JPH09206667A - Formation of non-staining coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the resistance to penetration of oil stain by forming a non-staining coating film by layering an elastic type coating film having a specified coating film elongation as a first layer, an urethane resin coating layer having a specified coating film elongation as a second layer, and a layer of a specified non-staining coating composition having a specified coating film elongation as a third layer. SOLUTION: A non-staining coating film consisting of a first layer having 50-800% elongation of a coating film, a second layer having 2-300% elongation, and a third layer having 0.5-200% elongation is formed. IN this case, the second layer is formed by layering a composition containing polyols with 5,000-80,000 weight average molecular weight and 20-150KOHmg/g hydroxyl value. Also, the layer is firmed by layering a composition consisting of 100 pts.wt. (based in solids) of polyols with 5,000-80,000 weight average molecular weight and 20-150KHOmg/g hydroxyl value, 0.1-20 pts.wt. (based on solids) of alkoyxysilanes with 150-3,500 weight average molecular weight, alklsilicates having the formula (R stands for alkyl with 1-10 carbons), etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for surface finishing a building or civil engineering structure formed of various materials such as metal, glass, porcelain tile, concrete, siding board, extruded board and plastic. Yes, more specifically, it relates to a method for forming a non-staining coating film.

[0002]

2. Description of the Related Art Conventionally, coating finish has been carried out for the purpose of protecting the skeleton of buildings, civil engineering structures, etc., imparting design characteristics, and improving aesthetics. In particular, with the advent of highly durable paints such as fluororesin paints, acrylic silicone resin paints or acrylic urethane resin paints in recent years, great progress has been made in the protection of the body. 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, even if the surface of the coating film formed by the coating material before these highly durable coating materials is deteriorated by the ultraviolet rays of sunlight and the adhesion of contaminants is caused, it is peeled off together with the deteriorated portion of the coating film 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. Especially recently, in urban areas and suburbs, where oily pollutants are suspended in the atmosphere due to exhaust gas from automobiles, etc., these oily pollutants are coating films formed from highly durable paint. If it adheres to the surface,
In some cases, soot or streak-like pollution was generated, and the paint finish applied to improve the cityscape did not make sense.

In order to solve such a problem, a non-polluting paint in which the surface of the coating film is made hydrophilic and the adhered oily pollutants are peeled off and washed away by the action of rainwater during rain spreading on the surface of the coating film. Have been announced. Furthermore, a method for forming a coating film with such a non-contaminating paint has been announced. JP-A-7-136584 discloses a method for forming a non-staining coating film by coating an inorganic base material with (1) an undercoat paint, and (2) then a polyisocyanate-curable solvent-based paint or a specific vinyl monomer. (3) Preventing stains on building exteriors by coating an organosilicon-curable solvent-based paint prepared by mixing a metal chelate compound with a copolymer obtained by copolymerizing A method of forming a topcoat is disclosed. According to this, it is preferable to use a multi-layer finish paint as the undercoat paint, particularly, an uncured synthetic resin emulsion-based multi-layer finish paint, a reaction-curable water-soluble epoxy resin multi-layer pattern finish paint, a reaction-curable type. Solvent-based epoxy resin multi-layer finish paints and the like are preferred.

Generally, there are hard type and elastic type waterproof multi-layer finish coating materials as the multi-layer finish coating material. Waterproof multi-layer finish coating materials are generally 120% at 20 ° C
It shows the above elongation (according to JIS A6909 (1995) architectural finish coating material). When a non-staining type coating film as described above was laminated on an elastic type coating film showing such a large elongation, defects such as cracks, glossiness, swelling, peeling, etc. appeared over time and durability was a problem. Occurred.

It is said that the elastic coating film is particularly liable to get dirty over time. It is considered that the reason is that the elastic coating film has a soft surface, which causes physical adsorption of pollutants and makes it impossible to wash away with water due to rainfall or the like.
However, the elastic coating film has advantages such as being able to follow cracks in the base and being excellent in waterproofness. Although there is a demand for a coating film that does not contaminate while making use of such advantages, at present, a satisfactory coating film has not been obtained.

Therefore, an attempt was made to laminate a non-staining coating film on the elastic coating film to form a laminated coating film having both the advantages of the elastic coating film and the non-staining property. Has occurred.

The topcoat paint in JP-A-7-136584 is an organosilicon-curable solvent-based paint mixed with an organosilicate, but the coating film formed by the paint is very hard. It ’s an organosilicate

Embedded image This is because the reaction is such that crosslinking occurs. Therefore, as the film ages, the coating becomes harder. When such a hard coating film is laminated on a hard coating film of an ordinary multi-layer finish coating material, no problem occurs, but on an elastic coating film such as a coating film of a waterproof type multi-layer finish coating material. When laminated on, the top non-contaminating coating film will crack, gloss,
There was a problem that defects such as swelling and peeling appeared, and in reality, such finishing could not be performed.

It is said that the sealing material used in the joints on the surface of the building is easily contaminated.
Even when a very hard coating such as a coating made of non-contaminating paint containing silicate is directly laminated on such a sealing material, it causes cracks and peeling, and in reality, such finish I couldn't.

On the other hand, non-contaminating paints such as those prepared by blending an organosilicate, such as the top-coat paint in JP-A-7-136584, and non-contaminating coating films formed by other conventional non-contaminating paints have There is also a problem that it takes a long time to make hydrophilic.

In order to solve such a problem, a non-contaminating paint containing an organosilicate will be taken as an example. When a large amount of an organosilicate was added in order to further increase the hydrophilicity of the surface, a coating solution was obtained. The cross-linking density of the film becomes too high, the coating film becomes brittle, the chemical resistance decreases, and the weather resistance of the coating film deteriorates. Therefore, it is necessary to add a large amount of organosilicate to make it hydrophilic, but there is a contradiction that the physical properties of the coating film are impaired if a large amount is added.

Furthermore, the conventional non-polluting coating film made of non-polluting paint has the main purpose of flowing down pollutants due to rainfall,
Since we are only focusing on making the surface hydrophilic,
There is a problem in that the dirt that has once adhered is inferior in resistance to resistance, and if there is no contact with water due to rainfall or the like for a long period of time, oily dirt that is a contaminant penetrates into the coating film. As a result, even if water subsequently comes into contact with water due to rainfall or the like, it is no longer possible to flow it down, and the pollutants will adhere permanently.

[0012]

As described above, it can be said that the following problems occur in forming a non-staining coating film.

When forming a coating film using a conventional non-polluting paint, when the base is an elastic waterproof material such as an elastic coating film or a sealing material, when the base coating film stretches due to cracking of the base material, The non-staining coating film could not follow, and problems such as cracking and peeling occurred, and the non-staining coating material could not be applied on the substantially elastic coating film. This is especially common in non-staining paints containing a large amount of organosilicate.

A conventional coating film formed from a non-staining type paint requires a long time to make the surface hydrophilic, and the non-staining property is poor in the initial stage after the coating film is formed. In a short period of time, it will result in rain streak contamination. 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, the occurrence of stains even betrays the expectations of these users and owners even in the early stages after the coating film is formed, and even the non-contaminating effect over a long period of time may cause anxiety. Will be given.

The conventional non-polluting paint is mainly used for the purpose of flowing down pollutants due to rainfall, so that it is poor in the resistance to soaking of stains once adhered, and when there is no rainfall for a long period of time, it will be contained in the coating film. Oily dirt penetrates, leaving behind dirt that is difficult to flow down due to rainfall.

Therefore, the problem to be solved by the present invention is
Due to the action that occurs after the coating film is formed, such as rainfall, the coating film does not become hydrophilic for the first time, but the surface becomes hydrophilic immediately after the coating film is formed, and the effect of washing away contaminants is produced, and a specific cross-linking structure is created. The result is a non-contaminating coating film that is strong, yet does not become brittle, has excellent resistance to penetration of oily stains, and has good weather resistance and other coating film physical properties, especially on elastic coating films and elastic waterproof materials. The present invention provides a method for forming a non-staining coating film.

