JP7051233B2 - Coating composition - Google Patents

Description

The present invention relates to a coating composition.

As an alternative to the 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 appliance parts, housings, containers, films, and sheets. In particular, transparent plastic is used for, for example, various windows, optical lenses, mirrors, eyeglasses, goggles, sound insulation walls, lenses for traffic lights, headlight lenses, curved mirrors, windshields, name plates and the like. However, in a resin base material such as plastic, dew condensation occurs when one surface of the base material becomes below the dew point temperature or when a sudden change in temperature and humidity occurs due to the temperature and humidity chain with the outside air. , Fine water droplets may adhere to the surface and scatter transmitted light. In such a case, the transparency of the resin molded body is impaired and so-called cloudiness occurs.

As a method for preventing this fogging, for example, the following proposals have been made.
(1) A method for forming a coating film of a water-absorbent compound on the surface of a substrate.
(2) A method for 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-absorbent crosslinked resin layer made of a cured epoxide resin or a urethane resin is provided, and the water-absorbent layer is prevented from containing metal oxide fine particles. Cloudy articles and the like have been proposed. Further, Patent Document 2 proposes an anti-fog 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 Documents 3 and 4 disclose hydrophilic and antifouling coating films characterized in that the surface of the coating film is 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. 2010/10146

However, in the methods such as Patent Documents 1 and 2, the anti-fog property of the article can be maintained up to a certain level, but when water having a water absorption capacity or higher aggregates and adheres to the article, anti-fog occurs. Therefore, there is an inconvenience that it is necessary to increase the film thickness in order to exhibit high anti-fog durability.

Further, the methods including Patent Document 3 are characterized in that colloidal silica is unevenly distributed on the outermost surface of the coating film. Therefore, although it is excellent in initial hydrophilicity and anti-fog property, in a harsh environment such as a high temperature environment, when polymer particles are contained, the hydrophilicity tends to be significantly reduced due to bleeding out of aqueous phase components. There is. As a result, the anti-fog 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 component is used, and cracks are likely to occur and the particles tend to be easily peeled off.

In view of the above-mentioned 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.

As a result of diligent studies and repeated experiments in order to solve the above problems, unexpectedly, (A) a metal oxide having a number average particle diameter of 1 to 400 nm and (B) a polymer particle aqueous dispersion. The present invention has been completed by finding that the above-mentioned problems can be solved by preparing a coating composition containing a hydrolyzable silicon compound containing a body and a predetermined amount of a linear alkyl group in the component (B). It came to.

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) Including a polymer particle aqueous dispersion
The component (B) is
It is a polymer particle aqueous dispersion 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) 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.
A coating composition having a mass ratio (b1-1) / (b1-2) of (b1-1) and (b1-2) in the range of 0.1 to 3.0.
[2]
The coating composition according to [1], wherein the mass ratio (A) / (B) of the component (A) 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 number average particle diameter of the component (B) is 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. The coating composition 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]
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, [1] to [ 5] The coating composition according to any one of.
[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) contains 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 base material and / or a glass base material 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 anti-fog coating film.

According to the present invention, it is an object of the present invention to provide a coating composition having heat resistance and capable of suppressing cracks.

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

As used herein, "(meth) acrylic" means "acrylic" and its corresponding "methacrylic", and "(meth) acrylate" means "acrylate" and its corresponding methacrylate, "(meth) acrylate". ) Acryloyl "means" acryloyl "and its corresponding methacryloyl".

<Coating composition>
The coating composition of the present embodiment is
(A) A metal oxide having a number average particle diameter of 1 nm to 400 nm,
(B) Including a polymer particle aqueous dispersion
The component (B) is
It is a polymer particle aqueous dispersion containing (b4) water and polymer particles containing a polymer composed of (b1) a hydrolyzable silicon compound, (b2) a vinyl monomer and (b3) an emulsifier.
(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.
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 of the present embodiment contains (A) component: a metal oxide having a number average particle diameter of 1 nm to 400 nm. This makes it possible to obtain a coating film having high transparency and hydrophilicity. 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, but for example, a functional group generally possessed by the component (A) (for example, a hydroxyl group) and a functional group possessed by the component (B) (eg, a hydroxyl group, a carboxyl group, an amide group, an amino group, and the like). Examples thereof include a hydrogen bond with the ether group), a chemical bond (for example, condensation) between the functional group generally possessed by the component (A) and the component (B).

<(A) Metal oxide>
The particle size of the component (A) means a number average particle size (a mixture of primary particles and secondary particles, or 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 even more preferably 5 nm to 50 nm. By setting the number average particle diameter of the component (A) in the above range, it can contribute to the optical characteristics of the obtained coating film, laminate, and the like. 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 diameter (hereinafter, may be simply abbreviated as “particle diameter”) is measured according to the method of Examples described later.

The form of the component (A) is not particularly limited, and examples thereof include powders, dispersions, and sol. The "dispersion liquid" and "sol" as used herein mean 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. It means a state in which the particles are dispersed as at least one of the primary particles or the secondary particles at the concentration of. The hydrophilic organic solvent is not particularly limited, and is, for example, 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, tetrahydrofuran, and the like. Examples thereof include ethers such as dioxane, amides such as dimethylacetamide and dimethylformamide, dimethylsulfoxide and nitrobenzene, and mixtures of two or more thereof.

