JP2003128998A - Coating material, wall material and method for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material and wall material having weather resistance and soil resistance over a long period, and a method for coating excellent in workability. SOLUTION: This coating material blended with 200-1,500 pt.wt. aggregates based on 100 pts.wt. solid resin portion of a synthetic resin emulsion is provided by containing 0.3-3 wt.% each of hindered amine-based photo stabilizer and ultraviolet light-absorbing agent, and 0.3-5 wt.% each of a phosphoric acid ester expressed by the formula (1) in the specification [wherein, R<1> is an alkyl or an alkylaryl; R<2> is H or R<1> (CH2 CH2 O)n ; and (n) is 2-25 integer] and having 5-18 HLB value, and a silicate expressed by the formula (2) in the specification [wherein, R<3> is an alkyl; and (m) is 4-12 integer].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating material mainly used for finishing exteriors of buildings, a wall material obtained by applying the coating material to a base material, and the coating material applied to the base material. It relates to the painting method.

[0002]

2. Description of the Related Art An outer wall of a building or the like is often finished by applying a coating material composed of a synthetic resin and an aggregate or the like from the viewpoint of protecting the outer wall and imparting a design property. Among them, a coating material in which a relatively large amount of aggregate is mixed with a synthetic resin can be finished by forming unevenness on the coating material or the wall surface by applying the coating material. It is mainly used as a decorative material to give a texture.

However, since the coating material is composed of an organic synthetic resin as a binder,
A coating film finished with the coating material tends to gradually deteriorate when exposed to ultraviolet rays or wind and rain.

Therefore, in consideration of such problems, the top coat is conventionally used to suppress the deterioration. The topcoat is a method in which a resin having high weather resistance and water repellency such as silylated acrylic copolymer resin or fluorocarbon hydrocarbon copolymer resin is applied to the surface of the coating film.

By applying such a top coat, deterioration of the coating film over time can be prevented, and rainwater containing pollutants can be repelled by the high water repellency to prevent adhesion of dirt. Further, the surface of the coating film can be made glossy to be finished in a glossy state.

[0006]

However, in a stone-like coating film finished with a coating material containing a relatively large amount of aggregate as described above, the surface of the coating film is fine and fine due to the aggregate. Since the resin is cured in the state of having complicated irregularities, the thickness of the top coat layer is likely to be nonuniform when the top coat is applied thereon. In addition, if the thickness of the top coat becomes uneven, the coating film surface has uneven gloss, which adversely affects the design of the wall surface.

Further, there is a possibility that the top coat may disappear in a relatively short period in a portion having a small thickness by being exposed to ultraviolet rays and wind and rain for a long period of time, and such a partial disappearance of the top coat. Causes unevenness in the gloss of the surface of the coating film, leading to deterioration in designability. Further, in the part where the top coat layer has disappeared, the coating film is directly exposed to ultraviolet rays and wind and rain, and there is a problem that the deterioration of the coating film progresses rapidly.

Further, there is a problem that stains and the like are easily accumulated on the uneven portion on the wall surface having the unevenness as described above, and the designability is deteriorated by such a factor.

In view of such problems of the prior art, the present invention provides a coating material and a wall material having weather resistance and stain resistance for a long period of time, and is excellent in workability. An object is to provide a coating method.

[0010]

The present invention has been made in order to solve the above problems, and the means for solving the problems is that 200 parts of aggregate is used for 100 parts by weight of resin solid content of a synthetic resin emulsion. In the coating material blended in a proportion of ˜1500 parts by weight, the hindered amine light stabilizer and the ultraviolet absorber are respectively contained in an amount of 0.3 to 3% by weight, and

[Chemical 3] (In the formula, R ¹ is an alkyl group or an alkylallyl group, R ² is a hydrogen atom or a R ¹ (CH ₂ CH ₂ O) n group, and n is 2 to 25.
Indicates an integer. ) And having an HLB value of 5 to 18, and

[Chemical 4] (In the formula, R ³ is an alkyl group, and m is an integer of 4 to 12.) The coating material is characterized by containing 0.3 to 5% by weight of a silicate represented by each. In the present invention, the contents of the hindered amine light stabilizer, the ultraviolet absorber, the phosphoric acid ester and the silicate refer to the amount based on the resin solid content.

