C), hexylene glycol (carbon number 6, boiling point 197°C), octylene glycol (carbon number 8, boiling point 175°C), etc., but are not limited thereto.

[0034] Specific examples of alkylene glycol ethers include ethylene glycol monomethyl ether (having 3 carbon atoms and a boiling point of 124°C), ethylene glycol monoethyl ether (having 4 carbon atoms and a boiling point of 135°C), ethylene glycol diethyl ether (having 6 carbon atoms and a boiling point of 121°C), ethylene glycol monoisopropyl ether (having 5 carbon atoms and a boiling point of 141°C), ethylene glycol monobutyl ether (having 6 carbon atoms and a boiling point of 171°C), propylene glycol monomethyl ether (having 4 carbon atoms and a boiling point of 120°C), propylene glycol monoethyl ether (having 5 carbon atoms and a boiling point of 132°C), propylene glycol mononormal propyl ether (having 6 carbon atoms and a boiling point of 149°C), propylene glycol mononormal butyl ether (having 7 carbon atoms and a boiling point of 171°C), but are not limited thereto. Among these, propylene glycol monomethyl ether is preferred. In the present invention, as the solvent (C), the above solvents can be used alone or in combination of two or more.

[0035] <Adhesive (D)> The adhesive (D) is preferably a urethane resin, an acrylic resin, or a silicate partial hydrolysis condensation oligomer having an alkoxysilyl group or a phenyl group. The alkoxysilyl group can react with the silicate binder (B), the colloidal silica (A), or the base material layer to form a crosslink. And the urethane resin, the resin having a phenyl group, and the (meth)acrylic resin can enhance the affinity and adhesion to the resin base material layer. Specific examples of the adhesive (D) include an acrylic resin having an alkoxysilyl group, a urethane resin having an alkoxysilyl group, and a phenyl group-substituted alkyl silicate partial hydrolysis condensation oligomer having an alkoxysilyl group. In order to obtain high adhesion, for example, the weight average molecular weight of the acrylic resin having an alkoxysilyl group by gel permeation chromatography (GPC) is preferably 1500 to 100000.

[0036] <Sliding material (E)> For the sliding member (E), a silicone-based sliding member and / or a fluorine-based sliding member can be used. The silicone-based sliding member and the fluorine-based sliding member can reduce the surface friction coefficient of the antireflection layer and enhance the slidability.

[0037] [Silicone-based sliding member] The silicone-based sliding member is a polydimethylsiloxane-modified silicate oligomer. The polydimethylsiloxane-modified silicate oligomer can be synthesized, for example, by subjecting a polydimethylsiloxane having a hydroxy group and a silicate oligomer having an alkoxy group to a dehydration condensation reaction. In order to obtain high slidability, the number average molecular weight in terms of polystyrene of the polydimethylsiloxane-modified silicate oligomer by gel permeation chromatography (GPC) is preferably from 1,500 to 100,000.

[0038] [Fluorine-based sliding member] The fluorine-based sliding member is a fluorine-substituted silane-modified silicate oligomer. The fluorine-substituted silane-modified silicate oligomer can be synthesized, for example, by subjecting a fluorine-substituted silane compound and a silicate oligomer having an alkoxy group to a dehydration condensation reaction.

[0039] Specific examples of the fluorine-substituted silane compound include, but are not limited to, trifluoropropyltrimethoxysilane, dimethoxy(methyl)(3,3,3-trifluoropropyl)silane, trimethoxy(1H,1H,2H,2H-perfluorohexyl)silane, triethoxy(1H,1H,2H,2H-perfluorohexyl)silane, trimethoxy(1H,1H,2H,2H-perfluoro-n-octyl)silane, triethoxy(1H,1H,2H,2H-perfluoro-n-octyl)silane, triethoxy[5,5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl]silane, trimethoxy(1H,1H,2H,2H-heptadecafluorodecyl)silane, triethoxy-1H,1H,2H,2H-heptadecafluorodecylsilane, etc. Among these, trimethoxy(1H,1H,2H,2H-perfluoro-n-octyl)silane and triethoxy(1H,1H,2H,2H-perfluoro-n-octyl)silane are preferred. The above fluorine-substituted silane compound can be used alone or in combination of two or more.