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

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 Stober et al; J. Mol. Colloid and Interface Sci. , 26, 62-69 (1968), Rickey D. Badley et al; Lang muir 6, 792-801 (1990), Journal of Japan Society of Color Material, 61 [9] 488-493 (1988) and the like can be referred to. 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 colloidal silica is 1 to 400 nm, preferably 1 to 100 nm, and more preferably 4 to 50 nm. When the number average particle size of colloidal silica is 1 nm or more, the storage stability of the coating composition tends to be good. Further, when the number average particle size of 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 state of an aqueous dispersion, whether it is acidic or basic. When 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 as a commercial product, for example, Snowtex (registered trademark) -OXS, Snowtex-OS, Snowtex-O, Snowtex manufactured by Nissan Chemical Industry Co., Ltd. -OL, Snowtex-OYL, Adelite (registered trademark) AT-20Q manufactured by Asahi Denka Kogyo Co., Ltd., Clevosol (registered trademark) 20H12 manufactured by Clariant Japan Co., Ltd., Clevosol 30CAL25, etc. can be used.

The basic colloidal silica is not particularly limited, and includes, for example, silica stabilized by the addition of alkali metal ion, ammonium ion, and amine. Commercially available products are not particularly limited, but for example, Nissan Chemical Industries, Ltd. Snowtex-20, Snowtex-30, Snowtex-C, Snowtex-C30, Snowtex-CM40, Snowtex-N, Snowtex. -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, Adelite AT-50, etc. manufactured by Asahi Denka Kogyo Co., Ltd. Can also be used. Further, Clariant Japan Co., Ltd.'s Crevosol 30R9, Crevosol 30R50, Crevosol 50R50, etc., and DuPont's Ludox (registered trademark) HS-40, Ludox HS-30, Ludox LS, Ludox SM-30, etc. can also be used. be.

The colloidal silica using a water-soluble solvent as a dispersion medium is not particularly limited, and is, for example, MA-ST-M (a methanol dispersion type having a number average particle diameter of 20 to 25 nm) manufactured by Nissan Chemical Industry Co., Ltd., IPA. -ST (isopropyl alcohol dispersion type with a number average particle diameter of 10 to 15 nm), EG-ST (ethylene glycol dispersion type with a number average particle diameter of 10 to 15 nm), EG-ST-ZL (number average particle diameter of 70 to 70 to 100 nm ethylene glycol dispersion type), 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 silica may be used individually or in combination of two or more types. Further, alumina, sodium aluminate and the like may be contained as a small amount component. Further, colloidal silica may contain an inorganic base (sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc.), an organic base (tetramethylammonium, etc.) and the like as stabilizers.

<(B) Polymer particle aqueous dispersion>
As described above, the component (B) is a polymer particle containing a polymer composed of a component (b1): a hydrolyzable silicon compound, a component (b2): a vinyl monomer, and a component (b3): an emulsifier. , (B4): Polymer particle aqueous dispersion containing water. As the component (B), it is preferable to use a compound in which the hydroxyl group derived from the component (b1) and the polymerization product of the component (b2) are complexed by hydrogen bonds or the like.

In the coating composition of the present embodiment, (b1) contained in (B) is (b1-1): a hydrolyzable silicon compound having a linear alkyl group having 3 to 16 carbon atoms and (b1-b1-). 2): 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 the range of, it has heat resistance and can suppress cracks.

<(B1)>
The component (b1) is not particularly limited, and examples thereof include a compound represented by the following formula (I), a condensation product thereof, a silane coupling agent, and the like.
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 is 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 substituted alkyl group having 1 to 20 carbon atoms or 1 carbon atom. Represents at least one hydrocarbon group selected from the group consisting of ~ 20 alkoxy groups or aryl groups having 6 to 20 carbon atoms substituted with halogen atoms. 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. Further, 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 methacrylic 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, 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, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3 -Isocyanatopropyltrimethoxysilane, 3-Isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acrylicoxypropyltrimethoxysilane, 3- (meth) acrylicoxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri -N-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, 3-ureidopro Trialkoxysilanes such as pyrutrimethoxysilane, 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 n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane; trimethylmethoxysilane, trimethylethoxysilane, etc. Monoalkoxysilanes and the like can be used. Further, these may be used alone or in combination 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. It is preferable to have.

The component (b1-1) is not particularly limited, but for example, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, and n-pentyltri. Methoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-heptiltrimethoxysilane, n-heptiltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane Silane, n-octyltriethoxysilane, n-decyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-hexadecyltrimethoxysilane, n-hexadecyltriethoxysilane, 1,6 bis Ekoxysilane accumulation such as (trimethoxysilyl) hexane and 1,8 bis (trimethoxysilyl) octane can be used. These may be used alone or in admixture of two or more.

Examples of the component (b1-2) include compounds 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, and an oxime group having 1 to 20 carbon atoms. Represents at least one group selected from the group consisting of an enoxy group, an aminoxi group and an amide group. W1, W2, and W3 may all have the same functional group or different functional groups.

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

Further, the component (b1) may contain a silicon alkoxide having a phenyl group (for example, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, etc.). When a silicon alkoxide having a phenyl group is used, the polymerization stability is good in the presence of water and an emulsifier, which is preferable. When a silicon alkoxide having a phenyl group is used as the component (b1), it is preferably 0.1 to 30 parts by mass, more preferably 1.0 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (b1). The unit is preferable. Within this range, the polymerization stability is sufficient and the heat resistance of the obtained coating film is also good.

Further, as the component (b1), a tetrafunctional silicon alkoxide (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, etc.) may be included. When a tetrafunctional silicon alkoxide is used, the strength and antifouling property of the obtained coating film are good, preferably 0.1 to 10 parts by mass, more preferably 10 with respect to 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 stain resistance of the obtained coating film is good, which is preferable. The silane coupling agent having a thiol group is not particularly limited, and for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and the like can be used.

