JP2001220543A - Ultraviolet-absorbing coating material resin composition and coated article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet-absorbing coating material resin composition capable of obtaining coating films which are hard to reduce the ultraviolet- absorbing power event when irradiated with ultraviolet rays for a long period of time, and a coated article using the same. SOLUTION: The ultraviolet-absorbing coating material resin composition contains a silica dispersion organosilane oligomer, an acrylic resin obtained by copolymerizing a (meth)acrylic ester having an ultraviolet-absorbing group, a silanol group-containing polyorganosiloxane, and a curing catalyst. The coated article has a cured coating film of the ultraviolet-absorbing coating material resin composition on the surface of a base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a UV-absorbing coating resin composition in which a UV-absorbing agent is introduced into a silicone-based coating material. Composition.

[0002]

2. Description of the Related Art Conventionally, regarding a UV-absorbing coating resin composition in which a UV-absorbing agent is introduced into a silicone-based coating material, the UV-absorbing ability due to deterioration or migration of the UV-absorbing agent itself when exposed to ultraviolet light for a long time. However, there is a problem that the long-term durability is low, and there is a need for improvement. As an example of improving long-term durability, as disclosed in JP-A-58-213075, a functional group represented by a general formula -Si (OR ⁷ ) ₃ (where R ⁷ is the same Or a different type of substituted or unsubstituted monovalent hydrocarbon group) is synthesized, and the ultraviolet absorber is reacted with a silicone-based coating material to immobilize the ultraviolet absorber on silicone. Has been proposed. However, there is a problem that it is difficult to obtain an ultraviolet absorber provided with this specific functional group. As another example of improving the long durability different from this method, a method of easily fixing an ultraviolet absorber to silicone has been proposed as disclosed in JP-A-9-143404. However, this UV-absorbing coating material was subjected to a 1200-hour accelerated test with an accelerated weathering tester (Sunshine Super Long Life Weather Meter).
However, as a result of the accelerated test for 2000 hours, the reduction rate of the ultraviolet absorbing ability is 30% or more. This does not yet provide sufficient weather resistance for building members and outdoor members that require a long service life of 10 to 20 years, and do not satisfy the market requirements. Therefore, there is a need for a means that can be easily obtained and that further improves long-term durability.

[0003]

SUMMARY OF THE INVENTION In view of the above circumstances, it is an object of the present invention to provide a UV-absorbing coating material resin composition capable of obtaining a coating film whose UV-absorbing ability is hardly reduced even when irradiated with UV light for a long time. An object of the present invention is to provide a coated product using the same.

[0004]

Means for Solving the Problems The resin composition for ultraviolet absorbing coating material according to claim 1 comprises the following (A):
Contains components (B), (C) and (D). 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) Hydrolyzable organosilane is partially hydrolyzed in colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof in the presence of water. A silica-dispersed oligomer of an organosilane (hereinafter sometimes referred to as “silica-dispersed oligomer (A)”). Component (B): a monomer represented by the general formula CH ₂ ＣＲCR ² (COOR ³ ) (II) (where R ² represents a hydrogen atom and / or a methyl group), wherein R ³ is a hydrogen atom Or a substituted or unsubstituted C 1-9
First and (meth) acrylic acid ester is a valence hydrocarbon group, at least 1 R ³ is selected from the group consisting of a hydrocarbon group containing at least one of an alkoxysilyl group, a halogenated silyl group, and their A second group (meth) acrylate which is a kind group or a siloxy group, and a ^third group wherein R ³ is a hydrocarbon group containing an ultraviolet absorbing group.
Acrylic resin obtained by copolymerizing monomers containing at least (meth) acrylic acid ester (hereinafter sometimes referred to as “acrylic resin (B)”; in the present specification, (meth) acrylic The acid ester refers to one or both of an acrylate and a methacrylate). Component (C): represented by an average composition formula R ⁴ _a Si (OH) _b O _{(4-ab) / 2} (III) (where R ⁴ 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 + b <4), and a polyorganosiloxane containing a silanol group in the molecule (hereinafter, referred to as “a + b <4”).
This is sometimes referred to as "(silanol group-containing) polyorganosiloxane (C)").

[0005] Component (D): a curing catalyst (hereinafter sometimes referred to as "curing catalyst (D)"). The ultraviolet absorbing coating material resin composition according to claim 2 is the ultraviolet absorbing coating material resin composition according to claim 1,
R ^{4 of the} component (C) is a phenyl group. The ultraviolet absorbent coating material resin composition according to claim 3,
The ultraviolet absorbent coating material resin composition according to claim 1, further comprising the following component (E). Component (E): a monomer represented by the general formula CH ₂ ＣＲCR ⁵ (COOR ⁶ ) (IV) (where R ⁵ represents a hydrogen atom and / or a methyl group), wherein R ⁶ is substituted or A group consisting of an unsubstituted first (meth) acrylic ester which is a monovalent hydrocarbon group having 1 to 9 carbon atoms, and R ⁶ is an epoxy group, a glycidyl group or a hydrocarbon group containing at least one of these A second (meth) acrylate which is at least one group selected from the group consisting of: and a third (meth) acryl wherein R ⁶ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. An acrylic resin obtained by copolymerizing monomers containing at least an acid ester (hereinafter, this may be referred to as “acrylic resin (E)”).

According to a fourth aspect of the present invention, there is provided an ultraviolet absorbing coating material resin composition according to any one of the first to third aspects, wherein the component (B) is 1,000 to 10,000. It has a weight average molecular weight in the range. The ultraviolet absorbing coating material resin composition according to claim 5 is the ultraviolet absorbing coating material resin composition according to any one of claims 1 to 4, wherein the compounding amount of the component (B) is the same as that of the component (A). , (C) in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the total solid content. According to a sixth aspect of the present invention, there is provided a coated article comprising, on a surface of a substrate, an ultraviolet-absorbing coating layer composed of a cured coating of the resin composition for an ultraviolet-absorbing coating material according to any of the first to fifth aspects.

BEST MODE FOR CARRYING OUT THE INVENTION The silica-dispersed oligomer used as the component (A) of the resin composition of the ultraviolet absorbing coating material of the present invention has a hydrolyzable function as a functional group which is subjected to a curing reaction when forming a cured film of the composition. It is a main component of the base polymer having the group (X). This is, for example,
Organic solvent or water (may be a mixed solvent of organic solvent and water)
One or more hydrolyzable organosilanes represented by the general formula (I) are added to the colloidal silica dispersed in water, and water (water previously contained in the colloidal silica and / or water added separately) is added. Obtained by partially hydrolyzing the hydrolyzable organosilane with water.

The group R ¹ in the hydrolyzable organosilane represented by the general formula (I) is 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;
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 groups such as 3,3-trifluoropropyl group; substituted hydrocarbons such as γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group And the like. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

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 of its availability and easy preparation of the silica-dispersed oligomer (A). As specific examples of the hydrolyzable organosilane,
Mono- in which m in the general formula (I) is an integer of 0 to 3,
Examples thereof include di-, tri-, and tetra-functional alkoxysilanes, acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, and amidosilanes. Among these, alkoxysilanes are preferable because they are easily available and the silica-dispersed oligomer (A) is easily prepared.