[0017]

[Means for Solving the Problems] In order to solve such problems, as a result of intensive studies by the present inventors, the surface was hydrophilic immediately after the formation of a coating film and was excellent in the resistance to oil stain penetration. The inventor has invented a method for forming a non-staining coating film capable of forming a non-staining coating film on an elastic coating material or an elastic waterproof material. That is, the present invention relates to the following method for forming a non-staining coating film.

1. On the surface of a building or civil engineering structure, (1) the elongation rate (α) of the coating film at the temperature of 20 ° C. is 50 to 80.
On the first layer formed by the elastic coating material or the elastic waterproof material, which is 0%, (2) is composed of (A) and (B) shown below, and the temperature is 2
Second layer formed by urethane resin paint having elongation (β) of 2 to 300% at 0 ° C. (A) Polyol having weight average molecular weight of 5,000 to 80,000 and hydroxyl value of 20 to 150 KOHmg / g (B ) Polyisocyanate is laminated so that the OH / NCO ratio is 0.6 to 1.5 with respect to the hydroxyl group of (A) polyol, and (3) the following (C), (D) and (E) are shown. (F), the elongation (γ) of the coating film at a temperature of 20 ° C. is 0.5 to 20.
Third layer formed by 0% non-contaminating coating composition (C) Polyol having a weight average molecular weight of 5,000 to 80,000 and a hydroxyl value of 20 to 150 KOHmg / g in a solid content of 100.
Parts by weight (D) 0.1 to 20 parts by weight in solid content of an alkoxysilane compound having an alkylene oxide chain whose repeating unit is 2 to 40 and having a weight average molecular weight of 150 to 3500 (E) General formula

[Chemical 6] 1 to 40 parts by weight of a solid content of an alkyl silicate represented by and / or a condensate thereof, and (F) polyisocyanate in an OH / NCO ratio of 0.6 to 1.5 with respect to the hydroxyl group of the (C) polyol. A method for forming a non-staining coating film, which comprises laminating a mixture so that 2. On the surface of a building or civil engineering structure, (1) the elongation rate (α) of the coating film at the temperature of 20 ° C. is 50 to 80.
On the first layer formed by the elastic coating material or the elastic waterproof material, which is 0%, (2) is composed of (A) and (B) shown below, and the temperature is 2
Second layer formed by urethane resin paint having elongation (β) of 2 to 300% at 0 ° C. (A) Polyol having weight average molecular weight of 5,000 to 80,000 and hydroxyl value of 20 to 150 KOHmg / g (B ) Polyisocyanate is laminated so that the OH / NCO ratio is 0.6 to 1.5 with respect to the hydroxyl group of the (A) polyol, and (3) the following (G) (D) (E). (F), the elongation (γ) of the coating film at a temperature of 20 ° C. is 0.5 to 20.
Third layer (G) having a number average molecular weight of 3,000 to 30,000, a fluorine content of 10 to 30% by weight and a hydroxyl value of 10 to 30 KOHmg / g. 100 parts by weight of polymer in solid content (D) 0.1 to 20 parts by weight in solid content of alkoxysilane compound having a weight average molecular weight of 150 to 3500 and containing an alkylene oxide chain whose repeating unit is 2 to 40 (E) General formula

Embedded image 1-40 parts by weight of the alkyl silicate and / or the condensate thereof represented by the formula (F) polyisocyanate (G) with respect to the hydroxyl group of the fluorine-containing copolymer in an OH / NCO ratio of 0.6- A method for forming a non-staining coating film, which comprises laminating the composition so as to be 1.5. 3. On the surface of a building or civil engineering structure, (1) the elongation rate (α) of the coating film at the temperature of 20 ° C. is 50 to 80.
On the first layer formed by the elastic coating material or the elastic waterproof material, which is 0%, (2) is composed of (A) and (B) shown below, and the temperature is 2
Second layer formed by urethane resin paint having elongation (β) of 2 to 300% at 0 ° C. (A) Polyol having weight average molecular weight of 5,000 to 80,000 and hydroxyl value of 20 to 150 KOHmg / g (B ) Polyisocyanate is laminated so that the OH / NCO ratio is 0.6 to 1.5 with respect to the hydroxyl group of (A) polyol, and (3) the following (H) (D) (E) is shown. And a third layer (H) represented by the general formula (H), which is formed of a non-contaminating coating composition having an elongation (γ) of 0.5 to 200% at a temperature of 20 ° C.

Embedded image 100 parts by weight of an alkoxysilyl group-containing acrylic copolymer containing a group represented by (D) an alkoxysilane compound having a weight average molecular weight of 150 to 3500 containing an alkylene oxide chain having 2 to 40 repeating units. 0.1 to 20 parts by weight in terms of solid content (E) General formula

Embedded image A method for forming a non-staining coating film, which comprises laminating 1 to 30 parts by weight of a solid content of an alkyl silicate represented by and / or a condensate thereof. 4. The elongation rate (α) of the first layer coating film is 120 to 800%, the elongation rate (β) of the second layer coating film is 20 to 200%,
The elongation (γ) of the coating film of the third layer is 20 to 150%. From 3. The method for forming a waterproof non-staining coating film according to any one of 1. 5. The elongation percentage (β) of the second layer coating film is less than or equal to the elongation percentage (α) of the first layer coating film, and the elongation percentage (γ) of the third layer coating film is less than that of the second layer coating film. 1. Elongation rate (β) or less [(α) ≧ (β) ≧ (γ)] From 4. The method for forming a non-staining coating film according to any one of 1.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail along with its embodiments. <Substrate for forming uncontaminated coating film> The laminated coating film formed by the method of the present invention is formed on the surface of a building or a civil engineering structure. The surface of this building or civil engineering structure is formed of various materials such as metal, glass, porcelain tile, concrete, siding board, extruded board, and plastic. These surfaces are
In some cases, a primer, a sealer, or a surface adjusting material generally called a surfacer can be used to adjust the surface. Especially concrete and siding boards,
When coating on a porous material such as an extruded plate,
It is necessary to adjust the groundwork.

<First Layer> The first layer of the present invention has an air temperature of 20 ° C.
The coating film is formed of an elastic coating material or an elastic waterproof material having an elongation (α) of 50 to 800%. Elastic Coating Material or Elastic Waterproof Material As the elastic coating material or elastic waterproof material in the present invention, JI
S A6916 (1995) An undercoating material as defined in the undercoating material for finish coating materials, which has an elongation of 50 to 800%, may be mentioned. In addition, waterproof membranes such as those specified in JIS A6021 (1995) Roof waterproof membranes and JIS A6909 (19
95) Among the finishing coating materials for construction, waterproof type multilayer coating material E, waterproof type multilayer coating material CE, waterproof type multilayer coating material RE and waterproof type multilayer coating material R
S, a sealing material, etc. are mentioned. Other examples include hydrated solidified waterproof membranes and general waterproof membranes. Among them, the first layer has a coating film elongation of 50 to 800%.

[0021] JIS A6916 (1995) is a ground control material for finish coating material, a ground control material using cement and acrylic resin, ethylene vinyl acetate-based, styrene butadiene rubber-based, chloroprene rubber-based synthetic resin emulsion as an admixture, or Among the above-mentioned base conditioning materials which use the synthetic resin emulsion alone or as a mixed system as a binder, the elongation percentage of the coating film is 50 to 80.
0% can be used. Among JIS A6021 (1995) roof waterproofing materials, acrylic rubber-based, chloroprene rubber-based, and urethane rubber-based waterproofing materials are particularly suitable because they have a good compatibility with the urethane resin coating of the second layer. Used.
JIS A6909 (1995) Waterproof multilayer coating material E for architectural finish coating material is a waterproof type of synthetic resin emulsion type multilayer coating material, and is mainly used for synthetic resin emulsions such as acrylic type and vinyl acetate type. A single substance or a mixture is used as a binder. JIS A6909 (1995) Waterproof multilayer coating material RS for architectural finish coating material is a waterproof type of synthetic resin solution type multilayer coating material, and mainly synthetic resins such as acrylic type and vinyl type are xylene, The binder is a single substance or a mixture of synthetic resin solutions, such as those dissolved in an organic solvent such as toluene, or reaction-curable synthetic resins such as epoxy or urethane that are dissolved in an organic solvent such as xylene or toluene. . JIS A6909 (1995) Waterproof multi-layer coating material CE for architectural finish coating material is a waterproof type of polymer cement-based multi-layer coating material, and is acrylic and ethylene vinyl acetate for cement and cement mixture. The binder is a polymer dispersion for cement admixture, which is a system, a vinyl acetate system, a synthetic rubber system, or a mixture thereof. JIS A690
9 (1995) The waterproof multilayer coating material RE for architectural finishing coating material is a waterproof type of reaction curing type synthetic resin emulsion type multilayer coating material, and is a synthetic resin that is reactively cured when used such as epoxy type. The emulsion is used as a binder.

