JP2010237279A - Antireflection coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection coating composition superior in antifouling properties and antireflection properties. <P>SOLUTION: The antireflection coating composition includes a component (A): a metal oxide having a particles size of 1 to 400 nm and a component (B): polymer emulsion particles having a particle size of 10 to 800 nm; wherein the component (B) is polymer emulsion particles obtained by polymerizing a polymerization stock solution containing: a component (b1) being a hydrolyzable silicon compound; a component (b2) being a vinyl monomer having at least one functional group selected from a group of hydroxyl groups, carboxyl groups, amide groups, amino groups, and ether groups; a component (b3) being an emulsifier: and a component (b4) being water. A mass ratio of the component (A) to the component (B) is A/B=50/100 to 450/100. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antireflection coating composition, an antireflection composite, and the like.

  Various display panels such as liquid crystal display panels, cold cathode ray tube panels, plasma displays, displays such as signboards displayed outdoors, and electric bulletin boards are reflected to prevent reflection of external light and improve image quality. A protective film is used. These display panels are often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust, and the like, and are required to have scratch resistance. In addition, when used outdoors, there is also a demand for antifouling properties that allow dust and the like adhering to the surface to flow down with rainwater.

  As a material for the low refractive index layer of the antireflection film, for example, a fluororesin-based paint containing a hydroxyl group-containing fluoropolymer is known (see, for example, Patent Documents 1, 2, and 3).

  Further, as a technique for developing antifouling properties, Patent Document 4 applies a coating solution in which tungstic acid dissolved in ammonia water and distilled water are added onto an anatase-type titanium oxide-containing layer, and is baked at 700 ° C. A technique for forming a surface layer by performing a treatment to form a layer made of tungsten oxide is disclosed. By the anatase-type titanium oxide-containing layer having a photocatalytic function, organic substances attached to the surface layer are decomposed, and the surface exhibits hydrophilicity. Further, the hydrophilicity of the surface is maintained by the layer made of tungsten oxide. Thereby, the condensed water and water droplets adhering to the surface are easily spread over the entire surface, and the surface can be prevented from being fogged.

  Furthermore, Patent Documents 5 and 6 disclose techniques for expressing antifouling properties with a water-based organic-inorganic composite composition having a small environmental load.

JP 57-34107 A JP 59-189108 A JP 60-67518 A JP-A-10-114545 JP 2009-19072 A International Publication No. 2007-069596 Pamphlet

  However, in order to cure the coating film of the fluororesin-based paint disclosed in Patent Documents 1, 2, and 3, a hydroxyl group-containing fluoropolymer and a curing agent such as melamine resin are heated under an acid catalyst. May need to be crosslinked. Furthermore, depending on heating conditions, there is a problem that the curing time becomes excessively long and the types of base materials that can be used are limited. Moreover, although the obtained coating film is excellent in weather resistance, it tends to be poor in scratch resistance and durability. Moreover, the technique disclosed in Patent Document 4 requires a baking process at a high temperature, and has a problem that it can be used only with a specific base material, and a problem that the base material is decomposed by a photocatalyst. Further, Patent Documents 5 and 6 do not disclose a specific description regarding antireflection. Accordingly, an object of the present invention is to provide an antireflection coating composition having excellent antifouling properties and antireflection properties.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention
[1]
The following components (A) and (B)
(A) component: a metal oxide having a particle diameter of 1 nm to 400 nm,
(B) component: polymer emulsion particles having a particle diameter of 10 nm to 800 nm,
An antireflective coating composition comprising:
(B) component is each component of the following (b1)-(b4),
(B1) component: a hydrolyzable silicon compound;
(B2) component: a vinyl monomer containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an ether group;
(B3) component: an emulsifier,
(B4) component: water,
Polymer emulsion particles obtained by polymerizing a polymerization stock solution containing
The gist is that the coating composition for antireflection has a mass ratio of the component (A) to the component (B) of A / B = 50/100 to 450/100.

[2]
In the antireflection coating composition of [1], even if the mass ratio (b2) / (B) between the component (b2) and the component (B) is 0.1 / 1 to 0.5 / 1. Good.
[3]
In the antireflection coating composition according to [1] or [2], the mass ratio (b2) / (A) of the component (b2) to the component (A) is 0.1 / 1 to 1/1. May be.
[4]
In the antireflection coating composition according to any one of [1] to [3], the component (B) comprises a core layer and one or more shell layers covering the core layer. It may have a structure.
[5]
In the core layer of the antireflection coating composition of [4], the mass ratio (b2) / (b1) of the component (b2) to the component (b1) is 0.01 / 1 to 1/1, and the shell layer In the outermost layer, the mass ratio (b2) / (b1) between the component (b2) and the component (b1) may be 0.1 / 1 to 5/1.

[6]
In the antireflection coating composition according to [4] or [5], the component (B) is obtained by polymerizing a polymerization stock solution in the presence of seed particles forming the core layer, and the seed particles are the component (b1). , (B2) and at least one selected from the group consisting of vinyl monomers copolymerizable with component (b2) may be obtained.
[7]
In the antireflection coating composition according to any one of [1] to [6], the component (b2) may be a vinyl monomer having a secondary and / or tertiary amide group.
[8]
In the antireflection coating composition according to any one of [1] to [7], the particle size of the component (B) may be 120 to 450 nm.
[9]
In the antireflective coating composition according to any one of [1] to [8], component (C): a hydrolyzable silicon compound represented by the following formula (1), the following formula (2), or the following formula (3) An antireflective coating composition further comprising:
The mass ratio of the component (A) to the component (B) is A / B = 150/100 to 450/100,
The mass ratio of the component (A) to the component (C) may be C / A = 0.2 / 100 to 60/100.
R ¹ _n SiX _4-n (1)
(In Formula 1, R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, or a substituent thereof, X represents a hydrolyzable group, and n represents 0 to 3 (It is an integer.)
X ₃ Si—R ² _n —SiX ₃ (2)
(In Formula 2, X represents a hydrolyzable group, R ² represents an alkylene group having 1 to 6 carbon atoms or a phenylene group, and n is 0 or 1.)
R ³ — (O—Si (OR ³ ) ₂ ) _n —OR ³ (3)
(In the formula 3, R ³ represents an alkyl group having 1 to 6 carbon atoms, n is an integer of 2-8.)

[10]
The gist is an antireflective composite formed from the antireflective coating composition according to any one of [1] to [9].
[11]
The gist is an antireflective composite comprising the antireflective coating composition according to any one of [1] to [9].
[12]
The gist of the present invention is a display comprising the antireflection composite according to [10] or [11].
[13]
The gist of the invention is an exterior display member comprising the antireflection composite according to [10] or [11].

  According to the present invention, it is possible to provide an antireflection coating composition having excellent antifouling properties and antireflection properties.

