JP2000119596A - Antifouling hard coating material composition and its coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject antifouling hard coating material composition that can form coating layers having excellent antifoulancy, surface hardness, abrasion resistance, resistance to surface flaw and the like by using a specific silicone resin and a filler as essential components. SOLUTION: This composition comprises as essential components, (A) a tetrafunctional silicone resin in which more than 90 wt.% is prepared by partial hydrolysis of a tetrafunctional alkoxy silane of the formula: Si(OR)4 (R is a 1-8C alkyl) in the presence of an acidic catalyst, having a weight-average molecular weight of 500-1,000 calculated as polystyrene, and (B) at least one kind of filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antifouling hard coating material composition capable of forming a coating film having excellent functions such as antifouling properties, surface hardness, abrasion resistance, and difficulty in scratching the surface. And the paintings.

[0002]

2. Description of the Related Art A coating material containing a filler in a cured silicone resin is formed by applying a coating material containing a filler in an inorganic coating material containing a silicone resin as a main component to a substrate surface and curing the coating material. The method is known,
It is applied to various substrates.

[0003]

However, the above-mentioned conventional paint has the following problems. Silicone resins include those having 1 to 4 functional groups. When a silicone resin having 3 or less functional groups is used, the resulting coating film has reduced antifouling properties, surface hardness and abrasion resistance. Therefore, the surface is easily stained or scratched when the surface is polished. In particular, when a glass substrate is used as the substrate, if a part of the surface is damaged, the value as a product is reduced by half. On the other hand, 4
When a functional silicone resin is used, the antifouling property, surface hardness, and abrasion resistance of the coating film are improved. However, if the molecular weight of the tetrafunctional silicone resin is too large, the silicone resin is unstable, and the molecular weight during storage is increased. It increases and eventually gels easily. For this reason, the storage stability of the paint is deteriorated.

Accordingly, an object of the present invention is to form a coating film which exhibits excellent antifouling properties, has excellent surface hardness and abrasion resistance, is hardly scratched on the surface, and has excellent storage stability. An object of the present invention is to provide an antifouling hard coating material composition which can be used and a coated product thereof.

[0005]

The antifouling hard coating material composition according to the present invention contains a silicone resin and at least one filler as essential components, and 90% by weight or more of the silicone resin is represented by the following (A). ) Components. Component (A): represented by the general formula Si (OR) ₄ (1) (where R is the same or different and has 1 to 8 carbon atoms)
A tetrafunctional alkoxysilane having a weight average molecular weight of 500 to 1,000 in terms of polystyrene, which is obtained by partially hydrolyzing a tetrafunctional alkoxysilane in the presence of an acidic catalyst.

[0006] The coated article according to the present invention comprises:
A coating layer comprising a cured coating film of the antifouling hard coating material composition according to the present invention is provided.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Silicone resin, which is one of the essential components of the antifouling hard coating composition of the present invention, is used as a binder resin and a film forming component.
90% by weight or more of the silicone resin is made of a tetrafunctional silicone resin (hereinafter sometimes simply referred to as "component (A)"). The tetrafunctional silicone resin is a component that imparts surface anti-fouling properties by rainwater washing to the coating film by imparting surface hydrophilicity (water wettability) to the coating film of the anti-fouling hard coating material composition. In addition, the coating film is 4
The use of the functional silicone resin provides excellent surface hardness, abrasion resistance, and surface scratch resistance.

4 for all silicone resins used
The proportion of the functional silicone resin is usually 90% by weight or more, preferably 95% by weight or more, and most preferably 100% by weight, based on the resin solid content in terms of the condensation compound. When the proportion of the tetrafunctional silicone resin is less than 90% by weight, the coating properties such as surface hydrophilicity, antifouling property for rainwater washing, surface hardness, abrasion resistance, and difficulty in scratching the surface are deteriorated.

The tetrafunctional silicone resin used in the present invention is a partial hydrolyzate of the tetrafunctional alkoxysilane represented by the above general formula (1), and the tetrafunctional alkoxysilane is partially hydrolyzed in the presence of an acidic catalyst. Obtained by decomposition. As the tetrafunctional alkoxysilane, those represented by the general formula (1) are used. In the general formula (1),
R is easy to obtain, easy to prepare paint, 4
When a coating containing a functional silicone resin is applied and cured, a condensation reaction is likely to occur, and as a result, it is an alkyl group having 1 to 8 carbon atoms from the viewpoint of easily forming a hard coating film. Represents a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like. Among these alkyl groups, those having 3 or more carbon atoms may be linear such as n-propyl group, n-butyl group, etc., isopropyl group, isobutyl group, t-butyl group. It may have a branch such as a group. The tetrafunctional alkoxysilane has four R groups in one molecule, and these four R groups may be the same or different from each other.

Specific examples of the tetrafunctional alkoxysilane are not particularly limited. For example, tetraalkoxy such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane and tetra-t-butoxysilane Silane. Further, an organosilane compound generally called a silane coupling agent is also included in the tetrafunctional alkoxysilane.

As the tetrafunctional alkoxysilane, only one kind may be used, or two or more kinds may be used in combination. The amount of water used for partially hydrolyzing the tetrafunctional alkoxysilane is not particularly limited. For example, the amount of water can be represented by the molar ratio of water (H ₂ O) to the alkoxy group (OR group) of the tetrafunctional alkoxysilane. If 0 <H ₂ O /
OR <1, more preferably 0.3 <H ₂ O / OR <
Satisfies 0.7. If the amount of water is 1 or more, the resulting 4
The molecular weight of the functional silicone resin is larger than 1000, and the storage stability tends to deteriorate, which is not preferable.

