JP2695113B2 - Method for repairing inorganic hardened body or metal surface having silicon-based coating layer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for repairing an inorganic hardened material or a metal surface having a silicon alkoxide coating layer.

[0002]

2. Description of the Related Art In recent years, a cured inorganic material or metal coated with a silicon alkoxide has excellent weather resistance and durability, and is therefore widely used as an outer wall material for buildings. Therefore, cutting and nailing may be performed at the construction site, and damage may occur during transportation. Therefore, it is necessary to repair those places.

As a repairing method, the present inventors proposed a repairing method using a room temperature curing type paint in Japanese Patent Laid-Open No. 3-242268. However, coloring such as yellowing of the primer occurs due to long-term outdoor exposure. There was a problem that the appearance changed. In addition, a room temperature curing type repair coating (for example, fluorine-based or acrylic silicone-based coating)
Also causes a gradual change in appearance, and causes a discomfort in appearance with a silicon alkoxide-based coating layer having excellent weather resistance. Further, there is a problem in that long-term adhesion can be secured even if repair is performed with a room temperature curable inorganic coating having excellent weather resistance.

[0004]

In the above situation,
The present invention is an inorganic cured product having a silicon alkoxide-based coating layer that is improved in coloring such as yellowing with respect to long-term outdoor exposure, and that is capable of maintaining long-term adhesion with a room temperature-curable inorganic coating topcoat repair material or It is an object to provide a method for repairing a metal surface.

[0005]

According to the present invention, a primer composition comprising the following components (a), (b), (c) and (d) is preliminarily provided on a portion requiring repair of an inorganic hardened material or a metal surface. It is a method for repairing an inorganic hardened body having a silicon alkoxide coating layer or a metal surface, which comprises applying and then applying a room temperature hardening type inorganic coating material. (A) Epoxy compound having two or more epoxy groups in one molecule (b) Organosilicon compound having one or more mercapto groups and two or more alkoxy groups in one molecule (c) One in one molecule Organosilicon compounds having one or more amino groups and two or more alkoxy groups (d) Organic solvent

There is no particular limitation on the above-mentioned repair-required portion, but, for example, when the cured inorganic material or metal is transported or applied, a scratch or a crack in the coating film occurs in the silicon alkoxide coating layer. Included are areas where you want to change colors, etc. Further, the repair-required place is not limited to the part where the inorganic hardened body or metal is exposed, and a silicon alkoxide-based coating layer, a repaired material applied to a damaged part or a joint of the inorganic hardened body or metal, or the like appears. Part is also included. The repair material is, for example, putty,
Examples include silicone caulking materials, stainless steel, screw nails, and color nails. Color nails are nails coated with acrylic paint, urethane paint, or the like for coloring or the like.

Hereinafter, the present invention will be described in detail.

(1) The epoxy compound (or epoxy resin) of the component (a) used in the present invention must have two or more epoxy groups in one molecule. If the number of epoxy groups is less than 2, it cannot be used because the effect of adhering a room temperature curing inorganic coating or the like to a silicon alkoxide coating surface is not exhibited. Examples of the epoxy compound include bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, sorbitol diglycidyl ether, polyglycerol diglycidyl ether, resorcin diglycidyl ether, and the like. Examples thereof include those obtained by epoxidizing an unsaturated group of a hydrocarbon having an unsaturated bond of (1) with peracetic acid or the like. Of these, the last-exemplified ones are preferable because they give particularly good adhesiveness, and among them, those having 4 to 30 carbon atoms are particularly recommended for the same reason. The main function of this component (a) is to make the coating film formed by drying and hardening the primer composition tough,
Further, it is to impart adhesiveness to a primer coating of a room temperature curing type coating material such as an inorganic coating material.