  Hereinafter, modes for carrying out the present invention (hereinafter sometimes abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary. Here, the antireflection coating composition according to the embodiment includes (A) component: a metal oxide having a particle size of 1 nm to 400 nm, and (B) component: polymer emulsion particles having a particle size of 10 nm to 800 nm. ,including. The component (B) includes at least one functional group selected from the group consisting of the component (b1): a hydrolyzable silicon compound and the component (b2): a hydroxyl group, a carboxyl group, an amide group, an amino group, and an ether group. Polymer emulsion particles obtained by polymerizing a polymerization stock solution containing a vinyl monomer to be contained, (b3) component: emulsifier, and (b4) component: water. Moreover, mass ratio of (A) component and (B) component is A / B = 50 / 100-450 / 100.

  In the embodiment, the component (A) interacts with the component (B) and can act as a curing agent for the component (B). Examples of the interaction include a hydrogen bond between a hydroxyl group that the component (A) generally has and a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an ether group that the component (B) has. Or the condensation (chemical bond) of the hydroxyl group generally possessed by the component (A) and the polymerization product of the component (b1) constituting the component (B). Moreover, it is preferable that a continuous layer is formed between the particles of (B) component, while (A) component interacts with (B) component. Thereby, the transparency and weather resistance of the resulting coating composition can be further improved.

  Examples of the metal oxide used in the component (A) include silicon dioxide, aluminum oxide, antimony oxide, titanium oxide, indium oxide, tin oxide, zirconium oxide, and lead oxide from the viewpoint of interaction with the component (B). Iron oxide, calcium silicate, magnesium oxide, niobium oxide, cerium oxide, and the like can be used. Of these, silicon dioxide (silica), aluminum oxide (alumina), antimony oxide, and complex oxides thereof having a large surface hydroxyl group are preferable from the viewpoint of the strength of interaction. In addition, you may use 2 or more types of the metal oxide mentioned above together as (A) component.

  Furthermore, from the viewpoint of imparting antifouling properties to the metal oxide used in the component (A), a compound that expresses photocatalytic activity and / or hydrophilicity by light irradiation (hereinafter sometimes simply referred to as “photocatalyst”). ) May be used. By using a compound that exhibits photocatalytic activity by light irradiation as the component (A), the surface of the resulting coating composition can exhibit excellent decomposition activity and contamination resistance of the contaminating organic substance. In the present embodiment, “hydrophilic” means that the contact angle of water (23 ° C.) with respect to the surface of the measurement object is preferably 60 ° or less, more preferably 30 ° or less, and even more preferably 20 ° or less. Means that.

As a photocatalyst, more _{specifically, TiO 2, ZnO, SrTiO 3} , BaTiO 3, BaTiO 4, BaTi 4 O 9, K 2 NbO 3, Nb 2 O 5, Fe 2 O 3, Ta 2 O 5, K 3 Ta ₃ Si ₂ O ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , BiVO ₄ , NiO, Cu ₂ O, RuO ₂ , CeO _{2 and the} like can be used. Further, a layered oxide having at least one element selected from Ti, Nb, Ta, and V as a photocatalyst (for example, JP-A-62-274452, JP-A-2-172535, JP-A-7-24329). JP-A-8-89799, JP-A-8-89800, JP-A-8-89804, JP-A-8-198061, JP-A-9-248465, JP-A-10-99694. JP, 10-244165, A, etc.) can be used. Among these photocatalysts, TiO ₂ (titanium oxide) is preferable because it is harmless and has excellent chemical stability. As the titanium oxide, any of anatase type, rutile type, and brookite type can be used.

  In addition, as the metal oxide used for the component (A), a conductive metal oxide can be used from the viewpoint of expressing the antistatic performance and the like of the resulting coating composition. As the conductive metal oxide, for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), tin oxide, zinc oxide, or the like can be used.

  The component (A) is used in the form of, for example, a powder, a dispersion, or a sol. Here, the dispersion or sol means that the component (A) is a primary particle and a concentration of 0.01 to 80% by mass, preferably 0.1 to 50% by mass in water and / or a hydrophilic organic solvent. Means dispersed as secondary particles. Examples of the hydrophilic organic solvent include alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol and methanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane. Amides such as dimethylacetamide and dimethylformamide, dimethyl sulfoxide, nitrobenzene and the like, and a mixture of two or more of these.

  Number average particle diameter of component (A) observed in dispersion or sol (may be a mixture of primary particles and secondary particles, or only primary particles or secondary particles) Is preferably 1 nm to 400 nm, more preferably 1 nm to 100 nm, still more preferably 3 nm to 80 nm, and particularly preferably 5 nm to 50 nm. The number average particle diameter of the component (A) can contribute to the optical properties of the antireflection composite formed using the resulting coating composition. In particular, by setting the number average particle diameter to 100 nm or less, the transparency of the resulting antireflection composite can be greatly improved. In addition, the number average particle diameter (simply abbreviated as “particle diameter”) in the present embodiment is a value measured according to the method of Examples described later.

  As a metal oxide (A) used by embodiment, colloidal silica is preferable from a viewpoint of handleability. Colloidal silica may be prepared by a sol-gel method, or a commercially available product may be used. For preparation by the sol-gel method, Werner Stober et al; Colloid and Interface Sci. , 26, 62-69 (1968), Rickey D .; Badley et al; Lang muir 6, 792-801 (1990), Color Material Association Journal, 61 [9] 488-493 (1988), and the like. Colloidal silica is a dispersion of water or a water-soluble solvent of silica having silicon dioxide as a basic unit. The particle diameter of colloidal silica is 1 to 400 nm, preferably 1 to 100 nm, and more preferably 5 to 50 nm. When the particle diameter is 1 nm or more, the storage stability of the coating liquid tends to be good. Further, when the particle diameter is 400 nm or less, the transparency tends to be good.

  Colloidal silica having a particle size in the above range can be used in the state of an aqueous dispersion, whether acidic or basic, and is appropriately selected according to the stable region of the aqueous dispersion (B) to be mixed. be able to. Examples of the acidic colloidal silica using water as a dispersion medium include, as commercial products, Snowtex (registered trademark) -O manufactured by Nissan Chemical Industries, Ltd., Snowtex-OL, Adelite (registered trademark) manufactured by Asahi Denka Kogyo Co., Ltd. AT-20Q, Clariant Japan Co., Ltd. clebosol (registered trademark) 20H12, clebosol 30CAL25, etc. can be used.