The component (b1) is not particularly limited, but is, for example, 3- (meth) acrylicoxypropyltrimethoxysilane, 3- (meth) atacryloxypropyltriethoxysilane, and 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 a chemical bond by copolymerization with the component (b2) described later or a chain transfer reaction. Therefore, when a silane coupling agent having a vinyl polymerizable group or a thiol group is mixed or combined with the above-mentioned component (b1), the polymerization product of (b1) and the component (b2) described later are polymerized. The product can be polymerized by chemical bonding. The above-mentioned "vinyl polymerizable group" is not particularly limited, but is, for example, a vinyl group, an allyl group, or the like, and a 3- (meth) acrylic oxypropyl 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 containing the vinyl monomer having such a functional group, it is possible to chemically bond (for example, condensation, etc.) with the functional group of a component other than the component (B) (for example, a metal oxide in the component (A)). 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, but for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth). Various hydroxyalkyl (meth) acrylates such as acrylates; Various hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether; Various hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether. Kind; Monoesters of polyoxyalkylene glycols obtained from various polyether polyols typified by polyethylene glycol and various unsaturated carboxylic acids typified by (meth) acrylic acid; Additives of weights and various lactones typified by ε-caprolactone; various epoxy group-containing unsaturated monomers typified by glycidyl (meth) acrylate and various acids typified by acetic acid. Additives; various unsaturated carboxylic acids typified by (meth) acrylic acid and various monoepoxide compounds other than epoxides of α-olefins typified by "Cardura E" (trade name manufactured by Shell Co., Ltd., Netherlands). Additives and the like.

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

Specific examples of the amino group-containing vinyl monomer mentioned as the component (b2) are not particularly limited, but are, for example, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, and 2-di-n. -Various tertiary aminos such as propylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate or N- [2- (meth) acryloyloxy] ethylmorpholin. Group-containing (meth) acrylic acid esters; various tertiary amino group-containing aromatic vinyl-based monomers such as vinylpyridine, N-vinylcarbazole, N-vinylquinolin; N- (2-dimethylamino) ethyl. (Meta) acrylamide, N- (2-diethylamino) ethyl (meth) acrylamide, N- (2-di-n-propylamino) ethyl (meth) acrylamide, N- (3-dimethylamino) propyl (meth) acrylamide, Various tertiary amino group-containing (meth) acrylamides such as N- (4-dimethylamino) butyl (meth) acrylamide or N- [2- (meth) acrylamide] ethylmorpholin; N- (2-dimethylamino) Ethyl crotonic acid amide, N- (2-diethylamino) ethyl crotonic acid amide, N- (2-di-n-propylamino) ethyl crotonic acid amide, N- (3-dimethylamino) propyl crotonic acid amide or N- ( Various tertiary amino group-containing crotonic acid amides such as 4-dimethylamino) butyl crotonic acid amide; 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 3-dimethylaminopropyl vinyl ether or 4-dimethylaminobutyl vinyl ether. Examples thereof include various tertiary amino group-containing vinyl ethers such as.

Specific examples of the ether group-containing vinyl monomer mentioned as the component (b2) are not particularly limited, but are limited to polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, and polyoxyethylene-poly. Examples thereof include vinyl ethers having various polyether chains such as oxypropylene block copolymers on the side chains, allyl ethers, and vinyl monomers of (meth) acrylic acid esters. Commercially available products can be used as the ether group-containing vinyl monomer, for example, Blemmer PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, AE-350 (above, NOF). (Product name), MA-30, MA-50, MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114, MPG130-MA (above, Japan) (Product name) manufactured by Embroidery Co., Ltd. may be mentioned. 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 and N-alkylene substituted (meth) acrylamide. More specifically, but 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-N-n-propylacrylamide, N-Methyl-N-Isopropylacrylamide, N-Acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidin, N-methacryloylpiperidin, N-acryloylhexahydroazepine, N- Acryloyl morpholine, N-methacryloyl morpholine, N-vinylpyrrolidone, N-vinylcaprolactum, N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, N-vinylacetamide, diacetoneacrylamide, diacetonemethacrylamide , N-methylolacrylamide, N-methylolmethacrylamide 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 property with other components. In particular, a vinyl monomer having a tertiary amide group is preferable from the viewpoint of hydrogen bonding force.

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

<(B3)>
The component (b3) is not particularly limited, but is acidic, for example, alkylbenzene sulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylenealkylsulfate, polyoxyethylenealkylarylsulfate, polyoxyethylene distyrylphenylethersulfonic acid and the like. Anionic surfactants such as emulsifiers, alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, ammonium salts of acidic emulsifiers, fatty acid soaps; alkyltrimethylammonium bromide, alkylpyridinium bromide, imidazolinium laurate, etc. Primary ammonium salt, pyridinium salt, imidazolinium salt type cationic surfactant; polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxypropylene block copolymer, polyoxyethylene distyrylphenyl ether, etc. Nonionic type surfactant and the like can be mentioned. These may be used alone or in combination of two or more.

The component (b3) is a reaction having a radically polymerizable double bond from the viewpoint of improving the water dispersion stability of the obtained component (B) and improving the long-term antifouling property of the obtained coating film. It is preferable to use a sex emulsifier. The reactive emulsifier is not particularly limited, and is, for example, a vinyl monomer having a sulfonic acid group or a sulfonate group, a vinyl monomer having a sulfate ester group, and alkali metal salts, ammonium salts, polyoxyethylene and the like thereof. Examples thereof include a vinyl monomer having a nonionic group of the above, a vinyl monomer having a quaternary ammonium salt, and the like.