The present invention also resides in the above coating material, which is substantially free of color pigments. Here, the term "substantially free of color pigment" means that the color pigment is not contained at all or contains a trace amount of the color pigment that does not affect the coloring effect of the aggregate. Means that the amount of the coloring pigment is approximately 0.6 parts by weight or less based on 100 parts by weight of the aggregate.

The present invention also provides a wall material characterized in that the coating material is applied onto a base material.

Furthermore, the present invention is a coating method characterized by applying the coating material.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The hindered amine light stabilizer is a substance that traps radicals generated in a photochemical oxidation reaction (so-called photooxidation reaction) and suppresses oxidative deterioration of the coating film. Specifically, bis (N-methyl-2,2,6,6-
A method of dispersing a monomer such as tetramethyl-4-piperidinyl) sebacate or tetrakis (2,2,6,6-tetramethyl-4-piperidinyl) in a coating material;
Those having a polymerizable group such as 2,6,6-tetramethyl-4-piperidyl methacrylate and 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate are previously copolymerized with other polymerizable monomers. To disperse a polymerized polymer in a coating material, or to use a polymer having a polymerizable group in advance by incorporating it in a resin skeleton in a binder by copolymerizing it with another polymerizable monomer. is there.

The amount of the hindered amine light stabilizer compounded is 0.3 to 3 parts by weight based on 100 parts by weight of the resin solid content. If it is less than 0.3 parts by weight, sufficient weather resistance cannot be exerted for a long period of time, and if it exceeds 3 parts by weight, the hydrophilicity of the surface is hindered and the stain resistance is adversely affected. And increase the cost, both of which are not preferable.

Any ultraviolet absorber may be used as the ultraviolet absorber in the present invention as long as it absorbs ultraviolet rays having a wavelength of 300 to 400 nm. As such an ultraviolet absorber, specifically, a known ultraviolet absorber such as a salicylic acid ester derivative, a benzophenone derivative, a benzotriazole derivative, a cyanoacrylate derivative, and a benzophenone derivative or a benzotriazole derivative having a radical polymerizable double bond. Can be used.

The amount of the ultraviolet absorber blended is such that the resin solid content is 1
0.3 to 3 parts by weight with respect to 00 parts by weight. If it is less than 0.3 parts by weight, sufficient weather resistance cannot be exhibited for a long time, and if it exceeds 3 parts by weight,
Not only is it not preferable that the surface becomes hydrophilic, but it also causes an increase in cost.

On the other hand, as the phosphoric acid ester in the present invention, the phosphoric acid ester represented by the above formula (1) and having an HLB value of 5 to 18 is used. Specifically, examples of the phosphoric acid ester include polyoxyethylene alkyl ether phosphoric acid esters such as polyoxyethylene lauryl ether phosphoric acid ester, and polyoxyethylene alkyl allyl ether phosphoric acid esters such as polyoxyethylene diethylenated phenol ether phosphoric acid ester. An acid ester etc. can be illustrated.

When the HLB value is less than 5, the hydrophobicity becomes too high, and the phosphate ester does not easily bleed out from the coating film, and as a result, the cleaning effect as a surfactant is not sufficiently exhibited. On the other hand, if the HLB value exceeds 18, the hydrophilicity will be too high, and the phosphate ester will bleed out from the coating film too much, resulting in early outflow with rainwater, which is not preferable.

The compounding amount of the phosphoric acid ester is 1 resin solid content.
0.3 to 5 parts by weight with respect to 00 parts by weight. If it is less than 0.3 part by weight, the initial stain resistance cannot be sufficiently exhibited, and if it exceeds 5 parts by weight, the water resistance of the coating film is significantly reduced. Not preferable.

As the silicate in the present invention, the silicate represented by the above formula (2) is used. More specifically, examples of the silicate include a condensate of methyl silicate, ethyl silicate, propyl silicate, and butyl silicate.

The silicate content is 100% resin solids.
It is 0.3 to 5 parts by weight with respect to parts by weight. If the amount is less than 0.3 parts by weight, the silicate layer that covers the surface of the coating film cannot be formed, and if the amount is more than 5 parts by weight, the water resistance of the coating film cannot be further improved. On the contrary, it is not preferable because it causes a cost increase.