  Examples of basic colloidal silica include silica stabilized by addition of alkali metal ions, ammonium ions, and amines, such as SNOWTEX-20, SNOWTEX-30, SNOWTEX-C, manufactured by Nissan Chemical Industries, Ltd. SNOWTEX-C30, SNOWTEX-CM40, SNOWTEX-N, SNOWTEX-N30, SNOWTEX-K, SNOWTEX-XL, SNOWTEX-YL, SNOWTEX-ZL, SNOWTEX PS-M, and SNOWTEX PS -L etc. can be used. Alternatively, Adelite AT-20, Adelite AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, Adelite AT-40, Adelite AT-50, etc. manufactured by Asahi Denka Kogyo Co., Ltd. Can also be used. In addition, Clariant Japan Co., Ltd. clebosol 30R9, clebosol 30R50, clebosol 50R50, etc., DuPont Ludox (registered trademark) HS-40, Ludox HS-30, Ludox LS, Ludox SM-30, etc. can also be used. is there.

  Examples of colloidal silica using a water-soluble solvent as a dispersion medium include MA-ST-M (methanol dispersion type having a particle size of 20 to 25 nm), IPA-ST (particle size of 10) manufactured by Nissan Chemical Industries, Ltd. ˜15 nm isopropyl alcohol dispersion type), EG-ST (ethylene glycol dispersion type with particle diameter of 10 to 15 nm), EG-ST-ZL (ethylene glycol dispersion type with particle diameter of 70 to 100 nm), and NPC-ST ( An ethylene glycol monopropyl ether dispersion type) having a particle size of 10 to 15 nm can be used. These colloidal silicas may be used alone or in combination of two or more. Moreover, alumina, sodium aluminate, and the like may be included as a minor component. Furthermore, colloidal silica may contain an inorganic base (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia), an organic base (such as tetramethylammonium), or the like as a stabilizer.

  Next, as described above, the component (B) of the antireflection coating composition according to the embodiment includes (b1) component: hydrolyzable silicon compound and (b2) component: hydroxyl group, carboxyl group, amide group. A polymerization stock solution containing a vinyl monomer containing at least one functional group selected from the group consisting of amino group and ether group, component (b3): emulsifier, and component (b4): water. Polymer emulsion particles obtained in this way. As the component (B), it is preferable to use a compound in which a hydroxyl group derived from the component (b1) and a polymerization product of the component (b2) are combined by hydrogen bonding or the like.

As the component (b1), a compound represented by the following formula (4), a condensation product thereof, a silane coupling agent, or the like can be used.
SiWxRy (4)
(In Formula (4), W represents an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group, R represents at least one group selected from amide groups, and R represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and unsubstituted. Or at least one hydrocarbon group selected from an 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 substituted with a halogen atom, x. (It is an integer of 1 or more and 4 or less, and y is an integer of 0 or more and 3 or less, and x + y = 4.)

  The silane coupling agent means a compound in which a functional group having reactivity with an organic substance such as a vinyl polymerizable group, an epoxy group, an amino group, a methacryl group, a mercapto group, or an isocyanate group exists in the molecule.

  Specific examples of the compound represented by the formula (4) 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-butyltrimethoxysilane , N-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-tri Fluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, Captopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) ata Kryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, 3-ureidopropyltrimethoxysilane, 3 -Trialkoxysilanes such as ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxy Silane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di -N-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxy Dialkoxysilanes such as silane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane; monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane Etc. can be used. Moreover, these may be used independently and may be used in mixture of 2 or more types.

  As the component (b1), a silicon alkoxide having a phenyl group (for example, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, etc.) can be used. When a silicon alkoxide having a phenyl group is used, the polymerization stability in the presence of water and an emulsifier becomes good, which is preferable.

  Furthermore, the component (b1) may contain a silane coupling agent having a thiol group and a hydrolyzable silicon compound having a vinyl polymerizable group as the component (b1-1). When these are used, the long-term antifouling property of the obtained antireflection composite is good, which is preferable. As the silane coupling agent having a thiol group, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like can be used.

  Examples of the component (b1-1) include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and 2-trimethoxysilylethyl vinyl ether A silane coupling agent having a vinyl polymerizable group such as can be used.

  These silane coupling agents can generate chemical bonds by copolymerization or chain transfer reaction with the component (b2) described later. For this reason, when a silane coupling agent having a vinyl polymerizable group or a thiol group is used by mixing or combining with the component (b1) described above, the polymerization product of (b1) and the polymerization of the component (b2) described later are used. The product can be complexed by chemical bonds. The “vinyl polymerizable group” of the component (b1-1) is, for example, a vinyl group, an allyl group, and the like, and among them, a 3 (meth) acryloxypropyl group is preferable.

The component (b1) may contain a cyclic siloxane oligomer as the component (b1-2). By using the component (b1-2), the resulting antireflective composite is more flexible and suitable. As the cyclic siloxane oligomer, a compound represented by the following formula (5) can be used.
_{(R '2 SiO) m (} 5)
(In Formula (5), R ′ is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or carbon atom. It represents at least one selected from an 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 substituted with a halogen atom, m is an integer, and 2 ≦ m ≦ 20.)

  Among the cyclic siloxane oligomers, cyclic dimethylsiloxane oligomers such as octamethylcyclotetrasiloxane are preferable from the viewpoint of reactivity.

  In addition, when (b1) component is used as a condensation product, the polystyrene conversion weight average molecular weight (according to GPC method) of the condensation product is preferably 200 to 5000, and more preferably 300 to 1000. The mass ratio (b1) / (B) between the component (b1) and the component (B) is preferably 0.01 / 100 to 80/100, more preferably 0.1, from the viewpoint of polymerization stability. / 100 to 70/100. On the other hand, the mass ratio (b1-1) / (B) between the component (b1-1) and the component (B) is preferably 0.01 / 100 to 20/100 from the viewpoint of polymerization stability. More preferably, it is 0.5 / 100 to 10/100.

  The mass ratio (b1-1) / (b2) between the component (b1-1) and the component (b2) is preferably 0.1 / 100 to 100/100 from the viewpoint of polymerization stability. More preferably, it is 0.5 / 100 to 50/100. On the other hand, the mass ratio (b1-2) / (B) between the component (b1-2) and the component (B) is preferably 0.01 / 100 to 20/100 from the viewpoint of hydrophilicity, and more Preferably it is 0.5 / 100-5 / 100. Further, the mass ratio (b1-2) / (b2) between the component (b1-2) and the component (b2) is preferably 0.5 / 100 to 50/100 from the viewpoint of polymerization stability. More preferably, it is 1.0 / 100-20 / 100.

