JP2000239608A - Resin composition for coating material and article coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which forms a coating film excellent in adhesion and cracking resistance by including an organosilane oligomer with a polyorganosiloxane, silica, a curing catalyst, and a hydrolyzable organosilane. SOLUTION: This composition contains (A) an organosilane oligomer obtained by partially hydrolyzing a compound represented by formula I, (B) a polyorganosiloxane having silanol groups in the molecule and represented by formula II, (C) silica, (D) a curing catalyst, (E) a hydrolyzable organosilane represented by formula III, and (F) an acrylic resin. It contains 0.5-99.5 pts.wt. component A, 99.5-0.5 pts.wt. component B, 5-95 wt.%, based on the total weight of component A and C, component C, and components D, E and F in amounts of 0.0001-10 pts.wt., 0.1-20 pts.wt., and 0.1-100 pts.wt., per 100 pts.wt. total of components A, B and C, respectively. In the formulae, R1 and R2 are each a 1-8C monovalent hydrocarbon group; R3 is aminopropyl or the like; 0.2<=a<=2; 0.0001<=b<=3; and m is 0-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition for coating and a coated article using the same.

[0002]

2. Description of the Related Art The environment of outdoor painted products is more severe than that of indoors, and the environment such as acid rain and an increase in ultraviolet rays due to ozone layer destruction can be said to be further deteriorated. There is a long-awaited need for a coating resin having excellent coating performance such as weather resistance, heat resistance, and chemical resistance.

[0003] Typical coating resins include fluororesins, acrylic silicone resins, inorganic resins and the like. Fluororesins and acrylic silicone resins have also been developed as low-contamination type coating resins, but are not satisfactory as coating resins having the above-mentioned coating film properties. In consideration of environmental aspects, etc., inorganic resins are excellent in the performance of the above-mentioned coating film, but have problems such as high hardness, lack of toughness, high temperature treatment, poor adhesion to organic base materials, and the like. . As an inorganic resin which has solved these problems, there is, for example, a resin composition for coating described in JP-A-4-175388. This resin composition has high hardness and toughness, does not require high-temperature treatment, and has excellent adhesion to an organic base material.

[0004] However, if the substrate is a weather resistance test 100
In the case of an organic layer (for example, an organic layer of a vinyl chloride resin, a phthalic acid resin, or the like) that deteriorates in 0 hours or less, the toughness (or crack resistance) and the adhesion to such an organic layer are reduced. There was room for further improvement. On the other hand, a paint using an optical semiconductor has been proposed as a measure against contamination. When the underlayer to which this coating is applied is an organic layer, it is necessary to provide an inorganic protective layer between the coating containing the optical semiconductor and the organic layer in order to prevent the organic layer from being attacked by the optical semiconductor. is there. This inorganic protective layer also needs to be excellent in crack resistance and adhesion as described above.

[0005]

An object of the present invention is to provide a coating resin composition (inorganic paint) having excellent coating film performance as described above, and which, when applied to the surface of an organic layer, is coated with the organic layer. To provide a coating resin composition capable of forming a coating film having excellent adhesion and crack resistance.

[0006]

The resin composition for coating of the present invention is a resin composition for coating containing the following components (A), (B), (C) and (D):
It is further characterized by containing the following component (E). Component (A): represented by the general formula R ¹ _m SiX _4-m (I) (where R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M is an integer of 0 to 3, and X represents a hydrolyzable group.) The hydrolyzable organosilane is dissolved in an organic solvent, water or a mixed solvent thereof per 1 molar equivalent of the hydrolyzable group (X). An organosilane oligomer partially hydrolyzed under conditions using 0.001 to 0.5 mol of water (hereinafter sometimes referred to as “organosilane oligomer (A)”). Component (B): represented by an average composition formula R ² _a Si (OH) _b O _{(4-ab) / 2} (II) (where R ² is the same or different and is substituted or unsubstituted and has 1 to 1 carbon atoms) 8 represents a monovalent hydrocarbon group, wherein a and b are respectively 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦
3, a number that satisfies the relationship of a + b <4. ), A polyorganosiloxane containing a silanol group in the molecule (hereinafter sometimes referred to as “(silanol group-containing) polyorganosiloxane (B)”). Component (C): silica (hereinafter sometimes referred to as “silica (C)”). Component (D): a curing catalyst (hereinafter, this may be referred to as “curing catalyst (D)”). Component (E): represented by the general formula R ³ _m SiX _4-m (III) (where at least one of R ³ is an aminopropyl group, a glycidoxypropyl group, an allyl group, a methacryloxypropyl group) Any one selected from the group consisting of (when m is 2 or 3, R ³ is the same,
Alternatively, at least one of them is heterogeneous. When at least one of R ³ is different, R ³ is all selected from the group consisting of an aminopropyl group, a glycidoxypropyl group, an allyl group, a methacryloxypropyl group, or one of R ³ is Two of them are each independently any one of a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group. ), M represents an integer of 1 to 3, and X represents a hydrolyzable group. ) Hydrolyzable organosilane (hereinafter sometimes referred to as “hydrolyzable organosilane (E)”).

As the component (A), for example, in colloidal silica obtained by dispersing the component (C) in an organic solvent, water or a mixed solvent thereof, the hydrolyzable organosilane is converted to the hydrolyzable organosilane. It is partially hydrolyzed under the condition of using 0.001 to 0.5 mol of water per 1 mol equivalent of the group (X), and the component (C) is converted from the component (A) and the component (C). 5 to 95 as solids based on total amount
Silica-dispersed organosilane oligomers containing about 10% by weight can be used.

The component (A) is, for example, the component (A)
With respect to 100 parts by weight of the total solid content of the component and the component (C),
The hydrolyzable organosilane in which R ¹ is a phenyl group contains at least 10 parts by weight of a solid hydrolyzate. The component (E) is, for example, 0.1 parts by weight based on 100 parts by weight of the total solid content of the components (A), (B) and (C).
-20 parts by weight.

[0009] The coating resin composition of the present invention may further contain the following component (F). Component (F): a monomer represented by the general formula CH ₂ = CR ⁴ (COOR ⁵ ) (IV) (where R ⁴ represents a hydrogen atom and / or a methyl group), wherein R ⁵ is substituted Alternatively, the first (meth) acrylic acid ester which is an unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, and R ^{5 comprises an} epoxy group, a glycidyl group and a hydrocarbon group containing at least one of these groups a second (meth) acrylic acid ester is at least one group selected from the group, R ⁵
And a third (meth) acrylate ester, which is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group.

[0010] In the present specification, the term "(meth) acrylate" means one or both of an acrylate and a methacrylate. When the resin composition for coating of the present invention also contains the component (F), the amount of the component is 0.1 to 100 parts by weight of the total solid content of the components (A), (B) and (C). The proportion is preferably 1 to 100 parts by weight.

[0011] The coated article of the present invention is provided with a coated and cured film of the resin composition for coating of the present invention on the surface of a substrate. The substrate may have an organic resin layer on at least the surface on which the resin composition for coating is applied. The coated article of the present invention can be obtained by applying the resin composition for coating to the base material and then applying a resin layer containing an optical semiconductor.

The resin layer containing the optical semiconductor is, for example,
It is formed from an inorganic paint containing a photo-semiconductor containing a silicone resin as a film-forming component. The silicone resin is composed of 100 parts by weight of a silicon compound represented by the general formula R ⁶ Si (OR ⁷ ) ₃ and a silicon compound represented by the general formula Si (OR ⁷ ) ₄ and / or colloidal silica 5 to 100 parts by weight.
And 30000 parts by weight, the general formula R ⁶ ₂ Si (OR ⁷⁾ hydrolyzable mixture containing silicon compounds 0 to 60 parts by weight, represented by ₂ (wherein, R ^6, R ⁷ are each independently 1
Represents a monovalent hydrocarbon group. ) Is preferred.

The optical semiconductor is titanium oxide, zinc oxide,
Tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide And at least one metal oxide selected from the group consisting of nickel oxide and rhenium oxide.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The organosilane oligomer (A) used as the component (A) of the coating resin composition of the present invention is a hydrolyzable group as a functional group which is subjected to a curing reaction when forming a cured coating film. It is a main component of the base polymer having (X). This is because, for example, one or two types of the hydrolyzable organosilane represented by the general formula (I) are added to colloidal silica dispersed in an organic solvent or water (including a mixed solvent of an organic solvent and water). The above conditions were added, and water (water previously contained in the solvent and / or water separately added) was used under the conditions of using 0.001 to 0.5 mol of water per 1 mol equivalent of the hydrolyzable group (X). To partially hydrolyze the hydrolyzable organosilane.

The group R ¹ in the hydrolyzable organosilane represented by the general formula (I) is particularly the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Although not limited, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; Group, 2-phenylpropyl group,
Aralkyl groups such as 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group Halogen-substituted hydrocarbon groups such as; γ-methacryloxypropyl group,
Examples thereof include a substituted hydrocarbon group such as a γ-glycidoxypropyl group, a 3,4-epoxycyclohexylethyl group, and a γ-mercaptopropyl group. Among them, an alkyl group having 1 to 4 carbon atoms and a phenyl group (substituted or unsubstituted methyl group, ethyl group, propyl group, butyl group and phenyl group) are preferred from the viewpoint of ease of synthesis or availability. , A methyl group and / or a phenyl group are more preferred. In particular, the component (A) is obtained by adding a partial hydrolyzate of a hydrolyzable organosilane in which R ¹ is a phenyl group to 100 parts by weight of the total solid content of the components (A) and (C). Is preferably contained in an amount of 10 parts by weight or more, whereby the crack resistance of the cured coating film is further improved.