Other examples of the sealing material include modified silicone-based, acrylic urethane-based, polyurethane-based, acrylic-based, styrene-butadiene rubber-based and butyl rubber-based sealing materials. These include reaction-curing 2-component type, moisture-curing 1-component type, dry-curing 1-component type,
Used properly depending on the adherend. Among the sealing materials, silicone-based ones are not preferable because they have almost no adhesion to the urethane resin coating material of the second layer. Further, the polysulfide-based sealing material is not preferable because migration of the plasticizer to the coating film due to the urethane resin coating of the second layer is observed, which leads to contamination.

Examples of the hydrated coagulation type waterproofing material include acrylic, vinyl acetate, synthetic rubber and epoxy polymer dispersions and cement as binders. In addition, although a material called a general waterproof film can be used, an acrylic resin emulsion type, an epoxy type (solvent type) or the like is preferably used because of compatibility with the urethane resin coating material.

Elongation rate of coating film (α) As such an elastic coating material or elastic waterproof material, one having an elongation rate of 50 to 800% at a temperature of 20 ° C. is used. If the elongation is less than 50%, even if the hard non-contaminating paint is directly applied, no defects such as cracks are observed over time, but if the elongation is 50% or more, the hard If the stain-type paint is directly applied, there is a problem that defects such as cracks occur over time. The present invention has an elongation of 50.
% Effectively prevents the occurrence of cracks even when the content is at least%, the second layer of urethane resin coating, the second layer of non-contaminating coating composition on the first layer of elastic coating material or elastic waterproof material. By laminating with three layers, a good non-contaminating coating film can be obtained without defects such as cracks and peeling even with the passage of time. In particular, when forming a waterproof non-polluting coating film, use a coating film with an elongation rate (α) of 120% or more as specified in JIS A6909 (1995) Building Finishing Material. It becomes possible by.

Method of forming first layer coating film This elastic coating material or elastic waterproofing material is used for newly-constructed coating work on the surface of a building or civil engineering structure, if necessary after adjusting the groundwork or as it is. Apply directly. In the case of renovation painting work, when the old coating film is an elastic coating material or an elastic waterproof material, the old coating film is used as the first layer and the urethane resin paint of the second layer and the non-polluting paint composition of the third layer are used. Just apply the thing. In addition, when the old coating film is a hard coating film, the elastic coating material or the elastic waterproof material may be applied as it is, or the elastic coating material or the elastic waterproof material may be applied after adjusting the base material with a filler, a sealer or the like. May be applied. In addition, it is possible to apply the elastic coating material or elastic waterproof material after adjusting the substrate after completely removing the old coating film, or to apply the elastic coating material or elastic waterproof material as it is. is there. If a sealant is used in joints of buildings, etc., the sealant may be used as the first layer, and the urethane resin paint of the second layer and the non-polluting paint composition of the third layer may be applied. Good.

The first layer can be coated by various methods such as brush coating, spray coating and roller coating. As for the other sealing material, the joint portion is formed by a usual method such as filling to form the first layer.

<Second Layer> The second layer of the present invention is composed of the following (A) and (B), and has a coating film elongation rate (β) of 2 to 300% at a temperature of 20 ° C. It is formed of resin paint. (A) Polyol having a weight average molecular weight of 5,000 to 80,000 and a hydroxyl value of 20 to 150 KOHmg / g (B) Polyisocyanate such that the OH / NCO ratio is 0.6 to 1.5 with respect to the hydroxyl group of the (A) polyol. Blend (A) Polyol The polyol of (A) (hereinafter referred to as the component (A)) means an oligomer polyol generally used in the polyurethane technical field, and by mixing and reacting with a polyisocyanate which is a curing agent, It is the main element for forming the second layer coating film.

Examples of 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 of propylene oxide, ethylene oxide, butylene oxide, styrene oxide and the like to one or more of polyhydric alcohols such as trimethylolpropane, pentaerythritol, glucose, sorbitol and sucrose. And polyoxytetramethylene polyols obtained by adding tetrahydrofuran to the polyhydric alcohol by ring-opening polymerization.

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. With glutaric acid, adipic acid, pimelic acid, speric acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, hydrogenated dimer acid or other low molecular weight dicarboxylic acid or oligomeric acid, or two or more of them. Examples thereof include polyols such as a ring-opening polymer of a ring-opening ester such as a combination, propiolactone, caprolactone, and valerolactone.

In the acrylic copolymer, β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, β-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, β-acrylate Hydroxyalkyl esters of acrylic acid such as hydroxypentyl or similar hydroxyalkyl esters of methacrylic acid, acrylic acid monoesters of polyhydric alcohols such as glycerin and trimethylolpropane, or methacrylic acid monoesters similar to these, N-methylolacrylamide Alternatively, an acrylic polyol having two or more hydroxyl groups in one molecule, which is a copolymerizable monomer of a monoethylenically unsaturated monomer having a hydroxyl group such as N-methylolmethacrylamide, can be used.

In addition, polymer polyols, urea-dispersed polyols, carbonate polyols in which monomers such as phenol resin polyols, epoxypolyols, polybutadiene polyols, polyisoprene polyols, polyester-polyether polyols, acryl and styrene are vinyl-added or dispersed. Etc. can be used as the polyol of the present invention. These polyols can be used in general solvent type as well as non-aqueous dispersion (NA
The D) type can also be used. Particularly, acrylic polyol is preferable from the viewpoint of durability.

The weight average molecular weight of the polyol used in the present invention is 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, the hydroxyl value of these polyols is 2
0 to 150 KOHmg / g, preferably 30 to 100 KOHmg
/ G. If the hydroxyl value is less than 20 KOHmg / g,
The durability and stain resistance of the coating film are poor, and when it exceeds 150 KOHmg / g, the durability and flexibility of the coating film are insufficient.

The glass transition point of these polyols is -10 ° C to 150 ° C, preferably 10 ° C to 100 ° C. If the temperature is lower than -10 ° C, the durability of the formed coating film tends to deteriorate. On the other hand, when the temperature is higher than 150 ° C, the flexibility and durability deteriorate.

(B) Polyisocyanate In the polyurethane resin coating material for the second layer, (B) polyisocyanate (hereinafter referred to as "component (B)") is blended and crosslinked and cured to form the second layer. 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, a derivative of an isocyanate monomer such as hydrogenated MDI by alohanate, biuret, dimerization (uretdione), trimerization (isocyanurate), adduct formation, carbodiimide reaction, or reaction with polyester polyol or caprolactam, And mixtures thereof can be used. These components (B) are preferably used as a solution in a solvent containing no active hydrogen. Furthermore, these (B) components are alcohols,
It can also be used in the form of a blocked isocyanate using a blocking agent such as phenols, ε-caprolactam, oximes and active methylene compounds. These components (B) are also preferably used as a solution in a solvent containing no active hydrogen.

The mixture of the component (B) and the component (A) is such that the OH / NCO ratio is 0.6 to 1.5, preferably 0.
It is performed at a ratio such that it becomes 8 to 1.2. At this time OH / N
If the CO ratio is smaller than 0.6 or larger than 1.5, the durability and curability of the coating film are poor, and the durability of the coating film as a whole of the laminated coating film is poor.