[0040] <Surfactant (F)> For the surfactant (F), various commercially available surfactants can be used and are not particularly limited. For example, a quaternary ammonium salt can be used. By adding the surfactant (F) to the antireflection treatment agent of the present invention, the wettability of the substrate can be improved. Examples of the quaternary ammonium salt include monoalkylammonium chloride and dialkylammonium chloride.

[0041] Specific examples of the monoalkylammonium chloride include, but are not limited to, N,N,N-trimethyl-1-octadecylammonium chloride, N,N,N-trimethyl-1-octadecylammonium chloride, alkyl (C14 - C18) trimethylammonium chloride, hexadecyltrimethylammonium chloride, N,N,N-trimethyl-1-octadecylammonium chloride, behenyltrimethylammonium chloride, benzalkonium chloride, etc. Specific examples of the dialkylammonium chloride include, but are not limited to, didecyldimethylammonium chloride, jatropha oil alkyldimethylammonium chloride, dialkyldimethylammonium chloride, etc. In the present invention, as the surfactant (F), the above surfactants can be used alone or in combination of two or more.

[0042] <Method for producing an antireflection treatment agent> The antireflection treatment agent of the present invention can be produced, for example, by the following method. 1) A catalyst composed of an acid or a base is dropped into a solvent and stirred and mixed to prepare a catalyst solution. 2) Colloidal silica (A), silicate binder (B), and solvent (C) are stirred and mixed. 3) While dropping the catalyst solution prepared above, it is stirred and mixed at 10 - 60 °C for about 1 hour. 。 4) If necessary, a solvent, an adhesion material (D), and a sliding material (E) are added and stirred and mixed. 5) A solvent is added so that the concentration and viscosity are adjusted according to the desired coating method and coating conditions to obtain an antireflection treatment agent. 6) The obtained antireflection treatment agent may be filtered, for example, through a filter with a mesh of 0.5 - 2 μm.

[0043] <Method for using an antireflection treatment agent> The antireflection treatment agent of the present invention can be applied to the substrate layer by spray coating, spin coating, or roll coating, but is not limited thereto. The antireflection treatment agent of the present invention cures at room temperature, but may also be subjected to a baking treatment at a high temperature. Specifically, 1 to 75 minutes is preferable at 15 to 160°C, 1 to 60 minutes is more preferable, and 45 to 60 minutes at 25 to 50°C is even more preferable. However, depending on the composition of the antireflection treatment agent and the composition of the base material layer, it is also possible to dry and cure at a higher temperature and for a longer time than the above. In the case of a room temperature curing type, room temperature drying and curing such as 1 minute, 10 minutes, 1 hour, etc. are possible at 15 to 40°C. However, it is preferable to contain a solvent that dries sufficiently at room temperature. The standard conditions are 80°C and 1 to 10 minutes. However, when subjected to a baking treatment at a high temperature, the hardness of the hydrophilic antifouling layer increases, but when the base material layer is made of a resin base material, there is a risk of deformation of the base material layer.

[0044] 2. Regarding the antireflection laminate The antireflection laminate of the present invention is a laminate having at least a base material layer and an antireflection layer composed of only one layer, and has excellent antireflection properties, high adhesion between the base material layer / antireflection layer, excellent appearance, and excellent high surface hardness. Further, the antireflection laminate of the present invention may be an antireflection antifouling laminate having a base material layer, an antireflection layer, and an antifouling layer adjacent to each other in this order. By having the antifouling layer as the surface layer of the antireflection antifouling laminate, the surface hardness, water repellency or hydrophilicity can be further enhanced.

[0045] [Base material layer] The base material layer is the object to be coated with the antireflection treatment agent of the present invention. The base material layer is composed of an inorganic material or an organic material. Examples of inorganic materials include ceramics and glass. As an example of a base material using glass, a glass plate, a glass cloth, etc. can also be used. Examples of organic materials include resins such as PMMA, PC, and PET. Among these, PMMA is preferable. The thickness of the base material layer is not particularly limited, but 0.1 to 5.0 mm is preferable. The surface of the base material layer may be subjected to an anti-glare treatment (AG treatment). By the anti-glare treatment, the surface roughness Ra is preferably 0.5 to 20 nm.

[0046] [Anti-reflection layer] The anti-reflection layer is a layer formed from the anti-reflection treatment agent of the present invention and has a low light reflectance in a wide wavelength range of 380 nm to 780 nm of the light wavelength. The minimum light reflectance of the anti-reflection layer is preferably 0.3% or more and 1.5% or less, more preferably 0.4% or more and 1.2% or less, and still more preferably 0.5% or more and 1.0% or less. It is difficult to obtain a minimum light reflectance smaller than the above range, and if the minimum light reflectance is larger than the above range, the anti-reflection property is likely to be inferior.

