JP3161590B2 - 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 finishes have been performed to protect the frame of buildings, civil engineering structures, and the like, impart design, and improve aesthetics. In particular, in recent years, with the advent of highly durable paints such as fluororesin paints, acrylic silicone resin paints, and polyurethane resin paints, great progress has been made in protecting the frame. These durable paints, due to their durability,
On the contrary, the problem of contamination of the coating film surface was brought up. In other words, the coatings formed by the coatings prior to these weather-resistant coatings had their surfaces deteriorated by the ultraviolet rays of sunlight, and even if contaminants had adhered, they were peeled off together with the deteriorated portions of the coatings surface. However, since the durability of the coating film was improved, the mechanism of deterioration and peeling of the coating film surface could not function. In recent years, especially in urban and suburban areas, where oily contaminants are floating in the air due to exhaust gas from automobiles and other vehicles, these oily contaminants are coated with highly durable paint. If adhered to the surface, significant soot-like or streak-like contamination (hereinafter referred to as "rain streak") may occur, and the paint finish that should have been applied to improve the cityscape may not be meaningful. .

[0003] As a method for preventing such highly durable paint from being easily contaminated, WO 94/06870 is known.
It has been practiced to incorporate a specific organosilicate and / or a condensate thereof into a coating as disclosed in US Pat. This is a technique in which a specific organosilicate is blended to make the surface of the coating film hydrophilic, making it difficult for oily contaminants to adhere, and even if it adheres, it is washed away with water drops such as rainfall.

[0004] However, most of such anti-pollution type highly durable paints are generally solvent-type paints. In recent years, however, due to increasing environmental awareness, the use of solvent-type paints to weak solvent-type paints and further to water-based paints has been increasing. The conversion has been eagerly awaited.

[0005]

Accordingly, the present inventors have determined that the resin applicable to the weak solvent type paint, that is, the solubility parameter (hereinafter, referred to as "SP") is 6.5-9.
The application of a pollution control technique to paints using a polyol which is 5 and can be dissolved and / or dispersed in a solvent having low solubility was attempted.

[0006] First, isocyanate is added to an acrylic polyol having an SP of 8.7, and methyl silicate (weight average molecular weight: 1000, silica remaining ratio: 56% by weight) available from Company A is added thereto, followed by painting on an aluminum plate. As a result, the resulting resin film became cloudy. This phenomenon is presumed to be due to poor compatibility between the urethane resin and methyl silicate. Further, the same methyl silicate was added to a coating of the same urethane resin to prepare a coating containing methyl silicate. When this was applied to an aluminum plate to form a coating film and then exposed outdoors, rain streak stains were generated, and it could not be said that the film was a pollution control coating film.

In general, when an organosilicate (that is, an alkyl silicate) is incorporated into a paint, it is considered that when a coating film is formed, it reacts with moisture in the air to cause the following hydrolysis. ing.

Embedded image This hydrolysis reaction renders the coating hydrophilic, and makes it difficult for oil-based contaminants to adhere. Even if it adheres, the coating is washed away by moisture such as rainfall. This is based on the premise that the alkyl silicate is oriented on the surface of the coating film.

When a resin that is soluble only in a solvent having a high dissolving power is used, the coating is certainly hydrophilic and a non-staining effect can be obtained, so that such surface orientation occurs. However, when a resin that dissolves or disperses in a solvent with low dissolving power is used, the phenomenon that the film is not cloudy or the non-staining effect is not obtained as described above has occurred. It was thought that the surface orientation did not occur.

Therefore, the compatibility and stain resistance of a urethane resin using a polyol having an SP of about 6.5 to 9.5 and a commercially available alkyl silicate were examined. The result was that both the compatibility and the stain resistance were not excellent.
Therefore, in particular, a urethane resin-based paint using a polyol having an SP of 6.5 to 9.5 cannot be a non-stained paint simply by adding a commercially available alkyl silicate.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies, and as a result, they have been able to dissolve and / or dissolve even in a solvent having a particularly low dissolving power.
Or, in a urethane resin-based paint using a polyol capable of being dispersed and having a SP of 6.5 to 9.5, by blending a tetraalkoxysilane low-condensate having a specific structure and an amine compound into the paint, It is possible to provide a coating film which is excellent in stain resistance and interlayer adhesion and has good durability. Further, if necessary, a polyalkylene oxide chain-containing alkoxysilane compound can be blended to improve the initial staining property immediately after the formation of the coating film. It has been found that by adjusting the solvent composition of the above, it can be suitably used for renovation work, and the present invention has been completed.

That is, the present invention relates to the following non-staining paint composition. 1. (A) solubility parameter is 6.5 to 9.5, weight average molecular weight is 5,000 to 150,000, and hydroxyl value is 15
~ 100 KOHmg / g, dissolved in non-aqueous solvent and / or
Alternatively, (B) an isocyanate is contained in an amount of 0.7 to 2.0 in NCO / OH ratio with respect to 100 parts by weight of the resin solid content of the dispersed polyol, and (C) average condensation of tetraalkoxysilane A condensate having a degree of 4 to 20 and an alkyl group in the condensate having 1 to 3 carbon atoms and 4 carbon atoms.
And a mixture in which the alkyl group having 4 to 12 carbon atoms is 5 to 50% of the total alkyl group in the condensate is 1.0% in terms of SiO _2.
A non-staining paint composition characterized by containing 0.02 to 5.0 parts by weight of (D) an amine compound in solid content. 2. (C) is a general formula

