JP2001310919A - Resin composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having a high weather resistance, an excellent hardness, a high heat resistance and an excellent/surface stain-proof property for various kinds of substrates and also is excellent in durabilities of the properties, and to provide a resin composition for coating. SOLUTION: The resin is provided by copolymerization of a (a1) poly dialkyl siloxane having at least one ethylenic unsaturated group per molecule, an (a2) organopoly silsesquioxane, an (a3) alkoxy silane having an ethylenic unsaturated group and a (a4) compound having an ethylenic unsaturated group [however, (a1), (a2) or (a3) is excepted]. The resin composition for coating is provided by containing the resin (A), the curing accelerator (B) and the organosilicate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin used as a coating material for various substrates. Further relates to a resin composition for top coat used for the purpose of modifying the surface of various substrates, more specifically, high weather resistance, high hardness, high heat resistance, excellent in stain resistance represented by magic repellency The present invention relates to a resin composition for coating.

[0002]

2. Description of the Related Art Weather resistance is achieved by a coating method (coating).
As a material for imparting water repellency, oil resistance, magic repellency, releasability, etc. to the surface of various substrates, a fluorine compound or a fluorine resin, a silicone compound or a silicone resin having a small surface energy is generally used. In particular, silicone-based compounds and silicone-based resins have attracted attention as environmentally friendly materials in recent years. Among them, silicone-based resins have been spotlighted from the viewpoints of non-staining properties, weather resistance, heat resistance, and high hardness.

Examples of the silicone resin used for this purpose include a resin obtained by copolymerizing a monomer or oligomer containing silicon and having a radical polymerizable reactive group such as a vinyl group with another vinyl monomer. Examples include resins obtained by grafting a silicon-containing monomer or oligomer to various resins. In addition, there are resins in which a silicon-containing compound having a reactive group such as an epoxy group, an amino group, and a mercapto group is introduced into various resins, and further, a resin in which a silicon-containing resin, an oligomer, or the like is mixed with another resin.

In recent years, radical-polymerizable silicone macromonomers and other polymers have been developed as silicone resins having not only the characteristics possessed by silicone but also excellent modification effects and long-lasting performance without impairing the inherent performance of coating films. High weather resistant paint using a copolymer of a radical polymerizable monomer (JP-A-61-151272) and an active energy ray-curable silicone graft polymer obtained by copolymerizing a compound having an active energy ray-reactive functional group ( Showa 61
No. -19606), a coating composition comprising a copolymer obtained by copolymerizing a silicone macromonomer, an acrylic monomer and a monomer having a hydrolyzable silyl group (Japanese Patent Laid-Open No. Sho 62).
-275132) and the like have been proposed.

[0005] JP-A-61-151272 discloses that
A graft copolymer of a radical polymerizable compound mainly composed of (meth) acrylate and a radical polymerizable silicone macromonomer, and a highly weather-resistant paint mainly composed of a graft copolymer obtained by adding a crosslinkable monomer thereto have been proposed. However, the hardness is not sufficient and the heat resistance is not high.

Similarly, the silicone macromonomer copolymers disclosed in JP-A-61-19606, JP-A-1-146983, JP-A-62-275132 and the like also have weather resistance, high hardness and heat resistance. Properties and magic repellency are not sufficient, and especially heat resistance and high hardness are not sufficient.

[0007] Further, as a composition for a paint containing a copolymer having a hydrolyzable alkoxysilyl group as a component, a vinyl polymer and γ-methacryloxypropyltrimethoxysilane as a trifunctional alkoxysilyl group-containing monomer are used. Containing a copolymer obtained by radical copolymerization of
No. 9-45130), a composition containing a copolymer of a vinyl polymer and a bifunctional alkoxysilyl group-containing monomer (Japanese Patent Publication No. 63-60046), and further a vinyl polymer and a mono- to tri-functional alkoxy. A composition in which an acid anhydride and a specific polyamine compound are added to a copolymer with a silyl group-containing monomer (JP-A-4-168171) has been proposed.

[0008] However, none of them exhibit a stain removal property represented by magic repellency and a sufficient heat resistance.

As described above, the conventional coating resin composition has the properties required for the coating resin, that is, sufficient water repellency, weather resistance, high hardness, high heat resistance, non-staining property, etc., on the surface of various substrates. Was not sufficiently provided by one kind of paint.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a coating resin which can impart high weather resistance, high hardness, high heat resistance and non-staining properties to the surface of various substrates and which has excellent sustained stability. Is to provide. Still another object of the present invention is to provide a coating resin composition containing the resin.

[0011]

DISCLOSURE OF THE INVENTION The present inventors have developed a coating resin and a coating resin composition having high weather resistance, high hardness, high heat resistance, and excellent non-staining properties represented by magic repellency. As a result of diligent studies to obtain, a specific organopolysiloxane, an organopolysilsesquioxane and a coating resin incorporating a hydrolyzable alkoxysilyl group capable of forming a crosslinked structure into the molecular skeleton and the resin It has been found that the above object can be achieved by the coating resin composition, and the present invention has been completed.