As the synthetic resin constituting the coating material of the present invention, an acrylic resin, an ethylene-vinyl acetate resin, a urethane resin, a vinyl chloride resin, etc., which can form a coating film only by forming a film. Can be used. In addition, a water-soluble polyisocyanate is mixed with a synthetic resin emulsion containing a hydroxyl group that is reactive with an isocyanate group, or a reaction-curing two-component liquid containing a polyamine or a polyamide mixed with a synthetic resin emulsion containing an epoxy group. A type can also be used. Among them, acrylic resins are particularly preferable because they are inexpensive and have good weather resistance and water resistance.

Further, the aggregate constituting the coating material of the present invention is not particularly limited, and a general natural stone crushed product, artificial stone crushed product, metal powder or a colored bone obtained by coloring these, which is used for architectural makeup. Aggregates such as timber can be used. Above all,
It is preferable to use one or more kinds of crushed natural stone, crushed artificial stone, or colored aggregate.

As the crushed natural stone, marble (cold stone,
Calcium carbonate, quartz, silica stone (silica powder, silica sand), natural mica, granulated natural stones such as granite can be crushed.

As the crushed artificial stone, crushed ceramics, glass and ceramics, artificial jewels and the like can be used.

As the metal powder, powders of a simple metal such as stainless flakes and aluminum flakes and powders of metal oxides such as titanium oxide flakes and iron oxide flakes can be used, and in the present invention, Plastic flake or glass flake having metal powder deposited thereon can also be used as the metal powder.

As the colored aggregate, the natural stone crushed product, artificial stone crushed product, metal powder, jewel, hollow filler, glass, plastic or the like is used as the colored substance, and the surface thereof is treated with an inorganic binder such as water glass and a pigment. Baked and colored,
Alternatively, it is possible to use those whose surface is colored and coated with an organic binder such as an epoxy resin or urethane resin and a pigment.

The particle size of the aggregate is not particularly limited, but from the viewpoint of creating a stone-like design, particles having a particle size of 0.3 to 3.0 mm are 30 to 70 of the total aggregate.
Those containing about wt% are preferable. The coating material according to the present invention contains 200 to 1500 parts by weight of the aggregate with respect to 100 parts by weight of the synthetic resin emulsion.
Stabilizes texture, inorganic feeling, color tone, surface gloss, etc.
In order to finish the wall material or wall surface with a high degree of perfection, it is preferable that the aggregate is also 600 parts by weight or more.

The coating material according to the present invention preferably contains substantially no inorganic pigment such as iron oxide or chromium oxide, or coloring pigment such as an organic pigment such as phthalocyanine or dioxazine. If the coloring pigment is not substantially contained, the coloring method of the coating material basically depends on the aggregate, and a so-called stone material-like coating film having a transparent feeling can be finished.

Next, the wall material according to the present invention comprises the above-mentioned coating material applied on a base material to be coated. As the base material, ceramic base materials such as slate, inorganic base materials such as cement mortar, ALC plate and gypsum board, PP
Any base material such as a board, a resin base material such as a vinyl chloride board, a wood base material such as a plywood or a particle board, or a metal base material such as a galvanium plate or an iron plate can be used.
Moreover, what applied the sealer to these surfaces can be used as needed. The thickness of the coating film applied on the substrate is arbitrary, but it is preferable that the coating film has irregularities with a depth of about 0.1 to 3 mm and has a film thickness of about 1.0 to 10 mm as a whole. Such unevenness represents a natural shadow on the surface of the coating film, and further improves the designability. Further, even in the case of a stone material, the unevenness has the effect of improving the texture.

In the coating method using the coating material, the coating material is prepared in advance and then coated on a desired surface to be coated. As the coated surface, in addition to the above-mentioned base material,
The inner and outer wall surfaces and floor surfaces of buildings and the like can be mentioned. At the time of coating, any equipment such as a spray gun, a roller, a trowel, and a roll coater can be used.

As described above, since the coating material according to the present invention contains the hindered amine light stabilizer and the ultraviolet absorber in combination, the weather resistance of the coating material is remarkably improved. Does not require a conventional topcoat for imparting weather resistance. Therefore, in the coating film obtained by applying the coating material, the texture expressed by the unevenness of the coating film surface as described above is not hindered by the top coat layer, and a more natural texture can be produced.

Further, the coating material according to the present invention contains the phosphoric ester and silicate in addition to the hindered amine-based light stabilizer and the ultraviolet absorber, and both are complementarily functioned to have good properties for a long time. Since it exhibits excellent pollution-reducing performance, it becomes possible to further prolong this natural texture.

