JP2000086975A - Resin composition for fouling-resistant coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of providing a coating film excellent in adhesion to substrates, weatherability, etc., and antifoulancy compatible with removing properties of foulings by compounding a copolymer resin containing a specific organopolysiloxane integrated into a skeleton with a specified cross-linking agent and an organosilicate. SOLUTION: This composition contains (A) a copolymer resin obtained from (i) a polymerizable unsaturated group-containing organopolysilsesquioxane and (ii) a polymerizable unsaturated group-containing compound (e.g. maleic anhydride), (B) a crosslinking agent having >=2 reactive groups reactive with active hydrogens and capable of forming a crosslinked structure and (C) an organosilicate (preferably methyl silicate, etc.). The component A preferably contains 0.5-20 wt.% of a component derived from the component (i) and 80-99.5 wt.% of a component derived from the component (ii) and the hydroxyl value based on 1 g of the resin is preferably 10-130 KOHmg. An isocyanate or melamine or both are preferred as the reactive groups of the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition containing a silicone polymer having a ladder-like structure (hereinafter referred to as "ladder silicone polymer"), and more particularly to various kinds of buildings, building materials, structures, vehicles and the like. The present invention relates to a resin composition for top coat coating having weather resistance and excellent stain resistance, used for the purpose of modifying the surface of a substrate.

[0002]

2. Description of the Related Art Heretofore, coating on buildings, building materials, structures, vehicles, and the like has been performed for the purpose of maintaining durability and imparting its beauty. Studies have been conducted on the prevention of contamination, graffiti prevention, and sticker prevention by painting, but the main means is to prevent the adhesion of dirt, graffiti ink, glue on stickers, etc., mainly by making the coating surface hydrophobic. there were.
For this reason, paints based on fluororesins or silicone resins having weather resistance and a large contact angle with water or solvents have been studied. However, the surfaces coated with these paints are often impractical because the surfaces are easily damaged or charged with static electricity, which in turn promotes the attachment of contaminants. In addition, a method of preventing contamination due to exposure by applying a silicate resin to the coating resin to make the coating film surface hydrophilic by some means has been studied, but this method has poor durability of the coating film, Initially, the dirt spreads over the entire surface to prevent contamination, but once the contaminant adheres, it is not easy to remove the contaminant.

On the other hand, ladder silicone polymers (organopolysilsesquioxanes) exhibit excellent properties such as hardness, weather resistance and heat resistance, and have been attempted to be used as outdoor coating materials (see, for example, Japanese Patent Application Laid-Open No. 6-20
No. 7925, JP-A-6-287307, JP-A-8-2
No. 31924). Silicone polymers having a ladder-like structure have excellent weather resistance and high hardness of the coating film surface, so that the coating film surface is hardly damaged and relatively hard to stain. Furthermore, it has a feature that the contaminant can be easily removed even if the contaminant adheres once (hereinafter, referred to as decontamination property).

[0004] However, the ladder silicone polymer described above has insufficient pollution control performance against lipophilic contaminants, and the market has strongly demanded further improvement including sustainability for stain resistance.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a coating film having good adhesion to a substrate, excellent weather resistance, and removal of dirt due to dust and rainwater in the atmosphere when a coated product is exposed outdoors. It is an object of the present invention to provide a stain-resistant coating resin composition which can be prevented from being noticeable and easily wipe off stains once adhered, that is, form a coating film having both low stainability and stain removal properties.

[0006]

Means for Solving the Problems The present inventors have found that the adhesion of a coating film to a substrate is good, the weather resistance is excellent, and the dust in the atmosphere when exposed to a coating object is reduced.
In addition to preventing dirt due to rainwater and the like, the dirt is hardly noticeable, and dirt once adhered is easily wiped off. In other words, diligent studies are conducted to obtain a stain-resistant coating resin composition that forms a coating film that achieves both low contamination and stain removal. As a result of the overlapping, a specific organopolysiloxane was incorporated into the molecular skeleton, and a cross-linking agent having two or more reactive groups in the molecule capable of reacting with active hydrogen to form a cross-linked structure and a specific silicate were blended. It has been found that the above object can be achieved by using a resin composition for coating, and the present invention has been completed.