[0047] And the light reflectance of the light with a wavelength of 430 nm is preferably 3% or less, the light reflectance of the light with a wavelength of 580 nm is preferably 0.3% or more and 1.5% or less, and the light reflectance of the light with a wavelength of 780 nm is preferably 0.3% or more and 3% or less. The light reflectance of the light with a wavelength of 430 nm is more preferably 0.3% or more and 1.2% or less, the light reflectance of the light with a wavelength of 580 nm is more preferably 0.3% or more and 1% or less, and the light reflectance of the light with a wavelength of 780 nm is more preferably 0.3% or more and 2% or less. It is difficult to obtain a light reflectance smaller than the above range, and if the light reflectance is larger than the above range, the anti-reflection property is likely to be inferior.

[0048] The thickness of the anti-reflection layer is preferably 50 to 500 nm, and more preferably 100 to 300 nm. If it is thinner than the above range, the light reflectance is likely to increase and the surface hardness is likely to decrease. Even if it is thicker than the above range, the light reflectance and the surface hardness do not change so much.

[0049] The surface roughness Ra of the anti-reflection layer is preferably 0.5 to 20 nm, and more preferably 0.5 to 15 nm. It is difficult to obtain an Ra smaller than the above range, and if it is larger than the above range, haze is likely to occur. The surface hardness of the anti-reflection layer is preferably such that the surface hardness measured in accordance with JIS K5600-5-4 "Scratch hardness (pencil method)" is H or more.

[0050] [Anti-fouling layer] The antifouling layer of the antireflection laminate of the present invention is formed from an antifouling treatment agent. There is no particular limitation on the antifouling treatment agent, and a commercially available antifouling treatment agent can be used. However, as a constituent component, it is preferably contained silicon, fluorine, or the like. The thickness of the antifouling layer is not particularly limited, but is preferably 5 to 100 nm, more preferably 10 to 30 nm. If it is thinner than the above range, it is likely to be difficult to obtain sufficient surface hardness, and even if it is thicker than the above range, the performance as an antifouling layer does not change so much. The surface hardness of the antifouling layer is preferably 6H or more in terms of the surface hardness measured in accordance with JIS K5600-5-4 "scratch hardness (pencil method)". The surface of the antifouling layer may be water-repellent (hydrophobic) or hydrophilic, but water-repellent (hydrophobic) is preferred. In the case of water-repellent (hydrophobic), the contact angle with respect to water measured in accordance with JIS R3257 is preferably 100 degrees or more, more preferably 105 degrees or more.

[0051] [Method for manufacturing an antireflection laminate] The antireflection laminate of the present invention can be produced by a production method including the following step 1, or a production method including step 1 and step 2 in this order.

[0052] Step 1; Step of forming an antireflection layer on a substrate layer Substrate layer temperature: 15 to 40 °C, Coating method of the antireflection treatment agent: spray coating, spin coating, or roll coating, Drying and heat curing conditions of the antireflection layer: 15 to 160 °C, 1 to 75 minutes, (standard: 80 °C, 10 minutes), Layer thickness of the antireflection layer: 50 to 500 nm,

[0053] Step 2; Step of forming an antifouling layer on the antireflection layer, Substrate layer temperature: 15 to 40 °C, Coating method of the antifouling treatment agent: spray coating, spin coating, or roll coating, Drying and heat curing conditions of the antifouling layer: 15 to 140 °C, 1 to 60 minutes, Thickness of the antifouling layer: 10 to 300 nm,

[0054] By adjusting the composition of the antireflection treatment agent and the antifouling treatment agent, and the process conditions of Step 1 and Step 2, the surface roughness Ra of the antireflection layer and the antifouling layer can be adjusted to 0.5 to 20 nm.

[0055] The application of the antireflection treatment agent and / or the antifouling treatment agent may be performed by any of spray coating, spin coating, roll coating, and dip coating. However, spray coating is preferred because of its high productivity, ease of adjusting the appearance and film thickness, ease of environmental consideration, and simplicity.