  Next, examples of the hydroxyl group-containing vinyl monomer as the component (b2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Various hydroxyalkyl (meth) acrylates; various hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; various hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether; polyethylene glycol Monoesters of polyoxyalkylene glycols obtained from various polyether polyols as typified by, and various unsaturated carboxylic acids as typified by (meth) acrylic acid, etc .; Hydroxyl group-containing single And adducts of various lactones such as ε-caprolactone, various epoxy group-containing unsaturated monomers such as glycidyl (meth) acrylate, acetic acid, etc. Adducts with various acids as typified; Furthermore, various unsaturated carboxylic acids as typified by (meth) acrylic acid and the like, and “Cardura E” (trade name, manufactured by Shell, Netherlands) Various hydroxyl-containing vinyl monomers such as adducts with various monoepoxy compounds other than epoxides of α-olefin as represented by the above can be used.

  In addition, the carboxyl group-containing vinyl monomer as the component (b2) includes various kinds of solvents such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid and fumaric acid. Saturated carboxylic acids; saturated with unsaturated dicarboxylic acids such as monomethyl itaconate, mono-n-butyl itaconate, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate, and mono-n-butyl fumarate Monoesters with monohydric alcohols (half esters); Monovinyl esters of various saturated dicarboxylic acids such as monovinyl adipate and monovinyl succinate; succinic anhydride, glutaric anhydride, phthalic anhydride, and tri Various saturated polycarboxylic acid anhydrides, such as merit acid, Products of addition reaction with acid group-containing vinyl monomers; and monomers obtained by addition reaction of various carboxyl group-containing monomers and lactones as described above can be used. is there.

  As the amide group-containing vinyl monomer as the component (b2), for example, N-alkyl or N-alkylene-substituted (meth) acrylamide can be used. More specifically, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methyl-N -N-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloyl Sahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, N-vinylacetamide, diacetone Acrylamide, diacetone methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like can be used.

  Examples of the amino group-containing vinyl monomer (b2) include 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 3 -Various tertiary amino group-containing (meth) acrylic esters such as dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate, and N- [2- (meth) acryloyloxy] ethylmorpholine Various tertiary amino group-containing aromatic vinyl monomers such as vinylpyridine and N-vinylcarbazole N-vinylquinoline; N- (2-dimethylamino) ethyl (meth) acrylamide, N- (2 -Diethylamino) ethyl (meth) acrylamide, N- (2-di-n-propylamino) Such as ethyl (meth) acrylamide, N- (3-dimethylamino) propyl (meth) acrylamide, N- (4-dimethylamino) butyl (meth) acrylamide, and N- [2- (meth) acrylamide] ethylmorpholine Various tertiary amino group-containing (meth) acrylamides; N- (2-dimethylamino) ethylcrotonic acid amide, N- (2-diethylamino) ethylcrotonic acid amide, N- (2-di-n-propylamino) Various tertiary amino group-containing crotonic acid amides such as ethyl crotonic acid amide, N- (3-dimethylamino) propyl crotonic acid amide, and N- (4-dimethylamino) butyl crotonic acid amide; 2-dimethylamino Ethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 3-dimethylamino B pills vinyl ether, and 4 various tertiary amino group-containing vinyl ethers such as dimethyl amino butyl vinyl ether or the like can be used.

  Examples of the ether group-containing vinyl monomer as component (b2) include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, and polyoxyethylene-polyoxypropylene block copolymer. Vinyl ethers having various polyether chains in the side chain, allyl ethers or vinyl monomers such as (meth) acrylic acid esters can be used. Specifically, Bremer PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, AE-350 [above, manufactured by NOF Corporation], MA-30, MA- 50, MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114, and MPG130-MA [above, manufactured by Nippon Emulsifier Co., Ltd.] can be used. . Here, as for the oxyethylene unit of a polyoxyethylene chain, 2-30 are preferable. If it is less than 2, the flexibility of the coating film may be insufficient, and if it exceeds 30, the coating film may become soft and the blocking resistance may deteriorate.

  The vinyl monomer as the component (b2) preferably has a secondary and / or tertiary amide group from the viewpoint of further improving the hydrogen bondability with other components.

  The mass ratio (b2) / (B) between the component (b2) and the component (B) is preferably 0.1 / 1 to 0.5 / 1, more preferably 0, from the viewpoint of polymerization stability. .2 / 1 to 0.4 / 1. In addition, the mass ratio (b2) / (A) between the component (b2) and the component (A) is preferably 0.1 / 1 to from the viewpoint of hydrogen bonding property and blending stability with the component (A). 1/1, more preferably 0.2 / 1 to 0.8 / 1.

  Next, as the emulsifier as the component (b3), for example, alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylenealkylsulfuric acid, polyoxyethylenealkylarylsulfuric acid, polyoxyethylene distyrylphenyl ether sulfonic acid, etc. Acidic emulsifiers, alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, ammonium salts of acidic emulsifiers and anionic surfactants such as fatty acid soaps; alkyltrimethylammonium bromide, alkylpyridinium bromide, imidazolinium laurate Quaternary ammonium salts such as quaternary ammonium salts, pyridinium salts, and imidazolinium salt type cationic surfactants; polyoxyethylene alkyl aryl ethers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene Carboxymethyl propylene block copolymers, and nonionic surfactants such as polyoxyethylene distyryl phenyl ether can be used. These may be used individually by 1 type, or may use 2 or more types together.

  As the component (b3), from the viewpoint of improving the water dispersion stability of the component (B) to be obtained and from the viewpoint of improving the long-term antifouling property of the resulting antireflection composite, a radical polymerizable double bond It is preferable to use a reactive emulsifier having More specifically, reactive emulsifiers include vinyl monomers having a sulfonic acid group or sulfonate group, vinyl monomers having a sulfate ester group, and alkali metal salts, ammonium salts, and nonions such as polyoxyethylene. A vinyl monomer having a group, a vinyl monomer having a quaternary ammonium salt, or the like can be used.

  As the vinyl monomer having a sulfonic acid group or a sulfonate group, for example, it has a radical polymerizable double bond, and a part thereof is substituted by a substituent such as an ammonium salt, a sodium salt or a potassium salt of the sulfonic acid group. Selected from the group consisting of substituted alkyl groups having 1 to 20 carbon atoms, alkyl ether groups having 2 to 4 carbon atoms, polyalkyl ether groups having 2 to 4 carbon atoms, phenyl groups, naphthyl groups, and succinic acid groups. A compound having a substituent; a vinyl sulfonate compound having a vinyl group to which a substituent is bonded, such as an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group, can be used.

  As the vinyl monomer having a sulfate ester group, for example, it has a radical polymerizable double bond and is partially substituted by a substituent such as an ammonium salt, sodium salt or potassium salt of the sulfate ester group. A compound having a substituent selected from the group consisting of 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 4 carbon atoms, a phenyl group, and a naphthyl group Is possible.