The vinyl monomer having a sulfonic acid group or a sulfonate group has, for example, a radically polymerizable double bond and is partially substituted with a substituent such as an ammonium salt, a sodium salt or a potassium salt of the sulfonic acid group. Substitution 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, a naphthyl group, and a succinic acid group. Compounds having a group; Examples thereof include vinyl sulfonate compounds having a vinyl group to which a substituent such as an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group is bonded.

The vinyl monomer having a sulfate group has, for example, a radically polymerizable double bond and is partially substituted with a substituent such as an ammonium salt, a sodium salt or a potassium salt of the sulfate group. Examples thereof 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. Be done.

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 allylsulfosuccinate and the like. More specifically, for example, Eleminor JS-2 (manufactured by Sanyo Chemical Industries, Inc., trade name), Latemul S-120, S-180A or S-180 (manufactured by Kao Corporation, trade name) and the like can be mentioned.

Specifics 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 thereof include Aqualon HS-10 or KH-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name), Adecaria Soap SE-1025N or SR-1025 (manufactured by Asahi Denka Kogyo Co., Ltd., trade name) and the like.

Specifically, as the vinyl monomer having a nonionic group, 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 alkyl propenylphenyl ether (trade names: Aqualon RN-10, RN-20, RN-30, RN-50, etc., No. 1 (Manufactured by Pharmaceutical Industry Co., Ltd.).

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

The component (B) is, for example, the component (b1), the component (b2) and the component (b3) in the polymerization stock solution containing the above-mentioned components (b1) to (b3) and the component (b4) (that is, water). It is preferably a polymer particle aqueous dispersion 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 addition to the components (b1) to (b4), various components can be further mixed in the polymerization stock solution. First, it is preferable to further mix the component (b5): another vinyl monomer copolymerizable with the component (b2) in the polymerization stock solution. The use of such a component (b5) is characterized by the characteristics (glass transition temperature, molecular weight, hydrogen bonding force, polarity, dispersion stability, weather resistance) of the produced polymerization product, and the hydrolyzable silicon compound which is the component (b1). It is suitable from the viewpoint of controlling the compatibility with the polymerization product of the above.

The component (b5) is not particularly limited, and is, for example, an acrylic acid ester, a methacrylate ester, an aromatic vinyl compound, vinyl cyanide, an epoxy group-containing vinyl monomer, a carbonyl group-containing vinyl monomer, and an anion. Examples thereof include a monomer containing a functional group such as a type vinyl monomer.

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

A chain transfer agent can be mixed with the polymerization stock solution. The chain transfer agent is not particularly limited, and is, for example, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan; Examples thereof include thiocarboxylic acids or salts thereof or alkyl esters thereof, polythiols, diisopropylxanthogen disulfides, di (methylenetrimethylolpropane) xanthogen disulfides and thioglycols, and allyl compounds such as dimers of α-methylstyrene. ..

The amount of these chain transfer agents used 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, but is, for example, various water-soluble oligomers selected from the group consisting of polycarboxylic acid and sulfonate, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, and maleized alkyd resin. , Polyacrylic acid (salt), polyacrylamide, synthetic or natural water-soluble or water-dispersible various water-soluble polymer substances such as water-soluble or water-dispersible acrylic resin can be used. In addition, one kind or a mixture of two or more kinds 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, and more preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the polymer particles (B).

The polymerization of the polymerization stock solution is preferably carried out in the presence of a polymerization catalyst. The polymerization catalyst of the component (b1) is not particularly limited, but for example, hydrogen halides such as hydrochloric acid and hydrofluoric acid, carboxylic acids such as acetic acid, trichloracetic acid, trifluoroacetic acid and lactic acid, sulfuric acid and p-toluenesulfonic acid. Cyclic acids such as alkylbenzene sulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylenealkylsulfate, polyoxyethylenealkylarylsulfate, polyoxyethylene distyrylphenyl ether sulfonic acid and other acidic emulsifiers, acidic or weakly acidic Acidic compounds such as inorganic salts, phthalic acid, phosphoric acid, and nitrate; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine, diazabicyclo Basic compounds such as undecene, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) -aminopropyltrimethoxysilane; dibutyltin octylate, and dibutyltin dilaurate. Such as tin compounds can be used. Among them, as the polymerization catalyst of the hydrolyzable silicon compound (b1), acidic emulsifiers that act as emulsifiers as well as polymerization catalysts, particularly alkylbenzene sulfonic acid having 5 to 30 carbon atoms (dodecylbenzene sulfonic acid, etc.) are preferable. ..

Further, as the polymerization catalyst of the component (b2), a radical polymerization catalyst that undergoes radical decomposition by heat or a reducing substance to cause addition polymerization of the vinyl monomer is suitable. Water-soluble or oil-soluble persulfates, peroxides, azobis compounds and the like are preferably used. More specifically, but not particularly limited, for example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butylhydroperoxide, t-butylperoxybenzoate, 2,2-azobisisobutyi. Lonitrile, 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 with respect to 100 parts by mass of the total vinyl monomer. If it is desired to accelerate the polymerization rate and polymerize at a low temperature such as 70 ° C. or lower, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, and longalit 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, but if they are carried out at the same time, micro-organic / inorganic composites due to hydrogen bonds or the like are formed. It is preferable because it can be achieved.

As a method for obtaining the component (B), so-called emulsion polymerization in which the component (b1) and the component (b2) are polymerized in the presence of a sufficient amount of water for the emulsifier to form micelles is suitable. As a 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, are collectively or divided, or continuously in a reaction vessel. In the presence of a polymerization catalyst, preferably under a pressure from atmospheric pressure to 10 MPa if necessary, a method of polymerizing at a reaction temperature of about 30 to 150 ° C. can be mentioned. However, if necessary, polymerization may be carried out at a pressure higher than this or under temperature conditions lower than this.