That is, the present invention relates to the following items. 1) a copolymer resin (A) produced from an organopolysilsesquioxane having a polymerizable unsaturated group (a-1) and a compound having a polymerizable unsaturated group (a-2), and active hydrogen A resin composition for coating, comprising: a crosslinking agent (B) having at least two reactive groups capable of forming a crosslinked structure by reacting with a crosslinking agent (B) in a molecule; and an organosilicate (C). The copolymer resin (A) contains 0.5 to 20.0% by weight of a component derived from (a-1) and 8% of a component derived from (a-2).
0.0-99.5% by weight, and 1 g of resin
3) The resin composition for coating according to 1) above, wherein the hydroxyl value per unit is 10 to 130 KOH mg. 3) A crosslinking agent having two or more reactive groups in a molecule capable of forming a crosslinked structure by reacting with active hydrogen. The reactive group of B) is
The resin composition for coating according to the above 1) or 2), which is an isocyanate group and / or a melamine group. 4) The resin composition according to the above 1) to 3), which contains 1 to 30% by weight of an organosilicate (C). 5) The above-mentioned 1) to 4), wherein the organosilicate (C) is at least one kind of an organosilicate selected from methyl silicate, ethyl silicate and butyl silicate and / or a hydrolytic condensate thereof. A resin composition for coating.

The above resin composition for coating is particularly useful for top coating of buildings, building materials, structures, vehicles and the like.

Hereinafter, the present invention will be described in detail. The “(meth) acryl” described in the present invention means “acryl”
It means any of "methacrylic". In the copolymer resin (A) produced from the organopolysilsesquioxane having a polymerizable unsaturated group and the compound having a polymerizable unsaturated group in the present invention, the organopolymer having a polymerizable unsaturated group used for copolymerization is used. Polysilsesquioxane is described in Nakahama et al. [Poymer Preprints Japan 2
9 (1) p. 73 (1980)] and JP-A-3-281.
616, JP-A-4-28722, JP-A-6-287
No. 307 and the like, for example, obtained by hydrolysis and co-condensation of a trialkoxysilane having a polymerizable unsaturated group such as a vinyl group, an acryl group or a methacryl group, and an alkyltrialkoxysilane described below. The main structure is an oligomer having a polymerizable unsaturated group and an alkyl group in a side chain, a main skeleton of a molecule having a ladder shape, and preferably having a number average molecular weight of several hundreds to several 10,000s. It is.

Examples of the trialkoxysilane having a polymerizable unsaturated group such as a vinyl group, an acryl group and a methacryl group include vinyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ -(Meth) acryloyloxypropyltriethoxysilane and the like. Further, instead of the trialkoxysilane, a trihalosilane can be used. Examples of the trihalosilane include vinyltrichlorosilane, γ- (meth) acryloyloxypropyltrichlorosilane, and the like.

Examples of the alkyltrialkoxysilanes to be hydrolyzed and co-condensed with these silane compounds include alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane. Alternatively, an alkyltrihalosilane may be used in place of the alkyltrialkoxysilane, and examples thereof include methyltrichlorosilane, ethyltrichlorosilane, etc., and substituted or unsubstituted phenyltrimethoxysilane, phenyltriethoxysilane or phenyltrichlorosilane. A silane compound having a substituted phenyl group is also exemplified. One or more of these silane compounds and alkylsilane compounds having a polymerizable unsaturated group can be used.

