JP7360274B2 - Highly durable anti-fog coatings and coating compositions - Google Patents

Description

The present invention relates to a coating film and a coating composition for forming the same. The present invention particularly relates to highly durable antifogging coatings and coating compositions for forming the same.

Resin molded bodies are widely used as an alternative to glass plates from the viewpoint of weight reduction and moldability. Its applications span a wide range of fields, including automobile parts, home appliance parts, housings, containers, films, and sheets. In particular, transparent plastics are used for various windows, optical lenses, mirrors, glasses, goggles, soundproof walls, traffic light lenses, headlight lenses, curved mirrors, windshields, nameplates, etc. However, with resin base materials such as plastics, dew condensation may occur on the surface of the base material when one side of the base material falls below the dew point temperature or when a sudden change in temperature and humidity occurs due to the difference in temperature and humidity with the outside air. , fine water droplets may adhere to the surface and scatter the transmitted light. In such a case, the transparency of the resin molded article is impaired and so-called cloudiness occurs.
The following proposals have been made as a method to prevent this clouding.
(1) A method of producing a coating film of a water-absorbing compound on the surface of a substrate.
(2) A method of making the surface of a substrate hydrophilic by creating a coating film of a hydrophilic compound such as a surfactant on the surface of the substrate.

Specifically, as the method (1), Patent Document 1 discloses an antifogging method having a water-absorbing crosslinked resin layer made of a cured epoxide resin or a urethane resin, and the water-absorbing layer containing metal oxide fine particles. Goods, etc. are proposed. Further, Patent Document 2 proposes an antifogging article that includes a water absorbing layer containing a cured epoxy resin and a polyoxyethylene alkyl ether surfactant.
However, in these methods, although antifogging properties can be maintained up to a certain level, fogging occurs when water in excess of the water absorption capacity aggregates and adheres to the article. Therefore, there is a disadvantage that the film needs to be thick in order to exhibit high antifogging durability.

As the method (2), Patent Document 3 and Patent Document 4 disclose a hydrophilic and antifouling coating film characterized in that the coating surface is made of colloidal silica. Specifically, Patent Document 3 discloses an antifouling coating film containing colloidal silica and a nonionic surfactant, and Patent Document 4 discloses an antifouling coating film containing polymer particles and colloidal silica. . However, the coating films of these documents are all characterized by colloidal silica being unevenly distributed on the outermost surface of the coating film. Therefore, although it has excellent initial hydrophilicity and antifogging properties, it has poor adhesion to the substrate, and furthermore, when placed in harsh environments such as high temperature and humidity, a decrease in antifogging properties and poor appearance may occur.

Further, Patent Document 5 discloses an antifogging coating composition and a laminate containing a siloxane binder, silica particles, and a water-absorbing organic polymer, and having a water absorption amount and a water contact angle within a specific range. However, since there is little structure that exhibits cohesiveness with the substrate, adhesion is poor, and when exposed to harsh environments, anti-fogging properties may be reduced, hydrophilic compounds may be leached from the coating surface, and the coating may There is a possibility that poor appearance due to whitening (occurrence of water drop marks) caused by overall elution cannot be resolved satisfactorily.

International Publication No. 2012/161330 International Publication No. 2015/008672 Patent No. 4812902 International Publication No. 2010/104146 International Publication No. 2018/092543

In view of the problems of the prior art, the present inventors have discovered that the coating has excellent anti-fog properties and adhesion properties, and maintains good anti-fog properties, adhesion properties, and paint film appearance even when exposed to rapid environmental changes. The objective is to provide a coating film.

The present inventors have completed the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is as follows.
[1].
Water resistance that contains a metal oxide (A) and a hydrophilic compound (B) and is achieved by immersing a coating film in deionized water at 25°C for 240 hours and then leaving it for 1 hour in an environment of 23°C and 50% RH. A coating film characterized in that the change in refractive index before and after a property test is -5% or more and +5% or less.
[2].
The coating film according to item [1] above, further comprising polymer particles (C).
[3].
The coating film according to item [1] or [2] above, further comprising a crosslinking agent (D).
[4].
The coating film according to any one of items [1] to [3] above, which has a water contact angle value of less than 40°.
[5].
The coating film according to any one of items [1] to [4] above, wherein the metal oxide (A) contains silica.
[6].
According to any one of items [1] to [5] above, wherein the hydrophilic compound (B) is bonded to the surface of the metal oxide (A) via a non-covalent bond and/or a covalent bond. coating.
[7].
The coating film according to any one of items [1] to [6] above, wherein the hydrophilic compound (B) has an alkylene glycol moiety in the molecule.
[8].
The coating film according to any one of items [1] to [7] above, wherein the polymer particles (C) include portions in contact with each other.
[9].
For producing the coating film according to any one of items [1] to [8] above, wherein the metal oxide (A) contains at least one of an alkoxysilane and a hydrolyzed condensate of an alkoxysilane. coating composition.
[10].
The coating composition for producing a coating film according to any one of items [1] to [8] above, wherein the metal oxide (A) contains at least one of silicone particles and acrylic silicone particles.
[11].
The coating composition according to item [9] or [10] above, wherein the hydrophilic compound (B) contains at least one kind of an alkoxysilyl group and a silanol group in the molecule.
[12].
The coating composition according to any one of items [9] to [11] above, further comprising a polymer particle (C), wherein the polymer particle (C) contains a reactive functional group.
[13].
Any one of the above items [9] to [11], which contains a metal oxide (A) and a hydrophilic compound (B), and further contains at least one of polymer particles (C) and a crosslinking agent (D). Coating composition as described in section.
[14].
A laminate of any one of a resin base material and a glass base material and the coating film according to any one of items [1] to [8] above.
[15].
The coating film according to any one of items [1] to [8] above, which is used as an antifogging coating film.
[16].
The coating film according to any one of items [1] to [8] above, which is used as a coating film for automobile exterior parts.
[17].
The coating film according to any one of items [1] to [8] above, which is used as a coating film for a lamp cover.

According to the present invention, it is possible to provide a coating film that maintains good antifogging properties, adhesion, and coating appearance even when exposed to rapid environmental changes.

Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as "embodiments") will be described in detail. Note that the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

Each component of the present invention will be explained.

The coating film in the present invention is formed by, for example, coating a coating composition (sometimes abbreviated as "aqueous dispersion") dispersed in a solvent such as water on a substrate and drying the coating composition. Therefore, basically, the coating film and the coating composition have the same component composition and proportions except for the solvent. That is, unless otherwise specified, the coating film according to the present invention has the characteristics and quantitative ratios of the component groups of the coating composition described below. Therefore, below, the composition of the coating composition will be mainly explained.

The coating composition in the present invention contains a metal oxide as the component (A) and a hydrophilic compound as the component (B).

(A) Component: Metal oxide From the viewpoint of interaction with component (B), examples of metal oxides used for component (A) include silicon dioxide, aluminum oxide, antimony oxide, titanium oxide, indium oxide, Tin oxide, zirconium oxide, lead oxide, iron oxide, calcium silicate, magnesium oxide, niobium oxide, cerium oxide, and the like can be used. Among these, from the viewpoint of the strength of interaction, silicon dioxide (silica), aluminum oxide (alumina), antimony oxide, and composite oxides thereof, which have many surface hydroxyl groups, are preferable. In addition, as component (A), two or more types of metal oxides mentioned above may be used in combination.

Furthermore, from the viewpoint of imparting stain resistance, the metal oxide used in component (A) is a compound that exhibits photocatalytic activity and/or hydrophilicity upon irradiation with light (hereinafter sometimes simply abbreviated as "photocatalyst"). ) may be used. By using a compound that exhibits photocatalytic activity upon irradiation with light as component (A), it is possible to exhibit excellent decomposition activity and stain resistance for contaminant organic substances on the surface of the coating film formed from the coating composition. In addition, in this specification, "hydrophilicity" of a coating film means that the contact angle (water contact angle) of water (23°C) with respect to the surface of the measurement object is preferably 40° or less, more preferably 30° or less, and furthermore This means that the angle is preferably 20° or less. The method for measuring the water contact angle will be described later in Examples. Note that the term "compound that exhibits hydrophilicity upon irradiation with light" as used herein is distinguished from the hydrophilic compound of component (B), which inherently has hydrophilicity.

More specifically, as _a photocatalyst, _{TiO2 ,} ZnO, _SrTiO3 , _BaTiO3 , _BaTiO4 , _{BaTi4O9 , K2NbO3 , Nb2O5 , Fe2O3} , _Ta2O5 , _{K3 Ta3Si2O3 , WO3} , _SnO2 , _Bi2O3 , _BiVO4 , NiO, _Cu2O , _RuO2 , _{CeO2, etc.} can be _used . Furthermore, as a photocatalyst, a layered oxide containing at least one element selected from Ti, Nb, Ta, and V (for example, JP-A-62-74452, JP-A-2-172535, JP-A-7-1999) 24329, JP 8-89799, JP 8-89800, JP 8-89804, JP 8-198061, JP 9-248465, JP 10-99694 (see Japanese Patent Laid-Open Publication No. 10-244165, etc.) can be used. Among these photocatalysts, TiO ₂ (titanium oxide) is preferred because it is harmless and has excellent chemical stability. As titanium oxide, any of anatase type, rutile type, and brookite type can be used.

Further, as the metal oxide used in component (A), a metal oxide having electrical conductivity can be used from the viewpoint of exhibiting antistatic performance of the coating film formed from the coating composition. Examples of conductive metal oxides that can be used include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), tin oxide, and zinc oxide.

Component (A) is used as a raw material for the coating composition, for example, in the form of powder, dispersion, sol, or the like. Here, the dispersion liquid or sol refers to component (A) containing primary particles and /or means dispersed as secondary particles. Examples of hydrophilic organic solvents include alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol, methanol, and 2-ethylhexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, and diacetone alcohol. , ketones such as cyclopentanone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, dimethyl sulfoxide, nitrobenzene, N-methylpyrrolidone, etc., and mixtures of two or more of these can be used. It is.

The metal oxide used in component (A) may be silicone particles and/or acrylic silicone particles.
As an example, the silicone particles may be composed of the (c4) component of the polymer particle (C) described below, and the acrylic silicone particles may be composed of the (c1) and (c4) components. Further, the silicone particles may include polyalkylene glycol containing an alkoxysilane and/or silanol group in the molecule, which will be described later. In this case, the alkoxysilane and/or silanol moiety may be made into a metal oxide (A), the polyalkylene glycol moiety may be made into a hydrophilic compound (B), or separately, the metal oxide (A) and/or the hydrophilic compound may be made into a hydrophilic compound (B). A compound (B) may also be added.

Number average particle diameter of component (A) observed in powder, dispersion, or sol (may be a mixture of primary particles and secondary particles, or only primary particles or secondary particles) ) is preferably 1 nm or more and 400 nm or less. The lower limit of the number average particle diameter is more preferably 3 nm, and even more preferably 4 nm, from the viewpoint of storage stability of the coating composition. Moreover, the upper limit of the number average particle diameter is more preferably 100 nm, still more preferably 80 nm, and particularly preferably 50 nm, from the viewpoint of the transparency of the coating film. The number average particle diameter within the specified range is usually maintained even in the formed coating film. Note that the number average particle diameter (sometimes simply abbreviated as "particle diameter") in this specification for component (A) is a value measured according to the method of Examples described below.

In the present invention, the metal oxide (A) is preferably silica from the viewpoint of ease of handling. The basic unit of silica is silicon dioxide, and it may be prepared by a sol-gel method or a commercially available product may be used. When preparing by the sol-gel method, the method described by Werner Stober et al; J. Colloid and Interface Sci. , 26, 62-69 (1968), Rickey D. Badley et al; Lang muir 6, 792-801 (1990), Color Materials Association Journal, 61 [9] 488-493 (1988), etc. can be referred to. Among them, colloidal silica is a dispersion of silica in water or a water-soluble solvent, and is preferred from the viewpoint of ease of handling. The number average particle diameter of silica is preferably in the same range as the number average particle diameter described above for component (A).

Silica having a number average particle diameter within the above range can be used in the form of an aqueous dispersion, regardless of whether it is acidic, basic, or cationic. The liquid properties can be appropriately selected depending on the stability range of the hydrophilic compound (B) to be mixed. The shape of silica is not particularly limited, and examples thereof include spherical, chain-like, bead-like, plate-like, needle-like, and the like. When silica and a hydrophilic compound are immobilized through a non-covalent bond, the pH is preferably 10 or less because the non-covalent bond becomes strong. Examples of acidic silica using water as a dispersion medium include commercially available products such as Snowtex (registered trademark)-OXS, Snowtex-OS, Snowtex-O, Snowtex-O-40, and Snowtex (registered trademark) manufactured by Nissan Chemical Industries, Ltd. -OL, Snowtex-OYL, Snowtex-OUP, Snowtex-PS-SO, Snowtex-PS-MO, Adelite (registered trademark) AT-20Q manufactured by ADEKA Co., Ltd., Crebosol (registered trademark) manufactured by Clariant Japan Co., Ltd. 20H12, Crebosol 30CAL25, etc. can be used.

Examples of basic silica include silica stabilized by the addition of alkali metal ions, ammonium ions, and amines. For example, Snowtex-20, Snowtex-30, Snowtex-C, Snowtex-C30, Snowtex-CM40, Snowtex-N, Snowtex-N30, Snowtex-K, Snowtex-K, manufactured by Nissan Chemical Industries, Ltd. -XL, Snowtex-YL, Snowtex-ZL, Snowtex PS-M, Snowtex PS-L, etc. can be used. Alternatively, Aderite AT-20, Aderite AT-30, Aderite AT-20N, Aderite AT-30N, Aderite AT-20A, Aderite AT-30A, Aderite AT-40, Aderite AT-50, etc. made by ADEKA Co., Ltd. can also be used. It is. Furthermore, Klebosol 30R9, Klebosol 30R50, and Klebosol 50R50 manufactured by Clariant Japan Co., Ltd., and W. R. Ludox (registered trademark) HS-40, Ludox HS-30, Ludox LS, Ludox SM-30, etc. manufactured by Grace Corporation can also be used.

As the cationic silica, for example, Snowtex-AK, Snowtex-AK-L, Snowtex-AK-YL manufactured by Nissan Chemical Industries, Ltd. can be used.

In addition, examples of silica using a water-soluble solvent as a dispersion medium include MA-ST-M (methanol dispersion type with a number average particle size of 20 to 25 nm) manufactured by Nissan Chemical Industries, Ltd., IPA-ST (number average particle size 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 (ethylene glycol dispersion type with a number average particle diameter of 70 to 100 nm) , and NPC-ST (ethylene glycol monopropyl ether dispersion type with a number average particle diameter of 10 to 15 nm), etc. can be used.
Note that these silicas may be used alone or in combination of two or more. In addition, alumina, sodium aluminate, etc. may be included as minor components. Furthermore, silica may contain an inorganic base (sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc.), an organic base (tetramethylammonium, etc.), etc. as a stabilizer.