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

Further, when carrying out emulsion polymerization, it is preferable to use a seed polymerization method from the viewpoint of appropriately growing or controlling the particle size. The seed polymerization method is a method in which emulsion particles (seed particles) are previously present in the aqueous phase to polymerize. The pH in the polymerization system when the seed polymerization method is carried out is preferably 1.0 to 10.0, and more preferably 1.0 to 6.0. The pH during the polymerization can be adjusted by using, for example, disodium phosphate, volax, or a pH buffer such as sodium hydrogen carbonate or ammonia.

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) can be obtained in the presence of a solvent, if necessary. 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 substrate. It is preferable to have. As a method for forming the core-shell structure, multi-stage emulsion polymerization in which emulsion polymerization is carried out in multiple stages is very useful. The core-shell structure can be observed, for example, by morphological observation with a transmission electron microscope or analysis by viscoelasticity measurement.

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 seed. The particles contain the component (b1), the component (b2) and the component (b5) (at least one component selected from the group consisting of other vinyl monomers copolymerizable with the component (b2)). It is more preferable that the particles are obtained by polymerization. In this case as well, multi-stage emulsion polymerization is useful.

Specifically, the multi-stage emulsion polymerization is specifically selected from the group consisting of the (b1) component, the (b2) component and the (b5) component in the presence of the (b3) component and the (b4) component, for example, as the first step. A polymerization stock solution containing one or more components to form seed particles, and as a second step, the components (b1) and (b2) and, if necessary, the component (b5) in the presence of the seed particles. Is added and polymerized (two-stage polymerization method). When performing multi-stage emulsion polymerization in three or more stages, for example, as the third stage, the polymerization stock solution containing the component (b1) and the component (b2) and, if necessary, the component (b5) may be added and polymerized. can. Such a method is also suitable from the viewpoint of polymerization stability.

When the two-stage polymerization method is adopted, 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 step (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, the particle size of the seed particles (volume average particle size / number average particle size) did not change significantly from the viewpoint of polymerization stability, and the particle size was increased by the second stage polymerization. It is preferable to have 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 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, 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 are less likely to occur, which is preferable. In this embodiment, Tg can be measured by a differential scanning calorimetry device (DSC).

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

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. Is. The surface area of each component can be calculated from the particle size of each of the components (A) and (B), the mass of each, and the specific gravity of each, 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 property of the obtained coating film. The hydrolyzable silicon-containing compound used as the component (C) is not particularly limited, but is represented by, for example, the hydrolyzable silicon-containing compound (c1) represented by the following formula (IV) and the following formula (V). One or more selected from the group consisting of the hydrolyzable silicon-containing compound (c2) and the 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 may have a hydrogen atom, a halogen group, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group or an epoxy group, and has 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 it is a group in which a hydroxyl group is generated 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 or a phenylene group having 1 to 6 carbon atoms. 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.

The component (c1) and the component (c2) are not particularly limited, but are, for example, tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, and tetra (c1). 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, methyldiethoxy Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (triphenyloxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane , Bis (triphenoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,3-bis (triphenyloxysilyl) propane, 1,4-bis (Trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane , 3-Mercaptopropyltrimethoxysilane, 3-Mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxy Propyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraacetoxysilane, tetrakis (trichloroacetoxy) silane, tetrakis (trifluoroacetoxy) silane, triacetoxysilane, tris (trichloroacetoxy) ) Silane, Tris (trifluoroacetoxy) silane, Methyltriacetoxysilane, Methyltris (trichloroacetoxy) silane, Tetrak Lorosilane, Tetrabromosilane, Tetrafluorosilane, Trichlorosilane, Tribromosilane, Trifluorosilane, Methyltrichlorosilane, Methyltribromosilane, Methyltrifluorosilane, Tetrakiss (methylethylketoxim) silane, Tris (methylethylketoxim) silane, Methyltris (Methylethylketoxim) silane, phenyltris (methylethylketoxim) silane, bis (methylethylketoxim) silane, methylbis (methylethylketoxim) 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 particularly limited, but for example, a partially hydrolyzed condensate of tetramethoxysilane (trade name "M silicate 51" manufactured by Tama Chemical Industry Co., Ltd., trade name "MSI51". "Corcourt Co., Ltd.), trade name" MS51 "," MS56 "manufactured by Mitsubishi Chemical Co., Ltd.), partial hydrolysis condensate of tetraethoxysilane (trade name" Silicate 35 "," Silicate 45 "Tama Chemical Industry ( Made by Co., Ltd., trade name "ESI40", "ESI48" manufactured by Corcote Co., Ltd.), and a co-partially hydrolyzed condensate of tetramethoxysilane and tetraethoxysilane (trade name "FR-3", Tama Chemical Industry Co., Ltd.) , Product name "EMSi48" manufactured by Corcourt Co., Ltd.) and the like can be used.

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

The mass ratio ((b2) / (A)) of the component (b2) to the component (A) is preferably 0.01 / 1/1 to 1 / from the viewpoint of enhancing the hydrogen bonding force with the metal oxide. It is 1, more preferably 0.05 / 1 to 0.8 / 1, and even 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 0.5 to 4 from the viewpoint of hydrophilicity and film forming property. It is 8.8, more preferably 1.1 to 4.8, still more preferably 1.1 to 3.0, and even more preferably 1.5 to 2.5. By setting the mass ratio ((A) / (B)) to such a ratio, antifouling property, transparency, and hydrophilicity can be further improved, and impact resistance / durability, high temperature, high humidity, and so on. Alternatively, the hydrophilicity of the coating film surface under high temperature and high humidity can be made excellent.