The organopolysilsesquioxane having a polymerizable unsaturated group used in the copolymer resin (A) of the present invention is, for example, a functional organopolysilsesquioxane described in JP-A-8-73593. It is preferable that the terminal of the main chain is blocked with a silylating agent. The amount of the organopolysilsesquioxane having a polymerizable unsaturated group to be used is preferably 0.5 to 20.0% by weight, more preferably 1.0 to 15.0% by weight of the copolymer resin (A). % By weight. If the amount of the organopolysilsesquioxane having a polymerizable unsaturated group is less than 0.5% by weight, the heat resistance and stain resistance of the resin may be insufficient. If the amount is more than 10% by weight, gelation tends to occur during the polymerization, and the pot life of the coating resin composition containing a predetermined amount of the curing agent may be significantly reduced, which is not economically preferable.

The content of the polymerizable unsaturated group (for example, an acryl group or a methacryl group) in the organopolysilsesquioxane having the polymerizable unsaturated group is determined by the content of the organopolysilyl group having the polymerizable unsaturated group. It is preferably from 5 to 60 mol%, more preferably from 8 to 50 mol%, even more preferably from 8 to 40 mol% of all side chains of sesquioxane. When the content of the polymerizable unsaturated group is less than 5 mol%, the curability of a coating resin composition containing a predetermined amount of a crosslinking agent may be insufficient. Gelation tends to occur in the inside, and the raw material price becomes large, which is not economically preferable.

The hydroxyl value of the copolymer resin (A) of the present invention is preferably from 10 to 130 KOH mg / g, more preferably from 20 to 120 KOH mg / g of the resin. If the hydroxyl value per 1 g of the resin is less than 10 KOHmg, the curability may be insufficient and the stain resistance may not be obtained satisfactorily.
On the other hand, when the amount exceeds 130 KOH mg, the coating resin composition obtained by blending a predetermined amount of a crosslinking agent may be hard and brittle, which is not preferable.

As a method for providing a hydroxyl group to the copolymer resin (A) of the present invention, for example, a commonly used method of copolymerizing a hydroxyl group-containing polymerizable unsaturated compound is employed. Examples of the hydroxyl-containing polymerizable unsaturated compound include, for example, allyl alcohol, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, (meth)
Hydroxybutyl acrylate, 2- (meth) acrylate
Hydroxyl-containing polymerizable unsaturated compounds such as hydroxybutyl, and adducts of hydroxyl-containing (meth) acrylic monomers with lactones such as ε-caprolactone (for example, “Placcel F
A-1], "Placcel FA-2", "Placcel FA
-3 "," PLAXEL FM-1 "," PLAXEL FM-
2 "and" Placcel FM-3 ": trade names manufactured by Daicel Chemical Industries, Ltd.).

The other polymerizable unsaturated compounds used in the production of the copolymer resin (A) of the present invention are not particularly limited, and compounds which can be relatively easily copolymerized are preferred. That is, such compounds have 1 to about 2 carbon atoms.
0 is a polymerizable unsaturated compound substituted with a linear, branched or cyclic saturated or unsaturated hydrocarbon, and specifically, maleic anhydride, (meth) acrylic acid, (meth) acrylic acid Methyl, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth)
Isobutyl acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, ethylene, propylene, butylene-1, ethyl vinyl ether, isobutyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, lactic acid Vinyl, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl pivalate, (meth) acrylonitrile, styrene, vinyltoluene, α-methylstyrene, (meth) acrylamide,
Dimethylaminoethyl (meth) acrylate and the like can be mentioned.

The production of the copolymer resin (A) of the present invention can be carried out, for example, by the method described in the Paint Technology Handbook (edited by the Japan Paint Technology Association, 1987, Nikkan Kogyo Shimbun, p. 154). For example, an organopolysilsesquioxane having a polymerizable unsaturated group, a hydroxyl group-containing polymerizable unsaturated compound and a polymerizable compound appropriately selected from the group of polymerizable unsaturated compounds other than those mentioned above as necessary. ,
It can be obtained by, for example, radical copolymerization in an organic solvent.

The number average molecular weight of the copolymer resin (A) of the present invention thus obtained is not particularly limited.
Preferably it is 2,000 to 100,000, more preferably 5,000 to 50,000.