That is, the present invention relates to the following matters. [1] A polydialkylsiloxane having at least one ethylenically unsaturated group per molecule (a1), an organopolysilsesquioxane having an ethylenically unsaturated group (a2), an alkoxysilane having an ethylenically unsaturated group Compound (a3) and a compound having an ethylenically unsaturated group [however, excluding (a1), (a2) and (a3)]. ] A resin obtained by copolymerizing (a4). [2] The polydialkylsiloxane (a1) is represented by the following general formula (1):

Embedded image (Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms), and a compound having an organic group having an ethylenically unsaturated group as a terminal group. Yes, organopolysilsesquioxane (a2)
Is the following general formula (2),

Embedded image (Wherein, R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms or an organic group having an ethylenically unsaturated group, and the organic group having an ethylenically unsaturated group is 5 to 60)
Mol%. ) And the following general formula (3):

Embedded image (Wherein, R ³ and R ⁴ have the same meaning as described above. R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a trimethylsilyl group, of which 30 mol%
The above is the trimethylsilyl group. ) Is a compound having a terminal group represented by the formula:
3) is the following general formula (4),

Embedded image (However, R ⁷ represents an alkyl group having 1 to 4 carbon atoms,
R ⁸ represents an organic group having an ethylenically unsaturated group. [1]
The resin described in the above. [3] 0.5 to 10% by mass of the component (a1), (a2)
Component 0.5 to 20% by mass, component (a3) 1 to 60% by mass, component (a4) 10 to 98% [where (a1)
The sum of the components (a4) to (a4) is 100%. ] The resin according to [1] or [2], obtained by copolymerizing [4] The resin according to [1] to [3], wherein the polydialkylsiloxane (a1) has a number average molecular weight of 500 to 50,000.

[5] Polydialkylsiloxane (a
The resin according to [1] to [4], wherein the ethylenically unsaturated group in 1) is a vinyl group or a substituted vinyl group. [6] A coating resin composition comprising the resin (A) according to [1] to [5] and a curing accelerator (B). [7] The coating resin composition according to [6], wherein the curing accelerator (B) is 0.1 to 10 parts by mass based on 100 parts by mass of the resin (A). [8] The curing accelerator (B) is at least one compound selected from the group consisting of organotin compounds, phosphorus compounds, epoxy compounds, organic zirconium compounds, organic acid compounds and amines [ 6] or the resin composition for coating according to [7].

[9] The coating resin composition according to any one of [6] to [8], which contains an organosilicate (C). [10] The resin composition for coating according to [9], wherein the organosilicate (C) is a compound selected from the group consisting of tetramethoxysilane, tetraethoxysilane, and a hydrolyzed condensate thereof. [11] Organosilicate (C) is resin (A) 10
The coating resin composition according to [9] or [10], which is 200 parts by mass or less based on 0 parts by mass. [12] A paint containing the resin or the resin composition for coating according to [1] to [11].

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The term “(meth) acryl” used in the present invention represents “methacryl” and / or “acryl”. Polydialkylsiloxane (a1) having at least one ethylenically unsaturated group per molecule used in the resin (A) of the present invention
Are linear silicone oligomers having an organic group having a (meth) acrylate-type ethylenically unsaturated group at the terminal of the molecular chain. Examples thereof include JP-A-58-154766, JP-A-59-126478, and JP-A-59-126478. Examples thereof include silicone macromonomers described in JP-A-59-20360 and JP-A-61-151272, which can be used in the present invention. Preferably, the following general formula (1):

Embedded image (Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms), and a compound having an organic group having an ethylenically unsaturated group as a terminal group. is there.

The preferred range of the molecular weight of the polydialkylsiloxane (a1) is that the number average molecular weight is from 500 to 5
It is 0000.

When the number average molecular weight is less than 500, the stability of magic repellency is insufficient, and when the number average molecular weight exceeds 50,000, the compatibility of the resin and the coating on the base material are reduced. Lack of (coating) properties, especially about 1
When coating is performed with a thickness of less than g / m ^2, the thickness may be uneven, which is not preferable.

Further, polydialkylsiloxane (a1)
Is preferably 0.5 to 10 with respect to the resin (A).
% By mass. When the amount used is less than 0.5% by mass, the sustainability of the magic repellency is insufficient, while when the amount used exceeds 10% by mass, the coating properties on the substrate, especially the thin film coating properties, are lacking. . In addition, when used in combination with another resin, the compatibility becomes poor.

The polyorganosilsesquioxane having an ethylenically unsaturated group (a2) used in the present invention has been reported by Nakahama et al. [Poymer Preprints Japan].
29 (1) P. 73 (1980)] and Japanese Patent Laid-Open No.
81616, JP-A-4-28722, JP-A-6-2
As known in JP 87307 and the like, for example, it can be obtained by hydrolyzing and co-condensing a trialkoxysilane having an ethylenically unsaturated group such as a vinyl group and a (meth) acryl group with an alkyltrialkoxysilane. Its main structure is an oligomer having an organic group having an ethylenically unsaturated group in its side chain, an alkyl group, and the like, and having a number average molecular weight of several hundreds to tens of thousands in which the main skeleton of the molecule is ladder-like.

The polyorganosilsesquioxane (a)
Examples of the trialkoxysilane having an ethylenically unsaturated group such as a vinyl group and a (meth) acryl group used in the production of 2) include vinyltrimethoxysilane, vinyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ- Acryloxypropyltriemethoxysilane,
γ-methacryloxypropyltrimethoxysilane, γ-
Methacryloxypropyltriethoxysilane is exemplified. Further, instead of the trialkoxysilane, a trihalosilane can be used. Examples of the trihalosilane include vinyltrichlorosilane, γ-acryloxypropyltrichlorosilane, γ-methacryloxypropyltrichlorosilane, and the like.

The above polyorganosilsesquioxane (a)
Examples of the alkyltrialkoxysilane used in the production of 2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, and the like. An alkyltrihalosilane is used instead of the alkyltrialkoxysilane. May be
Examples thereof include methyltrichlorosilane and ethyltrichlorosilane, and silane compounds having a substituted or unsubstituted phenyl group such as phenyltrimethoxysilane, phenyltriethoxysilane or phenyltrichlorosilane.

One or more of these silane compounds and alkylsilane compounds having an ethylenically unsaturated group can be used.