The acidic catalyst used for partially hydrolyzing the tetrafunctional alkoxysilane is not particularly limited. For example, acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutar Organic acids such as acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, and oxalic acid; inorganic acids such as hydrochloric acid, nitric acid, and halogenated silane; and acidic sol-like fillers such as acidic colloidal silica and titanium oxide sol. These can be used alone or in combination of two or more.

The partial hydrolysis of the tetrafunctional alkoxysilane may be carried out by heating (for example, heating to 40 to 100 ° C.) if necessary. The partial hydrolysis of the tetrafunctional alkoxysilane may be performed, if necessary, by diluting the tetrafunctional alkoxysilane with an appropriate solvent. Such a diluting solvent (reaction solvent) is not particularly limited. For example, methanol, ethanol, isopropanol, n-
Lower aliphatic alcohols such as butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol And one or more selected from the group consisting of these can be used.
One or two or more of toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can be used in combination with these hydrophilic organic solvents.

When the tetrafunctional alkoxysilane is partially hydrolyzed in the presence of an acidic catalyst, the weight average molecular weight (Mw) of the resulting tetrafunctional silicone resin is expressed in terms of polystyrene.
Usually 500-1000, preferably 600-1000,
More preferably, it is adjusted to be 700 to 1,000. When the weight average molecular weight is less than 500, the coating film cannot maintain sufficient hardness. In addition, the weight average molecular weight is 100
If it is larger than 0, the tetrafunctional silicone resin is unstable, easily gelated, and has disadvantages such as reduced storage stability.

It is preferable that the pH of the obtained tetrafunctional silicone resin is adjusted in the range of 0.5 to 6.
If the pH is within this range, within the above-mentioned range of molecular weight,
A tetrafunctional silicone resin can be used stably. If the pH is out of this range, the stability of the tetrafunctional silicone resin is poor, so that the usable period from the preparation of the antifouling hard coating material composition is limited. Here, the method of adjusting the pH is not particularly limited. For example, after the synthesis of the tetrafunctional silicone resin, the pH is adjusted.
Is less than 0.5, for example, the pH may be adjusted to a value within the above range using a basic reagent such as ammonia. When the pH exceeds 6, for example, an acidic reagent such as hydrochloric acid may be used. It may be adjusted by using this. Also, depending on the pH,
When the reaction does not proceed while the molecular weight is small and it takes time to reach the molecular weight range, the reaction may be promoted by heating the tetrafunctional silicone resin, or the reaction may be performed by lowering the pH with an acidic reagent. After proceeding, the basic reagent
It may return to H.

The filler contained as an essential component together with the silicone resin in the antifouling hard coating material composition of the present invention further increases the hardness of the cured coating film of the composition and improves the surface smoothness and crack resistance. It is used for various purposes such as. The filler is not particularly limited, and examples thereof include inorganic fillers such as silica and optical semiconductors, and organic fillers such as carbon black. Only one filler may be used, or two or more fillers may be used in combination.

The silica is not particularly limited.
Known ones can be used. The silica is not particularly limited, but is introduced into the antifouling hard coating material composition by dispersing it in the form of colloidal silica in a reaction solvent used in the preparation of the tetrafunctional silicone resin. Is preferable in terms of film forming property and simplification of the process. However, it is not limited to this. For example, after mixing silica with a tetrafunctional silicone resin prepared without silica, the resulting mixture may be introduced into an antifouling hard coating material composition, or silica may be mixed with a tetrafunctional silicone resin. The resin may be introduced into the antifouling hard coating material composition separately from the resin.

The form of silica when introduced into the antifouling hard coating material composition is not particularly limited.
It may be in the form of powder or colloidal silica. The colloidal silica is not particularly limited, and for example, water-dispersible or non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used. Generally, such colloidal silica has a silica content of 20%.
-50% by weight, and the silica content can be determined from this value. When water-dispersible colloidal silica is used, water present as a component other than solid components in the colloidal silica can be used for hydrolysis of tetrafunctional alkoxysilane which is a raw material of tetrafunctional silicone resin. (Added to the amount of water used during hydrolysis), and can be used as a curing agent for the antifouling hard coating material composition. Water-dispersible colloidal silica is
Usually made from water glass, it is readily available as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersible colloidal silica can be easily obtained as a commercial product similarly to the water-dispersible colloidal silica. In organic solvent dispersible colloidal silica,
The type of the organic solvent in which the colloidal silica is dispersed is not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol;
Ethylene glycol derivatives such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether;
And diacetone alcohol and the like, and one or more kinds selected from the group consisting of these can be used. In combination with these hydrophilic organic solvents, toluene, xylene, hexane, heptane,
One or more of ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used.

The antifouling hard coating material composition of the present invention not only obtains various functions by the photocatalytic effect described later, but also increases the surface hydrophilicity of the formed coating film by the photocatalytic effect or maintains it for a long period of time. For this reason, it is preferable to include an optical semiconductor as the filler. The optical semiconductor is not particularly limited, but for example, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, oxide In addition to metal oxides such as copper, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, nickel oxide, rhenium oxide, etc., strontium titanate and the like harden coating films (especially at low temperatures including room temperature) Is preferable in that an effect of promoting the curing can be obtained. Among these, the above metal oxides are preferable in that they can be easily used practically, and among the metal oxides, titanium oxide is particularly preferable, because of its photocatalytic performance, curing acceleration performance, safety, availability and cost reduction. Preferred in terms of surface. When titanium oxide is used as an optical semiconductor, the use of an anatase-type (anatase-type) crystal as the photocatalyst performance and curing acceleration performance is the strongest. This is preferable in that the accelerating performance is expressed in a shorter time.

