JP6270444B2 - Coating composition and antireflection film - Google Patents

Description

  The present invention relates to a coating composition and an antireflection film.

  In recent years, the global warming phenomenon has heightened awareness of the environment, and a new energy system that does not generate greenhouse gases such as carbon dioxide is attracting attention. In particular, solar cells are attracting attention because they are excellent in safety and ease of handling.

  In many solar cells, a textured glass substrate having a concavo-convex structure on the surface is used as a protective cover from the viewpoints of antiglare properties and light transmittance.

  In order to further improve the light transmittance of the solar cell protective cover, for example, Patent Document 1 discloses a coating-type antireflection film.

International Publication No. 2010/104146 Pamphlet

  However, when an anti-reflection coating is applied to the surface of a substrate having a surface uneven structure, the liquid accumulates in the recessed portion, and the thickness of the dried coating film is thicker in the recessed portion of the substrate, and in the protruding portion of the substrate. Uneven film thickness is generated. As a result, there arises a problem that the antireflection performance is deteriorated in a thin coating film.

  The present invention has been made in view of the above problems, and even when applied to a substrate surface having a surface uneven structure, it is possible to reduce film thickness unevenness and realize a coating film having excellent antireflection characteristics. An object of the present invention is to provide an antireflection film having a coating composition and an antireflection layer.

  As a result of intensive studies on the above problems, the present invention is a coating composition containing the metal oxide (A) and the polymer particles (B) and having the viscosity and the surface tension adjusted to a predetermined range. The present inventors have found that the above problems can be solved and have completed the present invention.

That is, the present invention is as follows.
[1]
A metal oxide (A) and polymer particles (B),
The viscosity is 5-50 cp,
A coating composition having a surface tension of 30 to 40 mN / m.
[2]
The coating composition according to item [1], further comprising a hydrolyzable silicon compound (C).
[3]
The metal oxide (A) is a spherical metal oxide (a1) having an aspect ratio (major axis / minor axis) of less than 3 and / or a chain metal oxide having an aspect ratio (major axis / minor axis) of 3 to 25. The coating composition according to [1] or [2] above, comprising the product (a2).
[4]
The polymer particles (B) polymerize a hydrolyzable silicon compound (b1) and a vinyl monomer (b2) having a secondary and / or tertiary amide group in the presence of water and an emulsifier. The coating composition according to any one of [1] to [3] above, comprising polymer particles obtained by the steps described above.
[5]
The polymer particles (B) are polymer particles obtained by polymerizing a hydrolyzable silicon compound (b1) in the presence of water and an emulsifier, and a vinyl monomer having a secondary and / or tertiary amide group. The coating composition according to any one of [1] to [3] above, comprising polymer particles obtained by polymerizing the body (b2).
[6]
An antireflection film comprising: a base material; and an antireflection layer including the coating composition according to any one of [1] to [5], which is disposed on at least one surface of the base material.
[7]
The antireflection film according to [6], wherein the antireflection layer is a layer obtained by applying and drying the coating composition on the substrate and then heat-treating at 400 ° C to 1000 ° C.
[8]
The antireflection film according to [6] or [7], wherein the ten-point average height Rz of the substrate surface is 1-1000 μm.
[9]
After applying and drying the coating composition according to any one of [1] to [5] on at least one surface of the base material and the base material, heat treatment is performed at 400 ° C. to 1000 ° C. to reflect The manufacturing method of an antireflection film including the process of obtaining a prevention layer.
[10]
A base material, and an antireflection layer containing a silicon compound disposed on at least one surface of the base material,
The ten-point average height Rz of the substrate surface is 1-1000 μm,
The antireflection film whose ratio of the area in which the film thickness of the antireflection layer is in the range of 80 to 150 nm is 70% or more.

  According to the present invention, even when applied to the surface of a substrate having an uneven surface structure, it is possible to reduce film thickness unevenness, to achieve a coating film having excellent anti-reflection properties, high mechanical strength and antifouling performance. An antireflection film having a possible coating composition and an antireflection layer can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are exemplifications for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

[Coating composition]
The coating composition of the present embodiment is
Including a metal oxide (A) and polymer particles (B),
The viscosity is 5-50 cp,
The surface tension is 30 to 40 mN / m.

  In the antireflection layer obtained using the coating composition of the present embodiment, the metal oxide (A) and the polymer particles (B) are heteroaggregated or the metal oxides (A) are aggregated. Therefore, it is considered that there are voids between the aggregated particles. By having such a space, the antireflection characteristic is further improved.

  In addition, the coating composition of the present embodiment forms an antireflection layer by the metal oxide (A) and the polymer particles (B) interacting such as hydrogen bonding or condensation (chemical bonding). It may be a thing. By performing such an interaction, the mechanical strength of the antireflection layer obtained from the coating composition of the present embodiment is further improved. The interaction between the metal oxide (A) and the polymer particle (B) is not particularly limited. Specifically, the hydroxyl group that the metal oxide (A) may have and the polymer particle (B) Polymerization product of a hydrolyzable metal compound that can be contained in the polymer particle (B), a hydrogen bond with a secondary and / or tertiary amide group that can have, a hydroxyl group that the metal oxide (A) can have, and a polymer particle (B) And condensation (chemical bond) with the functional group.

〔viscosity〕
The viscosity of the coating composition of this Embodiment is 5-50 cp, Preferably it is 8-30 cp, More preferably, it is 8-20 cp. When the viscosity of the coating composition is 5 cp or more, the film thickness unevenness when the coating composition is applied to the substrate surface having the surface uneven structure is further reduced. Moreover, the mixing | blending stability of a coating composition improves more because the viscosity of a coating composition is 50 cp or less.

  The method of adjusting the viscosity of the coating composition to the above range is not particularly limited, but includes a method of adding a thickener to the coating composition because adjustment is easy. Although it does not specifically limit as a thickener, For example, polyether, urethane modified polyether, polyacrylic acid, polyacrylsulfonic acid salt, polyvinyl alcohol, polysaccharide etc. are mentioned. Among these, polyether, modified polyacrylic sulfonate, and polyvinyl alcohol are preferable from the viewpoint of blending stability. Although it does not specifically limit as a commercial item of a thickener, For example, San Nopco (made) SN thickener 601 (polyether), SN thickener 615 (modified | denatured polyacrylic sulfonate), Wako Pure Chemical Industries Ltd. polyvinyl Examples include alcohol (degree of polymerization of about 1000), polyvinyl alcohol (degree of polymerization of about 1500), polyvinyl alcohol (degree of polymerization of about 2000), and the like.

  The content of the thickener is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 3.0% by mass, further preferably 0, based on the total amount of the coating composition. 0.1-1.0%. When the content of the thickener is within the above range, the film thickness unevenness when the coating composition is applied to the surface of the substrate having a surface uneven structure is further reduced, and the blending stability of the coating composition is further improved. Tend to.

〔surface tension〕
The surface tension of the coating composition of the present embodiment is 30 to 40 mN / m, preferably 30 to 35 mN / m. When the surface tension of the coating composition is within the above range, film thickness unevenness when applied to the surface of the substrate having a surface uneven structure is further reduced.

  Although it does not specifically limit as a method of adjusting the surface tension of a coating composition to the said range, For example, the method of adding a surface tension regulator to a coating composition is mentioned. Although it does not specifically limit as a surface tension modifier, For example, leveling agents, such as an acryl-type compound, a vinyl type compound, a silicone type compound, a fluorine-type compound; Organic solvents, such as an alcohol solvent, an ether solvent, and an ester solvent; Surfactants such as aliphatic surfactants, linear alkylbenzene surfactants, higher alcohol surfactants, ammonium salt surfactants and the like can be mentioned. Among these, from the viewpoint of blending stability, it is preferable to use alcohol solvents such as 2-butoxyethanol and texanol, and linear alkylbenzene surfactants such as dodecylbenzenesulfonic acid.

  The content of the surface tension modifier is preferably 0.05 to 5.0% by mass, more preferably 0.1 to 1.0% by mass, based on the total amount of the coating composition. When the content of the surface tension adjusting agent is within the above range, the film thickness unevenness when applied to the surface of the substrate having a surface uneven structure tends to be further reduced.