The copolymer resin (A) produced by radical polymerization in an organic solvent as described above is obtained as a resin solution of the organic solvent used, and is reacted with a crosslinking agent (B) to be added next. The resin solution may be used as it is, or the resin solution may be further diluted with an organic solvent before use. Of course, the copolymer resin (A) may be once isolated and then used in the reaction.

Next, the reactive group of the cross-linking agent having two or more reactive groups in the molecule which can react with active hydrogen to form a cross-linked structure, which is the component (B) used in the present invention, includes the following. Are exemplified. Epoxy group, isocyanate group, melamine group such as methylolmelamine, dimethylolmelamine, triethylolmelamine, oxazoline group, acylcarbamate group, β-hydroxycarbamate group, methylolated amino group, acetal group, amide glycolate ether group, acetoacetoxy Group, or acid anhydride group. Among these reactive groups, isocyanate groups and melamine groups are particularly preferred. The component (B) may be two or more compounds.

The compound containing an isocyanate group as the component (B) includes, in addition to known monomers having two or more isocyanate groups, urethane-modified, allophanate-modified, isocyanurate-modified, buret-modified, It is also possible to use modified isocyanates such as modified carbodiimides and blocked isocyanates.

The modified isocyanate is used by modifying an isocyanate monomer described below for the purpose of improving undesired physical properties such as toxicity and controlling the reaction rate. The urethane-modified product is obtained by modifying an isocyanate monomer (or diisocyanate) with a shortage of polyol. The modified allophanate is produced by adding an isocyanate group to a urethane group. The modified isocyanurate has an isocyanurate ring in the molecule, and tends to have improved heat resistance. The modified buret is a compound in which an isocyanate group is added to a urea bond, and is a compound from which free isocyanate has been removed. In the modified carbodiimide, a carbodiimide bond is generated from a 2 mol isocyanate group by a decarboxylation gas reaction. When isocyanate is further added, urethane imine is produced, and carbodiimide and urethane imine coexist in equilibrium. Blocked isocyanates can be obtained by reacting various blocking agents to temporarily mask the activity of isocyanate groups. Examples of the blocking agent include phenol-based blocking agents such as phenol and xylenol, and active hydrogen compounds such as oximes, lactams, and alcohols.

Examples of the isocyanate monomer or the isocyanate monomer forming a modified product include triresin isocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), and naphthylene diisocyanate (NDI). ),
Paraphenylene diisocyanate (PPDI), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), lysine diisocyanate (LDI), isopropylidene bis (4-cyclohexyl isocyanate) ) (IPC), hydrogenated xylylene diisocyanate (hydrogenated XDI), cyclohexyl diisocyanate (CHDI), tolidine diisocyanate (TODI) and the like. The isocyanate monomer used in the present invention is not limited thereto, and is described in detail, for example, in "Synthesis, blending, functionalization and application development of latest polyurethane" (Technical Information Association, 1989). Can be used.

The compound having a melamine group of the component (B) is a compound having two or more melamine groups in one molecule, which is generally obtained by an addition condensation reaction of melamine with an aldehyde compound such as formaldehyde. There are monomethylol melamine, dimethylol melamine, and trimethylol melamine. These methylolated melamine compounds can be used as they are, or compounds that have been etherified by reacting with various alcohols can also be used. As the alcohol used in this case,
Generally, lower alcohols such as methanol, ethanol, propanol, and butanol are exemplified.

Next, the organosilicate as the component (C) used in the present invention is tetraalkoxysilane and its hydrolytic condensate. Among them, tetramethoxysilane and its hydrolytic condensate (methyl silicate), tetraethoxysilane Silane and its hydrolytic condensate (ethyl silicate), tetrabutoxysilane and its hydrolytic condensate (butyl silicate) are preferred,
As the component (C), two or more compounds may be used.
The molecular weight of the above compound varies depending on the type of alkoxysilane and the degree of polymerization, but is preferably from 200 to 2,000. The amount of the organosilicate used is preferably in the range of 1 to 30% by weight, more preferably 3 to 20% by weight, in the coating resin composition of the present invention.
It is. If the amount used is less than 1% by weight, the stain resistance may be insufficient. If the amount used exceeds 30% by weight, the coatability on the base material becomes insufficient and a uniform coating film is hardly obtained. None of them is preferable.