Among 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 the above general formula (I), preferably at least 50 mol%, more preferably at least 60 mol%, further preferably at least 70 mol%, m = 1 It is a trifunctional thing represented by. If the amount is less than 50 mol%, sufficient hardness of the coating film cannot be obtained, and the dry curability of the coating film tends to be poor. Colloidal silica in the silica-dispersed oligomer (A) has the effect of increasing the hardness of the applied cured film of the ultraviolet absorbent coating material resin composition and improving the smoothness and crack resistance. 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 and cure of the UV-absorbing coating material resin composition. It can be used as an agent. 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. 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 colloidal silica in the silica-dispersed oligomer (A) has the above-mentioned effects, but if the amount is too large, the cured film of the resin composition of the ultraviolet absorbing coating material becomes too hard and cracks of the film occur. May be caused. Therefore, in the silica-dispersed oligomer (A), the colloidal silica is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and still more preferably 20 to 85% by weight, based on silica as a solid content.
It is contained within the range of. If the content is less than 5% by weight, a desired coating hardness tends to be not obtained. On the other hand, when the content exceeds 95% by weight, it is difficult to uniformly disperse the colloidal silica, so that the component (A) may cause inconvenience such as gelation or may easily cause cracks. The solid content of the component (A) refers to a component generated when the component (A) is cured and solidified,
For example, it is a solid content obtained by leaving the component (A) at room temperature for 48 hours.

The amount of water used for preparing the silica-dispersed oligomer (A) is preferably from 0.001 to 0.5 per mole equivalent of the hydrolyzable group (X) of the hydrolyzable organosilane. It is in the range of moles, more preferably in the range of 0.01 to 0.4 moles. When the amount of water used is less than 0.001 mol, a sufficient partial hydrolyzate cannot be obtained, and as a result, the strength of the coating film tends to be insufficient. Decomposition products tend to have poor stability. Here, the amount of water used in the partial hydrolysis reaction of the hydrolyzable organosilane is separately determined when colloidal silica containing no water (for example, colloidal silica using only an organic solvent as a dispersion medium) is used. It is the amount of water added. When colloidal silica containing water (for example, colloidal silica using only water or a mixed solvent of an organic solvent and water as a dispersion medium of colloidal silica) is used, It is the amount of water previously contained in at least the colloidal silica of the water previously contained and the water separately added. If the amount of water was previously contained in the colloidal silica alone and the amount used was sufficient, it was not necessary to separately add water, but the amount of water was previously contained in the colloidal silica. 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 colloidal silica and water added separately. In addition, even in the case where only the water previously contained in the colloidal silica is sufficient for the above use amount, water may be separately added, and in such a case, the use amount of the water is included in the colloidal silica in advance. It is the total amount of water added and water added separately. In addition, this total amount is the upper limit of the preferable range (0.5 mol per 1 mol equivalent of the hydrolyzable group (X)).
It is preferable to add water separately so as not to exceed.

The method for partially hydrolyzing the hydrolyzable organosilane is not particularly limited. For example, the hydrolyzable organosilane may be mixed with colloidal silica (whether the colloidal silica 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,
In order to accelerate the partial hydrolysis reaction, if necessary, heating (for example, 60 to 100 ° C.) or a catalyst may be used. Examples of the catalyst include, but are not limited to, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, and malonic acid. , And one or more of organic acids and inorganic acids such as toluenesulfonic acid and oxalic acid.

The component (A) preferably has a pH of 2.0 to 2.0 in order to stably obtain its performance over a long period of time.
It is good to set it to 7.0, More preferably, it is 2.5-6.5, More preferably, it is 3.0-6.0. 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. But,
The adjustment method is not particularly limited.

[0015] The first to third (meth) acrylic esters which are monomers constituting the acrylic resin (copolymer) (B) used as the component (B) in the resin composition of the ultraviolet absorbing coating material of the present invention. Among them, the third (meth) acrylic ester is represented by R ³ in the general formula (II).
Since the UV-absorbing group is fixed in the polymer skeleton of the acrylic resin (B), migration is less likely to occur as compared with a conventional simple addition type UV-absorbing agent. Further, the second (meth) acrylic acid ester forms a chemical bond between the acrylic resin (B) and the (A) component and the (C) component when the coating film of the ultraviolet absorbing coating material resin composition is cured, This makes acrylic resin (B)
Are immobilized in the coating. As a result, a highly durable ultraviolet absorbing coating film is obtained.

The first (meth) acrylic acid ester, which is one of the monomers constituting the acrylic resin (B), is such that R ³ in the above formula (II) represents a hydrogen atom, or A substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s
an alkyl group such as an ec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl, a heptyl group, and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; a 2-phenylethyl group;
Aralkyl groups such as 2-phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; chloromethyl group, γ-chloropropyl group, 3,3 and
A halogenated hydrocarbon group such as a 3-trifluoropropyl group; a hydroxy hydrocarbon group such as a 2-hydroxyethyl group or a hydroxypropyl group; and the like.

The second (meth) acrylic acid ester which is another constituent monomer of the acrylic resin (B) is represented by the formula (II) in which R ³ is an alkoxysilyl group (for example, triethoxysilyl). Group, diethoxymethylsilyl group, etc.), halogenated silyl group (eg, trichlorosilyl group, dichloromethylsilyl group, etc.), and hydrocarbon groups containing these alkoxysilyl groups and / or halogenated silyl groups (eg, trimethoxysilyl group) Propyl group, dimethoxymethylsilylpropyl group, monomethoxydimethylsilylpropyl group, triethoxysilylpropyl group, diethoxymethylsilylpropyl group, ethoxydimethylsilylpropyl group, trichlorosilylpropyl group, dichloromethylsilylpropyl group, chlorodimethylsilylpropyl Group, chlorodimet It is at least one selected from the group consisting of a xylsilylpropyl group, a dichloromethoxysilylpropyl group and the like, and a siloxy group (for example, a tris (trimethylsiloxy) silyl group, a polydiethylsiloxy group and a polydimethylsiloxy group).

The third (meth) acrylic acid ester, which is still another constituent monomer of the acrylic resin (B), is represented by the formula (II) wherein R ³ is a hydrocarbon group containing an ultraviolet absorbing group. At least one of the things. The ultraviolet absorbing group is not particularly limited, and examples thereof include, for example, a benzotriazole group such as a hydroxyphenylbenzotriazole group; a benzophenone group such as a hydroxybenzophenone group; a salicylate group; an oxalic anilide group; A triazine group such as a group; a salicylic acid group; a cyanoacrylate group; and a para-aminobenzoic acid group. Among these ultraviolet absorbing groups, at least one selected from the group consisting of a hydroxyphenylbenzotriazole group, a hydroxybenzophenone group and a hydroxyphenyltriazine group absorbs the energy of ultraviolet rays to produce heat energy harmless to the coating film. This is preferable because the effect of the conversion is long. Specific examples of the third (meth) acrylic acid ester containing an ultraviolet absorbing group are not particularly limited. For example, when the benzotriazole-based ultraviolet absorbing group is exemplified, 2- (2′- Hydroxy-5'-
(Meth) acryloyloxyethylphenyl) -2H-
Benzotriazole, 2- (2'-hydroxy-5'-
(Meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2′-hydroxy -5 '-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole,
-(2'-hydroxy-3'-tert-butyl-5'-
(Meth) acryloyloxyethylphenyl) -2H-
Benzotriazole, 2- (2'-hydroxy-3'-
tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole and the like, and benzophenones include 2-hydroxy-4- {2- (meth) acryloyloxy}. Ethoxybenzophenone, 2-hydroxy-4- {2- (meth)
Acryloyloxydibutoxybenzophenone, 2,
2'-dihydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4
-{2- (meth) acryloyloxy} ethoxy-4 '
-(2-hydroxyethoxy) benzophenone and the like are triazine-based 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-.
S-triazine, 2,4-bis (2-methylphenyl)
-6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-S-triazine, 2,4-bis (2-
Methoxyphenyl) -6- [2-hydroxy-4- (2
-Acryloyloxyethoxy)]-S-triazine,
2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-
S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-S-triazine, 2,4-diphenyl-6- [2-hydroxy -4- (2-methacryloyloxyethoxy)]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-
4- (2-methacryloyloxyethoxy)]-S-triazine, 2,4-bis (2-ethylphenyl) -6
[2-hydroxy-4- (2-methacryloyloxyethoxy)]-S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy)]- S-triazine,
2,4-bis (2,4-dimethoxyphenyl) -6- [
2-hydroxy-4- (2-methacryloyloxyethoxy)]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-
Acryloyloxyethoxy)]-S-triazine,
2,4-bis (2,4-diethoxylphenyl) -6-
[2-hydroxy-4- (2-acryloyloxyethoxy)]-S-triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- (2-
Acryloyloxyethoxy)]-S-triazine and the like.