As the optical semiconductor, only one kind may be used.
A combination of more than one species may be used. It should be noted that the material used as the optical semiconductor material can be used as long as it finally shows the properties of the optical semiconductor. It is known that an optical semiconductor generates active oxygen (photocatalytic property) when irradiated with light (ultraviolet light) having an excitation wavelength (for example, 400 nm). Since active oxygen can oxidize and decompose organic substances, its properties are used to make use of the properties of carbon-based dirt components attached to painted products (for example, carbon fractions contained in exhaust gas from automobiles, and dust from cigarettes). Self-cleaning effect to decompose, etc .; deodorant effect to decompose malodorous components represented by amine compounds and aldehyde compounds; antibacterial effect to prevent the generation of bacterial components represented by Escherichia coli and Staphylococcus aureus; Obtainable. In addition, when ultraviolet light is applied to a coating film containing an optical semiconductor, the optical semiconductor converts water into hydroxyl radicals by the photocatalysis, and the hydroxyl radicals decompose water-repellent organic substances and the like attached to the coating film surface. By the removal, the hydrophilicity (wetting property) of the coating film with respect to water is further improved, and a higher level of antifouling property or the like by rainwater washing can be obtained or maintained for a long time. However, there is also an effect that an antifogging property that is hardly fogged by water drops can be obtained.

Further, there is an antistatic function by the photocatalytic action of the optical semiconductor, and this function further improves the antifouling effect. For example, when the coating film containing the optical semiconductor is irradiated with ultraviolet light, the surface resistance of the coating film is reduced due to the action of the optical semiconductor contained in the coating film, thereby exhibiting an antistatic effect. Become. The mechanism by which the surface resistance of the coating decreases when the optical semiconductor-containing coating is irradiated with ultraviolet light has not yet been clearly identified, but the electrons and holes generated by the irradiation of the ultraviolet light act on the coating. It is considered that the surface resistance value of the coating film is reduced by performing the method.

When a metal is carried on the surface of the optical semiconductor, the photocatalytic effect of the optical semiconductor becomes higher. Although the mechanism has not yet been clearly confirmed, the metal is carried on the surface of the optical semiconductor to promote the charge separation of the optical semiconductor, and the disappearance of electrons and holes generated by the charge separation is established. It is thought that smaller is related.

The metal which may be carried on the surface of the optical semiconductor includes, for example, silver, copper, iron, nickel, zinc, platinum,
Gold, palladium, cadmium, cobalt, rhodium, ruthenium and the like are preferable in that charge separation of the optical semiconductor is further promoted. The supported metal may be only one kind or two or more kinds. The amount of the metal carried is not particularly limited, but is preferably, for example, 0.1 to 10% by weight, and more preferably 0.2 to 5% by weight, based on the optical semiconductor. If the loading is less than 0.1% by weight, the loading effect tends not to be sufficiently obtained. If the loading exceeds 10% by weight, the effect does not increase so much. Problems tend to occur.

The method for supporting the metal is not particularly limited, and examples thereof include an immersion method, an impregnation method, and a photoreduction method. As the filler, a clay crosslinked body in which an optical semiconductor is inserted between layers may be used. This is because the optical semiconductor is dispersed in the form of fine particles between the layers to improve the photocatalytic performance. The filler that can be used in the present invention may be in any form as long as it can be dispersed in the antifouling hard coating material composition, such as powder, fine particle powder, and solution-dispersed sol particles. In the case of a sol having a pH of 7 or less, curing proceeds in a shorter time, and the sol is excellent in convenience in use.

The dispersion medium for dispersing the filler in the antifouling hard coating material composition is not particularly limited as long as it can uniformly disperse the filler. Solvents can also be used. The aqueous solvent that can be used as a dispersion medium for the filler is not particularly limited. For example, in addition to water alone,
Hydrophilic organic solvents (eg, methanol, ethanol,
Lower aliphatic alcohols such as isopropanol, n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; diacetone alcohol and the like )) And a mixed solvent of water and at least one of them. Among these aqueous solvents,
Water-methanol mixed solvent, dispersion stability of the filler,
It is preferable from the viewpoint of drying property of the dispersion medium after coating.

Further, an aqueous sol may be used as the sol-like filler, which may also function as an acidic catalyst at the time of hydrolysis of the tetrafunctional alkoxysilane. The non-aqueous solvent that can be used as a filler dispersion medium is not particularly limited. For example, at least one non-aqueous solvent selected from the group consisting of the above-mentioned hydrophilic organic solvents and hydrophobic organic solvents such as toluene and xylene. Seeds can be used. Among these non-aqueous solvents, methanol is preferred in terms of the dispersion stability of the filler and the drying property of the dispersion medium after coating.

As the filler, in order to ensure the smoothness and gloss of the surface when the antifouling hard coating material composition is applied to a glass substrate or the like and the transparency of the coating film,
It is preferable to use fine particles. The average primary particle diameter is preferably 50 μm or less, and 5 μm
It is more preferably not more than 0.5 μm, more preferably not more than 0.5 μm. The average primary particle diameter of the filler when mixed with the tetrafunctional silicone resin is 5 to 10
It is preferably 0 nm.

The compounding amount of the filler is not particularly limited. For example, the weight ratio of the filler to the total amount of all the condensed compounds of the silicone resin is 0.1% based on the solid content.
Preferably, 1 ≦ filler / total silicone resin ≦ 4, more preferably 0.2 ≦ filler / total silicone resin ≦ 3, and even more preferably, 0.5 ≦ filler / total silicone resin ≦ 2. preferable. When the above ratio is less than 0.1, the effect of adding the filler tends to be hardly obtained, and when it exceeds 4, the coating film performance tends to be reduced, for example, cracks are easily generated. The method for uniformly dispersing the filler in the antifouling hard coating material composition is not particularly limited. For example, a homogenizer, a disper, a paint shaker, a common various dispersing method using a bead mill, or the like may be used. Can be.