Other Additives The urethane resin coating material for the second layer in the present invention may be mixed with a coloring pigment to form a colored (enamel) coating film. Examples of such color pigments include inorganic materials such as titanium oxide, zinc oxide, carbon black, ferric oxide (bengal), lead chromate (molybdate orange), yellow lead, yellow iron oxide, ocher, ultramarine blue and cobalt green. Series pigments, azo series,
Organic pigments such as naphthol type, pyrazolone type, anthraquinone type, perylene type, quinacridone type and quinophthalone type can be used. Also, heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate,
It is also possible to use an extender pigment such as white carbon or diatomaceous earth.

In addition to the above, various additives which can be usually added to the coating material can be added to such an extent that the effects of the present invention are not affected. Examples of such additives include plasticizers, antiseptics, antifungal agents, antialgal agents, antifoaming agents, leveling agents,
Examples thereof include pigment dispersants, anti-settling agents, anti-sagging agents, matting agents, and ultraviolet absorbers.

Elongation rate of coating film (β) The second layer in the present invention is formed by a urethane resin coating material having an elongation rate of 2 to 300% at a temperature of 20 ° C. If the elongation of the coating film is less than 2%, the coating film of the second layer itself becomes too hard, and the elongation of the first layer cannot be followed and cracking occurs. On the contrary, if the elongation percentage of the coating film is more than 300%, cracks are likely to occur in the coating film of the third layer, which is not preferable. Further, when forming the waterproof non-polluting coating film, the elongation percentage (β) of the coating film is preferably 20% to 200%. In particular, the elongation of the first layer coating film (α)
Compared with the above, those having the same or smaller elongation are preferably used.

Method of Forming Second Layer The second layer can be formed by various coating film forming methods such as brush coating, spray coating and roller coating.

<Third Layer> The third layer in the present invention is formed by any of the following non-contaminating paint compositions. Non-contaminating coating composition A coating composition comprising the following (C) (D) (E) (F) and having a coating film elongation rate (γ) of 0.5 to 200% at an air temperature of 20 ° C. (C) Polyol having a weight average molecular weight of 5,000 to 80,000 and a hydroxyl value of 20 to 150 KOHmg / g is 100 in terms of solid content.
Parts by weight (D) 0.1 to 20 parts by weight in solid content of an alkoxysilane compound having an alkylene oxide chain whose repeating unit is 2 to 40 and having a weight average molecular weight of 150 to 3500 (E) General formula

Embedded image 1 to 40 parts by weight of a solid content of an alkyl silicate represented by and / or a condensate thereof, and (F) polyisocyanate in an OH / NCO ratio of 0.6 to 1.5 with respect to the hydroxyl group of the (C) polyol. Compounded to be

Non-contaminating coating composition A coating composition composed of the following (G), (D), (E), and (F) and having an elongation (γ) of the coating film at a temperature of 20 ° C. of 0.5 to 200%. Stuff. (G) 100 parts by weight of a solvent-soluble fluorine-containing copolymer having a number average molecular weight of 3,000 to 30,000, a fluorine content of 10 to 30% by weight and a hydroxyl value of 10 to 30 KOHmg / g as a solid content. 0.1 to 20 parts by weight in solid content of an alkoxysilane compound having a weight average molecular weight of 150 to 3500 and containing an alkylene oxide chain of 40 to 40 (E) General formula

Embedded image 1 to 40 parts by weight of a solid content of an alkyl silicate represented by and / or a condensate thereof, and (F) polyisocyanate in an OH / NCO ratio of 0.6 to 1.5 with respect to the hydroxyl group of the (C) polyol. Compounded to be

Non-contaminating coating composition A coating composition comprising the following (H) (D) (E) and having a coating film elongation rate (γ) of 0.5 to 200% at an air temperature of 20 ° C. (H) General formula

Embedded image 100 parts by weight of an alkoxysilyl group-containing acrylic copolymer containing a group represented by (D) an alkoxysilane having a weight average molecular weight of 150 to 3500 containing an alkylene oxide chain having 2 to 40 repeating units. 0.1 to 20 parts by weight of compound in solid content (E) General formula

Embedded image 1 to 30 parts by weight of the solid content of the alkyl silicate represented by

Each component is shown below. (C) Polyol The polyol of (C) (hereinafter referred to as “component (C)”) means an oligomer polyol that is generally used in the polyurethane technical field, and is mixed with a polyisocyanate that is a curing agent to react It is the main element for forming a three-layer coating film. This polyol can be the same as the polyol (A) shown in the column of the second layer.

(G) Fluorine-containing copolymer The (G) fluorine-containing copolymer (hereinafter referred to as the component (G)) of the present invention is a fluorine-containing copolymer having a hydroxyl group, which is generally used for room temperature-curable fluorine resin coatings. Include all. The fluorine-containing copolymer is obtained by copolymerizing a fluorine monomer and a copolymerization monomer. Examples of the fluorine monomer include tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoro. Examples include ethylene.

A vinyl monomer is used as the copolymerization monomer, and as the vinyl ether among the vinyl monomers, cyclohexyl vinyl ether, alkyl vinyl ether, hydroxyalkyl vinyl ether, glycidyl vinyl ether and the like are used. Alternatively, a part of the alkyl vinyl ether and hydroxy vinyl ether monomers may be carboxylated by reacting with an acid such as a dibasic acid anhydride. The modification of the vinyl ether moiety with acid may be performed after the copolymer is formed. For vinyl ether, tetrafluorovinyl ether and carboxy group as functional group, other vinyl group,
Vinyl ether having a hydroxyl group, a glycidyl group or an amino group can also be used.

The vinyl ester can be generally used, but from the viewpoint of price, Veova-9, -10 (manufactured by Ciel) and the like are preferably used. Vinyl acetate and vinyl pivalate are also used. Vinyl crotonate or hydroxyalkyl vinyl crotonate having a functional group may be used. Vinyl benzoate and maleic acid diester are also used. Copolymers using vinyl ether or vinyl ester and those having a carboxyl group in part of these copolymers may be used. Further, a copolymer having a crosslinkable functional group such as a hydroxy group, an isocyanate group or a glycidyl group is preferably used.

The component (G) of the present invention has a number average molecular weight of 30.
00-30000, fluorine content 10-30% by weight, hydroxyl value 30-100 KOHmg / g, glass transition temperature 0
A solvent-soluble substance at 70 ° C can be used. When the number average molecular weight is less than 3,000, the reactivity with the curing agent is poor, and the physical properties of each coating film are inferior. On the contrary, when the number average molecular weight is more than 30,000, the polyalkylene oxide chain-containing alkoxysilane compound or alkyl silicate to be mixed is used. Is inferior in compatibility, which is not preferable. Also, the fluorine content is 1
When it is less than 0% by weight, the weather resistance of the resulting coating film is not sufficient. On the contrary, when it is more than 30% by weight, the curability and flexibility of the coating film are poor and a high gloss value cannot be obtained. Therefore, it is not preferable. On the other hand, when the hydroxyl value is less than 30 KOHmg / g, the crosslink density is low, so the physical properties and stain resistance of each coating film are poor, and conversely, when it is greater than 100 KOHmg / g, the curing shrinkage due to the crosslinking reaction increases. Durability decreases.
In addition, if the glass transition temperature is lower than 0 ° C., the surface hardness is insufficient, causing physical attachment of contaminants, resulting in permanent stains that cannot even be washed. On the other hand, if it is higher than 70 ° C., the flexibility of the coating film is inferior and cracks are generated over time, which is not preferable.

(H) Alkoxysilyl Group-Containing Acrylic Copolymer The (H) alkoxysilyl group-containing acryl copolymer of the present invention (hereinafter referred to as component (H)) has the general formula

Embedded image It is a polymer having at least one, preferably two or more alkoxysilyl groups represented by in one molecule. The alkoxysilyl group is the end of the main chain of the component (H) or
It may be contained in the side chain or both. When the number of alkoxysilyl groups in one molecule of the component (H) is less than 1, the solvent resistance of the coating film of the third layer tends to decrease.