Specifically, first, in the initial stage, the surface of the coating film is washed by the surface-active effect of the phosphoric acid ester. That is, the phosphate ester gradually eluted from the coating film, which is usually applied to a thickness of several mm, is adsorbed on the surface of the contaminant attached to the surface of the coating film, and the contaminant is flushed away with rainwater etc. by the emulsification action. . Then, the phosphate ester remaining in the coating film is sequentially eluted so as to compensate for the phosphate ester that has flown out in this way, whereby the initial low contamination can be maintained.

Further, the hydrolysis of the alkoxysilyl group in the silicate is activated by the acidic component in rainwater,
The produced silanol groups are bonded to each other, and a hard glassy film is gradually formed on the surface of the coating film, which prevents the attachment of contaminants. Furthermore, since the silanol groups that are not involved in crosslinking are hydrophilic, the silanol groups present on the surface of the coating film make the surface of the coating film hydrophilic. In this way, even after the effect of reducing the pollution by the phosphoric acid ester is reduced, the constant effect of reducing the pollution by the silicate is exhibited.

Therefore, coating was performed using a coating material prepared by mixing 200 to 1500 parts by weight of the aggregate with 100 parts by weight of the resin solid content of the synthetic resin emulsion, and the surface of the coating film was finely divided by the aggregate. Moreover, even when a complicated uneven pattern is formed, it becomes difficult for dirt to adhere to the surface of the coating film, and the natural texture can be further prolonged.

Further, according to the present invention, the hindered amine-based light stabilizer and the ultraviolet absorber are deactivated to have a low molecular weight,
Even when bleeding out on the surface of the coating film, it is considered that the phosphoric acid ester is adsorbed to these and flows away, and it is considered that such contamination from the inside of the coating film can be prevented.

Further, if the coating material is substantially free of color pigments, it will be finished in a stone material having a transparent feeling. However, in the stone material coating film, due to deterioration of the resin. Since the influence of white turbidity and the stains caused by contaminants are conspicuous, the effect of preventing deterioration by the hindered amine light stabilizer or the ultraviolet absorber and the effect of preventing contamination by the phosphoric acid ester or silicate become more remarkable.

Further, according to the coating method of the present invention, it is not necessary to apply a top coat, and the coating process can be simplified. Specifically explaining the case of applying a stone-like coating as described above, the first step of applying a sealer to the substrate, the second step of applying the coating material of the present invention,
Then, the third step of applying the coating material of the present invention, that is, the third step can be completed, and the top coat as the fourth step is unnecessary. Furthermore, as a base treatment, when a sealer surfacer of the same color as the coating material is applied to the base material, it is possible to conceal the color development of the base material by this layer, so that the first step of applying the sealer surfacer It is possible to finish by the two steps of applying the coating material according to the present invention, that is, the top coat as the third step is not required.

It should be noted that the coating material according to the present invention may appropriately contain additives such as a thickener, a defoaming agent, a viscosity adjusting agent, a film-forming aid and a hydrophilic aid.

[0043]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. First, the coating materials of Examples and Comparative Examples with the mixing ratios shown in Table 1 were prepared by using the materials of Example 1 and Comparative Examples 1 to 6 according to the formulations shown in Table 1 below.

[0044]

[Table 1]

(Materials) Em: Acrylic synthetic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc., VONCOAT3981, solid content 50%, light stabilizer: bis (N-methyl-2,2,6,6-tetra) Methyl-4-pyridinyl) sebacate, manufactured by Ciba Geigy Co., Ltd., TINUBIN765, UV absorber: 2- (3-t-butyl-2-humanoxy-5-methylphenyl) -5-chloro-2H-benzazotriazole, Ciba Geigy ( Co., Ltd., TINUBIN3
27, phosphoric acid ester: polyoxyethylene lauryl ether phosphoric acid ester, HLB: 1
6.2, Dai-ichi Kogyo Seiyaku Co., Ltd., Prysurf A219
B, silicate: tetramethoxysilane condensate (average degree of condensation 4), Tama Chemical Industry Co., Ltd., M silicate 51, # 20 Black: colored silica sand, Seto Ceramy Co., Ltd., KD-1: Kansui stone, Seto Ceramy Co., Ltd., KD-100: Kansui stone, Seto Ceramy Co., Ltd., Defoaming agent: Big Chemie Japan Co., Ltd., BYK-02
2. Dispersant: BYK-19, manufactured by BYK Japan KK
0, Viscosity adjusting agent: Rohm and Haas Japan Co., Ltd., Primal RM-8W, Top coat: Nippon Shokubai Co., Ltd., Uddable C-3300 1
00 parts by weight, Asahi Kasei Corp., Duranate TPA-100 4.6
Parts by weight, xylene 10 parts by weight, (OH / NCO = 1 /
1),