(2) 1 of the component (b) used in the present invention
The organosilicon compound having one or more mercapto groups and two or more alkoxy groups in the molecule is an essential component for obtaining adhesion to a silicon alkoxide-based coating surface and the like. Since the component (b) has a mercapto group, it has excellent adhesiveness, and if it does not have a mercapto group, it has no adhesive effect. The mercapto group is, for example, a mercaptoalkyl group (wherein the alkyl group has, for example, 1 carbon atom).
~ 6) and so on. Further, the component (b) has a coating film having two or more alkoxy groups, but the coating film cannot be formed if it has only one or no alkoxy group. Examples of such an organosilicon compound (b) include HS (CH ₂ ) ₃ Si (OC
_{H 3) 2, HS (CH} 2) 3 Si (OC 2 H 5) 3, HS (C
_{H 2) 3 Si (OCH 3} ) 3, HS (CH 2) 3 Si (OC 2
_{H 5) 3, HS (CH} 2) 3 Si (CH 3) (OCH 3) silane or their hydrolysis condensate of such ₂ and the like. These may be used alone or in combination of two or more. The blending amount of the organosilicon compound of the component (b) in the primer composition is 1 with respect to 100 parts by weight of the component (a).
0 to 500 parts by weight. If the blending amount of the component (b) is less than 10 parts by weight, the adhesiveness is not sufficiently exhibited, and conversely, if it exceeds 500 parts by weight, the strength of the primer coating is lowered and the adhesiveness is lost, which is not preferable.

The component (a) and the component (b) may be mixed separately, but they may be reacted in advance, that is, the epoxy group of the component (a) may be added to the component (b).
You may add and use the mercapto group of. When the component (a) and the component (b) are previously reacted in this way, the adhesive effect is further enhanced.

(3) The organosilicon compound having one or more amino groups and two or more alkoxy groups in one molecule of the component (c) acts as a hydrolysis catalyst for the alkoxy group of the component (b), In addition, it has adhesiveness to a silicon alkoxide-based coating surface and the like, and is for forming a tough primer film immediately after coating.

The component (c) having an amino group accelerates the hydrolysis of the component (b). A film is formed when the component (c) has two or more alkoxy groups. Examples of the organic silicon compound (c), for _{example, H 2 N (CH 2)} 3 Si (OCH 3) 3, H
₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , H ₂ N (CH ₂ ) _{3
Si (CH 3) (OC 2} H 5) 2, H 2 N (CH 2) 2 NH
_{(CH 2) 3 Si (OCH} 3) 3, H 2 N (CH 2) 2 NH
_{(CH 2) 3 Si (CH} 3) (OCH 3) 2, H 2 N (CH 2)
Examples thereof include silane such as ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ and hydrolytic condensation products thereof. These may be used alone or in combination of two or more.

The proportions of the components (4) (a), (b) and (c) can be appropriately determined by those skilled in the art.
Component (b) 10 to 10 parts by weight of normal component (a)
500 parts by weight and 5 to 200 parts by weight of the component (c).

The organic solvent of component (d) (5) is used for the purpose of facilitating the coating operation of the primer composition. These organic solvents include aromatic hydrocarbons such as toluene and xylene; carboxylic acid esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran. It is illustrated. These solvents may be used alone or in combination of two or more. Component (d)
The use ratio of is not particularly limited as it can be set appropriately because the performance is guaranteed even in a considerably wide range.

(6) The primer composition used in the repair method of the present invention includes methyl silicate, ethyl silicate,
Alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane; pigments such as titanium oxide, carbon black and iron oxide; other additives can be added.

(7) The top coating for the above primer composition is a room temperature curing type inorganic coating, and commercially available fluorine type room temperature curing type coating, modified silicone type room temperature curing type coating and the like are used. Not limited to.
A room temperature curable inorganic coating material having excellent weather resistance is preferable.

The room temperature curing type inorganic coating material will be described below.

The room temperature curable inorganic coating material is an inorganic coating material in which a pigment is dispersed in an inorganic coating agent containing silicon alkoxide, colloidal silica and high molecular silanol as a resin component, and the silicon alkoxide is represented by the general formula (I). Is a compound represented by.

(R ¹ ) _n Si (OR ² ) _4-n (I)

(Wherein R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms;
Is 1, 2 or 3, and R ² represents a monovalent hydrocarbon group having 1 to 8 carbon atoms)

The colloidal silica is colloidal silica used in a state of being dispersed in water or an organic solvent.

Further, the polymeric silanol used here is a compound represented by the general formula (II) as an average composition formula.

(R ³ ) _a Si (OH) _b O _{(4-ab) / 2} (II)

(Wherein R ³ is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms;
And b are 0.2 ≦ a ≦ 2.0 and 0.0001 ≦, respectively.
It is a number that satisfies the relationship of b ≦ 3.0 and a + b <4)

This room-temperature-curable inorganic coating agent is prepared from a solution in which silicon alkoxide (I) is partially hydrolyzed in the presence of water, colloidal silica, and a polymer silanol (II). The curing catalyst is added as needed. Then, a pigment as a colorant and a dispersion aid are added to the inorganic coating agent to form an inorganic coating material. The pigment is not particularly limited, but titanium oxide, barium sulfate, calcium carbonate, alumina, iron oxide red, other complex oxide pigments,
An organic pigment or the like is used.