Embedded image (Wherein R _{1 to} R ₄ are a mixture of an alkyl group having 1 to 3 carbon atoms and an alkyl group having 4 to 12 carbon atoms). 2
0, a low-condensation product of tetraalkoxysilane condensed to have a weight average molecular weight of 500 to 5,000. A non-staining paint composition according to claim 1. 3. (C) is (a) general formula

Embedded image (Wherein, R ₅ is an alkyl group having 1 to 3 carbon atoms, and n is 4
An alkyl silicate low-condensate represented by the general formula (b):

Embedded image (In the formula, R ₆ is an alkyl group having 4 to 12 carbon atoms), (a) a compound obtained by transesterifying 5 to 50% of the alkyl groups of the alkyl silicate low-condensate. Features 1. A non-staining paint composition according to claim 1. 4. And (E) a polyalkylene oxide chain having 2 to 40 repeating units and a weight average molecular weight of 1
(A) 0.1 to 20 parts by weight of a solid content with respect to 100 parts by weight of a resin solid content of a polyol. ~
3. A non-staining paint composition according to any one of the above. 5. It is characterized in that at least 50% by weight of the total solvent in the paint is an aliphatic hydrocarbon. ~ 4. A non-staining paint composition according to any one of the above.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on its embodiments. (A) Polyol The (A) polyol (hereinafter, referred to as “(A) component”) in the present invention has an SP of 6.5 to 9.5, a weight average molecular weight of 5,000 to 150,000, and a hydroxyl value of 15 to 100.
Use KOH mg / g which is dissolved and / or dispersed in a non-aqueous solvent.

(1) Polyol The component (A) is dissolved or dispersed in a non-aqueous solvent, but the dissolved one is a dissolved polyol and the dispersed one is a non-aqueous solvent. A water dispersion type (hereinafter referred to as “NAD type”) polyol;
Can be classified into one.

Soluble Polyols Soluble polyols are soluble in non-aqueous solvents, and are specifically polyols having two or more hydroxyl groups in one molecule, such as alkyd polyols and acrylic polyols. Acrylated alkyd polyols or polyester polyols. Suitable for dissolving in non-aqueous solvent, SP is 6.5-9.
Examples of the polyol 5 include an alkyd polyol having an oil length of 40% or more, an alkyd polyol containing a material having a high affinity for a solvent such as pt-butylbenzoic acid, isobutyl methacrylate, and 2-ethylhexyl methacrylate. An acrylic polyol containing a raw material having a high affinity for a solvent having a low solubility such as acrylate can be given.

NAD-type polyol NAD-type polyol is a resin which is dispersed as a resin particle in a non-aqueous solvent, and has both a resin portion soluble in a non-aqueous solvent and a resin portion which does not dissolve in a non-aqueous solvent. is there. The resin portion soluble in a non-aqueous solvent is one having a solubility in a non-aqueous solvent of 99.0% by weight or more.
This depends on the type of the non-aqueous solvent, and may be any as long as it can be dissolved in the non-aqueous solvent to be finally dispersed. Conversely, the resin portion that does not dissolve in the non-aqueous solvent is one that does not dissolve in the non-aqueous solvent at all or has a very small amount (for example, the solubility is less than 1.0% by weight). Since this also depends on the type of the non-aqueous solvent, one that hardly dissolves in the non-aqueous solvent to be finally dispersed is used. As a specific example, an NAD-type polyol using an acrylic polyol as a soluble resin portion may be mentioned.

In the present invention, a soluble polyol or an NAD polyol can be used alone or in combination as the component (A).

The SP of the component (A) is used in the range of 6.5 to 9.5. By using such an SP, even a solvent having a weak solvent called a weak solvent can be used. It becomes dissolvable and / or dispersible and can be a weak solvent type paint. Of course, it is also possible to use it after dissolving it in a strong solvent having a strong dissolving power.

(2) Non-Aqueous Solvent The non-aqueous solvent includes all solvents other than water that can be used for polyols, and common solvents include organic solvents. Examples of the organic solvents include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, esters, ketones, and the like. As the aliphatic hydrocarbon solvent,
For example, n-hexane, n-pentane, n-octane,
In addition to n-nonane, n-decane, n-undecane, and n-dodecane, terpine oil, mineral spirit and the like can be exemplified. Examples of the aromatic hydrocarbon solvent include toluene, xylene, and solvent naphtha. Examples of other solvents include ethyl acetate, butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. Among such non-aqueous solvents, one kind or a combination of two or more kinds may be used.

The component (A) of the present invention has a weight average molecular weight of 5,000 to 150,000 and a hydroxyl value of 15 to 15,
100 KOH mg / g can be used. When the weight average molecular weight is less than 5,000, an appropriate viscosity cannot be obtained as a paint, and the properties of each coating film are inferior. On the contrary, when the weight average molecular weight is more than 150,000, the sharpness and gloss of the coating film are reduced, so that it is preferable. Absent. When the hydroxyl value is less than 15 KOHmg / g, the crosslink density is low, so that the properties of various coatings and stain resistance are poor. Conversely, when the hydroxyl value is more than 100 KOHmg / g, the crosslink density becomes high (C). It is not preferable because the surface orientation of the low-condensation product of tetraalkoxysilane is hindered.