In the general formula (I), the hydrolyzable group X is not particularly limited, but includes, for example, an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminooxy group, an amide group and the like. Can be Among these, an alkoxy group is preferable because it is easily available and the silica dispersed oligomer solution of organosilane (A) is easily prepared.

Specific examples of the hydrolyzable organosilane include mono-, di-, tri- and tetra-functional alkoxysilanes wherein m in the general formula (I) is an integer of 0 to 3. , Acetoxysilanes, oxime silanes,
Examples include enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are preferable because they are easily available and the silica-dispersed oligomer solution of organosilane (A) is easily prepared.

Of the alkoxysilanes, m = 0
Examples of the tetraalkoxysilane include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane having m = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and phenyltrimethoxysilane. ,
Examples thereof include phenyltriethoxysilane and 3,3,3-trifluoropropyltrimethoxysilane. Further, as the diorganodialkoxysilane of m = 2,
Examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Examples of the triorganoalkoxysilane having m = 3 include trimethylmethoxysilane, trimethylethoxysilane, and trimethylisopropoxysilane. And dimethylisobutylmethoxysilane. Further, an organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

Of these hydrolyzable organosilanes represented by formula (I), at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%,
It is a trifunctional compound represented by m = 1. This is 50
If it is less than mol%, sufficient coating film hardness cannot be obtained,
The dry curability of the coating film tends to be poor. As described above, the amount of water used for preparing the organosilane oligomer (A) is 0.001 to 0.5 mol per 1 mol equivalent of the hydrolyzable group (X) of the hydrolyzable organosilane. , Preferably in the range of 0.01 to 0.4 mol. If the amount of water is less than 0.001 mol, a sufficient partial hydrolyzate cannot be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate deteriorates. Here, the amount of water used in the partial hydrolysis reaction of the hydrolyzable organosilane is the amount of water separately added when only an organic solvent is used as a reaction solvent, and only water or an organic solvent is used as a reaction solvent. When a mixed solvent of a solvent and water is used, it is the amount of water previously contained in the reaction solvent at least among water previously contained in the reaction solvent and water separately added. If the amount of water is only the water previously contained in the reaction solvent and the amount used is sufficient, it is not necessary to separately add water, but the amount of water was previously contained in the reaction solvent. If water alone is not sufficient for the above usage, it is necessary to separately add water until the usage reaches the above usage. In this case, the amount of water used is the total amount of water previously contained in the reaction solvent and water added separately. In addition, even when only the water previously contained in the reaction solvent is sufficient for the above usage amount,
Water may be added separately, and in that case, the amount of the water used is the total amount of water previously contained in the reaction solvent and water added separately. However, water is separately added so that the total amount does not exceed the upper limit (0.5 mol per 1 mol equivalent of the hydrolyzable group (X)).

The method for partially hydrolyzing the hydrolyzable organosilane is not particularly limited. For example, the hydrolyzable organosilane may be mixed with a reaction solvent (whether the reaction solvent contains no water or If the required amount is not included, add water here. At that time, the partial hydrolysis reaction proceeds at room temperature, but if necessary, heating (for example, 60 to 60) may be performed to promote the partial hydrolysis reaction.
100 ° C.) or a catalyst may be used. The catalyst is not particularly limited, but includes, for example, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid,
One or more organic acids and inorganic acids such as benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, and oxalic acid can be used. .

The organosilane oligomer (A) is adjusted to have a pH in order to stably obtain its performance over a long period of time.
Preferably 2.0 to 7.0, more preferably 2.5 to
6.5, more preferably 3.0 to 6.0. When the pH is out of this range, the performance continuity of the component (A) is remarkably reduced particularly under the condition that the amount of water used is 0.3 mol or more per 1 mol equivalent of the hydrolyzable group (X). When the pH of the component (A) is out of the above range, the pH may be adjusted by adding a basic reagent such as ammonia or ethylenediamine if the pH is more acidic than the above range. The pH may be adjusted using an acidic reagent such as hydrochloric acid, nitric acid, and acetic acid. However, the adjustment method is not particularly limited. The silanol group-containing polyorganosiloxane (B) used as the component (B) of the coating resin composition of the present invention is a base polymer having a hydrolyzable group as a functional group subjected to a curing reaction. It is a cross-linking agent for forming a three-dimensional cross-link in the cured film by a condensation reaction with the component, and is a component having an effect of absorbing the strain due to the curing shrinkage of the component (A) and preventing the occurrence of cracks.

In the above average composition formula (II) representing the silanol group-containing polyorganosiloxane (B), R ² is
The same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group. An alkyl group such as a cycloalkyl group or an octyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an aralkyl group such as a 2-phenylethyl group, a 2-phenylpropyl group, or a 3-phenylpropyl group;
Aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; halogen-substituted hydrocarbon groups such as chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group; Examples thereof include substituted hydrocarbon groups such as methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, and γ-mercaptopropyl group, and preferably have 1 to 4 carbon atoms. Alkyl group, phenyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-aminopropyl group, substituted hydrocarbon group such as 3,3,3-trifluoropropyl group, more preferably Is a methyl group and a phenyl group. Further, in the above formula (II), a and b are numbers satisfying the above-mentioned relationship, respectively, and when a is less than 0.2 or b exceeds 3, cracks occur in the cured coating of the resin composition for coating. There are inconveniences. When a is more than 2 and 4 or less, or when b is less than 0.0001, curing does not proceed well.

The silanol group-containing polyorganosiloxane (B) is not particularly limited.
Methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane,
Alternatively, it can be obtained by hydrolyzing one or a mixture of two or more of the corresponding alkoxysilanes with a large amount of water by a known method. When a silanol group-containing polyorganosiloxane (B) is hydrolyzed by a known method using alkoxysilane, a small amount of an unhydrolyzed alkoxy group may remain. That is, a polyorganosiloxane in which a silanol group and a trace amount of an alkoxy group coexist may be obtained, but in the present invention, such a polyorganosiloxane may be used.

The component (C) of the coating resin composition of the present invention, ie, silica (C), has the effect of increasing the hardness of the cured coating film of the coating resin composition and improving the smoothness and crack resistance. . The silica (C) is not particularly limited, and a known silica can be used. In addition,
The silica (C) is not particularly limited, but is introduced into the coating resin composition by dispersing it in the form of colloidal silica in a reaction solvent used in the preparation of the component (A). This is preferable in terms of film forming properties and simplification of the process. However, it is not limited to this. For example, after the silica (C) is mixed with the component (A) obtained and prepared without the silica (C), the resulting mixture may be introduced into the coating resin composition, or the silica (C) C) may be introduced into the coating resin composition separately from the component (A).

The form of silica (C) when introduced into the coating resin composition is not particularly limited, and may be, for example, a powder form or a colloidal silica form. 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 contains 20 to 50% by weight of silica as a solid content, and the amount of silica can be determined from this value. When water-dispersible colloidal silica is used, water present as a component other than the solid content can be used for hydrolysis of the hydrolyzable organosilane which is a raw material of the component (A) (water at the time of hydrolysis). It is used as a curing agent for the coating resin composition. Water-dispersible colloidal silica is
It is usually made from water glass, but can be easily obtained 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. One or more selected from the group consisting of these can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used.

The silica (C) has the above-mentioned effects, but if the amount is too large, the cured film of the resin composition for coating may be too hard, which may cause cracks in the film. is there. Therefore, the silica (C) preferably has a solid content of 5 to 95% by weight, more preferably 10 to 90% by weight, and still more preferably 20 to 85% by weight based on the total amount of the component (A). It is contained in. If the content is less than 5% by weight, a desired coating hardness tends to be not obtained. On the other hand, 95% by weight
When it exceeds, it is easy to cause cracks,
Alternatively, it becomes difficult to uniformly disperse the silica (C), and when the silica (C) is mixed with the component (A), the component (A) may cause inconvenience such as gelation.

The component (D), that is, the curing catalyst (D), contained in the coating resin composition promotes the condensation reaction between the components (A) and (B), and forms a coating film of the coating resin composition. Is a component that cures. Examples of the curing catalyst (D) 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-aminoethyl-γ-aminopropyltrimethoxysilane; N-β-amino Amine-based silane coupling agents such as ethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid, and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; lithium acetate, lithium formate; Alkali metal salts such as sodium phosphate, potassium phosphate and potassium hydroxide; Titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate and titanium tetraacetylacetonate; halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane and trimethylmonochlorosilane And the like.
However, other than these, there is no particular limitation as long as it is effective for promoting the condensation reaction between the component (A) and the component (B).

The component (E) contained in the coating resin composition, that is, the hydrolyzable organosilane (E)
Is for improving the adhesion to the organic base material and the resin, and preferably includes (A), (B),
It exists stably in the components (C) and (D). When m = 1, the group R ³ in the general formula (III) is any one selected from the group consisting of an aminopropyl group, a glycidoxypropyl group, an allyl group and a methacryloxypropyl group; m = 2 Wherein two are independently (identical or different) selected from the group consisting of aminopropyl, glycidoxypropyl, allyl and methacryloxypropyl, or one is aminopropyl A group selected from the group consisting of a glycidoxypropyl group, an allyl group and a methacryloxypropyl group, and the other is a methyl group, an ethyl group, a propyl group, a butyl group or a phenyl group;
In the case of 3, three are independent of each other (same or different),
One selected from the group consisting of an aminopropyl group, a glycidoxypropyl group, an allyl group and a methacryloxypropyl group, or one consisting of an aminopropyl group, a glycidoxypropyl group, an allyl group and a methacryloxypropyl group One selected from the group, two are independently (identical or different) methyl, ethyl, propyl, butyl, and phenyl, or two are independently (identical) Or different) aminopropyl group, glycidoxypropyl group, allyl group and methacryloxypropyl group, one of which is a methyl group, an ethyl group,
It is any of a propyl group, a butyl group and a phenyl group.