(B) Component: Hydrophilic Compound The hydrophilic compound used as component (B) improves the dispersibility of component (A) and immobilizes it on the surface of component (A) through non-covalent bonds and/or covalent bonds. Improved anti-fogging properties of the paint film, improved moisture resistance, improved appearance sustainability, improved elution resistance (suppression of elution on the surface of the paint film and further elution from the entire paint film), and effect of suppressing the formation of water drop marks. It is contained in the coating composition for the purpose of improving the properties and film formability of the coating film.
In order to improve the above-mentioned coating film performance, it is sufficient that the component (B) is fixed to the component (A) through either a non-covalent bond or a covalent bond. From the viewpoint of suppressing scars, it is preferable to immobilize through two types of bonds.

The hydrophilic compound (B) may be at least one selected from the group consisting of nonionic compounds, anionic compounds, and zwitterionic compounds. As the nonionic compound, anionic compound, and amphoteric ionic compound, any of the known compounds having these ionic properties can be used.
Examples of nonionic compounds include compounds having a hydroxyl group, carboxyl group, amide group, amino group, alkylene oxide moiety, etc. as a hydrophilic moiety.
Examples of anionic compounds include compounds having carboxylic acid sites, sulfonic acid sites, phosphoric acid sites, and boronic acid sites.
Examples of zwitterionic compounds include anionic sites such as carboxylic acid sites, sulfonic acid sites, phosphoric acid sites, and boronic acid sites, and cationic sites such as quaternary ammonium sites, imidazolium sites, pyridinium sites, sulfonium sites, and phosphonium sites. Examples include compounds that have a sexual site within the same molecule.

As the hydrophilic compound used in component (B), compounds that can be dissolved and/or dispersed in water can be used from the viewpoint of dispersion stability of the coating composition. It may have a hydrophobic group in addition to a hydrophilic group as long as it is soluble and/or dispersible in water. In addition, when component (B) is immobilized on (A) via a non-covalent bond, component (B) contains an interaction site with metal oxide (A), which increases the durability of the coating film. Preferable from a gender perspective. Examples of such interaction sites include hydroxyl groups, amino groups, amide groups, carboxyl groups, silanol groups, sulfo groups, polyoxyalkylene sites, ammonium salt sites, pyridinium salt sites, imidazolium salt sites, alkoxysilane sites, etc. can be mentioned.

The hydrophilic compound (B) may have at least one functional group in its molecule that can react with the crosslinking agent (D) described below. A hydrophilic compound having two or more functional groups capable of reacting with the crosslinking agent (D) in its molecule is more preferred. In this case, a two-dimensional and/or three-dimensional crosslinked product is formed by the reaction with the crosslinking agent (D), and the durability of the resulting coating film (for example, anti-fogging of the coating film when exposed to rapid environmental changes) It is even more preferable from the viewpoints of sustainability, adhesion sustainability, and appearance sustainability. Examples of functional groups that can react with the crosslinking agent (D) include isocyanate groups, blocked isocyanate groups, keto groups, aldehyde groups, epoxy groups, hydroxyl groups, carboxyl groups, alkoxysilyl groups, carbodiimide groups, amide groups, and amino groups. However, a hydroxyl group is more preferred.

By using a hydrophilic compound that has an interaction site with the metal oxide (A), it is immobilized on the surface of the metal oxide (A) (e.g., silica) through non-covalent bonds and/or covalent bonds, and rapidly Improves the anti-fog durability, adhesion durability, and appearance durability of the coating film when exposed to environmental changes.
In addition, by using a hydrophilic compound that has one or more functional groups that can react with isocyanate groups in its molecule, the hydrophilic compound is immobilized in the coating film and prevents elution due to contact with water. can do.
Specifically, examples of the hydrophilic compound (B) having two or more functional groups in the molecule that are the interaction sites and can react with the crosslinking agent (D) include, but are not particularly limited to, polyoxyalkylene. Glycol, polyoxyalkylene phenyl ether, polyoxyalkylene alkylaryl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyethylene oxypropylene block copolymer, polyoxyethylene oxypropylene oxyethylene triblock copolymer, polyoxypropylene oxyethylene oxypropylene triblock Examples include copolymers, alkylene glycol moiety-containing polymers such as fatty acid polyoxyalkylene sorbitan, polyvinyl alcohol, polyhydroxyalkyl (meth)acrylates, and copolymers of hydroxyalkyl (meth)acrylates and alkyl (meth)acrylates. These may be used alone or in combination of two or more. The number of carbon atoms in "alkylene" and "alkyl" herein is not particularly limited, but is, for example, 1 to 10, more preferably 2 to 6, and most preferably 2 or 3.
These hydrophilic compounds (B) are preferably used in coating compositions containing the crosslinking agent (D) (and coating films formed therefrom), but in coating compositions that do not contain the crosslinking agent (D). (and coating films formed from this).

Among these hydrophilic compounds (B), when a polyalkylene oxide having three or more functional groups capable of reacting with an isocyanate crosslinking agent is contained, the fixation of the coating film to the silica surface, initial antifogging property, initial adhesion, It is preferable from the viewpoints of antifogging durability, adhesion durability, and appearance durability when exposed to rapid environmental changes. Examples of polyalkylene oxides having three or more functional groups that can react with the isocyanate crosslinking agent include glycerol ethoxylate, trimethylpropane ethoxylate, and fatty acid polyoxyalkylene sorbitan. Examples of fatty acid polyoxyalkylene sorbitans include monofatty acid polyoxyalkylene sorbitans. A specific example of the monofatty acid polyoxyalkylene sorbitan includes polyoxyethylene sorbitan monolaurate. Examples of fatty acids here include lauric acid, stearic acid, oleic acid, etc., but are not particularly limited.
It is more preferable for the coating composition to have three or more functional groups capable of reacting with the above-mentioned isocyanate crosslinking agent in terms of the durability of the coating film. When the coating composition contains a hydrophilic compound (B) having four or more functional groups capable of reacting with an isocyanate crosslinking agent, a three-dimensional crosslinked product is formed even if the reaction rate with the isocyanate crosslinking agent is less than 100%. Therefore, it is more preferable in terms of the durability of the coating film. Examples of such compounds include 4-branched polyalkylene glycols, 8-branched polyalkylene glycols, hyperbranched polymers, and the like.
A hydrophilic compound (B) having four or more functional groups capable of reacting with an isocyanate crosslinking agent such as monofatty acid polyoxyalkylene sorbitan, 4-branched polyalkylene glycol, 8-branched polyalkylene glycol, or hyperbranched polymer, Not only coating compositions containing an isocyanate crosslinking agent (and coating films formed therefrom), but also coating compositions containing no isocyanate crosslinking agent or containing a crosslinking agent (D) described below (and coating films formed therefrom). It can also be used for

The hydrophilic compound (B) may have one or more functional groups capable of forming a covalent bond with the metal oxide (A) in its molecule. Examples of functional groups that can form covalent bonds with the metal oxide (A) include hydroxyl groups, silanol groups, alkoxysilane groups, and isocyanate groups. By using a hydrophilic compound having one or more functional groups capable of forming a covalent bond with the metal oxide (A), the hydrophilic compound is fixed in the coating film through the covalent bond. Even when the hydrophilic compound is exposed to harsh environments such as contact with water or high temperature and humidity, the hydrophilic compound can remain in the coating without separating from the coating.

Examples of the hydrophilic compound (B) include polyalkylene oxides containing alkoxysilane and/or silanol groups in the molecule.
Such polyalkylene oxides containing alkoxysilane and/or silanol groups in the molecule include, for example, polyoxyalkylene alkyl ether, polyoxyalkylene phenyl ether, polyoxyalkylene alkylaryl ether, and molecules having one hydroxyl group in the molecule. Polyoxyalkylene glycol having two hydroxyl groups within the molecule, fatty acid polyoxyalkylene sorbitan having three hydroxyl groups within the molecule, glycerol ethoxylate, trimethylpropane ethoxylate, four-branched polyalkylene glycol having four hydroxyl groups within the molecule, Examples include a reaction product of an 8-branched polyalkylene glycol having eight hydroxyl groups in the molecule and a silane coupling agent having a functional group capable of reacting with the hydroxyl groups.

Examples of the silane coupling agent having a functional group that can react with a hydroxyl group include 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl Examples include methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. Among these, isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane are preferred from the viewpoint of reactivity.

A catalyst may optionally be added to the reaction between the above-mentioned polyoxyalkylene alkyl ether having one hydroxyl group in the molecule and the isocyanate-based silane coupling agent. Examples of the catalyst include, but are not limited to, tin-based compounds such as dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin dineodecanoate, and tin bis(2-ethylhexanoate); 2-ethylhexanoic acid. Zinc compounds such as zinc and zinc naphthenate; Titanium compounds such as titanium 2-ethylhexanoate and titanium diisopropoxybis(ethylacetonate); Cobalt compounds such as cobalt 2-ethylhexanoate and cobalt naphthenate; 2-ethyl Examples include bismuth compounds such as bismuth hexanoate and bismuth naphthenate; zirconium compounds such as zirconium tetraacetylacetonate, zirconyl 2-ethylhexanoate, and zirconyl naphthenate; and amine compounds.

Among these hydrophilic compounds (B), polyalkylene oxides have a branched polyalkylene oxide chain in the molecule and contain a primary aliphatic hydroxyl group and an alkoxysilane and/or silanol group at the end of the polyalkylene oxide chain. is preferable from the viewpoint of initial antifogging properties, adhesion, durability, elution resistance, and the effect of suppressing the generation of water drop marks. Such a hydrophilic compound (B) can be produced by, for example, reacting a polyalkylene oxide having two or more, more preferably three or more, hydroxyl groups in the molecule with a silane coupling agent having a functional group that can react with the hydroxyl groups. Can be synthesized. The rate of introduction of the silane coupling agent into the hydroxyl groups of the hydrophilic compound (B) can be measured by NMR or the like. This introduction rate is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more, from the viewpoint of water droplet suppression effect. Further, from the viewpoint of adhesion, the upper limit of this introduction rate is preferably 100% or less, more preferably 95% or less, and still more preferably 90% or less.

The molecular weight of the hydrophilic compound (B) is preferably 400 or more, more preferably 1000 or more, still more preferably 2000 or more from the viewpoint of moisture resistance and suppression of water drop marks.

From the viewpoint of moisture resistance, the mass ratio of the hydrophilic compound (B) to the metal oxide (A) ((B mass)/(A mass)) is preferably 0.005 or more, more preferably 0.01 or more, and Preferably it is 0.03 or more. Further, from the viewpoint of elution resistance and suppression of water droplet formation, this mass ratio is preferably 1 or less, more preferably 0.7 or less, and even more preferably 0.5 or less.

When particles are used as the metal oxide (A), the ratio of the number of molecules of the hydrophilic compound (B) to the surface area of the metal oxide (A) ((number of B molecules)/(A surface area nm ² )) is the moisture resistance. From this point of view, it is 0.01/nm ² or more, more preferably 0.05/nm ² or more, even more preferably 0.1/nm ² or more. In addition, from the viewpoint of elution resistance and suppression of water droplet formation, this ratio is preferably 4.0/nm ² or less, more preferably 3.0/nm ² or less, and even more preferably 2.0/nm ² or less. .

Generally, in a coating film obtained by applying a coating composition containing a metal oxide and water, the metal oxide component is present on the outermost surface. Therefore, for example, when using a coating composition containing the above-mentioned silica, the silica component will be present on the outermost surface of the coating film. When such a coating film is exposed to a high temperature and high humidity environment, contamination occurs due to adsorption of foreign matter, and the antifogging property is lost.
On the other hand, in the case of a coating film containing a large amount of hydrophilic compounds, excess hydrophilic compounds that are not immobilized on the metal oxide (A) may become localized within the coating film in a high temperature and humid environment. Such localization causes poor appearance such as whitening of the paint film (elution from the surface of the paint film and further from the entire paint film, resulting in water drop marks).

In one embodiment, the coating film of the present invention has an elemental concentration ratio (C1s/M) of C element and metal element obtained from a C1s spectrum and a metal (M) spectrum derived from a metal oxide in elemental analysis by XPS of the surface. may be in the range of 0.1 to 5, but is not particularly limited. When C1s/M is 0.1 or more, the degree of exposure of metal oxides on the coating surface becomes smaller, contamination by foreign substances is suppressed when exposed to a high temperature and humidity environment, and antifogging properties are desired. can be maintained at a level of When C1s/M is 5 or less, the amount of organic components that are not immobilized on the metal oxide surface becomes smaller, and the appearance sustainability, elution resistance, and water droplet suppression effect are maintained at the desired level. can be done.

Furthermore, by setting the relative element concentration of C element obtained from the C1s spectrum derived from carbon-oxygen bonds and/or carbon-nitrogen bonds in the range of 5 to 50 atomic% in elemental analysis by XPS of the surface, the coating film can be prevented. Cloudiness and hydrophilicity can be further improved. When the content is 5 atomic% or more, the density of the hydrophilic groups on the surface of the coating film becomes higher, and the hydrophilicity and antifogging properties of the coating film can be improved. When the content is 50 atomic% or less, the solubility in water can be maintained within a desired range, and the elution resistance of the coating film and the effect of suppressing the generation of water drop marks can be improved.

In elemental analysis by XPS of the coating surface, the lower limit of C1s/M is more preferably 0.3 or more, still more preferably 0.4 or more. The upper limit is more preferably 8 or less. In other words, C1s/M is in the range 0.2-8, in the range 0.3-10, in the range 0.3-8, in the range 0.4-10, or in the range 0.4-8. It's good.
Furthermore, in elemental analysis of the coating surface by XPS, the lower limit of the relative element concentration in the C1s spectrum derived from carbon-oxygen bonds and/or carbon-nitrogen bonds is more preferably 10 atomic% or more. The upper limit is more preferably 40 atomic% or less. In other words, the relative element concentration in the C1s spectrum derived from carbon-oxygen bonds and/or carbon-nitrogen bonds is in the range of 5 to 40 atomic%, in the range of 10 to 50 atomic%, or in the range of 10 to 40 atomic%. It's fine.
Elemental analysis of the coating surface by XPS can be performed, for example, using the following equipment and measurement conditions.
As the equipment used, for example, Verasa probe II manufactured by ULVAC-PHI Co., Ltd. can be used, and monoAlK (15 kV x 3.3 mA) can be used as the excitation source. A 1 mm x 2 mm mask is placed over the surface of the coating film of the measurement sample to define the measurement range.
The photoelectron extraction angle is 45°, and the survey scan is performed in the range of 0 to 1,100 eV, and the narrow scan is performed in the C1s, N1s, Si2p, and O1s regions. Moreover, Pass Energy is performed at 117.5 eV for Survey scan and 46.95 eV for Narrow scan.

