JP2020050808A - Coating composition - Google Patents

Abstract

To provide a coating composition having heat resistance and capable of suppressing cracks.SOLUTION: There is provided a coating composition containing (A) metal oxide having number average particle diameter of 1 nm to 400 nm, and (B) polymer particle water dispersion, in which the (B) component is a polymer particle water dispersion containing (b1) a hydrolyzable silicon compound, a polymer particle containing a polymer consisting of (b2) a vinyl monomer and (b3) an emulsifier, and (b4) water, (b1) contains (b1-1) a hydrolyzable silicon compound having a linear alkyl group having 3 to 16 carbon atoms and (b1-2) a hydrolyzable silicon compound having a methyl group, and a mass ratio of (b1-1) and (b1-2), (b1-1)/(b1-2) is in a range of 0.1 to 3.0.SELECTED DRAWING: None

Description

  The present invention relates to coating compositions.

  As a substitute for a glass plate, a resin molded body is widely used from the viewpoint of weight reduction and moldability. Specific applications of the resin molded body include, for example, a wide range of fields such as automobile parts, home electric parts, housings, containers, films, sheets and the like. In particular, transparent plastics are used, for example, for various windows, optical lenses, mirrors, glasses, goggles, sound insulation walls, lenses for traffic lights, headlight lenses, curved mirrors, windshields, nameplates, and the like. However, when a resin substrate such as a plastic substrate has a temperature / humidity chain with the outside air, the surface of the substrate may condense when one surface of the substrate becomes lower than the dew point temperature or when a sudden change in temperature / humidity occurs. In some cases, fine water droplets adhere to the surface and scatter transmitted light. In such a case, the transparency of the resin molded body is impaired, and so-called fogging occurs.

As a method for preventing this fogging, for example, the following proposals have been made.
(1) A method of producing a coating film of a water-absorbing compound on a substrate surface.
(2) A method of making the surface of a substrate hydrophilic by forming a coating film of a hydrophilic compound such as a surfactant on the surface of the substrate.

  Specifically, as the method (1), for example, in Patent Document 1, a water-absorbing crosslinked resin layer made of a cured epoxide resin or a urethane resin is provided, and the water-absorbing layer contains metal oxide fine particles. Fogging articles and the like have been proposed. Further, Patent Document 2 proposes an antifogging article provided with a water-absorbing layer containing a cured epoxy resin and a polyoxyethylene alkyl ether-based surfactant.

  As the method (2), for example, Patent Literature 3 and Patent Literature 4 disclose a hydrophilic and antifouling coating film characterized in that the coating film surface is made of colloidal silica. Specifically, an antifouling coating film containing polymer particles and colloidal silica is disclosed.

International Publication No. 2012/161330 International Publication No. 2015/008672 Patent No. 4812902 International Publication No. WO 2010/104146

  However, in the methods including Patent Literatures 1 and 2, although the anti-fogging property of the article can be maintained to a certain level, clouding occurs when water having a water absorbing ability or more agglomerates and adheres to the article. Therefore, there is an inconvenience that it is necessary to increase the film thickness in order to exhibit high antifogging durability.

  Further, in the method including Patent Literature 3, colloidal silica is unevenly distributed on the outermost surface of the coating film. Therefore, although the initial hydrophilicity and antifogging properties are excellent, under severe environments such as high temperature environment, when polymer particles are contained, the aqueous phase component bleeds out and the hydrophilicity tends to decrease significantly. There is. As a result, the antifogging property after the high temperature test, that is, the heat resistance tends to decrease. On the other hand, when the polymer particles are not used, only the inorganic components are present, and cracks are liable to occur and tend to come off.

  In view of the above prior art, an object to be solved by the present invention is to provide a coating composition having heat resistance and capable of suppressing cracks.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and repeated experiments. As a result, unexpectedly, (A) a metal oxide having a number average particle diameter of 1 to 400 nm and (B) an aqueous dispersion of polymer particles It has been found that the above problems can be solved by forming a coating composition containing a hydrolyzable silicon compound having a predetermined amount of a linear alkyl group in the component (B), and the present invention is completed. Reached.

That is, the present invention is as follows.
[1]
(A) a metal oxide having a number average particle diameter of 1 nm to 400 nm;
(B) an aqueous dispersion of polymer particles,
The component (B) includes:
An aqueous dispersion of polymer particles containing (b1) a polymer particle containing a polymer composed of a hydrolyzable silicon compound, (b2) a vinyl monomer and (b3) an emulsifier, and (b4) water,
(B1) includes (b1-1) a hydrolyzable silicon compound having a linear alkyl group having 3 to 16 carbon atoms and (b1-2) a hydrolyzable silicon compound having a methyl group,
A coating composition wherein the mass ratio (b1-1) / (b1-2) of (b1-1) and (b1-2) is in the range of 0.1 to 3.0.
[2]
The coating composition according to [1], wherein a mass ratio (A) / (B) of the component (A) (solid content) to the polymer particles in the component (B) is 0.5 to 3.0. .
[3]
The coating composition according to [1] or [2], wherein the component (B) has a number average particle size of 5 nm to 200 nm.
[4]
(1) or (2), wherein the component (b2) contains a vinyl monomer having 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. A coating composition as described.
[5]
The coating composition according to any one of [1] to [4], wherein the polymer particles in the component (B) have a core-shell structure.
[6]
[1] to [1], wherein the mass ratio (b1-1) / (b1-2) of (b1-1) and (b1-2) in the component (B) is in the range of 0.1 to 1.5. 5] The coating composition according to any one of the above.
[7]
The coating composition according to any one of [1] to [6], wherein (b1-1) is a hydrolyzable silicon compound having a linear alkyl group having 3 to 8 carbon atoms.
[8]
The coating composition according to any one of [1] to [7], wherein the component (b2) includes a vinyl monomer having a secondary amide group, a tertiary amide group, or both.
[9]
The coating composition according to any one of [1] to [7], wherein the component (A) is colloidal silica.
[10]
A laminate of a resin substrate and / or a glass substrate and the coating composition according to any one of [1] to [9].
[11]
The coating composition according to any one of [1] to [9], which is used as an antifogging coating film.

  According to the present invention, there is provided a coating composition having heat resistance and capable of suppressing cracks.

  Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The following embodiment is an exemplification for describing the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the invention.

  As used herein, “(meth) acryl” means “acryl” and its corresponding “methacryl”, “(meth) acrylate” means “acrylate” and its corresponding methacrylate, and “(meth) acryl”. ) "Acryloyl" means "acryloyl" and its corresponding methacryloyl.

<Coating composition>
The coating composition of the present embodiment,
(A) a metal oxide having a number average particle diameter of 1 nm to 400 nm;
(B) an aqueous dispersion of polymer particles,
The component (B) includes:
(B1) an aqueous dispersion of polymer particles containing a polymer particle comprising a polymer comprising a hydrolyzable silicon compound, (b2) a vinyl monomer and (b3) an emulsifier, and (b4) water;
(B1) includes (b1-1) a hydrolyzable silicon compound having a linear alkyl group having 3 to 16 carbon atoms and (b1-2) a hydrolyzable silicon compound having a methyl group,
The mass ratio (b1-1) / (b1-2) between (b1-1) and (b1-2) is in the range of 0.1 to 3.0.

  The coating composition of the present embodiment contains the component (A): a metal oxide having a number average particle diameter of 1 nm to 400 nm. Thereby, a coating film having high transparency and high hydrophilicity can be obtained. The component (A) is considered to act as a curing agent for the component (B) by interacting with the component (B) (however, the action is not limited to this). The interaction is not particularly limited. For example, a functional group (for example, a hydroxyl group) generally included in the component (A) and a functional group (for example, a hydroxyl group, a carboxyl group, an amide group, an amino group, A hydrogen bond with an ether group or the like, a chemical bond (for example, condensation) between the functional group generally contained in the component (A) and the component (B), and the like.