  As described above, the surface tension and viscosity of the coating composition of the present embodiment are adjusted to a specific range by appropriately selecting the type and amount of the thickener, leveling agent, and surfactant. be able to. Among these, a combination of a polyvinyl alcohol thickener or a modified polyacrylic sulfonate thickener and an alcohol solvent is particularly preferable.

[Metal oxide (A)]
Although it does not specifically limit as a metal oxide (A), For example, oxides, such as silicon, aluminum, titanium, zirconium, zinc, tin, indium, gallium, germanium, antimony, molybdenum, are mentioned. Further, the metal oxide (A) is not particularly limited. For example, a spherical metal oxide (a1) having an aspect ratio (major axis / minor axis) of less than 3 and / or an aspect ratio (major axis / minor axis) is used. Those containing 3 to 25 chain metal oxides (a2) are preferred.

(Spherical metal oxide (a1))
Here, the metal oxide which exists in the particle | grain state whose aspect-ratio (major axis / minor axis) of spherical metal oxide (a1) is less than three is said. The spherical metal oxide (a1) may be primary particles or aggregated particles. When the spherical metal oxide (a1) is agglomerated particles, the shape does not need to be a perfect sphere, and may have corners, for example. By having such a metal oxide (a1), the antifouling property due to surface hydrophilicity tends to be further improved.

  Although it does not specifically limit as spherical metal oxide (a1), For example, oxides, such as silicon, aluminum, titanium, zirconium, zinc, tin, indium, gallium, germanium, antimony, molybdenum, are mentioned. Examples of the commercially available spherical metal oxide (a1) include SNOWTEX OXS, SNOWTEX OS, SNOWTEX O and the like manufactured by Nissan Chemical Industries, Ltd.

  The aspect ratio (major axis / minor axis) of the spherical metal oxide (a1) is preferably less than 3, more preferably 2.0 to 1.0, still more preferably 1.5 to 1.0. is there. When the aspect ratio of the spherical metal oxide (a1) is within the above range, the mechanical strength of the obtained antireflection layer tends to be further improved. As used herein, the aspect ratio refers to the aspect ratio of primary particles for those present in the primary particles themselves, and refers to the aspect ratio of aggregated particles for those present as aggregated particles. . Here, the aspect ratio of the spherical metal oxide (a1) is determined by measuring the minor axis and the major axis of the metal oxide particles photographed with a transmission microscope (TEM), and obtaining the major axis / minor axis from the measured values. Can be determined by The minor axis and the major axis are the short side and the long side of the circumscribed rectangle that minimizes the area circumscribing the metal oxide particles, respectively.

  The average particle diameter of the spherical metal oxide (a1) is preferably 1 to 100 nm, more preferably 1 to 50 nm, and further preferably 1 to 20 nm. When the average particle diameter of the spherical metal oxide (a1) is within the above range, the transparency and mechanical strength of the obtained antireflection layer tend to be further improved. Here, the average particle diameter means the primary particle diameter when the particles are present in the form of primary particles, and the aggregate particle diameter (secondary particle diameter) when the particles are present in the form of aggregated particles. . In addition, the average particle diameter is a particle of a corresponding particle existing in a transmission microscope (TEM) photograph obtained by adjusting 100 to 200 spherical metal oxide (a1) particles. It can be determined by measuring the diameter (biaxial average diameter, that is, the average value of the minor axis and the major axis) and determining the average value of the measured particle diameters.

  From the viewpoint of transparency and mechanical strength of the antireflection layer, the spherical metal oxide (a1) has an aspect ratio (major axis / minor axis) of 3 to 1 and an average particle diameter of 1 to 100 nm. Preferably, the aspect ratio (major axis / minor axis) is 2-1 and the average particle diameter is 1 to 50 nm.

(Linear metal oxide (a2))
The chain metal oxide (a2) is a metal oxide having an aspect ratio (major axis / minor axis) of 3 to 25, and is not particularly limited. For example, primary particles of metal oxide (fine) particles are beaded. And composite particles linked to. By using such a metal oxide (a2), the porosity of the coating film increases and the antireflection properties tend to be superior.

  The chain metal oxide (a2) is not particularly limited, and examples thereof include oxides such as silicon, aluminum, titanium, zirconium, zinc, tin, indium, gallium, germanium, antimony, and molybdenum. Commercial products of chain metal oxide (a2) include “Snowtex-OUP (registered trademark)” manufactured by Nissan Chemical Industries, Ltd., “Snowtex-UP (registered trademark)” manufactured by the same company, “Snowtex” manufactured by the same company. -PSSO (registered trademark) "and" Snowtex-PSS (registered trademark) "manufactured by the same company. This chain-like silica sol has a three-dimensionally curved shape.

  The aspect ratio (major axis / minor axis) of the chain metal oxide (a2) is preferably 3 to 25, more preferably 3 to 15, and further preferably 3 to 10. The particles in the above aspect ratio range can be used in combination. The aspect ratio of the chain metal oxide (a2) can also be measured by the same method as the method for measuring the aspect ratio of the spherical metal oxide (a1).

  The average major axis of the chain metal oxide (a2) is preferably 20 to 250 nm, more preferably 30 to 150 nm, and further preferably 40 to 100 nm. When the average major axis of the chain metal oxide (a2) is within the above range, the refractive index of the obtained antireflection layer is lowered, and the porosity, transparency, and antireflection performance tend to be further improved. . Note that the average major axis of the chain metal oxide (a2) is a transmission microscope (TEM) photograph taken by adjusting the chain metal oxide (a2) particles so that 100 to 200 particles are captured. It can be determined by measuring the major axis of the corresponding particles present in the sample and determining the average value of the measured major axes.

  From the viewpoint of the porosity and refractive index of the antireflection layer, the chain metal oxide (a2) preferably has an aspect ratio (major axis / minor axis) of 3 or more and an average major axis of 20 nm or more, and is transparent. From the viewpoints of performance and antireflection performance, those having an aspect ratio (major axis / minor axis) of 25 or less and an average major axis of 250 nm or less are preferable.

  The coating composition of the present embodiment includes, for example, boron, phosphorus, silicon, aluminum, titanium, zirconium, zinc, tin, indium, gallium, germanium in addition to the metal oxide (a1) and / or (a2). Further, a metal oxide composed of antimony, molybdenum, or the like may be included.

[Polymer particles (B)]
Although it does not specifically limit as a polymer which comprises polymer particle (B), For example, a polyurethane type polymer, a polyester type polymer, a poly (meth) acrylate type polymer, a polyvinyl acetate type polymer, a polybutadiene type polymer, for example , Polyvinyl chloride polymer, chlorinated polypropylene polymer, polyethylene polymer, polystyrene polymer, polystyrene- (meth) acrylate copolymer, rosin derivative, styrene-maleic anhydride copolymer alcohol Examples thereof include polymers composed of adducts, polycarbonyl compounds such as cellulose resins, and the like.

  The polymer particles (B) preferably have a core / shell structure formed of two or more layers. Thereby, it exists in the tendency which the mechanical physical property (strength of a strength and a softness | flexibility etc.) of the antireflection layer obtained improves more.

  The polymer particles (B) used in the present embodiment are not particularly limited, but in the presence of water and an emulsifier, a hydrolyzable silicon compound (b1) and a vinyl having a secondary and / or tertiary amide group. It is preferable to include polymer particles obtained by polymerizing the monomer (b2). By including such polymer particles, the weather resistance, chemical resistance, optical properties, strength, and the like of the obtained antireflection layer tend to be further improved.