In order to further promote the curability of the resin composition for coating of the present invention, if necessary, for example, hydrochloric acid,
Inorganic acids such as nitric acid, phosphoric acid, sulfuric acid and salts thereof, formic acid, acetic acid,
Organic acids and derivatives thereof such as oxalic acid, maleic acid, phthalic acid, benzoic acid and paratoluenesulfonic acid, di-n-butyltin diacetate, di-n-butyltin dioctate, di-n-butyltin dilaurate and the like. Organotin compounds, organic zirconium compounds such as tetrabutyl zirconate, butoxytris (acetylacetonate) zirconium, amine compounds such as ethylenediamine, diethylenetriamine, metaphenylenediamine, diethanolamine, triethanolamine, and tris (acetylacetonate)
Organic aluminum compounds such as aluminum and tris (ethylacetonate) aluminum can be used. Further, if necessary, known antioxidants, light stabilizers, heat stabilizers, coloring agents, flame retardants, fillers, plasticizers, and the like may be added as long as the desired performance is not lost.

The resin composition for coating of the present invention is prepared by adding an organic solvent, various additives and the like to the copolymer resin (A), the crosslinking agent (B) and the organosilicate (C), if necessary. It can be manufactured by a well-known method generally used by parties in the paint industry and the like.
Useful organic solvents 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; aromatic hydrocarbons such as toluene and xylene; and tetrahydrofuran. And ethers such as dioxane, alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol and propylene glycol, and the like. Generally, the organic solvents are often used in a mixture of two or more.

The coating resin composition of the present invention can be used as a clear coating without adding a pigment.
It can also be used as a colored enamel paint by adding a pigment.

When a pigment is added to the resin composition for coating of the present invention and enameled, any of an organic pigment and an inorganic pigment can be used, and the pigment is kneaded in advance with a solvent or a resin solution. It is also possible to add and knead the pigment directly.

The thus obtained resin composition for a stain resistant coating for forming a coating film having both low stain and stain removal properties of the present invention can be obtained by a coating method and apparatus generally used in the art. Can be used. Usually, a method of applying the resin solution of the resin composition for coating mainly by hand using a brush or a roller, a spray coating method, a roll coater method and the like are employed.

The thus-obtained coating film coated with the coating resin composition of the present invention not only has extremely good weather resistance but also has little rain streak contamination, that is, low contamination and good stain removal. It gives a coating film.

[0032]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to 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) Preparation of Test Coating Substrate The coating resin composition prepared to have a solid content of 30% by weight was sprayed onto an aluminum substrate previously coated with a commercially available white urethane paint on the urethane coating surface. Was applied so that the thickness of the coating film after curing became 25 to 30 μm, and this was dried and cured to form a cured coating film.

(2) Weather Resistance Test The coated substrate prepared by the above method was measured for gloss retention (%) after irradiating for 3000 hours in accordance with an ultraviolet fluorescent lamp type test method according to JIS D0205.

(3) Stain resistance test The coated substrate prepared by the above method was exposed outdoors for 6 months in the Kawasaki area, and the contamination state of the coated substrate was visually judged. Those with clear rain streak contamination were judged as "contamination x", those without rain streak contamination were judged as "contamination ○", and those with a little rain streak contamination were judged as "contamination △".

(4) Stain Removal Test The coating substrate prepared by the above method was spray-coated with the test contaminant shown below, and the substrate was heated at 80 ° C. for 60 minutes and then heated to 40 ° C. After conditioning for 24 hours, the contaminants were wiped off with a gauze soaked in soapy water to visually evaluate the decontamination property. Those that did not remove dirt were designated as "stain removal property 0", and those where dirt was completely removed were designated as "stain removal property 5". Composition of contaminated liquid for test Carbon black (channel carbon) 17.0% by weight Burned Kanto loam (8 kinds of test dust) 70.0% by weight Tar (medium pitch JIS K2439) 13.0% by weight 0.5 g of the above component The suspension was used in 1 L of deionized water.