(B) Isocyanate In the present invention, an isocyanate (hereinafter, referred to as “component (B)”) is blended and crosslinked and cured to form a non-contaminated coating film.
Examples of such a curing agent include Vernock DN-990,
DN-991, DN-992 (both manufactured by Dainippon Ink and Chemicals, Inc.), Duranate TSA (manufactured by Asahi Kasei Corporation), Takenate D-177N (manufactured by Takeda Pharmaceutical Co., Ltd.), Desmodur Z-4270 ( Sumitomo Bayer Urethane Co., Ltd.). These curing agents can be suitably used because they dissolve in a solvent having a low dissolving power. In addition, toluene diisocyanate (TD
I), 4,4-diphenylmethane diisocyanate (p
ure-MDI), polymeric MDI, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (I
Isocyanate monomers such as PDI), hydrogenated XDI, and hydrogenated MDI are converted into allohanate, biuret, dimerization (uretidione), trimerization (isocyanurate), adduct,
It is also possible to use those derivatized by a carbodiimide reaction or the like, or a mixture thereof in a solvent having a strong dissolving power. As the solvent for dissolving the component (B), the same solvents as those exemplified for the component (A) (2) non-aqueous solvent can be used.

Further, these components (B) can be used in the form of a blocked isocyanate using a blocking agent such as alcohols, phenols, ε-caprolactam, oximes and active methylene compounds. These are also preferably used as a solution with a solvent.

The mixing of the component (B) and the component (A) is carried out at a ratio such that the NCO / OH ratio is 0.7 to 2.0, preferably 0.8 to 1.5. At this time NC
When the O / OH ratio is smaller than 0.7, the crosslinking ratio of the coating film is lowered, and the curability and durability are deteriorated. In addition, the contaminants enter into the molecules having a low density of the coating film. Even if it is carried out, it is difficult to remove the contaminants, resulting in poor pollution recovery. On the other hand, if it is larger than 2.0, unreacted isocyanate remains, deteriorating the initial drying property, causing tackiness on the surface called tack and contaminants being physically attached, On the contrary, the initial contamination is inferior.

(C) Low Condensate of Tetraalkoxysilane The low condensate of tetraalkoxysilane having a specific structure (C) used in the present invention (hereinafter referred to as “component (C)”) has an average degree of condensation of tetraalkoxysilane. 4 to 20 condensates, wherein the alkyl group in the condensate is a mixture of C 1 to C 3 and C 4 to C 12, and the mixture ratio is an alkyl group of C 4 to C 12 Is a compound of 5 to 50% of all alkyl groups in the condensate.

The component (C) is a low-condensation product of tetraalkoxysilane, but the one having a high degree of condensation (average degree of condensation is greater than 20) and a high molecular weight are difficult to manufacture and are difficult to handle due to an increase in viscosity. It is not preferable because it is inconvenient. Conversely, those having an average degree of condensation of 3 or less and a low molecular weight are not preferred because they have high volatility and are also inconvenient to handle.

The compatibility of the component (C) with the component (A) is remarkably improved because the alkyl group in the component (C) contains one having 1 to 3 carbon atoms and 4 to 12 carbon atoms. A non-contaminated coating film having excellent surface orientation and excellent coating film physical properties can be formed. If the alkyl group is only an alkyl group having 1 to 3 carbon atoms, the compatibility with the component (A) is poor and the surface orientation is poor. Moreover, the carbon number is 4-1.
The use of only 2 alkyl groups is not preferred because the non-staining effect is significantly reduced. The presence of an alkyl group having 13 or more carbon atoms is not preferred because stain resistance is lost. In addition, as the number of carbon atoms of the alkyl group increases, the above-described hydrolysis reaction tends to be less likely to occur.
It is not preferable that only an alkyl group having a large number of carbon atoms be present. The component (C) is such that about 5 to 50% of the total alkyl group of the low-condensate is an alkyl group having 4 to 12 carbon atoms. Is preferred because of its excellent stain resistance.

The component (C) of the present invention can be produced by the following method, but is not limited thereto. General formula

Embedded image (Wherein, R _{1 to} R ₄ are a mixture of an alkyl group having 1 to 3 carbon atoms and an alkyl group having 4 to 12 carbon atoms).
(Preferably 6 or more), having a weight average molecular weight of 500 to 50.
The condensation is carried out so as to be 00 (preferably 800 or more). The condensation method is based on a known method.

In the formula, a part of the alkyl group represented by R _{1 to} R ₄ is
By having a mixture of one having 1 to 3 carbon atoms and one having 4 to 12 carbon atoms, the compatibility with the component (A) is dramatically improved, the surface orientation is excellent, and the coating film properties are excellent. A non-contaminated coating film can be formed. When such a tetraalkoxysilane is condensed to form a low condensate, about 5 to 50% of all alkyl groups are alkyl groups having 4 to 12 carbon atoms (A). It is preferable because it has excellent compatibility with the components and excellent stain resistance of the coating film.
During the condensation, other alkyl silicates (the alkyl group having 1 to 3 carbon atoms) are mixed and condensed so that about 12 to about 50% of the total alkyl groups may be present. Is an effective means.

Specific examples include, but are not limited to, low-condensation products such as monobutoxytrimethoxysilane, monopentoxytrimethoxysilane, monohexoxytrimethoxysilane, dibutoxydiethoxysilane, and the like. .