As R ¹ and R ² in the formula (I), methyl, ethyl, propyl, butyl, pentyl,
Alkyl groups such as hexyl, heptyl and octyl; cycloalkyl groups such as cyclopentyl and cyclohexyl;
Aralkyl groups such as 2-phenylethyl and 3-phenylpropyl; aryl groups such as phenyl and tolyl; alkenyl groups such as vinyl and allyl; chloromethyl, γ-
Halogen-substituted hydrocarbon groups such as chloropropyl and 3,3,3-trifluoropropyl; substituted hydrocarbon groups such as γ-methacryloxypropyl, γ-glycidoxypropyl, 3,4-epoxycyclohexylethyl and γ-mercaptopropyl A group can be exemplified. Among these, an alkyl group having 1 to 4 carbon atoms or a phenyl group is preferable because of ease of synthesis and availability.

In the silicon alkoxide (I), tetramethoxysilane and tetraethoxysilane can be exemplified as the tetraalkoxysilane with n = 0; n =
Examples of the organotrialkoxysilane of 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane; Examples of the organodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane; examples of the triorganoalkoxysilane of n = 3 include trimethylmethoxysilane, trimethylethoxysilane, and Examples are trimethylisopropoxysilane and dimethylisobutylmethoxysilane.

It is preferable that 50 mol% or more of the silicon alkoxide (I) of the inorganic coating agent is a trifunctional silicon alkoxide represented by n = 1 in order to finally obtain a coating film having high hardness. , And more preferably 60
It is at least mol%, most preferably at least 70 mol%.

The liquid of the inorganic coating agent in which colloidal silica is dispersed contains 20 to 50% by weight of silica as a solid content.
The content of silica is determined, and the content of silica is determined from this content. When colloidal silica dispersed in water is used, the existing water can be used for the above-mentioned hydrolysis of silicon alkoxide. Such water-dispersed colloidal silica is usually made of water glass, but there are commercially available products that can be easily obtained. A liquid in which colloidal silica is dispersed in an organic solvent can be prepared by substituting water of the water-dispersed colloidal silica with an organic solvent for preparation, and such an organic solvent-dispersed colloidal silica is commercially available and easy. Can be obtained at.

Examples of the organic solvent for dispersing the colloidal silica include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate and the like. Ethylene glycol derivatives; diethylene glycol, diethylene glycol monobutyl ether and other diethylene glycol derivatives; diacetone alcohol and the like, and one or more selected from the group consisting of these can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone,
Methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used.

The amount of water used for the partial hydrolysis of the silicon alkoxide (I) is 0.001 to 1 mol of water with respect to 1 mol of the OR ² group which is a hydrolysis group in the formula (I).
It is preferable to use 0.5 mol. If it exceeds 0.5 mol, the stability of the partially hydrolyzed product may be deteriorated.
There is no particular limitation on the method for partially hydrolyzing the silicon alkoxide, and it is sufficient to mix the silicon alkoxide and the colloidal silica dispersion and add the required amount of water. You may heat at 60-100 degreeC in order to accelerate | stimulate. To further accelerate the partial hydrolysis reaction, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluene sulfone. An organic acid such as acid or oxalic acid or an inorganic acid may be used as a catalyst.

In order to obtain a mixture (mixture) in which a necessary amount of water is added by mixing the silicon alkoxide and the colloidal silica dispersion, and having long-term stable properties, the pH of this mixture is set to 2. 0-7.0, preferably 2.5-6.
5, more preferably 3.0 to 6.0. Regarding the pH adjustment, if the pH of the mixed solution is more acidic than the above range, ammonia may be adjusted by adding a basic reagent such as ethylenediamine, and if it is the basic side, hydrochloric acid, nitric acid,
It may be adjusted using an acidic reagent such as acetic acid.

The high molecular silanol in the present invention is a compound represented by the average composition formula (II), (II)
Examples of R ³ in the formula include the same ones as R ¹ and R ² in the formula (I), preferably an alkyl group having 1 to 4 carbon atoms; a phenyl group; a vinyl group; a γ-glycid It is a substituted hydrocarbon group such as xypropyl, γ-methacryloxypropyl, γ-aminopropyl, 3,3,3-trifluoropropyl, and more preferably a methyl group or a phenyl group.