The drying temperature of the dispersion medium after coating is not particularly limited, and may be appropriately set according to the type of the dispersion medium, the desired surface hardness of the coating film, the abrasion resistance and the like. The antifouling hard coating material composition of the present invention does not need to include a curing catalyst when cured by heating, but promotes the curing of the applied film by promoting the condensation reaction of the silicone resin or cures at room temperature. If necessary, the composition may further include a curing catalyst. Examples of the curing catalyst include, but are not particularly limited to, alkyl titanates; carboxylic acid metal salts such as tin octylate, dibutyltin dilaurate, and dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine acetate;
Amine salts such as ethanolamine acetate; quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-
Amine-based silane coupling agents such as aminoethyl-γ-aminopropyltrimethoxysilane and N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane;
acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; alkali metal salts such as lithium acetate, potassium acetate, lithium formate, sodium formate, potassium phosphate and potassium hydroxide; Titanium compounds such as isopropyl titanate, tetrabutyl titanate, and titanium tetraacetylacetonate; halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylmonochlorosilane;
However, other than these, there is no particular limitation as long as it is effective for accelerating the condensation reaction of the silicone resin.

When the antifouling hard coating material composition of the present invention also contains a curing catalyst, its amount is determined on the basis of solids content.
The amount is preferably 10% by weight or less, more preferably 5% or less, based on the total amount of all the condensed compounds of the silicone resin. If it exceeds 10% by weight, the storage stability of the antifouling hard coating material composition may be impaired. The antifouling hard coating material composition of the present invention uses a curing catalyst and heats it to a low temperature of 100 ° C. or lower or leaves it at room temperature to form functional groups of the silicone resin (OR group and OR group, OR group). An OH group or an OH group and an OH group) undergo a condensation reaction to form a cured film. Therefore,
Such an antifouling hard coating material composition is hardly affected by humidity even when cured at room temperature. In addition, when a heat treatment at 100 ° C. or higher is performed, a cured film can be formed by promoting a condensation reaction without using a curing catalyst.

It should be noted that even if additives such as a leveling agent, an ultraviolet absorber, a dye, a pigment, and a conductive agent are contained in the antifouling hard coating material composition within a range that does not adversely affect the effects of the present invention. Good. The antifouling hard coating material composition of the present invention can be used after being diluted with various organic solvents, if necessary, because of its easy handling. The type of organic solvent is
It can be appropriately selected according to the kind of the alkyl group of the tetrafunctional silicone resin or the molecular weight of the tetrafunctional silicone resin. Such an organic solvent is not particularly limited, but includes, for example, methanol, ethanol, isopropanol, n-butanol,
Lower aliphatic alcohols such as isobutanol; ethylene glycol, ethylene glycol monobutyl ether,
Ethylene glycol derivatives such as ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and toluene, xylene, hexane,
Heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol and the like can be mentioned, and one or more selected from the group consisting of these can be used. The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be appropriately determined as needed.

The method for producing the antifouling hard coating material composition of the present invention is not particularly limited, and each component may be mixed using a usual method and apparatus. Regarding the form of each component when introduced into the antifouling hard coating material composition, liquid or powder such as a liquid itself, a solution dissolved in a solvent, a dispersion liquid dispersed in a dispersion medium, and the like There is no particular limitation irrespective of the solid state of the body or the like. When each component is introduced in the form of a solution or a dispersion, for example, water, the above-mentioned organic solvent, or a mixture of water and the above-mentioned organic solvent can be used as the solvent or dispersion medium. Further, each component may be added separately, or 2
The components may be mixed in advance and then mixed with the remaining components, or all the components may be mixed at the same time, and there is no particular limitation on the timing of addition or mixing.

The method for applying the antifouling hard coating material composition of the present invention is not particularly limited, and examples thereof include brush coating, spray coating, dipping (also referred to as dipping and dip coating), roll coating, and flow coating. Various general coating methods such as a coat (flow coating method in which a coating material is flown from the upper portion of a base material to be coated), a curtain coat, a knife coat, a spin coat, a bar coat and the like can be selected.

The method for curing the coating film of the antifouling hard coating material composition of the present invention may be a known method, and is not particularly limited. Further, the temperature at the time of curing is not particularly limited, and can be in a wide range from room temperature to heating temperature depending on the desired cured film performance, the heat resistance of the filler and the base material, and the like. The thickness of the applied cured film formed from the antifouling hard coating material composition of the present invention is 0.01 to 0.5 in order to prevent cracking and peeling.
It may be about μm, but in order to more effectively exert various functions of the coating film and shorten the curing time at room temperature, and to ensure that the applied cured coating adheres and holds stably for a long period of time Is preferably 0.05 to 0.3 μm,
It is more preferably from 0.5 to 0.2 μm.

The substrate on which the antifouling hard coating material composition of the present invention is applied (which is also the substrate used for the coated article of the present invention) is not particularly limited. A transparent substrate is preferred from the viewpoint of effectively utilizing the excellent antifouling property of the coating film to be formed. Although it does not specifically limit as a transparent base material, For example, a glass base material etc. are mentioned. In particular, the use of the glass substrate, not only the excellent antifouling properties of the coating formed from the antifouling hard coating material composition of the present invention, but also the high surface hardness of the coating,
Abrasion resistance, surface scratch resistance, and the like can also be effectively utilized, which is preferable.

The glass substrate is not particularly limited, and examples thereof include sodium glass, Pyrex glass, quartz glass, and alkali-free glass. Further, the glass substrate may be a plate of these glasses, a molded body thereof, or a structure partially provided with at least one of them.

[0037]

The present invention will be described in detail below with reference to examples and comparative examples. In Examples and Comparative Examples, all “parts” represent “parts by weight” and all “%” represent “% by weight” unless otherwise specified. The molecular weight was measured by GPC (gel permeation chromatography) using a standard curve of standard polystyrene using HLC8020 manufactured by Tosoh Corporation as a measuring model, and measuring the converted value. In addition, this invention is not limited to a following example.