These tertiary (meth) acrylic esters containing an ultraviolet absorbing group may be used alone or in combination of two or more. In some cases, hindered amines having a polymerization side chain may be used. It may be copolymerized with a stabilizer. The acrylic resin (B) is a copolymer of (meth) acrylic ester containing at least one kind in the first, second and third (meth) acrylic esters, respectively, and at least three kinds in total. An additional one selected from the first, second and third (meth) acrylates
A kind or two or more kinds of monomers may be copolymerized, or a copolymer obtained by copolymerizing one or more kinds of monomers selected from (meth) acrylates other than the above. It does not matter.

The second (meth) acrylic acid ester used as a constituent monomer of the acrylic resin (B) is obtained by curing the acrylic resin (B) with the component (A) and (C) when the coating film of the ultraviolet absorbent coating material resin composition is cured. And (2) a component which forms a chemical bond with the component, whereby the acrylic resin (B) is fixed in the coating film. The second (meth) acrylic acid ester also has the effect of improving the compatibility between the acrylic resin (B) and the components (A) and (C). The molecular weight of the acrylic resin (B) greatly affects the compatibility of the acrylic resin (B) with the components (A) and (C). Therefore, the acrylic resin (B) is preferably from 1,000 to 50,000, more preferably from 1,000 to 20,000.
000, more preferably in the range of 1,000 to 10,000. Polystyrene-equivalent weight average molecular weight of acrylic resin (B) is 50
If it exceeds 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.

In the resin composition of the ultraviolet absorbing coating material,
The blending amount of the acrylic resin (B) is not particularly limited as long as it is an amount capable of sufficiently absorbing ultraviolet light in the state of the cured film. For example, the total solid content of the components (A) and (C) is 1
The ratio is 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 with respect to 00 parts by weight. If the amount is less than 0.1 part by weight, there is a tendency that a sufficient ultraviolet absorbing effect does not appear. 10
If the amount exceeds 0 parts by weight, the curing of the coating film tends to be inhibited. As a method for synthesizing the acrylic resin (B), for example, a radical polymerization method by solution polymerization, emulsion polymerization, or suspension polymerization in a known organic solvent, or an anion polymerization method or a cationic polymerization method can be used. It is not limited to.

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, A polymerization initiator is added, and the mixture is heated and reacted under a nitrogen stream. The organic solvent used at this time is not particularly limited as long as a desired copolymer can be obtained.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 ether acetate or the like is used. The radical polymerization initiator is not particularly limited, but examples thereof include cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, and di-tertiary peroxide.
Butyl peroxide, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, azobisisobutyronitrile,
Hydrogen peroxide-Fe ²⁺ 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. The chain transfer agent is not particularly limited, for example,
Quinones such as monoethylhydroquinone and P-benzoquinone; mercaptoacetic acid-ethyl ester, mercaptoacetic acid-n-butyl ester, mercaptoacetic acid-2-ethylhexyl ester, mercaptocyclohexane, mercaptocyclopentane, 2-mercapto Thiols such as ethanol; thiophenols such as di-3-chlorobenzenethiol, p-toluenethiol, and benzenethiol;
Thiol derivatives such as γ-mercaptopropyltrimethoxysilane; phenylpicrylhydrazine; diphenylamine; tert-butylcatechol and the like can be used.

The silanol group-containing polyorganosiloxane (C), which is the component (C) of the resin composition of the ultraviolet absorbing coating material of the present invention, is a base polymer having a hydrolyzable group as a functional group to be subjected to a curing reaction. A cross-linking agent for forming a three-dimensional cross-link in the cured film by a condensation reaction with the component (A), and a component having an effect of preventing cracks by absorbing distortion caused by curing shrinkage of the component (A). It is. R ⁴ in the above average composition formula (III) representing the silanol group-containing polyorganosiloxane (C) is not particularly limited, and is the same as R ¹ in the above formula (I), but is preferably Is an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group, a γ-glycidoxypropyl group, a γ-methacryloxypropyl group, a γ-aminopropyl group, a 3,3,3-trifluoropropyl group, etc. Substituted hydrocarbon groups, more preferably methyl and phenyl groups. In particular, a phenyl group, (B) preferably from the standpoint of the compatibility with component, its content is not particularly limited, for example, 5 to 50 mol% based on the total R ⁴ groups phenyl group as R ⁴ Is preferably contained at a ratio of
When the content ratio of the phenyl group is less than 5 mol%, the effect of improving the compatibility with the component (B) is small, and the coating film may be whitened or peeled. If the content of the phenyl group exceeds 50 mol%, the curing may be too slow.

Further, in the above formula (III), a and b are numbers satisfying the above-mentioned relationship, respectively. is there. When a is more than 2 and 4 or less, or when b is less than 0.0001, there is a disadvantage that the curing does not proceed sufficiently. The silanol group-containing polyorganosiloxane (C) is not particularly limited, but may be, for example, one of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or an alkoxysilane corresponding thereto. It can be obtained by hydrolyzing a mixture of two or more kinds with a large amount of water by a known method. When a silanol group-containing polyorganosiloxane (C) 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 curing catalyst (D) used as the component (D) in the resin composition of the ultraviolet absorbing coating material promotes the condensation reaction between the components (A) to (C) and cures the coating film. . Examples of the curing catalyst (D) include, but are not particularly limited to, alkyl titanates; carboxylic acid metal salts such as tin octylate dilaurate, dibutyltin dilaurate, and dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine Amine salts such as acetate and ethanolamine acetate; quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropyltrimethoxysilane; N-β Amine silane coupling agents such as -aminoethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; lithium acetate Alkali metal salts such as lithium formate, sodium formate, potassium phosphate and potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, titanium tetraacetylacetonate; methyl trichlorosilane, dimethyldichlorosilane, trimethylmonochlorosilane and the like And halogenated silanes.
However, other than these, there is no particular limitation as long as it is effective for promoting the condensation reaction between the components (A) to (C).