As a method for coating the surface of the metal oxide (A) with an organic component such as a hydrophilic compound (B) via a non-covalent bond, for example, the number average particle diameter (D _A ), the density ( ρ _A ), the weight ratio of (B) to (A) (W _B ), the average particle diameter of the hydrophilic compound (B) (D _B ), and the density of the component (B) (ρ _B ), (B) ) The content of the organic component is such that the coverage (P) of (A) is controlled within the range of 1% or more and less than 100% in order to improve the anti-fogging durability, appearance durability, and durability of the coating film. It is preferable from the viewpoint of elution property and the effect of suppressing the generation of water droplets. This coverage (P) is more preferably 3% or more and less than 70%, and even more preferably 5% or more and less than 50%.
In addition, the average particle diameter (D _B ) of the hydrophilic compound (B) can be calculated from the molecular weight and density of the hydrophilic compound (B). When the coverage rate (P) is 1% or more, the amount of metal oxide exposed on the coating surface becomes smaller, and the antifogging property can be maintained even when exposed to a high temperature and high humidity environment.

When the coverage rate (P) is less than 100%, uneven distribution of the hydrophilic compound (B) that is not immobilized on the metal oxide surface on the coating film surface and elution into water are suppressed, and the coating film is Appearance persistence, elution resistance, and water droplet suppression effect can be adjusted to desired levels.
Here, the weight ratio (W _B ) of (B) to (A) depends on the particle diameters of (A) and (B). When the particle size of (A) is 1 to 400 nm, in order for the coverage to be 1% or more and less than 100%, 0.00008<W _B <3.

As a method for coating the surface of a metal oxide (A) with an organic component such as a hydrophilic compound (B) via a covalent bond, for example, an organic compound having reactivity with a functional group on the surface of the metal oxide is reacted in advance. An example of this is letting people know. For example, when colloidal silica is used as the metal oxide, a hydrophilic compound having a functional group that reacts with a silanol group on the surface of the colloidal silica can be used. Examples of such functional groups include alkoxy groups, silanol groups, hydroxyl groups, amino groups, oxime groups, acetoxy groups, and the like.

Change in refractive index due to water resistance test The coating film containing the components (A) and (B) was immersed in deionized water at 25°C for 240 hours, and then left standing at 23°C in an environment of 50% RH for 1 hour. It is preferable for the refractive index change after the test (hereinafter referred to as the water resistance test) to be -5% or more and +5% or less compared to before the test, from the viewpoint of long-lasting adhesion and long-lasting appearance. . The lower limit of the refractive index change is preferably -4%, more preferably -3%, and even more preferably -2%. Further, the upper limit of the refractive index change is preferably +4%, more preferably +3%, and even more preferably +2%. Here, deionized water is water from which salts and residual chlorine have been removed using an ion exchange resin. Alternatively, distilled water, which is water from which salts and residual chlorine have been removed using a distillation machine, or purified water specified by the Japanese Pharmacopoeia may be used instead. Methods for measuring the refractive index include, for example, the critical angle method, the V-block method, the spectroscopic ellipsometry method, the dispersion method, and the optical interference method. Ellipsometry and optical interferometry are preferred.

Component (C): Polymer particles The coating composition for forming the coating film according to the present invention may contain polymer particles as the component (C) in addition to the components (A) and (B).
Furthermore, it is preferable that the polymer particles (C) contain a functional group reactive with the crosslinking agent (D) described below. Examples of reactive functional groups contained in component (C) include isocyanate groups, blocked isocyanate groups, keto groups, aldehyde groups, epoxy groups, hydroxyl groups, carboxyl groups, alkoxysilyl groups, carbodiimide groups, amide groups, amino groups, etc. can be mentioned.
Component (C) is selected from the group consisting of component (c1): isocyanate group, blocked isocyanate group, keto group, aldehyde group, epoxy group, hydroxyl group, carboxyl group, alkoxysilyl group, carbodiimide group, amide group, and amino group. These are polymer particles obtained by polymerizing a polymer stock solution containing a vinyl monomer containing at least one selected reactive functional group and component (c2): water.

The component (A) can interact with the component (C) and act as a curing agent for the component (C). The interaction is, for example, between a hydroxyl group that component (A) generally has and an isocyanate group, blocked isocyanate group, keto group, aldehyde group, epoxy group, hydroxyl group, carboxyl group, or alkoxysilyl group that component (C) has. , the formation of a hydrogen bond with a reactive functional group selected from the group consisting of a carbodiimide group, an amide group, and an amino group, or a hydroxyl group that component (A) generally has and component (c1) constituting component (C). and condensation (chemical bond) with polymerization products. Further, it is preferable that component (A) interacts with component (C) to form a continuous layer between particles of component (C). Thereby, the initial adhesion of the resulting coating film, the antifogging property when exposed to rapid environmental changes, the adhesion, and the appearance of the coating film can be further improved.

Examples of the isocyanate group-containing vinyl monomer as component (c1) include isocyanatoethyl (meth)acrylate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and the like. Alternatively, a vinyl compound in which a vinyl monomer having a hydroxyl group is partially reacted with a diisocyanate or triisocyanate, or a polyisocyanate containing the diisocyanate or triisocyanate described above, leaving one or more isocyanate groups may be used.
Examples of the diisocyanate and triisocyanate include 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanato)hexanoate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4 - or aliphatic diisocyanates such as 2,4,4-trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2-isocyanate Aliphatic triisocyanates such as ethyl (2,6-diisocyanato)hexanoate; 1,3- or 1,4-bis(isocyanatomethylcyclohexane), 1,3- or 1,4-diisocyanatocyclohexane, 3 , 5,5-trimethyl(3-isocyanatomethyl)cyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, 2,5- or 2,6-diisocyanatomethylnorbornane; 2 , 5- or 2,6-diisocyanate methyl-2-isocyanate propylnorbornane; m-xylylene diisocyanate, α,α,α'α'-tetramethyl-m-xylylene diisocyanate Aralkylene diisocyanates such as isocyanates; m- or p-phenylene diisocyanate, tolylene-2,4- or 2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4-diisocyanate Aromatic diisocyanates such as '-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyldiphenyl, 3-methyl-diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate; triphenyl Aromatic triisocyanates such as methane triisocyanate and tris(isocyanatophenyl)thiophosphate are mentioned.
Further, the polyisocyanate includes a diisocyanate or polyisocyanate having a uretdione structure obtained by cyclizing and dimerizing the isocyanate groups of the diisocyanate and triisocyanate; polyisocyanate having an isocyanurate structure obtained by reacting the above diisocyanate or triisocyanate with water; polyisocyanate having a burette structure obtained by reacting the above diisocyanate or triisocyanate with carbon dioxide; oxadiazinetrione obtained by reacting the above diisocyanate or triisocyanate with carbon dioxide. Polyisocyanate having an allophanate structure obtained by reacting the above diisocyanate or triisocyanate with various alcohols; Polyisocyanate having an allophanate structure obtained by reacting the above diisocyanate or triisocyanate with various alcohols; Examples include polyisocyanates obtained by reacting with compounds contained therein.

Among the above polyisocyanate compounds, aliphatic or alicyclic diisocyanates or triisocyanates, aralkylene diisocyanates, or polyisocyanates derived therefrom are particularly preferred in terms of weather resistance and pot life. Furthermore, the polyisocyanate preferably has a structure such as biuret, isocyanurate, urethane, uretdione, or allophanate in the molecule. Those having a bullet structure often have excellent adhesive properties. Those having an isocyanurate structure often have excellent weather resistance. Those having a urethane structure using an alcohol compound with a long side chain often have excellent elasticity and extensibility. Those having a uretdione structure or an allophanate structure often have a low viscosity.

The blocked isocyanate group-containing vinyl monomer as component (c1) can be obtained by reacting the isocyanate group-containing vinyl monomer with a blocking agent. The blocking agent is not particularly limited, but includes, for example, oxime compounds, alcohol compounds, acid amide compounds, acid imide compounds, phenol compounds, amine compounds, active methylene compounds, imidazole compounds, and Examples include pyrazole compounds. Examples of oxime compounds include, but are not limited to, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime. Examples of alcoholic compounds include, but are not limited to, methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-ethoxyethanol. Butoxyethanol is mentioned. Examples of acid amide compounds include, but are not limited to, acetanilide, acetate amide, ε-caprolactam, δ-valerolactam, and γ-butyrolactam. Acid imide compounds include, but are not particularly limited to, succinimide and maleic imide. Examples of the phenolic compound include, but are not limited to, phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoic acid ester. Examples of the amine compound include, but are not limited to, diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, and isopropylethylamine. Examples of the active methylene compound include, but are not limited to, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. Examples of imidazole compounds include, but are not limited to, imidazole and 2-methylimidazole. Examples of the pyrazole compound include, but are not limited to, pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.

Examples of the keto group- or aldehyde group-containing vinyl monomer as component (c1) include acrolein, diacetone acrylamide, diacetone methacrylamide, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, acryloxyalkyl Examples include propanals, methacryloxyalkylpropanals, diacetone acrylate, diacetone methacrylate, acetonyl acrylate, 2-hydroxypropyl acrylate acetylacetate, butanediol-1,4-acrylate acetylacetonate.

Examples of the epoxy group-containing vinyl monomer as component (c1) include 4-hydroxybutyl acrylate glycidyl ether, glycidyl methacrylate, 2-methyl-2,3-epoxypropyl methacrylate, 2,3-epoxybutyl methacrylate, , 3-epoxy-1-methyl-propyl methacrylate, 2,3-epoxy-1,2-dimethyl-propyl methacrylate, 2,3-epoxy-1-methylbutyl methacrylate, 2,3-epoxy-2-methylbutyl methacrylate etc.

Examples of the hydroxyl group-containing vinyl monomer as component (c1) include various types such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Hydroxyalkyl (meth)acrylates; various hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; various hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether; polyethylene glycol, etc. Monoesters of polyoxyalkylene glycol obtained from various polyether polyols such as those represented and various unsaturated carboxylic acids such as (meth)acrylic acid; various hydroxyl groups such as those mentioned above. Adducts of containing monomers and various lactones such as ε-caprolactone; various epoxy group-containing unsaturated monomers such as glycidyl (meth)acrylate; Adducts with various acids such as acetic acid; Furthermore, adducts with various unsaturated carboxylic acids such as (meth)acrylic acid, and "Cardura E" (manufactured by Shell in the Netherlands). Examples include adducts of α-olefins with various monoepoxy compounds other than epoxides, such as those typified by (trade name).

Examples of the carboxyl group-containing vinyl monomer as component (c1) include various unsaturated compounds such as (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Carboxylic acids; unsaturated dicarboxylic acids such as monomethyl itaconate, mono-n-butyl itaconate, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate, and mono-n-butyl fumarate; Monoesters (half esters) with alcohols; monovinyl esters of various saturated dicarboxylic acids such as monovinyl adipate and monovinyl succinate; succinic anhydride, glutaric anhydride, phthalic anhydride, and trimellitic anhydride Addition reaction products between various saturated polycarboxylic acid anhydrides such as acids and the various hydroxyl group-containing vinyl monomers described above; Examples include monomers obtained by addition reaction with lactones.

Examples of the alkoxysilyl group-containing vinyl monomer as component (c1) include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloyloxy Propylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltri-n-propoxysilane, 3-(meth)acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and 2- Examples include silane coupling agents having a vinyl polymerizable group such as trimethoxysilylethyl vinyl ether.

The carbodiimide group-containing vinyl monomer as component (c1) can be used to remove carbon dioxide by, for example, dimerizing the isocyanate group-containing vinyl monomer or reacting the isocyanate group-containing vinyl monomer with another isocyanate. It can be obtained by a condensation reaction involving

In addition, in order to polymerize component (C) by emulsion polymerization and improve the water dispersion stability of the polymerized component (C), an emulsifier can be used as component (c3) in the polymerization stock solution. For example, acidic emulsifiers such as alkylbenzene sulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkyl sulfate, polyoxyethylene alkylaryl sulfate, polyoxyethylene distyrylphenyl ether sulfonic acid, alkali metals (Li, Na , K, etc.) salts, ammonium salts of acidic emulsifiers, and anionic surfactants such as fatty acid soaps; quaternary ammonium salts such as alkyltrimethylammonium bromide, alkylpyridinium bromide, imidazolinium laurate, pyridinium salts, and imidazoli Nonionic surfactants such as polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxypropylene block copolymer, and polyoxyethylene distyrylphenyl ether are used. It is possible. These may be used alone or in combination of two or more.

As component (c3), a radically polymerizable double bond is selected from the viewpoint of improving the water dispersion stability of the resulting component (C) and the long-term stain resistance of the resulting coating film. It is preferable to use a reactive emulsifier having the following properties. More specifically, reactive emulsifiers include vinyl monomers having a sulfonic acid group or sulfonate group, vinyl monomers having a sulfuric acid ester group, and their alkali metal salts, ammonium salts, and nonions such as polyoxyethylene. A vinyl monomer having a group, a vinyl monomer having a quaternary ammonium salt, etc. can be used.

Vinyl monomers having a sulfonic acid group or a sulfonate group include, for example, a vinyl monomer that has a radically polymerizable double bond and is partially treated by a substituent such as an ammonium salt, sodium salt, or potassium salt of the 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 substituent; vinyl sulfonate compounds having a vinyl group to which a substituent such as an ammonium salt, sodium salt or potassium salt of a sulfonic acid group is bonded can be used.

Examples of vinyl monomers having a sulfate ester group include those having a radically polymerizable double bond and partially substituted with a substituent such as ammonium salt, sodium salt, or potassium salt of the sulfate ester group. , a compound having a substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polyalkyl ether group having 2 to 4 carbon atoms, a phenyl group, and a naphthyl group is used. It is possible.

As a compound having a succinic acid group partially substituted with a substituent such as an ammonium salt, sodium salt, or potassium salt of a sulfonic acid group, specifically, allyl sulfosuccinate can be used. More specifically, Eleminor JS-2 (trade name) (manufactured by Sanyo Kasei Co., Ltd.), Latemul S-120, S-180A, and S-180 (trade name) (manufactured by Kao Corporation) can be used. be.