(5) Adhesion test The coated substrate prepared by the above method was measured by a grid test method (100 squares) according to JIS K5400.

[Production of Organopolysilsesquioxane D1 Having a Polymerizable Unsaturated Group] In a 300 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, γ-methacryloyloxypropyltrimethoxysilane 89 was added. 0.41 g (360 mmol), 128.38 g (720 mmol) of methyltriethoxysilane, 23.8 g (120 mmol) of phenyltrimethoxysilane and 64.87 g (3,600 mmol) of pure water were charged.
The solution temperature was maintained at 5 ° C. while stirring under a nitrogen stream. Next, 12.15 g of a 3.6% by weight aqueous hydrochloric acid solution was added to 3 parts.
After the dropwise addition over 0 minutes, the solution temperature was maintained at 10 ° C. for 60 minutes. The solution was heated to 70 ° C. and reacted for 180 minutes, and then 31.88 g of hexamethyldisiloxane (19.
(6.32 mmol) and the silylation reaction was carried out at 70 ° C. for 180 minutes. The obtained reaction solution was cooled to 40 ° C. and 15.8% by weight of a 4.25% by weight aqueous potassium hydroxide solution.
4 g was added to neutralize the inside of the system and left at room temperature for 12 hours.
The lower layer of the liquid separated into two layers was collected, and 12
Add 0 g of butyl acetate, and stir at 40 ° C 200m
After concentrating under reduced pressure of mHg, and distilling off 120 g of the liquid, 380 g of butyl acetate was further added at room temperature to give 6 g.
Stirring was performed for 0 minutes. The obtained solution was filtered with a 0.8 μ filter to obtain 460 g of a colorless and transparent solution. The number average molecular weight of the organopolysilsesquioxane having a polymerizable unsaturated group measured by GPC (gel permeation chromatography) was 2500 (in terms of polystyrene, the same applies hereinafter). 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 polymerizable unsaturated group. From the analysis of the ¹ H-, ¹³ C- and ²⁹ Si-NMR spectra, the molar ratio of the γ-methacryloyloxypropyl group, methyl group and phenyl group in the side chain is equal to the molar ratio of the charged silane monomer, 3: 6: 1. Met. This organopolysilsesquioxane having a polymerizable unsaturated group is hereinafter abbreviated as polymer D1.

[Production of organopolysilsesquioxane D2 having a polymerizable unsaturated group] Using the same apparatus as that of D1, 26.82 g (108 mmol) of γ-methacryloyloxypropyltrimethoxysilane and 192 of methyltriethoxysilane An organopolysilsesquioxane having a polymerizable unsaturated group was produced under the same conditions as in D1, except that 0.57 g (1080 mmol) and 2.38 g (12 mmol) of phenyltrimethoxysilane were used. The number average molecular weight was 3,500 according to GPC measurement. The GP
As a result of the C analysis, no peak derived from the raw material silane monomer was detected, and it was considered that there was no unreacted monomer in the obtained organopolysilsesquioxane having a polymerizable unsaturated group. Also, ¹ H-, ¹³ C- and
^From the analysis of the ²⁹ Si-NMR spectrum, the molar ratio of the side chain γ-methacryloyloxypropyl group, methyl group and phenyl group was equal to the molar ratio of the charged silane monomer, and was 9: 9.
0: 1. This organopolysilsesquioxane having a polymerizable unsaturated group is hereinafter referred to as polymer D2.

[Production of Copolymer 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 reaction rate of the following monomer determined by GPC was 99%. Polymer D1 (as solid content) 5 parts by weight Methyl methacrylate 23 parts by weight n-butyl methacrylate 46 parts by weight Hydroxyethyl methacrylate 23 parts by weight Acrylic acid 2 parts by weight Azobisisobutyronitrile 1 part by weight 100 parts by weight butyl acetate Thus, the number average molecular weight determined by GPC measurement was 12,000,
A copolymer A1 having a weight average molecular weight of 45,000 was obtained.