<(A) Metal oxide>
The particle diameter of the component (A) means a number average particle diameter (which may be a mixture of primary particles and secondary particles, or may be only one of primary particles and secondary particles). It is 1 nm to 400 nm, preferably 1 nm to 100 nm, more preferably 3 nm to 80 nm, and still more preferably 5 nm to 50 nm. By setting the number average particle diameter of the component (A) in the above range, it is possible to contribute to the optical properties and the like of the obtained coating film and laminate. In particular, setting the number average particle diameter to 100 nm or less can greatly improve the light transmittance of the obtained coating film or laminate. In the present embodiment, the number average particle size (hereinafter, may be simply abbreviated as “particle size”) is measured according to the method described in Examples below.

  The form of the component (A) is not particularly limited, and examples thereof include a powder, a dispersion, and a sol. The term "dispersion" or "sol" as used herein means that the component (A) is 0.01 to 80% by mass, preferably 0.1 to 50% by mass in water, a hydrophilic organic solvent or a mixed solvent thereof. At a concentration of at least one of primary particles and secondary particles. The hydrophilic organic solvent is not particularly limited, for example, ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol, alcohols such as methanol, acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone, tetrahydrofuran, Examples include ethers such as dioxane, amides such as dimethylacetamide and dimethylformamide, dimethylsulfoxide and nitrobenzene, and mixtures of two or more of these.

  The metal oxide used for the component (A) is not particularly limited, but includes, for example, silicon dioxide (silica), aluminum oxide (alumina), antimony oxide, titanium oxide, indium oxide, tin oxide, zirconium oxide, lead oxide, Examples include iron oxide, calcium silicate, magnesium oxide, niobium oxide, cerium oxide, and their composite oxides. Among them, from the viewpoint of the strength of interaction, silicon dioxide (silica), aluminum oxide (alumina), antimony oxide, And composite oxides thereof.

  In one embodiment, the component (A) is preferably colloidal silica from the viewpoint of handleability. Colloidal silica may be prepared by a sol-gel method, or a commercially available product may be used. When prepared by the sol-gel method, Werner Stover et al; Colloid and Interface Sci. , 26, 62-69 (1968), Rickey D. et al. Badley et al; Lang muir 6, 792-801 (1990), Journal of the Society of Color Materials, 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 number average particle size of the colloidal silica is 1 to 400 nm, preferably 1 to 100 nm, and more preferably 4 to 50 nm. When the number average particle diameter of the colloidal silica is 1 nm or more, the storage stability of the coating composition tends to be good. When the number average particle diameter of the colloidal silica is 400 nm or less, the transparency of the coating film obtained from the coating composition tends to be good.

  Colloidal silica having a number average particle size in the above range can be used in the form of an aqueous dispersion, whether acidic or basic. When the colloidal silica and the hydrophilic compound are immobilized via a non-covalent bond, the pH is preferably 10 or less because the non-covalent bond becomes strong. The acidic colloidal silica using water as a dispersion medium is not particularly limited, but, for example, as commercial products, Snowtex (registered trademark) -OXS, Snowtex-OS, Snowtex-O, Snowtex, manufactured by Nissan Chemical Industries, Ltd. -OL, Snowtex-OYL, Adelite (registered trademark) AT-20Q manufactured by Asahi Denka Kogyo KK, Clevosol (registered trademark) 20H12 manufactured by Clariant Japan KK, and Clevosol 30CAL25 can be used.

  Examples of the basic colloidal silica include, but are not particularly limited to, silica stabilized by addition of an alkali metal ion, an ammonium ion, and an amine. Although it does not specifically limit as a commercial item, For example, Snowtex-20, Snowtex-30, Snowtex-C, Snowtex-C30, Snowtex-CM40, Snowtex-N, Snowtex made by Nissan Chemical Industries, Ltd. -N30, Snowtex-K, Snowtex-XL, Snowtex-YL, Snowtex-ZL, Snowtex PS-M, Snowtex PS-L and the like 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, and Adelite AT-50 manufactured by Asahi Denka Kogyo KK Can also be used. Furthermore, Clariant Japan Co., Ltd. Crevosol 30R9, Crevosol 30R50, Crevosol 50R50 and the like, DuPont Ludox (registered trademark) HS-40, Ludox HS-30, Ludox LS, Ludox SM-30 and the like can also be used. is there.

  The colloidal silica using a water-soluble solvent as a dispersion medium is not particularly limited, and examples thereof include Nissan Chemical Industries, Ltd.'s MA-ST-M (methanol dispersion type having a number average particle diameter of 20 to 25 nm) and IPA. -ST (isopropyl alcohol dispersion type having a number average particle diameter of 10 to 15 nm), EG-ST (ethylene glycol dispersion type having a number average particle diameter of 10 to 15 nm), EG-ST-ZL (number average particle diameter of 70 to Ethylene glycol dispersion type of 100 nm), NPC-ST (ethylene glycol monopropyl ether dispersion type having a number average particle diameter of 10 to 15 nm) and the like can be used.

  In addition, these colloidal silicas may be used alone or in combination of two or more. Also, alumina and sodium aluminate may be contained as minor components. Further, the colloidal silica may contain an inorganic base (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia) or an organic base (such as tetramethylammonium) as a stabilizer.

<(B) Aqueous dispersion of polymer particles>
As described above, the component (B) includes, as described above, a polymer particle containing a polymer composed of the component (b1): a hydrolyzable silicon compound and the component (b2): a vinyl monomer, and the component (b3): an emulsifier. , (B4): an aqueous dispersion of polymer particles containing water. 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 complexed by hydrogen bonding or the like.

  In the coating composition of the present embodiment, (b1) contained in (B) includes (b1-1): a hydrolyzable silicon compound having a linear alkyl group having 3 to 16 carbon atoms, and (b1-). 2): It contains a hydrolyzable silicon compound having a methyl group, and the mass ratio (b1-1) / (b1-2) of (b1-1) and (b1-2) is 0.1 to 3.0. Within this range, heat resistance and cracks can be suppressed.

<(B1)>
The component (b1) is not particularly limited, and examples thereof include a compound represented by the following formula (I), a condensation product thereof, and a silane coupling agent.
SiWxRy (I)
Here, in the formula, W is 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, and an amide. Represents at least one group selected from the group consisting of groups; R represents 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 an alkyl group having 1 to 20 carbon atoms or 1 carbon atom. Represents at least one hydrocarbon group selected from the group consisting of an alkoxy group having from 20 to 20 or an aryl group having from 6 to 20 carbon atoms substituted with a halogen atom. x is an integer of 1 or more and 4 or less, and y is an integer of 0 or more and 3 or less. Also, x + y = 4.

  The silane coupling agent means a silane derivative in which a functional group reactive with an organic substance such as a vinyl polymerizable group, an epoxy group, an amino group, a methacryl group, a mercapto group, and an isocyanate group is present in the molecule.

  The compound represented by the formula (I) is not particularly limited, but specifically, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and the like Tetraalkoxysilanes; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxy Silane, 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- Hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyl Triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane, 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-ureidopro Trialkoxysilanes such as pilltrimethoxysilane and 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyl Diethoxysilane, diisopropyldimethoxysilane, 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- Dialkoxysilanes such as -cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane; trimethylmethoxysilane and trimethylethoxysilane Monoalkoxysilanes and the like can be used. These may be used alone or as a mixture of two or more.

  The component (b1-1) is a hydrolyzable silicon compound having a linear alkyl group having 3 to 16 carbon atoms, and a hydrolyzable silicon compound having a linear alkyl group having 3 to 8 carbon atoms. Preferably, there is.

  The component (b1-1) is not particularly limited, but may be, for example, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrisilane. Methoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-heptyltrimethoxysilane, n-heptyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxy Silane, n-octyltriethoxymethoxysilane, n-decyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-hexadecyltrimethoxysilane, n-hexadecyltriethoxysilane, 1,6-bis (Trimethoxysi Le) hexane, 1,8-bis (trimethoxysilyl) alkoxysilane Ruito octane can be used. These may be used alone or as a mixture of two or more.

Examples of the component (b1-2) include a compound represented by the formula (II).
SiW1W2W3CH ₃ (II)
Here, in the formula (II), W1, W2, and W3 are 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, It represents at least one group selected from the group consisting of an enoxy group, an aminoxy group and an amide group. W1, W2 and W3 may all be the same functional group or different functional groups.