[0056] The following are preferred as the conditions for spray coating. Nozzle diameter: 0.1 to 10 mm, more preferably 0.1 to 2.0 mm Atomization pressure: 150 to 700 kPa Discharge rate: 0.5 to 20 ml / min Spraying distance: 10 to 200 mm Head speed: 50 to 500 mm / sec Pitch: 0.5 to 10 mm

[0057] When adjusting the surface roughness Ra of the antireflection layer and the antifouling layer to 0.5 to 20 nm, a nozzle diameter of 0.1 to 2.0 mm is particularly preferred.

Examples

[0058] Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to the following examples. The raw materials used in the examples are as follows. <Raw materials> [Colloidal silica] · Colloidal silica sol 1: Snowtex ST-OUP manufactured by Nissan Chemical Industries, Ltd., an acidic sol-type chain nano-silica sol. Particle size 12 nm, solid content 15 wt%, solvent is water. · Colloidal silica sol 2: Snowtex ST-PS-SO manufactured by Nissan Chemical Industries, Ltd., an acidic sol-type pearl necklace-shaped nano-silica sol. Particle size 15 nm, solid content 15 wt%, solvent is water. · Colloidal silica sol 3: Snowtex IPA-ST manufactured by Nissan Chemical Industries, Ltd., a nano-silica sol. Particle size 10 - 15 nm, solid content 30 wt%, solvent is IPA.

[0059] [Silicate oligomer] · Silicate oligomer 1: Silicate 40 manufactured by Tama Chemical Industry Co., Ltd. A mixture of polyethyl silicate, tetraethoxysilane and a solvent, with a non-volatile content of 100 mass%. 60 - 70 mass% of the non-volatile content is polyethyl silicate.

[0060] [Silane compound] · Alkoxysilane 1: KBM403 manufactured by Shin-Etsu Chemical Co., Ltd. 3-Glycidoxypropyltrimethoxysilane (an alkoxysilane having an epoxy group).

[0061] [Adhesive] · Adhesive 1: Silicon-modified acrylic polymer, 8SQ-1100 manufactured by Daisheng Fine Chemical Co., Ltd. Non-volatile content 50 mass%. · Phenyl group-containing alkyl silicate 1: KBE103 manufactured by Shin-Etsu Chemical Co., Ltd., phenyltriethoxysilane. Non-volatile content 100 mass%.

[0062] [Sliding material] · Reactive polysiloxane 1: Reactive silicone, Silaplane FM-0815 manufactured by JNC. It has an alkoxysilyl group as a functional group. Number average molecular weight 4000. Non-volatile content 100 mass%. · Fluorine-substituted silane compound 1: Triethoxy(1H,1H,2H,2H-perfluoro-n-octyl)silane manufactured by Unichem Co., Ltd. Non-volatile content 100 mass%.

[0063] [Commercially available antifouling treatment agent] · Antifouling treatment agent 1: NB06-04 manufactured by Katsurayama Technology Co., Ltd. Contains a fluorine-based resin and a fluorine-based solvent.

[0064] <Synthesis Example> [Preparation of Nitric Acid Solution 1] The following were mixed to obtain Nitric Acid Solution 1 as a catalyst. 10% Aqueous Nitric Acid 1.0 part by mass Water 3.0 parts by mass Ethanol 30 parts by mass

[0065] [Preparation of Silicate Binder 1] First, the following were mixed to obtain a mixed solution. Silicate Oligomer 1 8.0 parts by mass Ethanol 30 parts by mass While dropping 34 parts by mass of Nitric Acid Solution 1 obtained above, the mixture was stirred and mixed at 40°C for 1 hour. Next, the following were further added and stirred and mixed to obtain Silicate Binder 1. Ethanol 28.0 parts by mass

[0066] [Adjustment of Silicate Binder 2] First, the following were mixed to obtain a mixed solution. Silicate Oligomer 1 6.0 parts by mass Alkoxysilane 1 2.0 parts by mass Ethanol 30 parts by mass While dropping 34 parts by mass of Nitric Acid Solution 1 obtained above, the mixture was stirred and mixed at 40°C for 1 hour for partial hydrolysis and condensation. Next, the following were further added and stirred and mixed to obtain Silicate Binder 2. Ethanol 28.0 parts by mass

[0067] [Preparation of Adhesive 2] The following were mixed and stirred and mixed at 40°C for 1 hour to obtain Adhesive 2. Phenyl Group-Containing Alkyl Silicate 1 50 parts by mass Water 10 parts by mass Ethanol 40 parts by mass