The hydrolyzable group X in the general formula (III) is not particularly limited, but includes, for example, an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminooxy group, an amide group and the like. Can be Among these, availability and (A), (B),
An alkoxy group is preferred because of good dispersibility in the components (C) and (D).

Specific examples of the hydrolyzable organosilane (E) include mono-, di- and tri-functional alkoxysilanes wherein m in the general formula (III) is an integer of 1 to 3. , Acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes,
Amidosilanes and the like. Among these, alkoxysilanes are preferable because of easy availability and good dispersibility.

Among the alkoxysilanes, in particular, m = 1
Examples of the organotrialkoxysilanes include allyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltris (methoxyethoxy) silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-glycidyl. Xylpropyltrimethoxysilane and the like can be exemplified. Examples of the diorganodialkoxysilane having m = 2 include 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane,
Aminopropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane and the like can be exemplified, and m = 3
Examples of triorganoalkoxysilanes include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylmethoxysilane, methacryloxypropyldimethylethoxysilane And methacryloxypropyldimethylmethoxysilane.

The mixing ratio of the components (A) and (B) in the resin composition for coating is not particularly limited. )) Component (A) 0.5 to 99.5 parts by weight, Component (B) 9
9.5 to 0.5 part by weight is preferable, and component (A) 2.5 to 0.5 parts by weight.
97.5 parts by weight, 97.5 to 2.5 parts by weight of component (B), more preferably 5 to 95 parts by weight of component (A), and even more preferably 95 to 5 parts by weight of component (B). 10-9
0 parts by weight and 90 to 10 parts by weight of the component (B) are most preferred. When the amount of the component (A) is less than 0.5 part by weight (the amount of the component (B) exceeds 99.5 parts by weight), the curability at room temperature tends to be poor, and sufficient film hardness tends not to be obtained. on the other hand,
When the component (A) exceeds 99.5 parts by weight (the component (B) is less than 0.5 part by weight), the curability is unstable,
In addition, a good coating film may not be obtained.

The mixing ratio of the component (D) in the resin composition for coating is not particularly limited. For example, based on the solid content, the total amount of the component (A) and the total condensation of the component (B) are calculated. The amount is preferably in the range of 0.0001 to 10 parts by weight, more preferably in the range of 0.0005 to 8 parts by weight, and still more preferably, based on 100 parts by weight of the total of the compound conversion amount and the solid content of the component (C). It is in the range of 0.0007 to 5 parts by weight. If the amount of (D) is less than 0.0001 part by weight, the room-temperature curability tends to decrease, and sufficient film hardness tends not to be obtained. If the amount exceeds 10 parts by weight, the heat resistance and weather resistance of the cured film may be reduced, and the hardness of the cured film may be too high to cause cracks.

The mixing ratio of the component (E) in the resin composition for coating is not particularly limited. For example, based on the solid content, the amount of the component (A) in terms of the total condensed compound and the component (B) It is preferably in the range of 0.1 to 20 parts by weight, more preferably in the range of 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the compound conversion amount and the solid content of the component (C). If the amount of (E) is less than 0.1 part by weight, the adhesion to the organic base material and the resin may not be easily improved. If the amount exceeds 20 parts by weight, the surface of the cured film may be easily cracked.

The resin composition for coating is prepared by leaving the hydrolyzable group of the organosilane oligomer (A) and the silanol group of the polyorganosiloxane (B) at room temperature or in the presence of a curing catalyst (D). Heating at a low temperature causes a condensation reaction to form a cured film. Therefore, such a coating resin composition is hardly affected by humidity even when it is cured at room temperature. In addition, a heat treatment can promote a condensation reaction to form a cured film.

The acrylic resin (F) used as an optional component (F) in the coating resin composition of the present invention has the effect of improving the toughness of the cured coating film of the coating resin composition. Thereby, the occurrence of cracks is prevented and the film thickness can be increased. In addition, the acrylic resin (F) is incorporated into a condensation cross-linked product of the component (A) and the component (B), which becomes a three-dimensional skeleton of the cured coating film of the resin composition for coating, and converts the condensation cross-linked product to an acrylic modification. I do. When the condensation crosslinked product is modified with acrylic, the adhesion of the cured coating film of the coating resin composition to the substrate is improved.

The first (meth) acrylic acid ester, which is one of the constituent monomers of the acrylic resin (F), is represented by the formula (IV) wherein R ⁵ has 1 to 9 carbon atoms, substituted or unsubstituted. A monovalent hydrocarbon group such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group,
alkyl groups such as i-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; 2-phenylethyl group; Aralkyl groups such as phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; halogenated hydrocarbons such as chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group A hydroxy hydrocarbon group such as a 2-hydroxyethyl group; and the like.

The second (meth) acrylic acid ester which is another constituent monomer of the acrylic resin (F) is such that R ⁵ in the above formula (IV) represents an epoxy group, a glycidyl group and at least one of these. It is at least one selected from the group consisting of at least one group selected from the group consisting of hydrocarbon groups containing one of them (for example, γ-glycidoxypropyl group).

The third (meth) acrylic acid ester, which is another constituent monomer of the acrylic resin (F), is represented by the formula (IV) wherein R ⁵ is an alkoxysilyl group and / or a halogenated silyl group. Hydrocarbon groups including, for example, trimethoxysilylpropyl group, dimethoxymethylsilylpropyl group, monomethoxydimethylsilylpropyl group, triethoxysilylpropyl group, diethoxymethylsilylpropyl group, ethoxydimethylsilylpropyl group, trichlorosilylpropyl group , A dichloromethylsilylpropyl group, a chlorodimethylsilylpropyl group, a chlorodimethoxysilylpropyl group, a dichloromethoxysilylpropyl group, or the like.

The acrylic resin (F) comprises the first, second,
The third (meth) acrylic acid ester is a (meth) acrylic acid ester copolymer containing at least one kind and a total of at least three kinds in the first, second, and third (meth) acrylic acids. Another one selected from esters
Or one or more selected from (meth) acrylic esters other than the above, or two or more.
Copolymers containing more than one species may be used.

The first (meth) acrylic acid ester is an essential component for improving the toughness of the cured coating film of the resin composition for coating. Also has the effect of improving the compatibility of For this purpose, the substituted or unsubstituted hydrocarbon group of R ⁵ preferably has a certain volume or more, and preferably has 2 or more carbon atoms.

The second (meth) acrylic acid ester is an essential component for improving the adhesion between the cured coating film of the resin composition for coating and the substrate. The third (meth) acrylic acid ester forms a chemical bond between the acrylic resin (F) and the components (A) and (B) during curing of the coating film of the resin composition for coating, thereby forming an acrylic resin. The resin (F) is fixed in the applied cured film. Further, the third (meth) acrylic acid ester also has an effect of improving the compatibility between the acrylic resin (F) and the components (A) and (B).

The molecular weight of the acrylic resin (F) greatly affects the compatibility of the acrylic resin (F) with the components (A) and (B). Therefore, the acrylic resin (F) is preferably 1000 to 50,000, more preferably 1,000.
It has a weight average molecular weight in terms of polystyrene in the range of ２０20,000. If the weight average molecular weight in terms of polystyrene of the acrylic resin (F) exceeds 50,000, phase separation may occur and the coating film may be whitened. If the molecular weight is less than 1,000, the toughness of the coating film tends to decrease, and cracks tend to occur.

The second (meth) acrylate is desirably at least 2% by mole of the monomer in the copolymer. If it is less than 2%, the adhesion of the coating film tends to be insufficient. The third (meth) acrylic acid ester is desirably in the range of 2 to 50% by mole ratio of monomers in the copolymer. If it is less than 2%, the compatibility between the acrylic resin (F) and the components (A) and (B) is poor, and the coating film may be whitened. On the other hand, if it exceeds 50%, the bond density of the acrylic resin (F) with the components (A) and (B) becomes too high, and the improvement in toughness, which is the original purpose of the acrylic resin, tends not to be observed.

As a method for synthesizing the acrylic resin (F), for example, a known radical polymerization method by solution polymerization, emulsion polymerization, or suspension polymerization in an organic solvent, or an anion polymerization method or a cationic polymerization method can be used. , Is not specific to this. In the radical polymerization method by solution polymerization, for example, the first, second, and third (meth) acrylate monomers are dissolved in an organic solvent in a reaction vessel by a known method, and the radical polymerization is started. Add the agent,
Heat and react under a stream of nitrogen. Although the organic solvent used at this time is not particularly limited, for example, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl acetate Etc. are used. Further, the radical polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, ditertiary butyl peroxide, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, and azo peroxide. Bisisobutyronitrile, hydrogen peroxide- ^{Fe2 +} salt, persulfate-
NaHSO ₃ , cumene hydroperoxide-Fe ²⁺ salt,
Benzoyl peroxide-dimethylaniline, peroxide-triethylaluminum and the like are used. In order to control the molecular weight, a chain transfer agent can be added. Examples of the chain transfer agent include, but are not limited to, quinones such as monoethyl hydroquinone and p-benzoquinone; mercaptoacetic acid-ethyl ester, mercaptoacetic acid-
n-butyl ester, mercaptoacetic acid-
Thiols such as 2-ethylhexyl ester, mercaptocyclohexane, mercaptocyclopentane and 2-mercaptoethanol; thiophenols such as di-3-chlorobenzenethiol, p-toluenethiol and benzenethiol; and γ-mercaptopropyltrimethoxysilane Thiol derivatives; phenylpicrylhydrazine; diphenylamine; tert-butylcatechol and the like can be used.