  The mass ratio (b1-1) / (b1-2) of the component (b1-1) to the component (b1-2) is in the range of 0.1 to 3.0, and from the viewpoint of polymerization stability, Preferably it is 0.1-2.0, More preferably, it is 0.1-1.5.

  Further, the component (b1) may include a silicon alkoxide having a phenyl group (for example, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and the like). When a silicon alkoxide having a phenyl group is used, polymerization stability in the presence of water and an emulsifier becomes favorable, which is preferable. When a silicon alkoxide having a phenyl group is used as the component (b1), preferably 0.1 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, based on 100 parts by mass of the total amount of the component (b1). Parts are preferred. When it is in this range, the polymerization stability is sufficient, and the heat resistance of the obtained coating film is also good.

  As the component (b1), tetrafunctional silicon alkoxides (for example, tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, tetra (n-butoxy) silane, tetra (i -Butoxy) silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, and the like. When a tetrafunctional silicon alkoxide is used, the strength and antifouling property of the obtained coating film are preferably 0.1 to 10 parts by mass, more preferably 10 based on 100 parts by mass of the total amount of the component (b1). It is suitable.

  Further, the component (b1) may be used in combination with a silane coupling agent having a thiol group or a hydrolyzable silicon compound having a vinyl polymerizable group. When these are used, the long-term antifouling property of the obtained coating film becomes favorable, which is preferable. The silane coupling agent having a thiol group is not particularly limited, but for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like can be used.

  The component (b1) is not particularly limited, but may be, for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) attacryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyl. Dimethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and 2-trimethoxy A silane coupling agent having a vinyl polymerizable group such as silyl ethyl vinyl ether can be used.

  These silane coupling agents can form chemical bonds by copolymerization or chain transfer reaction with the component (b2) described below. For this reason, when a silane coupling agent having a vinyl polymerizable group or a thiol group is used by mixing or complexing with the above-mentioned component (b1), polymerization of the polymerization product of (b1) and the below-mentioned component (b2) The product can be complexed by chemical bonding. The “vinyl polymerizable group” is not particularly limited, but is, for example, a vinyl group, an allyl group or the like, and among them, a 3- (meth) acryloxypropyl group is preferable.

<(B2)>
The component (b2) is a vinyl monomer. The component (b2) preferably contains a vinyl monomer having 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. By including the vinyl monomer having such a functional group, a chemical bond (for example, condensation or the like) with a functional group of another component other than the component (B) (for example, the metal oxide or the like in the component (A)) can be obtained. It becomes easier and the interaction can be enhanced.

  Specific examples of the hydroxyl group-containing vinyl monomer mentioned as the component (b2) are not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) Various hydroxyalkyl (meth) acrylates such as acrylate; various hydroxyl-containing vinyl ethers such as 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether; various hydroxyl-containing allyl ethers such as 2-hydroxyethyl allyl ether Monoesters of polyoxyalkylene glycol obtained from various polyether polyols represented by polyethylene glycol and various unsaturated carboxylic acids represented by (meth) acrylic acid; Adducts of hydroxyl group-containing monomers with various lactones represented by ε-caprolactone; various epoxy group-containing unsaturated monomers represented by glycidyl (meth) acrylate and various adducts represented by acetic acid Adducts with acids; various unsaturated carboxylic acids typified by (meth) acrylic acid and various monocarboxylic acids other than epoxides of α-olefins typified by “Cardura E” (trade name of Shell Co., Netherlands) Adducts with epoxy compounds and the like can be mentioned.

  Specific examples of the carboxyl group-containing vinyl monomer mentioned as the component (b2) are not particularly limited. For example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid, or Various unsaturated carboxylic acids such as fumaric acid; esters of unsaturated carboxylic acids such as methyl (meth) acrylate and butyl (meth) acrylate with saturated monohydric alcohols; monomethyl itaconate, monoitaconate Monoesters (half esters) of unsaturated dicarboxylic acids such as n-butyl, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate and mono-n-butyl fumarate with saturated monohydric alcohols ); Various saturated dicals such as monovinyl adipate or monovinyl succinate Monovinyl esters of acid; various saturated polycarboxylic acid anhydrides such as succinic anhydride, glutaric anhydride, phthalic anhydride or trimellitic anhydride, and the above-mentioned various hydroxyl-containing vinyl monomers. Addition products of the following: monomers obtained by the addition reaction of the above-mentioned various carboxyl group-containing monomers with lactones; hydrolyzable silicon compounds such as 3-methacryloxypropyltrimethoxysilane, etc. Is mentioned.

  Specific examples of the amino group-containing vinyl monomer mentioned as the component (b2) are not particularly limited. For example, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n Various tertiary aminos such as -propylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate or N- [2- (meth) acryloyloxy] ethylmorpholine Group-containing (meth) acrylic esters; various tertiary amino group-containing aromatic vinyl monomers such as vinylpyridine, N-vinylcarbazole, and N-vinylquinoline; N- (2-dimethylamino) ethyl (Meth) acrylamide, N- (2-diethylamino) ethyl (meth) a Lilamide, N- (2-di-n-propylamino) ethyl (meth) acrylamide, N- (3-dimethylamino) propyl (meth) acrylamide, N- (4-dimethylamino) butyl (meth) acrylamide or N- [2- (meth) acrylamide] Various tertiary amino group-containing (meth) acrylamides such as ethylmorpholine; N- (2-dimethylamino) ethylcrotonamide, N- (2-diethylamino) ethylcrotonamide Tertiary such as N- (2-di-n-propylamino) ethylcrotonamide, N- (3-dimethylamino) propylcrotonamide or N- (4-dimethylamino) butylcrotonamide Amino group-containing crotonamides; 2-dimethylaminoethyl vinyl ether, 2-die Le aminoethyl vinyl ether, 3-dimethylaminopropyl vinyl ether or various tertiary amino group-containing vinyl ethers such as 4-dimethylaminopyridine butyl vinyl ether.

  Specific examples of the ether group-containing vinyl monomer mentioned as the component (b2) are not particularly limited, but include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, and polyoxyethylene-poly. Examples include vinyl monomers such as vinyl ethers, allyl ethers, and (meth) acrylic esters having various polyether chains in side chains, such as oxypropylene block copolymers. As the ether group-containing vinyl monomer, a commercially available product may be used. For example, Blemmer PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, AE-350 (all of which are Nippon Oil & Fats) MA-30, MA-50, MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114, MPG130-MA (all Japan) Emulsifier, trade name). Here, the number of oxyethylene units in the polyoxyethylene chain is preferably 2 to 30. When the number of oxyethylene units in the polyoxyethylene chain is 2 or more, the flexibility of the coating film tends to be good, and when it is 30 or less, the coating film does not become too soft and tends to have excellent blocking resistance. .

  Specific examples of the amide group-containing vinyl monomer mentioned as the component (b2) are not particularly limited, and examples thereof include N-alkyl or N-alkylene-substituted (meth) acrylamide. More specifically, although not particularly limited, for example, 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-NN-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N- Acryloylhexahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N, N′-methylenebisacrylamide, N, N′-methylenebismethacrylamide, N-vinylacetamide, Examples include diacetone acrylamide, diacetone methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and the like.

  The component (b2) is preferably a vinyl monomer having a secondary amide group, a tertiary amide group, or both, from the viewpoint of further improving the hydrogen bonding with other components. Particularly, a vinyl monomer having a tertiary amide group is preferable from the viewpoint of hydrogen bonding power.

  The mass ratio of the content of the component (b2) to the component (B) ((b2) / (B)) is preferably from 0.005 / 1 to 0.2 / 1, and more preferably from the viewpoint of polymerization stability. 0.01 / 1 to 0.05 / 1.

<(B3)>
The component (b3) is not particularly limited. For example, acidic components such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylenealkylsulfuric acid, polyoxyethylenealkylarylsulfuric acid, and polyoxyethylenedistyrylphenylethersulfonic acid. Anionic surfactants such as emulsifiers, alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, ammonium salts of acidic emulsifiers, and anionic surfactants such as fatty acid soaps; Grade ammonium salt, pyridinium salt, imidazolinium salt type cationic surfactant; polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxy B propylene block copolymer, nonionic surface active agent polyoxyethylene distyryl phenyl ether, and the like. These may be used alone or in combination of two or more.

