JPS58147447A - Manufacture of colored cement roofing tile - Google Patents

Abstract

PURPOSE:To apply a colored coating film having excellent durability and resistant to cracking and efflorescence to a roofing tile, by coating the surface of an uncured cement roofing tile with a specific coating composition, coating further with a solvent-type acrylic resin coating composition, and hardening and curing the tile. CONSTITUTION:A coating composition composed of water and a mixture containing an emulsion of a (meth)acrylic acid ester resin or its copolymer with styrene, an emulsion of bisphenol-type epoxy resin, a filler, cement, a color pigment, ad polyamide resin hardener or an aliphatic amine hardener at specific ratios, is applied to the surface of an uncured cement roofing tile at a dry thickness of 40-100mu, and the coated surface is further coated with a solvent- type acrylic resin coating composition composed of mixture of (meth)acrylic acid ester resin or its copolymer with styrene, a filler, a color pigment and a solvent at a dry thickness of 15-50mu, and the tile and the coating film are hardened and cured at the same time.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a colored cement tile having excellent weather resistance and other properties.

In recent years, with the trend toward prefabricated housing and lower costs, the use of cement tiles has rapidly increased in place of traditional Japanese tiles and Western tiles due to their advantages in construction and manufacturing costs. * is predicted to increase. Cement roof tiles are made by mixing cement, hard fine aggregate, water, etc., pressurizing the mixture, and curing for a long period of time to harden it before it is put into service. Although such cement tiles are sometimes used in 1,000 tts, recently they are mostly used rolled and colored to give a more luxurious appearance. A common coloring method is to apply a colored paint made of a polymeric material to the hardened cement tiles. However, the high baking temperature of such a molecular material (To) often results in an unsatisfactory peeling phenomenon, which is not satisfactory.

On the other hand, a mixture of colored cement and water is applied to white cement, a colored layer is formed and cured, and if necessary, a polymeric material is added on top of it. A method of applying poultry pigment to create a luxurious look is also being considered. However, in these cases as well, discoloration such as efflorescence occurred), and problems such as cracks and peeling due to insufficient closeness between the cement tile and the colored layer are likely to occur. 11KFi, in order to prevent efflorescence and discoloration of colored cement tiles as mentioned above, to give roundness and durability, a top coat such as a solvent lid paint or a water-based paint may be applied.In this case, a colored layer may be applied. If the time after application and before the anti-am coating is applied is not properly selected, it is difficult to prevent effacement. However, the adhesion between the eyebrows often decreases, resulting in problems such as cracks, cracks, and peeling.

As described above, the conventional methods of coloring cement tiles and the coating materials used have certain deficiencies in terms of performance and application.

In view of the above-mentioned conventional techniques, the present invention has four objectives: to provide an excellent method for applying a colored coating to cement roof tiles.

Honsha I on 41! In A, it can be applied to uncured cement tiles such as cement tiles immediately after pressing such as ground tiles and primary curing tiles (tiles immediately after dust removal) such as utility tiles, and is thick without causing cracks or cracks. It is possible to form a thick film with zero
The object of the present invention is to provide a method for forming a coating with excellent properties such as antiresence effect. This purpose is (a) (11 acrylic acid or methacrylic acid ester copolymer emulsion resin (ester is an alkyl group with vertical prime number 1 to 8)) or a copolymerization emulsion resin of the above acrylic acid or methacrylic acid ester and styrene. (Styrene content is 30% by weight or less) Solid content
・・・・・・2～40% by weight (11) Hisphenol lid epoxy emulsion resin solid content ・・・・・・
・0.5-5% by weight stiff filler ・・・・・・1
0~85% by weight (-cement...5~6
031% by weight (V) Colored pigment...0.
1-15% by weight and the epoxy emulsion resin No. 0
．． 8 to 1.2% of polyamide resin curing M is preceded by an aliphatic polyvalent amine curing agent, and if necessary, various additives are added. , 100 parts by weight of a mixture ranging from 1 to 1), and 30 to 300 parts by weight of water (fb), and a coating composition (A) having a viscosity of 5 to 30 voids, was applied to the surface of an uncured cement tile with a dry film thickness of about 4゜J ~ 1000μ, and (C) (11 acrylic acid or methacrylic acid ester copolymerization (11 fatty acid (ester is an alkyl group having 1 to 8 carbon atoms)) To not the above acrylic acid or methacrylic acid Copolymer resin of ester and stele/(styrene content is 30% by weight or less) vA type content...
55-95% by weight・I) Photonic agent...
0-15% by weight-) Colored pigment...3
~20% by weight more! A solvent-covered acrylic resin M coating composition (B) consisting of 100 parts by weight of a mixture consisting of small amounts of various additives and 60 to 20 parts by weight of (dl # agent) was applied in layers to a dry thickness of approximately 15 to 50 μm. , if necessary, after low-temperature heating, the cement tiles and m1m are combined by curing and hardening at the same time.