  As the compound having a succinic acid group partially substituted with a substituent such as ammonium salt, sodium salt or potassium salt of sulfonic acid group, specifically, allylsulfosuccinate can be used. More specifically, Eleminol JS-2 (trade name) (manufactured by Sanyo Chemical Co., Ltd.), Latemuru S-120, S-180A, and S-180 (trade name) (manufactured by Kao Corporation) are used. Is possible.

  In addition, as a compound having a C2-C4 alkyl ether group or a C2-C4 polyalkyl ether group partially substituted with a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group Specifically, Aqualon HS-10 or KH-1025 (trade name) (Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE-1025N or SR-1025 (trade name) (Asahi Denka Kogyo Co., Ltd.) Etc.) can be used.

  As the vinyl monomer having a nonionic group, specifically, 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.) and polyoxyethylene alkylpropenyl phenyl ether (trade names: Aqualon RN-10, RN-20, RN-30, RN) -50, etc. (Daiichi Pharmaceutical Co., Ltd.) can be used.

  In addition, the usage-amount of (b3) component from a viewpoint of superposition | polymerization stability, Preferably it is 10 mass parts or less with respect to 100 mass parts of (B) component, More preferably, it is 0.001-5 mass parts. .

  The component (B) of the antireflection coating composition according to the embodiment is obtained by polymerizing a polymerization stock solution containing the components (b1) to (b3) described above and water as the component (b4). Combined emulsion particles. In addition, the usage-amount of (b4) component becomes like this. Preferably it is 30-99.9 mass% as a content rate in a polymerization undiluted | stock solution from a viewpoint of polymerization stability. In addition to the components (b1) to (b4), various components can be further mixed into the polymerization stock solution. For example, the polymerization stock solution may be mixed with another vinyl monomer copolymerizable with the component (b2) as the component (b5). Viewpoints for controlling the properties (such as glass transition temperature, molecular weight, hydrogen bonding strength, polarity, dispersion stability, weather resistance, and compatibility of the hydrolyzable silicon compound (b1) with the polymerization product) Therefore, it is preferable to use the component (b5).

  As the component (b5), for example, acrylic ester, methacrylic ester, aromatic vinyl compound, vinyl cyanide, epoxy group-containing vinyl monomer, carbonyl group-containing vinyl monomer, anionic vinyl monomer A monomer containing a functional group such as a body can be used. The proportion of the component (b5) in the total vinyl monomer is preferably in the range of 0.001 to 30% by mass, more preferably in the range of 0.05 to 10% by mass. From the viewpoint of controlling the glass transition temperature, molecular weight, hydrogen bonding force, polarity, dispersion stability, weather resistance, compatibility with the polymerized product of the hydrolyzable silicon compound (b1), etc. It is preferable to do.

  Further, a chain transfer agent may be mixed in the polymerization stock solution. Examples of the chain transfer agent include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan; Thiocarboxylic acids or their salts or their alkyl esters, or polythiols, diisopropylxanthogen disulfide, di (methylenetrimethylolpropane) xanthogen disulfide and thioglycol, and allyl compounds such as α-methylstyrene dimers can be used. It is. The amount of the chain transfer agent used is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the total amount of all vinyl monomers from the viewpoint of polymerization stability. Part.

  Further, a dispersion stabilizer may be mixed in the polymerization stock solution. Examples of the dispersion stabilizer include various water-soluble oligomers selected from the group consisting of polycarboxylic acids and sulfonates, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid ( Salt), polyacrylamide, synthetic or natural water-soluble or water-dispersible water-soluble polymer substances such as water-soluble or water-dispersible acrylic resins can be used, and one or more of these can be used. Can be used. The amount of the dispersion stabilizer to be 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 emulsion particles (B).

  The polymerization of the polymerization stock solution is preferably carried out in the presence of a polymerization catalyst. Examples of the polymerization catalyst for component (b1) include hydrogen halides such as hydrochloric acid and hydrofluoric acid, carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid, sulfonic acids such as sulfuric acid and p-toluenesulfonic acid, Acid emulsifiers such as alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, polyoxyethylene distyryl phenyl ether sulfonic acid, acidic or weakly acidic inorganic salt, phthalic acid Acidic compounds such as sodium hydroxide, phosphoric acid and nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine, diazabicycloundecene, ethylene Basic compounds such as amines, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) -aminopropyltrimethoxysilane; such as dibutyltin octylate and dibutyltin dilaurate Tin compounds and the like can be used. Among them, as a polymerization catalyst for the hydrolyzable silicon compound (b1), acidic emulsifiers that act not only as a polymerization catalyst but also as an emulsifier, particularly alkylbenzene sulfonic acids having 5 to 30 carbon atoms (such as dodecylbenzene sulfonic acid) are used. preferable.

  As the polymerization catalyst for component (b2), a radical polymerization catalyst that undergoes radical decomposition by heat or a reducing substance to cause addition polymerization of a vinyl monomer is suitable. Water-soluble or oil-soluble persulfates, peroxides, azobis compounds and the like are preferably used. More specifically, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2- Azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like can be used.

  The amount of the polymerization catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total vinyl monomer. In the case where acceleration of the polymerization rate and polymerization at a low temperature such as 70 ° C. or lower are desired, for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, and Rongalite is combined with a radical polymerization catalyst. It is advantageous to use it.

  In the present embodiment, the polymerization of the component (b1) and the polymerization of the component (b2) can be carried out separately. Can be achieved.

  As a method for obtaining the component (B) of the antireflection coating composition according to the embodiment, the component (b1), the component (b2), and the component (b2) in the presence of a sufficient amount of water for the emulsifier to form micelles. So-called emulsion polymerization is preferred. As a method of emulsion polymerization, for example, (b1) component and (b2) component, and further, if necessary, (b3) component as it is or in an emulsified state, in a batch or divided or continuously in a reaction vessel. A method of polymerizing at a reaction temperature of about 30 to 150 ° C. by dropping into the inside and preferably in the presence of a polymerization catalyst, preferably from atmospheric pressure to a pressure of 10 MPa as necessary. In some cases, the polymerization may be carried out at a higher pressure or lower temperature. In addition, as a mixing | blending of superposition | polymerization undiluted | stock solution, from a viewpoint of superposition | polymerization stability, final solid content is 0.1-70 mass%, Preferably each of (b1)-(b4) is used as the range of 1-55 mass%. It is preferable to blend the components.

  Furthermore, when performing emulsion polymerization, it is preferable to use a seed polymerization method from the viewpoint of appropriately growing or controlling the particle diameter. The seed polymerization method is a method in which emulsion particles (seed particles) are previously present in an aqueous phase for polymerization. The pH in the polymerization system when performing the seed polymerization method is preferably 1.0 to 10.0, and more preferably 1.0 to 6.0. The pH during the polymerization can be adjusted using a disodium phosphate, borax, or a pH buffer such as sodium bicarbonate or ammonia.