(Test Method) Preparation of Specimen Using a 4 mm-thick slate plate according to JIS A 5430 as a base material, the coating materials of Example 1 and Comparative Examples 1 to 6 having the formulations shown in Table 1 have a thickness of 2 mm. The sample thus obtained was coated with an applicator and cured at 20 ° C. for 7 days.

Contamination resistance test The inside of a tester mainly consisting of an oil smoke generator and a sample rotating device is kept at 70 ° C., and while the oil smoke is circulated in the tester, the test body is exposed to rotation for 60 minutes. After the exposure, the product was washed with a 1% sodium alkylbenzene sulfonate aqueous solution to completely remove excess oil smoke, and then a colorimetric color difference meter (Nippon Denshoku Industries Co., Ltd.)
Manufactured by ZE2000), and the Y value was measured and numerically expressed by the following equation. Contamination resistance (%) = (diffuse reflectance Y ₁ after contamination / diffuse reflectance Y ₀ before contamination) × 100

Water resistance test Half of each test body was immersed in water and allowed to stand at 20 ° C. for 24 hours, after which the surface condition of the immersed part and non-immersed part was compared to evaluate the whitening property. As an evaluation criterion, a considerably whitened product was rated as x, a slightly whitened product was rated as Δ, a whitening product that was hardly whitened was rated as ◯, and a product that was not whitened at all was rated as ◎. The results are shown in Table 2.

Weather resistance test Each test piece was subjected to accelerated exposure for 2000 hours with a sunshine weatherometer (S80, manufactured by Suga Test Instruments Co., Ltd.), and the color difference ΔE before and after the test was measured to evaluate the weather resistance. I went.

[0050]

[Table 2]

As shown in Table 2, it can be seen that the test body of Example 1 according to the present invention is extremely excellent in stain resistance, and at the same time, has good water resistance and weather resistance.

[0052]

As described above, according to the present invention, it is possible to provide a coating material and a wall material having weather resistance and stain resistance for a long period of time.

Further, according to the coating method of the present invention, it is not necessary to apply the top coat, and the coating process of the coating film can be simplified.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) E04F 13/02 E04F 13/02 AF terms (reference) 4D075 CA32 CA34 CA37 CA38 CA47 CB21 DA06 DB02 DB05 DB12 DB14 DB22 DB25 DB36 DB38 DC02 EA13 EB13 EB15 EB19 EB22 EB33 EB38 EB39 EB43 EB45 EB47 EB56 EC07 EC13 EC47 EC49 EC54 4J038 CD021 CF031 CG001 DB001 DB002 DG001 DH001 DL021 HA066 J22 J03 J03 JB06 JB38 J28 J03 JB21 J03JB21 J03 JB21 J03J2821

Claims (4)

[Claims] 1. A resin solid content of 10 in a synthetic resin emulsion.
In a coating material in which the aggregate is mixed in an amount of 200 to 1500 parts by weight with respect to 0 parts by weight, a hindered amine light stabilizer and an ultraviolet absorber are added in an amount of 0.3 to 3% by weight, respectively.
Contains, and further (In the formula, R ¹ is an alkyl group or an alkylallyl group, R ² is a hydrogen atom or a R ¹ (CH ₂ CH ₂ O) n group, and n is 2 to 25.
Indicates an integer. ) And having an HLB value of 5 to 18, and (In the formula, R ³ represents an alkyl group, and m represents an integer of 4 to 12.) A coating material containing 0.3 to 5% by weight of a silicate represented by each. 2. The coating material according to claim 1, which contains substantially no coloring pigment. 3. A wall material obtained by applying the coating material according to claim 1 or 2 onto a base material. 4. A coating method comprising applying the coating material according to claim 1 or 2.