(A) General formula

Embedded image (Wherein, R ₅ is an alkyl group having 1 to 3 carbon atoms, and n is 4
An alkyl silicate low-condensate represented by the following general formula (b):

Embedded image (Wherein, R ₆ is an alkyl group having 4 to 12 carbon atoms) (hereinafter, referred to as “component (b) component”) using about 5 to 5 of the alkyl group portion of component (a). Transesterify 50%.

As the component (a), specifically, tetramethyl silicate, tetraethyl silicate, tetra-n
Low-condensates such as -propyl silicate and tetra-i-propyl silicate. In particular, tetramethyl silicate and tetraethyl silicate are generally used. The average degree of condensation is preferably from 4 to 20, and it is not preferable that the average degree of condensation is large or small because handling becomes inconvenient. As the component (b), specifically, n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol, n
-Undecyl alcohol and n-dodecyl alcohol.

When the component (a) is transesterified with the component (b), all the alkyl groups (R ₅ ) of the component (a)
Is not transesterified to the alkyl group (R ₆ ) of the component (b), but a transesterification of about 5 to 50% of the total alkyl group of the component (a) is used. As for the exchange ratio, the ester exchange may be performed using 1 to 12 moles of the component (b) with respect to 1 mole of the component (a). The exchange ratio is appropriately adjusted depending on the average degree of condensation of the component (a).
By transesterifying 0%, the compatibility with the component (A) and the stain resistance of the coating film can be made excellent. When the transesterification rate is low, the compatibility becomes poor and the surface orientation becomes insufficient. When the transesterification rate is high, the hydrolysis reaction is less likely to occur, the coating film is less likely to be hydrophilic, and the stain resistance tends to be worse.

The component (C) thus produced is
With respect to 100 parts by weight of the resin solid content of the component (A), SiO
1.0 to 50.0 parts by weight ₂ equivalent, preferably 2.0 to 3
0.0 parts by weight can be added. This is because if the amount is less than 1.0 part by weight, the hydrophilicity of the coating film is not sufficient, so that the stain resistance is inferior. If the amount exceeds 50.0 parts by weight, the appearance of the cured coating film deteriorates and cracks occur. Is to come out.

The term "SiO ₂ equivalent" as used herein means that when a compound having a Si—O bond such as alkoxysilane or silicate is completely hydrolyzed and then calcined at 900 ° C., it becomes silica (SiO ₂ ). It is expressed in minutes. In general, alkoxysilanes and silicates have a property of reacting with water to cause a hydrolysis reaction to form silanol, and to further cause a condensation reaction between silanols or silanol and alkoxy. When this reaction is performed to the ultimate, it becomes silica (SiO ₂ ). These reactions are

Embedded image This is a conversion formula of the amount of the remaining silica component based on this reaction formula. The actual calculation is

(Equation 1) The equation was used.

(D) Amine compound (D) The amine compound (hereinafter, referred to as "D") used in the present invention.
The “(D) component”) is preferably a water-soluble amine, and includes ethylamine, dimethylamine, diamylamine,
Primary and secondary amines such as cyclohexylamine, aniline, hexamethylenediamine, and ethylenediamine; amine compounds having only an alkyl group as a substituent; trimethylamine and triethylamine; and ethanolamine and diethanolamine as those containing an alkanol group as a substituent. Compounds containing an aminoalkyl group such as dimethylethanolamine, N-methyldiethanolamine, triethanolamine, and ethylphenylethanolamine include triethylenediamine ([2,2,2] diazabicyclooctane), tetramethylethylenediamine, Examples thereof include organic amines such as pyridine and morpholine, and methyldiethylenetriamine. As in the case of the above triethylenediamine, the aminoalkyl group-substituted amine compound has the general formula

Embedded image Among the compounds represented by the formula, those in which R ₇ , R ₈ , and R ₉ 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 aminomethyltriethoxysilane, diaminomethyldiethoxysilane, γ
And aminosilanes such as -aminoisobutyltrimethoxysilane and γ-aminopropylmethyldiethoxysilane.

By incorporating the component (D), a coating film having excellent non-staining properties can be formed, and the adhesion between layers when the non-staining coating composition of the present invention is applied repeatedly is improved. A film could be formed, and a non-contaminated coating film having extremely excellent durability could be obtained.

Among the components (D), the above-mentioned general formula

Embedded image (R ₁₀ , R ₁₁ and R ₁₂ are selected from an alkyl group having 1 to 5 carbon atoms, 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 same or different groups) are 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 and easily reacts with the NCO group of the isocyanate. When the NH group and the NCO group react, a urea bond is formed.
The formation of a urea bond by the reaction between the OH group and the NCO group
Faster than the CO groups react to form urethane bonds,
Therefore, the presence of the NH 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 component (D) 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). It is. (D)
When the amount of the component is less than 0.02 parts by weight, the stain resistance is deteriorated, and the interlayer adhesion tends to be deteriorated. In particular, the interlayer adhesion over time is lost. 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 component (D) may be handled and added in the same manner as a usual coating material.

(E) Alkoxysilane Compound Containing Polyalkylene Oxide Chain Next, in the present invention, (E) an alkoxysilane compound containing a polyalkylene oxide chain (hereinafter referred to as “component (E)”)
) Can make the surface of the coating film more hydrophilic than the initial stage, and it is possible to obtain better stain resistance than the initial stage. The component (E) is a compound having an alkylene oxide repeating unit and at least one or more alkoxysilyl groups. In the polyalkylene oxide repeating unit of the component (E), the alkylene moiety has 2 to 4 carbon atoms, and the number of repeating units is 2 to 40, preferably 2 to 20.