The mixing ratio of the components (A) and (C) in the resin composition of the UV-absorbing coating material of the present invention is not particularly limited. ) Component and component (C) total 10
0.5 to 99.5 parts by weight of the component (A) with respect to 0 parts by weight,
(C) 99.5 to 0.5 part by weight of the component is preferable, and (A)
Component 2.5 to 97.5 parts by weight, component (C) 97.5 to
The amount is more preferably 2.5 parts by weight, more preferably 5 to 95 parts by weight of the component (A) and 95 to 5 parts by weight of the component (C).
Component (A) is less than 0.5 parts by weight (component (C)
9.5 parts by weight), and is inferior in room temperature curability.
There is a tendency that sufficient coating hardness cannot be obtained. On the other hand, (A)
If the amount of the component exceeds 99.5 parts by weight (the component (C) is less than 0.5 part by weight), the curability is unstable and a good coating film may not be obtained.

The proportion of the component (D) in the resin composition of the ultraviolet absorbing coating material of the present invention is not particularly limited. For example, the solid content of the component (A) in terms of the total condensed compound and the total component (C) It 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 0.0007 to 5 parts by weight based on 100 parts by weight of the total solid content in terms of the condensed compound. Within the range of parts. If the amount of the component (D) is less than 0.0001 part by weight, the room-temperature curability tends to be low, and sufficient coating 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 resin composition for ultraviolet-absorbing coating material according to the present invention comprises a hydrolyzable group contained in the oligomer of the organosilane contained in the component (A) and a silanol group contained in the polyorganosiloxane contained in the component (C). Are left to stand at room temperature or heated at a low temperature in the presence of the curing catalyst (D) to undergo a condensation reaction to form a cured film. Therefore, unlike the conventional moisture-curable coating material, the ultraviolet absorbent coating material resin composition of the present invention is hardly affected by humidity even when cured at normal temperature. In addition, a heat treatment can promote a condensation reaction to form a cured film.

The ultraviolet absorbing coating material resin composition of the present invention can be cured not only by heat but also at room temperature, so that it can be used in a wide range of dry curing conditions or temperatures. Therefore, not only can a substrate having a shape difficult to apply heat uniformly, a substrate having a large size or a substrate having poor heat resistance be coated, but also when performing a coating operation outdoors or the like. Since it can be painted even when it is difficult to apply heat, its industrial value is high. The resin composition of the present invention preferably further contains an acrylic resin (E) as the component (E) for the following reasons. That is, the acrylic resin (E) has an effect of improving the toughness of the cured coating film of the composition of the present invention, thereby preventing the occurrence of cracks and increasing the film thickness. Further, the acrylic resin (E) assists the compatibility of the acrylic resin (B). Further, the acrylic resin (E) is incorporated into the condensation cross-linked product of the component (A) and the component (C), which becomes the three-dimensional skeleton of the cured coating film of the composition of the present invention, 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 composition of the present invention to the substrate is improved.

The first (meth) acrylic acid ester, which is one of the constituent monomers of the acrylic resin (E), is represented by the formula (IV) in which R ⁶ is substituted or unsubstituted and has 1 carbon atom.
To 9 monovalent hydrocarbon groups 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 (E) is such that R ⁶ in the above formula (IV) represents epoxy group, 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 still another constituent monomer of the acrylic resin (E), is a compound in which R ⁶ in the above formula (IV) represents an alkoxysilyl group and / or a halogenated silyl group. Hydrogen group, for example, trimethoxysilylpropyl group, dimethoxymethylsilylpropyl group, monomethoxydimethylsilylpropyl group, triethoxysilylpropyl group, diethoxymethylsilylpropyl group, ethoxydimethylsilylpropyl group, trichlorosilylpropyl group, dichloromethyl At least one of silylpropyl, chlorodimethylsilylpropyl, chlorodimethoxysilylpropyl, dichloromethoxysilylpropyl and the like.

The acrylic resin (E) comprises the first, second,
Less in each of the third (meth) acrylates
(Meth) acrylic containing at least 3 types in total
A copolymer of an acid ester, the first, second, and third
Further one selected from (meth) acrylates
Species or two or more, or other (meta)
One or more selected from lylic esters
Copolymers containing more than one species may be used. The first
The (meth) acrylic acid ester comprises the component (A) and the component (C).
To improve the compatibility between the components and the acrylic resin (B)
Component, a UV-absorbing coating material
It also has the effect of improving the toughness of the cured cloth coating. For this
Is R ⁶To some extent substituted or unsubstituted hydrocarbon groups
It is desirable to have a volume of at least 2
Preferably.

The second (meth) acrylic acid ester is a component for improving the adhesion between the applied cured film of the composition of the present invention and the substrate. The third (meth) acrylate is a component for forming a chemical bond between the acrylic resin (E) and the components (A) and (C) at the time of curing the coating film of the composition of the present invention. With this, the acrylic resin (E) is fixed in the applied cured film. Also, the third
The (meth) acrylic acid ester of the acrylic resin (E)
There is also an effect of improving the compatibility between the components (A) and (C). The molecular weight of the acrylic resin (E) greatly affects the compatibility of the acrylic resin (E) with the components (A) and (C). Therefore, the acrylic resin (E) is preferably from 1,000 to 50,000, more preferably from 1,000 to 50,000.
It has a weight average molecular weight in terms of polystyrene in the range of 20,000. If the weight average molecular weight in terms of polystyrene of the acrylic resin (E) exceeds 50,000, phase separation may occur and the coating film may be whitened. When the molecular weight is less than 1,000,
There is a tendency that the toughness of the coating film decreases and cracks are easily generated.

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 (E) and the components (A) and (C) is poor, and the coating film may be whitened. If it exceeds 50%, the bond density between the acrylic resin (E) and the components (A) and (C) becomes too high, and the improvement in toughness, which is the original purpose of the acrylic resin, tends not to be observed.

In the resin composition of the ultraviolet absorbing coating material,
The blending amount of the acrylic resin (E) is not particularly limited. For example, the total solid content of the components (A) and (C) is 1%.
The ratio is 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 with respect to 00 parts by weight. If the amount is less than 0.1 part by weight, the expression effect of the acrylic resin (E) tends to be weak. If the amount exceeds 100 parts by weight, curing of the coating film tends to be inhibited. The method for synthesizing the acrylic resin (E) is not particularly limited, and for example, the same method as the method for synthesizing the acrylic resin (B) can be used.

The resin composition of the present invention can be toned by further containing a coloring agent such as a pigment or a dye, if necessary. Examples of usable pigments include, but are not particularly limited to, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa yellow;
Inorganic pigments such as titanium oxide, barium sulfate, red iron oxide, and composite metal oxides are preferred, and one or more of them may be used in combination. The dispersion of the pigment is not particularly limited, and may be performed by a usual method, for example,
A method of directly dispersing the pigment powder using a dyno meal, a paint shaker, or the like may be used. At that time, a dispersant, a dispersing aid, a thickener, a coupling agent, and the like can be used. The amount of the pigment to be added is not particularly limited since the concealing property varies depending on the type of the pigment.
The amount is from 80 to 80 parts by weight, more preferably from 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 dye that can be used is not particularly limited.
And thiazole, methine, nitro and nitroso dyes. One kind selected from these groups or a combination of two or more kinds may be used. The amount of the dye added is not particularly limited because the concealing property varies depending on the type of the dye.
It is 80 parts by weight, 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.