  The polymer particles (B) are not particularly limited. For example, polymer particles (B1) obtained by polymerizing the hydrolyzable silicon compound (b1) in the presence of water and an emulsifier, and 2 in the presence of water and an emulsifier. Polymer particles obtained by polymerizing vinyl monomer (b2) having a secondary and / or tertiary amide group, polymer particles obtained by polymerizing hydrolyzable silicon compound (b1), and secondary and / or In the presence of particles, water and an emulsifier, the composite particles of polymer particles obtained by polymerizing a vinyl monomer having a tertiary amide group (b2), water and an emulsifier, secondary and Alternatively, polymer particles obtained by polymerizing a vinyl monomer (b2) having a tertiary amide group may be included. By including such polymer particles, the weather resistance, chemical resistance, optical properties, strength, and the like of the obtained antireflection layer tend to be further improved. In addition, although it does not specifically limit as a composite aspect, For example, each polymer particle is compounded by various coupling | bondings, such as a hydrogen bond and a chemical bond.

  Although it does not specifically limit as a number average particle diameter of a polymer particle (B), Preferably it is 10-800 nm. In the present embodiment, the number average particle diameter of the polymer particles (B) can be measured by the method described in Examples described later.

(Hydrolyzable silicon compound (b1))
It does not specifically limit as a hydrolysable silicon compound (b1), For example, the compound represented by following formula (1), a silane coupling agent, or these 1 type, or 2 or more types of condensation products are mentioned. . Moreover, a hydrolyzable silicon compound (b1) may be used individually by 1 type, or may use 2 or more types together.
SiW _x R _y (1)
(Wherein W is independently a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an acetoxy group having 1 to 20 carbon atoms, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy R represents at least one hydrolyzable group selected from the group consisting of a group and an amide group, wherein R represents a linear or branched alkyl group having 1 to 30 carbon atoms, or a cyclohexane having 5 to 20 carbon atoms. At least one selected from an alkyl group and an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents a hydrocarbon group, x is an integer of 1 or more and 4 or less, y is an integer of 0 or more and 3 or less, and x + y = 4.

  The silane coupling agent is not particularly limited. For example, a functional group having reactivity with organic substances such as a vinyl polymerizable group, an epoxy group, an amino group, a methacryl group, a mercapto group, and an isocyanate group exists in the molecule. A hydrolyzable silicon compound is mentioned. Among these, the weather resistance of the obtained antireflection layer tends to be further improved by using a silane coupling agent having a vinyl polymerizable group. By using a silane coupling agent having a vinyl polymerizable group or a thiol group, the weather resistance, chemical resistance, optical properties, strength, etc. of the resulting antireflection layer tend to be further improved. Moreover, a silane coupling agent may be used individually by 1 type, or may use 2 or more types together.

  The hydrolyzable silicon compound (b1) is not particularly limited, and examples thereof include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane. ; Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxy Silane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysila , Vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3 , 3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxy Ethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltrie Xysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, 3-ureidopropyltri Trialkoxysilanes such as methoxysilane and 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxy Silane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyl Dimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n- Siku Dialkoxysilanes such as hexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and 3- (meth) acryloyloxypropylmethyldimethoxysilane; mono such as trimethylmethoxysilane and trimethylethoxysilane Examples include alkoxysilanes.

  Moreover, these hydrolysable silicon compounds (b1) can be used individually or in mixture of 2 or more types.

  Among the hydrolyzable silicon compounds (b1) described above, a silicon alkoxide having a phenyl group, such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, etc. is excellent in polymerization stability in the presence of water and an emulsifier. Therefore, it is preferable.

  Among the hydrolyzable silicon compounds (b1), 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyl Dimethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 2-trimethoxysilyl Silane coupling agents having a vinyl polymerizable group such as ethyl vinyl ether; silane coupling agents having a thiol group such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc. It preferred because copolymerized or chain transfer reaction with vinyl monomer (b2) having a grade amide group it is possible to generate a chemical bond.

  Further, when the hydrolyzable silicon compound (b1) is one or more condensation products selected from the group consisting of the compound represented by the formula (1) and a silane coupling agent, The weight average molecular weight in terms of polystyrene by GPC measurement is preferably 200 to 5000, more preferably 300 to 1000, and still more preferably 400 to 800. When the weight average molecular weight in terms of polystyrene of the hydrolyzable silicon compound (b1) is within the above range, the polymerization stability tends to be more excellent.

  The use amount of the hydrolyzable silicon compound (b1) is preferably 0.005 or more and 1.0 or less as the mass ratio (b1) / (B) with respect to the total amount of the polymer particles (B) to be obtained. More preferably, it is 0.01 or more and 0.7 or less, and further preferably 0.05 or more and 0.5 or less. When the amount of the hydrolyzable silicon compound (b1) used is within the above range, the polymerization stability tends to be more excellent. Here, the “total amount of polymer particles (B) to be obtained” means a hydrolyzable silicon compound (b1), a vinyl monomer (b2), and a vinyl monomer (b3) added as necessary. And the total mass (calculated value) of the polymerization product obtained when all are polymerized.

  Moreover, the compounding quantity of the silane coupling agent which has a vinyl polymerizable group and a thiol group is 0.1 mass part or more with respect to 100 mass parts of vinyl monomers (b2) which have a secondary and / or tertiary amide group. It is preferable that it is 100 mass parts or less from a viewpoint of superposition | polymerization stability, and 0.5 mass part or more and 50 mass parts or less are more preferable.

(Vinyl monomer having secondary and / or tertiary amide group (b2))
Although it does not specifically limit as a vinyl monomer (b2) which has a secondary and / or tertiary amide group used for manufacture of a polymer particle (B), For example, N-alkyl or N-alkylene substituted (meth) acrylamide Etc. can be illustrated. The N-alkyl or N-alkylene-substituted (meth) acrylamide is not particularly limited. For example, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmeta Acrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmeta Acrylamide, Nn-propylmethacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, -Acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N, N'-methylenebisacrylamide, N, N'- Examples include methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, diacetone methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like. Moreover, the vinyl monomer (b2) having a secondary and / or tertiary amide group may be used alone or in combination of two or more.

  The amide group of the vinyl monomer (b2) used for producing the polymer particles (B) may be either secondary or tertiary, but when a vinyl monomer having a tertiary amide group is used. The hydrogen bonding property between the obtained polymer particles (B) and the metal oxide (A) tends to be stronger, which is preferable. Among them, in particular, N, N-diethylacrylamide is very excellent in polymerization stability in the presence of water and an emulsifier, and also has a hydroxyl group or metal that can be possessed by the polymerization product of the hydrolyzable silicon compound (b1) described above. Since it is possible to form a strong hydrogen bond with the hydroxyl group that the oxide (A) may have, it is more preferable.

  The use amount of the vinyl monomer (b2) having a secondary and / or tertiary amide group is preferably as a mass ratio (b2) / (B) with respect to the total amount of the polymer particles (B) to be obtained. It is 0.05 or more and 0.7 or less, More preferably, it is 0.1 or more and 0.6 or less, More preferably, it is 0.2 or more and 0.5 or less. When the amount of the vinyl monomer (b2) having a secondary and / or tertiary amide group is within the above range, the hydrogen bonding force tends to be more excellent. Here, the “total amount of polymer particles (B) to be obtained” means a hydrolyzable silicon compound (b1), a vinyl monomer (b2), and a vinyl monomer (b3) added as necessary. And the total mass (calculated value) of the polymerization product obtained when all are polymerized.

(Other copolymerizable vinyl monomer (b3))
Polymerization of the polymer particles (B) is carried out by using a vinyl monomer (b2) having a secondary and / or tertiary amide group and another vinyl monomer copolymerizable with the vinyl monomer (b2) ( b3) and the properties of the polymer particles (B) to be produced (glass transition temperature, molecular weight, hydrogen bonding force, polarity, dispersion stability, weather resistance, polymerization of hydrolyzable silicon compound (b1)) It is possible to more effectively control the compatibility with the product.

  The vinyl monomer (b3) is not particularly limited. For example, (meth) acrylic acid ester, aromatic vinyl compound, vinyl cyanide compound, carboxyl group-containing vinyl monomer, hydroxyl group-containing vinyl monomer, epoxy Examples thereof include a group-containing vinyl monomer and a carbonyl group-containing vinyl monomer.

  The (meth) acrylic acid ester is not particularly limited. For example, a (meth) acrylic acid alkyl ester having 1 to 50 carbon atoms in the alkyl portion and a (poly) oxyethylene dialkylate having 1 to 100 ethylene oxide groups. (Meth) acrylate etc. are mentioned.