In addition, as 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 group that is an ammonium salt, sodium salt, or potassium salt of a sulfonic acid group, Specifically, Aqualon HS-10 or KH-1025 (product name) (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE-1025N or SR-1025 (product name) (manufactured by ADEKA Co., Ltd.), etc. Available for use.

In addition, as a vinyl monomer having a nonionic group, specifically, α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω-hydroxypolyoxyethylene (trade name: ADEKA Reasap NE-20, NE-30, NE-40, etc., manufactured by ADEKA Co., Ltd.), and polyoxyethylene alkyl propenyl phenyl ether (product name: Aqualon RN-10, RN-20, RN-30, RN-50, etc.) , manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc. can be used.

In addition, from the viewpoint of polymerization stability, the amount of component (c3) used in the polymerization stock solution is preferably 10 parts by mass or less, more preferably 0.0 parts by mass or less, based on 100 parts by mass of the polymer particles of component (C). 001 to 5 parts by mass.

Furthermore, a hydrolyzable silicon compound may be used as component (c4) in the polymerization stock solution. A compound represented by the following formula (1), a condensation product thereof, a silane coupling agent, etc. can be used.
SiW _x R _y (1)
(In formula (1), 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, Represents at least one group selected from amide 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 a substituted represents at least one hydrocarbon group selected from alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, or aryl groups having 6 to 20 carbon atoms substituted with halogen atoms.x is an integer between 1 and 4, and y is an integer between 0 and 3. Also, x+y=4.)

Note that the silane coupling agent refers to a compound 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, or an isocyanate group, is present in the molecule.

Examples of the compound represented by formula (1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane; methyl trimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, 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 Silane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 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 - Trialkoxysilanes such as (meth)acryloyloxypropyltriisopropoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxy Silane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyl Dimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n- Octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane Monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane can be used. Further, these may be used alone or in combination of two or more.

Furthermore, as the component (c4), silicon alkoxides having a phenyl group (eg, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, etc.) can be used. When a silicon alkoxide having a phenyl group is used, the polymerization stability in the presence of water and an emulsifier becomes good, which is preferable.

Furthermore, component (c4) may be used in combination with a silane coupling agent having a thiol group or a hydrolyzable silicon compound having a vinyl polymerizable group as component (c4-1). When these are used, the resulting coating film has good long-term stain resistance, which is preferable. As the silane coupling agent having a thiol group, for example, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane can be used.

In addition, as the component (c4-1), for example, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3 -(meth)acryloyloxypropyltri-n-propoxysilane, 3-(meth)acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 2-trimethoxysilylethyl vinyl ether, etc. A silane coupling agent having a vinyl polymerizable group can be used.

These silane coupling agents can form a chemical bond through copolymerization or chain transfer reaction with the component (c1). Therefore, when a silane coupling agent having a vinyl polymerizable group or a thiol group is mixed or combined with the above-mentioned component (c1), the polymerization product of (c1) and the polymerization product of component (c4) are used. and can be combined by chemical bonding. Note that the "vinyl polymerizable group" of component (c4-1) is, for example, a vinyl group, an allyl group, etc., and a 3-(meth)acryloxypropyl group is particularly preferable.

Furthermore, the component (c4) may contain a cyclic siloxane oligomer as the component (c4-2). The use of component (c4-2) is preferable because it increases the flexibility of the resulting composite of the coating film and the base material.
As the cyclic siloxane oligomer, a compound represented by the following formula (2) can be used.
(R' ₂ SiO) _m (2)
(In formula (2), R' is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or Represents at least one type selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom.m is an integer, and 2≦ m≦20.)

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

Note that the ratio (c1)/(C) of the mass of component (c1) in the polymerization stock solution to the mass of polymer particles of component (C) is preferably 0.01/100 to 100 from the viewpoint of polymerization stability. The ratio is 80/100, more preferably 0.1/100 to 70/100.

Furthermore, other vinyl monomers can be used as component (c5) in the polymerization stock solution. For example, vinyl monomers containing an alkyl group, an amide group, an amino group, or an ether group can be used. By using component (c5), it is possible to control the properties (glass transition temperature, molecular weight, hydrogen bond strength, polarity, dispersion stability, weather resistance, etc.) of the polymerized product produced.

Examples of the alkyl group-containing vinyl monomer as component (c5) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and i-butyl (meth)acrylate. ) acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, ) acrylate, stearyl (meth)acrylate, etc.

As the amide group-containing vinyl monomer as component (c5), for example, N-alkyl or N-alkylene substituted (meth)acrylamide can be used. More specifically, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N-ethylmethacrylamide, N-Methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methyl-N -n-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine, N-methacryloyl Morpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, diacetone methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide, etc. can be used.

The amino group-containing vinyl monomer as the component (c5) includes 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate, 2-di-n-propylaminoethyl (meth)acrylate, 3 - Various tertiary amino group-containing (meth)acrylic acid esters such as dimethylaminopropyl (meth)acrylate, 4-dimethylaminobutyl (meth)acrylate, and N-[2-(meth)acryloyloxy]ethylmorpholine. various aromatic vinyl monomers containing tertiary amino groups such as vinylpyridine, N-vinylcarbazole and N-vinylquinoline; N-(2-dimethylamino)ethyl(meth)acrylamide, N-(2-dimethylamino)ethyl(meth)acrylamide, -diethylamino)ethyl (meth)acrylamide, N-(2-di-n-propylamino)ethyl (meth)acrylamide, N-(3-dimethylamino)propyl(meth)acrylamide, N-(4-dimethylamino)butyl (meth)acrylamide and various tertiary amino group-containing (meth)acrylamides such as N-[2-(meth)acrylamido]ethylmorpholine; N-(2-dimethylamino)ethylcrotonic acid amide, N-( 2-diethylamino)ethylcrotonamide, N-(2-di-n-propylamino)ethylcrotonamide, N-(3-dimethylamino)propylcrotonamide, and N-(4-dimethylamino)butylcroton various tertiary amino group-containing crotonic acid amides such as acid amides; Vinyl ethers containing amino groups can be used.

Examples of the ether group-containing vinyl monomer as the component (c5) include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene higher fatty acid ester, and polyoxyethylene-polyoxypropylene block copolymer. Vinyl monomers such as vinyl ethers, allyl ethers, or (meth)acrylic acid esters having various polyether chains in their side chains can be used. Specifically, Blenmar PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, AE-350 [manufactured by NOF Corporation], MA-30, MA-50 , MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114, and MPG130-MA [all manufactured by Nippon Nyukazai Co., Ltd.], etc. can be used. Here, the number of oxyethylene units in the polyoxyethylene chain is preferably 2 to 30. When the number of oxyethylene units is 2 or more, appropriate flexibility of the coating film is obtained, and when it is 30 or less, excessive softening of the coating film is suppressed and blocking resistance is maintained.

The vinyl monomer as component (c5) preferably has a secondary and/or tertiary amide group from the viewpoint of further improving hydrogen bonding properties with other components.
The ratio (c5)/(C) of the mass of component (c5) in the polymerization stock solution to the mass of polymer particles of component (C) is preferably 10/100 to 95/100 from the viewpoint of polymerization stability. Yes, more preferably 30/100 to 80/100.

Component (C) of the coating film in the present invention is a polymer particle obtained by polymerizing a polymer stock solution containing the above-mentioned (c1) and (c2) and optionally (c3) to (c5). Note that the amount of component (c2) to be used may preferably be 30.0 to 99.9% by mass in terms of content in the polymerization stock solution from the viewpoint of polymerization stability. In addition to the components (c1) to (c5), various components can be mixed in the polymerization stock solution.

Further, a chain transfer agent may be mixed in the polymerization stock solution. Examples of chain transfer agents include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecylbenzyl mercaptan; and thiomalic acid. Thiocarboxylic acids or salts thereof or alkyl esters thereof, polythiols, diisopropylxanthogen disulfide, di(methylenetrimethylolpropane)xanthogen disulfide, thioglycol, and allyl compounds such as α-methylstyrene dimer can be used. It is. From the viewpoint of polymerization stability, the amount of chain transfer agent used is preferably 0.001 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of all vinyl monomers. Department.

Furthermore, a dispersion stabilizer may be mixed into the polymerization stock solution. Examples of dispersion stabilizers include various water-soluble oligomers selected from the group consisting of polycarboxylic acids and sulfonates, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, maleated alkyd resins, and polyacrylic acid ( Various synthetic or natural water-soluble or water-dispersible polymeric materials can be used, such as salts), polyacrylamides, and water-soluble or water-dispersible acrylic resins. Moreover, one type 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 (C).

The polymerization of the polymerization stock solution is preferably carried out in the presence of a polymerization catalyst. Examples of the polymerization catalyst for component (c4) include hydrogen halides such as hydrochloric acid and hydrofluoric acid, carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid, and lactic acid, sulfonic acids such as sulfuric acid, and p-toluenesulfonic acid; Acidic emulsifiers such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkyl sulfate, polyoxyethylene alkylaryl sulfate, polyoxyethylene distyrylphenyl ether sulfonic acid, acidic or weakly acidic inorganic salts, phthalic acid , phosphoric acid, and nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine, diazabicycloundecene, ethylenediamine, Basic compounds such as diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, and γ-(2-aminoethyl)-aminopropyltrimethoxysilane; tin compounds such as dibutyltin octylate and dibutyltin dilaurate etc. are available. Among these, as a polymerization catalyst for the hydrolyzable silicon compound (c4), acidic emulsifiers that act not only as a polymerization catalyst but also as an emulsifier, especially alkylbenzenesulfonic acids having 5 to 30 carbon atoms (such as dodecylbenzenesulfonic acid) are used. preferable.

Furthermore, as the polymerization catalyst for each component (c1), (c4-1), and (c5), a radical polymerization catalyst that causes addition polymerization of vinyl monomers by radical decomposition using heat or a reducing substance is suitable. It is. Water-soluble or oil-soluble persulfates, peroxides, azobis compounds, etc. are preferably used. More specifically, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2- Azobis(2-diaminopropane) hydrochloride, 2,2-azobis(2,4-dimethylvaleronitrile), and the like can be used.

The amount of the polymerization catalyst used in the polymerization stock solution is preferably 0.001 to 5 parts by weight based on 100 parts by weight of the total vinyl monomer. In addition, if acceleration of the polymerization rate and polymerization at low temperatures such as 70°C or lower are desired, for example, reducing agents such as sodium bisulfite, ferrous chloride, ascorbate, and Rongalit may be combined with the radical polymerization catalyst. It is advantageous to use it.

The polymerization of each of the components (c1) and (c5) and the polymerization with the component (c4) can be carried out separately, but if carried out simultaneously, a microscopic organic-inorganic composite due to hydrogen bonding etc. This is preferable because it can achieve

As a method for obtaining component (C) of the coating film according to the present invention, each component (c1), (c4), and (c5) is mixed in the presence of a sufficient amount of water for the emulsifier to form micelles. Polymerization, so-called emulsion polymerization, is suitable. As a method for emulsion polymerization, for example, each component (c1), (c4), and (c5) is dropped into a reaction vessel as it is or in an emulsified state, all at once, in portions, or continuously, and polymerization is carried out. A method may be used in which the polymerization is carried out in the presence of a catalyst, preferably at a pressure from atmospheric pressure to 10 MPa if necessary, and at a reaction temperature of about 30 to 150°C. Depending on the case, polymerization may be carried out at higher pressures or lower temperature conditions. In addition, from the viewpoint of polymerization stability, each component (c1) to (c5) is blended in the polymerization stock solution so that the final solid content is in the range of 0.1 to 70% by mass, preferably 1 to 55% by mass. It is preferable to mix.

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

In addition, as a method for obtaining component (C), in the presence of components (c2) and (c3) necessary for polymerizing each component (c1), (c4), and (c5), (c1), It is also possible to use a method in which each component (c4) and (c5) is polymerized in the presence of a solvent if necessary, and then water is added until the polymerization product becomes an emulsion.

Furthermore, component (C) is a core layer and one or more shell layers covering the core layer, from the viewpoint of improving the adhesion to the substrate of a coating film formed using the resulting coating composition. It is preferable to have a core/shell structure with the following. Multistage emulsion polymerization, in which emulsion polymerization is performed in multiple stages, is useful as a method for forming the core/shell structure.

In multi-stage emulsion polymerization, for example, in the presence of components (c2) and (c3), at least one selected from the group consisting of components (c1), (c4), and (c5) is polymerized to form seed particles. A first step of forming is carried out, and then a second step of adding and polymerizing a polymerization stock solution containing the remaining components in the presence of seed particles is carried out (two-stage polymerization method). Furthermore, when performing multistage emulsion polymerization of three or more stages, a third stage of polymerization by adding a polymerization stock solution containing at least one of the components (c1), (c4), and (c5) may be performed. good. Such a method is also suitable from the viewpoint of polymerization stability.

In the two-stage polymerization method, the mass ratio of the solid content mass (M1) in the polymerization stock solution used in the first stage to the solid content mass (M2) in the polymerization stock solution added in the second stage is the polymerization stability. From this viewpoint, (M1)/(M2) is preferably 90/10 to 10/90, more preferably 80/20 to 20/80.

In addition, from the viewpoint of polymerization stability, the core/shell structure allows the particle size to increase during the second stage of polymerization without significantly changing the particle size distribution (volume average particle size/number average particle size) of the seed particles. It is preferable to have a structure. Note that 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, for example, by morphological observation using a transmission electron microscope or the like, analysis using 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. When the glass transition temperature (Tg) of the core layer is within this range, the physical properties of the resulting coating film are excellent in flexibility at room temperature and less prone to cracking. Note that Tg here can be measured with a differential scanning calorimeter (DSC).

In the present invention, the number average particle diameter of component (C) in the coating composition (and the coating film formed therefrom) is, for example, 10 nm to 800 nm. By forming a composition by combining component (C) with a number average particle size of 10 nm to 800 nm and component (A) with a number average particle size of 1 nm to 400 nm, the resulting coating film has weather resistance and stain resistance. becomes good. Furthermore, from the viewpoint of the optical properties and hard coat performance of the resulting coating film, the number average particle diameter of component (C) is preferably 20 nm to 250 nm. As for the method for measuring the number average particle diameter of component (C), the same method as for component (A) may be employed.

The mass ratio (A)/(C) of component (A) and component (C) in the coating composition (and the coating film formed therefrom) is preferably 10/100 to 1000/100, more preferably It is 50/100 to 300/100. By blending within this range, a coating film with excellent hydrophilicity, antifogging properties, optical properties, and stain resistance can be formed. Further, the ratio (SA)/(SB) of the surface area (SA) of all particles of component (A) to the surface area (SB) of all particles of component (B) is preferably in the range of 0.001 to 1000. . Note that the surface area here can be calculated from the particle diameter of each of component (A) and component (B), and the blended mass number (that is, particle diameter distribution) of each component.