The polyorganosilsesquioxane (a2) of the present invention preferably has the following general formula (2):

Embedded image (Wherein, R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms or an organic group having an ethylenically unsaturated group, and the organic group having an ethylenically unsaturated group is 5 to 60)
Mol%. ) And the following general formula (3):

Embedded image (Wherein, R ³ and R ⁴ have the same meaning as described above. R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a trimethylsilyl group, of which 30 mol%
The above is the trimethylsilyl group. ) Is a compound having a terminal group represented by the formula:

Organopolysilsesquioxane (a2)
For example, those having a main chain terminal capped with a silylating agent, such as a functional organopolysilsesquioxane described in JP-A-8-73593, can be preferably used. The amount of the organopolysilsesquioxane (a2) used is 0.5 to 20% by mass, preferably 1.0 to 15% by mass, based on the mass of the resin (A). If the amount used is less than 0.5% by mass, the heat resistance and stain resistance of the resin are insufficient, whereas if the amount used exceeds 20% by mass, gelation tends to occur during polymerization, and the curing agent ( Not only is the pot life of the coating resin composition obtained by blending B) in a predetermined amount remarkably lacking, but it is economically unfavorable.
Further, the content of the organic group having an ethylenically unsaturated group [for example, a (meth) acryloxy group] in the organopolysilsesquioxane (a2) is about the total side chain of the polysilsesquioxane (a2). 5 to 60 mol%, preferably 8 to
It is 50 mol%, more preferably 8 to 40 mol%. When the content of the organic group having an ethylenically unsaturated group is less than 5 mol%, the curability of the coating resin composition containing a predetermined amount of the organosilicate (C) is insufficient, and is 60 mol%. If it exceeds, gelation tends to occur during the polymerization reaction of the resin (A), and the raw material price becomes large, which is not economically preferable.

The alkoxysilane compound having an ethylenically unsaturated group (a3) used in the present invention is a trialkoxysilane compound having an organic group having an ethylenically unsaturated group. Preferably, the following general formula (4):

Embedded image (However, R ⁷ represents an alkyl group having 1 to 4 carbon atoms,
R ⁸ represents an organic group having an ethylenically unsaturated group. ). Examples include vinyltrimethoxysilane, vinyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and the like. .

The alkoxysilane compound (a3) of the present invention
Is 1 to 60% by mass based on the mass of the resin (A). When the amount is less than 1% by mass, the heat resistance is poor and the hardness does not increase. If the amount used is 60% by mass or more, swelling tends to occur during the polymerization reaction of the resin (A), and this is not economically advantageous.

The compound (a4) having an ethylenically unsaturated group other than the above used in the production of the resin (A) of the present invention is not particularly limited, and may be any compound that can be relatively easily copolymerized.

That is, such a compound is a polymerizable unsaturated group compound substituted with a straight-chain, branched or cyclic saturated or unsaturated hydrocarbon having 1 to about 20 carbon atoms, For example, (meth) acrylic acid, maleic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate,
Isobutyl (meth) acrylate, (meth) acrylic acid 2
-Ethylhexyl, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, ethylene, propylene, butylene-1, ethyl vinyl ether, isobutyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, capron Examples thereof include vinyl acid, vinyl pivalate, acrylonitrile, methacrylonitrile, styrene, vinyl toluene, α-methylstyrene, acrylamide, methacrylamide, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and the like.

The number average molecular weight of the resin (A) of the present invention thus obtained is not particularly limited.
Approximately 2,000-200,000, preferably 5,
000 to 50,000. The curing accelerator (B) of the present invention is a curing catalyst which causes the alkoxysilyl groups of the resin (A) to react with each other and / or the alkoxysilyl group and the later-described organosilicate (C) to cause the resin to crosslink. Specific examples include organic tin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, tin octylate; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monoacryloyl phosphate, monooctyl phosphate, monodecyl phosphate , Dimethyl phosphate, diethyl phosphate, dibutyl phosphate, diacryloyl phosphate, dioctyl phosphate, phosphorus-based compounds such as phosphate esters such as didecyl phosphate: propylene oxide, butylene oxide, cyclohexene oxide,
Glycidyl methacrylate, glycidol, acrylic glycidyl ether, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane,
Epoxy compounds such as glycidoxypropylmethyldimethoxysilane, glycidyl ether type epoxy resin and alicyclic epoxy resin; organic aluminum compounds such as aluminum tris (ethylacetoacetate) and aluminum tris (acetylacetonate); tetrabutyl zirconate And organic zirconium compounds such as tetrakis (acetylacetonato) zirconium, tetraisobutylzirconate, butoxytris (acetylacetonato) zirconium: oxalic acid, maleic acid, adipic acid, itaconic acid, citric acid, succinic acid, phthalic acid, tricarboxylic acid Organic acid compounds such as melitic acid, pyromellitic acid, and their anhydrides and paratoluenesulfonic acid; hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecyla Down, amines such as dodecyl amine, and the like. Preferably, a mixture of two or more of these compounds may be used.

The amount of the curing accelerator (B) in the coating resin composition of the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin (A). When the amount is less than 0.1 part by mass, the accelerated curing is small, and when the amount is more than 10 parts by mass, the curing is too fast, the pot life of the liquid of the resin composition is shortened, and not only the coating property is lowered, but also the physical properties of the coating film are deteriorated.

The organosilicate (C) of the present invention is a tetraalkoxysilane compound or a hydrolyzed condensate thereof, for example, tetramethoxysilane, its hydrolyzed condensate (methylsilicate), tetraethoxysilane, its hydrolysis There is a condensate (ethyl silicate).

