JP2903297B2 - Non-staining paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-staining paint composition used for surface finishing of various materials such as metal, glass, porcelain tile, concrete, siding board, extruded board, and plastic.

[0002]

2. Description of the Related Art Conventionally, paint finishing has been carried out for protecting a frame of a building, a civil engineering structure, etc., imparting designability, and improving aesthetic appearance. In particular, in recent years, a fluorine resin paint, an acrylic silicone resin paint or an acrylic paint has been used. With the advent of highly durable paints such as urethane resin paints, great progress has been made in the protection of skeletons. However, these high-durability paints have resulted in the problem of contamination of the coating film surface being rather highlighted due to the excellent durability. That is, the coating film formed by the paint before the appearance of these highly durable paints, the surface is deteriorated by ultraviolet rays of sunlight,
Even if contaminants adhered, they were peeled off along with the deteriorated part of the coating surface.However, the appearance of the highly durable paint improved the durability of the coating, and the mechanism of the deterioration and peeling of the coating surface Has stopped working. Especially recently, in the city center and the suburbs, the exhaust gas from automobiles etc.
When oily contaminants are suspended in the atmosphere and these oily contaminants adhere to the surface of a coating film made of highly durable paint, the mechanism of deterioration and peeling of the coating film surface cannot function. Underneath, remarkable soot-like or streak-like contamination (rain streak stain) was generated and remained on the coating film surface, and the paint finish applied to improve the cityscape sometimes did not make sense.

[0003] As a method of solving such a problem, a non-contamination type paint which makes the surface of the coating film hydrophilic and uses the action of spreading rainwater during rainfall on the surface of the coating film to peel off and remove the attached oily contaminants. Have been announced. For example, Japanese Patent Application Laid-Open No. Hei 4-370176 discloses that a coating composition contains a segmented polymer containing a hydrophilic segment such as a polyalkylene oxide segment and a hydrophobic segment such as a polysiloxane to impart hydrophobicity and hydrophilicity to the coating film surface. Some of them are expected to provide the property simultaneously, suppress the adhesion of pollutants, and have a cleaning effect by rainfall. The hydrophilicity of the coating film surface is represented, for example, by the contact angle of the coating film surface with water as shown in FIG. 1, and the smaller this value is, the more hydrophilic the coating film is. Due to the hydrophilicity of the coating film surface, water derived from precipitation or the like permeates and flows into the interface between the coating film and the contaminant, and an effect of washing away the contaminant together with the water (soil release effect) is obtained.

The mechanism of making the surface of the coating film hydrophilic is described in the magazine “Surface” Vol. 32 No. 6 (199
4) On pages 55 to 61, "the surface properties of silicone-based polymer as a coating material" is introduced by the inventor of JP-A-4-370176 described above.
It is described as follows that the conversion of hydrophilicity / hydrophobicity of the coating film surface is caused by a morphological change. A silicone macromonomer having a structure in which an acylurethane bond serving as a hydrophilic segment and a siloxane bond serving as a hydrophobic segment are adjacent to each other is synthesized, and a copolymer thereof (containing 20% by weight of silicone macromonomer) on a film surface,
As a result of examining the relationship between the orientation state of each hydrophilic / hydrophobic segment and the atmosphere of the coating film surface, the initial contact angle with water on the copolymer film surface was 90 °,
After immersing the coating film in water at room temperature for 2 weeks, the surface becomes hydrophilic at 74 °, which is lower than that of a silicone-free system. Showed a tendency. In the acrylic copolymer film containing no silicone macromonomer as a comparative sample,
Such a phenomenon is not shown, and it can be assumed that the conversion phenomenon between hydrophilicity and hydrophobicity is caused by the structure of the silicone macromonomer. In addition, the surface after drying (DRY) and the surface immediately after immersion in water (WET) for 2 weeks were analyzed in the depth direction by ESCA. Elemental analysis is performed by selecting Si as the element indicating the concentration on the surface of the segment, and considering the state of the surface layer of the coating film based on the concentration ratio of both, when the environment of the coating film surface is hydrophobic, the silicone segment is It was presumed that when concentrated and conversely hydrophilic, the morphology change in which the acylurethane segment was concentrated occurred.

[0005] The phenomenon described in the above-mentioned document is that the hydrophilic portion localized near the surface of the coating film is caused by the localization of the hydrophobic segment portion having a low surface free energy on the coating film surface. This indicates that a morphological change has occurred in which the water is present on the surface of the coating film, that is, when water is present due to rainfall or the like, the water migrates to the coating film surface and is localized. However, as described in the above literature, the morphological change from hydrophobic to hydrophilic of the coating surface is not actually performed immediately, but rainfall on the coating surface is somewhat long, When the contact time with water is long, it can gradually shift to hydrophilicity.

Further, when there is no rainfall for a long period of time, that is, when sunny weather continues, the surface of the coating film goes back to hydrophobicity. Again, prolonged contact with water is required. One of the measures to make the surface of the coating film hydrophilic by contact with water for a short period of time is to set the glass transition point of the polymer for forming the coating film low in order to easily cause a morphological change. However, in such a case, the surface hardness of the coating film is reduced, and as a result, dust that cannot be washed away due to the soil release effect is physically attached, which leads to permanent contamination.

On the other hand, Japanese Patent Application No. 6-506632 (International Publication No. WO94 / 06870) discloses that a coating is mixed with an organosilicate, and the reaction between the two is to impart both hydrophilicity to the coating film surface and improvement in hardness. The intended method is shown. Generally, an organosilicate is represented by the following reaction formula [Chemical formula 7]
The silanol groups generated by such a reaction cause the hydrophilicity of the coating film surface. Therefore, in order to make the surface of the coating film hydrophilic and improve the hardness, the hydrolysis reaction due to the presence of the first-stage acid catalyst is rate-determining. For this reason, in the paint, a surface treatment with an acid or the like is required in order to promote the reaction of the organosilicate. Considering the painting on the actual building exterior,
It is thought that the reaction proceeds due to acid rain, etc., but as described above, it takes a considerable period of time after the formation of the coating film to become a hydrophilic surface necessary for fully exhibiting the soil release effect. Oily stains adhere and permeate before becoming hydrophilic.