[0068] [Preparation of Sliding Material 1] First, the following were mixed to obtain a mixed solution. Silicate oligomer 1: 7.7 parts by mass Reactive polysiloxane 1: 0.3 parts by mass Ethanol: 30 parts by mass While dropping 34 parts by mass of Nitric acid solution 1 obtained above, it was stirred and mixed at 40°C for 1 hour. Next, the following were further added and stirred and mixed to obtain sliding material 1. Ethanol: 28.0 parts by mass

[0069] [Preparation of sliding material 2] First, the following were mixed to obtain a mixed solution. Silicate oligomer 1: 7.7 parts by mass Fluorine-substituted silane compound 1: 0.3 parts by mass Ethanol: 30 parts by mass While dropping 34 parts by mass of Nitric acid solution 1 obtained above, it was stirred and mixed at 40°C for 1 hour. Next, the following were further added and stirred and mixed to obtain sliding material 2. Ethanol: 28.0 parts by mass

[0070] [Example] [Example 1] The following were stirred and mixed at room temperature for 30 minutes to obtain an antireflection treatment agent. Colloidal silica sol 1: 14.2 parts by mass Silicate oligomer 1: 4.7 parts by mass Ethanol: 81.1 parts by mass Then, using the prepared antireflection treatment agent, an antireflection layer was formed on the substrate layer, and using antifouling treatment agent 1, an antifouling layer was formed, and various evaluations were performed. The antireflection layer was formed by spin-coating the antireflection treatment agent on a glass substrate layer at 25°C to a film thickness of about 30 nm using a spin coater (MS-A100, manufactured by Mikasa Co., Ltd.), and drying and curing at 100°C for 30 minutes. Furthermore, the antifouling layer was formed by spin-coating antifouling treatment agent 1 on the antireflection layer to a film thickness of about 30 nm using a spin coater (MS-A100, manufactured by Mikasa Co., Ltd.), and drying and curing at 100°C for 30 minutes.

[0071] [Examples 2 to 10, Comparative Examples 1 to 4] The raw materials to be stirred and mixed were changed according to the descriptions in Tables 1 to 3, and the same operations as in Example 1 were performed to obtain an antireflection treatment agent. Then, the same operations as in Example 1 were performed to form an antireflection layer and an antifouling layer, and the evaluation was carried out in the same manner.

[0072] [Comparative Example 5] A laminate having a two-layer (high refractive index layer / low refractive index layer) low-reflection layer was prepared using a commercially available treatment agent for a low-reflection layer, and the evaluation was carried out in the same manner as in Example 1. First, commercially available organic TC-200 (manufactured by Matsumoto Fine Chemical Co., Ltd.) and normal butanol were stirred and mixed at room temperature for 30 minutes in the following parts by mass to prepare a high refractive index treatment agent close to the base material layer. Organic TC-200 50 parts by weight Normal butanol 50 parts by weight Then, using a spin coater (MS-A100, manufactured by Mikasa), the high refractive index treatment agent prepared above was spin-coated on the base material layer at room temperature, and dried and cured at 100 °C for 30 minutes to form a high refractive index layer. Next, using a spin coater (MS-A100, manufactured by Mikasa), commercially available Honeyceran PI 300 (manufactured by Honey Chemical Co., Ltd.) was spin-coated on the high refractive index layer at 25 °C, and dried and cured at 100 °C for 30 minutes to form a low refractive index layer. Furthermore, the formation of the antifouling layer was carried out by spin-coating an antifouling treatment agent 1 on the antireflection layer using a spin coater (MS-A100, manufactured by Mikasa), and drying and curing at 100 °C for 30 minutes.

[0073] [Evaluation Method] [Appearance of Antireflection Layer] A black tape was attached to the back surface of the glass base material layer, sunlight was applied, and the presence or absence and degree of abnormalities of the antireflection layer formed on the glass base material layer were observed visually. The meanings of the symbols in the table are as follows. 〇: Uniform and transparent appearance △: Slight unevenness or other abnormalities ×: Strong unevenness or other abnormalities

[0074] [Light reflectance of the antireflection layer] The back surface of the glass substrate layer was painted black, and a black tape was further attached so that light would not pass through the substrate layer. Using an ultraviolet-visible spectrophotometer (UV-2600, manufactured by Shimadzu Corporation), the light reflectance (%) in the wavelength range of 380 to 780 nm on the surface of the antireflection layer was measured. Then, the minimum reflectance (%) in the above wavelength range and the light reflectance (%) at wavelengths of 430 nm, 580 nm, and 780 nm were determined.