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

The surfactant is not particularly limited, but is, for example, an anionic surfactant such as alkylbenzene sulfonic acid, fatty acid sodium, alkyl sulfate, alkylpolyoxyethylene sulfate, alkyl phosphate, alkyltrimethylammonium salt, dialkyldimethyl. Cationic surfactants such as ammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium chlorides, benzalkonium chlorides, polyoxyethylene-polyoxypropylene condensates, polyoxyethylene alkyl ethers, alkyl polyglucosides, alkyl monoglyceryl ethers. Nonionic surfactants such as, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, lauric acid diethanolamide, oleic acid diethanolamide, stearic acid diethanolamide, glycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylphenyl ether. , Lauryl dialkylaminoacetic acid betaine, stearyldialkylaminoacetic acid betaine, dodecylaminomethyldialkylsulfopropylbetaine, hexadecylaminomethyldialkylsulfopropylbetaine, octadecylaminomethyldialkylsulfopropylbetaine, cocamidopropylbetaine, cocamidopropylhydroxysultaine, Amphoteric ionics such as alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, sodium lauroyl glutamate, potassium lauroyl glutamate, lauroylmethyl-β-alanine, lauryldimethylamine N-oxide, oleyldimethylamine N-oxide. Examples include surfactants. By using these in combination with a hydrophilic compound, the hydrophilicity, anti-fog property, and water resistance of the obtained coating film are further improved. Among these, when a surfactant having a long-chain alkyl group having 10 or more carbon atoms and / or a surfactant having a fluorine atom in the molecule is used, these surfactants can be used from inside the coating film. Since elution into water tends to be suppressed, it is more preferable from the viewpoint of water resistance.

The cross-linking reaction catalyst and / or the curing catalyst is not particularly limited, and for example, a dialkyltin dicarboxylate such as dibutyltin dilaurate, dioctylstindilaurate, or dibutyltin diacetate, a tin oxide compound such as dibutyltin oxide, or 2-ethylhexanoic acid. Metal carboxylates such as tin, zinc 2-ethylhexanoate, cobalt salts, triethylamine, pyridine, methylpyridine, benzyldimethylamine, N, N-dimethylcyclohexylamine, N-methylpiperazine, pentamethyldiethylenetriamine, N, N' -Endoethylene piperazine and tertiary amines such as N, N'-dimethylpiperazine and the like can be mentioned.

As the light stabilizer, for example, a hindered amine-based light stabilizer is preferably used. Of these, a radically polymerizable light stabilizer having a radically polymerizable double bond in the molecule is preferable. The ultraviolet absorber is not particularly limited, and examples thereof include an organic ultraviolet absorber. Examples of such an organic ultraviolet absorber include, but are not limited to, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and the like. Among these, it is preferable to use a radically polymerizable ultraviolet absorber having a radically 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. The combined use of both may contribute to the improvement of the weather resistance of the obtained coating film. Further, these organic ultraviolet absorbers, light stabilizers, and various additive components can be simply blended with the components (A) and (B), and when synthesizing the component (B), they can be simply blended. It is also possible to coexist.

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

<Base material>
The base material is positioned as an object to which the coating layer imparts particularly excellent anti-fog property and anti-fog durability. Various materials can be adopted as the base material. In one embodiment, the base material is preferably made of resin. The base material made of resin (resin base material) is not particularly limited, and examples thereof include organic base materials such as synthetic resin and natural resin.

As the synthetic resin, a thermoplastic resin and a curable resin (thermosetting resin, photocurable resin, moisture curable resin, etc.) 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, polysulphon resin, polyphenylene sulfone resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, phenol resin, melamine resin, epoxy resin, urethane Examples thereof include resin, silicone-acrylic resin and the like. However, the present invention is not limited to the above.

The natural resin is not particularly limited, and examples thereof include cellulose-based resins, isoprene-based resins such as natural rubber, and protein-based resins such as casein.

In one embodiment, the surface of the resin base material may be subjected to surface treatment such as corona discharge treatment, frame treatment, plasma treatment, etc., 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 intended use.

<Manufacturing of coating composition>
In a typical embodiment, the coating composition according to the present invention comprises a step of mixing the component (A) and the component (B) in advance and then mixing them with water, and a step of stirring at a temperature of less 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 diluting each component contained in the coating composition with water and then mixing, a method of mixing each component in water, and a method of mixing each component in advance are performed. , The method of diluting with water and the like. 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 form a strong interaction. The coating film obtained from the coating composition thus prepared is preferable because it has excellent water resistance. Further, by stirring at a temperature lower 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. The 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 anti-fog coating film because it has excellent anti-fog properties.

The laminate according to the present embodiment is formed by applying, for example, a coating composition (sometimes abbreviated as "aqueous dispersion") dispersed in a solvent such as water onto a substrate and drying it. Will be 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 0.1 to 100,000 mPa · s, preferably 1 to 10,000 mPa · s at 20 ° C. The coating method is not particularly limited, and is, for example, a spray 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 a flexographic printing method. Law etc. can be used. The laminate is formed, for example, by drying the coating film on a substrate and then heat-treating or irradiating with ultraviolet rays at preferably 20 ° C. to 500 ° C., more preferably 40 ° C. to 250 ° C. May be good.

The thickness of the coating film is preferably 0.05 to 100 μm, more preferably 0.1 to 10 μm. 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 stain resistance. In the present embodiment, the "coating film" does not necessarily have 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, but the present embodiments are not limited to the following examples as long as the gist of the present embodiments is not exceeded.
Various physical properties were evaluated by the following methods.