In such a component (E), both ends of the polyalkylene oxide chain may be alkoxysilyl groups, and one end may be an alkoxysilyl group and the other end may be another functional group. Good. Examples of such a functional group that can be present at one end include a vinyl group,
Examples include 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 (E), for example, those 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-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, isocyanate-functional silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, and the like.

The synthesis of the component (E) 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 as 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 dimaleate, or dioctyltin dimaleate.

As the component (E) 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.

Among these components (E), those having an alkylene oxide chain of an ethylene oxide chain and one terminal of a hydroxyl group are most preferred because of their high stain-preventing effect, that is, high stain resistance and high penetration resistance.

The compounding ratio of the component (E) is 0.1 to 20 parts by weight, preferably 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, no effect can be seen.
This results in poor compatibility with the resin and poor water resistance of the cured product.

<Others> The non-staining paint composition of the present invention is transparent (clear) due to the components (A), (B), (C), and (D) (to which the (E) component may be added). ) Coloring (enamel) by blending coloring pigments in addition to coatings
Such coloring pigments which may be used as a coating film include titanium oxide, zinc oxide, carbon black, ferric oxide (bengara), lead chromate (molybdate orange), graphite, yellow iron oxide, ocher, and ultramarine. , Inorganic pigments such as cobalt green, azo, naphthol, pyrazolone,
Anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole,
Organic pigments such as phthalocyanine and quinophthalone 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 non-staining paint composition of the present invention, it is possible to add various additives which can be usually added to the paint to such an extent that the effects of the present invention are not affected. Examples of such additives include plasticizers, preservatives, fungicides, anti-algal agents, defoamers, leveling agents, pigment dispersants, anti-settling agents, anti-sag agents, matting agents, ultraviolet absorbers and the like. can give.

<Applied Surface / Coating Method> The non-staining paint composition of the present invention can be used for metal, glass, porcelain tile, concrete,
It can be used for surface finishing of various materials such as siding boards, extruded plates, plastics, etc., and is mainly used for protection of buildings such as buildings and civil engineering structures.
At this time, the non-staining paint composition of the present invention is applied to the final finished surface, and can be applied directly to the base material, or can be applied after some surface treatment (base treatment, etc.). Although it is also possible to do so, there is no particular limitation.

Further, the non-staining paint composition of the present invention is prepared by adding various additives to form a paint, and then diluted with a non-aqueous solvent, followed by brush coating, spray coating, roller coating, roll coater, flow coater. It can be painted by various methods. The non-aqueous solvent used for dilution is
What is necessary is just to use the thing similar to what was illustrated as a non-aqueous solvent of (A) component in various combinations.

At this time, 50% by weight or more of the total solvent component (the combination of the non-aqueous solvent used in the component (A) and the component (B) and the diluting solvent) in the paint at the time of coating is applied. When is an aliphatic hydrocarbon, it can be suitably used also for repair work. This is because when a paint using a solvent having strong dissolving power is repainted, a phenomenon called “lifting” occurs, which is a phenomenon called “lifting” of an old paint film.
This is because such a lifting phenomenon does not occur when the content is not less than% by weight.

[0057]

EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention. (Synthesis example 1) Synthesis example of alkoxysilane compound 1 Weight average molecular weight 500, average degree of condensation about 4, nonvolatile content 10
To 100% by weight of 0% methyl silicate (hereinafter referred to as "methyl silicate A"), 44.4 parts by weight of n-butyl alcohol and 0.03 part by weight of dibutyltin dilaurate as a catalyst were added, and after mixing, 75 parts by weight were added. The methanol removal reaction was carried out for 8 hours at
Was synthesized. The transesterification rate of this alkoxysilane compound 1 was about 30%, and the residual silica ratio obtained by calcining at 900 ° C. was 40.7% by weight.

(Synthesis Example 2) Synthesis Example of Alkoxysilane Compound 2 100 parts by weight of methyl silicate A, 20.4 parts by weight of n-hexyl alcohol, dibutyltin dilaurate 0.1 part by weight.
03 parts by weight were mixed, and an alkoxysilane compound 2 was synthesized in the same manner as in Synthesis Example 1. The transesterification rate of this alkoxysilane compound was about 10%, and the residual silica ratio was 44.7% by weight.

(Synthesis Example 3) Synthesis Example of Alkoxysilane Compound 3 Weight average molecular weight: 1000, average condensation degree: about 8, nonvolatile content: 1
100% by weight of a 00% methyl silicate (hereinafter, referred to as "methyl silicate B"), 51.8 parts by weight of n-butyl alcohol and 0.03 parts of dibutyltin dilaurate
By weight, the alkoxysilane compound 3 was synthesized in the same manner as in Synthesis Example 1. This alkoxysilane compound 3
Was about 38%, and the residual silica ratio was 43.2% by weight.

(Synthesis Example 4) Synthesis Example of Alkoxysilane Compound 4 100 parts by weight of methyl silicate B, 35.2 parts by weight of n-amyl alcohol, 0.0 of dibutyltin dilaurate
3 parts by weight were mixed, and an alkoxysilane compound 4 was synthesized in the same manner as in Synthesis Example 1. The transesterification rate of this alkoxysilane compound 4 was about 22%, and the residual silica ratio was 45.7% by weight.