  Although it does not specifically limit as (meth) acrylic-acid alkylester, Specifically, (meth) acrylic-acid methyl, (meth) acrylic-acid ethyl, (meth) acrylic-acid n-butyl, (meth) acrylic-acid 2- Examples include ethylhexyl, methyl cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and the like.

  The (poly) oxyethylene di (meth) acrylate is not particularly limited, and specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate.

  In the present specification, (meth) acrylic is a simple description of methacrylic or acrylic.

  The content of the (meth) acrylic acid ester in the polymer particles (B) is preferably 0 to 99.9% by mass, more preferably based on the total amount of the vinyl monomers (b2) and (b3). Is 5 to 80% by mass.

  It does not specifically limit as an aromatic vinyl compound, For example, styrene, vinyl toluene, etc. are mentioned.

  The vinyl cyanide compound is not particularly limited, and examples thereof include acrylonitrile and methacrylonitrile.

  The carboxyl group-containing vinyl monomer is not particularly limited, and examples thereof include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, or maleic anhydride, or itaconic acid, maleic acid, or fumaric acid. And the like. By using a vinyl monomer containing a carboxylic acid group, a carboxyl group can be introduced into the polymer particles (B), and an electrostatic repulsive force between the particles is provided to give an emulsion of the polymer particles (B). As a result, it is possible to provide resistance to an external dispersion breaking action such as agglomeration during stirring. At this time, in order to further improve the electrostatic repulsion force, the introduced carboxyl group should be partially or completely neutralized with amines such as ammonia, triethylamine and dimethylethanolamine, and bases such as NaOH and KOH. You can also.

  The content of the carboxyl group-containing vinyl monomer in the polymer particles (B) is preferably 0 to 50% by mass, more preferably based on the total amount of the vinyl monomers (b2) and (b3). It is 0.1-10 mass%, More preferably, it is 0.1-5 mass%. When the content of the carboxyl group-containing vinyl monomer is within the above range, the water resistance of the resulting antireflection film tends to be further improved.

  The hydroxyl group-containing vinyl monomer is not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropy (meth) acrylate, 2-hydroxybutyl (meth) Hydroxyalkyl esters of (meth) acrylic acid such as acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate Hydroxyalkyl esters of fumaric acid such as: (poly) oxyethylene mono (meth) acrylate having 1 to 100 allyl alcohol or ethylene oxide groups; (poly) oxypropylene mono having 1 to 100 propylene oxide groups (Meta) a Further, “Placcel FM, FA monomer” (trade name of caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.) and other hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acid, etc. be able to.

  By using the hydroxyl group-containing vinyl monomer, it becomes easy to control the hydrogen bonding force between the metal oxide (A) and the polymer particles (B), and the water dispersion stability of the polymer particles (B). Tend to improve more.

  The content of the hydroxyl group-containing vinyl monomer in the polymer particles (B) is preferably 0 to 80% by mass, more preferably 0, based on the total amount of the vinyl monomers (b2) and (b3). 0.1 to 50% by mass, and more preferably 0.1 to 10% by mass. When the content of the hydroxyl group-containing vinyl monomer is within the above range, the hydrogen bonding force between the metal oxide (A) and the polymer particles (B) is further improved, and the water dispersion of the polymer particles (B) is improved. The stability tends to be further improved.

  It does not specifically limit as an epoxy group containing vinyl monomer, For example, a glycidyl group containing vinyl monomer etc. are mentioned. The glycidyl group-containing vinyl monomer is not particularly limited, and examples thereof include glycidyl (meth) acrylate, allyl glycidyl ether, and allyl dimethyl glycidyl ether. By using an epoxy group-containing vinyl monomer, the resulting polymer particles (B) have reactivity with one or more selected from the group consisting of hydrazine derivatives, carboxylic acid derivatives and isocyanate derivatives. . Therefore, when the coating composition contains, as an optional component, one or more selected from the group consisting of hydrazine derivatives, carboxylic acid derivatives and isocyanate derivatives, polymer particles (B), hydrazine derivatives, carboxylic acid derivatives and isocyanates By crosslinking with one or more selected from the group consisting of derivatives, the solvent resistance of the antireflection layer tends to be further improved.

  The content of the epoxy group-containing vinyl monomer in the polymer particles (B) is preferably 0 to 50% by mass with respect to the total amount of the vinyl monomers (b2) and (b3).

  The carbonyl group-containing vinyl monomer is not particularly limited, and examples thereof include diacetone acrylamide. By using a carbonyl group-containing vinyl monomer, the resulting polymer particles (B) have reactivity with one or more selected from the group consisting of hydrazine derivatives, carboxylic acid derivatives and isocyanate derivatives. . Therefore, when the coating composition contains, as an optional component, one or more selected from the group consisting of hydrazine derivatives, carboxylic acid derivatives and isocyanate derivatives, polymer particles (B), hydrazine derivatives, carboxylic acid derivatives and isocyanates By crosslinking with one or more selected from the group consisting of derivatives, the solvent resistance of the antireflection layer tends to be further improved.

[Production method of polymer particles (B)]
In the presence of water and an emulsifier, the polymer particles (B) are hydrolyzable silicon compound (b1), a vinyl monomer (b2) having a secondary and / or tertiary amide group, and, if necessary. It can be obtained by polymerizing with another vinyl monomer (b3), preferably in the presence of a polymerization catalyst.

  Polymerization of the hydrolyzable silicon compound (b1) and the vinyl monomer (b2) having a secondary and / or tertiary amide group can be carried out separately, but by carrying out at the same time, It is preferable because a micro organic / inorganic composite can be achieved by hydrogen bonding between the two.

  The number average particle diameter of the polymer particles (B) (primary particle diameter; the number average particle diameter of the primary particles of the polymer particles (B)) is preferably 10 to 800 nm, more preferably 50 to 300 nm. More preferably, it is 50-300 nm. When the number average particle diameter of the polymer particles (B) is within the above range, the resulting antireflection layer has weather resistance, chemical resistance, optical properties, antifouling properties, antifogging properties, antistatic properties, etc. Tend to improve more. Moreover, when the number average particle diameter of the polymer particles (B) is 50 to 300 nm, the transparency of the obtained antireflection layer tends to be further improved. The number average particle diameter of the polymer particles (B) can be measured by the method described in the examples.

  A method for obtaining the polymer particles (B) having such a number average particle diameter is not particularly limited, but the hydrolyzable silicon compound (b1) in the presence of a sufficient amount of water for the emulsifier to form micelles. And so-called emulsion polymerization in which a vinyl monomer (b2) having a secondary and / or tertiary amide group is polymerized is preferred.

  A specific method of emulsion polymerization is not particularly limited, but for example, a hydrolyzable silicon compound (b1), a vinyl monomer (b2) having a secondary and / or tertiary amide group, and as necessary. The other vinyl monomer (b3) is dropped into the reaction vessel as it is or in an emulsified state, all at once or continuously, and continuously dropped into the reaction vessel, and preferably in the presence of a polymerization catalyst, preferably from atmospheric pressure to 10 MPa. The method of making it superpose | polymerize at the reaction temperature of about 30-150 degreeC under the pressure of this. You may change a pressure and reaction temperature as needed. The ratio of the total amount of the hydrolyzable silicon compound (b1), the vinyl monomer (b2), and the other vinyl monomer (b3) to water is not particularly limited. The polymer obtained when all the monomers are polymerized (value calculated based on the total mass (calculated value) of the polymer of the vinyl (co) polymer and the hydrolyzable silicon compound (b1)) is The content is preferably set to 0.1 to 70% by mass, and more preferably 1.0 to 55% by mass.