In the following, first, the coating material compositions of the respective examples were prepared, and thereafter, a coating cured film was formed using these coating material compositions, and the performance was evaluated. [Preparation of Coating Material Composition]: <Example 1> A methanol-dispersed silica sol (trade name “MT-ST”, manufactured by Nissan Chemical Industries, Ltd., solid content 30) was mixed with 208 parts of tetraethoxysilane in 208 parts of acidic colloidal silica.
%, An average primary particle diameter of 15 nm), diluted with 108.8 parts of methanol, further added with 43.2 parts of water, and stirred. The obtained liquid was heated in a 60 ° C. constant temperature bath for 2 hours to adjust the weight-average molecular weight (Mw) of the reaction product tetrafunctional silicone resin to 950, thereby obtaining a silicone resin solution. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 960. Then
The silicone resin solution after storage was diluted with methanol so that the total solid content was 5% to obtain an antifouling hard coating material composition containing a silica resin mixed with a silicone resin.

Preparation conditions: [Water] / [OR] molar ratio 0.6 ・ Weight average molecular weight of tetrafunctional silicone resin 950 ・ Tetrafunctional silicone resin / Total silicone resin 100% ・ Filler / Total silicone resin (condensation compound conversion) ) Weight ratio 0.6 <Example 2> In 208 parts of tetraethoxysilane, methanol-dispersed silica sol as acidic colloidal silica (trade name “MT-ST”, manufactured by Nissan Chemical Industries, Ltd., solid content 30)
%, An average primary particle diameter of 15 nm), diluted with 152.4 parts of methanol, further added with 39.6 parts of water, and stirred. The obtained liquid was heated in a 60 ° C. constant temperature bath for 2 hours to adjust the weight-average molecular weight (Mw) of the reaction product tetrafunctional silicone resin to 950, thereby obtaining a silicone resin solution. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 960. Then
The silicone resin solution after storage was diluted with methanol so that the total solid content was 5% to obtain an antifouling hard coating material composition containing a silica resin mixed with a silicone resin.

Preparation conditions: [Water] / [OR] molar ratio 0.55 • Weight average molecular weight of tetrafunctional silicone resin 950 • Tetrafunctional silicone resin / Total silicone resin 100% • Filler / Total silicone resin (condensation compound conversion) ) Weight ratio 1.0 <Example 3> In 208 parts of tetraethoxysilane, methanol-dispersed silica sol as acidic colloidal silica (trade name “MT-ST”, manufactured by Nissan Chemical Industries, Ltd., solid content 30)
%, An average primary particle diameter of 15 nm), diluted with 110 parts of methanol, further added with 36 parts of water, and stirred. The obtained liquid was heated in a 60 ° C. constant temperature bath for 2 hours to adjust the weight average molecular weight (Mw) of the tetrafunctional silicone resin as a reaction product to 700, thereby obtaining a silicone resin solution. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 720. Next, the above-mentioned silicone resin solution after storage was diluted with methanol so that the total solid content was 5%, whereby an antifouling hard coating material composition containing a silica resin mixed with a silicone resin was obtained.

Preparation conditions: [Water] / [OR] molar ratio 0.5 • Weight average molecular weight of tetrafunctional silicone resin 700 • Tetrafunctional silicone resin / Total silicone resin 100% • Filler / Total silicone resin (condensation compound equivalent) ) Weight ratio 0.6 <Example 4> A methanol-dispersed silica sol (trade name: MT-S) as acidic colloidal silica was added to 208 parts of tetramethoxysilane and 6.1 parts of methyltrimethoxysilane.
T "(manufactured by Nissan Chemical Industries, Ltd., solid content 30%, average primary particle size 15 nm) (125 parts), diluted with 123 parts of methanol, further added with 40.9 parts of water, and stirred. The obtained liquid was heated in a 60 ° C. constant temperature bath for 2 hours to adjust the weight average molecular weight (Mw) of the tetrafunctional silicone resin, which is a reaction product, to 900, thereby obtaining a silicone resin solution. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 920. Next, the above-mentioned silicone resin solution after storage was diluted with methanol so that the total solid content was 5%, whereby an antifouling hard coating material composition containing a silica resin mixed with a silicone resin was obtained.

Preparation conditions: [Water] / [OR] molar ratio 0.55 ・ Weight average molecular weight of tetrafunctional silicone resin 900 ・ Tetrafunctional silicone resin / 95% of all silicone resin ・ Filler / total silicone resin (condensation compound conversion) ) Weight ratio 0.6 <Example 5> 208 parts of tetraethoxysilane was diluted with 356 parts of methanol, and 18 parts of water and 18 parts of 0.1N hydrochloric acid were further added and stirred. By heating the obtained liquid in a thermostat at 60 ° C. for 2 hours, 4
The weight average molecular weight (Mw) of the functional silicone resin is 95
By adjusting to 0, a silicone resin solution was obtained. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 970. Next, a titanium oxide aqueous sol (trade name "STS-01", manufactured by Ishihara Sangyo Co., Ltd., solid content 30%) as an optical semiconductor filler is added to the silicone resin solution after storage.
After adding a filler / total silicone resin (condensation compound equivalent) weight ratio of 1.0 to the filler / total silicone resin (average primary particle diameter: 7 nm), the optical semiconductor is diluted with methanol so that the total solid content is 5%. An antifouling hard coating material composition containing a filler-mixed silicone resin was obtained.