The amount of the acrylic resin (F) in the coating resin composition is not particularly limited, but may be, for example, 100 parts by weight of the total solid content of the components (A), (B) and (C). And preferably 0.1 to 100 parts by weight, more preferably 1 to 90 parts by weight, and still more preferably 5 to 80 parts by weight. If the amount is less than 0.1 part by weight, the expression of toughness tends to be weak. If the amount exceeds 100 parts by weight, curing of the coating film tends to be inhibited.

The resin composition for coating may optionally contain a pigment. Pigments that can be used include:
Although not particularly limited, for example, carbon black,
Quinacridone, naphthol red, cyanine blue, cyanine green, hansa yellow, fluororesin pigment,
Organic pigments such as acrylic resin-based pigments; inorganic pigments such as silica, titanium oxide, zinc oxide, barium sulfate, red iron oxide, and composite metal oxides are preferred, and one or more selected from these groups may be used. No problem. Among these, at least one selected from the group consisting of inorganic pigments, fluororesin-based pigments, and acrylic resin-based pigments is preferred because it is less likely to deteriorate and the stains are more easily removed. The dispersion of the pigment is not particularly limited, and may be a usual method, for example, a method of directly dispersing the pigment powder using a dyno meal, a paint shaker, or the like. At that time, a dispersant, a dispersing aid, a thickener, a coupling agent, and the like can be used.

If necessary, a leveling agent, a dye,
Metal powder, glass powder, antibacterial agent, antioxidant, antistatic agent,
An ultraviolet absorber or the like may be included in the coating resin composition within a range that does not adversely affect the effects of the present invention. The coating resin composition can be used by diluting it with various organic solvents as necessary because of ease of handling.
Further, the solution may be diluted with the same organic solvent. The types of the organic solvent include the components (A), (B), and (E) (and (A), (B), (E),
The type of the monovalent hydrocarbon group of the component (F), or
(A), (B), and (E) components (and (A), (B), (E), and (F) components if they contain the (F) component) should be selected according to the molecular weight. Can be. Examples of such an organic solvent are not particularly limited, but include, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl acetate. And ethylene 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. And one or more selected from the group consisting of these. The dilution ratio in the organic solvent is
There is no particular limitation, and the dilution ratio may be appropriately determined as needed.

The method for applying the coating resin composition to the substrate is not particularly limited, and may be any of various common methods such as brushing, spraying, dipping (dipping), flow, roll, curtain, knife coat and the like. An application method can be selected. The method of curing the coating resin composition applied to the substrate may be a known method, and is not particularly limited. The temperature at the time of curing is not particularly limited, either, and can be in a wide range from room temperature to heating temperature according to the desired performance of the applied and cured film.

The thickness of the cured coating film formed from the resin composition for coating is not particularly limited.
The thickness may be about 0.1 to 100 μm, and particularly preferably 1 to 50 μm in order to stably adhere and hold the applied cured film over a long period and to prevent cracking or peeling. The substrate on which the resin composition for coating is applied (which is also the substrate used in the coated article of the present invention) is not particularly limited, but includes, for example, an inorganic substrate, an organic substrate, an inorganic-organic composite substrate, Further, a coating base material having at least one inorganic coating film and / or at least one organic coating film on any of these surfaces may be used. The substrate need not be used indoors, but may be used outdoors.

Examples of the inorganic substrate include, but are not particularly limited to, a metal substrate; a glass substrate; an enamel; a water glass decorative plate, an inorganic building material such as an inorganic cured product, and ceramics. The metal substrate is not particularly limited. For example, non-ferrous metals [for example, aluminum (JIS-H4000 etc.), aluminum alloys (duralumin etc.), copper, zinc etc.], iron, steel [for example, rolled steel (JIS) -G3101 etc.), hot-dip galvanized steel (JIS
-G3302 etc.), (rolled) stainless steel (JIS-G
4304, G4305, etc.), tinplate (JIS-G3)
303 etc.) and other metals in general (including alloys).

The glass substrate is not particularly limited, and examples thereof include sodium glass, Pyrex glass, quartz glass, and alkali-free glass. The enamel is obtained by baking and coating a glassy enamel on a metal surface. Examples of the base metal include, but are not particularly limited to, mild steel sheets, steel sheets, cast iron, and aluminum. The enamel may be a normal enamel, and is not particularly limited.

The water glass decorative board refers to, for example, a decorative board obtained by applying sodium silicate to a cement base such as slate and baking the same. The inorganic hardened material is not particularly limited. For example, a fiber reinforced cement board (J
IS-A5430, etc.), ceramic siding (JIS-
A5422), wood wool cement board (JIS-A5404)
Pulp cement board (JIS-A5414 etc.), slate / wood wool cement laminate board (JIS-A5426)
Gypsum board products (JIS-A6901 etc.), clay roof tiles (JIS-A5208 etc.), thick slate (JIS-A6901 etc.)
A5402), ceramic tile (JIS-A5209)
Etc.), concrete blocks for construction (JIS-A540)
6), terrazzo (JIS-A5411, etc.), prestressed concrete double T slab (JIS-A5412)
Etc.), ALC panel (JIS-A5416 etc.), hollow prestressed concrete panel (JIS-A6511)
Etc.), and all types of base materials obtained by curing and molding inorganic materials such as ordinary bricks (JIS-R1250 etc.).

The ceramic substrate is not particularly limited, but examples thereof include alumina, zirconia, silicon carbide, silicon nitride and the like. As an organic substrate,
Although not particularly limited, for example, plastic, wood,
Examples include wood and paper. As a plastic substrate,
Although not particularly limited, for example, a thermosetting or thermoplastic plastic such as a polycarbonate resin, an acrylic resin, an ABS resin, a vinyl chloride resin, an epoxy resin, a phenolic resin, and a phthalic acid resin, and a nylon fiber or the like And a fiber reinforced plastic (FRP) reinforced with organic fibers.

The inorganic-organic composite substrate is not particularly limited.
Fiber reinforced plastics (FRP) reinforced with inorganic fibers such as carbon fibers, and the like. Examples of the organic film constituting the coating substrate include, but are not particularly limited to, acrylic, alkyd, polyester, epoxy, urethane, acrylic silicone, chlorinated rubber, phenol, melamine, and phthalate. A cured film of a coating material containing an organic resin such as an acid or acrylic urethane resin may be used.

The inorganic coating constituting the coating substrate is not particularly limited, and includes, for example, a cured coating of a coating material containing an inorganic resin such as a silicone resin. When applying the coating resin composition to the substrate, depending on the material and surface condition of the substrate, it may be difficult to obtain adhesion or weather resistance if the coating resin composition is applied as it is, so if necessary, A primer layer may be previously formed on the surface of the base material before forming a cured coating film of the coating resin composition. The primer layer is not particularly limited, whether organic or inorganic.Examples of the organic primer layer include nylon resin,
Alkyd resin, epoxy resin, acrylic resin, organically modified silicone resin (for example, acrylic silicone resin), chlorinated rubber resin, urethane resin, phenol resin,
At least one organic resin selected from the group consisting of polyester resin and melamine resin
Examples of the inorganic primer layer include a cured resin layer of an inorganic primer composition containing 90% by weight or more as a solid content of an inorganic resin such as a silicone resin. And the like.

The thickness of the primer layer is not particularly limited, but is preferably, for example, 0.1 to 50 μm, and 0.5 to 50 μm.
-10 μm is more preferable. If the thickness is too thin, adhesion and weather resistance may not be obtained, while if too thick, foaming or the like may occur during drying. A substrate having at least one organic primer layer and / or inorganic primer layer on its surface is included in the category of the coated substrate. That is, the coating film on the surface of the coating substrate may be the primer layer.

The primer layer may contain a coloring agent such as a pigment or a dye for toning as required. Examples of usable colorants include those described above as those that can be added to the coating resin composition. The preferred numerical range of the amount of the coloring agent to be added to the primer layer is the same as in the case of the coating resin composition described above. However, although it is based on solid content, it is specified not with respect to 100 parts by weight of the total condensed compound but with respect to 100 parts by weight of the total resin in the total amount of the primer composition.

The form of the substrate is not particularly limited, and examples thereof include a film, a sheet, a plate, and a fiber. Further, the base material may be a molded body of a material having these shapes, or a structure partially including at least one of the material having the shape or the molded body. The base material may be made of the above-mentioned various materials alone, a composite material obtained by combining at least two of the above-described various materials, or a laminated material obtained by laminating at least two of the above-described various materials. May be.