[0008]

Embedded image

Further, Japanese Patent Application Laid-Open No. Hei 6-145453 discloses a method of obtaining a hydrophilic coating film by mixing an organosilicate with an acrylic silicone resin. Acrylic silicone resin has the same curing mechanism because the functional group contributing to its curing is a hydrolyzable silyl group similar to organosilicate, and therefore, usually an acid or base is cured for coating film formation. It is mixed as a catalyst. Since these catalysts cause the reaction of the organosilicate to proceed at the same time, the surface of the coating film is hydrophilized relatively quickly. However, as described in JP-A-6-145453, an acrylic silicone resin which originally contains a hydrolyzable silyl group in a part of its molecule and adjusts the degree of crosslinking of a coating film has many crosslinking sites. When a large amount of the organosilicate is blended, the crosslink density of the coating film becomes too large, the coating film becomes brittle, and ionic bonds are strong, and a large number of siloxane bonds highly hydrolyzable by an acid or a base are introduced. The chemical resistance of the film is reduced, and as a result, the weather resistance of the coating film is reduced. Therefore, in order to improve the hydrophilicity of the coating film, a large amount of the organosilicate is required, but there is a contradiction that when the amount is too large, the physical properties of the coating film are impaired.

[0010]

Among the coating films formed by conventional non-staining paints, those which require a long period of time for hydrophilicity of the surface are those which are not contaminated in the initial stage after the formation of the coating film. Due to the low property, rain streaks and the like are generated in a very short time after the completion of the painting work. Originally, the effect of not contaminating non-contamination type paint is to make the effect, and the user who uses it and the client who requests the painting work are expecting the effect. Therefore, even in the early stage after the formation of the coating film, the occurrence of stains does not occur.
It temporarily disappoints the expectations of these users and owners, and gives anxiety to long-term non-polluting effects. In addition, conventional non-polluting paints are mainly intended for the flow of pollutants due to rainfall,
It was found that the resistance to penetration of dirt once adhered was inferior, and when there was no rainfall for a long period of time, oily dirt penetrated into the coating film, and dirt that would no longer flow down due to rainfall remained.

Further, a paint obtained by simply mixing an organosilicate for the purpose of imparting a non-staining property to a generally used urethane resin paint is particularly applied once on a base material in the case of on-site coating. As a result, it was found that the influence of the uneven surface of the base and uneven coating due to uneven suction occurred. In addition, if a coating containing only this organosilicate is applied once more on the first coating to cover the uneven coating, an apparently beautiful coating can be formed, but the interlayer adhesion is remarkable. Blisters that are thought to be caused by the drop are generated over time on the coating film surface, and cracking of the coating film is also observed, and the high durability performance characteristic of the original urethane resin paint is missing It became clear that. Therefore, when coating is performed a plurality of times, particularly in the case of repair coating or the like, since partial coating is performed again after a long period of time, such a decrease in interlayer adhesion becomes a serious problem. In the case of a urethane resin paint in which only an organosilicate is simply mixed into a general urethane resin paint, it takes a certain amount of time for the urethane resin to undergo a crosslinking and curing reaction, while the organosilicate is localized on the coating film surface. It is considered that a coating film having a very high crosslink density on the surface was formed because of a tendency to react with the moisture in the air. It is presumed that such a coating film having a high crosslink density on the surface causes an extreme decrease in the adhesion between the film and the second layer of the overcoating film, thereby causing the above-described decrease in the interlayer adhesion. You.

Therefore, the problem to be solved by the present invention is:
Due to the action that occurs after the film formation such as rainfall, the film does not become hydrophilic for the first time, but immediately after the film formation, the surface becomes hydrophilic, has a soil release effect to wash away contaminants, and has a specific cross-linking effect Due to its structure, it is strong but not brittle, and has excellent resistance to oily stain penetration, weather resistance,
Other properties of coating film are good, and it has excellent interlayer adhesion (hereinafter referred to as "recoating property") when performing multiple coatings, and effectively prevents blisters, cracks, or lifting from occurring over time. An object of the present invention is to obtain a non-staining paint composition which forms a non-staining type coating film.

[0013]

Means for Solving the Problems The present invention relates to the following non-staining paint composition. That is, 1. (A) 100 parts by weight of the solid content of a polyol having a weight average molecular weight of 5,000 to 80,000 and a hydroxyl value of 20 to 150 KOHmg / g, and (B) an alkylene having 2 to 40 repeating units per 100 parts by weight. An alkoxysilane compound containing an oxide chain and having a weight average molecular weight of 150 to 3500 is 0.1 to 20 parts by weight in solid content;

Embedded image embedded image Si (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (R ₁ , R ₂ , R ₃ and R ₄ are the same or different alkyl groups having 1 to 10 carbon atoms) 1 to 40 parts by weight of a solid content of an alkyl silicate or a condensate thereof, 0.02 to 5.0 parts by weight of a (D) amine compound in a solid content, and (E) a polyisocyanate as a curing agent Is OH / NC with respect to the hydroxyl group of the polyol (A).
The present invention relates to a non-staining paint composition characterized by being contained so that the O equivalent ratio is 0.6 to 1.5. Also,

2. (A) 5000 to 5,000 in weight average molecular weight
80000, hydroxyl value 20 KOHmg / g-150 KOHmg
/ G of a polyol (B) having 2 to 40 repeating units.
Weight average molecular weight containing an alkylene oxide chain of 1
(E) a polysilane comprising 50 to 3500 alkoxysilane compounds, (C) at least one of the alkyl silicate represented by the general formula [Chem. 8] or a condensate thereof, and (D) a main agent containing an amine compound; It is composed of two packs of a curing agent containing isocyanate, and (B) is 0.1 to 20 parts by weight in terms of solids with respect to 100 parts by weight of solids in use (A).
(C) is 1 to 40 parts by weight, (D) is 0.02 to 5.0 parts by weight, and (E) is based on the hydroxyl group of (A).
The present invention also relates to a two-pack type non-staining paint composition which is used by mixing a base resin and a curing agent so that the OH / NCO equivalent ratio becomes 0.6 to 1.5. As a combination of components constituting the coating composition,

3. A main agent containing the polyol of the component (A) and the amine compound (D);
The composition comprises two packs of an alkoxysilane compound as a component, (C) at least one of the alkyl silicate represented by the general formula [Chem. 7] or a condensate thereof, and (E) a curing agent containing a polyisocyanate. Paint composition,

4. A main ingredient containing the polyol as the component (A), the alkoxysilane compound as the component (B), and the amine compound as the component (D);
(C) a coating composition comprising two packs of at least one of an alkyl silicate represented by the general formula [7] or a condensate thereof, and (E) a curing agent containing polyisocyanate, or ,

5. A main component containing the polyol as the component (A), and (C) at least one of the alkyl silicate represented by the general formula [7] or a condensate thereof, and the amine compound as the component (D). ,
It consists of two packs of an alkoxysilane compound as the component (B) and a curing agent containing the polyisocyanate as the component (E). Based on 100 parts by weight of the solid content at the time of use (A), ( B) is 0.1 to 20 parts by weight,
(C) is 1 to 40 parts by weight, (D) is 0.02 to 5 parts by weight, and (E) is OH relative to the hydroxyl group of (A).
The present invention also relates to a non-staining paint composition used by mixing a main agent and a curing agent so that the / NCO ratio becomes 0.6 to 1.5. The polyol of the component (A) used in the non-staining paint composition of the present invention is preferably an acrylic polyol.