[Production of Copolymer 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. The reaction rate of the following monomer measured by GPC was 99%. Polymer D2 (as solid content) 10 parts by weight Methyl methacrylate 17 parts by weight n-butyl methacrylate 49 parts by weight Hydroxyethyl methacrylate 21 parts by weight Acrylic acid 2 parts by weight Azobisisobutyronitrile 1 part by weight 100 parts by weight butyl acetate Thus, the number average molecular weight by GPC measurement was 11,000,
A copolymer A2 having a weight average molecular weight of 26,000 was obtained.

[Production of Copolymer Resin E1] 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 of the following monomer determined by GPC was 99%. Methyl methacrylate 29 parts by weight N-butyl methacrylate 44 parts by weight Hydroxyethyl methacrylate 24 parts by weight Acrylic acid 2 parts by weight Azobisisobutyronitrile 1 part by weight 100 parts by weight of butyl acetate Thus, the number average molecular weight by GPC measurement is 12,000. ,
A copolymer E1 having a weight average molecular weight of 25,000 was obtained.

(Example 1) The copolymer A1 (resin concentration 50% by weight) produced by the above method and methyl silicate (Si51 manufactured by Mitsubishi Chemical Corporation) were blended so that the mixing ratio became 95/5. Then, the composition was mixed with ethyl acetate / xylene =
After diluting with a 1/1 mixed solvent so that the resin concentration becomes 30% by weight, the polyisocyanate (Sumitomo Bayer Urethane (Sumitomo Bayer Urethane) is used such that the isocyanate group becomes 1.0 times the hydroxyl group in the resin solution. Sumijur N-3 manufactured by K.K.
500) and uniformly stirred to obtain a coating resin composition of the present invention. Using the resin composition for coating, weather resistance, stain resistance, stain removal property, adhesion, weather resistance, stain resistance, stain removal property, and adhesion were evaluated. Table 1 shows the results.

(Example 2) Copolymer A2 (resin concentration 50% by weight) produced by the above method instead of copolymer A1
A resin composition for coating of the present invention was prepared in the same manner as in Example 1 except that the resin composition was used. Table 1 shows the results of evaluating weather resistance, stain resistance, stain removal properties, and adhesion using the resin composition for coating.

(Example 3) The copolymer A1 (resin concentration: 50% by weight) produced by the above method and methyl silicate (Si51 manufactured by Mitsubishi Chemical Corporation) were blended so that the mixing ratio became 90/10. A coating resin composition of the present invention was prepared in the same manner as in Example 1 except for the above. Table 1 shows the results of evaluating weather resistance, stain resistance, stain removal properties, and adhesion using the resin composition for coating.

(Example 4) The copolymer A1 (resin concentration 50% by weight) produced by the above method and methyl silicate (Si51 manufactured by Mitsubishi Chemical Corporation) were blended so that the mixing ratio was 80/20. Other than the above, a resin composition for coating of the present invention was prepared in the same manner as in Example 1, and the weather resistance, stain resistance, stain removal property, and adhesion were evaluated using the resin composition for coating. Are shown in Table 1.

(Example 5) The copolymer A1 (resin concentration 50% by weight) produced by the above method and methyl silicate (Si51 manufactured by Mitsubishi Chemical Corporation) were blended so that the mixing ratio became 95/5. Then, the composition was mixed with ethyl acetate / xylene =
After diluting with a 1/1 mixed solvent so that the resin concentration becomes 30% by weight, the melamine resin (Mitsui Chemicals Co., Ltd.) is used so that the methylol melamine group becomes 1.0 times the hydroxyl group in the resin solution. ) Co., Ltd. was mixed and uniformly stirred to obtain a coating resin composition of the present invention.
Table 1 shows the results of evaluating weather resistance, stain resistance, stain removal properties, and adhesion using the resin composition for coating.