  As the component (b3), a reaction having a radically polymerizable double bond from the viewpoint of improving the aqueous dispersion stability of the obtained component (B) and improving the long-term antifouling property of the obtained coating film. It is preferable to use an acidic emulsifier. The reactive emulsifier is not particularly limited, but includes, for example, a vinyl monomer having a sulfonic acid group or a sulfonate group, a vinyl monomer having a sulfate group, and an alkali metal salt, an ammonium salt, a polyoxyethylene and the like thereof. And a vinyl monomer having a quaternary ammonium salt.

  The vinyl monomer having a sulfonic acid group or a sulfonate group includes, for example, a radically 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 a sulfonic acid group. Substituted alkyl group having 1 to 20 carbon atoms, alkyl ether group having 2 to 4 carbon atoms, polyalkyl ether group having 2 to 4 carbon atoms, phenyl group, naphthyl group, and succinic acid group Compounds having a group; vinyl sulfonate compounds 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.

  As the vinyl monomer having a sulfate group, for example, having a radical polymerizable double bond, and partially substituted with a substituent such as an ammonium salt, a sodium salt or a potassium salt of the sulfate group, Examples include compounds 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. Can be

  Specific examples of the compound having a succinic acid group partially substituted with a substituent such as an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group include allyl sulfosuccinate. More specifically, for example, Eleminor JS-2 (trade name, manufactured by Sanyo Kasei Co., Ltd.), Latemul S-120, S-180A or S-180 (trade name, manufactured by Kao Corporation) are exemplified.

  Specific examples of a compound having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms, which is partially substituted with a substituent such as an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group Examples include Aqualon HS-10 or KH-1025 (Daiichi Kogyo Seiyaku Co., Ltd., trade name), Adecaria Soap SE-1025N or SR-1025 (Asahi Denka Kogyo Co., Ltd., trade name), and the like.

  Specific examples of the vinyl monomer having a nonionic group include, for example, α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (trade name: Adecaria soap NE) -20, NE-30, NE-40, etc., manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene alkylpropenyl phenyl ether (trade name: Aqualon RN-10, RN-20, RN-30, RN-50, etc.) Manufactured by Pharmaceutical Industries, Ltd.).

  The content of the component (b3) is preferably 10 parts by mass or less, more preferably 0.001 to 5 parts by mass, based on 100 parts by mass of the component (B), from the viewpoint of polymerization stability.

  The component (B) is, for example, a component (b1), a component (b2) and a component (b3) in a polymerization stock solution containing the components (b1) to (b3) and the component (b4) (that is, water). It is preferably an aqueous dispersion of polymer particles obtained by polymerizing the components. The content of the component (b4) is preferably 30 to 99.9% by mass as the content in the polymerization stock solution from the viewpoint of polymerization stability.

  In the polymerization stock solution, various components can be further mixed in addition to the components (b1) to (b4). First, it is preferable to further mix (b5) component: another vinyl monomer copolymerizable with the (b2) component in the polymerization stock solution. The use of such a component (b5) can reduce the properties of the resulting polymerization product (glass transition temperature, molecular weight, hydrogen bonding strength, polarity, dispersion stability, weather resistance, hydrolyzable silicon compound as the component (b1)). From the viewpoint of controlling the compatibility with the polymerization product of the present invention).

  The component (b5) is not particularly restricted but includes, for example, acrylates, methacrylates, aromatic vinyl compounds, vinyl cyanides, epoxy group-containing vinyl monomers, carbonyl group-containing vinyl monomers, anions Monomers containing a functional group such as a type vinyl monomer are exemplified.

  The proportion of the component (b5) in the total vinyl monomer is preferably from 0.001 to 30% by mass, and more preferably from 0.05 to 10% by mass. The use of the component (b5) in this range means that the glass transition temperature, the molecular weight, the hydrogen bonding strength, the polarity, the dispersion stability, the weather resistance, the compatibility with the polymerization product of the hydrolyzable silicon compound as the component (b1). It is preferable from the viewpoint of controlling the above.

  A chain transfer agent can be mixed with the polymerization stock solution. Examples of the chain transfer agent include, but are not particularly limited to, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan; and thiomalic acid. Such thiocarboxylic acids or salts thereof or alkyl esters thereof, or polythiols, diisopropylxanthogen disulfide, di (methylenetrimethylolpropane) xanthogen disulfide and allyl compounds such as dimers of thioglycol and α-methylstyrene. .

  The use amount of these chain transfer agents is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the total amount of all vinyl monomers. It is preferable to use a chain transfer agent in this range from the viewpoint of polymerization stability.

  Further, a dispersion stabilizer may be mixed with the polymerization stock solution. The dispersion stabilizer is not particularly limited, for example, various water-soluble oligomers selected from the group consisting of polycarboxylic acids and sulfonates, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, maleated alkyd resin Various synthetic or natural water-soluble or water-dispersible water-soluble polymer substances such as polyacrylic acid (salt), polyacrylamide, and water-soluble or water-dispersible acrylic resin can be used. Further, one or a mixture of two or more of these can be used. The amount of the dispersion stabilizer used in the polymerization stock solution is preferably 10 parts by mass or less, more preferably 0.001 to 5 parts by mass, based on 100 parts by mass of the polymer particles (B).

  The polymerization of the polymerization solution is preferably carried out in the presence of a polymerization catalyst. The polymerization catalyst of the component (b1) is not particularly limited, but examples thereof include hydrogen halides such as hydrochloric acid and hydrofluoric acid, carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid, and lactic acid, sulfuric acid, and p-toluenesulfonic acid. Acidic emulsifiers such as sulfonic acids, such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylenealkylsulfuric acid, polyoxyethylenealkylarylsulfuric acid, and polyoxyethylene distyrylphenyl ether sulfonic acid; Acidic compounds such as inorganic salts, phthalic acid, phosphoric acid, and nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine, diazabicyclo Basic compounds such as ndecene, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) -aminopropyltrimethoxysilane; dibutyltin octylate, and dibutyltin dilaurate Such tin compounds and the like can be used. Above all, as the polymerization catalyst for the hydrolyzable silicon compound (b1), acidic emulsifiers which act not only as a polymerization catalyst but also as an emulsifier, particularly alkylbenzenesulfonic acids having 5 to 30 carbon atoms (such as dodecylbenzenesulfonic acid) are preferable. .

  Further, as the polymerization catalyst of the component (b2), a radical polymerization catalyst which causes radical decomposition by heat or a reducing substance to cause addition polymerization of a vinyl monomer is preferable. Water-soluble or oil-soluble persulfates, peroxides, azobis compounds and the like are preferably used. More specifically, although not particularly limited, for example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyi Ronitrile, 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 in the polymerization stock solution is preferably 0.001 to 5 parts by mass based on 100 parts by mass of all vinyl monomers. In addition, if it is desired to accelerate the polymerization rate, and polymerization at a low temperature such as 70 ° C. or lower, 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.

  In one embodiment, the polymerization of the component (b1) and the polymerization of the component (b2) can be carried out separately. However, if they are carried out simultaneously, micro-organic-inorganic composite formation due to hydrogen bonding or the like may occur. It is preferable because it can be achieved.

  As a method for obtaining the component (B), a so-called emulsion polymerization in which the component (b1) and the component (b2) are polymerized in the presence of water in an amount sufficient for the emulsifier to form micelles is suitable. As the method of emulsion polymerization, for example, the component (b1) and the component (b2), and if necessary, the component (b3) as they are, or in an emulsified state, in a lump or divided manner, or continuously in a reaction vessel And polymerization at a reaction temperature of about 30 to 150 ° C. in the presence of a polymerization catalyst, preferably at a pressure from atmospheric pressure to 10 MPa if necessary. However, if necessary, the polymerization may be carried out at a higher pressure or at a lower temperature.