As the alkoxysilane compound as the component (B), it is preferable to use a compound having a polyalkylene oxide chain having an ethylene oxide chain whose one end is a hydroxyl group. Even an alkoxysilane compound having a polyethylene oxide chain having a hydroxyl group at one end can be used as a component of a two-pack type coating composition.

Further, as the alkyl silicate as the component (C), it is preferable to use at least one of tetramethyl silicate and tetraethyl silicate. As the amine compound of the component (D), a general formula

Embedded image N (R ₅ ) (R ₆ ) (R ₇ ) (R ₅ , R ₆ and R ₇ are an alkyl group having 1 to 5 carbon atoms, an alkanol group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. Use of an amine compound represented by the same or different groups selected from aminoalkyl groups and alkoxysilyl groups having 1 to 5 carbon atoms) is a major feature of the non-staining coating composition of the present invention.

It is preferable that the polyisocyanate of the component (E) is dissolved in a solvent containing 5% by weight or more of a ketone from the viewpoint of storage stability. (A) ~
In addition to the component (E), it is also preferable to contain a color pigment as the component (F), and such a color pigment is preferably added to the main agent. Including an extender pigment as the component (G) instead of or together with the color pigment is also an effective method for obtaining a non-staining paint composition having a matte coating film. As in the case of the color pigment as the component (F), the extender of the component (G) is preferably contained in the main component.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail along with its embodiments. The polyol of the component (A) means a polyol generally used in the technical field of polyurethane, particularly in the technical field of polyurethane paint. By mixing and reacting with a polyisocyanate as a curing agent, the polyol is used as a component of the non-staining paint composition. In the formed non-contaminated coating film, it is a main component of the coating film formation.

Such polyols include polyether polyols, polyester polyols and acrylic polyols. As a polyether polyol,
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin,
Obtained by adding one or more kinds of polyhydric alcohols such as trimethylolpropane, pentaerythritol, glucose, sorbitol, and sucrose to one or more kinds of propylene oxide, ethylene oxide, butylene oxide, styrene oxide and the like. And polyoxytetramethylene polyols obtained by adding tetrahydrofuran to the polyhydric alcohol by ring-opening polymerization.

Examples of the polyester polyols include one or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, pentaerythritol and other low molecular weight polyhydric alcohols. Polycondensation with glutaric acid, adipic acid, pimelic acid, speric acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, hydrogenated dimer acid or other low-molecular dicarboxylic acid or oligomeric acid; Examples thereof include polyols such as union, ring-opening polymers of ring-opening esters such as propiolactone, caprolactone, and valerolactone.

In the acrylic copolymer, β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, β-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, β-hydroxybutyl acrylate Hydroxyalkyl esters of acrylic acid such as hydroxypentyl or similar hydroxyalkyl esters of methacrylic acid; furthermore, glycerin, acrylate monoesters of polyhydric alcohols such as trimethylolpropane or methacrylic monoesters similar thereto, N-methylol acrylamide Alternatively, acrylic polyl having two or more hydroxyl groups in one molecule using a monoethylenically unsaturated monomer having a hydroxyl group such as N-methylol methacrylamide as a copolymerization monomer can be used. In addition, phenolic resin polyols, epoxy polyols, polybutadiene polyols, polyisoprene polyols, polyester-polyether polyols, polymer polyols obtained by vinyl addition or dispersion of monomers such as acryl and styrene, urea-dispersed polyols, carbonate polyols, and the like. It can be used as the polyol of the invention. In particular, in consideration of the weather resistance of a non-stained coating film formed from the composition of the present invention, an acrylic polyol is desirable.

The polyol used in the present invention has a weight average molecular weight of 5,000 to 80,000, preferably 20,000 to 60,000. Molecular weight 5000
When it is smaller, the curability and durability of the coating film are not sufficient, and when it is more than 80000, the finish property of the coating film is not sufficient.

Further, these polyols have a hydroxyl value of 2
0 KOHmg / g to 150 KOHmg / g, preferably 30 KOH
mg / g to 100 KOHmg / g. Hydroxyl value is 20 KOH
If the amount is less than mg / g, the durability and stain resistance of the coating film are poor.
If it exceeds 50 KOHmg / g, the durability and flexibility of the coating film are not sufficient. The glass transition point of these polyols is from -10C to 150C, preferably from 10C to 100C. When the temperature is lower than -10 ° C, the stain removal property and the contamination recovery property are poor. When the temperature is higher than 150 ° C, flexibility and durability are poor.

Next, the alkoxysilane compound containing a polyalkylene oxide chain, which is the component (B) used in the present invention (hereinafter, simply referred to as the component (B)) is composed of at least one alkylene oxide repeating unit. It is a compound having the above alkoxysilyl group. In the polyalkylene oxide repeating unit of the component (B), the alkylene portion has 2 to 4 carbon atoms, and the number of repeating units is 2 to 40, preferably 2 to 20.
In the component (B), both ends of the polyalkylene oxide chain may be alkoxysilyl groups, one end may be an alkoxysilyl group, and the other end may be another functional group. Examples of such a functional group that can be provided at one end include a vinyl group, a hydroxyl group, an epoxy group, an amino group, an isocyanate group, and a mercapto group. Particularly, the use of a hydroxyl group (hydroxyl group) is preferred. Further, the functional group may be bonded to an alkoxysilyl group via a urethane bond, a urea bond, a siloxane bond, an amide bond, an ether bond, or the like.

As the component (B), for example, a compound synthesized by reacting a compound containing a polyalkylene oxide chain with a compound containing an alkoxysilyl group (hereinafter, referred to as a coupling agent) can be used.

The polyalkylene oxide chain-containing compound preferably has a weight average molecular weight of 150 to 3500,
200 to 1500 are more preferred. When the weight-average molecular weight is less than 150, the cured film finally obtained is inferior in hydrophilicity, and a cleaning effect of contaminants due to rainfall cannot be obtained. When the weight-average molecular weight exceeds 3500, the water resistance of the cured product and Hardness decreases.