Regarding a and b in the formula (II),
When a is less than 0.2 or b is more than 3.0, there is an inconvenience such as cracking in the cured coating film, and when a is more than 2.0 or b is less than 0.0001, curing is suitable. Does not progress. Also, the molecular weight of the high molecular silanol is 700
It is preferably ˜20,000. The molecular weight here is the weight average molecular weight in terms of standard polystyrene measured by GPC. When it is less than 700, the curability of the coating film is slow and cracks are likely to occur. 20,000
When it exceeds, the coating film obtained from the coating material to which the pigment is added has no gloss and the smoothness is not good.

Such a polymer silanol is obtained by hydrolyzing methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane or a corresponding alkoxysilane, or a mixture of two or more thereof, with a large amount of water. Can be obtained at It should be noted that it is possible to use a polymer silanol having a small amount of unhydrolyzed alkoxy groups remaining.

For the purpose of accelerating the condensation reaction of the component containing the partially hydrolyzed silicon alkoxide and colloidal silica and the polymer silanol component to cure the coating film, a curing catalyst can be added if necessary. As the curing catalyst, metal salts of carboxylic acids such as alkyl titanate, tin octylate, dibutyltin dilaurate and dioctyltin dimaleate; amine salts such as dibutylamine-2-hexoate, dimethylamine acetate, ethanolamine acetate; tetraethylpenta Amines such as min; amine silane coupling agents such as N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane;

Acids such as P-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; alkali catalysts such as potassium hydroxide; tetraisopropyl titanate, tetrabutyl titanate, titanium tetraacetylacetonate and the like. Titanium compounds; methyltrichlorosilane,
Examples thereof include halogenated silanes such as dimethyldichlorosilane and trimethylmonochlorosilane, but other ones are also preferable as long as they are effective for the condensation reaction of the partial hydrolyzate of silicon alkoxide and the polymer silanol. There is no limit.

The compounding ratio of the component containing the partially hydrolyzed silicon alkoxide and colloidal silica and the polymer silanol component is such that the component containing the partially hydrolyzed silicon alkoxide and colloidal silica is the component (A) and the polymer silanol component. When expressed as the component (B), the component (A) and the component (B)
Of the component (A) based on 100 parts by weight of the total (resin component)
1 to 99 parts by weight, component (B) 99 to 1 parts by weight, more preferably component (A) 5 to 95 parts by weight, component (B) 95 to 5 parts by weight, and most preferably component (A) 10 to 90 parts by weight and component (B) 90 to 10 parts by weight. When the amount of the component (A) is less than 1 part by weight in a total of 100 parts by weight of the component (A) and the component (B), the curability is poor and sufficient coating hardness cannot be obtained. If it exceeds the above range, there arises a problem that the curability is unstable and the coating film performance is poor.

The addition amount of the curing catalyst is preferably 0.0001 to 10 parts by weight based on 100 parts by weight of the total of the components (A) and (B) (resin component). It is more preferably 0.0005 to 8 parts by weight, most preferably 0.0007 to 5 parts by weight. 0.00
If it is less than 01 parts by weight, the curability will be poor, and if it exceeds 10 parts by weight, the heat resistance and weather resistance of the coating film will be poor.

The inorganic coating used in the method of the present invention can be diluted with various organic solvents before use. As the organic solvent for dilution, methanol, ethanol, isopropanol, n-butanol, which is shown as a dispersion solvent of colloidal silica,
Lower aliphatic alcohols such as isobutanol; ethylene glycol, ethylene glycol monobutyl ether,
Ethylene glycol derivatives such as ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. One or more selected from the group consisting of these. Can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can also be used.

In addition to the above-mentioned designations of component (A) and component (B), the method for storing the room-temperature-curable inorganic coating composition is as follows.
It is common to take a three-pack form in which the three components of the component (A ′), the component (B) and the curing catalyst are independently stored, but a mixture of the component (A ′) and the curing catalyst, It is also possible to divide the two components (B) into two and form them in two packages, and mix both of them at the time of use, or one package in which all the components are mixed and stored in one container. However, when storing a mixture of the component (A ') and the curing catalyst,
After adjusting the pH of the component (A ') to 2 to 7, it is preferable to add a curing catalyst, and further to 1 mol of the hydrolyzable group (OR ² group) of the silicon alkoxide in the component (A'). The amount of water used is preferably 0.3 mol or less.