Preparation conditions: [Water] / [OR] molar ratio 0.6 ・ Weight average molecular weight of tetrafunctional silicone resin 950 ・ Tetrafunctional silicone resin / Total silicone resin 100% ・ Filler / Total silicone resin (condensation compound conversion) ) Weight ratio 1.0 <Example 6> 208 parts of tetraethoxysilane was diluted with 356 parts of methanol, and 18 parts of water and 18 parts of 0.1N hydrochloric acid were further added and stirred. By heating the obtained liquid in a thermostat at 60 ° C. for 2 hours, 4
The weight average molecular weight (Mw) of the functional silicone resin is 95
By adjusting to 0, a silicone resin solution was obtained. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 970. Next, a titanium oxide aqueous sol (trade name "STS-01", manufactured by Ishihara Sangyo Co., Ltd., solid content 30%) as an optical semiconductor filler is added to the silicone resin solution after storage.
An average primary particle diameter of 7 nm is added so that the filler / total silicone resin (condensation compound conversion) weight ratio becomes 2.0, and then diluted with methanol so that the total solid content becomes 5%. An antifouling hard coating material composition containing a filler-mixed silicone resin was obtained.

Preparation conditions: [Water] / [OR] molar ratio 0.6 ・ Weight average molecular weight of tetrafunctional silicone resin 950 ・ Tetrafunctional silicone resin / Total silicone resin 100% ・ Filler / Total silicone resin (condensation compound conversion) ) Weight ratio 2.0 <Example 7> 208 parts of tetraethoxysilane was diluted with 359.6 parts of methanol, and 16.2 parts of water and 16.2 parts of 0.1N hydrochloric acid were further added and stirred. The obtained liquid was heated in a 60 ° C. constant temperature bath for 2 hours to adjust the weight average molecular weight (Mw) of the tetrafunctional silicone resin as a reaction product to 700, thereby obtaining a silicone resin solution. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 720. Then, a titanium oxide aqueous sol (trade name "STS-01", manufactured by Ishihara Sangyo Co., Ltd., solid content 30%, average primary particle diameter 7 nm) was added to the silicone resin solution after storage as an optical semiconductor filler. Silicone resin (condensed compound equivalent) was added so that the weight ratio became 1.0, and then diluted with methanol so that the total solid content became 5%. A coating material composition was obtained.

Preparation conditions: [Water] / [OR] molar ratio 0.45 ・ Weight average molecular weight of tetrafunctional silicone resin 700 ・ Tetrafunctional silicone resin / Total silicone resin 100% ・ Filler / Total silicone resin (condensation compound conversion) <Example 8> 208 parts of tetraethoxysilane was diluted with 356 parts of methanol, and 18 parts of water and 18 parts of 0.1N hydrochloric acid were further added and stirred. By heating the obtained liquid in a thermostat at 60 ° C. for 2 hours, 4
The weight average molecular weight (Mw) of the functional silicone resin is 95
By adjusting to 0, a silicone resin solution was obtained. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 970. Next, a titanium oxide aqueous sol (trade name “PC-201”, manufactured by Titanium Industry Co., Ltd., solid content 25) is added to the above-mentioned silicone resin solution after storage as an optical semiconductor filler.
%, The average primary particle diameter of 20 nm) was added so that the weight ratio of filler / total silicone resin (condensation compound equivalent) was 1.0, and then diluted with methanol so that the total solid content was 5%. An antifouling hard coating material composition containing a silicone resin mixed with an optical semiconductor filler was obtained.

Preparation conditions: [Water] / [OR] molar ratio 0.6 ・ Weight average molecular weight of tetrafunctional silicone resin 950 ・ Tetrafunctional silicone resin / Total silicone resin 100% ・ Filler / Total silicone resin (condensation compound conversion) ) Weight ratio 1.0 <Example 9> 208 parts of tetraethoxysilane was diluted with 356 parts of methanol, and 18 parts of water and 18 parts of 0.1N hydrochloric acid were further added and stirred. By heating the obtained liquid in a thermostat at 60 ° C. for 2 hours, 4
The weight average molecular weight (Mw) of the functional silicone resin is 95
By adjusting to 0, a silicone resin solution was obtained. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 970. Next, a titanium oxide aqueous sol (trade name “PC-201”, manufactured by Titanium Industry Co., Ltd., solid content 25) is added to the above-mentioned silicone resin solution after storage as an optical semiconductor filler.
%, An average primary particle diameter of 20 nm) was added so that the filler / total silicone resin (condensation compound conversion) weight ratio was 2.0, and then diluted with methanol so that the total solid content was 5%. An antifouling hard coating material composition containing a silicone resin mixed with an optical semiconductor filler was obtained.

Preparation conditions: [Water] / [OR] molar ratio 0.6 ・ Weight average molecular weight of tetrafunctional silicone resin 950 ・ Tetrafunctional silicone resin / All silicone resin 100% ・ Filler / Total silicone resin (condensation compound conversion) ) Weight ratio 2.0 <Comparative Example 1> To 208 parts of tetraethoxysilane, methanol-dispersed silica sol as acidic colloidal silica (trade name “MT-ST”, manufactured by Nissan Chemical Industries, Ltd., solid content 30)
%, Average primary particle diameter 15 nm), diluted with 44 parts of methanol, further added with 108 parts of water, and stirred. The obtained liquid was heated in a 60 ° C. constant temperature bath for 2 hours to adjust the weight average molecular weight (Mw) of the tetrafunctional silicone resin, which is a reaction product, to 1500, thereby obtaining a silicone resin solution. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 11,000, and the viscosity of the solution increased. The solution gelled upon storage at room temperature for an additional two weeks.