  In carrying out the emulsion polymerization, in order to increase or control the number average particle diameter of the polymer particles (B), a seed polymerization method in which emulsion particles are preliminarily present in the aqueous phase may be performed. Thereby, polymer particle (B) with a more uniform particle diameter can be obtained. The substance to be a seed (nucleus) is not particularly limited, and a known substance can be used and can be appropriately selected according to reaction conditions and the like. The pH during the polymerization reaction is preferably 1.0 to 10.0, and more preferably 1.0 to 6.0. The pH during the polymerization reaction can be adjusted using a disodium phosphate, borax, or a pH buffer such as sodium bicarbonate or ammonia.

  As a method of obtaining the polymer particles (B), the hydrolyzable silicon compound (b1) in the presence of water and an emulsifier necessary for polymerizing the hydrolyzable silicon compound (b1) and, if necessary, a solvent. Alternatively, after polymerizing the vinyl monomer (b2) having a secondary and / or tertiary amide group, water may be added until the polymerization product becomes an emulsion.

(emulsifier)
The emulsifier used for the synthesis of the polymer particles (B) is not particularly limited. For example, alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, polyoxyethylene Acidic emulsifiers such as distyryl phenyl ether sulfonic acid; alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, anionic surfactants such as ammonium salts of acidic emulsifiers, fatty acid soaps; alkyltrimethylammonium bromide, alkylpyridinium bromide , Quaternary ammonium salts such as imidazolinium laurate, pyridinium salts, imidazolinium salt type cationic surfactants; polyoxyethylene alkyl aryl ethers, polyoxyethylene sorbitan fatty acid esters, Polyoxyethylene polyoxypropylene block copolymers, reactive emulsifier having a double bond of nonionic surface active agent and a radical polymerizable polyoxyethylene distyryl phenyl ether, and the like.

  Among these emulsifiers, reactive emulsifiers having a radical polymerizable double bond are preferred. By using such a reactive emulsifier, the water dispersion stability of the polymer particles (B) is further improved, and the water resistance, chemical resistance, optical properties, and strength of the resulting antireflection layer are further improved. It tends to improve.

  The reactive emulsifier is not particularly limited, and may be, for example, an alkali metal salt or an ammonium salt, a vinyl monomer having a sulfonic acid group or a sulfonate group; a vinyl monomer having a sulfate group; Examples thereof include vinyl monomers having a nonionic group such as ethylene; vinyl monomers having a quaternary ammonium salt.

  The vinyl monomer having a sulfonic acid group or a sulfonate group, which may be an alkali metal salt or an ammonium salt, is not particularly limited, and examples thereof include a radical polymerizable double bond and an ammonium salt, sodium salt, or potassium. A sulfonic acid group or sulfonate group, which may be a salt, an alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polyalkyl ether group having 2 to 400 carbon atoms, or 6 to 10 carbon atoms And a substituent selected from the group consisting of an aryl group and a succinic acid group; a vinyl sulfonate compound having a sulfonic acid group or a sulfonate group, which may be an ammonium salt, a sodium salt or a potassium salt; .

  The compound having a radical polymerizable double bond, a sulfonic acid group which may be an ammonium salt, a sodium salt or a potassium salt, and an alkyl group having 1 to 20 carbon atoms is not particularly limited.

  A radical polymerizable double bond; a sulfonic acid group which may be an ammonium salt, a sodium salt or a potassium salt; and an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 400 carbon atoms. It does not specifically limit as a compound to have, For example, Aqualon HS-10 or KH-1025 (brand name) (Daiichi Kogyo Seiyaku Co., Ltd. product), Adekaria soap SE-1025N or SR-1025 (brand name) ( Asahi Denka Kogyo Co., Ltd.).

  The compound having a radical polymerizable double bond, a sulfonic acid group which may be an ammonium salt, a sodium salt or a potassium salt, and an aryl group having 6 to 10 carbon atoms is not particularly limited.

  The compound having a radically polymerizable double bond, a sulfonic acid group that may be an ammonium salt, a sodium salt or a potassium salt, and a succinic acid group is not particularly limited, and examples thereof include allyl sulfosuccinate and the like. Is mentioned. These can also use a commercial item, and it is not specifically limited, For example, Eleminol JS-2 (brand name) (made by Sanyo Kasei Co., Ltd.), Latemuru S-120, S-180A, or S-180 (brand name) (Manufactured by Kao Corporation).

  The vinyl monomer having a sulfate group is not particularly limited.

  The vinyl monomer having a nonionic group is not particularly limited. For example, α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (trade name: ADEKA) Rear soap NE-20, NE-30, NE-40, etc., manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene alkylpropenyl phenyl ether (trade names: Aqualon RN-10, RN-20, RN-30, RN- 50, etc., manufactured by Daiichi Pharmaceutical Co., Ltd.).

  The vinyl monomer having a quaternary ammonium salt is not particularly limited.

  The amount of the emulsifier used is preferably 10 parts by mass or less, more preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the polymer particles (B) to be obtained.

(Polymerization catalyst)
The polymerization catalyst for the hydrolyzable silicon compound (b1) can be appropriately selected according to the components of the monomer used for the polymerization, and is not particularly limited. For example, hydrogen halides such as hydrochloric acid and hydrofluoric acid; Carboxylic acids such as trichloroacetic acid, trifluoroacetic acid and lactic acid; sulfonic acids such as sulfuric acid and p-toluenesulfonic acid; alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylenealkylsulfuric acid, polyoxyethylenealkylarylsulfuric acid, Acidic emulsifiers such as polyoxyethylene distyrylphenyl ether sulfonic acid; acidic or weakly acidic inorganic salts, acidic compounds such as phthalic acid, phosphoric acid, nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, acetic acid Sodium, tetramethylammonium chloride, tetramethyl Basic compounds such as ammonium hydroxide, tributylamine, diazabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamine, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane; Examples thereof include tin compounds such as dibutyltin octylate and dibutyltin dilaurate. Among these, acidic emulsifiers are preferable from the viewpoint of having an effect as an emulsifier as well as a polymerization catalyst, and alkylbenzenesulfonic acid having 5 to 30 carbon atoms is more preferable.

  The amount of the polymerization catalyst used for the hydrolyzable silicon compound (b1) is preferably 10 parts by mass or less, more preferably 0.1 to 7 parts by mass with respect to 100 parts by mass of the hydrolyzable silicon compound (b1). And more preferably 0.5 to 5 parts by mass.

  As the polymerization catalyst for the vinyl monomer (b2) having a secondary and / or tertiary amide group, a radical polymerization catalyst that causes radical polymerization by heat or a reducing substance to cause addition polymerization of the vinyl monomer is suitable. For example, water-soluble or oil-soluble persulfates, peroxides, azobis compounds and the like are used. Specific examples of the polymerization catalyst are not particularly limited. For example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azo Examples thereof include bisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like.

  The amount of the polymerization catalyst used for the vinyl monomer (b2) having a secondary and / or tertiary amide group is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total vinyl monomers. More preferably, it is 0.005-1 mass part, More preferably, it is 0.01-0.5 mass part. When it is desired to accelerate the polymerization rate and to perform polymerization at a low temperature of 70 ° C. or lower, it is advantageous to use a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, or longalite in combination with the radical polymerization catalyst. It is.

[Hydrolyzable silicon compound (C)]
The coating composition of the present embodiment preferably further contains a hydrolyzable silicon compound (C). When the coating composition of the present embodiment contains the hydrolyzable silicon compound (C), the silanol groups that the hydrolyzable silicon compound (C) can have and the hydroxyl groups that can exist on the surface of the metal oxide (A) It is considered that a bond is formed by a condensation reaction with or a hydrogen bond is formed between the hydrolyzable silicon compound (C) and the metal oxide (A). Thereby, it exists in the tendency which the mechanical strength of the antireflection layer obtained from the coating composition of this Embodiment improves more.

  In addition, since the antireflection layer formed from the coating composition of the present embodiment has surface hydrophilicity due to the metal oxide (A) and the hydrolyzable silicon compound (C), the antifouling layer The effect tends to be further improved. That is, since the antireflection layer formed from the coating composition of the present embodiment has surface hydrophilicity, adhesion of dirt such as dust is reduced due to its antistatic effect, and rainwater is attached even when dirt is adhered. It is thought that dirt is washed away. However, the mechanism does not depend on this.