Examples of such polyalkylene oxide chain-containing compounds include polyethylene glycol, polyethylene-propylene glycol, polyethylene-tetramethylene glycol, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyoxyethylene diglycolic acid, and polyethylene glycol. Examples include vinyl ether, polyethylene glycol divinyl ether, polyethylene glycol allyl ether, and polyethylene glycol diallyl ether. The polyalkylene oxide chain-containing compound can be selected from one kind or a combination of two or more kinds. When two or more types of monomers are used, they may be random copolymers or block copolymers.

On the other hand, the coupling agent is, for example, a compound having at least one or more alkoxysilyl groups and other substituents in one molecule. Specific examples of the coupling agent include β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, and N-β (Aminoethyl) γ-aminopropylmethyldimethoxysilane, N-
β (aminoethyl) γ-aminopropylmethyltrimethoxysilane, γ-aminopropyltrimethoxysilane,
Examples include γ-aminopropyltriethoxysilane, isocyanate-functional silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, and γ-methacryloxypropyltriethoxysilane.

The synthesis of the component (B) is not particularly limited, but a polyalkylene oxide chain-containing compound and a coupling agent are separately prepared. For example, for each compound having a polymerizable double bond, a radical polymerization initiator is used. In addition to copolymerization using an amino group, it can be synthesized by a known method such as an addition reaction of an amino group / epoxy group, an isocyanate group / hydroxyl group or an isocyanate group / amino group. It can also be synthesized by a method in which ethylene oxide is ring-opened to an alkoxysilyl compound having an active hydrogen group such as a primary or secondary amino group.

When the copolymerization is carried out using a radical polymerization initiator, at least one or more of the polyalkylene oxide chain-containing compounds having a polymerizable double bond and at least one or more of the coupling agents may be used in a non-reactive, appropriate manner. It can be obtained by reacting in a suitable solvent. At this time, as the radical polymerization initiator used, for example, benzoyl peroxide, dichlorobenzoyl peroxide, 2,5-
Di (peroxybenzoate) hexyne-3,1,3-
Bis (t-butylperoxyisopropyl) benzene,
Examples include perester compounds such as t-butyl perbenzoate, azo compounds such as azobisisobutyronitrile and dimethylazobutyrate, and organic peroxides.

As the polyalkylene oxide chain-containing compound having a polymerizable double bond, for example, polyethylene glycol vinyl ether can be used, and γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyl Methyldiethoxysilane and γ-methacryloxypropyltriethoxysilane can be used alone or in combination of two or more.

When the compound is synthesized by an addition reaction of isocyanate / polyol, for example, a compound having a hydroxyl group at a terminal such as polyethylene glycol is used for a compound containing a polyalkylene oxide chain, and an isocyanate such as an isocyanate-containing coupling agent is used as a coupling agent. Compounds having a group are mixed and synthesized. In this synthesis method, it is also possible to use an organometallic reaction catalyst known in the field of polyurethane synthesis, such as dibutyltin dilaurate, dibutyltin maleate or dioctyltin maleate.

As the component (B) synthesized by the above-mentioned reaction, a compound obtained by adding a coupling agent to both ends or one end of a polyalkylene oxide chain-containing compound can be obtained. And may be used as a mixture.

Of these components (B), those having an alkylene oxide chain of an ethylene oxide chain and a hydroxyl group at one end are the most preferred because of their high contamination-preventing effect, that is, high stain resistance and permeation resistance. preferable.

The compounding ratio of the component (B) is from 0.1 to 20 parts by weight, preferably from 0.2 to 10 parts by weight, based on 100 parts by weight of the resin solids of the component (A). If the amount is less than 0.1 part by weight, the obtained cured product is not sufficiently hydrophilic and 2
If the amount exceeds 0 parts by weight, the compatibility with the resin, the water resistance of the cured product, and the like will be poor.

Next, the alkyl silicate represented by the general formula [Chemical Formula 1] or the condensate thereof (hereinafter, simply referred to as the component (C)) used as the component (C) in the present invention is, for example, At least one selected from methyl silicate, tetraethyl silicate, tetra-n-propyl silicate and tetra-i-propyl silicate is obtained as a condensate by condensing the above tetraalkyl silicate under hydrolysis conditions. At least one selected from the group consisting of: Each of these alkyl silicates and their condensates may be used alone, a plurality of alkyl silicates may be used, or one or more alkyl silicates and their condensates may be used in combination. In particular, use of at least one of tetramethyl silicate and tetraethyl silicate or a condensate thereof is preferred from the viewpoint of the balance between flexibility and denseness of the formed coating film.
When a condensate is used, the degree of condensation is preferably from 2 to 20, and when the degree of condensation exceeds 20, the viscosity of the condensate increases, handling becomes inconvenient and compatibility with the polyol deteriorates, and the paint This results in cloudiness.

The mixing ratio of the component (C) is 1 to 40 parts by weight based on 100 parts by weight of the resin solids of the component (A).
Suitably, parts by weight, preferably 2 to 20 parts by weight, are suitable. When the amount is less than 1 part by weight, the surface hardness of the cured coating film is not sufficient, causing physical adhesion of contaminants, causing permanent contamination. This is because there is a problem that the appearance deteriorates and cracks occur.

Next, the amine compound as the component (D) used in the present invention is preferably a water-soluble amine, and may be a primary amine such as ethylamine, dimethylamine, diamylamine, cyclohexylamine, aniline, hexamethylenediamine or ethylenediamine. Secondary amines, amine compounds having only alkyl groups as substituents, such as trimethylamine and triethylamine, and ethanolamine, diethanolamine, dimethylethanolamine, N-methyldiethanolamine, triethanolamine as those containing alkanol groups as substituents, Compounds containing an aminoalkyl group such as ethylphenylethanolamine include triethylenediamine ([2,2,2] diazabicyclooctane), tetramethylethylenediamine, and pentamethyldiethylene. Riamin like, other pyridine, organic amines such as morpholine can be exemplified. As in the case of the above-mentioned triethylenediamine, in the aminoalkyl-substituted amine compound [formula 6], a compound in which R ₅ , R ₆ , and R ₇ form a cyclic structure linked via another nitrogen atom, Are also included in the scope of the present invention.

Examples of the amine compound having an alkoxysilyl group include aminosilanes such as aminomethyltriethoxysilane, diaminomethyldiethoxysilane, γ-aminoisobutyltrimethoxysilane, and γ-aminopropylmethyldiethoxysilane. You.