Note that a leveling agent, metal powder, glass powder,
Antibacterial agents, antioxidants, ultraviolet absorbers and the like may also be included in the resin composition of the ultraviolet absorbing coating material within a range that does not adversely affect the effects of the present invention. The ultraviolet absorbing coating material resin composition of the present invention can be used after being diluted with various organic solvents, if necessary, or may be diluted with the same organic solvent, because of easy handling. 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 of applying the resin composition to the ultraviolet-absorbing coating material is not particularly limited. Various coating methods can be selected. The method of curing the coating film of the ultraviolet absorbing coating material resin composition 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 substrate.

The thickness of the cured coating film formed from the resin composition of the ultraviolet absorbing coating material is not particularly limited, and may be, for example, about 1 to 50 μm, but the various functions of the coating film are more effectively exhibited. In addition, in order to ensure that the applied cured film is stably adhered and held for a long period of time and does not cause cracking or peeling, the thickness is preferably 5 to 20 μm,
-10 μm is more preferred. The substrate on which the ultraviolet absorbent coating material resin composition of the present invention is applied (which is also the substrate used for the coated article of the present invention) is not particularly limited, and examples thereof include an inorganic substrate, an organic substrate, and an inorganic substrate. An organic composite substrate, and at least one inorganic coating and / or at least one surface on any of these surfaces;
A coating substrate having an organic coating of a layer is exemplified.

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 a mild steel plate, a steel plate, cast iron, and aluminum, but are not particularly limited. The enamel may be a normal enamel, and is not particularly limited. The water glass decorative board refers to, for example, a decorative board or the like obtained by applying sodium silicate to a cement base material such as a slate and baking it.

The hardened inorganic material is not particularly limited. For example, a fiber reinforced cement board (JIS-A54
30), ceramic siding (JIS-A5422)
Etc.), wood wool cement board (JIS-A5404 etc.), pulp cement board (JIS-A5414 etc.), slate / wood wool cement board (JIS-A5426 etc.), gypsum board product (JIS-A6901 etc.), clay tile (JIS-A
5208), thick slate (JIS-A5402)
Etc.), ceramic tiles (JIS-A5209 etc.), concrete blocks for construction (JIS-A5406 etc.), terrazzo (JIS-A5411 etc.), prestressed concrete double T slabs (JIS-A5412 etc.), AL
It refers to all types of substrates obtained by curing and molding inorganic materials such as C panels (JIS-A5416, etc.), hollow prestressed concrete panels (JIS-A6511, etc.), and 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, and a phenol resin, and these plastics are reinforced with an organic fiber such as a nylon fiber. Fiber reinforced plastic (FRP).

The inorganic-organic composite substrate is not particularly limited.
Fiber reinforced plastics (FRP) reinforced with inorganic fibers such as carbon fibers, and the like. In particular, the UV-absorbing coating material resin composition of the present invention is a cured film obtained by applying the UV-absorbing coating material, which absorbs ultraviolet light, so that deterioration and discoloration of the plastic substrate and other articles to be coated due to ultraviolet irradiation,
An effect of preventing peeling of the coating film and the like can be obtained. The organic film constituting the coating substrate is not particularly limited, but includes, for example, acrylic, alkyd, polyester, epoxy, urethane, acrylic silicone,
A cured film of a coating material containing an organic resin such as a chlorinated rubber type, a phenol type, and a melamine type is exemplified. In particular,
The UV-absorbing coating material resin composition of the present invention, because the applied cured film absorbs UV rays, similarly to the case of the plastic substrate, deterioration of the organic coating substrate due to UV irradiation, discoloration, peeling of the coating film, etc. The effect of prevention can be obtained.

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 UV-absorbing coating material resin composition of the present invention to a substrate, depending on the material and surface condition of the substrate, adhesion and weather resistance can be obtained by directly applying the UV-absorbing coating material resin composition of the present invention. Since it may be difficult, a primer layer may be previously formed on the surface of the base material before forming an applied cured film of the resin composition of the present invention on the base material. The primer layer is not particularly limited, regardless of whether it is organic or inorganic. Examples of the organic primer layer include a nylon resin, an alkyd resin, an epoxy resin, an acrylic resin, and an organic modified silicone resin (for example, an acrylic silicone resin). , A cured resin layer of an organic primer composition containing at least one organic resin selected from the group consisting of a chlorinated rubber resin, a urethane resin, a phenol resin, a polyester resin, and a melamine resin in a solid content of 10% by weight or more. And as examples of the inorganic primer layer,
90% by weight of inorganic resin such as silicone resin as solid content
Examples include the cured resin layer of the inorganic primer composition contained above.

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 preferred. If the thickness is too small, adhesion and weather resistance may not be obtained. If the thickness is too large, foaming 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. In addition, the primer layer may contain a coloring agent such as a pigment or a dye for toning as required. Examples of the coloring agent that can be used include those described above as those that can be added to the resin composition of the ultraviolet absorbing coating material. The preferred numerical range of the amount of the colorant to be added to the primer layer is the same as in the case of the above-described resin composition for an ultraviolet absorbing coating material. However, the amount is specified not with respect to 100 parts by weight of the solid content in terms of the total condensed compound but with respect to 100 parts by weight of the total resin solid content 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-mentioned various materials, or a laminated material obtained by laminating at least two of the above-described various materials. May be. The UV-absorbing coating resin composition and the coated product of the present invention have an effect of preventing deterioration, discoloration, peeling of the coated film, etc. of various substrates and other coated articles due to UV irradiation since the coating film has an ultraviolet absorbing ability. And the like, and these effects are unlikely to be reduced even by long-term ultraviolet irradiation. Therefore, by equipping at least a part of various materials or articles with the applied cured film of the resin composition of the present invention, it can be suitably used for the following applications, for example.

Building-related members or articles, for example, exterior materials (eg, exterior wall materials, tiles such as flat tiles, Japanese tiles, metal tiles, etc.), and metal such as resin rain gutters such as PVC rain gutters and stainless steel rain gutters. Rain gutters such as rain gutters, gates and members for use therein (for example, gates, gate posts, gate walls, etc.), fences (fences) and members for use therein, garage doors,
Home terrace, door, pillar, car port, bicycle parking port, sign post, home delivery post, wiring equipment such as switchboard and switch, gas meter, interphone, TV door phone body and camera lens, electric lock, entrance pole,
Entrance, ventilation fan outlet, glass for buildings, etc .; windows (for example, daylighting windows, skylights, louvers, etc.) and members used therefor (for example, window frames, shutters, blinds, etc.), automobiles, railway vehicles, Aircraft, ships, machinery,
Road peripheral members (for example, soundproof walls, tunnel interior boards, various display devices, guardrails, car stops, railing, traffic signposts and signposts, traffic lights, post cones, etc.), advertising towers, outdoor or indoor lighting fixtures and Member to be used (for example, member made of at least one material selected from the group consisting of glass, resin, metal and ceramics), glass for solar cells, vinyl and glass house for agricultural use, outdoor unit for air conditioner , VHF / UH
Antennas such as F / BS / CS.

The resin composition of the present invention may be applied directly to at least a part of the above-mentioned various materials or articles and cured, but is not limited thereto. The ultraviolet absorbing film formed by applying the resin composition of the absorbing coating material to the surface of the film substrate and curing the adhesive 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.

The present invention will be described below in detail based on examples and comparative examples. In Examples and Comparative Examples, all “parts” represent “parts by weight” and all “%” represent “% by weight” unless otherwise specified. The molecular weight was measured by GPC (gel permeation chromatography) using a model name of HLC8.
Using 020 (manufactured by Tosoh Corporation), a calibration curve was prepared using standard polystyrene, and the curve was measured as a converted value. In addition, this invention is not limited to a following example.