[0075] [Surface hardness of the antireflection layer or antifouling layer] The surface hardness of the antireflection layer or antifouling layer on the glass substrate was measured in accordance with JIS K5600 "4.4 Scratch hardness (pencil method) of general test methods for paints".

[0076] [Adhesion of the antireflection layer] An antireflection layer was formed on a degreased glass substrate and a PC resin substrate. After attaching cellophane tape to the antireflection layer and then peeling it off, the peeling condition between the antireflection layer / substrate layer was evaluated by visual appearance. The meanings of the symbols in the table are as follows. 〇: No peeling of the antireflection layer △: Part of the antireflection layer is peeled off ×: All of the antireflection layer is peeled off

[0077] [Adhesion after water resistance] An antireflection layer was formed on a degreased glass substrate, immersed in deionized water at 100 °C for 30 minutes, taken out, and the deionized water was wiped off. Then, cellophane tape was attached to the antireflection layer and peeled off, and the peeling condition between the antireflection layer / substrate layer was evaluated by visual appearance. The meanings of the symbols in the table are as follows. 〇: No peeling of the antireflection layer △: Part of the antireflection layer is peeled off ×: All of the antireflection layer is peeled off

[0078] [Water repellency of the antifouling layer] Using a contact angle meter PCA-11 (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of the surface of the antifouling layer with respect to water was measured in accordance with JIS R3257. The meanings of the symbols in the table are as follows. 〇: Contact angle is 105 degrees or more △: Contact angle is 100 degrees or more and less than 105 degrees ×: Contact angle is less than 100 degrees

[0079]

Table 1

[0080]

Table 2

[0081]

Table 3

[0082] <Summary of Results> The antireflection treatment agents of all the examples showed a balance of excellent appearance, high surface hardness, low light reflectance, and high adhesion to the substrate layer, while the treatment agents of the comparative examples showed inferior results in some respects. Comparative Example 5 using a commercially available low-reflection treatment agent for a two-layer structure showed a low minimum reflectance but a narrow wavelength range of light showing low reflectance.

Industrial Applicability

[0083] The low-reflection treatment agent of the present invention can be used for transparent glass and resins used for displays for personal computers, showcases, partitions, etc., and the low-reflection laminate of the present invention can be used for displays for personal computers, showcases, partitions, etc.

Explanation of Symbols

[0084] 1 Antireflection and antifouling laminate 2 Substrate layer 3 Antireflection layer 4 Antifouling layer

Claims

Claim 1 An antireflection treatment agent for forming an antireflection layer on a substrate layer, the antireflection treatment agent contains colloidal silica (A), a silicate binder (B), and a solvent (C), the content of colloidal silica (A) in the solid content of the antireflection treatment agent is 70% by mass or more and 96% by mass or less, 60% by mass or more of the colloidal silica (A) is chain-like colloidal silica and / or pearl necklace-like colloidal silica, the antireflection treatment agent. Claim 2 The silicate binder (B) contains a partial hydrolysis condensate of an alkoxysilane having an epoxy group and an alkoxysilane or silicate oligomer having no epoxy group, the structural part derived from the alkoxysilane having an epoxy group in the partial hydrolysis condensate is 5 to 50% by mass, The antireflection treatment agent according to Claim 1. Claim 3 The antireflection treatment agent according to Claim 1, further containing an adhesion promoter (D). Claim 4 The antireflection treatment agent according to Claim 1, further containing a sliding material (E). Claim 5 The antireflection treatment agent according to Claim 1, which can further have an antifouling layer adjacent to the antireflection layer made of the antireflection treatment agent. Claim 6 An antireflection laminate having an antireflection layer consisting of only one layer adjacent to a substrate layer, the antireflection layer is a layer made of the antireflection treatment agent according to any one of Claims 1 to 5, the antireflection laminate. Claim 7 An antireflection and antifouling laminate having an antireflection layer consisting of only one layer and an antifouling layer adjacent to a substrate layer in this order, the antireflection layer is a layer made of the antireflection treatment agent according to any one of Claims 1 to 5, the antifouling layer is the surface layer of the antireflection and antifouling laminate, the antireflection and antifouling laminate.

Images