Although it does not specifically limit as hydrolysable silicon compound (C) used for this Embodiment, For example, 1 chosen from the group which consists of a compound represented by following formula (2), (3), and (4). It is preferable that it is a hydrolyzable silicon compound of a kind or more.
R ¹ _n SiX _4-n (2)
(In Formula (2), each R ¹ independently has a hydrogen atom, or a halogen group, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group, or an epoxy group. Represents an alkyl group having 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, each X independently represents a hydrolyzable group; It is an integer from 0 to 3.)
X ₃ Si—R ² _n —SiX ₃ (3)
(In the formula (3), X is each independently represents a hydrolyzable group, R ² is .n representing an alkylene group or a phenylene group having 1 to 6 carbon atoms is 0 or 1.)
R ³ — (O—Si (OR ³ ) ₂ ) _n —OR ³ (4)
(In Formula (4), each R ³ independently represents an alkyl group having 1 to 6 carbon atoms. N is an integer of 2 to 8.)

The hydrolyzable group is not particularly limited, for example, -OR ^3.

[Other additives]
In the coating composition, depending on the application and usage method, components usually added to and blended with paints and molding resins, such as thickeners, leveling agents, thixotropic agents, antifoaming agents, and freeze stabilizers , Matting agent, crosslinking reaction catalyst, pigment, curing catalyst, crosslinking agent, filler, anti-skinning agent, dispersant, wetting agent, light stabilizer, antioxidant, ultraviolet absorber, rheology control agent, antifoaming agent , Film forming aids, rust inhibitors, dyes, plasticizers, lubricants, reducing agents, antiseptics, antifungal agents, deodorants, anti-yellowing agents, antistatic agents or charge control agents, etc. Can do.

  The coating composition preferably contains a hydrazine derivative, a carboxylic acid derivative and an isocyanate derivative. By cross-linking the polymer particles (B) having a predetermined composition and at least one selected from the group consisting of hydrazine derivatives, carboxylic acid derivatives and isocyanate derivatives, the solvent resistance and the like of the antireflection layer are further improved. There is a tendency.

[Antireflection film]
The antireflection film according to the first aspect includes a base material and an antireflection layer including the coating composition, which is disposed on at least one surface of the base material. Although it does not specifically limit as a manufacturing method of the antireflection film of this Embodiment, For example, the method of apply | coating and drying the above-mentioned coating composition to a base material is mentioned.

(Antireflection layer)
The method for applying the above-described coating composition to the substrate is not particularly limited. For example, a spraying method, a flow coating method, a roll coating method, a brush coating method, a dip coating method, a spin coating method, a bar coating method, Screen printing method, casting method, gravure printing method, flexographic printing method and the like can be mentioned.

  The film thickness of the antireflection layer of the present embodiment is preferably 50 to 2000 nm, more preferably 80 to 150 nm, still more preferably 90 to 130 nm, and particularly preferably 100 to 120 nm. When the film thickness of the antireflection film is within the above range, transparency and antireflection characteristics tend to be further improved.

  In addition, the area ratio (thickness uniformity ratio) of the antireflection layer having a thickness of the antireflection layer in the range of 80 to 150 nm, preferably 90 to 130 nm, more preferably 100 to 120 nm is preferably 70% or more. More preferably, it is 80% or more, More preferably, it is 90% or more. When the area ratio (thickness uniformity ratio) of the antireflection layer having a predetermined thickness is within the above range, the antireflection effect of the antireflection film tends to be further improved.

(Base material)
Although it does not specifically limit as a base material, For example, organic base materials, such as inorganic base materials, such as glass, a synthetic resin, a natural resin, those combinations, etc. can be mentioned.

  The ten-point average height Rz defined in JIS B0601 on the surface of the substrate on which the antireflection film of the present embodiment is formed is preferably 1 to 1000 μm. When the 10-point average height Rz of the base material is within the above range, when the coating composition is applied to the base material and dried, film thickness unevenness can be further reduced, and the antireflection performance of the antireflection film is further improved. Tend to. In addition, the 10-point average height Rz of the base material after producing the anti-reflective film which apply | coated and dried the coating composition can be confirmed with SEM sectional drawing.

  The antireflection film according to the second aspect has a base material and an antireflection layer containing a silicon compound and disposed on at least one surface of the base material, and the ten-point average height Rz of the base material surface However, it is 1-1000 micrometers, and the ratio of the area in which the film thickness of an antireflection layer exists in the range of 80-150 nm is 70% or more. Accordingly, it is an object of the present invention to provide an antireflection film that is excellent in antireflection properties by reducing film thickness unevenness even when applied to the surface of a substrate having a surface uneven structure.

  The ratio of the area of the base material, the ten-point average height Rz of the base material surface, and the thickness of the antireflection layer in the range of 80 to 150 nm is the same as described above. The antireflection layer is not particularly limited as long as it contains a silicon compound, but for example, a layer containing the coating composition of the present invention is preferable.

  Although it does not specifically limit as an antireflection layer containing a silicon compound, For example, the antireflection layer containing the said hydrolysable silicon compound (b1) is mentioned.

(Use)
Since the antireflection film of the present embodiment is excellent in transparency and antireflection properties, solar cell members (glass, modules, etc.), solar cell condensing lenses, photovoltaic cells, liquid crystal displays, glasses, windows In glass, television, etc., it can be used as an antireflection film for a member that requires improved light transmission and / or prevention of reflection.

  Furthermore, the antireflection film of the present embodiment is excellent in antifouling properties, antifogging properties, antistatic properties, weather resistance, and chemical resistance, so that it is a mirror for solar power generation, a building, a steel structure, and a building material. It can be used as an antifouling coating for mortar, concrete, plastic, automobiles and the like.

[Production method of antireflection film]
The method for producing an antireflection film includes a base material, and a step of applying and drying the coating composition on at least one surface of the base material, followed by heat treatment at 400 ° C. to 1000 ° C. to obtain an antireflection layer. . Although it does not specifically limit as a manufacturing method of the antireflection film of this Embodiment, For example, the method of apply | coating and drying the above-mentioned coating composition to a base material is mentioned.

  The method for drying the coating composition is not particularly limited, and examples thereof include natural drying, hot air drying, and infrared drying. A drying temperature becomes like this. Preferably it is 5-400 degreeC, More preferably, it is 10-300 degreeC, More preferably, it is 20-200 degreeC.

  Furthermore, the antireflection layer is preferably a layer obtained by heat treatment after applying and drying the coating composition on the substrate. By such heat treatment, the organic components in the antireflection layer are volatilized and the voids in the antireflection layer increase, whereby the antireflection characteristics tend to be further improved. From the viewpoint of improving the antireflection properties, the heat treatment temperature is preferably 400 ° C to 1000 ° C, more preferably 500 ° C to 800 ° C.

  The present invention will be specifically described by the following examples, synthesis examples and comparative examples, but these do not limit the scope of the present invention. In Examples, Synthesis Examples and Comparative Examples, various physical properties were measured by the following methods.

(1) Measurement of viscosity The viscosity of the coating composition at a liquid temperature of 25 ° C was evaluated using a vibration viscometer CJV5000 (manufactured by AND Co., Ltd.).

(2) Measurement of surface tension The surface tension of the coating composition at a liquid temperature of 25 ° C was evaluated using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Chemical Co., Ltd.).

(3) Measurement of transmittance Using a spectrophotometer V670 (manufactured by JASCO Corporation), the spectral transmittance of 400 to 1100 nm is measured, and the transmittance of the antireflection film is evaluated according to the evaluation method defined in ISO 9050. did.

(4) Evaluation of film thickness Using an FE-3000 reflection spectrometer (manufactured by Otsuka Electronics Co., Ltd.), a reflection spectrum in the wavelength range of 230 to 800 nm is measured, and the film thickness of the antireflection film is determined by least squares analysis. Evaluated.

(5) Evaluation of film thickness uniformity ratio A color image was taken using a color 3D laser microscope VK-9700 (manufactured by Keyence Corporation), and the film was evaluated by the FE-3000 reflection spectrometer (manufactured by Otsuka Electronics Co., Ltd.). The area of a color image showing the same interference color as the thickness in the range of 80 to 150 nm was calculated using image analysis software Image J, and the thickness ratio of the antireflection layer was evaluated.