The amount of the organosilicate (C) used in the coating resin composition of the present invention is 100 (A).
It is preferably 200 parts by mass or less based on parts by mass. If the amount of the organosilicate (C) is large, the heat resistance is increased, but if it exceeds 200 parts by mass, the coating film becomes brittle and the coatability becomes poor.

The resin (A) of the present invention is produced by a radical polymerization reaction usually used in an organic solvent, and is obtained as a solution of the organic solvent used for the reaction in the resin (A). When preparing the coating resin composition of the present invention, a curing accelerator (B) and / or an organosilicate (C) may be added to the resin (A) solution and blended. Further, the resin (A) solution may be added to a solution further diluted with an organic solvent.

Examples of the organic solvent used for dilution include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as methyl acetate, ethyl acetate, butyl acetate and cellosolve acetate, and aromatic hydrocarbons such as toluene and xylene. Hydrogens, ethers such as tetrahydrofuran and dioxane, methanol, ethanol isopropyl alcohol, butanol,
Examples include alcohols such as ethylene glycol and propylene glycol. Generally, the organic solvents are often used in a mixture of two or more.

The coating resin composition of the present invention may contain, if necessary, known antioxidants, light stabilizers, heat stabilizers, coloring agents, flame retardants, fillers as long as the desired performance is not lost. Agents, plasticizers and the like may be blended.

The coating resin composition of the present invention may be prepared by adding an organic solvent to a composition comprising a resin (A), a curing accelerator (B) and / or an organosilicate (C), if necessary, in a coating or coating industry. It can be manufactured by a known method generally adopted between the parties. It is better to mix the resin (A), the curing accelerator (B) and / or the organosilicate (C) immediately before coating in consideration of the pot life. Further, other compatible acrylic resin, polyester resin, or the like can be added within a range that does not affect the effect of the present invention.

The coating resin composition of the present invention thus diluted to an appropriate solid content can be coated with a conventional coating apparatus such as spray coating, roll coating, curtain coating, brush coating, etc.
Various substrates are coated by a coating method.

The crosslinking reaction by curing after coating may be performed at room temperature, but may be performed by heat treatment. The heat treatment accelerates the development of hardness.

As a method of the heat treatment, a method generally employed in the art, for example, a heat oven,
A method using an infrared heater or the like can be applied.

In general, 50-200 ° C., especially 80
１５０150 ° C., and if necessary, after heating and curing, to further complete the curing, for example, 40 to 60 ° C.
Aging can be performed for several hours to several days in a temperature atmosphere at about the same level.

[0041]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, each physical property value in an Example and a comparative example was measured according to the following method.

(1) Weather Resistance A coating resin composition having a solid content adjusted to 30% by mass is applied onto a surface of an urethane coated film of an aluminum substrate which has been previously primed with a commercially available white urethane coating, and then cured by a spray method. The film was applied so that the film thickness became 25 to 30 μm, left to cure at room temperature for 24 hours, and then aged at 80 ° C. for 1 hour to form a cured coating film. This coated substrate is
According to the ultraviolet fluorescent lamp type test method of the SD0205 method,
The gloss retention (%) after irradiation for 3,000 hours was measured.

(2) The surface of an aluminum substrate previously sanded with a coating resin composition having a solid content adjusted to a hardness of 30% by mass,
The coating was applied by a spray method so that the thickness of the coating after curing was 25 to 30 μm, and left at room temperature for 24 hours to form a cured coating. Further, aging was performed at 80 ° C. for 1 hour to form a cured coating film. These two types of coating films were measured by a pencil hardness test in accordance with JIS-5400.

(3) Heat resistance A coating resin composition having a solid content adjusted to 30% by mass is applied to a surface of an aluminum substrate which has been previously subjected to a sanding treatment, and the coating film thickness after curing by a spray method is 25 to 30 μm.
And cured at room temperature for 24 hours, followed by aging at 80 ° C. for 1 hour to form a cured coating film. This coating film was exposed in an oven at 200 ° C. for 48 hours, and evaluated by discoloration of the coating film after cooling at room temperature.

(4) Magic repellency A coating resin composition having a solid content adjusted to 30% by mass was spray-cured on an urethane coated surface of an aluminum substrate previously coated with a commercially available white urethane paint. The coating was applied so that the coating thickness became 25 to 30 μm, and the coating was left standing at room temperature for 24 hours to be cured. After that, aging was further performed at 80 ° C. for 1 hour to form a cured coating. A thick line having a width of 6 mm was drawn with a length of about 3 cm using an oil-based ink (Zebra “Mackey (oil-based)” black) on the surface of the coating film, and the “repellency” of the ink was visually observed. After standing at room temperature, the wiping-removal property was evaluated with a tissue paper Magic cissing property ○: There was repelling on the whole △: Some repelling was not performed, but some parts were not repelled ×: No repelling was possible Magic removing property ○: Wipeable △: Can be wiped off, but remains partially ×: Cannot be wiped