Prior to the examples and comparative examples, the components used for them were prepared as follows. (Preparation Example of Component A): <Preparation Example A-1> In a flask equipped with a stirrer, a heating jacket, a condenser and a thermometer, isopropanol (hereinafter, referred to as “IPA”) dispersed colloidal silica sol (trade name “ IPA-ST ", particle diameter 10 to 20 nm,
Solid content 30%, moisture 0.5%, manufactured by Nissan Chemical Industry Co., Ltd.)
100 parts, 68 parts of methyltrimethoxysilane, and 1 part of water
0.8 parts, and a partial hydrolysis reaction was carried out at 65 ° C. for about 5 hours with stirring, followed by cooling to obtain a silica-dispersed oligomer solution of organosilane. This is called A-1. This had a solid content of 36% in terms of total condensed compounds when left at room temperature for 48 hours.

Preparation conditions of A-1:-Number of moles of water per mole equivalent of hydrolyzable group: 0.4 mole-Silica content of component (A-1): 47.3%-Hydrolysis of m = 1 Preparation Example A-2> Colloidal silica sol (trade name “XBA-”) mixed with a xylene / n-butanol mixed solvent was placed in a flask equipped with a stirrer, a heating jacket, a condenser, and a thermometer. ST ", particle diameter 10-20 nm, solid content 30
%, Moisture 0.2%, manufactured by Nissan Chemical Industry Co., Ltd.) and 68 parts of methyltrimethoxysilane, and after performing a partial hydrolysis reaction at 65 ° C. for about 5 hours with stirring. By cooling, an organosilane silica-dispersed oligomer solution was obtained. This is called A-2. This had a solid content of 36% in terms of total condensed compounds when left at room temperature for 48 hours.

Preparation conditions for A-2: • Number of moles of water per mole equivalent of hydrolyzable group 0.007 moles • Silica content of component (A-2) 47.3% • Hydrolysis with m = 1 100% by mol of soluble organosilane (Preparation example of component B): <Preparation example B-1> In a flask equipped with a stirrer, heating jacket, condenser, dropping funnel, nitrogen gas inlet / outlet, and thermometer. Under a nitrogen stream, 1.58 parts of n-butyl methacrylate (BMA), 1.24 parts of trimethoxysilylpropyl methacrylate (SMA), 2-
(2-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole (trade name: RUVA-
93, manufactured by Otsuka Chemical Co., Ltd.) and 2.33 parts of γ-mercaptopropylmethoxysilane as a chain transfer agent.
To a reaction solution obtained by dissolving 0392 parts in 8.49 parts of toluene, a solution obtained by dissolving 0.025 parts of azobisisobutyronitrile in 3 parts of toluene was added dropwise and reacted at 70 ° C. for 2 hours. Thus, a 40% toluene solution of an acrylic resin having a weight average molecular weight Mw = 1000 was obtained. This is B-1
Called.

Preparation conditions for B-1: monomer molar ratio BMA / SMA / RUVA-93 =
5/2/3 Weight average molecular weight 1000 Solid content 40% <Preparation Example B-2> In a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, a nitrogen gas inlet / outlet, and a thermometer. Under a nitrogen stream, 1.58 parts of n-butyl methacrylate (BMA), 1.24 parts of trimethoxysilylpropyl methacrylate (SMA), 2-
(2-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole (trade name: RUVA-
93, manufactured by Otsuka Chemical Co., Ltd.) 2.43 parts, and 0.4% of γ-mercaptopropylmethoxysilane as a chain transfer agent.
In a reaction solution obtained by dissolving 784 parts in 8.49 parts of toluene,
0.025 parts of azobisisobutyronitrile is toluene 3
What was dissolved in the part was dropped, and reacted at 70 ° C. for 2 hours. Thus, a 40% toluene solution of an acrylic resin having a weight average molecular weight Mw = 8000 was obtained. This is called B-2.

Preparation conditions for B-2: monomer molar ratio BMA / SMA / RUVA-93 =
5/2/3-Weight average molecular weight 8000-Solid content 40% <Preparation Example B-3> In a flask equipped with a stirrer, heating jacket, condenser, dropping funnel, nitrogen gas inlet / outlet, and thermometer. Under a nitrogen stream, 3.24 parts by weight of 2-ethylhexyl methacrylate (EHMA), 2.43 parts of tris (trimethylsiloxy) silylpropyl methacrylate (SMA-2) and 2- (2-hydroxy-5-methacryloxyethylphenyl) ) -2H-benzotriazole (trade name: RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) A reaction solution obtained by dissolving 2.43 parts by weight in 7.1 parts by weight of toluene was heated to 90 ° C., and then azobisbutyro was added. A solution obtained by dissolving 0.4 part by weight of nitrile in 2.6 parts by weight of toluene was added dropwise and reacted at 90 ° C. for another 4 hours. Thus, a 40% toluene solution of an acrylic resin having a weight average molecular weight Mw = 5000 was obtained. This is called B-3.

Preparation conditions for B-3: monomer molar ratio EHMA / SMA-2 / RUVA-
93 = 4/3/3 Weight-average molecular weight 5000 5000 Solid content 40% <Preparation Example B-4> A stirrer, a heating jacket, a condenser, a dropping funnel, a nitrogen gas inlet / outlet, and a thermometer were attached. In a flask, under a nitrogen stream, 2.43 parts by weight of 2-ethylhexyl methacrylate (EHMA) and trimethoxysilylpropyl methacrylate (SMA)
24 parts, 2- (2-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole (trade name:
(RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) A reaction solution obtained by dissolving 43 parts by weight in 7.1 parts by weight of toluene was used.
After heating to ℃, a solution prepared by dissolving 0.4 parts by weight of azobisbutyronitrile in 2.6 parts by weight of toluene was added dropwise,
By further reacting at 90 ° C. for 4 hours, a 40% toluene solution of an acrylic resin having a weight average molecular weight Mw = 5000 was obtained. This is called B-4.

Preparation conditions of B-4: monomer molar ratio EHMA / SMA / RUVA-93
= 3/4/3-Weight average molecular weight 5000-Solid content 40% <Preparation Example B-5> A flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, a nitrogen gas inlet / outlet, and a thermometer. Medium, under a nitrogen stream, 4.86 parts by weight of methyl methacrylate (MMA), 0.81 part of trimethoxysilylpropyl methacrylate (SMA), 2-
(2-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole (trade name: RUVA-
93, manufactured by Otsuka Chemical Co., Ltd.) A solution of 2.43 parts by weight in 7.1 parts by weight of toluene was heated to 90 ° C., and then 0.4 parts by weight of azobisbutyronitrile was added to 2.6 parts by weight of 2.6 parts by weight. The substance dissolved in toluene was added dropwise and reacted at 90 ° C. for another 4 hours to obtain a weight average molecular weight Mw = 5.
A 40% toluene solution of 000 acrylic resin was obtained. This is called B-5.