Synthesis Example 5 Synthesis Example of Alkoxysilane Compound 5 100 parts by weight of methyl silicate B, 20.4 parts by weight of n-hexyl alcohol, dibutyltin dilaurate 0.1 part by weight.
03 parts by weight were mixed, and an alkoxysilane compound 5 was synthesized in the same manner as in Synthesis Example 1. The transesterification rate of this alkoxysilane compound 5 was about 11%, and the residual silica ratio was 49.1% by weight.

(Synthesis Example 6) Synthesis Example of Alkoxysilane Compound 6 100 parts by weight of methyl silicate B, 58.0 parts by weight of n-heptyl alcohol, and 0.1 part by weight of dibutyltin dilaurate.
03 parts by weight were mixed, and an alkoxysilane compound 6 was synthesized in the same manner as in Synthesis Example 1. The transesterification rate of this alkoxysilane compound 6 was about 27%, and the residual silica ratio was 39.4% by weight.

(Synthesis Example 7) Synthesis Example of Alkoxysilane Compound 7 100 parts by weight of methyl silicate B, 88.8 parts by weight of n-butyl alcohol, 0.0 of dibutyltin dilaurate
3 parts by weight were mixed, and an alkoxysilane compound 7 was synthesized in the same manner as in Synthesis Example 1. The transesterification rate of this alkoxysilane compound 7 was about 66%, and the residual silica ratio was 37.2% by weight.

(Synthesis Example 8) Synthesis Example of Alkoxysilane Compound 8 100 parts by weight of methyl silicate B, 120.3 parts by weight of n-dodecyl alcohol, and 0.03 parts by weight of dibutyltin dilaurate were mixed. An alkoxysilane compound 8 was synthesized. The transesterification rate of this alkoxysilane compound 8 was about 33%, and the residual silica ratio was 27.8% by weight.

[Table 1]

Synthesis Example 9 Synthesis Example of Alkoxysilane Compound Containing Polyalkylene Oxide Chain Polyethylene glycol 200 (average molecular weight: 200; Wako Pure Chemical Industries, Ltd.) was placed in a reaction vessel equipped with a heating device, stirrer, reflux device, dehydration device, and thermometer. 20 parts by weight), 54.3 parts by weight of Y-9030 which is an isocyanate-containing silane (manufactured by Nippon Unicar Co., Ltd.) and 0.05 part by weight of dibutyltin dilaurate were charged and reacted at 50 ° C. for 8 hours. A light yellow polyethylene oxide chain-containing alkoxysilane compound was obtained. The weight average molecular weight of the alkoxysilane compound having a polyethylene oxide chain was 800 as measured by gel permeation chromatography (hereinafter referred to as GPC) in terms of polystyrene.

(Example 1) Evaluation of Compatibility Using raw materials as shown in Table 2, during formulation shown in Table 3,
Each component except the pigment was evaluated by blending as follows,
That is, polyol 1 (dissolved acrylic polyol) 20
0 parts by weight and 47.0 parts by weight of isocyanate are mixed (isocyanate is mixed so that the ratio of NCO / OH to hydroxyl group of acrylic polyol becomes 1.0), and 12.3 parts by weight of alkoxysilane compound 1 (12.3 parts by weight) 5.0 parts by weight in terms of SiO 2), amine compound 2
Was added and, after sufficiently stirring, 150 × 5
After spray-coating on a transparent glass plate of 0 × 3 mm so that the dry film thickness becomes 40 μm, after drying and curing at a temperature of 20 ° C. and a humidity of 65% (hereinafter referred to as “standard state”) for 24 hours,
The transparency of the film was visually evaluated. The evaluation is as follows. The results are shown in Table 5. ：: Completely transparent state △: Slightly opaque state ×: opaque and opaque state <Results> No turbidity or the like of the film was observed, indicating good compatibility.

2. Measurement of contact angle after immersion in water A coating composition was prepared using the raw materials as shown in Table 2 and the formulations shown in Table 3. That is, 80.0 parts by weight of rutile-type titanium oxide was added to 200 parts by weight of polyol 1 (soluble acrylic polyol), dispersed and mixed, and then NCO / O
47.0 parts by weight of isocyanate and 12.3 parts by weight of alkoxysilane compound 1 (mixed so as to be 5.0 parts by weight in terms of SiO ₂ ) so that the H ratio becomes 1.0, and the amine compound After adding 0.3 part by weight of No. 2 and mixing, a coating composition was prepared. 150 × 75 × 0.8m
m, an SK # 1000 primer (produced by SK Chemical Co., Ltd .: epoxy resin primer) is spray-coated so as to have a dry film thickness of about 30 μm, and dried under standard conditions for 8 hours. Thickness of dried product is 4
A test piece was prepared by spray coating so as to have a thickness of 0 μm. After the prepared test body was dried and cured in a standard state for 7 days, it was immersed in deionized water for 3 hours, dried for 18 hours, and measured for a contact angle (measured with a CA-A type contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd.). The same applies hereinafter). This operation (immersion in deionized water for 3 hours → drying for 18 hours → contact angle measurement) was repeated twice more as one set, and the contact angle was measured three times in total. <Results> This test artificially created conditions during actual rainfall, and assumes that rain is at normal pH, not acid rain. The results are shown in Table 5. It was found that good hydrophilicity can be obtained by rainfall at normal pH without being affected by acid rain or the like.