Production Example 1 [ Production of organopolysilsesquioxane (a2-1)] γ-methacryloxypropyltrimethoxysilane was placed in a 300 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. 24.84g (100mmo
l), 160.48 g of methyltriethoxysilane (90
0 mmol) and 54.06 g (3,000 mmol) of pure water.
l) was charged, and the solution temperature was maintained at 5 ° C. while stirring under a nitrogen stream. Then, a 3.6 mass% hydrochloric acid aqueous solution 1
After 0.13 g was added dropwise over 30 minutes, the solution temperature was raised to 10
C. for 60 minutes. The solution was heated to 70.degree.
Reaction for 0 minutes, then hexamethylsiloxane 2
4.9 g (153.35 mmol) was added and the silylation reaction was performed at 70 ° C. for 180 minutes. The obtained reaction solution was cooled to 40 ° C., and 13.2 g of a 4.25% by mass aqueous potassium hydroxide solution was added to neutralize the inside of the system, and the system was allowed to stand at room temperature for 12 hours. The lower layer portion of the liquid separated into two layers was collected, and 100 g of butyl acetate was added to the lower layer solution.
After concentrating under reduced pressure of 0 ° C./266 hPa, 100 g of the liquid was distilled off, and then 350 g of butyl acetate was further added at room temperature, followed by stirring for 60 minutes. The obtained solution was filtered through a 0.8 μm filter to give a colorless and transparent solution 44.
0 g was obtained. The number average molecular weight of the obtained organopolysilsesquioxane was determined by GPC (Gel Permeatio).
n Chromatography) and 3500
Met. As a result of the GPC analysis, no peak derived from the raw material silane monomer was detected, and it was considered that the obtained organopolysilsesquioxane contained no unreacted monomer. 1H-, 13C- and 29
From the analysis of the Si-NMR spectrum, the molar ratio of the side chain γ-methacryloxypropyl group and methyl group was equal to the molar ratio of the charged silane monomer, and was 1: 9. This organopolysilsesquioxane is hereinafter abbreviated as polymer (a2-1).

Production Example 2 [ Production of organopolysilsesquioxane (a2-2)] Using the same apparatus as in Production Example 1, 74.51 g of γ-methacryloxypropyltrimethoxysilane (300 mmol)
l), 124.82 g of methyltriethoxysilane (70
Except for 0 mmol), it was produced under the same conditions as in Production Example 1.
The number average molecular weight of the obtained organopolysilsesquioxane was 2,500 as measured by GPC. As a result of the GPC analysis, no peak derived from the raw material silane monomer was detected, and it was considered that the obtained organopolysilsesquioxane contained no unreacted monomer. From the analysis of 1H-, 13C- and 29Si-NMR spectra, the molar ratio of the γ-methacryloxypropyl group and the methyl group in the side chain was equal to the molar ratio of the charged silane monomer, and was 3: 7. This organopolysilsesquioxane is hereinafter abbreviated as polymer (a2-2).

Production Example 3 [ Production of organopolysilsesquioxane (a2-3)] Using the same apparatus as in Production Example 1, 22.35 g (90 mmo) of γ-methacryloxypropyltrimethoxysilane
l), 160.48 g of methyltriethoxysilane (90
0 mmol), 1.98 g of phenyltrimethoxysilane
Except for (10 mmol), it was produced under the same conditions as in Production Example 1. The number average molecular weight of the obtained organopolysilsesquioxane was 3,000 as measured by GPC. As a result of the GPC analysis, no peak derived from the raw material silane monomer was detected, and thus it was considered that there was no unreacted monomer in the obtained organopolysilsesquioxane having a group having an ethylenically unsaturated group. . Also, 1H-,
From the analysis of the 13C- and 29Si-NMR spectra, the molar ratio of the γ-methacryloxypropyl group, methyl group and phenyl group in the side chain was equal to the molar ratio of the charged silane monomer, and was 9: 90: 1. This organopolysilsesquioxane is hereinafter abbreviated as polymer (a2-3).

Production Example 4 Production of Resin A1 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. However, the conversion by GPC was 99%, and a resin A1 having a number average molecular weight of 13,300 and a mass average molecular weight of 58,000 was obtained. AK-32 (polydimethylsiloxane having a terminal methacryloxy group, number average molecular weight: 20,000) (silicon macromer manufactured by Toagosei Co., Ltd.) 1 part by mass Polymer (a2-1) 15 parts by mass γ-acryloxypropyltrimethoxysilane 40 Parts by mass Methyl methacrylate 18 parts by mass n-butyl methacrylate 25 parts by mass 2-ethylhexyl acrylate 1 part by mass azobisisobutyronitrile 1 part by mass butyl acetate 100 parts by mass

Production Example 5 Production of Resin A2 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. However, the conversion by GPC was 99%, and a resin A2 having a number average molecular weight of 15,800 and a mass average molecular weight of 43,000 was obtained. . AK-5 (polydimethylsiloxane having a terminal methacryloxy group, number average molecular weight; 5,000) (silicon macromer manufactured by Toa Gosei Co., Ltd.) 8 parts by mass Polymer (a2-2) 5 parts by mass γ-acryloxypropyltriethoxy Silane 30 parts by mass Methyl methacrylate 10 parts by mass n-butyl methacrylate 45 parts by mass 2-ethylhexyl acrylate 2 parts by mass Azobisisobutyronitrile 1 part by mass 100 parts by mass butyl acetate

Production Example 6 Production of Resin A3 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. However, the reaction rate by GPC was 99%, and a resin A3 having a number average molecular weight of 12,500 and a mass average molecular weight of 37,000 was obtained. . AK-30 (polydimethylsiloxane having a terminal methacryloxy group, number average molecular weight: 30,000) (silicon macromer manufactured by Toagosei Co., Ltd.) 5 parts by mass Polymer (a2-3) 10 parts by mass Vinyltrimethoxysilane 5 parts by mass methacrylic acid Methyl 15 parts by mass n-butyl methacrylate 60 parts by mass 2-ethylhexyl acrylate 5 parts by mass Azobisisobutyronitrile 1 part by mass 100 parts by mass of butyl acetate

Production Example 7 Production of Resin A4 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. However, the conversion by GPC was 99%, and a resin A4 having a number average molecular weight of 13,000 and a mass average molecular weight of 38,000 was obtained. AK-30 (polydimethylsiloxane having a terminal methacryloxy group, number average molecular weight: 30,000) (silicon macromer manufactured by Toagosei Co., Ltd.) 1 part by mass Polymer (a2-3) 5 parts by mass γ-acryloxypropyltriethoxysilane 5 Parts by mass Methyl methacrylate 20 parts by mass n-butyl methacrylate 50 parts by mass 19 parts by mass of 2-ethylhexyl acrylate 1 part by mass azobisisobutyronitrile 1 part by mass 100 parts by mass butyl acetate