The components of (b1) to (b4) are mixed so that the total solid content is in the range of 0.1 to 70% by mass, preferably 1 to 55% by mass, from the viewpoint of polymerization stability. It is preferable to mix them. The total solid content mass (% by mass) can be determined based on the following formula (III), by determining the dry mass obtained by placing the component (B) in an oven heated to 100 ° C. for 2 hours and drying.
Total solid content mass (mass%) = dry mass / mass of component (B) × 100 (III)

  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 preliminarily present in an aqueous phase and polymerized. The pH in the polymerization system at the time of performing the seed polymerization method is preferably from 1.0 to 10.0, and more preferably from 1.0 to 6.0. The pH during the polymerization can be adjusted using a pH buffer such as disodium phosphate or borax, or sodium hydrogen carbonate or ammonia.

  As a method for obtaining the component (B), the components (b3) and (b2) are added in the presence of the components (b3) and (b4) necessary for polymerizing the component (b1), After polymerization, a method of adding water until the polymerization product becomes an emulsion can also be applied.

  The polymer particles in the component (B) have a core-shell structure including a core layer and one or more shell layers covering the core layer, from the viewpoint of improving the adhesion of the obtained coating film to the base material. It is preferable to have As a method for forming the core-shell structure, multi-stage emulsion polymerization in which emulsion polymerization is performed in multiple stages is very useful. 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 component (B) is preferably polymer particles obtained by polymerizing the component (b1) and the component (b2) in the polymerization stock solution containing the seed particles forming the core layer, and The particles comprise the component (b1), the component (b2), and the component (b5) (at least one or more components selected from the group consisting of other vinyl monomers copolymerizable with the component (b2)). More preferably, the particles are obtained by polymerization. Also in this case, multi-stage emulsion polymerization is useful.

  Specifically, the multi-stage emulsion polymerization is, for example, at least one selected from the group consisting of the component (b1), the component (b2) and the component (b5) in the presence of the component (b3) and the component (b4) as the first step. One or more components are polymerized to form seed particles, and as a second step, a polymerization stock solution containing the components (b1) and (b2) and optionally the component (b5) in the presence of the seed particles. Is added to perform polymerization (two-stage polymerization method). When multistage emulsion polymerization of three or more stages is carried out, for example, as the third stage, polymerization may be carried out by further adding a polymerization stock solution containing the components (b1) and (b2) and, if necessary, the component (b5). it can. Such a method is suitable also from the viewpoint of polymerization stability.

  When the two-stage polymerization method is employed, the mass ratio of the solid content mass (M1) in the polymerization stock solution used in the first step to the solid content mass (M2) in the polymerization stock solution added in the second stage (M2) (M1) / (M2)) is preferably 9/1 to 1/9, more preferably 8/2 to 2/8, from the viewpoint of polymerization stability.

  Further, as the core-shell structure, from the viewpoint of polymerization stability, the particle diameter was increased by the second-stage polymerization without significantly changing the particle diameter distribution (volume average particle diameter / number average particle diameter) of the seed particles. It preferably has a structure. The volume average particle diameter can be measured in the same manner as the number average particle diameter. Further, the core-shell structure can be observed by, for example, morphological observation with a transmission electron microscope or the like or analysis by viscoelasticity measurement.

  The glass transition temperature (Tg) of the core layer having the core-shell structure is preferably 0 ° C. or lower. In this case, since a coating film having more excellent flexibility at room temperature can be obtained, it is possible to form a protective member for a solar cell in which cracks and the like hardly occur, which is preferable. In this embodiment, Tg can be measured by a differential scanning calorimeter (DSC).

  In one embodiment, the number average particle diameter of the component (B) contained in the coating composition (and the coating film formed therefrom) is preferably, for example, 10 nm to 800 nm. By forming a coating composition by combining the component (B) having a number average particle diameter of 10 nm to 800 nm and the component (A) containing a metal oxide having a number average particle diameter of 1 nm to 400 nm, a coating film obtained is obtained. Good weather resistance and stain resistance. Further, from the viewpoint of the optical properties and hard coat properties of the obtained coating film, the number average particle diameter of the component (B) is preferably from 20 nm to 250 nm, more preferably from 5 nm to 200 nm. As the method for measuring the number average particle diameter of the component (B), the same method as the method for measuring the number average particle diameter of the metal oxide in the component (A) can be employed.

  The ratio ((SA) / (SB)) of the surface area (SA) of the metal oxide in the component (A) to the surface area (SB) of the polymer particles in the component (B) is preferably in the range of 0.001 to 1000. It is. The surface area of each component can be calculated from the particle diameter, the mass, and the specific gravity of each of the components (A) and (B), assuming that the shape of the particles is a true sphere.

<(C) Hydrolyzable silicon compound>
The coating composition of the present embodiment preferably further contains a hydrolyzable silicon compound as the component (C) for the purpose of improving the strength and antifouling properties of the obtained coating film. The hydrolyzable silicon-containing compound used as the component (C) is not particularly limited. For example, the hydrolyzable silicon-containing compound (c1) represented by the following formula (IV) and the hydrolyzable silicon-containing compound represented by the following formula (V) One or more selected from the group consisting of a hydrolyzable silicon-containing compound (c2) and a hydrolyzable silicon compound (c3) represented by the following formula (VI) can be used.
R1 _n SiX _4-n (IV)
Here, in the formula (IV), R1 is a hydrogen atom, or a halogen atom, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group or an epoxy group, which may have 1 to 10 carbon atoms. Represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group. X represents a hydrolyzable group, and n is an integer of 0 to 3. The hydrolyzable group is not particularly limited as long as the group generates a hydroxyl group by hydrolysis, 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-R2 n -SiX 3} (V)
Here, in the formula (V), X represents a hydrolyzable group, and R2 represents an alkylene group having 1 to 6 carbon atoms or a phenylene group. n is 0 or 1.
R3- (O-Si (OR3) ₂ ) _n- OR3 (VI)
Here, in the formula (VI), R3 represents an alkyl group having 1 to 6 carbon atoms. n is an integer of 2 to 8.

  Although it does not specifically limit as a component (c1) and a component (c2) specifically, For example, 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, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane Methyldimethoxysilane, methyldiethoxysilane, 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-hydroxyp Pilltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraacetoxysilane, tetrakis (trichloroacetoxy) silane, tetrakis (trifluoroacetoxy) silane, triacetoxysilane, Tris (trichloroacetoxy) silane, tris (trifluoroacetoxy) silane, methyltriacetoxysilane, methyltris (trichloroacetoxy) silane, tetrac Lorosilane, tetrabromosilane, 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 and the like can be used.

  The component (c3) is not specifically limited. For example, a partially hydrolyzed condensate of tetramethoxysilane (trade name “M silicate 51” manufactured by Tama Chemical Industry Co., Ltd., trade name “MSI51”) "Colcoat Co., Ltd.), trade names" MS51 "," MS56 "manufactured by Mitsubishi Chemical Corporation), partially hydrolyzed condensates of tetraethoxysilane (trade names" silicate 35 "," silicate 45 "Tama Chemical Industries, Ltd.) Co., Ltd., trade names "ESI40" and "ESI48" manufactured by Colcoat Co., Ltd.) and co-partially hydrolyzed condensate of tetramethoxysilane and tetraethoxysilane (trade name "FR-3" Tama Chemical Industry Co., Ltd.) And "EMSi48" (trade name, manufactured by Colcoat Co., Ltd.).

  The hydrolyzable silicon compound (C) may be used alone or as a mixture of two or more. The mass ratio of the component (A) to the component (C) in the coating composition is (C) / (A) = 5/100 to 90/100, and preferably (C) / (A) = 5. / 100 to 70/100. When (C) / (A) is 5/100 or more, the scratch resistance of the formed coating film can be made sufficient, and (C) / (A) is 90/100 or less. Thereby, the strength of the coating film is appropriately maintained, and good hard coat performance is obtained.

  The mass ratio of the component (b2) to the component (A) ((b2) / (A)) is preferably 0.01 / 1 to 1/1, from the viewpoint of increasing the hydrogen bonding force with the metal oxide. 1, more preferably 0.05 / 1 to 0.8 / 1, and still more preferably 0.1 / 1 to 0.4 / 1.