3. Rain streak contamination evaluation A 300 × 150 × 3.0 mm aluminum plate was rolled up so that the angle α was 135 degrees at one third of the length from above as shown in FIG. An SK # 1000 primer was spray-coated so as to have a dry film thickness of about 30 μm, and dried under standard conditions for 8 hours. (The exposure plate has a convex surface.)
Next, 2. A paint composition was prepared in the same manner as described above, and the prepared paint composition was spray-coated on an exposure plate coated with the primer so that the dry film thickness was about 40 μm, and dried under standard conditions for 7 days. And The prepared specimen is
In Ibaraki city, Osaka, facing south, the large area (side a) was set to be vertical, and the smaller area (side b) was set up so that it was exposed outdoors. One month later, Three months later,
The presence or absence of rain streak stains after 6 months was visually evaluated. The evaluation is as follows. The results are shown in Table 5. ：: No rain streak stain on vertical surface ○: Slight rain streak stain on vertical surface △: Rain streak stain on vertical surface ×: Significant rain streak stain on vertical surface <Result> Particularly early It was found that there was no rain streak contamination and that it had excellent stain resistance.

4. Interlayer adhesion test Four 150 x 70 x 0.8 mm aluminum plates
The K # 1000 primer was spray-coated so as to have a dry film thickness of 30 μm, and dried under standard conditions for 8 hours.
Next, 2. The paint composition prepared in the same manner as described above was spray-coated so that the dry film thickness was 25 μm, and each was cured under standard conditions for 16 hours, 3 days, and 7 days, and then the dry film thickness was further increased. The coating composition was spray-coated again so as to have a thickness of 25 μm, and a test body was obtained. At this time, the dry film thickness of the entire non-contaminated coating film was 50 μm.
Each prepared specimen was cured under standard conditions for 7 days,
S K5400 (1990) 8.5 Adhesion was evaluated according to the 8.5.1 crosscut method of the adhesion test. The evaluation was performed using scores as shown in Table 7. The results are shown in Table 5. <Results> No problem was observed in the interlayer adhesion after 7 days.

5. SK # 100 on 150 × 75 × 0.8mm aluminum plate
The No. 0 primer was spray-coated so as to have a dry film thickness of 30 μm, and dried under standard conditions for 8 hours. Next, 2. The coating composition prepared in the same manner as described above was spray-coated so that the dry film thickness became 40 μm to prepare a test body. After the prepared test body was dried and cured in a standard state for 7 days, JIS K540
8.10 In accordance with the stain resistance test, a 15% by weight aqueous dispersion of carbon black was dropped onto the coated surface so as to have a diameter of 20 mm and a height of 5 mm, and was 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. The evaluation is as follows. The results are shown in Table 5. ：: No traces ○: Slight traces Δ: Traces present X: Remarkable traces <Results> Although traces were slightly observed, good results were obtained.

(Examples 2 to 8) The raw materials shown in Table 2 were used, and the compositions shown in Table 3 were evaluated in accordance with Example 1. <Results> The results were as shown in Table 5, and all of the results were good. In Example 8, after the pigment was dispersed in the polyol 1 in advance, other components were added to prepare a coating composition. In particular, Examples 4 to 7 containing a polyalkylene oxide chain-containing alkoxysilane compound
It was found that the decrease in contact angle due to repeated water immersion was large, the coating film surface became hydrophilic, and the initial stain resistance was good. Similarly, a result having excellent resistance to stain penetration was obtained.

(Comparative Examples 1 to 8) The raw materials shown in Table 2 were used, and the compositions shown in Table 4 were evaluated in accordance with Example 1. <Results> The results are shown in Table 6. In Comparative Examples 1 to 3 using a commercially available alkyl silicate, the compatibility and surface orientation were poor, so that the surface did not become hydrophilic, rain streaks occurred, and the stain resistance was poor. Understand. In addition, the stain resistance was poor. In Comparative Example 4 in which the transesterification rate of the alkyl group of the alkoxysilane compound was high, the surface was unlikely to be hydrophilic, so that rain streak contamination occurred and the stain resistance was poor. When the chain length of the alkyl group is too long, the hydrophilicity is not obtained as in Comparative Example 5, and the stain resistance is poor. In Comparative Example 6, although a normal weak solvent type paint was blended, it was found that rain streak contamination occurred and the stain resistance was poor. In Comparative Example 7 in which the amount of the alkoxysilane compound was small and no amine compound was contained, the stain resistance was poor as in Comparative Example 6, and in Comparative Example 8 in which the amount of the alkoxysilane compound was large and the amine compound was not contained, Although the surface of the coating film became hydrophilic, there was a problem in interlayer adhesion, and the surface became harder over time, causing cracks, resulting in a problem in durability of the coating film. In addition, all of the comparative examples having poor stain resistance are:
Poor stain resistance has also been obtained.

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

6. Lifting Test (Paint 1) The white paint composition formulated in Example 1 was further diluted by adding 100 parts by weight of xylene (diluted at an external rate of 30% by weight), mixed and stirred to obtain a white paint 1 for spraying. Was prepared. At this time, the content of the aliphatic hydrocarbon-based solvent in all the solvents was 37% by weight. (Paint 2) The white paint composition having the composition of Example 1 was further added to Laws (mineral spirit manufactured by Shell Sekiyu KK).
100 parts by weight were added and diluted (outside ratio, diluted by 30% by weight), and mixed and stirred to prepare a white paint for spraying 2. At this time, the content of the aliphatic hydrocarbon solvent in the total solvent was 6%.
It was 8% by weight.