(8) In the present invention, if necessary, a repair material is applied to the surface of the cured inorganic material having a silicon alkoxide-based coating layer or the surface of the metal, where necessary, and then the above (a) to (d) are applied. It is completed by applying a primer composition as an essential component, and then applying a room temperature curing type coating material such as an inorganic room temperature drying type coating material. The method of applying the primer composition and the room temperature curable coating material is not particularly limited, and may be appropriately performed by a method such as spraying or brush coating. The coating thickness (or coating thickness) can also be set appropriately.

The inorganic cured material or the silicon alkoxide coating layer on the metal surface applied in the present invention is, for example, the following general formula:

(R ') _m Si (OR ") _4-m

(In the formula, R'represents a methyl group or an ethyl group, R "represents an alkyl group having 1 to 4 carbon atoms, and m represents 0, 1 or 2.)

It is formed by a coating agent containing a silicon compound represented by and / or a partial hydrolyzate thereof as a main component. This coating agent may contain silica sol as another component, and also contains a colorant, a filler,
Surfactants, thickeners, anti-aging agents and the like may be added. A catalyst such as an inorganic acid or an organic acid, a quaternary ammonium salt, an amine salt, or an organic tin compound is added to these coating agents, and the coating agent is applied to an inorganic hardened material or a metal and heat-cured.

Alternatively, (A) general formula

(R ⁴ ) _r SiX _4-r (I)

(In the formula, R ⁴ is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms;
Is 0, 1, 2 or 3, and X represents a hydrolyzable group)

In the colloidal silica in which the hydrolyzable organosilane represented by: is dispersed in an organic solvent or water, 0.001 to 0.5 mol of water is used for 1 mol of X to partially hydrolyze the organosilane silica. With dispersed oligomer solution

(B) Average composition formula

(R ⁵ ) _c Si (OH) _d O _{(4-cd) / 2} (II)

(Wherein R ⁵ is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and c
And d are 0.2 ≦ c ≦ 2 and 0.0001 ≦ d ≦, respectively.
3, a number that satisfies the relationship of c + d <4)

A polyorganosiloxane having a silanol group represented by

(C) catalyst

A coating composition consisting of and may be applied.

These coating agents may be added with other components such as colorants, fillers, surfactants, thickeners and antiaging agents.

The inorganic hardened material is used, for example, as an outer wall material of a building, and is appropriately manufactured from raw materials such as cement, silica stone powder, pulp, asbestos, and synthetic fibers. In addition, metal is a metal processed product used for outer walls of buildings, rain gutters, window frames, etc.
A stainless steel base material such as 04, iron or aluminum metal from which oil and dirt have been removed by alkali degreasing or solvent degreasing, or a chemical conversion treatment such as chromate may be used. Further, the surface of the substrate may be patterned with an embossing roll or the like.

The above-mentioned primer composition is applied to the location where the silicon alkoxide coating layer on the surface of the inorganic hardened material or the metal is scratched or chipped, and then the room temperature-curable inorganic coating material is applied for repair.

[0060]

Since the primer composition containing the specific components (a), (b), (c) and (d) is applied, the room temperature curable inorganic coating material is applied. The weather resistance is improved, and the adhesiveness to the silicon alkoxide-based coating surface of the paint and the room-temperature-curable inorganic paint of the topcoat is improved. Since the coating material is a room temperature curing type, it does not require a baking treatment for forming a coating film.

The main function of the component (a) is to make the coating film formed by drying and curing the primer composition tough, and to impart the adhesiveness of the coating material such as the inorganic coating material to the primer coating film. . The component (b) is an essential component for obtaining the adhesion to the silicon alkoxide coating surface. The component (c) acts as a hydrolysis catalyst for the alkoxy group of the component (b), has adhesiveness to the silicon alkoxide coating surface, and forms a tough primer film promptly after coating. Yes, it maintains the curing balance with the room temperature curing type inorganic coating as the top coat, thereby improving the adhesion performance. Component (d)
Is for facilitating the coating operation of the primer composition.

[0062]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. "Parts" and "%" are "parts by weight" respectively.
And "% by weight".