In the formula, R ₁ is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. However, when the carbon number of R ₁ exceeds 10, the reactivity of the alkoxysilyl group decreases, and R ₁ The reaction also decreases when is a group other than an alkyl group, such as a phenyl group or a benzyl group. Specific examples of the alkyl group represented by R ₁ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group.

R ₂ in the formula is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 alkyl groups, aryl groups and aralkyl groups. In the hydrocarbon group represented by R ₂ , specific examples of the alkyl group include the same groups as R ₁ .
Specific examples of the aryl group include, for example, a phenyl group, and specific examples of the aralkyl group include, for example, a benzyl group.

Since the main chain of the component (H) is substantially composed of an acrylic copolymer chain, the coating film is excellent in weather resistance, chemical resistance and water resistance. Furthermore, in the component (H), if an alkoxysilyl group is bonded to a carbon atom,
The water resistance of the resulting coating film is further excellent, and the alkali resistance and acid resistance are also excellent.

The number average molecular weight of the component (H) is preferably 1,000 to 30,000, more preferably 3,000 to 25,000 from the viewpoint of physical properties such as durability of the coating film.

The component (H) is an acrylic monomer such as acrylic acid, methacrylic acid or a derivative thereof,
It can be obtained by a copolymer with an alkoxysilyl group-containing monomer. The acrylic monomer is not particularly limited, but specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth).
Acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) Acrylate, (meth) acrylonitrile, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Phosphate ester group which is a condensation product of hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acid such as N-methylol (meth) acrylamide, hydroxyalkyl esters of acrylic acid, and phosphoric acid or phosphoric acid ester Examples thereof include vinyl-based compounds, (meth) acrylates containing urethane bonds and siloxane bonds.

The alkoxysilyl group-containing monomer is not particularly limited except that it has a polymerizable double bond, and specific examples thereof include:

Embedded image

Embedded image Examples thereof include acrylates and methacrylates having an alkoxysilyl group at the terminal via a urethane bond or a siloxane bond. The proportion of the alkoxysilyl group-containing monomer in the component (H) is preferably 5 to 90%, more preferably 10 to 70% from the viewpoint of the curability and durability of the coating film.

The component (H) may contain a segment formed by a urethane bond or a siloxane bond in the main chain within a range not exceeding 50% and is derived from a monomer other than the (meth) acrylic derivative. It may include a segment. The monomer is not particularly limited, but specific examples thereof include aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene and vinyltoluene, and maleic acid. Unsaturated carboxylic acids such as fumaric acid and itaconic acid, their salts (alkali metal salts, ammonium salts, amine salts, etc.), their acid anhydrides (maleic anhydride, etc.), or those and carbon numbers 1-20 Of unsaturated carboxylic acids such as diesters or half esters with linear or branched alcohols, vinyl acetates such as vinyl acetate, vinyl propionate, diallyl phthalate and allyl compounds, vinyl pyridine, amino group containing aminoethyl vinyl ether, etc. Vinyl compounds, itaconic acid diamide, black Tonamide, maleic acid diamide, fumaric acid diamide, amide group-containing vinyl compounds such as N-vinylpyrrolidone, 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin Maleimide, N-vinylimidazole,
Other vinyl compounds such as vinyl sulfonic acid may be mentioned.

At least one kind of these alkoxysilyl group-containing monomers and at least one kind of radical-polymerizable monomer are mixed in a suitable non-reactive solvent and copolymerized by using a radical polymerization initiator. Thus, an alkoxysilyl group-containing acrylic copolymer can be obtained. Examples of the radical polymerization initiator include benzoyl peroxide, dichlorobenzoyl peroxide, 2,5-di (peroxybenzoate) hexyne-
Perester compounds such as 3,1,3-bis (t-butylperoxyisopropyl) benzene and t-butylperbenzoate, azo compounds such as azobisisobutyronitrile and dimethylazobutyrate, and organic peroxides Can be mentioned.

(D) Alkoxysilane Compound The (D) alkylene oxide chain-containing alkoxysilane compound (hereinafter referred to as the (D) component) of the present invention comprises a repeating unit of an alkylene oxide group and at least one or more alkoxysilyl groups. Is a compound having In the alkylene oxide group repeating unit of the component (D), the alkylene portion has 2 to 4 carbon atoms, and the repeating number is 2 to 40, preferably 2 to 20.

The component (D) may have an alkoxysilyl group at both ends, an alkoxysilyl group at one end, and another functional group at the other end. 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.
The functional group may be bonded to an alkoxysilyl group via a urethane bond, a urea bond, a siloxane bond, an amide bond, or the like. (D)
As the component, 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 a polyalkylene oxide chain-containing compound include polyethylene glycol, polyethylene-propylene glycol, polyethylene-tetramethylene glycol, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyoxyethylene diglycolic acid, polyethylene glycol vinyl ether, and polyethylene. Examples thereof include 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.

On the other hand, the coupling agent is, for example, a compound having at least one alkoxysilyl group 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 (D) is not particularly limited, but a polyalkylene oxide chain-containing compound and a coupling agent are prepared separately, and for example, for each compound having a polymerizable double bond, a radical polymerization initiator is used. In addition to copolymerization by using, it can be synthesized by a known method such as addition reaction of amino group / epoxy group, isocyanate group / hydroxyl group or 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 copolymerization is carried out using a radical polymerization initiator, at least one kind of polyalkylene oxide chain-containing compound having a polymerizable double bond and at least one kind of coupling agent are appropriately non-reactive. It can be obtained by reacting in a different solvent. At this time, as a radical polymerization initiator to be used, for example, benzoyl peroxide, dichlorobenzoyl peroxide, 2,5-di (peroxybenzoate) hexyne-3,1,3-bis (t-butylperoxy) Isopropyl) benzene, t
Perester compounds such as -butyl perbenzoate,
Examples include 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 may be used, and the coupling agent may be γ-methacryloxypropyltrimethoxysilane or γ-methacryloxypropyl. Methyldiethoxysilane, γ-methacryloxypropyltriethoxysilane and the like can be used alone or in combination of two or more.

In the case of synthesizing by an isocyanate / polyol addition reaction, for example, a compound having a hydroxyl group at the 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 groups are mixed and synthesized. In this synthetic method, it is also possible to use a reaction catalyst such as dibutyltin dilaurate, dibutyltin dimaleate or dioctyltin dimaleate.

In these reactions, it is synthesized (D)
As the component, a compound in which a coupling agent is added to both ends or one end of a polyalkylene oxide chain-containing compound is obtained, and these can be used alone or as a mixture of both.

Among these components (D), the one having an alkylene oxide chain of ethylene oxide chain and a hydroxyl group at one end is most preferred because it has a high anti-staining effect of the present invention, that is, a high anti-staining property and a soaking resistance. preferable.

The mixing ratio of the component (D) is (C),
The solid content is 0.1 to 20 parts by weight, preferably 0.2 to 100 parts by weight of the resin solid content of each of the components (G) and (H).
10 parts by weight. If it is less than 0.1 parts by weight, the hydrophilicity of the obtained cured product is not sufficient, and if it exceeds 20 parts by weight, the compatibility with each resin and the water resistance of the cured product are poor.

(E) Alkyl silicate (E) General formula of the present invention

Embedded image Examples of the alkyl silicate represented by and / or a condensate thereof (hereinafter referred to as component (E)) include tetramethyl silicate, tetraethyl silicate, tetra-
One or more selected from n-propyl silicate and tetra-i-propyl silicate, and the condensate may be one or more selected from those obtained by condensing the above tetraalkyl silicate under hydrolysis conditions. can give. In particular, use of at least one of tetramethyl silicate and tetraethyl silicate, or a condensation product thereof is preferable from the viewpoint of the balance between flexibility and denseness of the coating film formed. The condensation degree of the condensate is preferably 2 to 20, and when the condensation degree exceeds 20, the viscosity of the condensate increases and handling becomes inconvenient, and the phase of the (C), (G) and (H) components This results in poor solubility and cloudiness in the paint.