  In addition, as a method for obtaining the component (B), in the presence of the component (b3) and the component (b4) necessary for polymerizing the component (b1), the component (b1) and the component (b2) It is also possible to use a technique in which water is added after the polymerization in the presence until the polymerization product becomes an emulsion.

  Furthermore, the component (B) includes a core layer and one or more shell layers covering the core layer from the viewpoint of improving the substrate adhesion of the coating film formed using the resulting coating composition. And having a core / shell structure. As a method for forming the core / shell structure, multistage emulsion polymerization in which emulsion polymerization is performed in multiple stages is useful.

  In the multi-stage emulsion polymerization, for example, in the presence of the component (b3) and the component (b4), at least one selected from the group consisting of the components (b1), (b2), and (b5) is polymerized to form seed particles. The second stage is carried out by adding a polymerization stock solution containing the components (b1) and (b2) and, if necessary, the component (b5) in the presence of seed particles. Stages are carried out (two-stage polymerization process). Furthermore, when implementing multistage emulsion polymerization of 3 steps | paragraphs or more, the 3rd step | paragraph which superposes | polymerizes by adding the polymerization stock solution containing (b1) component, (b2) component, and (b5) component as needed may be implemented. . Such a method is also suitable from the viewpoint of polymerization stability. From the viewpoint of polymerization stability, the mass ratio (b2) / (b1) between the component (b2) and the component (b1) in the core layer is preferably 0.01 / 1 to 1/1. In the outermost layer of the shell layer, the mass ratio (b2) / (b1) between the component (b2) and the component (b1) is preferably 0.1 / 1 to 5/1, more preferably 0.00. 5/1 to 4/1.

  In the two-stage polymerization method, the mass ratio of the solid content mass (M1) in the polymerization stock solution used in the first stage to the solid content mass (M2) in the polymerization stock solution added in the second stage is determined by the polymerization stability. In view of the above, preferably (M1) / (M2) = 9/1 to 1/9, more preferably 8/2 to 2/8.

  In addition, in the core / shell structure, from the viewpoint of polymerization stability, the particle size distribution of the seed particles (volume average particle size / number average particle size) did not change greatly, and the particle size increased by the second stage polymerization. It preferably has a structure. The volume average particle diameter can be measured in the same manner as the number average particle diameter. The core / shell structure can be observed by, for example, morphological observation with a transmission electron microscope or the like, analysis by viscoelasticity measurement, or the like.

  The glass transition temperature (Tg) of the core layer of the core / shell structure is preferably 0 ° C. or lower. In this case, as a physical property of the obtained coating composition for solar cells, it is possible to form a solar cell cover material that is excellent in flexibility at room temperature and hardly causes cracking. In addition, Tg in this Embodiment can be measured with a differential scanning calorimeter (DSC).

  The particle diameter of the component (B) of the antireflection coating composition according to the embodiment is, for example, 10 nm to 800 nm. By forming the composition by combining the component (B) having a particle size of 10 nm to 800 nm and the component (A) having a particle size of 1 nm to 400 nm, the weather resistance and antifouling properties are improved. In addition, from the viewpoint of antireflection properties of the obtained coating film, the particle size of the component (B) is preferably 120 nm to 450 nm. However, when it is desired to maintain the transparency of the coating film, a particle diameter of 120 nm or less may be used.

  The mass ratio (A) / (B) between the component (A) and the component (B) is preferably 50/100 to 450/100, more preferably 100/100 to 250/100. By mix | blending in this range, the antireflection composite excellent in antireflection and antifouling property can be formed from a coating composition. The ratio (SA) / (SB) of the surface area (SA) of the component (A) and the surface area (SB) of the component (B) is preferably in the range of 0.001 to 1000. The surface area can be calculated from the particle diameter of each of the component (A) and the component (B) and the blending mass number.

  In the coating composition of the present embodiment, additive components that are usually added to and blended with paints and molding resins, for example, light stabilizers, ultraviolet absorbers, thickeners, depending on the application and usage method. Leveling agent, thixotropic agent, antifoaming agent, freezing stabilizer, matting agent, crosslinking reaction catalyst, pigment, curing catalyst, crosslinking agent, filler, anti-skinning agent, dispersing agent, wetting agent, antioxidant, UV absorbers, rheology control agents, film-forming aids, rust inhibitors, dyes, plasticizers, lubricants, reducing agents, antiseptics, antifungal agents, deodorants, anti-yellowing agents, antistatic agents or electrification A regulator or the like can be selected or combined depending on the purpose.

  As the light stabilizer, for example, a hindered amine light stabilizer is preferably used. Among these, a radical polymerizable light stabilizer having a radical polymerizable double bond in the molecule is preferable. Moreover, as an ultraviolet absorber, an organic type ultraviolet absorber can be used, for example. As the organic ultraviolet absorber, for example, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, and a triazine ultraviolet absorber can be used. Among these, it is preferable to use a radical polymerizable ultraviolet absorber having a radical polymerizable double bond in the molecule. Also preferred are benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers, which have a high ultraviolet absorbing ability. In addition, it is preferable to use a light stabilizer together with an organic ultraviolet absorber. By using both in combination, the weather resistance of the resulting coating composition can be improved. In addition, various additive components such as these organic ultraviolet absorbers and light stabilizers may be simply blended with the component (A) and the component (B), or coexist when the component (B) is synthesized. May be.

Furthermore, the antireflection coating composition according to the present embodiment further comprises (C) component: a hydrolyzable silicon compound represented by the following formula (6), the following formula (7), or the following formula (8). May be included. In this case, the mass ratio between the component (A) and the component (B) is, for example, A / B = 150/100 to 450/100, and the mass ratio between the component (A) and the component (C) is C / A = 0.2 / 100 to 60/100. Hereinafter, the hydrolyzable silicon-containing compound represented by the following formula (6) is referred to as component (c1), and the hydrolyzable silicon-containing compound represented by the following formula (7) is referred to as component (c2).
R ¹ _n SiX _4-n (6)
(In the formula (6), R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group. In addition, a halogen group, a hydroxy group, a mercapto group, an amino group is further added to these substituents. May have a functional group such as a group, a (meth) acryloyl group, an epoxy group, etc. X represents a hydrolyzable group, n is an integer of 0 to 3. A hydrolyzable group has a hydroxyl group by hydrolysis. Any group may be used, and examples thereof include a halogen atom, an alkoxy group, an acyloxy group, an amino group, a phenoxy group, and an oxime group.
X ₃ Si—R ² _n —SiX ₃ (7)
(In the formula (7), X represents a hydrolyzable group, R ² represents an alkylene group having 1 to 6 carbon atoms or a phenylene group, and n is 0 or 1.)