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

<Film thickness>
The film thickness of the obtained coating film was measured using a reflection spectroscopic film thickness meter (manufactured by Otsuka Electronics Co., Ltd., trade name "FE-3000"). The average of the measured values of three randomly selected points was calculated and used 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 100 times). The results were evaluated as follows.
◯: Almost no microcracks △: Many microcracks ×: Film formation is not possible

<Anti-fog test>
A test piece of the obtained coating film was placed at a height of 5 cm from the water surface of the hot water bath maintained at 80 ° C. so that the coating film surface was facing down, and steam from the hot water bath was continuously irradiated to the coating film. Then, the presence or absence of cloudiness 30 seconds after irradiation was visually evaluated as follows. If the evaluation is Δ or higher, there is no problem in practical use, and if it is ◯, it is more preferable.
○ (Good): No cloudiness at all.
Δ (Medium): Slightly cloudy immediately after steam irradiation.
× (defective): Cloudy.

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

<Synthesis Example 1 (Synthesis of Polymer Particles (HB-1))>
<Manufacturing example 1>
After charging 964 g of ion-exchanged water and 1.9 g of dodecylbenzene sulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature was heated to 80 ° C. under stirring. A mixed solution of 46 g of propyltrimethoxysilane and 54 g of methyltrimethoxysilane was added dropwise to the reaction vessel while maintaining the temperature in the reaction vessel at 80 ° C. for about 2 hours, and then the temperature in the reaction vessel was 80 ° C. Stirring was continued for about 1 hour in the state of. Next, a mixed solution 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 11. A mixed solution of 5 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 keeping the temperature in the reaction vessel at 80 ° C. Further, after continuing stirring for about 2 hours at a temperature of 80 ° C. in the reaction vessel, cooling to room temperature, filtering with a 100 mesh wire mesh, and then adjusting the solid content to 6.0% by mass with ion-exchanged water. , A polymer particle (HB-1) aqueous dispersion having a number average particle diameter of 40 nm was obtained.

<Synthesis Example 2 (Synthesis of Polymer Particles (HB-2))>
<Manufacturing example 2>
After charging 876 g of ion-exchanged water and 1.7 g of dodecylbenzene sulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature was heated to 80 ° C. under stirring. A mixed solution of 17 g of propyltrimethoxysilane and 83 g of methyltrimethoxysilane was added dropwise to the reaction vessel while maintaining the temperature in the reaction vessel at 80 ° C. for about 2 hours, and then the temperature in the reaction vessel was 80 ° C. Stirring was continued for about 1 hour in the state of. 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 10. A mixed solution of 9 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 keeping the temperature in the reaction vessel at 80 ° C. Further, after continuing stirring for about 2 hours at a temperature of 80 ° C. in the reaction vessel, cooling to room temperature, filtering with a 100 mesh wire mesh, and then adjusting the solid content to 6.0% by mass with ion-exchanged water. , A polymer particle (HB-2) aqueous dispersion having a number average particle diameter of 25 nm was obtained.

<Synthesis Example 3 (Synthesis of Polymer Particles (HB-3))>
<Manufacturing example 3>
After charging 997 g of ion-exchanged water and 1.9 g of dodecylbenzene sulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature was heated to 80 ° C. under stirring. A mixed solution of 72 g of propyltrimethoxysilane and 28 g of methyltrimethoxysilane was added dropwise over about 2 hours while keeping the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. Stirring was continued for about 1 hour in the state of. Next, a mixed solution 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 11. 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 added dropwise over about 2 hours while keeping the temperature in the reaction vessel at 80 ° C. Further, after continuing stirring for about 2 hours at a temperature of 80 ° C. in the reaction vessel, cooling to room temperature, filtering with a 100 mesh wire mesh, and then adjusting the solid content to 6.0% by mass with ion-exchanged water. , A polymer particle (HB-3) aqueous dispersion having a number average particle diameter of 100 nm was obtained.

<Synthesis Example 4 (Synthesis of Polymer Particles (HB-4))>
<Manufacturing example 4>
After charging 964 g of ion-exchanged water and 1.9 g of dodecylbenzene sulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature was heated to 80 ° C. under stirring. A mixed solution of 46 g of propyltrimethoxysilane and 54 g of methyltrimethoxysilane was added dropwise to the reaction vessel while maintaining the temperature in the reaction vessel at 80 ° C. for about 2 hours, and then the temperature in the reaction vessel was 80 ° C. Stirring was continued for about 1 hour in the state of. Next, a mixed solution 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 11. A mixed solution of 5 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 keeping the temperature in the reaction vessel at 80 ° C. Further, after continuing stirring for about 2 hours at a temperature of 80 ° C. in the reaction vessel, cooling to room temperature, filtering with a 100 mesh wire mesh, and then adjusting the solid content to 6.0% by mass with ion-exchanged water. , A polymer particle (HB-4) aqueous dispersion having a number average particle diameter of 50 nm was obtained.

<Synthesis Example 5 (Synthesis of Polymer Particles (HB-5))>
<Manufacturing example 5>
After charging 980 g of ion-exchanged water and 1.9 g of dodecylbenzene sulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature was heated to 80 ° C. under stirring. A mixed solution of 46 g of octyltrimethoxysilane and 54 g of methyltrimethoxysilane was added dropwise to this over a period of about 2 hours while keeping the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. Stirring was continued for about 1 hour in the state of. Next, a mixed solution 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 11. 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 keeping the temperature in the reaction vessel at 80 ° C. Further, after continuing stirring for about 2 hours at a temperature of 80 ° C. in the reaction vessel, cooling to room temperature, filtering with a 100 mesh wire mesh, and then adjusting the solid content to 6.0% by mass with ion-exchanged water. , A polymer particle (HB-5) aqueous dispersion having a number average particle diameter of 50 nm was obtained.