The coated article of the present invention may be obtained by applying the resin composition for coating of the present invention to a substrate, and further applying a resin layer containing an optical semiconductor. This resin layer is made of an inorganic paint containing an optical semiconductor (hereinafter, an inorganic paint containing an optical semiconductor may be referred to as a “functional inorganic paint”. ), Preferably formed from an inorganic coating containing an optical semiconductor containing a silicone resin as a film-forming component. Since the organic resin is easily decomposed by the optical semiconductor, an inorganic resin is preferable as a film forming component of the resin layer containing the optical semiconductor. The reason that silicone resin is preferable among inorganic resins is that the optical semiconductor is easily dispersed,
This is because a cured film is easily formed at room temperature.

The silicone resin that can be used for the functional inorganic coating is not particularly limited. However, in terms of the point that it does not deteriorate with time even when an optical semiconductor is mixed, and the weather resistance and hardness of the obtained coating film, the following ( Silicone resins containing component G) are preferred. Component (G): (G ₁ ) 100 parts by weight of a silicon compound represented by the general formula R ⁶ Si (OR ⁷ ) ₃ , and (G ₂ ) a silicon compound represented by the general formula Si (OR ⁷ ) ₄ and And / or 5 to 30,000 parts by weight of colloidal silica,
(G ₃₎ the general formula R ⁶ ₂ Si (OR ⁷⁾ hydrolyzable mixture containing silicon compounds 0 to 60 parts by weight, represented by ₂ (wherein R ^6, R ⁷ are each independently a monovalent A hydrolyzed polycondensate of a hydrocarbon group (which may be hereinafter referred to as "organosiloxane (G)").

As the raw material for the component (G), that is, the organosiloxane (G), the silicon compound (G ₁ )
A hydrolyzable mixture containing (G ₃ ) is used. Silicon compounds other than colloidal silica _{(G 1) ~ (G 3} ) has the general formula ^{_{R 6 p Si (OR 7)}} 4-p in ... (V) can be grossly expressed (wherein R ^6, R ⁷ Each independently represents a monovalent hydrocarbon group, and p is an integer of 0 to 2).

R ⁶ and R ⁷ are not particularly restricted but include, for example, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 8 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group;
Aralkyl groups such as -phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloromethyl group and γ-chloropropyl group , 3,
Halogen-substituted hydrocarbon group such as 3,3-trifluoropropyl group; hydroxy-substituted hydrocarbon group such as 2-hydroxyethyl group; γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexyl Examples include a substituted hydrocarbon group such as an ethyl group and a γ-mercaptopropyl group.

As R ⁶ and R ⁷ , an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability. Particularly, tetramethoxysilane, tetraethoxysilane and the like can be exemplified as the tetraalkoxysilane with p = 0, and as the organotrialkoxysilane with p = 1, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane can be exemplified. Phenyltrimethoxysilane, phenyltriethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. Examples of the diorganodialkoxysilane having p = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.

These R ⁶ and R ⁷ may be the same or different among the silicon compounds (G ₁ ) to (G ₃ ). The organosiloxane (G) is prepared by, for example, diluting the hydrolyzable mixture with a suitable solvent, adding water as a curing agent and, if necessary, a catalyst (eg, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid). Acids, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, oxalic acid, and other organic acids and inorganic acids, or one or more of them). Add the required amount (heat as needed (for example, 40-10
0 ° C.) may be prepared by hydrolysis and polycondensation to form a prepolymer. At that time, the weight average molecular weight (Mw) of the obtained prepolymer (hydrolyzed polycondensate) is adjusted to, for example, 900 or more, preferably 1000 or more in terms of polystyrene. When the molecular weight distribution (weight average molecular weight (Mw)) of the prepolymer is smaller than 900, the curing shrinkage at the time of polycondensation of the silicone resin (1) is large, and cracks are easily generated in the coating film after curing. There is a risk.

The amounts of the raw materials (G ₁ ) to (G ₃ ) used for preparing the organosiloxane (G) are based on the solid content.
(G ₂ ) 5 to 3000 parts _per 100 parts by weight of (G ₁ )
0 parts by weight (preferably 10 to 25,000 parts by weight, more preferably 20 to 20,000 parts by weight), (G ₃ ) 60 parts by weight or less (preferably 40 parts by weight or less, more preferably 3 parts by weight or less)
0 parts by weight or less). If the amount of (G ₂ ) used is smaller than the above range or the amount of (G ₃ ) used is larger than the above range, there is a problem that a desired hardness of the cured film cannot be obtained (hardness is lowered). . On the other hand, if the amount of (G ₂ ) is larger than the above range, the cured film has too high a cross-linking density and too high a hardness, so that there is a problem that cracks are easily generated.

As the raw material (G ₂ ),
Only one or both of the silicon compound and colloidal silica represented by (OR ⁷ ) ₄ are used. Silica has the effect of increasing the hardness of the applied cured film of the functional inorganic paint and improving smoothness and crack resistance.
The colloidal silica that can be used 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 contains 20 to 50% by weight of silica as a solid content, and the amount of silica can be determined from this value. When water-dispersible colloidal silica is used, water present as a component other than the solid content can be used as a curing agent as described later. The water-dispersible colloidal silica is usually made of water glass, but can be easily obtained 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 the 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 Ethylene glycol derivatives such as glycol, 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. Alternatively, two or more kinds can be used. Toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used in combination with these hydrophilic organic solvents.

When colloidal silica is used as at least a part of the raw material (G ₂ ), the amount of colloidal silica contained in the used amount of (G ₂ ) is part by weight as silica. In addition, silica may be added to and mixed with the organosiloxane (G) prepared without using silica at all, or even if silica is used for preparing the organosiloxane (G), Silica may be additionally mixed with the organosiloxane (G) as necessary. Silicas that can be used in those cases include:
There is no particular limitation, and known ones can be used. The form of the silica at that time is not particularly limited, and may be, for example, a powder form or the colloidal silica form.

Although silica has the above-mentioned effects, if the amount is too large, the cured coating of the functional inorganic coating may be too hard, which may cause cracks in the coating. Therefore, the compounding amount of silica in the total amount of the coating material using the silicone resin is preferably 1 to 50% by weight, more preferably 10 to 50% by weight, and more preferably 10 to 50% by weight as a solid content with respect to the total amount of the component (G). Preferably 10-3
It is contained within the range of 0% by weight. This content is 1% by weight
If it is less than the desired value, a desired film hardness tends to not be obtained. On the other hand, if it exceeds 50% by weight, cracks are likely to occur.

Water is used as a curing agent for the hydrolytic polycondensation reaction of the hydrolyzable mixture which is a raw material of the organosiloxane (G). Water is preferably 0.01 to 3.0 mol per mol equivalent of OR ⁷ group contained, and 0.3 to 3.0 mol.
1.5 mol is more preferred. As a diluting solvent used in the hydrolysis polycondensation reaction of the hydrolyzable mixture, methanol, ethanol, isopropanol, n-butanol, as described above as a dispersion solvent for colloidal silica,
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 diacetone alcohol. Can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be mentioned.

It is preferable that the pH of the organosiloxane (G) is adjusted in the range of 3.8 to 6.
If the pH is within this range, within the aforementioned molecular weight range,
The organosiloxane (G) can be used stably. If the pH is out of this range, the stability of the organosiloxane (G) is poor, so that the usable period from the preparation of the coating is limited. Here, the method of adjusting the pH is not particularly limited. For example, when mixing the raw materials of the organosiloxane (G) and the pH becomes less than 3.8, for example, a basic reagent such as ammonia is added. The pH may be adjusted to a value within the above range, and when the pH exceeds 6, it may be adjusted using, for example, an acidic reagent such as hydrochloric acid. 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 organosiloxane (G) may be heated to accelerate the reaction, After the pH is lowered with a reagent to proceed the reaction, the pH may be returned to a predetermined value with a basic reagent.

The silicone resin does not need to contain a curing catalyst. However, the silicone resin may accelerate the condensation reaction of the component (G) to accelerate the curing of the coating film.
Further, a curing catalyst can be included. 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, and ethanolamine acetate. Quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine;
amine silane coupling agents such as β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid, hydrochloric acid; Aluminum compounds such as aluminum alkoxides and aluminum chelates; lithium acetate, potassium acetate, lithium formate, sodium formate, potassium phosphate;
Alkali metal salts such as potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, and titanium tetraacetylacetonate; and 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 component (G).

When the silicone resin also contains a curing catalyst, the amount thereof is preferably 10% by weight or less, more preferably 8% or less, based on the total condensed compound of the organosiloxane (G), based on the solid content. is there. 10% by weight
If it exceeds, the storage stability of the functional inorganic paint may be impaired. When the silicone resin contained in the functional inorganic coating is an organosiloxane (G), the functional inorganic coating is heated at a low temperature or left at room temperature to form the hydrolyzable groups of the component (G). Undergo a condensation reaction to form a cured film. Therefore, such a functional inorganic paint is hardly affected by humidity even when it is cured at room temperature. Further, by performing the heat treatment, a condensation reaction can be promoted to form a cured film.

Although the optical semiconductor is not particularly limited, for example, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, and oxide In addition to metal oxides such as cadmium, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, nickel oxide, and rhenium oxide, strontium titanate and the like can be mentioned. Among these, the above-mentioned metal oxides are preferable in that they can be easily used practically, and among these metal oxides, titanium oxide is particularly preferable in terms of photocatalytic performance, safety, availability, and cost. In addition, when using titanium oxide as an optical semiconductor, it is preferable to use a crystal having an anatase type (anatase type) in terms of the strongest photocatalytic performance and long-term expression.