Further, in the present invention, from the viewpoint of adhesion and suppression of water droplet formation, it is preferable that the coating film includes a portion where the polymer particles (C) are in contact with each other. Here, contact between particles refers to a state in which the distance between particles approaches zero, for example, through fusion of particles or covalent or non-covalent bonds. As a method for confirming this state, for example, there is a method of observing a cross section of the coating film using SEM or TEM.

(D) Component: Crosslinking agent In addition to the above-mentioned components (A), (B), and (C), using a crosslinking agent as component (D) helps maintain the appearance when exposed to rapid environments. , is more preferable in terms of suppressing the occurrence of water drop marks. Component (D) is capable of crosslinking component (A), component (B), and component (C), but is particularly capable of crosslinking component (C) with other components. , the above effects can be achieved. The crosslinking agent can be selected depending on the exposed functional group, but examples include carbodiimide, polyvalent active hydrogen compounds (polyols, polyamines, alkanolamines, etc.), polyisocyanate, Examples include hydrazine type, semicarbazide type, and polycarboxylic acid.

The mass ratio of component (D) to the sum of the masses of component (A) and component (B) contained in the coating film and coating composition of the present invention is (D mass)/((A mass) + (B mass) )=0.5/100 or more and 200/100 or less is preferable. In view of the above effects, the lower limit of this range is more preferably 1/100, and even more preferably 2/100. In addition, from the viewpoint of coating film appearance and suppression of water drop marks, the upper limit of this range is more preferably 100/100, and even more preferably 50/100.
Further, the mass ratio of component (D) to component (C) is preferably (D mass)/(C mass) = 1/100 or more and 300/100 or less. In view of the above effects, the lower limit of this range is more preferably 2/100, and even more preferably 3/100. In addition, from the viewpoint of coating film appearance and suppression of water drop marks, the upper limit of this range is more preferably 200/100, and even more preferably 100/100.
The molar ratio of the reactive functional group of component (D) to the reactive functional group of component (C) is preferably (D mole)/(C mole) = 20/100 or more and 500/100 or less. The lower limit of this range is more preferably 30/100, and even more preferably 50/100. Further, the upper limit of this range is more preferably 400/100, and even more preferably 300/100.

The carbodiimide crosslinking agent as component (D) may have, for example, one or more carbodiimide groups (-N=C=N-) and/or cyanamide groups (NC-NH-) in the molecule. (for example, about 2 to 10). The carbodiimide compound is not particularly limited, and examples thereof include polycarbodiimide compounds. In addition, since carbodiimide (HN=C=NH) has a tautomeric relationship with cyanamide (NC-NH ₂ ), the carbodiimide crosslinking agent mentioned here has one or more than two molecules in the molecule. Compounds having a cyanamide group (NC-NH-) and compounds having a total of two or more cyanamide groups (NC-NH-) and carbodiimide groups (-N=C=N-) in the molecule may also be included. Therefore, as component (C), compounds having one or more crosslinkable functional groups selected from carbodiimide groups (-N=C=N-) and cyanamide groups (NC-NH-) in the molecule may also be used. Included.

The polyhydric active hydrogen compound as component (D) is not particularly limited, and examples thereof include polyols, polyamines, alkanolamines, and the like. These polyvalent active hydrogen compounds may be contained singly or in combination of two or more. Among these, polyols are preferred as the polyvalent active hydrogen compound.

[Polyol]
Examples of polyols include polyhydric alcohols, polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, fluorine polyols, polycarbonate polyols, and polyurethane polyols. These polyols may be contained singly or in combination of two or more types.

(Polyhydric alcohol)
Examples of the polyhydric alcohol include compounds having a single molecular weight and having two or more hydroxyl groups, or mixtures thereof. For example, ethylene glycol, propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,6-cyclohexanediol, 1,4-cyclohexanediol, Methylpentanediol, cyclohexanedimethanol, methylpentanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A, glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol , 2,4-hydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol and other alcoholic compounds, erythritol, D-threitol, L- Sugar alcohol compounds such as arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and rhamnitol; monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, and ribodesose; Examples include sugars, disaccharides such as maltose, cellobiose, gentiobiose, lactose, and melibiose, trisaccharides such as raffinose, gentianose, and meletitose, and tetrasaccharides such as stachyose.

(Polyester polyol)
A polyester polyol can be obtained, for example, by subjecting a dibasic acid alone or a mixture of two or more types and a polyhydric alcohol alone or a mixture of two or more types to a condensation reaction.
Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, and pentaerythritol. , 2-methylolpropanediol, ethoxylated trimethylolpropane, and the like.
Alternatively, for example, polycaprolactones obtained by ring-opening polymerization of lactones such as ε-caprolactone using a polyhydric alcohol can also be used as the polyester polyol.

(Polyether polyol)
The polyether polyols are not particularly limited, but include, for example, those shown in (1) to (3) below.
(1) Polyether polyols obtained by random or block addition of an alkylene oxide alone or a mixture to a polyhydric hydroxy compound or a mixture using a catalyst.
Examples of the catalyst include hydroxides (lithium, sodium, potassium, etc.), strong basic catalysts (alcolates, alkylamines, etc.), complex metal cyanide compounds (metallic porphyrins, zinc hexacyanocobaltate complexes, etc.), and the like. It will be done.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.
(2) Polyether polyols obtained by reacting a polyamine compound with an alkylene oxide.
Examples of the polyamine compound include ethylenediamines.
Examples of the alkylene oxide include those exemplified in (1).
(3) So-called polymer polyols obtained by polymerizing acrylamide or the like using the polyether polyols obtained in (1) or (2) as a medium.

(acrylic polyol)
Acrylic polyols are not particularly limited, but include, for example, a monomer or a mixture of ethylenically unsaturated bond-containing monomers having a hydroxyl group, and other monomers containing ethylenically unsaturated bonds that can be copolymerized with this monomer. or a mixture obtained by copolymerizing.
The ethylenically unsaturated bond-containing monomer having a hydroxyl group is not particularly limited, but includes, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and methacryl. Examples include hydroxybutyl acid. These may be used alone or in combination of two or more. Among these, hydroxyethyl acrylate or hydroxyethyl methacrylate is preferred.
Other ethylenically unsaturated bond-containing monomers that can be copolymerized with the above monomers include, for example, those shown in (1) to (6) below. These may be used alone or in combination of two or more.
(1) Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, acrylic acid Acrylic acid esters such as lauryl, benzyl acrylate, and phenyl acrylate.
(2) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Methacrylic acid esters such as lauryl, benzyl methacrylate, and phenyl methacrylate.
(3) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid.
(4) Unsaturated amides such as acrylamide, methacrylamide, N,N-methylenebisacrylamide, diacetone acrylamide, diacetone methacrylamide, maleic acid amide, and maleimide.
(5) Vinyl monomers such as glycidyl methacrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.
(6) Vinyl monomers having a hydrolyzable silyl group such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ-(meth)acryloxypropyltrimethoxysilane.

(Polyolefin polyol)
Examples of the polyolefin polyol include, but are not particularly limited to, polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and the like.
The statistical number of hydroxyl groups that one molecule of the polyol has (hereinafter sometimes referred to as "average number of hydroxyl groups") is preferably 2 or more. When the average number of hydroxyl groups in the polyol is 2 or more, it tends to be possible to further suppress a decrease in the crosslinking density of the coating film obtained by curing the one-component coating composition.

(Fluorine polyol)
As used herein, "fluorine polyol" means a polyol containing fluorine in the molecule. Specific examples of fluorine polyols include, for example, fluoroolefins, cyclovinyl ethers, and hydroxyl which are disclosed in JP-A-57-34107 (Reference 1), JP-A-61-275311 (Reference 2), etc. Examples include copolymers of alkyl vinyl ethers and monocarboxylic acid vinyl esters.

(Polycarbonate polyol)
Polycarbonate polyols are not particularly limited, but include, for example, those shown in (1) to (4) below:
(1) Dialkyl carbonate such as dimethyl carbonate;
(2) Alkylene carbonate such as ethylene carbonate;
(3) low-molecular carbonate compounds such as diaryl carbonates such as diphenyl carbonate;
(4) One obtained by condensation polymerization of the low molecular weight polyols used in the polyester polyols of (1) to (3) above.

(Polyurethane polyol)
The polyurethane polyol is not particularly limited, but can be obtained, for example, by reacting a polyol that does not contain a carboxyl group with an isocyanate component by a conventional method.
Examples of the polyol containing no carboxyl group include low molecular weight polyols such as ethylene glycol and propylene glycol. Furthermore, examples of high molecular weight polyols include acrylic polyols, polyester polyols, and polyether polyols.

[Hydroxyl value of polyol]
The hydroxyl value per resin of the polyol is not particularly limited, but is preferably 10 mgKOH/g of resin or more and 300 mgKOH/g of resin or less.
When the hydroxyl value per resin is greater than or equal to the above lower limit, it tends to be possible to suppress a decrease in crosslinking density and more fully achieve the desired physical properties. By controlling the hydroxyl value per resin to be less than or equal to the above upper limit, excessive increase in crosslinking density is suppressed, and the mechanical properties of the coating film obtained by curing the one-component coating composition are further improved. tends to be possible. Note that the hydroxyl value of the polyol can be measured in accordance with JIS K1557.

[Polyamine]
The polyamine is not particularly limited, but one having two or more primary amine groups or secondary amine groups in one molecule is preferable, and one having three or more primary amine groups or secondary amine groups in one molecule is more preferable. preferable.
Specific examples of polyamines include those shown in (1) to (3) below:
(1) Diamines such as ethylenediamine, propylene diamine, butylene diamine, triethylene diamine, hexamethylene diamine, 4,4'-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, isophorone diamine;
(2) Chain polyamines having three or more amino groups such as bishexamethylenetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, and tetrapropylenepentamine;
(3) 1,4,7,10,13,16-hexaazacyclooctadecane, 1,4,7,10-tetraazacyclodecane, 1,4,8,12-tetraazacyclopentadecane, 1,4, Cyclic polyamines such as 8,11-tetraazacyclotetradecane.

[Alkanolamine]
Further, as component (D), alkanolamine, which is a compound having an amino group and a hydroxyl group in one molecule, may be used.
Examples of alkanolamines include monoethanolamine, diethanolamine, aminoethylethanolamine, N-(2-hydroxypropyl)ethylenediamine, mono- or di-(n- or iso-)propanolamine, ethylene glycol-bis-propylamine. , neopentanolamine, methylethanolamine, and the like.

Examples of the polyisocyanate crosslinking agent as component (D) include diisocyanates, triisocyanates, and polyisocyanates made of the diisocyanates and triisocyanates listed on the left.
Examples of the diisocyanate and triisocyanate include 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanato)hexanoate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4 - or aliphatic diisocyanates such as 2,4,4-trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2-isocyanate Aliphatic triisocyanates such as ethyl (2,6-diisocyanato)hexanoate; 1,3- or 1,4-bis(isocyanatomethylcyclohexane), 1,3- or 1,4-diisocyanatocyclohexane, 3 , 5,5-trimethyl(3-isocyanatomethyl)cyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, 2,5- or 2,6-diisocyanatomethylnorbornane; 2 , 5- or 2,6-diisocyanate methyl-2-isocyanate propylnorbornane; m-xylylene diisocyanate, α,α,α'α'-tetramethyl-m-xylylene diisocyanate Aralkylene diisocyanates such as isocyanates; m- or p-phenylene diisocyanate, tolylene-2,4- or 2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4-diisocyanate Aromatic diisocyanates such as '-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyldiphenyl, 3-methyl-diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate; triphenyl Aromatic triisocyanates such as methane triisocyanate and tris(isocyanatophenyl)thiophosphate are mentioned.
Examples of the polyisocyanate include diisocyanates or polyisocyanates having a uretdione structure obtained by cyclizing and dimerizing the isocyanate groups of the diisocyanates and triisocyanates; A polyisocyanate having an isocyanurate structure obtained by reacting the above diisocyanate or triisocyanate with water; A polyisocyanate having a burette structure obtained by reacting the above diisocyanate or triisocyanate with carbon dioxide; polyisocyanate having an allophanate structure obtained by reacting the above diisocyanate or triisocyanate with various alcohols; polyisocyanate having an allophanate structure obtained by reacting the above diisocyanate or triisocyanate with various alcohols; Examples include polyisocyanates obtained by reacting with compounds.

Among the polyisocyanate crosslinking agents, aliphatic or alicyclic diisocyanates, triisocyanates, aralkylene diisocyanates, and polyisocyanates derived therefrom are particularly preferred in terms of weather resistance and pot life. . Furthermore, the polyisocyanate preferably has a structure such as biuret, isocyanurate, urethane, uretdione, or allophanate in the molecule. Those having a bullet structure often have excellent adhesive properties. Those having an isocyanurate structure often have excellent weather resistance. Those having a urethane structure using an alcohol compound with a long side chain often have excellent elasticity and extensibility. Those having a uretdione structure or an allophanate structure often have a low viscosity.
In addition, from the viewpoint of water dispersibility, the polyisocyanate compound having two or more isocyanate groups in one molecule and the hydroxyl group-containing hydrophilic compound having nonionic and/or ionic hydrophilic groups are combined with isocyanate groups/hydroxyl groups. A hydrophilic polyisocyanate-based crosslinking agent reacted with an equivalent ratio of 1.05 to 1000 is preferred. More preferably, this equivalent ratio ranges from 2 to 200, even more preferably from 4 to 100. When the equivalence ratio is 1.05 or more, the isocyanate group content in the hydrophilic polyisocyanate crosslinking agent is at a predetermined level or higher, which increases the number of crosslinking points in the crosslinkable aqueous coating composition and improves the curing speed. This is preferable because it increases the strength of coatings such as coatings. It is preferable that the equivalent ratio is 1000 or less because hydrophilicity is exhibited.
Such a hydrophilic polyisocyanate crosslinking agent may be used without any particular restriction as long as it has been introduced with a hydrophilic group by a conventionally known method. For example, the general formula R ¹ O(R ² O) _n -H (where R ¹ represents an alkyl group having 1 to 30 carbon atoms or a group containing two or more aromatic rings, and R ² represents a group containing 1 to 5 carbon atoms) represents an alkylene group (n is an integer from 2 to 250) and a polyisocyanate compound, or a reaction product of a vinyl polymer having a hydrophilic group and a hydroxyl group and a polyisocyanate compound. Examples include reaction products of polyisocyanate compounds and emulsifiers obtained by reacting alkoxy polyalkylene glycols with dialkanolamines. Among these, the general formula R ¹ O-(R ² O) _n -H (where R ¹ represents an alkyl group having 1 to 30 carbon atoms or a group containing two or more aromatic rings, and R ² represents a carbon represents an alkylene group of numbers 1 to 5, n is an integer of 2 to 250) and a polyisocyanate compound, a vinyl polymer having a hydrophilic group and a hydroxyl group, and a polyisocyanate compound. The reaction product is particularly preferred because it has excellent water dispersibility.