<Synthesis Example 6 (Synthesis of Polymer Particles (HB-6))>
<Manufacturing example 6>
After charging 1107 g of ion-exchanged water and 2.2 g of dodecylbenzene sulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature was heated to 80 ° C. under stirring. A mixed solution of 46 g of hexadecyltrimethoxysilane and 54 g of methyltrimethoxysilane was added dropwise to the reaction vessel while maintaining the temperature in the reaction vessel at 80 ° C. over about 2 hours, and then the temperature in the reaction vessel was 80. Stirring was continued for about 1 hour at ° C. Next, a mixed solution 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 mass% aqueous solution of ammonium persulfate was simultaneously added dropwise over about 2 hours while keeping the temperature in the reaction vessel at 80 ° C. Further, after continuing stirring for about 2 hours at a temperature of 80 ° C. in the reaction vessel, cooling to room temperature, filtering with a 100 mesh wire mesh, and then adjusting the solid content to 6.0% by mass with ion-exchanged water. , A polymer particle (HB-6) aqueous dispersion having a number average particle diameter of 50 nm was obtained.

<Synthesis Example 7 (Synthesis of Polymer Particles (HB-7))>
<Manufacturing example 7>
After charging 1187 g of ion-exchanged water and 2.0 g of dodecylbenzene sulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature was heated to 80 ° C. under stirring. To this, 100 g of methyltrimethoxysilane was added dropwise over about 2 hours while keeping 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 mixed solution 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 14. A mixed solution of 0 g, 1.0 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 keeping the temperature in the reaction vessel at 80 ° C. Further, after continuing stirring for about 2 hours at a temperature of 80 ° C. in the reaction vessel, cooling to room temperature, filtering with a 100 mesh wire mesh, and then adjusting the solid content to 6.0% by mass with ion-exchanged water. , A polymer particle (HB-7) aqueous dispersion having a number average particle diameter of 50 nm was obtained.

<Synthesis Example 8 (Synthesis of Polymer Particles (HB-8))>
<Manufacturing example 8>
After charging 1025 g of ion-exchanged water and 2.0 g of dodecylbenzene sulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature was heated to 80 ° C. under stirring. A mixed solution of 78 g of propyltrimethoxysilane and 22 g of methyltrimethoxysilane was added dropwise over about 2 hours while keeping the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. Stirring was continued for about 1 hour in the state of. Next, a mixed solution 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 12. A mixed solution of 2 g, 1.0 g of acrylic acid, and 40 g of a 2 mass% aqueous solution of ammonium persulfate was simultaneously added dropwise over about 2 hours while keeping the temperature in the reaction vessel at 80 ° C. Further, after continuing stirring for about 2 hours at a temperature of 80 ° C. in the reaction vessel, cooling to room temperature, filtering with a 100 mesh wire mesh, and then adjusting the solid content to 6.0% by mass with ion-exchanged water. , A polymer particle (HB-8) aqueous dispersion having a number average particle diameter of 100 nm was obtained.

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

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

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

In Examples 6 and 7, the (b1-2) 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 with respect to the hydrolyzable silicon compound contained was reduced, good heat resistance and crack resistance were shown within the permissible range of the present invention. On the other hand, when the relative amount of the (b1-1) hydrolyzable silicon compound having a linear alkyl group having 3 to 16 carbon atoms to the hydrolyzable silicon compound having a (b1-2) methyl group was increased, the amount was increased. Within the permissible range of the present invention, these properties have changed.

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 permissible range of the present invention.

In Examples 9 and 10, the carbon of the linear alkyl group in the hydrolyzable silicon compound having the (b1-1) linear 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 shown within the permissible range of the present invention.

On the other hand, as described above, in the case of Comparative Example 1 in which the (b1-1) hydrolyzable silicon compound having a linear alkyl group having 3 to 16 carbon atoms is not contained in the polymer particles in the component (B), the resistance is resistant. The crackability has dropped to a level that is unbearable for practical use.

In Comparative Example 2, the hydrolyzable silicon compound having a (b1-1) linear alkyl group having 3 to 16 carbon atoms contained in the polymer particles in the component (B) has a (b1-2) methyl group. Excessive amounts relative to the hydrolyzable silicon compound clearly reduced the initial antifogging property.

The coating composition of the present invention is excellent in the appearance of the coating film and the anti-fog property, and can maintain the anti-fog property for a long period of time even in a harsh environment such as a high temperature. Therefore, the coating composition of the present invention can be particularly preferably used as an anti-fog coating film that requires high anti-fog properties. Further, it can be used as a coating film for automobile exterior parts such as vehicle lighting fixtures such as automobile headlamps for applications requiring anti-fog durability in a high temperature environment. Further, the coating composition of the present invention can also be used for parts that cannot be easily taken out to remove fogging, such as internal parts of various devices and parts installed in high places. All of the above-mentioned features and advantages of the coating composition according to the present invention are also applied to these anti-fog coating films, coating films for automobile exterior parts, and coating films for internal parts.

Claims (11)

(A) A metal oxide having a number average particle diameter of 1 nm to 400 nm,
(B) Including a polymer particle aqueous dispersion
The component (B) is
It is a polymer particle aqueous dispersion 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) 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.
A coating composition having a mass ratio (b1-1) / (b1-2) of (b1-1) and (b1-2) 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) to the polymer particles in the component (B) is 0.5 to 3.0. .. The coating composition according to claim 1 or 2, wherein the number average particle diameter of the component (B) is 5 nm to 200 nm. The invention according to claim 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. 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. Claims 1 to 5 in which 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. The coating composition according to any one of the above. 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) contains 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 of a resin base material and / or a glass base material 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.