(Preparation of Silicon Alkoxide Coating Liquid) Reference Example 1: Preparation of Inorganic Cured Product or Clear Coating Liquid (C-1) for Metal Surface 100 parts of methyltrimethoxysilane, 20 parts of tetraethoxysilane, IPA silica sol (catalyst) Oscar 1432 manufactured by Kasei Kogyo KK, 105 parts of SiO ₂ content of 30%, 5 parts of dimethyldimethoxysilane and 100 parts of IPA were mixed. To this mixed solution, a catalytic amount of 1N hydrochloric acid 1 part and water 4.5
Parts were added to prepare a solution A. The composition was stirred at 500 rpm for 30 minutes in an atmosphere of 25 ° C.

The prepared solution A was stored in a tightly closed state at 25 ° C. for 1 week or more, and when used, 100 parts of solution A was mixed with water 42 parts.
Parts and 42 parts of IPA are added and 10 at 500 rpm at 25 ° C.
The mixture was stirred for a minute to obtain a coating liquid (C-1).

Reference Example 2: Preparation of Colored Coating Liquid (C-2) for Inorganic Cured Product or Metal Surface 100 parts of methyltrimethoxysilane, 10 parts of tetraethoxysilane, IPA silica sol (Oscar 1432, SiO ₂ manufactured by Catalyst Kasei Kogyo KK) 110 parts of a content of 30%), 20 parts of dimethyldimethoxysilane and 100 parts of IPA were mixed. To this mixed solution was added a catalytic amount of 0.85 part of 1N hydrochloric acid and 5 parts of water in the same manner as in (C-1) to prepare solution A '. The prepared A'solution was stored in the same manner as the above-mentioned A solution, and when used, 43 parts of water and IPA43 were added to 100 parts of the A'solution.
Parts were added to obtain solution A ″.

To 100 parts of this A ″ solution, 7.5 parts of commercially available titanium oxide, 0.3 part of finely powdered silica (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.), and 10% ethylcellulose 2 diluted with a toluene-IPA mixture solution were added. Glass beads were added to the container using a disper (disperser) and dispersed at 2,000 rpm for 15 minutes, and the resulting A ″ ′ solution was added at 25 ° C. for 3 days. When used, 27 parts of water and I of 100 parts of A '''solution were used.
PA (27 parts) and a catalytic amount of 1N hydrochloric acid (0.2 parts) were added, and a coating solution (C-2) was obtained in the same manner as in Reference Example 1.

Reference Example 3: Preparation of colored coating liquid (C-3) for inorganic hardened material or metal surface and preparation of room temperature-curable inorganic paint (A) Preparation of component: Stirrer, heating jacket, condenser and thermometer are attached. 100 parts of isopropylalcol-dispersed colloidal silica sol IPA-ST (particle diameter 10 to 20 mμ, solid content 30%, water content 0.5%, Nissan Chemical Industries, Ltd.), methyltrimethoxysilane 68 in a flask.
Parts, 18 parts of dimethyldimethoxysilane, 2.7 parts of water, and 0.1 parts of acetic anhydride are added, and a partial hydrolysis reaction is carried out at a temperature of 80 ° C. for about 3 hours while stirring and cooled (A).
The ingredients are obtained. This had a solid content of 36% when left at room temperature for 48 hours. The component (A) obtained here is called (A-1).

Similarly, the component (A) prepared under the following conditions is designated as (A-2).・ Number of moles of water to 1 mole of hydrolyzable group ……………… 0.1 ・ Content of silica in component (A) …………………… 40.2% ・ n = 1 Mol% of the hydrolyzable group-containing organosilane of 77 mol%

Preparation of component (B): A mixed solution of 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene was weighed and equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer. 108 parts of a 1% hydrochloric acid aqueous solution was dropped into the above-mentioned mixture in 20 minutes to hydrolyze methyltriisopropoxysilane. 40 drops
After a minute, the stirring was stopped and the lower layer water-isopropyl alcohol mixture containing a small amount of hydrochloric acid separated into two layers was separated.
Next, the remaining hydrochloric acid in the resin solution of toluene was washed with water to remove it, and toluene was further removed under reduced pressure. Then, the solution was diluted with isopropyl alcohol and diluted with isopropyl alcohol to obtain a 40% solution of polyorganosiloxane having a silanol group and an average molecular weight of 2,000. Got This is designated as (B-1).