Preparation conditions for B-5: monomer molar ratio MMA / SMA / RUVA-93
= 6/1/3-Weight average molecular weight 5000-Solid content 40% <Preparation Example B-6> Flask equipped with a stirrer, heating jacket, condenser, dropping funnel, nitrogen gas inlet / outlet, and thermometer Medium, under a nitrogen stream, 4.86 parts by weight of methyl methacrylate (MMA), 0.81 part of trimethoxysilylpropyl methacrylate (SMA), 2-
(2-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole (trade name: RUVA-
93, Otsuka Chemical Co., Ltd.) 2.43 parts by weight, 1, 2,
A reaction solution obtained by dissolving 0.08 parts by weight of 2,6,6-pentamethyl-4-piperidyl methacrylate (trade name: MARK LA-82, manufactured by Adeka Argus Chemical Co., Ltd.) in 7.1 parts by weight of toluene was used to prepare a reaction solution. After heating to ℃, a solution prepared by dissolving 0.4 parts by weight of azobisbutyronitrile in 2.6 parts by weight of toluene was added dropwise, and the mixture was further reacted at 90 ° C. for 4 hours to obtain a mixture having a weight average molecular weight Mw = 5000. A 40% toluene solution of an acrylic resin was obtained. This is B-
No. 6.

Preparation conditions for B-6: monomer molar ratio MMA / SMA / RUVA-93 /
LA-82 = 6/1/3 / 0.1 Weight-average molecular weight 5000 5000 Solid content 40% <Preparation Example B-7> Stirrer, heating jacket, condenser, dropping funnel, nitrogen gas inlet / outlet And 4.86 parts by weight of methyl methacrylate (MMA), 0.81 part of trimethoxysilylpropyl methacrylate (SMA), and 2-hydroxy-4- (methacryloxyethylethoxy) in a flask equipped with a thermometer and a nitrogen stream. After heating a reaction solution obtained by dissolving 2.43 parts by weight of benzophenone (trade name: ULS-611, manufactured by YAS Co., Ltd.) in 7.1 parts by weight of toluene to 90 ° C., azobisbutyronitrile 0 A solution obtained by dissolving 0.4 parts by weight in 2.6 parts by weight of toluene was added dropwise, and the mixture was further reacted at 90 ° C. for 4 hours to obtain a weight average molecular weight Mw = 50. 0 to obtain 40% toluene solution of an acrylic resin. This is called B-7.

Preparation conditions of B-7: monomer molar ratio MMA / SMA / ULS-611 =
6/1/3-Weight average molecular weight 5000-Solid content 40% <Adjustment example B-8> In a flask equipped with a stirrer, heating jacket, condenser, dropping funnel, nitrogen gas introduction / exhaust hole, and thermometer. Under a nitrogen stream, 4.86 parts by weight of methyl methacrylate (MMA), 0.81 part by weight of trimethoxysilylpropyl methacrylate (SMA), 2,
4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine (T-
(UVA) A reaction solution in which 2.43 parts by weight was dissolved in 7.1 parts by weight of toluene was heated to 90 ° C., and then 0.4 parts by weight of azobisbutyronitrile was dissolved in 2.6 parts by weight of toluene. Was added dropwise and reacted at 90 ° C. for further 4 hours to obtain a 40% toluene solution of an acrylic resin having a weight average molecular weight Mw = 5000. This is called B-8.

Condition for adjusting B-8: monomer weight ratio MMA / SMA / T-UVA = 6 /
As 1/3 Weight average molecular weight 5000, solids content 40% <Preparation Example TINUVIN (for Comparative Example)> benzotriazole ultraviolet absorbent, is -R ⁷ benzotriazole derivative represented by the following general formalized 1 -C (CH _{3) 3}
Wherein -R ⁸ is -C ₂ H ₄ COOC ₈ H ₁₇ benzotriazole ultraviolet absorber (trade name “TINUVI
N384 ", manufactured by CIBA-GAIGY) 2.6 parts. This ultraviolet absorbent is different from the acrylic resin (B) used as the component (B) of the ultraviolet absorbent coating material resin composition of the present invention, and is used as a single ultraviolet absorbent. A 40% toluene solution of this component is called TINUVIN (for comparison).

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<Preparation Example B-9 (for Comparative Example)> In a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, a nitrogen gas inlet / outlet, and a thermometer, n-butyl was added under a nitrogen stream. Methacrylate (BMA) 2.2
1 part, 2- (2-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole (trade name: R
UVA-93 (manufactured by Otsuka Chemical Co., Ltd.) (2.43 parts) and 0.784 parts of γ-mercaptopropylmethoxysilane as a chain transfer agent dissolved in 8.49 parts of toluene were added with azobisisobutyronitrile. A solution of 025 parts in 3 parts of toluene was added dropwise and reacted at 70 ° C. for 2 hours to obtain a 40% toluene solution of an acrylic resin having a weight average molecular weight Mw = 1000. This is B-9
(For comparison).

Preparation conditions of B-9 (for comparison) Monomer molar ratio BMA / SMA / RUVA-93 =
7/0/3 Weight average molecular weight 1000 Solid content 40% (Preparation example of component C): <Preparation example C-1> A flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, and a thermometer. 149.5 parts (1 mol) of methyltrichlorosilane and 150 parts of toluene were weighed into the mixture, and 108 parts of a 1% aqueous hydrochloric acid solution was added dropwise to the mixed solution over 20 minutes while stirring, so that methyltrichlorosilane was added to 60 parts. Hydrolyzed at ° C. Forty minutes after the completion of the dropwise addition, stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand to separate into two layers. By separating and removing the hydrochloric acid aqueous solution in the lower layer, washing and removing the hydrochloric acid remaining in the resin solution of the remaining toluene, and further removing the toluene under reduced pressure, the residue is diluted with isopropyl alcohol.
An isopropyl alcohol solution of the silanol group-containing polyorganosiloxane having a weight average molecular weight (Mw) of about 2000 was obtained. This is called C-1. The solid content of this solution C-1 in terms of the total condensed compound is 40%. It has also been confirmed that the silanol group-containing polyorganosiloxane in C-1 satisfies the above average composition formula (III).

<Preparation Example C-2 (containing phenyl group)> 1000 parts of water and 50 parts of acetone were weighed into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer. And 44.8 parts (0.3 mol) of methyltrichlorosilane and 84.6 parts (0.4 mol) of phenyltrichlorosilane in toluene 200
The solution dissolved in the part was hydrolyzed at 60 ° C. while dripping under stirring. Forty minutes after the completion of the dropwise addition, stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand to separate into two layers. The lower layer liquid containing hydrochloric acid was separated and removed, and water and hydrochloric acid remaining in the toluene solution of the polyorganosiloxane remaining were distilled off together with excess toluene by vacuum stripping to obtain a weight average molecular weight ( Mw) A toluene solution of about 3000 silanol group-containing polyorganosiloxane was obtained. This is called C-2. The solid content in terms of the total condensed compound in this solution C-2 is 60%. Further, it has been confirmed that the silanol group-containing polyorganosiloxane in C-2 satisfies the above average composition formula (III). (D component): N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane was used. This is called D-1. (Preparation Example of Component E): <Preparation Example E-1> In a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, a nitrogen gas inlet / outlet, and a thermometer, under a nitrogen stream, n-butyl. 5.69 parts of methacrylate (BMA), 1.24 parts of trimethoxysilylpropyl methacrylate (SMA), 0.71 part of glycidyl methacrylate (GMA), and 0.784 part of γ-mercaptopropylmethoxysilane as a chain transfer agent are added to toluene 8 A solution obtained by dissolving 0.025 part of azobisisobutyronitrile in 3 parts of toluene was dropped into a reaction solution dissolved in .49 parts, and reacted at 70 ° C. for 2 hours to obtain an acrylic having a weight average molecular weight Mw = 1000. A 40% toluene solution of the resin was obtained. This is called E-1.