By incorporating such an amine compound, the recoating property is particularly improved, a strong coating film can be formed, and a non-staining coating film having extremely excellent durability can be obtained. . Although the reason is not clear, the use of such an amine compound balances the crosslinking reaction of the compound having an alkoxysilyl group and the polyurethane formation reaction, and prevents the extreme localization of the alkyl silicate particularly on the coating film surface. It is presumed that, as a result, the proportion of the polyurethane component present on the coating film surface is increased, so that the recoating property is improved, and at the same time, the effect of the alkoxysilane compound having an alkylene oxide chain is sufficiently exerted.

Of these amine compounds, a tertiary amine compound represented by the aforementioned general formula [Chemical Formula 6] can be most preferably used. The reason is that when the amine compound is a primary amine or a secondary amine, an NH group exists, and this hydrogen atom is active,
This is because it easily reacts with the O group. When the NH group and the NCO group react, a urea bond is formed, but the urea bond is formed by the reaction between the NH group and the NCO group faster than the OH group and the NCO group react to form a urethane bond. This is because the presence of the group inhibits the urethane bond formation reaction and slightly affects the properties of the coating film. However, even if an NH group is present, this does not pose a serious problem in practical use in consideration of the amount of the amine compound added.

The mixing ratio of the amine compound is 0.02 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of the solid content of the component (A). . When the amount of the amine compound is less than 0.02 parts by weight, the recoating property is lost, and the effects intended by the present invention cannot be obtained. On the other hand, if it exceeds 5.0 parts by weight, the weather resistance of the coating film will be reduced, and it will be less practical. The amine compound may be handled and added in the same manner as a usual coating material.

In the present invention, the polyisocyanate (E) (hereinafter simply referred to as the component (E)) is blended and cured by crosslinking to form a non-contaminated coating film. As such a curing agent,
Toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, xylylene diisocyanate (XD
I), hexamethylene diisocyanate (HMDI),
Isophorone diisocyanate (IPDI), hydrogenated XD
I, allophanate, biuret, dimerization (uretidione) of isocyanate monomer such as hydrogenated MDI,
Derivatized products by trimerization (isocyanuration), adduct formation, carbodiimidization reaction, and the like, and mixtures thereof can be used. In particular, in consideration of yellowing of a formed coating film, it is preferable to use an aliphatic or alicyclic polyisocyanate or a mixture thereof. Further, these (E) components include alcohols, phenols, ε-caprolactam, oximes,
It can also be used in the form of a blocked isocyanate using a blocking agent such as active methylene compounds. These (E)
The components are also preferably used as a solution in a solvent that does not contain active hydrogen.

The mixing of the polyisocyanate and the component (A) is carried out at a ratio such that the OH / NCO ratio is 0.6 to 1.5, preferably 0.8 to 1.2. At this time, if the OH / NCO ratio is smaller than 0.6, the curability of the coating film,
As the durability decreases, the so-called stain recovery property, that is, the effect of adding a polyalkylene oxide chain-containing alkoxysialan compound to wash away stains also decreases, and the stain penetration resistance becomes insufficient. Conversely, if it is larger than 1.5, the NCO group becomes excessively large.
As a result, it takes a long time for the reaction of the O group to be completed. As a result, the curability is reduced, and the cured coating film has a high crosslink density. Since dirt enters the cracks, durability and decontamination properties are not sufficient.

These (A), (B), (C), (D),
The component (E) can form a non-contaminated coating film by mixing the components at the time of use, but usually, the components (A), (B), (C), and (D) A mixture obtained by mixing two packs of the component (E), a mixture obtained by mixing the components (A) and (D), and two packs of the components (B), (C) and (E), (A) and (B) , (D) and two packs of components (C) and (E), or a mixture of components (A), (C) and (D) and two packs of components (B) and (E). They may be stored at the time of use, and they may be mixed at a ratio such that an optimum OH / NCO ratio is obtained at the time of use. Particularly, two packs of a mixture of the components (A) and (D) and components (B), (C) and (E) are desirable from the viewpoint of storage stability of the components (B) and (C). In this case, according to a conventional method, a component containing a hydroxyl group is used as a main component,
A component containing an isocyanate group (NCO group) is called a curing agent. These components (E) are preferably used as a solution in a solvent containing no active hydrogen, and in particular, a ketone consisting of acetone, methyl ethyl ketone, 2-pentanone, 2-hexanone, cyclohexanone or the like alone or in a mixture of 5% by weight or more. The solvent used is preferable, and the solvent exhibits an excellent effect in terms of storage stability, and particularly, the effect that the compatibility of the system obtained by mixing the alkyl silicate as the component (C) with the component (E) is good. Also shown.
In particular, in order to prevent the isocyanate group from reacting and inactivating due to water entering the storage container, Ad is used.
Desirable is the addition of DI (manufactured by Bayer AG).

Further, when the above-mentioned blocked isocyanate is used, (A), (B), (C), (D),
(E) can be made into one pack. When this one-pack type paint is used, NCO groups are generated by dissociating the blocking agent by heating or the like after coating to crosslink and cure the coating film. Can be done. In this case, it is preferable to add a catalyst which is usually used for promoting the reaction between the isocyanate group and the hydroxyl group.

In the composition of the present invention, (A), (B),
In addition to the transparent (clear) coating of the components (C), (D) and (E), a coloring pigment may be blended to form a coloring (enamel) coating. , Zinc oxide, carbon black, ferric oxide (bengara), lead chromate (molybdo orange), graphite, yellow iron oxide, ocher, ultramarine, cobalt green and other inorganic pigments, azo, naphthol, pyrazolone , Anthraquinone, perylene, quinacridone, disazo,
Organic pigments such as isoindolinone type, benzimidazole type, phthalocyanine type and quinophthalone type can be used.

It is also possible to use extenders such as heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon, and diatomaceous earth. In particular, when a matte coating film is formed, it is optimal to use white carbon or diatomaceous earth which least impairs the non-staining effect on the coating film surface.
When these inorganic substances are added to the paint, it is preferable to treat the powder surface with a coupling agent or to add the coupling agent to the paint.

In the composition of the present invention, it is possible to add various additives which can be added to the coating material to such an extent that the effects of the present invention are not affected. Examples of such additives include a plasticizer, a preservative, a fungicide, an antialgal agent, an antifoaming agent, a leveling agent, a pigment dispersant, an anti-settling agent, an anti-sagging agent, and an ultraviolet absorber.