When the transparency of the coating film is required, the average primary particle diameter of the optical semiconductor is preferably 50 μm or less, more preferably 5 μm or less, and more preferably 0.5 μm or less.
m is more preferable. One kind of optical semiconductor may be used alone, or two or more kinds may be used in combination.

The optical semiconductor may be in any form as long as it can be dispersed in the coating material, such as powder, fine particle powder, and solution-dispersed sol particles. Curing proceeds in a shorter time, and is excellent in convenience in use. When a sol is used, the dispersion medium may be water or an organic solvent, but an organic solvent is preferred from the viewpoint of coating preparation.

Further, the material used as the optical semiconductor material is not limited as long as it finally shows the properties of the optical semiconductor. It is known that an optical semiconductor generates active oxygen when irradiated with ultraviolet light (photocatalytic property). Since active oxygen can oxidize and decompose organic substances, its properties are used to make use of the carbon-based dirt component attached to the coated product (for example, carbon fraction contained in automobile exhaust gas,
Self-cleaning effect to decompose tobacco tar); 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; Effects and the like can be obtained. In addition, when ultraviolet rays are 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 removing, the hydrophilicity (wetting property) of the coating film with respect to water is improved, and there is also an effect that antifogging property, antifouling property by rainwater washing and the like are obtained.

Further, there is also an antistatic function by the photocatalytic action of the optical semiconductor, and the antifouling effect can be obtained by this function. For example, when the coating film of the functional inorganic paint is irradiated with light, the surface resistance of the coating film is reduced by the action of the optical semiconductor contained in the coating film, thereby exhibiting an antistatic effect, and the coating film surface is hardly stained. Become. The mechanism by which the surface resistance of the coating decreases when light is applied to the coating containing optical semiconductors has not yet been clearly confirmed, but the electrons and holes generated by the light irradiation act. It is thought 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.

Examples of the metal that may be supported on the surface of the optical semiconductor include 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. Further, a clay crosslinked body in which an optical semiconductor is supported between layers may be used. By introducing the optical semiconductor between the layers, the optical semiconductor is supported by the fine particles, and the photocatalytic performance is improved. In the functional inorganic paint, the amount of the optical semiconductor is not particularly limited, but, for example, based on the solid content, if described as parts by weight of the total condensation compound of the silicone resin with respect to 100 parts by weight of all the optical semiconductor components, When the metal is not supported on the surface, the amount is, for example, 0.1 to 1000 parts by weight, preferably 1 to 500 parts by weight, more preferably 50 to 200 parts by weight, and the metal is supported on the surface of the optical semiconductor. In this case, for example, 0.1 to 5000 parts by weight, preferably 1
2,500 parts by weight, more preferably 50-500 parts by weight. When the compounding amount of the silicone resin is larger than the above range, there is a tendency that a sufficient photocatalytic function is hardly obtained, and when the compounding amount is smaller than the above range, the adhesion to a base is deteriorated, and the coating film performance tends to be reduced. There is. In addition, when the metal is supported on the surface of the optical semiconductor, the above-mentioned compounding amount of the optical semiconductor does not include the supported metal.

The functional inorganic paint used in the present invention can be toned by further containing a coloring agent such as a pigment or a dye, if necessary. The pigment that can be used is not particularly limited. For example, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa yellow; titanium oxide;
Inorganic pigments such as barium sulfate, red iron oxide, and composite metal oxides are preferred, and one or a combination of two or more selected from these groups may be used. The dispersion of the pigment is not particularly limited, and may be a usual method, for example, a method of directly dispersing the pigment powder using a dyno meal, a paint shaker, or the like. At that time, dispersant, dispersing aid, thickener,
Use of a coupling agent or the like is possible. The amount of the pigment to be added is not particularly limited because the concealing property varies depending on the type of the pigment.
Parts by weight, more preferably 10 to 70 parts by weight. When the amount of the pigment is less than 5 parts by weight, the concealing property tends to deteriorate, and when the amount exceeds 80 parts by weight, the smoothness of the coating film may deteriorate.

The dyes that can be used are not particularly limited, but include, for example, azo, anthraquinone, indicoid, sulfide, triphenylmethane, xanthene, alizarin, acridine, quinone imine,
And thiazole, methine, nitro and nitroso dyes. One or more of these groups may be used in combination. The amount of the dye added is not particularly limited because the concealing property varies depending on the type of the dye. For example, on a solid basis, preferably 5 to 80 parts by weight, based on 100 parts by weight of the total condensed compound in the total amount of the paint. And more preferably 10 to 70 parts by weight. When the amount of the dye is less than 5 parts by weight, the concealing property tends to be deteriorated, and when it exceeds 80 parts by weight, the smoothness of the coating film may be deteriorated.

Incidentally, a leveling agent, metal powder, glass powder,
Antibacterial agents, antioxidants, ultraviolet absorbers and the like may also be included in the functional inorganic coating as long as the effects of the present invention are not adversely affected. The functional inorganic paint can be used by diluting it with various organic solvents as necessary for ease of handling, or it may be diluted with the same organic solvent. The type of the organic solvent can be appropriately selected according to the type of the monovalent hydrocarbon group contained in each component of the silicone resin, the molecular weight of each component of the silicone resin, and the like.
Such an organic solvent is not particularly limited,
For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether; diethylene glycol such as diethylene glycol and diethylene glycol monobutyl ether Derivatives; 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. it can. 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 functional inorganic paint is not particularly limited, and the respective components may be mixed using a usual method and apparatus. Regarding the form of each component when introduced into the paint, a liquid itself, a solution dissolved in a solvent, a liquid such as a dispersion dispersed in a dispersion medium, a solid such as a powder, etc. Regardless, there is no particular limitation. When each component is introduced in the form of a solution or dispersion, the solvent or dispersion medium is, for example, water, the above-mentioned organic solvent, or
Mixtures of water and the above-mentioned organic solvents can be used. Each component may be added separately, or two or more components may be mixed in advance and then mixed with the remaining components,
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 of applying the functional inorganic paint is not particularly limited, and may be, for example, a brush coating, a spray, a dipping (dipping), a roll, a flow, a curtain, a knife coat, a spin coat, etc. You can choose the method. A method for curing the coating film of the functional inorganic paint may be a known method, and is not particularly limited. The temperature at the time of curing is not particularly limited, either, and can be in a wide range from room temperature to heating temperature according to the desired performance of the cured film and the heat resistance of the optical semiconductor.

The thickness of the cured coating film formed from the functional inorganic coating material is not particularly limited.
The thickness is preferably about 0 μm. However, in order to make the various functions of the coating film more effectively exerted, the applied cured coating is stably adhered and held for a long term, and cracks and peeling do not occur. 01-5 μm, preferably 0.05-2
μm is more preferred.

A coated article having a resin layer containing an optical semiconductor is
Because it contains optical semiconductors, when irradiated with ultraviolet light,
The various photocatalytic effects described above by the optical semiconductor are exhibited.
Therefore, by equipping at least a part of various materials or articles with the coating film, for example, it can be suitably used for the following applications. Building-related components or goods,
For example, exterior materials (for example, exterior wall materials, tiles such as flat tiles, Japanese tiles, metal tiles, etc.), resin rain gutters such as PVC rain gutters, metal rain gutters such as stainless steel gutters, gates, Members for use therein (for example, gates, gate posts, gate walls, etc.), fences (fences) and members for use therein,
Garage doors, home terraces, doors, pillars, car ports, bicycle parking ports, sign posts, home delivery posts, wiring equipment such as switchboards and switches, gas meters, intercoms, TV doorphones and camera lens units, electric locks, entrance poles, porch Windows (eg, daylighting windows, skylights, open / close windows such as louvers, etc.) and members for use therewith (eg, window frames,
Shutters, blinds, etc.), automobiles, railway vehicles, aircraft, ships, machinery, road peripherals (for example, soundproof walls, tunnel interior boards, various display devices, guardrails, bollards, railing, traffic signposts and signposts, Traffic lights, post cones, etc., advertising towers, outdoor or indoor lighting fixtures and members for use therein (eg, members made of at least one material selected from the group consisting of glass, resin, metal and ceramics, etc.) ), Glass for solar cells,
Agricultural vinyl and glass houses, outdoor units for air conditioners, antennas for VHF, UHF, BS, CS, etc.

The functional inorganic coating according to the present invention may be directly formed on at least a part of the above-mentioned various materials or articles, but is not limited thereto. The functional film formed on the surface of the film substrate may be attached to at least a part of the above-mentioned various materials or articles. As the material of the base material of such a film, for example, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, vinyl chloride resin, acrylic resin, fluororesin, polypropylene (PP) resin, and composite resin thereof The resin is not particularly limited.

In the above, the functional inorganic paint is described as a representative example of the paint for forming the resin layer containing the optical semiconductor, but other than the functional inorganic paint can be used.

[0091]

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 is measured by GPC (gel permeation chromatography) using HLC8020 manufactured by Tosoh Corporation as a measurement model, using a standard polystyrene as a calibration curve, and calculating the converted value. In addition, this invention is not limited to a following example.

Prior to the examples and comparative examples, each component used for them was prepared as follows. First, a preparation example of the component (A) will be described. In A-1 to A-4, the silica of the component (C) is blended when the component (A) is prepared. <Preparation Example A-1> In a flask equipped with a stirrer, a heating jacket, a condenser and a thermometer, methanol-dispersed colloidal silica sol (trade name “MTST”, particle diameter 10 to 20 nm, solid content 30%, moisture 0.5) %, Manufactured by Nissan Chemical Industries, Ltd.), 68 parts of methyltrimethoxysilane and 10.8 parts of water, and stirred at 65 ° C.
After performing a partial hydrolysis reaction at a temperature of about 5 hours,
By cooling, the component (A-1) was obtained. This had a solid content of 36% when left at room temperature for 48 hours.