General formula R ¹ O-(R ² O) _n -H (where R ¹ represents an alkyl group having 1 to 30 carbon atoms or a group containing two or more aromatic rings, and R ² represents an alkyl group having 1 to 30 carbon atoms or a group containing two or more aromatic rings; Examples of the alkylene group (n is an integer from 2 to 250) include polymethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monolauryl ether, polyoxyethylene-oxypropylene (random and/or block) glycol monomethyl ether, polyoxyethylene-oxytetramethylene (random and/or block) glycol polybutylene glycol monomethyl ether, etc. Contains two or more aromatic rings such as alkoxypolyalkylene glycols, (mono-penta)styrenated phenyl groups, mono (or di, tri)styryl-methyl-phenyl groups, tribenzylphenyl groups, β-naphthyl groups, etc. Examples include nonionic surfactants having groups such as Among these, polyethylene glycol monomethyl ether and nonionic surfactants having a (mono-penta)styrenated phenyl group are preferred in terms of self-emulsifying ability and pot life.
These general formulas R ¹ O-(R ² O) _n -H (where R ¹ represents an alkyl group having 1 to 30 carbon atoms or a group containing two or more aromatic rings, and R ² represents a group containing 1 to 5 carbon atoms) (n is an integer of 2 to 250) preferably has a molecular weight of 100 to 10,000, more preferably 300 to 5,000.

The hydrazine crosslinking agent as component (D) is usually a hydrazide compound having two or more hydrazino groups (-NHNH ₂ ) in the molecule. The hydrazide compound is not particularly limited, but includes, for example, an acid hydrazide compound having a structure represented by -CONHNH ₂ . For example, saturated dicarboxylic acid dihydrazide such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide; maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid Examples include unsaturated dicarboxylic acid dihydrazide such as dihydrazide. These may be used alone or in combination of two or more. Among these, glutaric acid dihydrazide, adipic acid dihydrazide, and pimelic acid dihydrazide are preferable, and adipic acid dihydrazide is more preferable.

The semicarbazide crosslinking agent as component (D) is obtained by reacting a polyisocyanate compound having two or more -NCO groups in one molecule with a hydrazine derivative, and includes a structure represented by -NHCONHNH ₂ . An example of the polyisocyanate compound used as a raw material is a polyisocyanate crosslinking agent as component (D).

The polycarboxylic acid crosslinking agent as component (D) is a compound having two or more carboxyl groups in one molecule, such as maleic acid, fumaric acid, adipic acid, succinic acid, glutaric acid, pimelic acid, and suberic acid. , azelaic acid, sebacic acid, aliphatic polycarboxylic acids such as dodecanedicarboxylic acid, and aromatic polycarboxylic acids such as o-phthalic acid.

(E) Component: Hydrolyzable silicon compound In addition to the (A) component and (B) component, the coating composition for forming the coating film according to the present invention contains a hydrolyzable silicon compound as the (E) component. That's fine. Moreover, the coating composition may contain a hydrolyzable silicon compound as the (E) component in addition to the (A) component, the (B) component, and the (C) component. Moreover, the coating composition may contain a hydrolyzable silicon compound as the (E) component in addition to the (A) component, the (B) component, and the (D) component. Moreover, the coating composition may contain a hydrolyzable silicon compound as the (E) component in addition to the (A) component, the (B) component, the (C) component, and the (D) component.

In the present invention, the coating composition (and the coating film formed therefrom) is composed of component (E): a hydrolyzable silicon compound represented by the following formula (6), the following formula (7), or the following formula (8). may further include. In this case, the mass ratio of component (A) and component (C) in the coating composition is, for example, A/C=50/100 to 1000/100, and the mass ratio of component (A) to component (E) is, for example, A/C=50/100 to 1000/100. is, for example, E/A=5/100 to 90/100. Hereinafter, the hydrolyzable silicon-containing compound represented by the following formula (6) will be referred to as the (e1) component, and the hydrolyzable silicon-containing compound represented by the following formula (7) will be referred to as the (e2) component.
R ¹ _n SiX _4-n (6)
(In formula (6), R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group. Furthermore, on these substituents, a halogen group, a hydroxy group, a mercapto group, an amino group, (meth)acryloyl group, epoxy group, isocyanate group, etc. X represents a hydrolyzable group, and n is an integer from 0 to 3. Any group that produces a hydroxyl group may be used, such as a halogen atom, an alkoxy group, an acyloxy group, an amino group, a phenoxy group, an oxime group, etc.)
X ₃ Si-R ² _n -SiX ₃ (7)
(In formula (7), X represents a hydrolyzable group, R ² represents an alkylene group or phenylene group having 1 to 6 carbon atoms, and n is 0 or 1.)

Specifically, the components (e1) and (e2) include tetramethoxysilane, tetraethoxysilane, tetra(n-propoxy)silane, tetra(i-propoxy)silane, tetra(n-butoxy)silane, and tetramethoxysilane. (i-butoxy)silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyl Trimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyl Diethoxysilane, 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-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2 -(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane Ethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraacetoxysilane, tetrakis(trichloroacetoxy)silane, tetrakis(trifluoroacetoxy)silane, triacetoxysilane, tris(trichloroacetoxy)silane , tris(trifluoroacetoxy)silane, methyltriacetoxysilane, methyltris(trichloroacetoxy)silane, tetrachlorosilane, tetrabromosilane, tetrafluorosilane, trichlorosilane, tribromosilane, trifluorosilane, methyltrichlorosilane, methyltribromo Silane, 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, etc. can be used.

Further, a hydrolyzable silicon-containing compound represented by the following formula (8) is used as the component (e3). Specifically, the component (e3) includes a partially hydrolyzed condensate of tetramethoxysilane (trade name "M Silicate 51" manufactured by Tama Chemical Industry Co., Ltd., product name "MSI51" manufactured by Colcoat Co., Ltd.), product name "MS51","MS56" manufactured by Mitsubishi Chemical Corporation), partial hydrolyzed condensates of tetraethoxysilane (product name "Silicate 35", "Silicate 45" manufactured by Tama Chemical Industry Co., Ltd., product name "ESI40", "ESI48") (manufactured by Colcoat Co., Ltd.), and co-partially hydrolyzed condensates of tetramethoxysilane and tetraethoxysilane (trade name "FR-3" manufactured by Tama Chemical Industry Co., Ltd., product name "EMSi48" manufactured by Colcoat Co., Ltd.), etc. are used. It is possible.
R ³ -(O-Si(OR ³ ) ₂ ) _n -OR ³ (8)
(In formula (8), R ³ represents an alkyl group having 1 to 6 carbon atoms. n is an integer of 2 to 8.)

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

Other Optional Components In addition to component (A) and component (B), the coating composition for forming the coating film according to the present invention includes optional components ((C), (D) or (other than component (E)). In addition to the (A) component, (B) component, and (C) component, the coating composition may also contain optional components (other than the (D) or (E) component) as exemplified below. . In addition to the (A) component, (B) component, and (D) component, the coating composition may also contain optional components (other than the (C) or (E) component) as exemplified below. . In addition to the (A) component, (B) component, and (E) component, the coating composition may also contain optional components (other than the (C) or (D) component) as exemplified below. . In addition to component (A), component (B), component (C), and component (D), the coating composition may also contain optional components (other than component (E)) as exemplified below. good. In addition to the (A) component, (B) component, (C) component, and (E) component, the coating composition may also contain optional components (other than the (D) component) as exemplified below. good. In addition to the (A) component, (B) component, (D) component, and (E) component, the coating composition may also contain optional components (other than the (C) component) as exemplified below. good. In addition to the (A) component, (B) component, (C) component, (D) component, and (E) component, the coating composition may also contain optional components as exemplified below.
In the present invention, the coating composition for obtaining a coating film includes additive components that are usually added to the paint or molding resin, such as a solvent, a light stabilizer, UV absorbers, thickeners, leveling agents, thixotropic agents, antifoaming agents, freeze stabilizers, matting agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, fillers, anti-skinning agents, dispersants, Wetting agents, antioxidants, ultraviolet absorbers, rheology control agents, film-forming aids, rust preventives, dyes, plasticizers, lubricants, reducing agents, preservatives, anti-mold agents, deodorants, anti-yellowing agents , an antistatic agent, a charge control agent, etc. can be selected or combined depending on the purpose. In addition, below, a crosslinking reaction catalyst and a curing catalyst may be collectively called a "curing acceleration catalyst."

The solvent is not particularly limited, but from the viewpoint of ease of handling, aqueous solvents are preferred. Examples of the aqueous solvent include water, methanol, ethanol, propanol, isopropanol, butanol, acetone, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylformamide.

Examples of surfactants include alkylbenzenesulfonic acids, sodium fatty acids, alkyl sulfates, alkyl polyoxyethylene sulfates, anionic surfactants such as alkyl phosphates, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyl Cationic surfactants such as dimethylammonium salts, alkylpyridinium chloride, benzalkonium chloride, polyoxyethylene-polyoxypropylene condensates, polyoxyethylene alkyl ethers, alkyl polyglucosides, alkyl monoglyceryl ethers, sorbitan fatty acid esters, Nonionic surfactants such as 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, stearyl dialkylaminoacetic acid betaine, dodecylaminomethyl dialkyl sulfopropyl betaine, hexadecyl aminomethyl dialkyl sulfopropyl betaine, octadecyl aminomethyl dialkyl sulfopropyl betaine, cocamidopropyl betaine, cocamidopropyl hydroxysultaine, alkyl-N-carboxy Zwitterionic surfactants such as methyl-N-hydroxyethylimidazolinium betaine, sodium lauroylglutamate, potassium lauroylglutamate, lauroylmethyl-β-alanine, lauryldimethylamine N-oxide, oleyldimethylamine N-oxide, etc. Can be mentioned. By using these together with the hydrophilic compound (B), the hydrophilicity, antifogging properties, and water resistance of the resulting coating film are further improved. Among these surfactants, especially when using a surfactant having a long chain alkyl group with 10 or more carbon atoms and/or a surfactant having a fluorine atom in the molecule, it is possible to Since elution into water tends to be suppressed, it is more preferable from the viewpoint of water resistance.

Examples of the curing accelerating catalyst include, but are not limited to, tin-based compounds such as dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin dineodecanoate, and tin bis(2-ethylhexanoate); 2-ethyl Zinc compounds such as zinc hexanoate and zinc naphthenate; Titanium compounds such as titanium 2-ethylhexanoate and titanium diisopropoxybis(ethylacetonate); Cobalt compounds such as cobalt 2-ethylhexanoate and cobalt naphthenate; 2 - Bismuth compounds such as bismuth ethylhexanoate and bismuth naphthenate; zirconium compounds such as zirconium tetraacetylacetonate, zirconyl 2-ethylhexanoate, and zirconyl naphthenate; aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate) , aluminum compounds such as alkyl acetoacetate aluminum diisopropylate such as aluminum monoacetylacetonate bis(ethylacetoacetate), aluminum monoacetylacetonate bisoleylacetoacetate, and ethyl acetoacetate aluminum diisopropylate; and amine compounds.

As the light stabilizer, for example, a hindered amine light stabilizer is preferably used. Among these, radically polymerizable light stabilizers having a radically polymerizable double bond in the molecule are preferred. Further, as the ultraviolet absorber, for example, an organic ultraviolet absorber can be used. Examples of organic UV absorbers that can be used include benzophenone UV absorbers, benzotriazole UV absorbers, and triazine UV absorbers. Among these, it is preferable to use a radically polymerizable ultraviolet absorber having a radically polymerizable double bond in the molecule. Furthermore, benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers, which have high ultraviolet absorption ability, are preferred. Note that it is preferable to use a light stabilizer together with an organic ultraviolet absorber. By using both in combination, the weather resistance of the coating film formed from the coating composition can be improved. In addition, various additive components such as these organic ultraviolet absorbers and light stabilizers may be simply blended with the (A) component and (C) component, or they may be allowed to coexist when synthesizing the (C) component. You can.
These optional components are usually 10 parts by mass or less and 5 parts by mass based on the components (A) and (B) and the optional components (C) and/or (D) and/or (E). It can be used in an amount of 3 parts by mass or less, or 3 parts by mass or less.

Substrate The substrate is positioned as an object to which particularly excellent antifogging properties and antifogging durability are imparted by the coating layer. Various materials such as resin, glass, and metal can be used as the base material. In addition, in the present invention, the base material is preferably made of resin. The 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, thermoplastic resins and curable resins (thermosetting resins, photocurable resins, moisture curable resins, etc.) can be used. More specifically, for example, silicone resin, acrylic resin, methacrylic resin, fluororesin, alkyd resin, amino alkyd 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 Examples include resins, silicone-acrylic resins, and the like. However, it is not limited to the above.
Further, the natural resin is not particularly limited, and examples thereof include cellulose resins, isoprene resins such as natural rubber, protein resins such as casein, and the like.
In the present invention, the surface of the resin plate may be subjected to surface treatments such as corona discharge treatment, flame 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 surface treatment are not particularly limited, and can be appropriately set depending on the application.

Manufacture of coating composition In a typical embodiment, the coating composition for forming the coating film according to the present invention includes the steps of premixing components (A) and (B) and then mixing with water; It can be produced by a method including a step of stirring at a temperature below 40°C for 10 minutes or more. Generally, when manufacturing a coating composition containing water, there are two methods: diluting each component in the coating composition with water and then mixing, mixing each component in water, and mixing each component in advance. , a method of diluting with water, etc. In the present invention, it is preferable to mix components (A) and (B) in advance. By pre-mixing, components (A) and (B) can form a strong interaction. The coating film obtained from the coating composition thus prepared is preferable because it has excellent water resistance. Furthermore, by stirring at a temperature below 40° C. for 10 minutes or more, a coating composition in which the components (A) and (B) are uniformly dispersed can be formed. The coating film obtained from the coating composition thus prepared is preferred because it has high transparency and excellent appearance.