In the coating composition of the present invention, each component can be mixed by a general stirring device such as a propeller type, and the obtained composition can be used for coating generally used in coating. It can be applied by a method, for example, spray coating, brush coating and the like. Further, a device that performs mixing and coating simultaneously, such as a multi-head type spray device, may be used.

[0054]

EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention. (Synthesis Example 1) Polyalkylene oxide chain-containing coupling agent 1 Synthesis Example Polyethylene glycol 200 (average molecular weight 200; Wako Pure Chemical Industries, Ltd.) was placed in a reaction vessel equipped with a heating device, a stirrer, a reflux device, a dehydration device, and a thermometer. 20 parts by weight) and 54.3 parts by weight of Y-9030 (manufactured by Nippon Unicar Co., Ltd.), which is an isocyanate-containing silane, and 0.05 parts by weight of dibutyltin dilaurate were charged at 50 ° C. The reaction was performed for 8 hours to obtain a pale yellow polyethylene oxide chain-containing coupling agent (1). The weight average molecular weight of this polyethylene oxide chain-containing coupling agent was 800 as measured by gel permeation chromatography (hereinafter referred to as GPC) in terms of polystyrene.

(Synthesis Example 2) Synthesis Example of Polyalkylene Oxide Chain-Containing Coupling Agent 2 Epolite 40E, which is a polyethylene glycol glycidyl ether (average), was placed in a reaction vessel equipped with a heating device, a stirrer, a reflux device, a dehydration device, and a thermometer. Molecular weight 170: 100 parts by weight (manufactured by Kyoeisha Chemical Co., Ltd.) and A-1100 (manufactured by Nippon Unicar Co., Ltd.) which is an amino group-containing silane.
0 parts by weight and reacted at 50 ° C. for 8 hours to obtain a pale yellow polyethylene oxide chain-containing coupling agent (2). The weight average molecular weight of the polyethylene oxide chain-containing coupling agent was 980 as measured by GPC in terms of polystyrene.

Example 1 150 mm × 70 mm × 0.
SK # 1000 primer (epoxy resin primer, manufactured by SK Chemical Co., Ltd.) was spray-coated on 12 8 mm aluminum plates so that the dry film thickness was about 30 μm. Drying was performed for hours. Next, using the raw materials shown in Table 1, 42 parts by weight of titanium oxide was uniformly kneaded with respect to 100 parts by weight of the solid content of the acrylic polyol 1 as shown in the mixing ratio of Table 2,
In addition, a polyethylene oxide chain-containing coupling agent 1
3.0 parts by weight, 10 parts by weight of methyl silicate 1 and 0.5 parts by weight of the amine compound 1 were blended to prepare a main agent of a white paint. A non-staining paint composition obtained by adding 7.5 parts by weight of a hexamethylene diisocyanate trimer as a curing agent to the base material was added to the SK # 1000 of the aluminum plate.
The primer surface was spray-coated so that the dry film thickness was 25 μm. The OH / NCO equivalent ratio in this reaction is 0.9.

<Preparation of Specimen> Seven of the twelve coated aluminum plates were cured for 3 days at a temperature of 20 ° C. and a humidity of 65% for the following tests (1) to (7). After that, the non-staining paint composition produced at the same compounding ratio was spray-coated again so that the dry film thickness became 25 μm. At this time, the dry film thickness of the entire non-contaminated coating film was 5
It was 0 μm.

<Test Method> (1) Evaluation of Appearance after Curing of Coating Film The test specimen was cured at a temperature of 20 ° C. and a humidity of 65% for 7 days, and then subjected to JIS.
K5400 (1990) 7.1 The appearance of the coating film was evaluated according to the appearance test of the coating film.

(2) Durability evaluation The test specimens were cured at a temperature of 20 ° C. and a humidity of 65% for 7 days,
K5400 (1990) 8.20 Following boiling water test, immerse in boiling water for 1 hour, shake off water, temperature 20 ° C, humidity 65%
The coating film after drying for 2 hours was evaluated for appearance.

(3) Evaluation of acid resistance The test specimen was cured at a temperature of 20 ° C. and a humidity of 65% for 7 days,
K5400 According to the 8.22 acid resistance test, after immersion treatment in a 5% by weight sulfuric acid aqueous solution at 20 ° C for 1 week, the coating surface was washed with water and
The coating film after drying for 2 hours was evaluated for appearance.

(4) Evaluation of Alkali Resistance The test specimen was cured for 7 days at a temperature of 20 ° C. and a humidity of 65%.
K5400 5 wt% at 20 ℃ according to 8.21 alkali resistance test
After being immersed in an aqueous sodium hydroxide solution for one week, the coating film surface was washed with water and dried at 20 ° C. for 2 hours, and the appearance of the coating film was evaluated.

(5) Measurement of Contact Angle to Water After the test piece was prepared, the contact angle was set at 20 ° C. and 65% for 24 hours for 7 hours.
After drying for 2 hours and 14 days, 0.2
Immediately after dropping cc of deionized water and dropping at 20 ° C, the contact angle one minute later was measured with a CA-A type contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd.

(6) Stain resistance After the test specimen was cured at a temperature of 20 ° C. and a humidity of 65% for 7 days,
Outdoor exposure was conducted in Ibaraki City, Osaka Prefecture at a 45 ° southward inclination, and the lightness difference (△ L value) between the initial and six months was measured using a TC-1800 type color difference meter manufactured by Tokyo Denshoku Co., Ltd. Colored.

(7) Resistance to dirt penetration The test specimen was cured at a temperature of 20 ° C. and a humidity of 65% for 7 days.
K5400 8.10 15% by weight on coating surface according to stain resistance test
Aqueous dispersion liquid of carbon black of 20m in diameter
m, and dropped at a height of 5 mm, and left in a constant temperature room at 50 ° C. for 2 hours. Thereafter, the film was washed in running water, and the degree of contamination on the coating film surface was visually evaluated.

<Preparation of Interlayer Adhesion Evaluation Specimen> The remaining 12 aluminum plates coated as described above were subjected to a temperature
After drying for 16 hours, 1 day, 3 days, 5 days, and 7 days at 0 ° C. and 65% humidity, using a non-staining paint composition prepared at the same mixing ratio, the dry film thickness becomes 25 μm. Then, spray coating was performed again to obtain a test piece for evaluating interlayer adhesion. At this time, the dry film thickness of the entire non-contaminated coating film was 50 μm.