Preparation conditions of A-1: the number of moles of water per mole of hydrolyzable group 0.4; the mole% of hydrolyzable organosilane of m = 1 100 mole% <Preparation Example A-2> In a flask equipped with a warm jacket, a condenser and a thermometer, methanol-dispersed colloidal silica sol (trade name “MTST”, particle diameter 10 to 20 nm, solid content 30%, moisture 0.5%, manufactured by Nissan Chemical Industries, Ltd.) 100 parts, 61.2 parts of methyltrimethoxysilane, 6.8 parts of phenyltrimethoxysilane and 10.8 parts of water were charged, and a partial hydrolysis reaction was carried out at 65 ° C. for about 5 hours while stirring. Then, by cooling, the component (A-2) was obtained. This had a solid content of 36% when left at room temperature for 48 hours.

Preparation conditions for A-2: The number of moles of water per mole of the hydrolyzable group 0.4; The mole% of the hydrolyzable organosilane with m = 1 100 mole% <Preparation Example A-3> In a flask equipped with a warm jacket, a condenser and a thermometer, methanol-dispersed colloidal silica sol (trade name “MTST”, particle diameter 10 to 20 nm, solid content 30%, moisture 0.5%, manufactured by Nissan Chemical Industries, Ltd.) 100 parts, 54.4 parts of methyltrimethoxysilane, 13.6 parts of phenyltrimethoxysilane and 10.8 parts of water were charged, and a partial hydrolysis reaction was carried out at 65 ° C. for about 5 hours while stirring. Then, by cooling, the component (A-3) was obtained. This had a solid content of 36% when left at room temperature for 48 hours.

Preparation conditions of A-3: The number of moles of water per mole of the hydrolyzable group is 0.4. The mole% of the hydrolyzable organosilane with m = 1 is 100% by mole. <Preparation Example A-4> In a flask equipped with a warm jacket, a condenser and a thermometer, methanol-dispersed colloidal silica sol (trade name “MTST”, particle diameter 10 to 20 nm, solid content 30%, moisture 0.5%, manufactured by Nissan Chemical Industries, Ltd.) 100 parts, 47.6 parts of methyltrimethoxysilane, 20.4 parts of phenyltrimethoxysilane and 10.8 parts of water were charged, and a partial hydrolysis reaction was carried out at 65 ° C. for about 5 hours while stirring. Then, by cooling, the component (A-4) was obtained. This had a solid content of 36% when left at room temperature for 48 hours.

Preparation conditions of A-4: the number of moles of water per mole of hydrolyzable group 0.4; the mole% of hydrolyzable organosilane with m = 1 100 mole% Next, an example of preparing the component B will be described. . <Preparation Example B-1> 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene are weighed and mixed in a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, and a thermometer, and mixed. While stirring the solution, 108 parts of a 1% aqueous hydrochloric acid solution was added dropwise thereto over 20 minutes, and methyltriisopropoxysilane was hydrolyzed at 60 ° C. with stirring. The stirring was stopped 40 minutes after the completion of the dropping.
When the reaction solution was transferred to a separating funnel and allowed to stand, it was separated into two layers. The mixed solution of the lower layer water and isopropyl alcohol containing a small amount of hydrochloric acid is separated and removed, and the remaining hydrochloric acid in the resin solution of the remaining toluene is removed by washing with water.
After further removing toluene under reduced pressure, the obtained reaction product was diluted with isopropyl alcohol to obtain a 40% solution of a silanol group-containing polyorganosiloxane having a weight average molecular weight (Mw) of about 2,000 in isopropyl alcohol. This is called B-1. It has been confirmed that the silanol group-containing polyorganosiloxane in B-1 satisfies the above average composition formula (II). (D component): N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane. (E component): <E-1> γ-glycidoxypropyltrimethoxysilane <E-2> γ-glycidoxypropylmethyldimethoxysilane (F component): <F-1> Stirrer, heating jacket, condenser 5.69 parts of n-butyl methacrylate (BMA) as a first (meth) acrylate in a flask equipped with a dropping funnel, a nitrogen gas inlet / outlet and a thermometer,
1.24 parts of trimethoxysilylpropyl methacrylate (SMA) as a third (meth) acrylate,
0.71 part of glycidyl methacrylate (GMA) as the second (meth) acrylic ester, and γ-mercaptopropyltrimethoxysilane 0.1 as the chain transfer agent.
To a reaction solution in which 784 parts were dissolved in 8.49 parts of toluene, a solution in which 0.025 part of azobisisobutyronitrile was dissolved in 3 parts of toluene was added dropwise under a nitrogen stream, and the mixture was reacted at 70 ° C. for 2 hours to obtain a molecular weight Mw = 1000 acrylic resin was obtained.
This resin is designated as F-1. (G component): 100 parts of methyltrimethoxysilane as <G-1> material (G _1), 10 parts of tetraethoxysilane as a raw material (G _2), similarly isopropanol dispersion is acidic colloidal silica as a raw material (G ₂₎ Organosilica sol (trade name “OSCAL1432”, Catalyst Chemical Industry Co., Ltd.)
90 parts, solid content 30%), dimethyldimethoxysilane 30 parts as raw material (G ₃ ), and isopropyl alcohol as a diluting solvent (may be abbreviated as IPA in this specification).
100 parts were mixed, and 90 parts of water was further added and stirred. The obtained liquid was heated in a 60 ° C. constant temperature bath for 5 hours to adjust the weight average molecular weight (Mw) of organosiloxane (G) as a reaction product to 1500 to obtain an alcohol solution of organosiloxane.

Preparation conditions of alcohol solution of organosiloxane: [Water] / [OR ⁷ ] molar ratio: 1.73 Weight-average molecular weight: 1500 Solid content calculated as total condensed compound: 23.3% Titanium sol (Titanium oxide sol manufactured by Catalysis Kasei Co., Ltd .: trade name "Queen Titanic 11-1020G") was used on the basis of solid content, based on 100 parts of all optical semiconductor components in the total amount of paint, and 2 parts of total condensed compound.
By adding and mixing so as to be 0 parts, a functional inorganic paint (1) was obtained.

(Examples 1 to 20) The components were mixed at the mixing ratios shown in Tables 1 to 3, and all were diluted with isopropyl alcohol so as to have a solid content of 20% to obtain a resin composition for coating. (Comparative Examples 1 to 3) The components were mixed at the compounding ratio shown in Table 3,
Each was diluted with isopropyl alcohol to a solid content of 20% to obtain a resin composition for comparative coating.

The appearance of each of the resin compositions obtained in Examples and Comparative Examples was visually observed, and the results are shown in Tables 1 to 3.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

[Table 3] (Examples 21 to 60 and Comparative Examples 4 to 9) The organic paints shown in Tables 4 to 6 were applied to an aluminum test piece (manufactured by Nippon Test Panel Co., Ltd.) by spray coating, and the test pieces were placed in a room at 20 ° C.
After standing for a week, the coating resin compositions of Examples 1 to 20 and the comparative resin compositions of Comparative Examples 1 to 3 were applied so that the cured coating thickness became 10 to 30 μm.
The coated product was obtained by drying in a room at 0 ° C. for one week to form a cured film.

The coatings obtained were evaluated for coating film performance by the following method. The results are shown in Tables 4 to 6. (Adhesion): Adhesion to the substrate is checked by using a cross-cut adhesive tape (using cellophane tape). The adhesive surface of the cellophane tape was pressed against the surface of the grid-like coating, and then peeled off to evaluate the number of grids of the coating remaining on the painted product.

(Weather resistance): After irradiating a sunshine carbon arc with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) for 1000 hours (irradiation conditions were JIS K540).
0), and the coating film was observed and evaluated according to the following criteria.
○ indicates that the weather resistance is good and the toughness is also good.

○: The coating film has no crack, blister, peeling, etc. ×: The coating film has cracks, blisters, or peeling.

[0106]

[Table 4]

[0107]

[Table 5]

[0108]

[Table 6] In Tables 4 to 6, "PVC" indicates vinyl chloride resin-based paint vinylon (manufactured by Kansai Paint Co., Ltd.), and "phthalic acid" indicates phthalic acid-based resin Himel (manufactured by Dainippon Paint Co., Ltd.). In addition, the initial appearance of the coating film was good (○) in the coated products of the above and below examples, whereas the coating product of Comparative Example 5 was poor (x, cracks occurred).

(Examples 61 to 66) Table 7 was spray-coated on an aluminum test piece (manufactured by Nippon Test Panel Co., Ltd.).
And left in a room at 20 ° C. for 1 week, and then applied the coating resin compositions of Examples 15, 18, and 19 so that the cured coating thickness thereof becomes 10 to 30 μm. The coated product was obtained by drying in a room for one week to form a cured film.

With respect to the obtained coated articles, Examples 15 and 1
The coating film performance was evaluated in the same manner as in Examples 8 and 19 (however, the irradiation time was 1000 hours and 3000 hours). Table 7 shows the results.