A coating composition in which components (A) and (B) which can form a covalent bond with the component (A) are bonded more firmly by the reaction between the components (A) and (B), water, and optionally After mixing a solvent and optionally a reaction catalyst, the mixture is stirred at 40°C or higher for 10 minutes or more, and optionally a component (C), and/or a component (D), and/or a component (E), and/or a curing accelerating catalyst. It can be manufactured by a method including a step of adding. In addition, after mixing component (A), component (C) and/or component (E), water, optionally a solvent, and optionally a reaction catalyst, the mixture is stirred at 40°C or higher for 10 minutes or more, and then component (B) is added. Produced by a method including a step of stirring at 40°C or higher for 10 minutes or more, and optionally adding component (C), and/or component (D), and/or component (E), and/or a curing accelerating catalyst. can do. The coating film obtained from the coating composition prepared in this manner has durability (e.g., anti-fog retention of the coating film when exposed to high temperature and high humidity environments, durability of appearance, resistance to elution, and water droplet formation). It is even more preferable from the viewpoint of the suppression effect).

Production of coating film The coating film according to the present invention is produced by, for example, coating a coating composition (sometimes abbreviated as "aqueous dispersion") dispersed in a solvent such as water on a substrate, and drying the coating composition. It can be formed by The drying here can be carried out at room temperature (for example, about 0° C. to 45° C.) without external heating. The viscosity of the aqueous dispersion is preferably 0.1 to 100,000 mPa·s at 20°C, preferably 1 to 10,000 mPa·s (measured with a vibrating viscometer). As a coating method, for example, spraying method, flow coating method, roll coating method, brush coating method, dip coating method, spin coating method, screen printing method, casting method, gravure printing method, flexographic printing method, etc. can be used. It is. Note that the composite of the base material and the coating film can be prepared, for example, after the coating film is dried on the base material, if desired, it may be subjected to heat treatment preferably at 20°C to 500°C, more preferably at 40°C to 250°C, or by irradiation with ultraviolet rays. It may be formed by doing the same.
In the present invention, after drying the coating film, it is preferable to perform heat treatment at a temperature of 50° C. or higher and lower than 150° C. for 10 to 60 minutes from the viewpoint of adhesion to the substrate, water resistance, and scratch resistance. The temperature of this heat treatment is more preferably 60° C. or higher from the viewpoint of the curing speed and adhesion of the coating film. The temperature of this heat treatment is preferably 130°C or lower, more preferably 120°C or lower, from the viewpoint of productivity and applicable substrate types.

The thickness of the coating film is preferably 0.05 to 100 μm, more preferably 0.1 to 10 μm. Preferably, the coating has a substantially uniform thickness (has a substantially flat surface). In terms of transparency, the coating film preferably has a thickness of 100 μm or less, and in order to exhibit functions such as weather resistance and stain resistance, it is preferably 0.05 μm or more. In the present invention, the "coating film" does not necessarily have to be a continuous film, and may be a discontinuous film, an island-like dispersed film, or the like.

Next, the present invention will be described in more detail with reference to Examples , Reference Examples , and Comparative Examples; however, the present invention is not limited to the following Examples unless it exceeds the gist thereof. The subject matter of the invention is to be determined solely by the scope of the appended claims, and includes modifications, equivalents, and the like that are obvious to those skilled in the art, in addition to their literal scope.

In addition, various physical properties were evaluated by the following methods.
<Number average particle diameter>
The sample was diluted with an appropriate solvent so that the solid content in the sample was 1 to 20% by mass, and measured using a zeta potential/particle size measurement system (manufactured by Otsuka Electronics, trade name "ELSZ1000").

<Appearance of paint film>
The appearance of the obtained coating film was visually observed. The results were evaluated as follows.
〇 (Good): Transparent.
△ (generally good): Partially cloudy.
× (Poor): The whole is cloudy.

<Water contact angle>
A drop of deionized water was placed on the coating film, and the coating was left at 23° C. for 10 seconds, and then measured using a contact angle measuring device (model CA-X150 contact angle meter, manufactured by Kyowa Kaimen Kagaku, Japan).

<HAZE>
The HAZE value of the sample was measured using a turbidity meter (manufactured by Nippon Denshoku Kogyo, NDH2000) according to JIS K7105.

<Refractive index>
The refractive index of the coating film was measured using a reflection spectroscopic film thickness meter (manufactured by Otsuka Electronics, trade name "FE-3000").

<Adhesion test (tape peeling test)>
The resulting coating film was evaluated as follows using a grid test of 100 1 mm squares according to JIS-K5600-5-6.
○ (Good): The ratio of the number of squares that have not peeled off is 80% or more.
Δ (moderate): The proportion of the number of unpeeled cells is less than 80% (more than 0%).
× (Poor): The ratio of the number of squares that have not peeled off is 0%.

<Anti-fog test>
A test piece of the resulting paint film was placed at a height of 5 cm from the water surface of a hot water bath maintained at 80°C with the paint surface facing down, and the paint film was continuously irradiated with steam from the hot water bath. The presence or absence of clouding 30 seconds after irradiation was visually evaluated as follows. It should be noted that if the evaluation is △ or higher, there is no practical problem, and if the evaluation is ○, it is more preferable.
○ (Good): No clouding at all.
△ (moderate): Slightly cloudy.
× (Poor): Cloudy.

<Water drop trace test>
Steam of 80° C. hot water was applied to the surface of the coating film prepared on the substrate in an environment of 23° C. and 50% RH for 90 seconds in an area of 50 cm ² at a distance of 5 cm from the water surface. After that, the coating film was stood vertically and dried at room temperature, and then the appearance was visually observed and water drop marks were evaluated.
〇 (Good): No change in appearance at all.
△ (medium): Water drop marks (white drip marks) are slightly visible.
× (Poor): Many water drop marks (white drip marks) are visible.

<Moisture resistance test>
The prepared coating film was exposed to an environment of 50° C. and 95% RH for 240 hours, and then left to stand in an environment of 23° C. and 50% RH for 1 hour. The resulting coating film was evaluated for adhesion, water contact angle, antifogging properties, and haze change. These evaluations indicate the adhesion, water contact angle, and durability of the coating film's antifogging properties in a hot and humid environment.

<Heat resistance test>
The produced coating film was exposed to an environment of 120° C. for 240 hours, and then left to stand in an environment of 23° C. and 50% RH for 1 hour. The resulting coating film was evaluated for adhesion, water contact angle, and antifogging properties. These evaluations indicate the adhesion, water contact angle, and durability of the coating film's antifogging properties under high-temperature environments.

<Water resistance test>
The produced coating film was immersed in deionized water at 25° C. for 240 hours, and then left to stand in an environment of 23° C. and 50% RH for 1 hour. The resulting coating film was evaluated for adhesion, water contact angle, antifogging properties, haze change, and refractive index change.

<Temperature/humidity cycle test>
After exposing the prepared coating film to an environment of 85°C and 85% RH for 20 hours, the temperature was lowered to -40°C at a cooling rate of 100°C/h, and after further exposure for 30 minutes, it was exposed to 85°C again at a heating rate of 100°C/h. After repeating the cycle of increasing the temperature to 85% RH at 0.degree. C. 10 times, it was allowed to stand in an environment of 23.degree. C. and 50% RH for 1 hour. The resulting coating film was evaluated for adhesion, water contact angle, antifogging properties, haze, and refractive index. These evaluations indicate the adhesion, water contact angle, antifogging properties, and sustainability of the appearance of the coating film when a sudden temperature change occurs in a hot and humid environment.

<Refractive index change>
The refractive index changes before and after the above water resistance test and temperature/humidity cycle test were calculated from the following formula.
・Refractive index change (%) =
{(Refractive index after water resistance test - refractive index before water resistance test)/Refractive index before water resistance test} x 100

<Appearance sustainability (change in HAZE value)>
As an index of the durability of the appearance of the coating film, the following evaluation was performed based on the change in HAZE value (ΔHAZE) before and after each of the above-mentioned moisture resistance test, water resistance test, and temperature/humidity cycle test. It should be noted that if the evaluation is △ or higher, there is no practical problem, and if the evaluation is ○, it is more preferable.
○ (Good): ΔHAZE less than 0.5 △ (Moderate): ΔHAZE 0.5 or more and less than 1.0 × (Poor): ΔHAZE 1.0 or more

<Synthesis Example 1 (Synthesis of hydrophilic compound (B)-1)>
In a reactor equipped with a reflux condenser, a dropping tank, a nitrogen inlet tube, a thermometer, and a stirring device, 100 g of polyethylene glycol monomethyl ether 4,000 (manufactured by Tokyo Chemical Industry Co., Ltd., solid content 100% by mass) and KBE-9007 ( After adding 6.2 g of each (manufactured by Shin-Etsu Chemical Co., Ltd.), the mixture was heated to 80° C. while blowing nitrogen gas. After that, 0.11 g of dibutyltin dilaurate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and stirring was continued for about 6 hours at a temperature of 80°C in the reaction vessel, and then cooled to room temperature to form a hydrophilic compound (B). I got -1.

<Synthesis Example 2 (Synthesis of hydrophilic compound (B)-2)>
Polysorbate (polyoxyethylene sorbitan monolaurate, trade name "Tween-20", manufactured by Tokyo Kasei Kogyo Co., Ltd., solid content 100 After adding 100 g (mass%) and 60.5 g of KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.), the mixture was heated to 80° C. while blowing nitrogen gas. After stirring was continued for about 6 hours while the temperature in the reaction vessel was 80°C, the mixture was cooled to room temperature to obtain hydrophilic compound (B)-2. The introduction rate of the silane coupling agent to hydroxyl groups was 90%.

<Synthesis Example 3 (Synthesis of hydrophilic compound (B)-3)>
Hydroxyethyl cellulose (manufactured by Tokyo Chemical Industry Co., Ltd., 4,500 mPa·s to 6,500 mPa·s (25°C 2% 10 g of aqueous solution) and 490 g of dehydrated dimethyl sulfoxide (manufactured by Kanto Kagaku Co., Ltd.) were added, heated to 80° C. while blowing nitrogen gas, and stirred for 1 hour. Thereafter, 9.8 g of KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.02 g of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the temperature in the reaction vessel was raised to 80°C while blowing nitrogen gas. After continuing stirring in this state for about 3 hours, the mixture was cooled to room temperature to obtain hydrophilic compound (B)-3. The introduction rate of the silane coupling agent to hydroxyl groups was 30%.

<Synthesis Example 4 (Synthesis of hydrophilic compound (B)-4)>
In a reactor equipped with a reflux condenser, a dropping tank, a nitrogen inlet pipe, a thermometer, and a stirring device, 100 g of polyvinyl alcohol (trade name "Kuraray Poval PVA217", manufactured by Kuraray Co., Ltd., solid content 94% by mass), KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.) 92.91 g were each added, and then heated to 95° C. while blowing nitrogen gas. Thereafter, 0.02 g of dibutyltin dilaurate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and stirring was continued for about 3 hours at a temperature of 95°C in the reaction vessel while blowing nitrogen gas, and then cooled to room temperature. Compound (B)-4 was obtained. The introduction rate of the silane coupling agent to hydroxyl groups was 20%.

<Synthesis Example 5 (Synthesis of polymer particle (C)-1 aqueous dispersion)>
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirring device, a mixed solution of 275 g of deionized water and 2.50 g of a 2% by mass aqueous solution of ammonium persulfate was heated to 80° C. with stirring. To this, a mixed solution of 1.65 g of methyl methacrylate and 3.15 g of N,N-diethylacrylamide, 1.20 g of 2-hydroxyethyl methacrylate, 0.50 g of 3-methacryloxypropyltrimethoxysilane, and a reactive emulsifier. ("Aqualon KH-1025", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 25% solids aqueous solution) and a mixture of 0.40 g and 25 g of deionized water were added in a reaction vessel with the temperature kept at 80°C. They were added simultaneously over a period of about 1 hour. Further, stirring was continued for about 2 hours while the temperature in the reaction vessel was 80°C, then cooled to room temperature, filtered through a 100 mesh wire mesh, and the solid content was adjusted to 2.0% by mass with deionized water. An aqueous dispersion of polymer particles (C)-1 having a number average particle diameter of 160 nm was obtained.

<Synthesis Example 6 (Synthesis of polymer particle (C)-2 aqueous dispersion)>
A mixture of 275 g of deionized water and 2.50 g of a 2% by mass aqueous solution of 2,2-azobis(2-methylpropionamidine) dihydrochloride was placed in a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirring device. , the temperature was increased to 80°C under stirring. To this, a mixed solution of 1.65 g of methyl methacrylate, 3.15 g of N,N-diethylacrylamide, 1.20 g of 2-hydroxyethyl methacrylate, 0.50 g of 3-methacryloxypropyltrimethoxysilane, N,N -Dimethylaminopropylacrylamide A mixture of 0.50 g of methyl chloride quaternary salt and 25 g of deionized water was simultaneously added dropwise over about 1 hour while the temperature in the reaction vessel was maintained at 80°C. Further, stirring was continued for about 2 hours while the temperature in the reaction vessel was 80°C, then cooled to room temperature, filtered through a 100 mesh wire mesh, and the solid content was adjusted to 2.0% by mass with deionized water. An aqueous dispersion of polymer particles (C)-2 having a number average particle diameter of 124 nm was obtained.

<Synthesis Example 7 (Synthesis of polymer particle (C)-3 aqueous dispersion)>
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirring device, a mixed solution of 275 g of deionized water and 2.25 g of a 2% by mass aqueous solution of ammonium persulfate was heated to 80° C. with stirring. To this, a mixed solution of 2.70 g of butyl methacrylate, 2.70 g of N,N-diethylacrylamide, 0.60 g of diacetone acrylamide, 0.50 g of 3-methacryloxypropyltrimethoxysilane, and a reactive emulsifier ("Aqualon KH -1025'', manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 0.40 g of 25% solids aqueous solution) and 25 g of deionized water for about 1 hour while maintaining the temperature in the reaction vessel at 80°C. and dripped at the same time. Further, stirring was continued for about 2 hours while the temperature in the reaction vessel was 80°C, then cooled to room temperature, filtered through a 100 mesh wire mesh, and the solid content was adjusted to 2.0% by mass with deionized water. An aqueous dispersion of polymer particles (C)-3 having a number average particle diameter of 91 nm was obtained.