(8) Evaluation of interlayer adhesion The prepared test specimen was cured for 7 days at a temperature of 20 ° C and a humidity of 65% for 7 days, and adhered according to JIS K5400 (1990) 8.5 Adhesion Test 8.5.1. The sex was evaluated. The evaluation was shown by the scores as shown in Table 2. The larger the evaluation score, the better the coating film.

<Evaluation Results> (Example 1) Evaluation of appearance of coating film after curing, durability, acid resistance,
In both of the alkali resistance evaluations, no abnormality was observed in the coating film, and the coating film was in a good state. The contact angle with water was 68 ° immediately after the dropping at the time of measurement after 24 hours, 62 ° at the time of 1 minute, 58 ° immediately after the dropping at the time of measurement after 72 hours, 52 ° at the time of 1 minute, and dropped at the time of 14 days. The contact angle was 58 ° immediately after and 52 ° after 1 minute, and the contact angle was lower at the initial time such as 24 hours and 72 hours than in the comparative examples. Further, in the stain resistance evaluation, the ΔL value was −
1.9, indicating that good stain resistance was obtained. Further, no trace was observed in the stain penetration resistance test.
Therefore, it was proved that the adhered stain was present only on the surface of the coating film and was an excellent non-staining paint which could completely flow down by rainfall.

Furthermore, it can be seen that good interlayer adhesion is exhibited and the recoating property is excellent. In particular, after a long period of time after the formation of the first coating film, the second layer is excellent in interlayer adhesion even when the second layer is applied by lamination,
It was proved to be a non-staining paint having excellent recoating properties.

(Examples 2 to 6) A mixture was prepared according to Example 1 with the composition shown in Table 3, and the same evaluation as in Example 1 was carried out. Also, the contact angle was lower at the initial time such as 24 hours and 72 hours than in the comparative example. In addition, good results were also obtained in the evaluation of stain resistance and stain penetration, and no peeling occurred in interlayer adhesion.

Comparative Example 1 Evaluation was performed in the same manner as in Example 1 except that polyethylene glycol 1 was used instead of the polyethylene oxide chain-containing coupling agent 1 as in the formulation shown in Table 4. The results were as shown in Table 6, and glossiness occurred in the water resistance, acid resistance, and alkali resistance tests of the coating film. Furthermore, the decrease in the contact angle in the initial stage was not as large as that of the example, and good results were not obtained in the evaluation of stain resistance and stain penetration. In addition,
There was no particular problem with the interlayer adhesion.

(Comparative Example 2) Evaluation was performed in the same manner as in Example 4 except that polyethylene glycol 2 was used instead of the polyethylene oxide chain-containing coupling agent 1 as in the formulation shown in Table 4. As a result as shown in Table 6, the cured coating film was glossy, and the coating film was glossy also in the water resistance, acid resistance, and alkali resistance tests. Furthermore, the decrease in the contact angle in the initial stage was not as large as that of the example, and good results were not obtained in the evaluation of stain resistance and stain penetration. There was no particular problem with the interlayer adhesion.

Comparative Example 3 Evaluation was performed in the same manner as in Example 3 except that polyethylene glycol 2 was used in place of the polyethylene oxide chain-containing coupling agent 1 as in the formulation shown in Table 4. The results were as shown in Table 6, and glossiness occurred in the water resistance, acid resistance, and alkali resistance tests of the coating film. Furthermore, the decrease in the contact angle in the initial stage was not as large as that of the example, and good results were not obtained in the evaluation of stain resistance and stain penetration. In addition,
There was no particular problem with the interlayer adhesion.

(Comparative Example 4) Evaluation was performed in the same manner as in Example 1 except that no amine compound was used, as in the composition shown in Table 4, and the results were as shown in Table 6. Although no particular problem occurred in the acid resistance and alkali resistance tests, the peeling of the interlayer adhesion was remarkably increased as the number of days elapsed before recoating increased.

Comparative Example 5 Evaluation was performed in the same manner as in Example 5 except that the amine compound 2 was 0.01 part by weight, which was outside the lower limit of the range specified in the present invention, as in the formulation shown in Table 4. As a result, the results were as shown in Table 6, and there was no particular problem in the durability, acid resistance, and alkali resistance tests of the coating film. As for the result, as the number of days elapsed before the recoating became longer, the peeling was remarkably caused.

Comparative Example 6 Evaluation was performed in the same manner as in Example 5 except that the amount of the amine compound 2 was 6 parts by weight, which was outside the upper limit of the range specified in the present invention, as in the formulation shown in Table 4. Was performed, the results shown in Table 6 were obtained, and the coating film was discolored in the durability, acid resistance, and alkali resistance tests. On the other hand, the decrease in the contact angle in the initial stage was inferior to that of the examples.
As for the interlayer adhesion, it was found that the longer the number of days elapsed before recoating, the more significant peeling occurred.

Comparative Example 7 Ethyl silicate 1 and a curing agent were mixed with acrylic polyol 2 as shown in Table 4 and evaluated in the same manner as in Example 1. As a result, there was no abnormality in the water resistance, acid resistance, and alkali resistance of the coating film.However, a decrease in the contact angle in the initial stage was not as large as in the examples, and good results were obtained in the evaluation of stain resistance and stain penetration. Did not. In addition, as for the interlayer adhesion, as the number of days elapsed before the recoating became longer, the peeling was remarkably caused.

[0077]

According to the non-staining paint composition of the present invention, the coating film is not made hydrophilic for the first time due to the action that occurs after the coating film formation such as rainfall, but the surface becomes hydrophilic immediately after the coating film formation. And because of high resistance to dirt penetration,
Pollutants are washed away together with rainwater by rainfall, and a urethane-based coating film having excellent weather resistance is obtained, so that the surface of the object to be coated can be kept beautiful without being stained. Further, as an incidental effect, the coating film containing the amine compound showed a decrease in the initial contact angle as compared with the coating film containing no amine compound, and it was found that the hydrophilicity was still improved.