Preparation conditions: [Water] / [OR] molar ratio 1.5 ・ Weight average molecular weight of tetrafunctional silicone resin 1500 ・ Tetrafunctional silicone resin / Total silicone resin 100% ・ Filler / Total silicone resin (condensation compound conversion) ) Weight ratio 0.6 <Comparative Example 2> A methanol-dispersed silica sol (trade name: MT-) was added to 208 parts of tetraethoxysilane and 40.6 parts of methyltrimethoxysilane.
ST "(manufactured by Nissan Chemical Industries, Ltd., solid content 30%, average primary particle size 15 nm) and 160 parts of methanol.
And then 48.4 parts of water was added and stirred.
The obtained liquid was heated in a 60 ° C. constant temperature bath for 2 hours to adjust the weight average molecular weight (Mw) of the tetrafunctional silicone resin, which is a reaction product, to 900, thereby obtaining a silicone resin solution. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 920. Subsequently, the silicone resin solution after storage was diluted with methanol so that the total solid content was 5%, to obtain a comparative antifouling hard coating material composition containing a silica resin mixed with a silicone resin.

Preparation conditions: [Water] / [OR] molar ratio 0.55 • Weight-average molecular weight of tetrafunctional silicone resin 900 • Tetrafunctional silicone resin / Total silicone resin 75% • Filler / Total silicone resin (condensation compound conversion) ) Weight ratio 0.6 <Comparative Example 3> 208 parts of tetraethoxysilane was diluted with 356 parts of methanol, and 18 parts of water and 18 parts of 0.1N hydrochloric acid were further added and stirred. By heating the obtained liquid in a thermostat at 60 ° C. for 2 hours, 4
The weight average molecular weight (Mw) of the functional silicone resin is 95
By adjusting to 0, a silicone resin solution was obtained. The solution was then stored at room temperature for 2 weeks. The weight average molecular weight of the tetrafunctional silicone resin after storage was 970. Next, the silicone resin solution after storage was diluted with methanol so that the total solid content was 5%, to obtain a comparative coating material composition containing no filler at all.

Preparation conditions: [Water] / [OR] molar ratio 0.6 ・ Weight average molecular weight of tetrafunctional silicone resin 950 ・ Tetrafunctional silicone resin / Total silicone resin 100% ・ Filler / Total silicone resin (condensation compound conversion) ) Weight ratio 0 [Formation of cured coating film]: After coating each coating material composition obtained above on the surface of a glass substrate with a spin coater coating machine, it was baked at 250 ° C for 30 minutes to form a cured coating film. By forming, each coated product was obtained. The cured film had a thickness of 0.2 to 0.3 μm. [Evaluation of coating film performance]: (Surface hardness): A pencil scratch test was performed according to JIS-K5400, and the presence or absence of scratches was observed with an optical microscope to check the pencil hardness at which scratches occurred.

(Abrasion resistance): Using a traverse abrasion tester, a canvas cloth was brought into contact with the painted surface of a painted product to
00 reciprocating slides (load 50g / cm ² , stroke 60
mm) to carry out a wear test. And
After the abrasion test, the degree of occurrence of scratches on the coating film surface was observed with an optical microscope. The criteria are as follows.

：: no scratch Δ: Several scratches were generated per 1 cm ² . ×: Many scratches occurred and peeled. In addition, about the antifouling hard coating material composition containing the optical semiconductor (Examples 5 to 9), the organic matter decomposability of the coating film surface before and after the abrasion test was also examined. The organic substance decomposability on the coating film surface was evaluated by the following method.

(Organic substance decomposability): The coated article was immersed in an acetone solution of oleic acid 1%, pulled up at a speed of 1.5 mm / sec, and dried at 60 ° C. for 5 minutes to give an organic substance (oleic acid ) Was deposited. The contact angle with respect to water was measured on the surface of the coating film on which the organic substance was adhered as described above. The measurement of the contact angle was performed before and after irradiating the surface of the coating film on which the organic substance was adhered with ultraviolet light of black light (5 mW / cm ² ) for 12 hours. The larger the contact angle is decreased by the irradiation of ultraviolet rays, the higher the performance of decomposing organic substances on the coating film surface is.

Table 1 shows the evaluation results.

[0055]

[Table 1]

[0056]

According to the antifouling hard coating material composition according to any one of claims 1 to 7, 90% by weight or more of the silicone resin contained as one of the essential components is 4%.
Since it is made of a functional silicone resin, it can have a surface hydrophilicity (water wettability), thereby forming a coating film exhibiting excellent performance such as anti-fouling property against rainwater washing. Further, the use of a silicone resin comprising 90% by weight or more of a tetrafunctional silicone resin makes the coating film excellent in surface hardness, abrasion resistance, and difficulty in scratching the surface.

In the antifouling hard coating material composition, since the tetrafunctional alkoxysilane represented by the general formula (1) is used as a raw material of the tetrafunctional silicone resin, the raw material is easily available and the paint is easily prepared. When a paint containing the obtained 4-functional silicone resin is applied and cured, there is an advantage that a condensation reaction easily occurs, and as a result, a hard coating film is easily formed.

In the antifouling hard coating material composition, since an acidic catalyst is used when synthesizing the tetrafunctional silicone resin contained therein, the time required for the production process of the composition can be shortened. The lower limit of the weight average molecular weight of the tetrafunctional silicone resin is 5 in terms of polystyrene.
Since it is 00, the surface hardness of the formed coating film can be sufficiently maintained. In addition, since the upper limit of the weight average molecular weight is 1000 in terms of polystyrene, the silicone resin is stable and hard to gel, so that the storage stability of the paint is improved.

Since the antifouling hard coating material composition is an inorganic type, the coating film performance is hardly impaired by the addition of various additives such as an optical semiconductor, and a coating film which is hardly deteriorated by ultraviolet rays is formed. can do. The antifouling hard coating material composition is not only heat-curable, but also can be cured at room temperature if a curing catalyst is included,
It can be used in a wide range of drying and curing conditions or temperature range. Therefore, a substrate having a shape that is difficult to apply heat evenly, a substrate having a large dimension, a substrate having an organic material such as an adhesive and having poor heat resistance, or a substrate having poor heat resistance itself (for example, organic Base material, etc.), and can be painted even when it is difficult to apply heat, such as when performing painting work outdoors or the like.
Its industrial value is high.