To 100 parts of (A-1), 50 parts of titanium oxide as a pigment, 7 parts of a dispersant, 0.2 part of a thickening agent, and 2 parts of fumed silica were added, and a sand mill was used to produce 1,000 parts.
It was treated with rpm for 20 minutes. To 100 parts of the obtained mixed liquid, 0.31 part of N-β-aminoethyl-γ-aminopropyldimethylmethoxysilane and 0.62 part of dibutyltin dilaurate were added as a curing catalyst, and a liquid containing a pigment (A '
-1) was prepared. Furthermore, (A'-1) :( B-1) = 1
Mixing at 60: 100, room temperature curing type inorganic coating (C-3)
I got

(Preparation of Primer) Reference Example 4: Preparation of Primer (P-1) Epoxy compound 100 obtained by epoxidizing a hydrocarbon mixture having unsaturated bonds (plurality) having 6 to 8 carbon atoms with peracetic acid.
, Γ-mercaptopropyltrimethoxysilane 20
0 part was added, and the mixture was heated with stirring at 80 ° C. for 8 hours under a nitrogen atmosphere. Then, after cooling to room temperature, 50 parts of γ-aminopropyltriethoxysilane and 500 parts of toluene are added,
The mixture was stirred to obtain a primer (P-1).

Reference Example 5: Preparation of primer (P-2) 100 parts of bisphenol A diglycidyl ether having a molecular weight of about 400, 300 parts of γ-mercaptopropyltriethoxysilane and N- (β-aminoethyl) -γ- Aminopropyltrimethoxysilane 100 parts, xylene 10
0 part and 100 parts of tetramethoxysilane were added and stirred to obtain a primer (P-2).

Reference Example 6: Preparation of primer (P-3) To 100 parts of the same epoxy compound used in preparing the primer (P-1) was added 100 parts of γ-mercaptopropyltriethoxysilane, and nitrogen was added. 80 ℃ in the atmosphere
The mixture was heated and stirred for 8 hours. Then, after cooling to room temperature,
75 parts of N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 700 parts of normal hexane and 100 parts of methyltrimethoxysilane were added and stirred to obtain a primer (P-3).

Reference Example (Comparison) 7: Primer P ′ As a comparison, based on JP-A-3-242268,
Primers were prepared as follows.

Epoxy compound 1 obtained by epoxidizing a hydrocarbon mixture having an unsaturated bond having 6 to 8 carbon atoms with peracetic acid.
100 parts of γ-mercaptopropyltriethoxysilane was added to 00 parts, and the mixture was heated and stirred at 80 ° C. for 8 hours in a nitrogen atmosphere. Then, after cooling to room temperature, 75 parts of tetraethyl titanate, 700 parts of normal hexane and 100 parts of methyltrimethoxysilane were added and stirred to obtain a primer P '.

(Preparation of Hardened Inorganic Material) Reference Example 8 Water and a thickener are added to a raw material composed of cement, silica stone powder, pulp, asbestos and propylene fiber, and mixed,
After extrusion molding, it was cured in an autoclave to obtain a cured inorganic material.

(Preparation of Metal Product) Reference Example 9 A metal plate having a stucco pattern on a SUS304 substrate with an embossing roll was degreased with alkali, washed and dried.

Examples 1 to 3 A urethane-modified alkoxide type silicone primer (manufactured by Toshiba Silicone Co., X
C99-8024) was applied in a solid content of about 20 g / m ^2, and after setting for about 5 minutes, it was heated and cured at 60 ° C. for about 30 minutes. Next, coating liquid (C-2)
Was applied at a solid content of about 20 g / m ^2, and after setting for about 5 minutes, it was heated and cured at 150 ° C. for about 20 minutes.

Finally, the coating solution (C-1) was applied in a solid content of about 10 g / m ² and after setting for about 5 minutes, it was heated and cured at 150 ° C. for about 30 minutes to form a silicon alkoxide coating layer. The obtained inorganic cured product was obtained.

Color nails (RM891A manufactured by Matsushita Electric Works, Ltd.), putty (Dainippon Paint Co., Ltd., Yumoto putty), silicone caulking (Toshiba Silicone manufactured, XE75-A0858) were applied to this inorganic cured body, and further partly. As shown in Table 1, primers (P-1) to (P-3) were applied to a repair-needed portion of the sample in which the cement underlayer was exposed and the cement substrate was exposed, and dried at room temperature for 30 minutes.
Next, the coating liquid (C-3) was applied using a paint brush and dried at room temperature for 7 days to obtain a test body.

The test pieces thus obtained were used to test the adhesion and weather resistance. The adhesiveness was determined by observing the number of peeled points by immersing the adhesive in a warm water of 60 ° C. for 20 days and then performing a cellophane adhesive tape adhesion test by the substrate test method. Those with no abnormal adhesion are marked with a circle.