  The mass ratio ((A) / (B)) of the component (A) (solid content) to the polymer particles in the component (B) is preferably from 0.5 to 4 from the viewpoint of hydrophilicity and film-forming properties. 0.8, more preferably 1.1 to 4.8, still more preferably 1.1 to 3.0, and still more preferably 1.5 to 2.5. By setting the mass ratio ((A) / (B)) to such a ratio, the antifouling property, transparency, and hydrophilicity can be further improved, and at the same time, impact resistance and durability, high temperature, high humidity, Alternatively, the hydrophilicity of the coating film surface under high temperature and high humidity can be made excellent.

<Other optional ingredients>
The coating composition of the present embodiment may contain, in addition to the above components, additive components that are usually added to and blended with paints and molding resins, depending on the use and the method of use. The additive component is not particularly limited, but includes, for example, a surfactant, a light stabilizer, an ultraviolet absorber, a thickener, a leveling agent, a thixotropic agent, an antifoaming agent, a freeze stabilizer, a matting agent, and a crosslinking reaction catalyst. , Pigments, curing catalysts, crosslinkers, fillers, anti-skinning agents, dispersants, wetting agents, antioxidants, ultraviolet absorbers, rheology control agents, film forming aids, rust inhibitors, dyes, plasticizers, lubrication Agents, reducing agents, preservatives, fungicides, deodorants, anti-yellowing agents, antistatic agents or charge control agents can be selected or combined according to the respective purposes, and can be blended. it can.

  Examples of the surfactant include, but are not particularly limited to, anionic surfactants such as alkylbenzenesulfonic acid, sodium fatty acid, alkyl sulfate, alkyl polyoxyethylene sulfate, and alkyl phosphate, alkyltrimethylammonium salt, and dialkyldimethyl. Cationic surfactants such as ammonium salt, alkylbenzyldimethylammonium salt, alkylpyridinium chloride, benzalkonium chloride, polyoxyethylene-polyoxypropylene condensate, polyoxyethylene alkyl ether, alkyl polyglucoside, alkyl monoglyceryl ether , Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, diethanolamide laurate, diethanolamide oleate, diethanol stearate Nonionic surfactants such as amide, glycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylphenyl ether, betaine lauryldialkylaminoacetate, betaine stearyldialkylaminoacetate, dodecylaminomethyldialkylsulfopropylbetaine, hexadecylaminomethyl Dialkylsulfopropylbetaine, octadecylaminomethyldialkylsulfopropylbetaine, cocamidopropylbetaine, cocamidopropylhydroxysultaine, alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, sodium lauroylglutamate, potassium lauroylglutamate, lauroyl Methyl-β-alanine, lauryldimethylamine N-oxide, oleyldimethyl Zwitterionic surfactants such as amine N-oxide and the like can be mentioned. By using these together with a hydrophilic compound, the hydrophilicity, antifogging property and water resistance of the obtained coating film are further improved. In the case where a surfactant having a long-chain alkyl group having 10 or more carbon atoms and / or a surfactant having a fluorine atom in a molecule is used among these surfactants, Since elution into water tends to be suppressed, it is more preferable from the viewpoint of water resistance.

  The crosslinking reaction catalyst and / or curing catalyst is not particularly limited. For example, dialkyltin dicarboxylates such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, tin oxide compounds such as dibutyltin oxide, and 2-ethylhexanoic acid Metal carboxylate such as tin, zinc 2-ethylhexanoate, cobalt salt, etc., triethylamine, pyridine, methylpyridine, benzyldimethylamine, N, N-dimethylcyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N, N ' Tertiary amines such as -endethylenepiperazine and N, N'-dimethylpiperazine;

As the light stabilizer, for example, a hindered amine light stabilizer is preferably used. Among them, a radical polymerizable light stabilizer having a radical polymerizable double bond in the molecule is preferable. The ultraviolet absorber is not particularly limited, and examples thereof include an organic ultraviolet absorber. Such organic UV absorbers are not particularly limited, and include, for example, benzophenone UV absorbers, benzotriazole UV absorbers, and triazine UV absorbers. Among these, it is preferable to use a radical polymerizable ultraviolet absorber having a radical polymerizable double bond in the molecule. Further, a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber having high ultraviolet absorbing ability are preferable.
The light stabilizer is preferably used in combination with an organic ultraviolet absorber. Using both of them can contribute to improving the weather resistance of the resulting coating film. Further, these organic ultraviolet absorbers, light stabilizers, and various additive components can be simply blended with the components (A) and (B), or when the component (B) is synthesized. They can coexist.

<Laminate>
The laminate of the present embodiment is a laminate of a resin substrate and / or a glass substrate and the above-described coating composition.

<Substrate>
The substrate is positioned as an object to which particularly excellent antifogging property and antifogging durability are provided by the coating layer. Various materials can be employed as the substrate. In one embodiment, the substrate is preferably made of resin. The resin base material (resin base material) is not particularly limited, and examples thereof include organic base materials such as synthetic resins and natural resins.

  As the synthetic resin, a thermoplastic resin and a curable resin (a thermosetting resin, a photocurable resin, a moisture-curable resin, and the like) can be used. More specifically, for example, silicone resin, acrylic resin, methacrylic resin, fluororesin, alkyd resin, aminoalkyd resin, vinyl resin, polyester resin, styrene-butadiene resin, polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, polycarbonate Resin, polyacetal resin, polyether ether ketone resin, polyphenylene oxide resin, polysulfone resin, polyphenylene sulfone resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, phenol resin, melamine resin, epoxy resin, urethane Resin, silicone-acrylic resin and the like can be mentioned. However, it is not limited to the above.

  Examples of the natural resin include, but are not limited to, cellulosic resins, isoprene-based resins such as natural rubber, and protein-based resins such as casein.

  In one embodiment, the surface of the resin substrate may be subjected to a surface treatment such as a corona discharge treatment, a flame treatment, and a plasma treatment, but these surface treatments are not essential.

  The type and thickness of the base material used and the thickness of the film formed by the surface treatment are not particularly limited, and can be appropriately set according to the application.

<Production of coating composition>
In a typical embodiment, the coating composition according to the present invention comprises a step of previously mixing the component (A) and the component (B), followed by mixing with water, and stirring at a temperature lower than 40 ° C. for 10 minutes or more. It can be manufactured by a method including: Generally, when producing a coating composition containing water, a method of mixing each component contained in the coating composition after dilution with water, a method of mixing each component in water, and a method of mixing each component in advance And a method of diluting with water. In the present embodiment, it is preferable to mix the component (A) and the component (B) in advance. By mixing in advance, the component (A) and the component (B) can firmly form an interaction. A coating film obtained from the coating composition thus prepared is preferable because of its excellent water resistance. Further, by stirring at less than 40 ° C. for 10 minutes or more, a coating composition in which the component (A) and the component (B) are uniformly dispersed can be formed. A coating film obtained from the coating composition thus prepared is preferable because of its high transparency and excellent appearance.

  The coating composition of the present embodiment is preferably used as an antifogging coating film because of its excellent antifogging property.

  The laminate according to the present embodiment is formed by, for example, applying a coating composition (may be abbreviated as “aqueous dispersion”) dispersed in a solvent such as water to a base material and drying the coating composition. Is done. Here, the solid content concentration of the aqueous dispersion is preferably 0.01 to 60% by mass, and more preferably 1 to 40% by mass. The viscosity of the aqueous dispersion is preferably from 0.1 to 100,000 mPa · s at 20 ° C., and more preferably from 1 to 10,000 mPa · s. The coating method is not particularly limited, but includes, 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 screen printing method, a casting method, a gravure printing method, and flexographic printing. The law can be used. The laminate may be formed by, for example, drying the coating film on a substrate and then performing heat treatment or ultraviolet irradiation at 20 ° C. to 500 ° C., more preferably at 40 ° C. to 250 ° C., if desired. Is also good.

  The thickness of the coating is preferably 0.05 to 100 μm, more preferably 0.1 to 10 μm. From the viewpoint of transparency, the thickness of the coating film is preferably 100 μm or less, and is preferably 0.05 μm or more in order to exhibit functions such as weather resistance and stain resistance. In the present embodiment, the “coating film” does not necessarily need to be 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 as long as the gist is not exceeded.
In addition, various physical properties were evaluated by the following methods.