  Specifically, as the component (c1) and the component (c2), tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, tetra (n-butoxy) silane, tetra (I-butoxy) silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyl Trimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, Rudiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (triphenoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ) Ethane, bis (triphenoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,3-bis (triphenoxysilyl) propane, 1,4 -Bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltri Ethoxysilane, 3 Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraacetoxysilane, tetrakis (trichloroacetoxy) silane, tetrakis (trifluoroacetoxy) silane, triacetoxysilane, tris (trichloroacetoxy) silane, Tris (trifluoroacetoxy) silane, methyltriacetoxysilane, methyltris (trichloroacetoxy) silane, tetrachlorosilane, tetrabromosila , Tetrafluorosilane, trichlorosilane, tribromosilane, trifluorosilane, methyltrichlorosilane, methyltribromosilane, methyltrifluorosilane, tetrakis (methylethylketoxime) silane, tris (methylethylketoxime) silane, methyltris (methylethylketoxime) Silane, phenyltris (methylethylketoxime) silane, bis (methylethylketoxime) silane, methylbis (methylethylketoxime) silane, hexamethyldisilazane, hexamethylcyclotrisilazane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethylsilane, Bis (dimethylamino) methylsilane, bis (diethylamino) methylsilane, or the like can be used.

Moreover, let the hydrolyzable silicon containing compound represented by following formula (8) be (c3) component. As the component (c3), specifically, a partial hydrolysis condensate of tetramethoxysilane (trade name “M silicate 51” manufactured by Tama Chemical Industry Co., Ltd., trade name “MSI51” manufactured by Colcoat Co., Ltd.), product Names “MS51” and “MS56” manufactured by Mitsubishi Chemical Corporation), partially hydrolyzed condensates of tetoethoxysilane (trade names “silicate 35” and “silicate 45” manufactured by Tama Chemical Industries, Ltd., trade name “ESI40” , "ESI48" manufactured by Colcoat Co., Ltd.), and a co-partial hydrolysis condensate of tetramethoxysilane and tetraethoxysilane (trade name "FR-3" manufactured by Tama Chemical Industry Co., Ltd., trade name "EMSi48" Colcoat ( Etc.) can be used.
R ³ — (O—Si (OR ³ ) ₂ ) _n —OR ³ (8)
(In the formula (8), R ³ is .n represents an alkyl group having 1 to 6 carbon atoms is an integer of 2-8.)

  The hydrolyzable silicon compound (C) can be used alone or as a mixture of two or more. Moreover, mass ratio of (A) component and (C) component is C / A = 0.2 / 100-60 / 100, Preferably it is C / A = 1 / 0.2-20 / 100. . When C / A is less than 0.2 / 100, the scratch resistance tends to be insufficient, and when C / A exceeds 60/100, the voids of the coating film are filled and the antireflection performance tends to be lowered. It is in.

  As a base material used in the present embodiment, glass, resin or the like is preferable. From the viewpoint of transparency, weather resistance, and weight reduction, at least one selected from the group consisting of glass, acrylic resin, polycarbonate resin, cyclic olefin resin, polyethylene terephthalate resin, and ethylene-fluoroethylene copolymer. A material or a composite material thereof is preferable. A weathering agent or the like may be further kneaded into the acrylic resin, polycarbonate resin, cyclic polyolefin resin, polyethylene terephthalate resin, or ethylene-fluoroethylene copolymer for the purpose of imparting weather resistance.

  The coating composition according to the present embodiment is not particularly limited, but may be prepared in a state of being dissolved or dispersed in a solvent such as water.

  The antireflection composite according to the present embodiment is applied, for example, by coating a coating composition (may be abbreviated as “water dispersion”) dispersed in a solvent such as water on a substrate, and drying. Formed. Here, as solid content concentration of an aqueous dispersion, Preferably it is 0.01-60 mass%, More preferably, it is 1-40 mass%. Further, the viscosity of the aqueous dispersion is preferably 0.1 to 100,000 mPa · s at 20 ° C., and preferably 1 to 10,000 mPa · s. Examples of coating methods that can be used include spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, and flexographic printing. It is. The composite is formed, for example, by drying the coating film on the substrate, and then performing heat treatment or ultraviolet irradiation at 20 ° C. to 500 ° C., more preferably 40 ° C. to 250 ° C., if desired. Also good.

  The thickness of a coating film becomes like this. Preferably it is 0.05-100 micrometers, More preferably, it is 0.1-10 micrometers. From the viewpoint of transparency, the coating film is preferably 100 μm or less, and preferably 0.05 μm or more in order to exhibit functions such as weather resistance and antifouling properties. In the present embodiment, the “coating film” is not necessarily a continuous film, and may be a discontinuous film, an island-shaped dispersion film, or the like.

  Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist. Various physical properties were evaluated by the following methods.

1. Number average particle diameter A sample was appropriately diluted by adding a solvent so that the solid content in the sample was 1 to 20% by mass, and measured using a wet particle size analyzer (Microtrac UPA-9230, manufactured by Nihon Koki Co., Ltd.).

2. Initial contact angle A drop of deionized water was placed on the anti-reflection composite (coating surface of the coating composition) and allowed to stand at 23 ° C. for 1 minute, and then contact angle measuring device (CA-X150 type contact, manufactured by Kyowa Interface Science, Japan) It was measured using a goniometer.

3. Initial haze Using a turbidimeter (Nippon Denshoku Industries Co., Ltd. NDH2000), the haze value of the coating film of the coating composition was measured according to JIS-K7105 (initial haze value).

4). Appearance of coating film The appearance of the antireflection composite (coating surface of the coating composition) was observed with a microscope (manufactured by Keyence Corporation) at a magnification of 100 times. The results were evaluated as follows. ○: There are almost no microcracks, △: There are many microcracks, ×: Film cannot be formed

5). Reflectivity The absolute reflectance of the antireflection composite was measured using a reflection spectral film thickness meter (FE3000 manufactured by Otsuka Electronics Co., Ltd.).

[Production example]
(Synthesis of polymer emulsion particles (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 3.7 g of dodecylbenzenesulfonic acid were added, and the temperature was heated to 80 ° C. with stirring. To this, a mixture of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane was added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was at 80 ° C. And stirring was continued for about 1 hour. Next, a mixed solution of 86 g of butyl acrylate, 133 g of phenyltrimethoxysilane, 1.3 g of 3-methacryloxypropyltrimethoxysilane, 137 g of diethylacrylamide, 3 g of acrylic acid, a reactive emulsifier (trade name “ADEKA rear soap SR-1025” Asahi Denka Co., Ltd., 25% solid content aqueous solution) 13 g, ammonium persulfate 2 mass% aqueous solution 40 g, and ion-exchanged water 1900 g mixed solution with the temperature in the reaction vessel kept at 80 ° C. for about 2 hours It was dripped at the same time. Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., then cooled to room temperature, filtered through a 100-mesh wire mesh, and the solid content was adjusted to 10.0% by mass with ion-exchanged water. A polymer emulsion particle (B-1) aqueous dispersion having a number average particle diameter of 130 nm was obtained.