Production Example 8 Production of Resin A5 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. However, the reaction rate by GPC was 99%, and a resin A5 having a number average molecular weight of 16,200 and a mass average molecular weight of 42,000 was obtained. . AK-30 (polydimethylsiloxane having a terminal methacryloxy group, number average molecular weight; 30,000) (silicon macromer manufactured by Toagosei Co., Ltd.) 8 parts by mass Polymer (a2-3) 15 parts by mass γ-methacryloxypropyltrimethoxysilane 30 Parts by mass Methyl methacrylate 10 parts by mass n-butyl methacrylate 30 parts by mass 7 parts by mass of 2-ethylhexyl acrylate 1 part by mass azobisisobutyronitrile 1 part by mass 100 parts by mass butyl acetate

Production Example 9 Production of Resin A6 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and reacted at 90 ° C. for 6 hours in a nitrogen stream. However, the reaction rate by GPC was 99%, and a resin A6 having a number average molecular weight of 12,800 and a mass average molecular weight of 62,000 was obtained. . AK-30 (polydimethylsiloxane having a terminal methacryloxy group, number average molecular weight: 30,000) (silicon macromer manufactured by Toa Gosei Co., Ltd.) 5 parts by mass Polymer (a2-3) 10 parts by mass Vinyl trimethoxysilane 50 parts by mass Methyl methacrylate 2 parts by mass n-butyl methacrylate 28 parts by mass 2-ethylhexyl acrylate 5 parts by mass Azobisisobutyronitrile 1 part by mass 100 parts by mass butyl acetate

Comparative Production Example 1 Production of Resin D1 The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and AK-32 was added.
The reaction was carried out in a nitrogen stream at 90 ° C. for 6 hours in the same manner as in Production Example 1 except that the amount of butyl acetate was changed to 99 parts by mass, except that the conversion by GPC was 99% and the number average molecular weight was 10%. , 200, and a resin D1 having a weight average molecular weight of 34,000 were obtained. Polymer (a2-1) 15 parts by mass γ-acryloxypropyltrimethoxysilane 40 parts by mass Methyl methacrylate 18 parts by mass n-butyl methacrylate 25 parts by mass 2-ethylhexyl acrylate 1 part by mass Azobisisobutyronitrile 1 part by mass Parts 99 parts by weight of butyl acetate

Comparative Production Example 2 [ Production of Resin D2] The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and the polymer (a2-1) was removed. Except that the amount of butyl was changed to 85 parts by mass, the same procedure as in the production of the resin A1 was carried out.
When reacted at 6 ° C. for 6 hours, the reaction rate by GPC was 9
9%, a resin D2 having a number average molecular weight of 11,500 and a mass average molecular weight of 32,000 was obtained. AK-32 (polydimethylsiloxane having a terminal methacryloxy group, number average molecular weight: 20,000) (silica gamma-acryloxypropyltrimethoxysilane manufactured by Toagosei Co., Ltd. 40 parts by mass methyl methacrylate 18 parts by mass n-butyl methacrylate 25) Parts by mass 2-ethylhexyl acrylate 1 part by mass azobisisobutyronitrile 1 part by mass butyl acetate 85 parts by mass

Comparative Production Example 3 [ Production of Resin D3] The following composition was placed in a 1 L flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube, and γ-acryloxypropyltrimethoxysilane was removed. In the same manner as in Production Example 4 except that the amount of the polymer (a2-1) was 9 parts by mass and the amount of butyl acetate was 54 parts by mass, the mixture was heated at 90 ° C.
For 6 hours, the reaction rate by GPC was 99%.
%, The number average molecular weight is 8,900, and the mass average molecular weight is 2
8,000 resins D3 were obtained. AK-32 (polydimethylsiloxane having a terminal methacryloxy group, number average molecular weight: 20,000) (silicon macromer manufactured by Toagosei Co., Ltd.) 1 part by mass Polymer (a2-1) 9 parts by mass Methyl methacrylate 18 parts by mass Methacrylic acid n -Butyl 25 parts by mass 2-Ethylhexyl acrylate 1 part by mass Azobisisobutyronitrile 1 part by mass 54 parts by mass of butyl acetate

Example 1 Resin A1 produced by the above method (resin concentration 50% by mass)
And 2 parts by weight of dibutyltin dilaurate and 30 parts by weight of MS-51 (methyl silicate manufactured by Mitsubishi Chemical Corporation) were added to 100 parts by weight of the resin solid content of the resin A1, and ethyl acetate / isopropyl alcohol = 1 The mixture was diluted with a mixed solvent of / 1 so that the resin concentration became 30% by mass, to obtain a resin composition for coating.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency using the resin composition for coating.

Example 2 In the same manner as in Example 1, using resin A2 (resin concentration 50% by mass), dibutyltin dilaurate 2 parts by mass and MS-51 (Mitsubishi Chemical ( 30 parts by mass of methyl silicate (manufactured by K.K.) was added and diluted with a mixed solvent of ethyl acetate / isopropyl alcohol = 1/1 so that the resin concentration became 30% by mass, to obtain a resin composition for coating.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency using the resin composition for coating.