<Number average particle size>
A solvent was appropriately added and diluted so that the solid content in the sample was 1 to 20% by mass, and the number average particle size was measured using a wet type particle size analyzer (Microtrack UPA-9230 manufactured by Nikkiso Co., Ltd., Japan).

<Thickness>
The thickness of the coating film obtained was measured using a reflection spectral thickness meter (trade name “FE-3000” manufactured by Otsuka Electronics Co., Ltd.). The average of three randomly selected measurement values was calculated and defined as the film thickness.

<Appearance of coating film (crack resistance)>
The appearance of the obtained coating film (coated surface of the coating composition) was observed with a microscope (manufactured by KEYENCE CORPORATION; magnification of 100). The results were evaluated as follows.
：: almost no minute cracks △: many minute cracks ×: film formation not possible

<Anti-fogging test>
A test piece of the obtained coating was placed at a height of 5 cm from the water surface of a hot water bath maintained at 80 ° C. so that the coating surface faced downward, and steam from the hot water bath was continuously irradiated on the coating film. Then, the presence or absence of fogging 30 seconds after the irradiation was visually evaluated as follows. In addition, there is no practical problem if the evaluation is Δ or more, and it is more preferable if the evaluation is ○.
（(Good): no fogging.
Δ (medium): slightly cloudy immediately after irradiation with steam.
X (bad): cloudy

<Heat resistance test>
The prepared coating film was exposed to an environment of 120 ° C. for 24 hours, and then allowed to stand for 1 hour in an environment of 23 ° C. and 50% RH. With respect to the obtained coating film, antifogging property and coating film appearance were evaluated.

<Synthesis Example 1 (Synthesis of Polymer Particle (HB-1))>
<Production Example 1>
After 964 g of ion-exchanged water and 1.9 g of dodecylbenzenesulfonic acid were charged into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, the temperature was increased to 80 ° C. with stirring. To this, a mixture of 46 g of propyltrimethoxysilane and 54 g of methyltrimethoxysilane 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 reduced to 80 ° C. In this state, stirring was continued for about 1 hour. Next, a mixture of 5.5 g of butyl acrylate, 2.8 g of phenyltrimethoxysilane, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and 16.8 g of tetraethoxysilane, and N, N-diethylacrylamide. A mixture of 5 g, 0.9 g of acrylic acid, and 40 g of a 2% by weight aqueous solution of ammonium persulfate was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Furthermore, after stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., the mixture was cooled to room temperature, filtered through a 100-mesh wire net, and the solid content was adjusted to 6.0% by mass with ion-exchanged water. Thus, an aqueous dispersion of polymer particles (HB-1) having a number average particle diameter of 40 nm was obtained.

<Synthesis Example 2 (Synthesis of Polymer Particle (HB-2))>
<Production Example 2>
After 876 g of ion-exchanged water and 1.7 g of dodecylbenzenesulfonic acid were charged into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, the temperature was increased to 80 ° C. with stirring. To this, a mixture of 17 g of propyltrimethoxysilane and 83 g of methyltrimethoxysilane 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 reduced to 80 ° C. In this state, stirring was continued for about 1 hour. Next, a mixed solution of 5.2 g of butyl acrylate, 2.5 g of phenyltrimethoxysilane, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and 15.3 g of tetraethoxysilane, and N, N-diethylacrylamide. A mixed solution of 9 g, 0.9 g of acrylic acid, and 40 g of a 2% by weight aqueous solution of ammonium persulfate was simultaneously dropped over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Furthermore, after stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., the mixture was cooled to room temperature, filtered through a 100-mesh wire net, and the solid content was adjusted to 6.0% by mass with ion-exchanged water. Thus, an aqueous dispersion of polymer particles (HB-2) having a number average particle diameter of 25 nm was obtained.

<Synthesis Example 3 (Synthesis of Polymer Particle (HB-3))>
<Production Example 3>
After putting 997 g of ion-exchanged water and 1.9 g of dodecylbenzenesulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, the temperature was heated to 80 ° C. with stirring. To this, a mixture of 72 g of propyltrimethoxysilane and 28 g of methyltrimethoxysilane 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 reduced to 80 ° C. In this state, stirring was continued for about 1 hour. Next, a mixture of 5.7 g of butyl acrylate, 2.9 g of phenyltrimethoxysilane, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and 17.4 g of tetraethoxysilane, and N, N-diethylacrylamide. A mixed solution of 9 g, 1.0 g of acrylic acid, and 40 g of a 2% by mass aqueous solution of ammonium persulfate was simultaneously dropped over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Furthermore, after stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., the mixture was cooled to room temperature, filtered through a 100-mesh wire net, and the solid content was adjusted to 6.0% by mass with ion-exchanged water. Thus, an aqueous dispersion of polymer particles (HB-3) having a number average particle diameter of 100 nm was obtained.

<Synthesis Example 4 (Synthesis of Polymer Particle (HB-4))>
<Production Example 4>
After 964 g of ion-exchanged water and 1.9 g of dodecylbenzenesulfonic acid were charged into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, the temperature was increased to 80 ° C. with stirring. To this, a mixture of 46 g of propyltrimethoxysilane and 54 g of methyltrimethoxysilane 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 reduced to 80 ° C. In this state, stirring was continued for about 1 hour. Next, a mixture of 5.5 g of methyl methacrylate, 2.8 g of phenyltrimethoxysilane, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and 16.8 g of tetraethoxysilane, and N, N-diethylacrylamide. A mixture of 5 g, 0.9 g of acrylic acid, and 40 g of a 2% by weight aqueous solution of ammonium persulfate was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Furthermore, after stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., the mixture was cooled to room temperature, filtered through a 100-mesh wire net, and the solid content was adjusted to 6.0% by mass with ion-exchanged water. Thus, an aqueous dispersion of polymer particles (HB-4) having a number average particle diameter of 50 nm was obtained.

<Synthesis Example 5 (Synthesis of polymer particles (HB-5))>
<Production Example 5>
After 980 g of ion-exchanged water and 1.9 g of dodecylbenzenesulfonic acid were charged into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, the temperature was increased to 80 ° C. with stirring. To this, a mixture of 46 g of octyltrimethoxysilane and 54 g of methyltrimethoxysilane 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 reduced to 80 ° C. In this state, stirring was continued for about 1 hour. Next, a mixture of 5.6 g of butyl acrylate, 2.8 g of phenyltrimethoxysilane, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and 17.1 g of tetraethoxysilane, and N, N-diethylacrylamide. A mixed solution of 7 g, 0.9 g of acrylic acid, and 40 g of a 2% by mass aqueous solution of ammonium persulfate was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Furthermore, after stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., the mixture was cooled to room temperature, filtered through a 100-mesh wire net, and the solid content was adjusted to 6.0% by mass with ion-exchanged water. Thus, an aqueous dispersion of polymer particles (HB-5) having a number average particle diameter of 50 nm was obtained.

<Synthesis Example 6 (Synthesis of polymer particles (HB-6))>
<Production Example 6>
After charging 1107 g of ion-exchanged water and 2.2 g of dodecylbenzenesulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature was raised to 80 ° C. with stirring. A mixture of 46 g of hexadecyltrimethoxysilane and 54 g of methyltrimethoxysilane was added dropwise thereto over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was reduced to 80 ° C. Stirring was continued for about 1 hour at a temperature of ° C. Next, a mixture of 6.3 g of butyl acrylate, 3.2 g of phenyltrimethoxysilane, 0.6 g of 3-methacryloxypropyltrimethoxysilane, and 19.3 g of tetraethoxysilane, and N, N-diethylacrylamide 13. A mixed solution of 2 g, 1.0 g of acrylic acid, and 40 g of a 2% by mass aqueous solution of ammonium persulfate was simultaneously dropped over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Furthermore, after stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., the mixture was cooled to room temperature, filtered through a 100-mesh wire net, and the solid content was adjusted to 6.0% by mass with ion-exchanged water. Thus, an aqueous dispersion of polymer particles (HB-6) having a number average particle diameter of 50 nm was obtained.