<Test Method> Miracle Sealer ES (manufactured by SK Kaken Co., Ltd .: one-pack epoxy resin sealer) was added to two 200 × 300 × 4 mm slate plates in a required amount of 0.1 mm.
Spray-painted to ₂ kg / m ₂ and dried under standard conditions for 1 hour, then SK acrylic color (one-component solvent-type acrylic resin top coating material manufactured by SK Kaken Co., Ltd.) 0.3 kg / m ₂ And then cured and dried under standard conditions for 7 days. Using this as an old coating film, the required amount of paint 1 and paint 2 was 0.15 kg each.
/ M ₂ and spray-coated to 24
After drying for an hour, the required amount of each paint is 0.15kg.
/ M ₂ was applied by spraying.

<Results> Observation of the state of the coating film surface at this time revealed that the slate plate sprayed with the paint 1 had spots on the surface, and a lifting phenomenon was observed. The slate plate sprayed with the paint 2 had a good surface condition and no lifting phenomenon was observed.

[0076]

According to the present invention, in a urethane resin-based paint using a polyol having a SP of 6.5 to 9.5 and dissolvable and / or dispersible even in a solvent having a low solubility, ordinary alkyl silicate has a compatibility. Poor, poor surface orientation, the coating does not become non-staining, whereas the non-staining coating composition of the present invention has good compatibility, excellent surface orientation, and hydrophilic coating. Therefore, a coating film having excellent non-staining properties can be obtained, and a coating composition having further excellent coating film properties can be obtained. Further, when the non-staining paint composition of the present invention is applied repeatedly, it also has an effect that interlayer adhesion is good. Furthermore, by adding a polyalkylene oxide chain-containing alkoxysilane compound,
From the very beginning, the surface of the coating film becomes hydrophilic, and it becomes possible to obtain a non-staining paint composition having excellent stain resistance. Further, when 50% by weight or more of the solvent component in the solvent of the whole paint is an aliphatic hydrocarbon, there is almost no lifting problem, and it can be suitably used particularly for renovation work.

[Brief description of the drawings]

FIG. 1 is a perspective view showing an exposure plate.

[Explanation of symbols]

 a: surface that becomes vertical when exposed b: surface that becomes the upper surface when exposed α: bending angle (135 °)

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Tadahiko Ikeuchi 1-25-10 Shimizu, Ibaraki-shi, Osaka Prefecture SK Chemicals Research Institute (72) Inventor Kensuke Kurimoto 1-25-10 Shimizu, Ibaraki-shi, Osaka No. SK Kaken Co., Ltd. (72) Inventor Hisashi Suzuki 1-25-10 Shimizu, Ibaraki-shi, Osaka SK Kaken Co., Ltd. (56) References Patent 3009361 (JP, B2) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 175/04

Claims (5)

(57) [Claims] (1) The solubility parameter (A) is 6.5 to 9.
5. The resin solid content of a polyol having a weight average molecular weight of 5,000 to 150,000, a hydroxyl value of 15 to 100 KOH mg / g, and being dissolved and / or dispersed in a non-aqueous solvent.
(B) isocyanate to NCO / O
An H ratio of 0.7 to 2.0, which is a condensate of (C) tetraalkoxysilane having an average degree of condensation of 4 to 20, wherein the alkyl group in the condensate has 1 to 3 carbon atoms.
And a compound having 4 to 12 carbon atoms in which the alkyl group having 4 to 12 carbon atoms is 5 to 50% of the total alkyl groups in the condensate is calculated as SiO ₂ 1.0 to 50.0 parts by weight of the amine compound (D)
A non-staining paint composition comprising 0.02 to 5.0 parts by weight of solid content. (C) is a compound represented by the general formula: (Wherein R _{1 to} R ₄ are a mixture of an alkyl group having 1 to 3 carbon atoms and an alkyl group having 4 to 12 carbon atoms). 2
The non-staining paint composition according to claim 1, wherein the composition is a low-condensation product of tetraalkoxysilane, which is condensed to have a weight average molecular weight of 500 to 5,000. (C) is (a) a general formula: (Wherein, R ₅ is an alkyl group having 1 to 3 carbon atoms, and n is 4
An alkyl silicate low-condensate represented by the general formula (b): (In the formula, R ₆ is an alkyl group having 4 to 12 carbon atoms), (a) a compound obtained by transesterifying 5 to 50% of the alkyl groups of the alkyl silicate low-condensate. The non-staining paint composition according to claim 1, wherein: 4. The method according to claim 1, wherein (E) the number of repeating units is 2 to 4.
A polyalkylene oxide chain of 0, an alkoxysilane compound having a weight average molecular weight of 150 to 3500,
(A) For 100 parts by weight of the resin solid content of the polyol,
The non-staining paint composition according to any one of claims 1 to 3, wherein the composition is contained in an amount of 0.1 to 20 parts by weight in terms of solid content. 5. The non-staining paint composition according to claim 1, wherein at least 50% by weight of the total solvent in the paint is an aliphatic hydrocarbon.