The mixing ratio of the component (E) is (C),
(G) 1 to 40 parts by weight, preferably 2 to 20 parts by weight, is suitable for 100 parts by weight of resin solid content of each component. This is because if the amount is less than 1 part by weight, the surface hardness of the cured coating film is not sufficient, causing physical attachment of contaminants and causing permanent contamination. If the amount exceeds 40 parts by weight, the compatibility with each resin,
This is because there are problems that the appearance of the cured product deteriorates and cracks occur. 1 to 30 parts by weight is suitable for 100 parts by weight of the resin solid content of the component (H). This is because the (H) component itself is cured by the same reaction mechanism as that of the (E) component. Therefore, if a large amount of the (E) component is mixed, the coating film formed will be very much. This is because it becomes hard, cannot follow the elongation of the second layer, and cracks easily occur.

(F) Polyisocyanate In the third layer, (F) polyisocyanate (hereinafter referred to as component (F)) is blended with the non-staining coating composition and cross-linked and cured to form the third layer. As the component (F), the same component as the component (B) can be used.

The component (F) has an OH / NCO ratio of 0.6 to 1. with respect to the hydroxyl groups of the components (C) and (G).
Must be compounded to give a value of 5. At this time OH
Even if the / NCO ratio is smaller than 0.6 or larger than 1.5, the durability and curability of the coating film of the third layer are poor,
The durability of the coating film as a whole laminated coating film is inferior.

Other Additives The non-contaminating coating composition and the present invention may be mixed with a coloring pigment to form a colored (enamel) coating film.
Such coloring pigments include titanium oxide, zinc oxide,
Inorganic pigments such as carbon black, ferric oxide (bengara), lead chromate (molybdate orange), yellow lead, yellow iron oxide, ocher, ultramarine, cobalt green, azo, naphthol, pyrazolone, anthraquinone ,
Perylene type, quinacridone type, disazo type, isoindolinone type, benzimidazole type, phthalocyanine type,
Organic pigments such as quinophthalone can be used.

It is also possible to use extender pigments such as heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon and diatomaceous earth. In particular, when forming a matte coating, it is optimal to use white carbon or diatomaceous earth, which has the least loss of the non-contaminating effect on the coating 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.

The non-contaminating paint composition of the present invention and various additives that can be usually added to the paint can be added to such an extent that the effects of the present invention are not affected.
Such additives include plasticizers, preservatives, antifungal agents,
Examples include algae-proofing agents, defoaming agents, leveling agents, pigment dispersants, anti-settling agents, anti-sagging agents, matting agents, and ultraviolet absorbers.

In addition, the non-contaminating coating composition of the present invention further comprises (I) hydrolysis of an alkoxysilyl group.
It is possible to add a condensation catalyst (hereinafter referred to as component (I)). Specific examples of the component (I) include dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, organic tin compounds such as tin octylate, phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, mono. Octyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate,
Phosphate esters such as didecyl phosphate, propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol,
Acrylic glycidyl ether, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, addition of epoxy compound with phosphoric acid and / or monoacidic phosphoric acid ester Reaction product, maleic acid,
Adipic acid, azelaic acid, sebacic acid, itaconic acid,
Examples thereof include citric acid, succinic acid, phthalic acid, trimetic acid, pyrometic acid, acid anhydrides thereof, and acidic compounds such as p-toluenesulfonic acid. Also included are mixtures or reactants of these acidic catalysts and amines. For example,
Hexylamine, N.I. Examples thereof include amines such as N-dimethyldodecylamine and dodecylamine, but organic tin compounds are preferable, and maleate type organic tin compounds are more preferably used because they are particularly excellent in hydrophilicity of the coating film surface at the initial stage of coating film formation. .

The amount of component (I) used is not particularly limited,
Generally, 0.1 to 20 parts by weight is suitable for 100 parts by weight of the total resin solid content of the components (H), (D) and (E),
0.1 to 10 parts by weight is more preferable. This is (I)
This is because if the amount of the component used is less than 0.1 part by weight, the curability tends to decrease, and if it exceeds 20 parts by weight, the appearance of the coating film tends to decrease.

Furthermore, from the viewpoint of long-term storage stability of the composition, a (J) dehydrating agent and / or an alkyl alcohol (hereinafter referred to as the (J) component) can be added to the non-contaminating coating composition. Specific examples of the dehydrating agent, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate,
Examples thereof include hydrolyzable ester compounds such as ethyl orthoacetate, methyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and vinyltrimethoxysilane. In addition, examples of the alkyl alcohol include low molecular weight alcohols such as methanol and ethanol.

These components (J) are preferably added to the component (H) in advance, but during the polymerization of the component (H),
It can be added before or after the polymerization, or during the polymerization. The amount of the component (J) used is not particularly limited, but is preferably 0.5 to 20 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the resin solid content of the component (H). When a dehydrating agent and an alkyl alcohol are used in combination, a remarkable effect is observed on the storage stability of the composition.

Elongation of coating film (γ) The third layer in the present invention is formed by a non-staining coating composition having an elongation of 0.5 to 200% at 20 ° C. If the elongation of the coating film is less than 0.5%,
The coating film is too hard and may crack, which is not preferable. On the other hand, if the elongation of the coating film is more than 200%, the stain resistance of the coating film is remarkably deteriorated, which is not preferable. Further, when forming a waterproof non-staining coating film, the elongation percentage (γ) of the coating film is preferably 20 to 150%. In particular, those having the same or smaller elongation than the elongation (β) of the second layer coating film are preferably used.

The third layer of the present invention can be coated by various methods such as brush coating, spray coating, roller coating and dipping.

<Non-Staining Coating> The non-staining coating of the present invention can be formed by sequentially laminating the first layer, the second layer and the third layer as described above. At that time, the elongation percentage (β) of the coating film of the second layer is less than or equal to the elongation percentage (α) of the coating film of the first layer, and the elongation percentage (γ) of the coating film of the third layer is Elongation rate (β)
It is preferable to stack as follows. In other words, it is desirable that the following relationships hold. (Α) ≧ (β) ≧ (γ) When the first layer to the third layer are laminated so as to satisfy this relationship, a strong coating film without cracking, swelling or peeling of the coating film should be formed. You can

When forming a coating film that is non-staining and waterproof, the elongation percentage of the coating film is (α) 120% to 800% (β) 20 to 200% (γ) 20 to It is preferable to stack so as to be 150%.

[0084]

According to the method for forming a non-staining coating film of the present invention, problems such as cracking, swelling, and peeling do not occur even on the elastic coating material layer and the elastic waterproof material layer, and it is strong and has a good appearance. It became possible to form a contaminated coating. This is because not only the coating film formed by the urethane resin paint of the second layer acts as a buffer layer, but also the third layer is formed by the non-contaminating paint composition of the special constitution in addition to the second layer. From that,
This is made possible by the combined effect of the second and third layers.
In addition, the formed coating film does not become hydrophilic for the first time due to the action that occurs after the coating film is formed, such as rainfall, but the surface becomes hydrophilic immediately after the coating film is formed, and the effect of washing away contaminants is produced. In addition, the composite effect of the first layer to the third layer does not make it brittle while being strong, and also has excellent resistance to penetration of oil stains, weather resistance, and other non-contaminating coating films with good coating physical properties. is there.