(6) Measurement of 10-point average height Rz Using a color 3D laser microscope VK-9700 (manufactured by Keyence Corporation), the 10-point average height Rz defined in JIS B0601 on the textured glass substrate surface was evaluated. .

(7) Measurement of pencil hardness Using the test pencil specified by JIS S6006, the pencil hardness of the antireflection film at 1 kg load was evaluated according to the pencil hardness evaluation method specified by JIS K5400.

(8) Measurement of surface water contact angle A drop of deionized water (1.0 μL) was placed on the surface of the antireflection layer and allowed to stand at 20 ° C. for 10 seconds, and then a CA-X150 type contact angle meter manufactured by Kyowa Interface Science, Japan. Was used to measure the initial contact angle of the antireflection film. The smaller the contact angle of water with the antireflection layer, the higher the hydrophilicity of the coating surface.

[Synthesis Example 1]
-Synthesis of polymer particle (B-1) aqueous dispersion Into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, 1600 g of ion-exchanged water and 7 g of dodecylbenzenesulfonic acid were added and stirred. The mixture (1) was obtained by heating to 80 ° C. To the obtained mixture (1), 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane (2) were added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. A liquid (3) was obtained. Thereafter, the mixed liquid (3) was stirred for about 1 hour while the temperature in the reaction vessel was 80 ° C. Next, to the obtained mixed liquid (3), 150 g of butyl acrylate, 30 g of tetraethoxysilane, 145 g of phenyltrimethoxysilane, and 1.3 g of 3-methacryloxypropyltrimethoxysilane, and diethyl 165 g of acrylamide, 3 g of acrylic acid, 13 g of reactive emulsifier (trade name “Adekaria soap SR-1025”, manufactured by Asahi Denka Co., Ltd., solid content 25% by mass aqueous solution), 40 g of 2% by mass aqueous solution of ammonium persulfate, and ion exchange A mixture (5) of 1900 g of water was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. to obtain a mixture (6). Further, as a heat curing, the mixture (6) was stirred for about 2 hours while the temperature in the reaction vessel was 80 ° C. Thereafter, the mixture (6) was cooled to room temperature and filtered through a 100 mesh wire net to obtain an aqueous dispersion (solid content: 14.09% by mass) of polymer particles (B-1) having a number average particle diameter of 87 nm. .

  In this example, the number average particle size of the polymer particles was measured with a dynamic light scattering particle size distribution analyzer UPA-UZ152 (manufactured by Nikkiso Co., Ltd.).

[Example 1]
An average particle as a raw material for spherical metal oxide (a1) 1.8 g of an aqueous dispersion of polymer emulsion particles (B-1) synthesized in Synthesis Example 1 as polymer particles (B) in 60 g of 27% ethanol aqueous solution Water-dispersed colloidal silica having a diameter of 5 nm (trade name “Snowtex OXS”, manufactured by Nissan Chemical Industries, Ltd., solid content 10 mass%) 2.5 g, average diameter of about 12 nm as a raw material for the chain metal oxide (a2) An aqueous dispersion of beaded silica composed of primary silica particles having an average major axis of about 70 nm and a majority of the particles having an aspect ratio (major axis / minor axis) of 3 to 25 (trade name “Snowtex”). OUP ", manufactured by Nissan Chemical Industries, Ltd., solid content 15% by weight (12.0 g), hydrolyzable silicon compound (C) as tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 1.7 g, as viscosity modifier 22.0 g of 5 wt% aqueous solution of livinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., degree of polymerization about 2000), and 0.50 g of 2-butoxyethanol (manufactured by Wako Pure Chemical Industries, Ltd.) as a surface tension adjusting agent Mixing and stirring were performed to obtain a coating composition (D-1). The resulting coating composition (D-1) had a viscosity of 10.4 cp and a surface tension of 33.2 mN / m.

  After applying the coating composition (D-1) to a textured glass substrate having a concavo-convex structure with a 10-point average height Rz of 50 μm using a bar coater so that the average film thickness becomes 120 nm, 70 Drying was performed at ° C for 30 minutes to obtain a test plate (F-1) having an antireflection layer (E-1).

  Since the obtained test plate (F-1) has a transmittance of 91.9% and the transmittance of the original base material is 89.4%, it is also referred to as a transmittance difference (hereinafter referred to as “AR”). ) Was 2.5%, indicating a very good antireflection effect. In addition, the film thickness uniformity ratio of the antireflection layer (E-1) was 95%, which was a very uniform antireflection layer. Furthermore, the antireflection layer (E-1) had a pencil hardness of 7H, indicating a very good hardness. Furthermore, the antireflection layer (E-1) exhibited very good antifouling performance with a surface water contact angle of less than 10 °.

[Example 2]
9.5 g of an aqueous dispersion of the polymer emulsion particles (B-1) synthesized in Synthesis Example 1 as polymer particles (B) in 60 g of a 27% ethanol aqueous solution, and an average particle as a raw material for the spherical metal oxide (a1) 6.7 g of water-dispersed colloidal silica with a diameter of 15 nm (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%), tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.) as the hydrolyzable silicon compound (C) 1.2 g, 2 wt% aqueous solution of polyvinyl alcohol (Wako Pure Chemical Industries, 2000) as a viscosity modifier, 24.0 g, and 2-butoxyethanol (Wako Pure Chemical Industries, Ltd.) as a surface tension modifier. (Co., Ltd.) 0.5 g was mixed and stirred to obtain a coating composition (D-2). The resulting coating composition (D-2) had a viscosity of 11.5 cp and a surface tension of 32.1 mN / m.

  After applying the coating composition (D-2) to a textured glass substrate having a concavo-convex structure with a 10-point average height Rz of 50 μm using a bar coater so that the average film thickness is 120 nm, 70 After drying at 30 ° C. for 30 minutes, heat treatment was performed at 700 ° C. for 3 minutes to obtain a test plate (F-2) having an antireflection layer (E-2).

  The obtained test plate (F-2) has a transmittance of 92.0% and the transmittance of the original base material is 89.4%. Therefore, AR is 2.6%, which is very good. Antireflection effect was shown. Moreover, the film thickness uniformity ratio of the antireflection layer (E-2) was 96%, which was a very uniform antireflection layer. Furthermore, the antireflection layer (E-2) had a pencil hardness of 7H, indicating a very good hardness. Furthermore, the antireflection layer (E-2) exhibited very good antifouling performance with a surface water contact angle of less than 10 °.

Example 3
9.5 g of an aqueous dispersion of the polymer emulsion particles (B-1) synthesized in Synthesis Example 1 as polymer particles (B) in 60 g of a 27% ethanol aqueous solution, and an average particle as a raw material for the spherical metal oxide (a1) Water-dispersed colloidal silica having a diameter of 10 nm (trade name “Snowtex OS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 7.9 g, polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) as a viscosity modifier, 24.0 g of a 5 wt% aqueous solution having a degree of polymerization of about 2000) and 0.5 g of 2-butoxyethanol (manufactured by Wako Pure Chemical Industries, Ltd.) as a surface tension adjusting agent were mixed and stirred to form a coating composition (D-3). Got. The resulting coating composition (D-3) had a viscosity of 11.3 cp and a surface tension of 32.5 mN / m.

  After applying the coating composition (D-3) to a textured glass substrate having a concavo-convex structure with a 10-point average height Rz of 50 μm using a bar coater so as to have an average film thickness of 120 nm, 70 After drying at 30 ° C. for 30 minutes, heat treatment was performed at 700 ° C. for 3 minutes to obtain a test plate (F-3) having an antireflection layer (E-3).

  The obtained test plate (F-3) has a transmittance of 92.0% and the transmittance of the original base material is 89.4%. Therefore, AR is 2.6%, which is very good. Antireflection effect was shown. Moreover, the film thickness uniformity ratio of the antireflection layer (E-3) was 96%, which was a very uniform antireflection layer. Furthermore, the antireflection layer (E-3) had a pencil hardness of 7H, indicating a very good hardness. Furthermore, the antireflection layer (E-3) exhibited very good antifouling performance with a surface water contact angle of less than 10 °.