Preparation conditions for E-1: monomer molar ratio BMA / SMA / GMA = 8/1 /
1. Weight average molecular weight 1000 Solid content 40% The following Examples and Comparative Examples were carried out using each component obtained as described above. (Examples 1 to 16 and Comparative Examples 1 to 3): Components shown in Tables 1 to 4 (other than the component (D)) were mixed at the ratios shown in the same table, and then the components shown above as the component (D) were mixed. They were mixed at the ratios shown in the same table. Thereafter, each of the obtained mixtures was diluted with isopropyl alcohol so as to have a solid content of 20%, so that the UV-absorbing coating resin composition of each example and the comparative UV-absorbing coating resin composition of each comparative example were prepared. I got

Next, each of the ultraviolet absorbing coating material resin compositions obtained above was applied on a quartz plate washed with ethanol so as to have a cured coating thickness of about 10 μm.
By curing at 30 ° C. for 30 minutes, a quartz plate having an ultraviolet absorbing layer was obtained. With respect to the quartz plate having the ultraviolet absorbing layer, the reduction rate of the ultraviolet absorbing ability was evaluated by the following test methods, and the results are shown in Tables 1 to 4. (Testing method for the rate of decrease in ultraviolet absorption capacity): An accelerated weathering tester (manufactured by Suga Test Instruments Co., Ltd., trade name "Sunshine Super Long Life Weather Meter", model number WEL-SUN-HC type) was used for the test sample. An accelerated weathering test was performed for 2,000 hours, and an accelerated test for a decrease in ultraviolet absorbing ability was performed. The ultraviolet absorption of the test sample before and after the accelerated weathering test was measured using a spectroscopic property tester, and the rate of decrease in ultraviolet absorption was calculated from the following equation.

Reduction rate of ultraviolet absorption capacity = (1—UV absorption rate after accelerated weathering test / UV absorption rate before accelerated weathering test)
× 100 However, the range of the ultraviolet absorptivity was 300 nm to 380 nm.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

From the results of Tables 1 to 4, it was confirmed that the rate of decrease in the ultraviolet absorbing ability of each of the examples was smaller than that of the comparative examples.

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The UV-absorbing coating material resin composition according to any one of claims 1 to 5, wherein the component (B) having UV-absorbing ability is a matrix resin of the coating film when the applied cured coating film is formed. It is fixed in the skeleton, and the compatibility between the matrix resin and the UV absorbing component is also improved. Irradiates a cured coating film whose ultraviolet absorption ability does not easily decrease. In the resin composition for an ultraviolet absorbing coating material according to the second aspect, since R ^{4 of the} component (C) is a phenyl group, the compatibility between the component (B) and the component (C) is improved.

The resin composition for ultraviolet absorbing coating material according to claim 3 further contains the component (E).
The toughness of the applied and cured film, the adhesion of the film to the substrate, the compatibility of the component (B), and the like are improved. In the ultraviolet absorbing coating material resin composition according to claim 4, the (B)
Since the components have a weight average molecular weight in the predetermined range,
It is possible to prevent the component (B) from phase separation and whitening of the coating film. In the resin composition of the ultraviolet absorbing coating material according to the fifth aspect, since the compounding amount of the component (B) is the predetermined ratio, a sufficient ultraviolet absorbing effect is exhibited without causing curing inhibition of the coating film. be able to.

The coated article according to the sixth aspect is the above-mentioned first aspect.
5. Since the ultraviolet absorbent coating layer comprising the applied cured film of the ultraviolet absorbent coating material resin composition according to any one of the above items 5 to 5 is provided, the ultraviolet absorbent coating material resin composition and the ultraviolet absorption formed therefrom are provided. It has the above-mentioned various excellent properties and advantages derived from the coating film.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takeyuki Yamaki 1048 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Works, Ltd. (72) Inventor Koichi Takahama 1048 Kazuma Kadoma, Kazuma City, Osaka Matsushita Electric Works Co., Ltd. (72 ) Inventor Kazuhiro Kono 463, Kasuno, Kawauchi-cho, Tokushima-shi, Otsuka Chemical Co., Ltd. (72) Inventor Koji Mori 463, Kasuno-cho, Kawauchi-cho, Tokushima-shi, Otsuka Chemical Co., Ltd. 3-27 Ote-dori, Chuo-ku Otsuka Chemical Co., Ltd. F-term (reference) 4J038 CG032 CG142 CL002 DL021 DL041 DL052 GA03 HA446 JC32 MA14 NA19

Claims (6)

[Claims] 1. The following (A), (B), (C) and (D)
An ultraviolet absorbing coating material resin composition containing a component. 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) Hydrolyzable organosilane is partially hydrolyzed in colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof in the presence of water. A silica-dispersed oligomer of an organosilane. Component (B): a monomer represented by the general formula CH ₂ ＣＲCR ² (COOR ³ ) (II) (where R ² represents a hydrogen atom and / or a methyl group), wherein R ³ is a hydrogen atom Or a substituted or unsubstituted C 1-9
First and (meth) acrylic acid ester is a valence hydrocarbon group, at least 1 R ³ is selected from the group consisting of a hydrocarbon group containing at least one of an alkoxysilyl group, a halogenated silyl group, and their A second group (meth) acrylate which is a kind group or a siloxy group, and a ^third group wherein R ³ is a hydrocarbon group containing an ultraviolet absorbing group.
An acrylic resin obtained by copolymerizing a monomer containing at least the above (meth) acrylate. Component (C): represented by an average composition formula R ⁴ _a Si (OH) _b O _{(4-ab) / 2} (III) (where R ⁴ 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 + b <4), a polyorganosiloxane containing a silanol group in the molecule. (D)
Component: curing catalyst. 2. The ultraviolet absorbing coating material resin composition according to claim 1, wherein R ^{4 of the} component (C) is a phenyl group. 3. The ultraviolet absorbent coating material resin composition according to claim 1, further comprising the following component (E). Component (E): a monomer represented by the general formula CH ₂ ＣＲCR ⁵ (COOR ⁶ ) (IV) (where R ⁵ represents a hydrogen atom and / or a methyl group), wherein R ⁶ is substituted or A group consisting of an unsubstituted first (meth) acrylic acid ester which is a monovalent hydrocarbon group having 1 to 9 carbon atoms, wherein R ⁶ is an epoxy group, a glycidyl group or a hydrocarbon group containing at least one of these; A second (meth) acrylic ester which is at least one group selected from the group consisting of: and a third (meth) acryl wherein R ⁶ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. An acrylic resin obtained by copolymerizing monomers containing at least an acid ester. 4. The composition according to claim 1, wherein said component (B) is 1,000 to 10,000.
The ultraviolet absorbent coating material resin composition according to any one of claims 1 to 3, having a weight average molecular weight within the range of. 5. The amount of said component (B) is as follows:
(C) 0.1 to 100 parts by weight of the total solid content of the component.
The ultraviolet absorbing coating material resin composition according to any one of claims 1 to 4, which is in a proportion of 100 parts by weight. 6. A coated article comprising a substrate and a UV-absorbing coating layer comprising a cured coating of the resin composition for UV-absorbing coating material according to any one of claims 1 to 5.