[0085]

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

Formulation Example 1 Using the raw materials shown in Table 1,
As in the compounding ratios in Table 2, 84 parts by weight of titanium oxide was uniformly kneaded with 100 parts by weight of the solid content of acrylic polyol 2 to prepare a main component of a white paint. A coating composition was obtained by adding 13.5 parts by weight of the curing agent 1 in terms of solid content so that the OH / NCO ratio was 1.2 with respect to this main agent. (Compounding Examples 2 to 3) Using the raw materials shown in Table 1, the coating compositions were obtained in the same proportions as in Table 2 in the same manner as in Formulation Example 1. (Compounding example 4) Using the raw materials shown in Table 1, 84 parts by weight of titanium oxide was uniformly kneaded with 100 solids of acrylic polyol 2 as shown in the blending ratio of Table 2, and polyethylene oxide chain was added thereto. 10 parts by weight of the contained coupling agent 1 and 10 parts by weight of methyl silicate were blended to prepare a main component of a white paint. The curing agent 1 was converted to 13.5 in terms of solid content so that the OH / NCO ratio was 1.2 with respect to this main agent.
A coating composition added in parts by weight was obtained. (Formulation Example 5) Using the raw materials shown in Table 1, the coating composition was obtained in the same manner as in Formulation Example 4 in the proportions shown in Table 2. (Compounding Example 6) Using the raw materials shown in Table 1, 84 parts by weight of titanium oxide was uniformly kneaded with 100 parts by weight of the solid content of the fluorocopolymer as shown in the blending ratio of Table 2, and 10 parts by weight of polyethylene oxide chain-containing coupling agent 1 and 20 parts by weight of ethyl silicate were blended with each other to prepare a main component of a white paint. With respect to this main agent, the curing agent 2 was converted to a solid content of 42. OH / NCO ratio of 1.2.
A coating composition containing 8 parts by weight was obtained. (Compounding example 7) Using the raw materials shown in Table 1, the alkoxysilyl group-containing acrylic copolymer 1 having the blending ratio shown in Table 2 was used.
84 parts by weight of titanium oxide were uniformly kneaded with 100 parts by weight of the solid content of 5 parts by weight, and 5 parts by weight of polyethylene oxide chain-containing coupling agent 1 and 5 parts by weight of methyl silicate were added to the mixture to prepare the main component of the white paint. It was made. A coating composition was obtained by adding 1 part by weight of dibutyl tin laurate, which is a curing catalyst, to this main agent. (Formulation Example 8 to Formulation Example 10) Using the raw materials shown in Table 1,
After the pigment was kneaded with the resin in the mixing ratio shown in Table 2, a curing agent or a catalyst was added to obtain a coating composition. (Compounding Examples 11 to 12) Using the raw materials shown in Table 1, Table 2
A coating composition was obtained in the same manner as in Formulation Example 4 with the compounding ratio of.

Example 1 Base Material for Specimen Two 150 mm × 300 mm × 6 mm slate plates,
Three 150 mm x 75 mm x 6 mm slate plates and 2
A total of eight 0 mm × 50 mm × 6 mm slate plates were used as test-substance base materials, and the back and side surfaces (total five surfaces) of each base material were used after being sealed with a solventless epoxy resin. Formation of laminated coating film On these substrates, the materials shown in Table 3 were used, and Table 4
The first layer to the third layer were laminated in the order shown by. First, EX sealer (chlorinated rubber solvent type undercoat material manufactured by SK Kaken Co., Ltd.) is required to adjust the base material to a required amount of 0.2.
Spray coating was performed so as to obtain kg / m ² and drying was performed for 4 hours at a temperature of 20 ° C. and a humidity of 65%. Next, Lena Excellent (acrylic rubber-based waterproof multi-layer coating material E manufactured by SK Kaken Co., Ltd.) was spray-coated as the first layer in ^two steps so that the required amount was 2.0 kg / m ² . Temperature 20 ℃, Humidity 6
It was dried at 5% for 24 hours. Further, the coating composition of Formulation Example 2 was spray-coated as the second layer so that the dry film thickness was 25 μm, and dried at a temperature of 20 ° C. and a humidity of 65% for 24 hours. Finally, as the third layer, the coating composition of Formulation Example 4 was spray-coated to a dry film thickness of 25 μm,
It was a test body.

Test Method (1) Evaluation of Appearance after Curing Coating Film One test piece of 150 mm × 300 mm × 6 mm was aged at a temperature of 20 ° C. and a humidity of 65% for 7 days, and then JIS K5400 (1990).
7.1 The appearance of the coating film was evaluated according to the appearance test of the coating film. (2) Repeated hot and cold test evaluation One test piece of 150 mm x 75 mm x 6 mm was used at an ambient temperature of 2
Cured for 7 days at 0 ° C and 65% humidity, JIS A6909 (1995) 6.11
The test was performed according to the hot and cold repeated test. However, 2
The appearance of the coating film was evaluated each time one cycle of 4 hours was completed. (3) Evaluation of boiling water resistance test One test piece of 150 mm × 75 mm × 6 mm was used at an ambient temperature of 2
Cured for 7 days at 0 ° C and 65% humidity, JIS K5400 (1990) 8.
20 The test was performed according to the boiling water resistance test. However, the immersion time was 4 hours. (4) Measurement of contact angle to water Three test pieces of 20 mm x 50 mm x 6 mm were placed at an ambient temperature of 20
Dry for 24 hours (1 day), 72 hours (3 days), and 14 days at ℃ and 65% humidity. After drying, the surface of the coating film has a density of
Add 2 cc of deionized water, the temperature is 20 ° C and the humidity is 65%.
The contact angles immediately after dropping and after 1 minute were measured with a CA-A type contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. (5) Contamination resistance evaluation One specimen of 150 mm × 300 mm × 6 mm was cured at a temperature of 20 ° C and a humidity of 65% for 7 days, and then exposed outdoors in Ibaraki City, Osaka Prefecture, at a 45 ° slope facing south. , Early and 6
The brightness difference (ΔL value) after months is TC- manufactured by Tokyo Denshoku Co., Ltd.
It measured using the 1800 type color difference meter. (6) Evaluation of resistance to penetration of dirt One test piece of 150 mm × 75 mm × 6 mm was measured at an air temperature of 2
After curing for 7 days at 0 ° C and 65% humidity, JIS K5400 (199
0) 8.10 According to the weather resistance test, 15% by weight of carbon black aqueous dispersion paste liquid was dropped onto the coating surface so that the diameter was 20 mm and the height was 5 mm, and the mixture was left in a high temperature chamber at 50 ° C. for 2 hours. Then, it was washed in running water, and the degree of contamination of the coating film surface was visually evaluated.

Evaluation Results As shown in Table 6, the appearance of the coating film after curing was evaluated to be good in coating properties. Especially, the hiding property was excellent, and no problem was observed. Repeated heating and cooling, durability tests such as stain resistance tests did not show the above, indicating extremely high durability. The contact angle with water was 68 ° immediately after dropping when measured after 24 hours,
1 minute after 62 °, 72 hours after measurement, 58 immediately after dropping
° after 1 minute is 52 °, after 14 days is 58
After one minute, it was 52 ° after 1 minute, and all had low values, indicating that the surface of the coating film was hydrophilic. further,
In the stain resistance evaluation, the result that the ΔL value is -2.7 was obtained, and it was found that the stain resistance was excellent.
No trace was observed in the stain penetration resistance test, and good results were obtained. Therefore, the adhered stains are present only on the surface of the coating film, and it is an excellent non-staining coating film that can be completely flowed down by rainfall, and it can firmly adhere to the substrate and form a beautiful laminated coating film. Became clear.

Example 2 Base Material for Specimen The same material as in Example 1 was used. Formation of laminated coating film The materials shown in Table 3 were used for the substrate, and the first layer to the third layer were laminated in the order shown in Table 4. First, as a base adjustment, Archiprimer (one-component polyurethane resin-based undercoat material manufactured by SK Kaken Co., Ltd.) is spray-coated to a required amount of 0.2 kg / m ^2, and the temperature is set to 20.
It was dried at a temperature of 65% and a humidity of 65% for 6 hours. Next, as the first layer, SK sealant (one-component modified silicone sealing material manufactured by SK Kaken Co., Ltd.) was applied with a trowel to give a dry film thickness of 5 mm, and dried at a temperature of 20 ° C. and a humidity of 65% for 3 days. Let Further, the coating composition of Formulation Example 2 was spray-coated as the second layer so that the dry film thickness was 25 μm, and dried at a temperature of 20 ° C. and a humidity of 65% for 24 hours. Finally, the coating composition of Formulation Example 5 was spray-coated as the third layer so that the dry film thickness was 25 μm, to give a test sample.

Test Method A test was carried out in accordance with Example 1. Evaluation results As shown in Table 6, as in Example 1, good results were obtained.