(Synthesis of polymer emulsion particles (B-2) 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 4.6 g of dodecylbenzenesulfonic acid were added, and then the temperature was heated to 80 ° C. with stirring. To this, a mixture of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane was added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was at 80 ° C. And stirring was continued for about 1 hour. Next, a mixed solution of 86 g of butyl acrylate, 133 g of phenyltrimethoxysilane, 1.3 g of 3-methacryloxypropyltrimethoxysilane, 137 g of diethylacrylamide, 3 g of acrylic acid, a reactive emulsifier (trade name “ADEKA rear soap SR-1025” Asahi Denka Co., Ltd., 25% solid content aqueous solution) 13 g, ammonium persulfate 2 mass% aqueous solution 40 g, and ion-exchanged water 1900 g mixed solution with the temperature in the reaction vessel kept at 80 ° C. for about 2 hours It was dripped at the same time. Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., then cooled to room temperature, filtered through a 100-mesh wire mesh, and the solid content was adjusted to 10.0% by mass with ion-exchanged water. A polymer emulsion particle (B-2) aqueous dispersion having a number average particle diameter of 100 nm was obtained.

(Synthesis of polymer emulsion particles (B-3) 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 2.6 g of dodecylbenzenesulfonic acid were added, and then the temperature was heated to 80 ° C. with stirring. To this, a mixture of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane was added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was at 80 ° C. And stirring was continued for about 1 hour. Next, a mixed solution of 86 g of butyl acrylate, 133 g of phenyltrimethoxysilane, 1.3 g of 3-methacryloxypropyltrimethoxysilane, 137 g of diethylacrylamide, 3 g of acrylic acid, a reactive emulsifier (trade name “ADEKA rear soap SR-1025” Asahi Denka Co., Ltd., 25% solid content aqueous solution) 13 g, ammonium persulfate 2 mass% aqueous solution 40 g, and ion-exchanged water 1900 g mixed solution with the temperature in the reaction vessel kept at 80 ° C. for about 2 hours It was dripped at the same time. Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., then cooled to room temperature, filtered through a 100-mesh wire mesh, and the solid content was adjusted to 10.0% by mass with ion-exchanged water. A polymer emulsion particle (B-3) aqueous dispersion having a number average particle diameter of 180 nm was obtained.

[Examples 1 to 3, Comparative Examples 1 and 2]
A product obtained by dispersing a product name “Snowtex O” (component (A)) (manufactured by Nissan Chemical Industries, Ltd.) in water (solid content: 10% by mass, number average particle size: 10 nm) and a polymer obtained in Production Example The emulsion particles (B) and tetraethoxysilane (C) were blended as shown in Table 1 to obtain an antireflection coating composition. Next, the obtained coating composition was bar-coated on a 5 cm × 5 cm glass so as to have a film thickness of 1 μm, and then dried at 70 ° C. for 10 minutes to obtain an antireflection composite. These evaluation results are shown in Table 1. As shown in Table 1, the antireflection composites according to Examples 1 to 3 exhibited a lower reflectance than the comparative example.

  The antireflective composite using the coating composition of the present invention is excellent in antifouling property and antireflective property, and can be used as various displays and outdoor display boards with good visibility.

Claims (13)

The following components (A) and (B)
(A) component: a metal oxide having a particle diameter of 1 nm to 400 nm,
(B) component: polymer emulsion particles having a particle diameter of 10 nm to 800 nm,
An antireflective coating composition comprising:
The component (B) is the following components (b1) to (b4):
(B1) component: a hydrolyzable silicon compound;
(B2) component: a vinyl monomer containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an ether group;
(B3) component: an emulsifier,
(B4) component: water,
Polymer emulsion particles obtained by polymerizing a polymerization stock solution containing
The coating composition for antireflection whose mass ratio of (A) component and (B) component is A / B = 50 / 100-450 / 100.   The antireflection coating composition according to claim 1, wherein a mass ratio (b2) / (B) of the component (b2) to the component (B) is 0.1 / 1 to 0.5 / 1. object.   The antireflection coating composition according to claim 1 or 2, wherein a mass ratio (b2) / (A) between the component (b2) and the component (A) is 0.1 / 1 to 1/1. object.   4. The component (B) according to claim 1, wherein the component (B) has a core / shell structure including a core layer and one or more shell layers covering the core layer. 5. Anti-reflection coating composition.   In the core layer, the mass ratio (b2) / (b1) between the component (b2) and the component (b1) is 0.01 / 1 to 1/1, and in the outermost layer of the shell layer, The antireflection coating composition according to claim 4, wherein a mass ratio (b2) / (b1) between the component (b2) and the component (b1) is 0.1 / 1 to 5/1. The component (B) is obtained by polymerizing the polymerization stock solution in the presence of seed particles that form the core layer,
The seed particles are obtained by polymerizing at least one selected from the group consisting of the vinyl monomer copolymerizable with the component (b1), the component (b2), and the component (b2). Item 6. The antireflection coating composition according to Item 4 or 5.   The coating composition for antireflection according to any one of claims 1 to 6, wherein the component (b2) is a vinyl monomer having a secondary and / or tertiary amide group. The antireflection coating composition according to any one of claims 1 to 7, wherein the particle size of the component (B) is 120 to 450 nm. (C) Component: An antireflection coating composition further comprising a hydrolyzable silicon compound represented by the following formula (1), the following formula (2), or the following formula (3),
The mass ratio of the component (A) to the component (B) is A / B = 150/100 to 450/100,
The antireflection coating composition according to any one of claims 1 to 8, wherein a mass ratio of the component (A) to the component (C) is C / A = 0.2 / 100 to 60/100.
R ¹ _n SiX _4-n (1)
(In Formula 1, R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, or a substituent thereof, X represents a hydrolyzable group, and n represents 0 to 3 (It is an integer.)
X ₃ Si—R ² _n —SiX ₃ (2)
(In Formula 2, X represents a hydrolyzable group, R ² represents an alkylene group having 1 to 6 carbon atoms or a phenylene group, and n is 0 or 1.)
R ³ — (O—Si (OR ³ ) ₂ ) _n —OR ³ (3)
(In the formula 3, R ³ represents an alkyl group having 1 to 6 carbon atoms, n is an integer of 2-8.)   An antireflection composite formed from the antireflection coating composition according to any one of claims 1 to 9.   An antireflection composite comprising the antireflection coating composition according to any one of claims 1 to 9.   A display comprising the antireflection composite according to claim 10.   An exterior display member comprising the antireflection composite according to claim 10.