[Comparative Example 1]
In 80 g of 20% ethanol aqueous solution, 1.8 g of an aqueous dispersion of the polymer emulsion particles (B-1) synthesized in Synthesis Example 1 as polymer particles (B), and an average particle as a raw material for the spherical metal oxide (a1) Water-dispersed colloidal silica having a diameter of 5 nm (trade name “Snowtex OXS”, manufactured by Nissan Chemical Industries, Ltd., solid content 10 mass%) 2.5 g, average diameter of about 12 nm as a raw material for the chain metal oxide (a2) An aqueous dispersion of beaded silica composed of primary silica particles having an average major axis of about 70 nm and a majority of the particles having an aspect ratio (major axis / minor axis) of 3 to 25 (trade name “Snowtex”). OUP ", manufactured by Nissan Chemical Industries, Ltd., solid content 15% by weight (12.0 g), hydrolyzable silicon compound (C), tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.7 g, and surface tension adjustment 2-butoxyethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.50g mixing and stirring to obtain a coating composition (D-3) as a. The resulting coating composition (D-3) had a viscosity of 3.5 cp and a surface tension of 33.5 mN / m.
After applying the coating composition (D-3) to a textured glass substrate having a concavo-convex structure with a 10-point average height Rz of 50 μm using a bar coater so as to have an average film thickness of 120 nm, 70 It dried at 30 degreeC for 30 minute (s), and the test board (G-3) which has an antireflection layer (E-3) was obtained.

  The obtained test plate (F-1) had a transmittance of 91.2%, and the transmittance of the original base material was 89.4%. Therefore, the AR was 1.8%, and the antireflection effect was low. It was. The film thickness uniformity ratio of the antireflection layer (E-3) was 55%, which was a nonuniform antireflection layer.

[Comparative Example 2]
In 66 g of pure water, 1.8 g of an aqueous dispersion of the polymer emulsion particles (B-1) synthesized in Synthesis Example 1 as polymer particles (B), and an average particle diameter of 5 nm as a raw material for the spherical metal oxide (a1) 2.5g of water-dispersed colloidal silica (trade name “Snowtex OXS”, manufactured by Nissan Chemical Industries, Ltd., solid content: 10% by mass), silica having an average diameter of about 12 nm as a raw material for the chain metal oxide (a2) An aqueous dispersion of beaded silica composed of primary particles having an average major axis of about 70 nm and a majority of particles having an aspect ratio (major axis / minor axis) of 3 to 25 (trade name “Snowtex OUP”) 12.0 g manufactured by Nissan Chemical Industries, Ltd., solid content 15% by weight), 1.7 g of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as the hydrolyzable silicon compound (C), and polyvinyl as the viscosity modifier Al Lumpur (manufactured by Wako Pure Chemical Industries, Ltd., about 2000 degree of polymerization) of 5 wt% aqueous solution 16.0g of mixing and stirring to obtain a coating composition of (D-4). The resulting coating composition (D-4) had a viscosity of 7.5 cp and a surface tension of 46.5 mN / m.

  After applying the coating composition (D-4) to a textured glass substrate having an uneven surface structure with a 10-point average height Rz of 50 μm using a bar coater so as to have an average film thickness of 120 nm, 70 Drying was performed at ° C for 30 minutes to obtain a test plate (F-4) having an antireflection layer (E-4).

  The obtained test plate (F-4) had a transmittance of 91.3%, and the transmittance of the original base material was 89.4%. Therefore, the AR was 1.9%, and the antireflection effect was low. It was. The thickness ratio of the antireflection layer (E-4) was 60%, which was a nonuniform antireflection layer.

[Comparative Example 3]
27 g of ethanol aqueous solution 27 g of polymer emulsion particles (B-1) synthesized in Synthesis Example 1 as polymer particles (B) 1.8 g of water dispersion, spherical metal oxide (a1) as average raw material Water-dispersed colloidal silica having a diameter of 5 nm (trade name “Snowtex OXS”, manufactured by Nissan Chemical Industries, Ltd., solid content 10 mass%) 2.5 g, average diameter of about 12 nm as a raw material for the chain metal oxide (a2) An aqueous dispersion of beaded silica composed of primary silica particles having an average major axis of about 70 nm and a majority of the particles having an aspect ratio (major axis / minor axis) of 3 to 25 (trade name “Snowtex”). OUP ", manufactured by Nissan Chemical Industries, Ltd., solid content 15% by weight (12.0 g), hydrolyzable silicon compound (C) as tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 1.7 g, as viscosity modifier 55.0 g of a 5 wt% aqueous solution of livinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., degree of polymerization about 2000), and 0.50 g of 2-butoxyethanol (manufactured by Wako Pure Chemical Industries, Ltd.) as a surface tension modifier Mixing and stirring were performed to obtain a coating composition (D-4). The resulting coating composition (D-4) had a viscosity of 60.5 cp and a surface tension of 35.5 mN / m, but the blending stability was low. The coating composition (D-4) was too viscous to be used for testing.

  The results of each example and each comparative example are shown in Table 1.

  As shown in Table 1, the antireflection layer of each example exhibited very good film thickness uniformity and antireflection effect, mechanical strength of the antireflection layer, and surface hydrophilicity. On the other hand, in the comparative example, although the mechanical strength and surface hydrophilicity of the antireflection layer were excellent, it was confirmed that the uniformity of the film thickness was low and the antireflection effect was low.

  The coating composition according to the present invention includes an antireflection film for a member that needs to improve light transmission and / or prevent reflection, such as a solar cell, a photovoltaic cell, a liquid crystal display, glasses, a window glass, and a television. It can use suitably for manufacture of the antifouling coat of this member.

Claims (8)

A metal oxide (A) and polymer particles (B),
The viscosity is 5-50 cp,
Ri surface tension 30~40mN / m der,
The thickener is included in an amount of 0.01 to 5.0% by mass with respect to the total amount of the coating composition, and the surface tension modifier is 0.05 to 5.0% by mass with respect to the total amount of the coating composition. Including
The polymer particles (B) polymerize a hydrolyzable silicon compound (b1) and a vinyl monomer (b2) having a secondary and / or tertiary amide group in the presence of water and an emulsifier. The coating composition containing the polymer particle obtained by this . A metal oxide (A) and polymer particles (B),
The viscosity is 5-50 cp,
Ri surface tension 30~40mN / m der,
The thickener is included in an amount of 0.01 to 5.0% by mass with respect to the total amount of the coating composition, and the surface tension modifier is 0.05 to 5.0% by mass with respect to the total amount of the coating composition. Including
The polymer particles (B) are polymer particles obtained by polymerizing a hydrolyzable silicon compound (b1) in the presence of water and an emulsifier, and a vinyl monomer having a secondary and / or tertiary amide group. And a polymer particle obtained by polymerizing the body (b2) . The coating composition according to claim 1 or 2 , further comprising a hydrolyzable silicon compound (C). The metal oxide (A) is a spherical metal oxide (a1) having an aspect ratio (major axis / minor axis) of less than 3 and / or a chain metal oxide having an aspect ratio (major axis / minor axis) of 3 to 25. The coating composition according to any one of claims 1 to 3, comprising the product (a2). The antireflection film which has a base material and the antireflection layer containing the coating composition of any one of Claims 1-4 distribute | arranged to the at least one surface of this base material. The antireflection film according to claim 5 , wherein the antireflection layer is a layer obtained by applying and drying the coating composition on the substrate and then heat-treating at 400 ° C. to 1000 ° C. The antireflection film according to claim 5 or 6 , wherein a ten-point average height Rz of the substrate surface is 1-1000 µm. After applying and drying the coating composition according to any one of claims 1 to 4 on at least one surface of the substrate and the substrate, the antireflection layer is formed by heat treatment at 400 ° C to 1000 ° C. The manufacturing method of an antireflection film including the process to obtain.