In the weather resistance test, the properties of the coating film were observed after 1,000 hours using a sunshine weather meter. Table 1 shows the results.

[0083]

[Table 1]

Examples 4 to 6 The same as Examples 1 to 3 except that the coating liquid (C-1) was not applied and the application of the coating liquid (C-2) was stopped. It was carried out. Table 1 shows the results.

Examples 7 to 9 In Examples 4 to 6, instead of the coating liquid (C-2), the coating liquid (C-3) had a solid content of about 20 g /
After applying m ² and setting for about 5 minutes, baking was performed in an atmosphere of 60 ° C. for about 20 minutes to prepare a test piece.
It carried out like Example 4-6. Table 1 shows the results.

Examples 10 to 12 Epoxy "E1 baking primer" (manufactured by Isamu Paint Co., Ltd.) was added to the metal products prepared in Reference Example 9 in a solid content of about 35 g /
After applying m ² and setting for about 5 minutes, it was heat-cured at 80 ° C. for about 20 minutes. Then, the coating liquid (C-2) was applied in a solid content of about 20 g / m ^2, and after setting for about 5 minutes, it was cured by heating in an atmosphere of 150 ° C. for 20 minutes.

Finally, the coating liquid (C-1) was applied at a solid content of about 10 g / m ² and after setting for about 5 minutes, it was heated and cured at 150 ° C. for about 30 minutes to form a silicon alkoxide coating layer. A stainless steel metal body was obtained.

After the silicon alkoxide coating layer of this test piece was scratched to expose the SUS metal substrate, the primers (P-1) to (P-3) having the compositions shown in Table 1 were repaired using a paint brush. It was applied to the required places and dried at room temperature for 30 minutes. Then, the coating liquid (C-
3) was applied using a paint brush and dried at room temperature for 7 days to obtain a test body. Table 1 shows the results.

Comparative Example 1 Specimens were prepared in the same manner as in Examples 1-3. However,
Instead of using the primers (P-1) to (P-3),
Primer P'was used. Table 1 shows the results.

Comparative Example 2 A test piece was prepared in the same manner as in Example 1. However, instead of the coating liquid (C-3), a fluorine-based paint (“New Germet” manufactured by Toa Paint Co., Ltd.) was used. Table 1 shows the results.

Comparative Examples 3 and 4 In the same manner as in Examples 1 to 3, after preparing an inorganic cured body having a silicon alkoxide coating layer, the primer (P-1) and P'shown in Table 1 were applied to a paint brush. Applied to the silicon alkoxide coating layer using
It was dried for a day to obtain a test body. Table 1 shows the results.

Comparative Example 5 Example 1 except that the primer of the present invention was not used.
It was carried out in the same manner as ~ 3. Table 1 shows the results.

[0093]

As described above, when the primer of the present invention is used, a room temperature curing type inorganic coating having excellent weather resistance to alkoxide type silicone treated surface, stainless steel, cement, putty, color nail and the like can be obtained. It is firmly adhered, and even if the primer part is exposed, it can be repaired with little color change.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C04B 41/68 C04B 41/68 41/71 41/71 C08G 59/40 C08G 59/40 C09D 163 / 00 C09D 163/00 (72) Inventor Norio Sato 6-23-1, Roppongi, Minato-ku, Tokyo Toshiba Silicone Co., Ltd. (72) Inventor Ken Sunaga 6-23-1, Roppongi, Minato-ku, Tokyo Toshiba Silicone Co., Ltd. (56) Reference JP-A-2-211278 (JP, A) JP-A-59-176359 (JP, A) JP-A-3-121171 (JP, A) JP-A-48-90365 (JP, A) JP-A-4-295077 (JP, A) JP-A-5-277435 (JP, A)

Claims (2)

(57) [Claims] 1. A primer composition comprising the following components (a), (b), (c) and (d) is previously applied to a portion of an inorganic hardened body or a metal surface where repair is required, and then the room temperature curable inorganic material is applied. A method for repairing an inorganic cured body or a metal surface having a silicon alkoxide coating layer, which comprises applying a paint. (A) Epoxy compound having two or more epoxy groups in one molecule (b) Organosilicon compound having one or more mercapto groups and two or more alkoxy groups in one molecule (c) One in one molecule Organosilicon compounds having one or more amino groups and two or more alkoxy groups (d) Organic solvent 2. The repair method according to claim 1, wherein a repair material is applied to a repair required portion and then the primer composition is applied.