<Synthesis Example 7 (Synthesis of polymer particles (HB-7))>
<Production Example 7>
After charging 1187 g of ion-exchanged water and 2.0 g of dodecylbenzenesulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature was raised to 80 ° C. with stirring. To this, 100 g of methyltrimethoxysilane was added dropwise over a period of about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., and then stirring was continued for about 1 hour while the temperature in the reaction vessel was 80 ° C. . Next, a mixture of 7.0 g of butyl acrylate, 2.8 g of phenyltrimethoxysilane, 1.0 g of 3-methacryloxypropyltrimethoxysilane, and 21.0 g of tetraethoxysilane, and N, N-diethylacrylamide. A mixture of 0 g, 1.0 g of acrylic acid, and 40 g of a 2% by weight aqueous solution of ammonium persulfate was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Furthermore, after stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., the mixture was cooled to room temperature, filtered through a 100-mesh wire net, and the solid content was adjusted to 6.0% by mass with ion-exchanged water. And an aqueous dispersion of polymer particles (HB-7) having a number average particle diameter of 50 nm.

<Synthesis Example 8 (Synthesis of polymer particles (HB-8))>
<Production Example 8>
After charging 1025 g of ion-exchanged water and 2.0 g of dodecylbenzenesulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, the temperature was raised to 80 ° C. with stirring. To this, a mixed solution of 78 g of propyltrimethoxysilane and 22 g of methyltrimethoxysilane 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 reduced to 80 ° C. In this state, stirring was continued for about 1 hour. Next, a mixture of 5.8 g of butyl acrylate, 3.0 g of phenyltrimethoxysilane, 0.5 g of 3-methacryloxypropyltrimethoxysilane, and 18.0 g of tetraethoxysilane, and N, N-diethylacrylamide. A mixed solution of 2 g, 1.0 g of acrylic acid, and 40 g of a 2% by mass aqueous solution of ammonium persulfate was simultaneously dropped over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Furthermore, after stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., the mixture was cooled to room temperature, filtered through a 100-mesh wire net, and the solid content was adjusted to 6.0% by mass with ion-exchanged water. Thus, an aqueous dispersion of polymer particles (HB-8) having a number average particle diameter of 100 nm was obtained.

[Examples 1 to 8 and Comparative Examples 1 and 2]
Colloidal silica (manufactured by Nissan Chemical Industries, trade name "Snowtex" (component (A)) dispersed in water (solid content: 10% by mass)) and polymer particles obtained in the production example ((B) Components: HB-1 to 8) and tetraethoxysilane (component (C)) were blended as shown in Tables 2 and 3 to obtain coating compositions. The number average particle diameter of colloidal silica (trade name “Snowtex” manufactured by Nissan Chemical Industries, Ltd.) described in Tables 2 and 3 is described in the catalog.
The obtained coating composition is coated on a polycarbonate plate (manufactured by Takiron, hereinafter also referred to as "PC") having a length of 60 mm x a width of 60 mm x a thickness of 2 mm by a spin coater under the conditions of 800 rpm x 5 seconds, and then at 120 ° C. After drying for 30 minutes, a laminate having a coating film was obtained. The thickness of all the obtained coating films was about 1.0 μm. The evaluation results are shown in Tables 2 and 3.

<Evaluation results>
In Examples 1 to 3, when the relative amount of (A) colloidal silica was increased or decreased with respect to (B) aqueous dispersion of polymer particles, heat resistance and crack resistance were within the allowable range of the present invention. Has changed. Particularly, in Example 1 in which the mass ratio of the polymer particles (B) to the colloidal silica (solid content) (A) was 1: 1, these characteristics were most excellent.

  In Examples 4 and 5, even when the number average particle diameter of the colloidal silica (A) to be blended was changed, good heat resistance and crack resistance were exhibited within the allowable range of the present invention.

  In Examples 6 and 7, the (b1-1) methyl group of the (b1-1) hydrolyzable silicon compound having a linear alkyl group having 3 to 16 carbon atoms used for the polymer particles in the component (B) was used. When the relative amount to the hydrolyzable silicon compound was reduced, good heat resistance and crack resistance were exhibited within the allowable range of the present invention. On the other hand, when the relative amount of (b1-1) a hydrolyzable silicon compound having a straight-chain alkyl group having 3 to 16 carbon atoms with respect to (b1-2) a hydrolyzable silicon compound having a methyl group was increased, These properties changed within the permissible range of the present invention.

  In Example 8, even when the (b2) vinyl monomer used for the polymer particles in the component (B) was changed, good heat resistance and crack resistance were exhibited within the allowable range of the present invention.

  In Examples 9 and 10, (b1-1) the carbon of the straight-chain alkyl group in the hydrolyzable silicon compound having a straight-chain alkyl group having 3 to 16 carbon atoms used for the polymer particles in the component (B). Even when the number was increased, good heat resistance and crack resistance were exhibited within the allowable range of the present invention.

  On the other hand, as described above, in the case of Comparative Example 1 in which (b1-1) the hydrolyzable silicon compound having a linear alkyl group having 3 to 16 carbon atoms and which is not contained in the polymer particles in the component (B), The cracking property has decreased to a level that cannot be put to practical use.

  In Comparative Example 2, (b1-1) a (b1-2) methyl group of a hydrolyzable silicon compound having a straight-chain alkyl group having 3 to 16 carbon atoms and contained in a polymer particle in the component (B). When the relative amount to the hydrolyzable silicon compound was excessive, the initial antifogging property was clearly reduced.

  The coating composition of the present invention has excellent coating film appearance and antifogging property, and can maintain the antifogging property for a long period of time even under severe environments such as high temperatures. Therefore, the coating composition of the present invention can be particularly suitably used as an anti-fog coating film requiring high anti-fog properties. Further, it can be used as a coating film for exterior parts of automobiles such as vehicle lamps such as headlamps of automobiles, for applications requiring anti-fog durability in a high-temperature environment. Further, the coating composition of the present invention can also be used for components which cannot be easily taken out for removal of fogging, such as internal components of various devices and components installed at high places. All of the features and advantages described above for the coating composition according to the invention also apply to these antifogging coatings, coatings for automotive exterior parts and coatings for internal parts.

Claims (11)

(A) a metal oxide having a number average particle diameter of 1 nm to 400 nm;
(B) an aqueous dispersion of polymer particles,
The component (B) includes:
An aqueous dispersion of polymer particles containing (b1) a polymer particle containing a polymer composed of a hydrolyzable silicon compound, (b2) a vinyl monomer and (b3) an emulsifier, and (b4) water,
(B1) includes (b1-1) a hydrolyzable silicon compound having a linear alkyl group having 3 to 16 carbon atoms and (b1-2) a hydrolyzable silicon compound having a methyl group,
A coating composition wherein the mass ratio (b1-1) / (b1-2) of (b1-1) and (b1-2) is in the range of 0.1 to 3.0.   The coating composition according to claim 1, wherein the mass ratio (A) / (B) of the component (A) (solid content) to the polymer particles in the component (B) is 0.5 to 3.0. .   The coating composition according to claim 1, wherein the component (B) has a number average particle diameter of 5 nm to 200 nm.   The component (b2) according to claim 1 or 2, wherein the component (b2) includes a vinyl monomer having 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. Coating composition.   The coating composition according to any one of claims 1 to 4, wherein the polymer particles in the component (B) have a core-shell structure.   The mass ratio (b1-1) / (b1-2) between (b1-1) and (b1-2) in the component (B) is in the range of 0.1 to 1.5. A coating composition according to any one of the preceding claims.   The coating composition according to any one of claims 1 to 6, wherein (b1-1) is a hydrolyzable silicon compound having a linear alkyl group having 3 to 8 carbon atoms.   The coating composition according to any one of claims 1 to 7, wherein the component (b2) includes a vinyl monomer having a secondary amide group, a tertiary amide group, or both.   The coating composition according to any one of claims 1 to 7, wherein the component (A) is colloidal silica.   A laminate comprising a resin substrate and / or a glass substrate and the coating composition according to any one of claims 1 to 9.   The coating composition according to any one of claims 1 to 9, which is used as an anti-fog coating film.