(Example 6) The copolymer A1 (resin concentration: 50% by weight) produced by the above method and methyl silicate (Si51 manufactured by Mitsubishi Chemical Corporation) were blended so that the mixing ratio was 90/10. A coating resin composition of the present invention was prepared in the same manner as in Example 5 except for the above. Table 1 shows the results of evaluating weather resistance, stain resistance, stain removal properties, and adhesion using the resin composition for coating.

Comparative Example 1 The copolymer A1 (resin concentration: 50% by weight) produced by the above method was diluted with a mixed solvent of ethyl acetate / xylene = 1/1 so that the resin concentration became 30% by weight. After that, the polyisocyanate (Sumijur N-manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added so that the isocyanate group was 1.0 times the hydroxyl group in the resin solution.
3500) and uniformly stirred to obtain a resin composition for coating. Using the coating resin composition,
Table 1 shows evaluations of weather resistance, stain resistance, stain removal properties, and adhesion. Since the organosilicate (C) of the present invention was not added, both the stain resistance and the stain removal property were not sufficient.

Comparative Example 2 A resin composition for coating was prepared in the same manner as in Example 1 except that the copolymer A1 (resin concentration: 50% by weight) produced by the above method was used instead of the copolymer A1. A product was made. Table 1 shows the results of evaluating weather resistance, stain resistance, stain removal properties, and adhesion using the resin composition for coating. Since the copolymer resin (A) containing an organopolysilsesquioxane group of the present invention was not added, it was found that the weather resistance and the stain removal property were not sufficient.

[0051]

[Table 1]

As shown in Table 1, the coating resin composition of the present invention is very excellent in terms of weather resistance, stain resistance, stain removal properties and adhesion, and is clearly a useful material. .

[0053]

The resin composition for coating according to the present invention comprises:
For the purpose of protecting the landscape, such as the prevention of pollution, which is currently a social problem, it has excellent weather resistance, pollution resistance, pollution removal properties and adhesion to substrates, and the surface of various substrates such as buildings, building materials, structures, vehicles, etc. It is very useful as a coating resin composition for a top coat used for the purpose of modification.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masaki Matsuoka 17-11 Ozudocho, Kohoku-ku, Yokohama-shi, Kanagawa Prefecture 405 Guroria Hatsuho Okurayama (72) Inventor Masaharu Yoshida Haseji 111, Higashi-Nagahara, Kato-cho, Kawanuma-gun, Fukushima Prefecture F-term in the Higashi-Nagahara Plant of Showa Denko KK (reference) 4J038 CE011 CG031 CG081 CG141 CH071 CH121 CH171 CJ011 CJ081 CJ101 CJ131 CJ141 CJ181 GA03 GA15 JA69 JB18 JB36 JC32 KA03 KA06 NA03 NA05 PB05 PC02

Claims (5)

[Claims] 1. A copolymer resin (A) produced from an organopolysilsesquioxane having a polymerizable unsaturated group (a-1) and a compound having a polymerizable unsaturated group (a-2). A resin composition for coating, comprising: a crosslinking agent (B) having two or more reactive groups capable of forming a crosslinked structure by reacting with active hydrogen in a molecule; and an organosilicate (C). . 2. The copolymer resin (A) contains 0.5 to 20.0% by weight of a component derived from (a-1) and 80.0 to 99.5% by weight of a component derived from (a-2). %, And the hydroxyl value per 1 g of the resin is from 10 to 130 KOHmg. 3. The reactive group of the crosslinking agent (B) having two or more reactive groups capable of forming a crosslinked structure by reacting with active hydrogen in a molecule is an isocyanate group and / or a melamine group. 3. The coating resin composition according to any one of 1 and 2. 4. The coating resin composition according to claim 1, wherein the content of the organosilicate (C) is 1 to 30% by weight. 5. The coating according to claim 1, wherein the organosilicate (C) is at least one organosilicate selected from methyl silicate, ethyl silicate and butyl silicate and / or a hydrolytic condensate thereof. Resin composition.