Since the antifouling hard coating material composition contains at least one kind of filler as a further essential component, the hardness of the cured coating film is further increased, and various functions of the coating film formed by the filler are provided. Can be provided. In the antifouling hard coating material composition according to claim 2, the amount of water used for partially hydrolyzing the tetrafunctional alkoxysilane is 0 <H ₂ O / OR.
Since the (molar ratio) <1 is satisfied, there is an advantage that a tetrafunctional silicone resin having the above-mentioned predetermined molecular weight is easily obtained.

Since the antifouling hard coating material composition according to claim 3 contains an optical semiconductor as the filler, it also has various properties derived from the photocatalytic action of the optical semiconductor, such as antibacterial properties and deodorant properties. It is possible to form an excellent coating film that sufficiently exhibits. In addition, the photocatalytic action of the optical semiconductor is to further improve the hydrophilicity (wetting property) of the coating film to achieve a higher level of antifouling property by rainwater washing, to maintain the property for a long time, and to prevent fogging. There is also an effect of imparting properties. Further, there is an antifouling effect by the antistatic function.

The optical semiconductor, once excited, can exhibit a photocatalytic action without being exposed to ultraviolet rays, so that a coating film containing the same can be used even in a portion where ultraviolet rays are hardly applied. In the period until the optical semiconductor exerts its effect, the effect of imparting hydrophilicity by the tetrafunctional silicone resin complements the function of the optical semiconductor (particularly, the hydrophilicity of the coating film surface). The coating film obtained from the material composition becomes an ideal hydrophilic coating film.

By changing the ratio of the resin and the optical semiconductor contained in the antifouling hard coating material composition containing the optical semiconductor, the above-mentioned various functions by photocatalysis and the properties of the coating film can be controlled according to the application. can do.
Since the antifouling hard coating material composition according to claim 4 contains a sol filler as the filler, the filler can be easily and uniformly dispersed in the composition. Therefore, various functions of the filler can be sufficiently exhibited.

In the antifouling hard coating material composition according to the fifth aspect, as the sol filler, an aqueous sol which also functions as an acidic catalyst at the time of hydrolysis of tetrafunctional alkoxysilane is used. The manufacturing process of the composition can be simplified, and the composition is excellent in convenience. The antifouling hard coating material composition according to claim 6 uses a filler having an average particle diameter of 5 to 100 nm as the filler, so that the surface smoothness when the composition is applied to a glass substrate or the like is improved. Gloss and transparency of the coating film can be secured.

In the antifouling hard coating material composition according to the present invention, the weight ratio of the filler (filler / total silicone resin; based on solid content) to the total amount of all the condensed compounds of all the silicone resins contained therein is 0. Since it is 1 or more, the effect of adding the filler can be sufficiently obtained. In addition, since the above ratio is 4 or less, generation of cracks due to excessive addition of filler can be suppressed, and deterioration of coating film performance can be prevented.

The coated article according to any one of claims 8 to 10 is obtained by coating the surface of a substrate with a cured coating film of the antifouling hard coating material composition according to any one of claims 1 to 7. Since it has a coating layer, it has the above-mentioned various excellent properties and advantages derived from the antifouling hard coating material composition and the coating film formed therefrom. Claim 9
The coated products described in the above, because a transparent substrate is used as the substrate,
The excellent antifouling property and the like of the coating film formed from the antifouling hard coating material composition can be effectively utilized.

The coated article according to claim 10 uses glass as a substrate, so that not only the excellent antifouling property of the coating film formed from the antifouling hard coating material composition, but also
The high surface hardness, abrasion resistance, and difficulty of scratching the surface of the coating film can be effectively utilized.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hiroshi Tamaru 1048 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Works, Ltd. Inventor Koichi Takahama 1048 Kazuma Kadoma, Kadoma City, Osaka Prefecture F-term (reference) 4F006 AB39 AB54 AB67 AB74 BA02 BA11 DA04 EA01 EA05 4G059 AA01 AC22 FA22 FA28 FB03

Claims (10)

[Claims] An antifouling hard coating material composition comprising a silicone resin and at least one filler as essential components, wherein at least 90% by weight of the silicone resin comprises the following component (A). Component (A): represented by the general formula Si (OR) ₄ (1) (where R is the same or different and has 1 to 8 carbon atoms)
A tetrafunctional alkoxysilane having a weight average molecular weight of 500 to 1,000 in terms of polystyrene, which is obtained by partially hydrolyzing a tetrafunctional alkoxysilane in the presence of an acidic catalyst. 2. The antifouling hard coating according to claim 1, wherein the amount of water used for partially hydrolyzing the tetrafunctional alkoxysilane satisfies 0 <H ₂ O / OR (molar ratio) <1. Material composition. 3. The filler according to claim 1, wherein the filler includes an optical semiconductor.
Or the antifouling hard coating material composition according to 2. 4. The antifouling hard coating material composition according to claim 1, wherein the filler contains a sol-like filler. 5. The antifouling hard coating material composition according to claim 4, wherein the sol-like filler is an aqueous sol and also functions as the acidic catalyst. 6. The filler has an average primary particle size of 5 to 100.
The antifouling hard coating material composition according to any one of claims 1 to 5, which has a nanometer. 7. The weight ratio of the filler to the total amount of all the condensed compounds of the entire silicone resin is based on solid content,
The antifouling hard coating material composition according to claim 1, wherein 0.1 ≦ filler / total silicone resin ≦ 4. 8. A coated article comprising, on the surface of a substrate, a coating layer comprising a cured coating of the antifouling hard coating material composition according to any one of claims 1 to 7. 9. The coated article according to claim 8, wherein said substrate is transparent. 10. The coated article according to claim 9, wherein said base material is glass.