Example 3 In the same manner as in Example 1, using resin A3 (resin concentration 50% by mass), dibutyltin dilaurate 2 parts by mass and MS-51 (Mitsubishi Chemical ( 30 parts by mass of methyl silicate (manufactured by K.K.) was added and diluted with a mixed solvent of ethyl acetate / isopropyl alcohol = 1/1 so that the resin concentration became 30% by mass, to obtain a resin composition for coating.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Example 4 In the same manner as in Example 1, using resin A4 (resin concentration: 50% by mass), 2 parts by mass of orthophosphoric acid, MS-51 (Mitsubishi Chemical Corporation) ) Co., Ltd. 30 parts by mass of methyl silicate) and a resin concentration of 3 with a mixed solvent of ethyl acetate / isopropyl alcohol = 1/1.
The mixture was diluted to 0% by mass to obtain a resin composition for coating.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Example 5 In the same manner as in Example 1, using resin A5 (resin concentration: 50% by mass), 100 parts by mass of resin solid content of resin A5, 2 parts by mass of oxalic acid dihydrate, MS-51 (Mitsubishi) (Methyl silicate manufactured by Chemical Co., Ltd.) was added and diluted with a mixed solvent of ethyl acetate / isopropyl alcohol = 1/1 so that the resin concentration became 30% by mass to obtain a resin composition for coating. Was.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Example 6 As in Example 1, using Resin A6 (resin concentration: 50% by mass), 0.5 parts by mass of orthophosphoric acid and 0 parts by weight of oxalic acid dihydrate were added to 100 parts by mass of the resin solid content of Resin A6. 0.5 parts by mass and 30 parts by mass of ES-28 (methyl silicate manufactured by Colcoat Co., Ltd.) were added, and ethyl acetate / isopropyl alcohol =
The mixture was diluted with a 1/1 mixed solvent so that the resin concentration became 30% by mass, to obtain a resin composition for coating.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Example 7 In the same manner as in Example 1, using resin A1 (resin concentration: 50% by mass), 0.5 parts by mass of orthophosphoric acid and 0 parts by weight of oxalic acid dihydrate were added to 100 parts by mass of the resin solid content of resin A1. .5 parts by mass, MS-
30 (methyl silicate manufactured by Colcoat Co., Ltd.) was added and ethyl acetate / isopropyl alcohol =
The mixture was diluted with a 1/1 mixed solvent so that the resin concentration became 30% by mass, to obtain a resin composition for coating.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Example 8 In the same manner as in Example 1, using resin A1 (resin concentration: 50% by mass), 0.5 parts by mass of orthophosphoric acid and 0 parts by weight of oxalic acid dihydrate were added to 100 parts by mass of the solid content of resin A1. .5 parts by mass, MS-
51 (Methyl silicate manufactured by Mitsubishi Chemical Corporation) was added in an amount of 30 parts by mass, and ethyl acetate / isopropyl alcohol = 1.
The mixture was diluted with a mixed solvent of / 1 so that the resin concentration became 30% by mass, to obtain a resin composition for coating.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Example 9 In the same manner as in Example 1, using resin A1 (resin concentration 50% by mass), 0.5 parts by mass of orthophosphoric acid and 0 parts by weight of oxalic acid dihydrate were used for 100 parts by mass of the resin solid content of resin A1. .5 parts by mass, MS-
56 (methyl silicate manufactured by Mitsubishi Chemical Corporation) was added in an amount of 30 parts by mass, and ethyl acetate / isopropyl alcohol = 1.
The mixture was diluted with a mixed solvent of / 1 so that the resin concentration became 30% by mass, to obtain a resin composition for coating.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Example 10 In the same manner as in Example 1, using resin A1 (resin concentration: 50% by mass), light ester PM (monomethacryloyl phosphate manufactured by Kyoeisha Chemical Co., Ltd.) was applied to 100 parts by mass of resin solid content of resin A1. Ethyl acetate / isopropyl alcohol = 2 parts by mass and without adding organosilicate
The mixture was diluted with a 1/1 mixed solvent so that the resin concentration became 30% by mass, to obtain a resin composition for coating.

Table 1 shows the evaluation results of weather resistance, hardness, heat resistance and magic repellency of the resin composition for coating in the same manner as in Example 1.

Example 11 As in Example 1, light ester PM (monomethacryloyl phosphate manufactured by Kyoeisha Chemical Co., Ltd.) was used for 100 parts by mass of resin solid content of resin A1 using resin A1 (resin concentration: 50% by mass). Add 2 parts by mass, add 50 parts by mass of MS-51 (Methyl silicate manufactured by Mitsubishi Chemical Corporation), and make the resin concentration 30% by mass with a mixed solvent of ethyl acetate / isopropyl alcohol = 1/1. Diluted as
A resin composition for coating was obtained.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Example 12 In the same manner as in Example 1, using resin A1 (resin concentration: 50% by mass), light ester PM (monomethacryloyl phosphate manufactured by Kyoeisha Chemical Co., Ltd.) was used for 100 parts by mass of resin solid content of resin A1. After adding 2 parts by mass, 150 parts by mass of MS-51 (Methyl silicate manufactured by Mitsubishi Chemical Corporation) is added, and the resin concentration becomes 30% by mass with a mixed solvent of ethyl acetate / isopropyl alcohol = 1/1. To obtain a coating resin composition.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Example 13 As in Example 1, 5 parts by mass of glycidyl methacrylate was added to 100 parts by mass of the resin solid content of resin A1 using resin A1 (resin concentration: 50% by mass), and MS-51 (Mitsubishi Corp.) (Methyl silicate manufactured by Chemical Co., Ltd.) was added and diluted with a mixed solvent of ethyl acetate / isopropyl alcohol = 1/1 so that the resin concentration became 30% by mass.
A resin composition for coating was obtained.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Example 14 In the same manner as in Example 1, 3 parts by mass of tris (acetylacetonato) aluminum was added to 100 parts by mass of the resin solid content of the resin A1 using the resin A1 (resin concentration: 50% by mass). MS-51 (methyl silicate manufactured by Mitsubishi Chemical Corporation) was added in an amount of 30 parts by mass, and a resin concentration of 30% by mass was mixed with a mixed solvent of ethyl acetate / isopropyl alcohol = 1/1.
To obtain a coating resin composition.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Example 15 In the same manner as in Example 1, 3 parts by weight of hexylamine was added to 100 parts by weight of the resin solid content of resin A1 using resin A1 (resin concentration: 50% by weight), and MS-51 (Mitsubishi Corp.) was used. (Methyl silicate manufactured by Chemical Co., Ltd.) was added and diluted with a mixed solvent of ethyl acetate / isopropyl alcohol = 1/1 so that the resin concentration became 30% by mass to obtain a resin composition for coating. Was.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency in the same manner as in Example 1 using the resin composition for coating.