<Synthesis Example 8 (Synthesis of polymer particle (C)-4 aqueous dispersion)>
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirring device, a mixed solution of 275 g of deionized water and 2.25 g of a 2% by mass aqueous solution of ammonium persulfate was heated to 80° C. with stirring. To this, a mixed solution of 1.65 g of methyl methacrylate and 3.15 g of N,N-diethylacrylamide, 1.20 g of 2-hydroxyethyl methacrylate, 0.50 g of 3-methacryloxypropyltrimethoxysilane, and a reactive emulsifier. ("Aqualon KH-1025", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 25% solid content aqueous solution) and a mixture of 0.40 g and 25 g of deionized water were heated in a reaction vessel while maintaining the temperature at 80°C. They were added simultaneously over a period of about 1 hour. After further stirring for about 2 hours while the temperature in the reaction vessel was 80°C, it was cooled to room temperature, and 2.63 g of 3-isocyanatepropyltriethoxysilane (solid content 60% EtOH diluted solution) blocked with pyrazole. After adding, the mixture was further stirred at room temperature for 2 hours, filtered through a 100-mesh wire mesh, the solid content was adjusted to 2.0% by mass with deionized water, and polymer particles (C) with a number average particle diameter of 116 nm were prepared. -4 water dispersion was obtained.

<Synthesis Example 9 (Synthesis of polymer particle (C)-5 aqueous dispersion)>
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirring device, a mixed solution of 275 g of deionized water and 2.25 g of a 2% by mass aqueous solution of ammonium persulfate was heated to 80° C. with stirring. To this, a mixed solution of 1.65 g of methyl methacrylate, 3.15 g of N,N-diethylacrylamide, 1.20 g of 2-carboxyethyl methacrylate, 0.50 g of 3-methacryloxypropyltrimethoxysilane, and a reactive emulsifier. ("Aqualon KH-1025", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 25% solids aqueous solution) and a mixture of 0.40 g and 25 g of deionized water were added in a reaction vessel with the temperature kept at 80°C. They were added simultaneously over a period of about 1 hour. Further, stirring was continued for about 2 hours while the temperature in the reaction vessel was 80°C, then cooled to room temperature, filtered through a 100 mesh wire mesh, and the solid content was adjusted to 2.0% by mass with deionized water. An aqueous dispersion of polymer particles (C)-5 having a number average particle diameter of 126 nm was obtained.

<Synthesis Example 10 (Synthesis of polymer particle (C)-6 aqueous dispersion)>
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirring device, a mixed solution of 275 g of deionized water and 2.25 g of a 2% by mass aqueous solution of ammonium persulfate was heated to 80° C. with stirring. To this, a mixed solution of 1.50 g of methyl methacrylate, 4.50 g of N,N-diethylacrylamide, 0.50 g of N,N-methylenebisacrylamide, and a reactive emulsifier ("Aqualon KH-1025", Daiichi Kogyo Seiyaku) A mixture of 0.40 g of 25% solids aqueous solution (manufactured by Co., Ltd.) and 25 g of deionized water was simultaneously added dropwise over about 1 hour while maintaining the temperature in the reaction vessel at 80°C. Further, stirring was continued for about 2 hours while the temperature in the reaction vessel was 80°C, then cooled to room temperature, filtered through a 100 mesh wire mesh, and the solid content was adjusted to 2.0% by mass with deionized water. An aqueous dispersion of polymer particles (C)-6 having a number average particle diameter of 174 nm was obtained.

<Synthesis Example 11 (Synthesis of polymer particle (C)-7 aqueous dispersion)>
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirring device, a mixed solution of 275 g of deionized water and 2.50 g of a 2% by mass aqueous solution of ammonium persulfate was heated to 80° C. with stirring. To this, a mixed solution of 1.65 g of methyl methacrylate, 1.95 g of N,N-diethylacrylamide, 2.40 g of 2-hydroxyethyl methacrylate, 0.50 g of 3-methacryloxypropyltrimethoxysilane, and a reactive emulsifier. ("Aqualon KH-1025", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 25% solid content aqueous solution) and a mixture of 0.40 g and 25 g of deionized water were heated in a reaction vessel while maintaining the temperature at 80°C. They were added simultaneously over a period of about 1 hour. After further stirring for about 4 hours while the temperature in the reaction vessel was 80°C, it was cooled to room temperature, and 5.27 g of 3-isocyanatepropyltriethoxysilane (solid content 60% EtOH diluted solution) blocked with pyrazole After adding, the mixture was further stirred at room temperature for 2 hours, filtered through a 100-mesh wire mesh, the solid content was adjusted to 2.0% by mass with deionized water, and polymer particles (C) with a number average particle diameter of 180 nm were prepared. -7 water dispersion was obtained.

<Synthesis Example 12 (Synthesis of polymer particle (C)-8 aqueous dispersion)>
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirring device, a mixed solution of 275 g of deionized water and 2.50 g of a 2% by mass aqueous solution of ammonium persulfate was heated to 65° C. with stirring. To this, 1.50 g of methyl methacrylate, 3.50 g of N,N-diethylacrylamide, 2-[(3,5-dimethylpyrazole)carboxyamino]ethyl methacrylate ("Karens MOI-BP", manufactured by Showa Denko K.K.) ) 0.60 g mixed solution, 0.50 g of 3-methacryloxypropyltrimethoxysilane, and 0.40 g of a reactive emulsifier ("Aqualon KH-1025", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 25% solids aqueous solution) , and a mixed solution of 25 g of deionized water were simultaneously added dropwise over about 0.5 hour while maintaining the temperature in the reaction vessel at 65°C. Further, stirring was continued for about 5 hours while the temperature in the reaction vessel was 65°C, then cooled to room temperature, filtered through a 100 mesh wire mesh, and the solid content was adjusted to 2.0% by mass with deionized water. An aqueous dispersion of polymer particles (C)-8 having a number average particle diameter of 164 nm was obtained.

<Synthesis Example 13 (Synthesis of metal oxide (A)-1)>
10 g of deionized water, 90 g of ethanol, 20 g of tetraethoxysilane, and 0.9 g of 28% aqueous ammonia were charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirring device, and then the temperature was heated to 40 °C. . Thereafter, stirring was continued for about 70 hours while the temperature in the reaction vessel was 40°C, and then the mixture was cooled to room temperature to obtain metal oxide (A)-1.

<Synthesis Example 14 (Synthesis of polyisocyanate crosslinking agent (D)-1)>
The inside of a four-neck flask equipped with a stirrer, a thermometer, and a cooling tube was purged with nitrogen, and 1000 parts by mass of HDI was charged. While stirring this at 60° C., tetramethylammonium capriate was added as a catalyst, and when the conversion rate reached 20%, 0.2 g of phosphoric acid was added to stop the reaction. Thereafter, the reaction solution was filtered, and unreacted HDI was removed using a thin film distillation apparatus to obtain polyisocyanate crosslinking agent (D)-1. The obtained polyisocyanate had a viscosity (25° C.) of 2,700 mPa·s and an isocyanate group concentration of 21.7 wt%.

<Synthesis Example 15 (Synthesis of polyisocyanate crosslinking agent (D)-2)>
In a four-neck flask equipped with a stirrer, a thermometer, and a cooling tube, 100 parts by mass of the polyisocyanate ((D)-1) obtained in Synthesis Example 14 and polyethylene oxide (manufactured by Nippon Nyukazai Co., Ltd., trade name "MPG") were added. 18.2 parts by mass of urethanization catalyst (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name "Neostane U-810") and 0.01 parts by mass of urethanization catalyst (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name "Neostan U-810") were charged, and the mixture was maintained at 80° C. for 2 hours under a nitrogen atmosphere. Thereafter, 43.8 parts by mass of 3,5-dimethylpyrazole was added, and it was confirmed by an infrared spectrum (manufactured by JASCO Corporation, product name FT/IR-4000) that the characteristic absorption of isocyanate groups had disappeared. 68.9 parts by mass of dipropylene glycol monomethyl ether was added and mixed with stirring for 30 minutes to obtain polyisocyanate crosslinking agent (D)-2.

<Synthesis Example 16 (Synthesis of semicarbazide crosslinking agent (D)-3)>
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was made into a nitrogen atmosphere, and 225 parts by mass of isopropanol and 57 parts by mass of hydrazine monohydrate were added and stirred at 25° C. for 30 minutes. A solution prepared by dissolving 50 parts by mass of isophorone diisocyanate in 450 parts by mass of tetrahydrofuran was added to this solution over 2 hours with stirring at 25°C, and the mixture was further stirred at 25°C for 1 hour. Semicarbazide crosslinking agent (D)-3 was obtained by distilling off isopropanol, tetrahydrofuran, excess hydrazine monohydrate, water, etc. in the resulting reaction solution under heating and reduced pressure.

[Example 1]
4.8 g of water-dispersed colloidal silica with a number average particle diameter of 4 nm (trade name "Snowtex-OXS", manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass) as metal oxide (A), hydrophilic compound (B) After mixing 0.02 g of Synthesis Example 1 (hydrophilic compound (B)-1), the mixture was stirred at 25° C. for 1 hour. Next, after mixing 5.2 g of deionized water, the mixture was further stirred at 25° C. for 1 hour to obtain a coating composition with a solid content of 5%. The obtained coating composition was coated on the entire polycarbonate plate (manufactured by Takiron C.I. Co., Ltd.) measuring 60 mm long x 60 mm wide x 2 mm thick using a spin coater at 800 rpm x 5 seconds, and dried for 30 minutes at 20°C. I let it happen. Thereafter, a test plate was obtained by drying at 120° C. for 30 minutes. The appearance of the obtained coating film was good (transparent). Furthermore, the water contact angle was 3°, indicating high hydrophilicity. As a moisture resistance test, the obtained test piece was placed in an environmental test chamber at a temperature of 50°C and 95% RH for 240 hours, and then left to stand in an environment of a temperature of 23°C and 50% RH for 1 hour, followed by HAZE and adhesion tests. The properties, water contact angle, and antifogging properties were evaluated. As a result, ΔHAZE was good at less than 0.5, adhesion, hydrophilicity (water contact angle), and antifogging properties were also maintained, and moisture resistance was generally good. In addition, the blending amount (parts by mass) of each raw material is shown in Table 1-1. Table 2-1 shows the evaluation results including initial characteristics.

[Examples 2 to 4, 6 to 56 and 60 to 65 , Reference Examples 5 and 57 to 59, and Comparative Examples 1 to 10]
In Examples 2 to 4, 6 to 56 and 60 to 65 , Reference Examples 5 and 57 to 59, and Comparative Examples 1 to 10, the types and amounts of raw materials ( A coating film was produced in the same manner as in Example 1 except that the weight (parts by mass) was changed, test pieces were prepared, and coating film performance was evaluated. The evaluation results of coating film performance including initial characteristics are shown in Tables 2-1 to 2-7.
The abbreviations shown in each table have the following meanings.
・STOXS: manufactured by Nissan Chemical Industries, Ltd., Snowtex-OXS (colloidal silica), solid content 10% by mass, acidic type, number average particle diameter 4 nm
・STOUP: Manufactured by Nissan Chemical Industries, Ltd., Snowtex-OUP (colloidal silica), solid content 15%, acidic type, number average particle size 40-70 nm
・STOL: manufactured by Nissan Chemical Industries, Ltd., Snowtex-OL (colloidal silica), solid content 20%, acidic type, number average particle diameter 45 nm
・E-02: Manufactured by Nisshinbo Co., Ltd., Carbodilite E-02, solid content 40% by mass
・HEC: Hydroxyethylcellulose ・MS51: Manufactured by Mitsubishi Chemical Corporation, MS-51 (siloxane oligomer)
・DX9740: Manufactured by Shin-Etsu Chemical Co., Ltd., DX-9740, solid content 100% by mass

Regarding Comparative Example 1, which did not use a hydrophilic compound, it was difficult to form a film on the base material, so it was impossible to evaluate various physical properties of the coating film.
In addition, in Comparative Example 2 in which no metal oxide was used, most of the coating film had eluted after the water resistance test, so it was impossible to evaluate various physical properties of the coating film after the water resistance test.

The coating film of the present invention can be particularly suitably used as an antifogging coating film that requires high antifogging properties, durability, and design. Furthermore, the coating film of the present invention can be used as a coating film for automotive parts such as vehicle lighting equipment such as automobile headlamps and rear lamps (especially low heat generation lamps such as LEDs and lasers), automotive camera lenses, and window glass. It can be suitably used in applications that require fogging properties and adhesion, antifogging properties and adhesion when exposed to rapid environmental changes, and maintenance of coating film appearance. Furthermore, the coating film of the present invention can be suitably used for parts that cannot be easily removed due to fogging or droplet removal, such as internal parts of various devices and parts installed at high places. can. Furthermore, the coating film of the present invention can be suitably used as an anti-fog coating film for mirrors, building materials (window glass, exterior walls, etc.), signboards, traffic lights, displays, camera lenses, goggles, eyeglass lenses, and the like. All of the features and advantages described above for the coatings according to the invention also apply to these antifogging coatings, coatings for automobile parts, and coatings for internal parts.

Claims (15)

A coating film containing a metal oxide (A) and a hydrophilic compound (B), which is immersed in deionized water at 25°C for 240 hours and then left to stand in an environment of 23°C and 50% RH for 1 hour. The refractive index change before and after the water resistance test is -5% or more and +5% or less,
The metal oxide (A) contains at least one of silica, silicone particles, and acrylic silicone particles,
The hydrophilic compound (B) is characterized in that it has a branched polyalkylene oxide chain in its molecule, and contains a primary aliphatic hydroxyl group, and an alkoxysilyl group and/or a silanol group at the end of the polyalkylene oxide chain. Paint film. The coating film according to claim 1, further comprising polymer particles (C). The coating film according to claim 1 or 2, further comprising a crosslinking agent (D). The coating film according to any one of claims 1 to 3, which has a water contact angle value of less than 40°. The coating film according to any one of claims 1 to 4, wherein the metal oxide (A) contains silica. The coating film according to any one of claims 1 to 5, wherein the hydrophilic compound (B) is bonded to the surface of the metal oxide (A) via a non-covalent bond and/or a covalent bond. . The coating film according to any one of claims 1 to 6 , wherein the polymer particles (C) include portions that are in contact with each other. The coating composition for producing a coating film according to any one of claims 1 to 7, wherein the metal oxide (A) contains at least one of an alkoxysilane and a hydrolyzed condensate of an alkoxysilane. . The coating composition for producing a coating film according to any one of claims 1 to 7 , wherein the metal oxide (A) contains at least one of silicone particles and acrylic silicone particles. The coating composition according to claim 8 or 9 , further comprising a polymer particle (C), the polymer particle (C) comprising a reactive functional group. The coating composition according to claim 8 or 9 , comprising a metal oxide (A) and a hydrophilic compound (B), and further comprising at least one of polymer particles (C) and a crosslinking agent (D). A laminate of any one of a resin base material and a glass base material and the coating film according to any one of claims 1 to 7 . The coating film according to any one of claims 1 to 7 , which is used as an anti-fog coating film. The coating film according to any one of claims 1 to 7 , which is used as a coating film for automobile exterior parts. The coating film according to any one of claims 1 to 7 , which is used as a coating film for a lamp cover.