(Examples 3 to 4) Using the materials shown in Table 3, and in the order shown in Table 4, test samples were prepared according to Example 1 and evaluated in the same manner as in Example 1. Where I went,
Good results were obtained as shown in Table 6.

(Comparative Examples 1 to 3 and Comparative Examples 5 to 6) The materials shown in Table 3 were used, and the first layer to the third layer were formed in the order shown in Table 5. A test body was prepared according to Example 1. When the same evaluation as in Example 1 was performed, the results shown in Table 7 were obtained.

(Comparative Example 4) Using the materials shown in Table 3, and in the order shown in Table 5, a test body was prepared according to Example 2 and evaluated in the same manner as in Example 1. By the way, Table 7
The result is as follows.

<Evaluation Results of Comparative Example> In Comparative Example 1, the general hard type acrylic resin coating is laminated on the second layer and the third layer, but it follows the elongation of Lena Excellent on the first layer. However, the durability of the laminated coating film became problematic, such as the occurrence of cracks over time. Further, Comparative Example 5 and Comparative Example 6
Then, the repeating unit which is the component (D) of the present invention has 2 to 4 units.
Since no alkoxysilane compound containing an alkylene oxide chain of 0 was included, the initial contact angle was higher than that of the present invention, and the result was that traces remained in the resistance to soaking. Further, in Comparative Example 5, swelling occurred in the boiling water resistance test, and in Comparative Example 6, the amount of methyl silicate which is the component (E) of the present invention was large, so that the appearance of the coating film was glossy compared to the others. It was found that the coating film was cracked in the repeated hot and cold tests, the boiling water resistance test and the outdoor exposure test, and there was a problem in the durability of the laminated coating film.

In addition, in Comparative Examples 2 to 4, the third layer is formed by using a general urethane resin paint, a fluororesin paint, an acrylic silicone resin paint, and any laminated coating film is durable. However, the contact angle was high, the coating film surface was water repellent, and the results were inferior in stain resistance and penetration resistance.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 183/02 PMQ C09D 183/02 PMQ // C09D 127/12 PFJ 127/12 PFJ (72) Inventor Nakasoya Takanori 1-25-10 Shimizu, Ibaraki-shi, Osaka SK Kaken Co., Ltd. (72) Inventor Hiroshi Nakai 1-25-10 Shimizu, Ibaraki-shi, Osaka SK Kaken Co., Ltd. (72) Inventor Ikeuchi Tadahiko 1-25-10 Shimizu, Ibaraki-shi, Osaka SK Kaken Co., Ltd. (72) Inventor Hideto Karuga 1-25-10 Shimizu, Ibaraki-shi, Osaka SK Kaken Co., Ltd. (72) Invention Kensuke Kurimoto 1-25-10 Shimizu, Ibaraki-shi, Osaka Inside SK Kaken Co., Ltd. (72) Inventor Hisashi Suzuki 1-25-10 Shimizu, Ibaraki-shi, Osaka SK Kaken Co., Ltd.

Claims (5)

[Claims] 1. The surface of a building or civil engineering structure has (1) an elongation rate (α) of the coating film at a temperature of 20 ° C. of 50 to 80.
On the first layer formed by the elastic coating material or the elastic waterproof material, which is 0%, (2) is composed of (A) and (B) shown below, and the temperature is 2
Second layer formed by urethane resin paint having elongation (β) of 2 to 300% at 0 ° C. (A) Polyol having weight average molecular weight of 5,000 to 80,000 and hydroxyl value of 20 to 150 KOHmg / g (B ) Polyisocyanate is laminated so that the OH / NCO ratio is 0.6 to 1.5 with respect to the hydroxyl group of (A) polyol, and (3) the following (C), (D) and (E) are shown. (F), the elongation (γ) of the coating film at a temperature of 20 ° C. is 0.5 to 20.
Third layer formed by 0% non-contaminating coating composition (C) Polyol having a weight average molecular weight of 5,000 to 80,000 and a hydroxyl value of 20 to 150 KOHmg / g in a solid content of 100.
Parts by weight (D) 0.1 to 20 parts by weight of an alkoxysilane compound containing an alkylene oxide chain whose repeating unit is 2 to 40 and having a weight average molecular weight of 150 to 3500 in terms of solid content (E) General formula: 1 to 40 parts by weight of a solid content of an alkyl silicate represented by and / or a condensate thereof, and (F) polyisocyanate in an OH / NCO ratio of 0.6 to 1.5 with respect to the hydroxyl group of the (C) polyol. A method for forming a non-staining coating film, which comprises laminating a mixture so that 2. The surface of a building or civil engineering structure has (1) an elongation percentage (α) of a coating film at a temperature of 20 ° C. of 50 to 80.
On the first layer formed by the elastic coating material or the elastic waterproof material, which is 0%, (2) is composed of (A) and (B) shown below, and the temperature is 2
Second layer formed by urethane resin paint having elongation (β) of 2 to 300% at 0 ° C. (A) Polyol having weight average molecular weight of 5,000 to 80,000 and hydroxyl value of 20 to 150 KOHmg / g (B ) Polyisocyanate is laminated so that the OH / NCO ratio is 0.6 to 1.5 with respect to the hydroxyl group of the (A) polyol, and (3) the following (G) (D) (E). (F), the elongation (γ) of the coating film at a temperature of 20 ° C. is 0.5 to 20.
Third layer (G) having a number average molecular weight of 3,000 to 30,000, a fluorine content of 10 to 30% by weight and a hydroxyl value of 10 to 30 KOHmg / g. 100 parts by weight of polymer in solid content (D) 0.1 to 20 parts by weight in solid content of alkoxysilane compound having a weight average molecular weight of 150 to 3500 and containing an alkylene oxide chain whose repeating unit is 2 to 40 (E) General formula: 1-40 parts by weight of the alkyl silicate and / or the condensate thereof represented by the formula (F) polyisocyanate (G) with respect to the hydroxyl group of the fluorine-containing copolymer in an OH / NCO ratio of 0.6- A method for forming a non-staining coating film, which comprises laminating the composition so as to be 1.5. 3. The surface of a building or civil engineering structure has (1) an elongation rate (α) of a coating film at an air temperature of 20 ° C. of 50 to 80.
On the first layer formed by the elastic coating material or the elastic waterproof material, which is 0%, (2) is composed of (A) and (B) shown below, and the temperature is 2
Second layer formed by urethane resin paint having elongation (β) of 2 to 300% at 0 ° C. (A) Polyol having weight average molecular weight of 5,000 to 80,000 and hydroxyl value of 20 to 150 KOHmg / g (B ) Polyisocyanate is laminated so that the OH / NCO ratio is 0.6 to 1.5 with respect to the hydroxyl group of (A) polyol, and (3) the following (H) (D) (E) is shown. And a third layer (H) represented by the general formula: (H) which is composed of a non-contaminating coating composition having an elongation (γ) of 0.5 to 200% at a temperature of 20 ° C. 100 parts by weight of an alkoxysilyl group-containing acrylic copolymer containing a group represented by (D) an alkoxysilane compound having a weight average molecular weight of 150 to 3500 containing an alkylene oxide chain having 2 to 40 repeating units. 0.1 to 20 parts by weight as solid content (E) General formula A method for forming a non-staining coating film, which comprises laminating 1 to 30 parts by weight of a solid content of an alkyl silicate represented by and / or a condensate thereof. 4. The elongation percentage (α) of the coating film of the first layer is 120-8.
00%, and the elongation rate (β) of the second layer coating film is 20 to 2
00%, the elongation (γ) of the third layer coating film is 20 to 150%
The method for forming a waterproof non-staining coating film according to claim 1, wherein 5. The elongation (β) of the coating film of the second layer is less than or equal to the elongation (α) of the coating film of the first layer, and the elongation (γ) of the coating film of the third layer is second or less. The elongation (β) of the coating film of the layer is equal to or less than [(α) ≧ (β) ≧ (γ)].
5. The method for forming a non-staining coating film according to claim 4.