Comparative Example 1 A resin composition for coating was obtained in the same manner as in Example 1 except that resin D1 (resin concentration: 50% by mass) was used instead of resin A1.

Table 1 shows the evaluation of weather resistance, hardness, heat resistance and magic repellency using the resin composition for coating.

Comparative Example 2 A coating resin composition was obtained in the same manner as in Example 1 except that resin D2 (resin concentration: 50% by mass) was used instead of resin A1.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency using the resin composition for coating.

Comparative Example 3 A resin composition for coating was obtained in the same manner as in Example 1 except that resin D3 (resin concentration: 50% by mass) was used instead of resin A1.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency using the resin composition for coating.

Comparative Example 4 A resin composition for coating was obtained in the same manner as in Example 1 except that dibutyltin dilaurate was omitted.

Table 1 shows the results of evaluation of weather resistance, hardness, heat resistance and magic repellency using the resin composition for coating.

[0096]

[Table 1] * 1: Measurement was not possible due to insufficient curing.

[0097]

The resin and the resin composition for coating of the present invention are extremely excellent in weather resistance, hardness, heat resistance and magic repellency, and are very useful materials for coating used indoors and outdoors. .

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoshiaki Nagao Haseji, Higashi-Nagahara, Kato-cho, Kawanuma-gun, Fukushima 111 F-term (Reference) 4J027 AF03 AF05 AJ01 BA04 BA05 BA07 BA07 BA09 BA10 BA13 BA14 CB00 CB08 CC02 CD08 4J038 CB031 CB032 CB091 CB092 CB121 CB122 CC021 CC022 CC071 CC072 CE051 CE052 CF011 CF012 CG031 CG032 CG081 CG082 CG141 CH2 CH1 CH2 172 172 172 DL022 FA172 GA02 GA15 HA416 JA23 JA39 JA41 JA69 JA75 JB03 JC13 JC24 JC32 JC34 JC38 JC41 KA03 KA04 MA14 NA03 NA05 NA11 NA14

Claims (12)

[Claims] 1. A polydialkylsiloxane having at least one ethylenically unsaturated group per molecule (a
1), an organopolysilsesquioxane having an ethylenically unsaturated group (a2), an alkoxysilane compound having an ethylenically unsaturated group (a3), and a compound having an ethylenically unsaturated group [where (a1), (a1) a2) and (a)
Except 3). ] A resin obtained by copolymerizing (a4). 2. The polydialkylsiloxane (a1) is
The following general formula (1): (Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms), and a compound having an organic group having an ethylenically unsaturated group as a terminal group. Yes, organopolysilsesquioxane (a2)
Is the following general formula (2): (Wherein, R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms or an organic group having an ethylenically unsaturated group, and the organic group having an ethylenically unsaturated group is 5 to 60)
Mol%. ) And the following general formula (3): (Wherein, R ³ and R ⁴ have the same meanings as above. R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a trimethylsilyl group, of which 30 mol%
The above is the trimethylsilyl group. ) Is a compound having a terminal group represented by the formula:
3) is represented by the following general formula (4): (However, R ⁷ represents an alkyl group having 1 to 4 carbon atoms,
R ⁸ represents an organic group having an ethylenically unsaturated group. The resin according to claim 1, which is a compound represented by the formula: 3. The composition according to claim 1, wherein the component (a1) is 0.5 to 10% by mass,
0.5 to 20% by mass of the component (a2) and 1% of the component (a3)
６０60 mass%, component (a4) is 10 to 98% [where the
The total of the components (a1) to (a4) is 100%. The resin according to claim 1 or 2, which is obtained by copolymerizing 4. The resin according to claim 1, wherein the polydialkylsiloxane (a1) has a number average molecular weight of 500 to 50,000. 5. The resin according to claim 1, wherein the ethylenically unsaturated group of the polydialkylsiloxane (a1) is a vinyl group or a substituted vinyl group. 6. A coating resin composition comprising the resin (A) according to claim 1 and a curing accelerator (B). 7. The coating resin composition according to claim 6, wherein the curing accelerator (B) is used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the resin (A). 8. A curing accelerator (B) comprising an organotin compound, a phosphorus compound, an epoxy compound, an organic zirconium compound,
The coating resin composition according to claim 6 or 7, wherein the resin composition is at least one compound selected from the group consisting of an organic acid compound and an amine. 9. The coating resin composition according to claim 6, further comprising an organosilicate (C). 10. The coating resin composition according to claim 9, wherein the organosilicate (C) is a compound selected from the group consisting of tetramethoxysilane, tetraethoxysilane, and a hydrolytic condensate thereof. 11. The coating resin composition according to claim 9, wherein the amount of the organosilicate (C) is 200 parts by mass or less based on 100 parts by mass of the resin (A). 12. A paint comprising the resin according to claim 1 or a resin composition for coating.