[0111]

[Table 7] In Table 7, "PVC" indicates vinyl chloride resin-based paint vinylon (manufactured by Kansai Paint Co., Ltd.), and "phthalic acid-based" indicates phthalic acid-based resin Himel (manufactured by Dainippon Paint Co., Ltd.). (Examples 67 to 106 and Comparative Examples 10 to 12) The organic paints shown in Tables 8 to 10 were applied to an aluminum test piece (manufactured by Nippon Test Panel Co., Ltd.) by spray coating, left in a room at 20 ° C. for 1 week, and then carried out. The resin compositions for coating of Examples 1 to 20 and the resin compositions for comparative coating of Comparative Examples 1 to 3 were applied such that the cured coating thickness thereof became 10 to 30 μm, and dried in a room at 20 ° C. for 1 day. The functional inorganic coating material (1) prepared above was applied so as to have a dry film thickness of 0.1 μm, and dried in a room at 20 ° C. for one week to form a cured film, thereby obtaining a coated product.

With respect to the obtained coated articles, Examples 1 to 20
The coating film performance was evaluated in the same manner as in Comparative Examples 1 to 3. The results are shown in Tables 8 to 10.

[0113]

[Table 8]

[0114]

[Table 9]

[0115]

[Table 10] In Tables 8 to 10, "PVC" indicates vinyl chloride resin-based paint vinylon (manufactured by Kansai Paint Co., Ltd.), and "phthalic acid" indicates phthalic acid-based resin Himel (manufactured by Dainippon Paint Co., Ltd.). (Examples 107 to 112) The organic paints shown in Table 11 were applied to aluminum test pieces (manufactured by Nippon Test Panel Co.) by spray coating, left in a room at 20 ° C. for one week, and then coated in Examples 15, 18, and 19. The resin composition for application is applied so that its cured coating thickness is 10 to 30 μm.
After drying in a room at 0 ° C. for 1 day, the functional inorganic paint (1) prepared above is further applied to a dry film thickness of 0.1 μm, and dried in a room at 20 ° C. for 1 week to form a cured film. To obtain a painted product.

With respect to the obtained coated articles, Examples 15 and 1
The coating film performance was evaluated in the same manner as in Examples 8 and 19 (however, the irradiation time was 1000 hours and 3000 hours). Table 11 shows the results.

[0117]

[Table 11] In Table 11, “PVC” indicates vinyl chloride resin-based paint vinylon (manufactured by Kansai Paint Co., Ltd.), and “phthalic acid-based” indicates phthalic acid-based resin Himel (manufactured by Dainippon Paint Co., Ltd.).

[0118]

The resin composition for coating according to the present invention comprises:
Since the composition contains the components (A), (B), (C), (D) and (E), a coating cured film having excellent adhesion and toughness can be formed on various substrates, especially organic substrates such as organic coating films. Can be formed. The component (A) has a partial hydrolyzate of a hydrolyzable organosilane in which R ¹ is a phenyl group as a solid content of 100 parts by weight of the total solid content of the component (A) and the component (C). When the content is not less than parts by weight, in addition to the above effects, an effect of further improving toughness is also exerted.

When the component (E) is contained at a ratio of 0.1 to 20 parts by weight based on 100 parts by weight of the total solid content of the components (A) to (C), in addition to the above effects, An effect of further improving the adhesion to the organic base material and the resin is also exerted. When the coating resin composition of the present invention also contains the component (F), in addition to the above-described effects, an effect of further improving toughness is also exerted.

The component (F) is used in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the total solid content of the components (A) to (C).
When contained in parts by weight, in addition to the above effects,
It also has the effect of being more excellent in weather resistance. Since the coated article of the present invention is provided with the applied and cured coating of the resin composition for coating of the present invention on the surface of the substrate, the coating is hardly peeled off and hardly cracked.

When the substrate of the present invention has an organic resin layer on at least the surface to which the resin composition for coating is applied, in addition to the above-mentioned effects, the coated article has a high surface hardness, is excellent in toughness, and has cracks and the like. An effect of being hardly generated (preferably, not generated) is also exerted. The coated article of the present invention, when the resin composition for coating is applied to the base material and then a resin layer containing an optical semiconductor is applied, in addition to the above-mentioned effects, excellent in stain resistance due to a photocatalytic action. Becomes

When the resin layer containing the optical semiconductor is made of an inorganic coating containing an optical semiconductor containing a silicone resin as a film-forming component, the resin layer is less likely to deteriorate with time. When the silicone resin is the organosiloxane (G), it is less susceptible to deterioration over time, and is more excellent in weather resistance and hardness.

The optical semiconductor is titanium oxide, zinc oxide,
Tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide When it is at least one kind of metal oxide selected from the group consisting of nickel oxide and rhenium oxide, in addition to the above-mentioned effects, an effect is obtained that dirt on the coating film surface is further reduced.

Claims (12)

[Claims] 1. The following (A), (B), (C) and (D)
What is claimed is: 1. A resin composition for coating comprising a component, further comprising the following component (E). Component (A): represented by the general formula R ¹ _m SiX _4-m (I) (where R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M is an integer of 0 to 3, and X represents a hydrolyzable group.) The hydrolyzable organosilane is dissolved in an organic solvent, water or a mixed solvent thereof per 1 molar equivalent of the hydrolyzable group (X). An organosilane oligomer partially hydrolyzed under conditions using 0.001 to 0.5 mol of water. Component (B): represented by an average composition formula R ² _a Si (OH) _b O _{(4-ab) / 2} (II) (where R ² is the same or different and is substituted or unsubstituted and has 1 to 1 carbon atoms) 8 represents a monovalent hydrocarbon group, wherein a and b are respectively 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦
3, a number that satisfies the relationship of a + b <4. ), Polyorganosiloxanes containing silanol groups in the molecule. Component (C): silica. Component (D): curing catalyst. Component (E): represented by the general formula R ³ _m SiX _4-m (III) (where at least one of R ³ is an aminopropyl group, a glycidoxypropyl group, an allyl group, a methacryloxypropyl group) Any one selected from the group consisting of (when m is 2 or 3, R ³ is the same,
Alternatively, at least one of them is heterogeneous. When at least one of R ³ is different, R ³ is all selected from the group consisting of an aminopropyl group, a glycidoxypropyl group, an allyl group, a methacryloxypropyl group, or one of R ³ is Two of them are each independently any one of a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group. ), M represents an integer of 1 to 3, and X represents a hydrolyzable group. ) Hydrolysable organosilanes. 2. The component (A) is obtained by dissolving the hydrolyzable organosilane in colloidal silica obtained by dispersing the component (C) in an organic solvent, water or a mixed solvent thereof. (X) water 0.001 to 1 molar equivalent
Partially hydrolyzed under the condition of using 0.5 mol,
2. The coating composition according to claim 1, wherein the component (C) is a silica-dispersed organosilane oligomer having a solid content of 5 to 95% by weight based on the total amount of the component (A) and the component (C). Resin composition. 3. The component (A) is a partial hydrolyzate of a hydrolyzable organosilane in which R ¹ is a phenyl group, based on 100 parts by weight of the total solid content of the components (A) and (C). The resin composition for coating according to claim 1, comprising 10 parts by weight or more as a solid content. 4. The component (E) is based on 100 parts by weight of the total solid content of the components (A), (B) and (C).
The coating resin composition according to any one of claims 1 to 3, wherein the proportion is 0.1 to 20 parts by weight. 5. The method according to claim 1, further comprising the following component (F).
5. The coating resin composition according to any one of items 1 to 4. Component (F): a monomer represented by the general formula CH ₂ ＣＲCR ⁴ (COOR ⁵ ) (IV) (where R ⁴ represents a hydrogen atom and / or a methyl group), wherein R ⁵ is substituted Alternatively, the first (meth) acrylic acid ester which is an unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, and R ⁵ is an epoxy group, a glycidyl group or a hydrocarbon group containing at least one of these groups. A second (meth) acrylic ester which is at least one group selected from the group; and a third (meth) acrylate wherein R ⁵ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. Acrylic resin which is a copolymer of acrylic acid ester. 6. The compounding amount of the component (F) is as follows:
The coating resin composition according to claim 5, wherein the ratio is 0.1 to 100 parts by weight based on 100 parts by weight of the total solid content of the components (B) and (C). 7. A coated article comprising a substrate and a cured coating of the resin composition for coating according to any one of claims 1 to 6 on the surface thereof. 8. The coated article according to claim 7, wherein said base material has an organic resin layer at least on a surface on which said resin composition for coating is applied. 9. The coated article according to claim 7, wherein after applying the resin composition for coating to the base material, a resin layer containing an optical semiconductor is applied. 10. The coated article according to claim 9, wherein the resin layer containing the optical semiconductor is formed of an inorganic paint containing an optical semiconductor containing a silicone resin as a film-forming component. 11. The silicone resin of the general formula R ⁶ S
i to (OR ⁷⁾ 100 parts by weight of silicon compound represented by _3, the general formula Si and silicon compound and / or colloidal silica 5-30000 parts by weight represented by (OR ⁷⁾ _4, the general formula R ⁶ ₂ Si (OR ⁷ ) ₂ A hydrolyzable mixture containing 0 to 60 parts by weight of a silicon compound represented by ₂ (wherein R ⁶ and R ⁷ each independently represent a monovalent hydrocarbon group). The coated article according to claim 10, which is a decomposition polycondensate. 12. The optical semiconductor according to claim 1, wherein said optical semiconductor is titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide,
Germanium oxide, lead oxide, cadmium oxide, copper oxide,
The metal oxide according to any one of claims 9 to 11, which is at least one metal oxide selected from the group consisting of vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, nickel oxide and rhenium oxide. Painted product as described.