[0078]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Brief description of the drawings]

FIG. 1 Contact angle between coating film and water

[Description of Signs] a Water Drop b Coating Film θ Contact Angle

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 171: 02) (72) Inventor Takanori Nakashoya 1-25-10 Shimizu, Ibaraki-shi, Osaka SK Chemical Research Laboratory Co., Ltd. (72) Inventor Hisashi Suzuki 1-25-10 Shimizu, Ibaraki-shi, Osaka SK Kaken Co., Ltd. Laboratory (56) References JP-A-1-249707 (JP, A) (58) Fields investigated (Int .Cl. ⁶ , DB name) C09D 175/04-175/16 C08G 18/32 C08G 18/40-18/64 C09D 5/16

Claims (15)

(57) [Claims] (A) a weight average molecular weight of 5,000 to 800
(B) 100 weight parts of a solid content of a polyol having a hydroxyl value of 20 KOHmg / g to 150 KOHmg / g, (B) a polyalkylene oxide chain having 2 to 40 repeating units, and a weight average molecular weight of 150 ~ 3500 alkoxysilane compounds in a solid content of 0.1 to 20 parts by weight,
(C) General formula: embedded image Si (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (R ₁ , R ₂ , R ₃ and R ₄ are the same or different and have 1 to 10 carbon atoms. (Alkyl group) or at least one of these condensates is 1 to 40 parts by weight in terms of solid content, and the amine compound (D) is in the range of 0.02 to 5.0 in terms of solid content.
Parts by weight and (E) a polyisocyanate having an OH / NCO equivalent ratio of 0.6 to the hydroxyl group of the polyol (A).
A non-staining paint composition, which is contained so as to be 1.5 or less. (A) a weight average molecular weight of 5,000 to 80;
000, hydroxyl value is from 20 KOHmg / g to 150 KOHmg / g
Weight average molecular weight 1 containing a polyalkylene oxide chain having 2 to 40 (B) repeating units.
An alkoxysilane compound of 50 to 3500, (C) a general formula: Si (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (R ₁ , R ₂ , R ₃ and R _{4 each} have 1 carbon atom) (E) an alkyl silicate represented by the same or different alkyl groups or condensates thereof, and (D) a main agent containing an amine compound, and (E) a curing agent containing a polyisocyanate. (B) is 0.1 to 20 parts by weight in terms of solids with respect to 100 parts by weight of solids in use (A), and (C)
Is 1 to 40 parts by weight, (D) is 0.02 to 5.0 parts by weight, and (E) is OH /
A non-staining paint composition used by mixing a main agent and a curing agent such that the NCO equivalent ratio is 0.6 to 1.5. (A) a weight average molecular weight of 5,000 to 80;
000, hydroxyl value is from 20 KOHmg / g to 150 KOHmg / g
(B) a base agent containing an amine compound; (B) a weight average molecular weight of 150 to 350 containing a polyalkylene oxide chain having 2 to 40 repeating units.
0, an alkoxysilane compound represented by the formula (C): embedded image Si (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (R ₁ , R ₂ , R ₃ and R _{4 each} have 1 to 10 carbon atoms) And (E) two packs of a curing agent containing a polyisocyanate and a solid content of 100% at the time of use (A). (B) is 0.1-20 parts by weight, (C) is 1-40 parts by weight, (D) is 0.02-5.0 parts by weight, and (E) ) Is a non-staining paint composition used by mixing a main agent and a curing agent so that the OH / NCO equivalent ratio is 0.6 to 1.5 with respect to the hydroxyl group in (A). (A) a weight average molecular weight of 5,000 to 80;
000, hydroxyl value is from 20 KOHmg / g to 150 KOHmg / g
Weight average molecular weight 1 containing a polyalkylene oxide chain having 2 to 40 (B) repeating units.
50 to 3500 alkoxysilane compounds, and (D)
A main agent containing an amine compound; (C) a general formula: Si (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (R ₁ , R ₂ , R ₃ , R ₄ has 1 to 1 carbon atoms) (E), two packs of an alkyl silicate represented by the same or different alkyl groups) or condensates thereof, and (E) a curing agent containing a polyisocyanate. (B) is 0.1 to 20 parts by weight, (C) is 1 to 40 parts by weight, (D) is 0.02 to 5 parts by weight, and (E) is 100 parts by weight.
However, a non-staining paint composition used by mixing a main agent and a curing agent such that the OH / NCO equivalent ratio is 0.6 to 1.5 with respect to the hydroxyl group of (A). (A) a weight average molecular weight of 5,000 to 80;
000, hydroxyl value is from 20 KOHmg / g to 150 KOHmg / g
(C) a general formula: Si (OR ₁ ) (OR ₂ ) (OR ₃ ) (OR ₄ ) (R ₁ , R ₂ , R ₃ , and R ₄ are the same having 1 to 10 carbon atoms. Or different alkyl groups) or at least one of these condensates, and (D) a main agent containing an amine compound; (B) a polyalkylene oxide chain having 2 to 40 repeating units. Weight average molecular weight of 150 to 350
(A) consisting of two packs of an alkoxysilane compound of formula (C) and a curing agent containing (E) a polyisocyanate.
(B) is 0.1 to 20 parts by weight, (C) is 1 to 40 parts by weight, (D)
Becomes 0.02 to 5 parts by weight, and (E) has an OH / NCO equivalent ratio of 0.6 to 1.5 with respect to the hydroxyl group of (A).
A non-staining paint composition used by mixing a base agent and a curing agent such that 6. The non-staining paint composition according to claim 1, wherein the polyol (A) is an acrylic polyol. 7. The compound according to any one of claims 1 to 5, wherein the compound (B) uses, as the polyalkylene oxide chain, an alkoxysilane compound having a polyethylene oxide chain having a hydroxyl group at one end. Non-staining paint composition. 8. The non-staining paint composition according to claim 1, wherein at least one of tetramethyl silicate and tetraethyl silicate is used as the alkyl silicate (C). 9. The amine compound of (D) is represented by the following general formula: N (R ₅ ) (R ₆ ) (R ₇ ) (R ₅ , R ₆ and R ₇ are alkyl groups having 1 to 5 carbon atoms; An amine compound represented by the same or different group selected from an alkanol group having 1 to 5 carbon atoms, an aminoalkyl group having 1 to 5 carbon atoms, and an alkoxysilyl group having 1 to 5 carbon atoms). The non-staining paint composition according to any one of claims 1 to 5, wherein 10. The method according to claim 1, wherein the polyisocyanate (E) is an aliphatic or alicyclic polyisocyanate, or a mixture thereof.
A non-staining paint composition according to any one of the above. 11. The non-staining paint composition according to claim 3, wherein the polyisocyanate (E) is dissolved in a solvent containing 5% by weight or more of a ketone. 12. The non-staining paint composition according to claim 1, further comprising (F) a color pigment as a component. 13. The non-staining paint composition according to claim 2, wherein the base material further contains (F) a color pigment. 14. The matte non-staining paint composition according to claim 1, further comprising (G) an extender pigment as a component. 15. The matte non-staining paint composition according to any one of claims 2 to 5, wherein the main component further comprises (G) an extender pigment.