Examples of alkyl esters of acrylic acid monomers that are components of the acrylic acid or methacrylic acid ester copolymer emulsion resin used in the coating composition (4) include methyl, ethyl, -butyl, isobutyl, Mesha 17-7' ethyl, 2-Ethylhexyl, benzyl, propyl, inglovir 1. . . -Butyl etc. are typically used. Esters with carbon atoms of 9 or more may generate a gel during emulsion polymerization, and the hydrophobicity of the emulsion carbon particles becomes bulky, resulting in the formation of an emulsion IIJi for cement mixing.
It is unsuitable for the synthesis of r. Copolymer emulsion resins of these acrylic (or methacrylic acid) esters and styrene are also used, but if more than 130,113 methacrylic acid is used, the weather resistance of the emulsion coating film will deteriorate considerably, so durability may be affected. It is not preferred as an injection resin for external use, which requires

Preferred acrylic acid or methacrylic esters include methyl methacrylate, ethyl acrylate, butyl acrylate, acrylic #12-ethylhexyl, and when using steret, 20% by weight or less is particularly preferred. If necessary, it is also possible to copolymerize several weight percent of functional group monomers such as acrylic acid, methacrylic acid, and memecryl eR2-hydroxyethyl. The acrylic acid (or methacrylic acid) ester co-emulsion resin or the acrylic acid (or methacrylic acid) ester and styrene co-emulsion resin used in this product F#4 has alkali resistance because it is mixed with cement. However, those with excellent cement mild stability are preferred, and the 109th one is phenol polyethylene ether in alcohol, polyoxyethylene polyether in alcohol, etc. as an emulsifier during emulsion polymerization.
Ethers such as polyoxyethylene alkyl allyl ether, polyethylene glycol oleyl ether, etc. Esters such as sorbin alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyglycol fatty acid ester; polyglobylene glycol polyethylene glycol polymer, polyoxy ethylene alkylamide,
Even if a nonionic surfactant such as polyoxyethylene alkylamine is used alone or in combination with an anionic surfactant, it is necessary to use a small amount of anionic surfactant steel, which contains a large amount of nonionic surfactant.

The molecular weight of these acrylic elution resins is 50,000 to 3
00,000, preferably 100,000 to 200,000.

First, the minimum film temperature is preferably 0 to 30 DEG C. If it is higher than 30 DEG C., the cured coating film will be too weak and cracks will occur, which is not preferred. These resins are used for the above-mentioned hot metals (a
) with a solid content of 2 to 40% by weight. If the resin is less than 2% by weight, the adhesion to the upper 111 film will be poor, and since the resin component is small, flexibility will be poor, and the KJlk film will be prone to cracking and peeling after a long period of time. On the other hand, if the resin content exceeds 40% by weight, curing of the cement and curing of the resin will be delayed, and sufficient strength will not be obtained and the water resistance of the coating will be reduced. The preferred blending ratio of resin is 10~
It is 30% by weight.

The bisphenol-based epoxy emulsion resin used in the four coating compositions (4) includes bisphenol A
The resulting aromatic diglyphyl ether resin with an average molecular weight of 1,350 to 1,000 is made into a water pattern shape using an emulsifier, and the solid content of the resin is 0.5% in the mixture (a). ~5% by weight is used. If the resin content is less than 0.5% by weight, the adhesion to the substrate will be reduced, and if it exceeds 5% by weight, the weather resistance of the coating will be seriously reduced. The preferred blending ratio of resin is 1-
It is 3% by weight.

Examples of fillers used in coating compositions (A) and K) include calcium carbonate, barium sulfate, magnesilla carbonate, Merck, clay, etc.
The aggregate is silica sand, etc. This filler is added to modify and increase the volume of Moro I5. The filler is
It is blended in the above mixture (a) in a proportion of 10 to 85% by weight. This range is preferred because it has a large electrodynamic effect that improves the denseness, brittleness, durability, etc. of the coating film, and it is more preferably blended in an amount of 40 to 80% by weight.

Examples of the cement used in the paint composition include Portland cement, blast furnace cement, silica cement, alumina cement, etc., but the types thereof are not limited (there is no restriction).

The cement used in the method of the present invention is the above compound (1).
It is blended in a proportion of 5 to 60% by weight. If the cement content is less than 5% by weight, the coating film hardness will not be improved sufficiently. On the other hand, if the content exceeds 60% by weight, the moisture necessary for hardening the cement will not be sufficiently supplied, and therefore the water utilization reaction will not proceed sufficiently, making it impossible to obtain a dense and hard coating film and making it brittle.

The coloring raw material used in the coating composition (4) may be an organic pigment having alkali resistance and weather resistance, depending on the color, typically inorganic Ill family.

For example, if the color is bad, KFi, carbon black,
Examples include iron oxide, etc. for red, chromium oxide, etc. for fish, cyanine blue, etc. for back, and teta dioxide for white. Color pigments are used in the method according to the invention in the above mixture (0.1 to 15% by weight in the phase).
By blending within this range, sufficient coloring can be achieved.

Additives used in the coating composition (A) include:
For example, pigment fractionality, Jli! A round dispersant that improves workability and storage stability, etc. - 4-layer MINIM, etc. that includes a thickening agent, preservative, and antifungal agent to improve the film forming properties of the coating film. can be announced.

The curing agent for epoxy resins used in AK is polyamide resin obtained by polycondensation of dianne or sheaine #4 and dibasic acid or dibasic conductor, etc., or ethylene diamine, diethylene triamine, triamine, etc. Aliphatic polyvalent amines such as ethylenetetramine and metaxylene diamine or aliphatic polyvalent amines modified with epoxy resin in phenol-formalin resin are used.The amount of curing agent used is 0.8 to 1 of the epoxy group of the epoxy resin. It is necessary to use it so that it becomes .2 equivalent.0
．． If the amount is less than 8 equivalents or more than 1.2 equivalents, the original properties of the epoxy resin, such as adhesion and lineability, will be significantly reduced, and other performances such as durability will also be deteriorated, which is not preferable.

Furthermore, in the coating composition (A), the above compound (1)
Medium (1) Acrylic #1 (or Methacrylic #), X? Copolymerized emulsion resin or copolymerized emulsion of acrylic # (or methacrylic acid) ester and styrene 1I
The weight ratio of the solid content of Ii fat (!: +i>
1) +(++) ) / (&/) = 0.1~1
It is. If this ratio is less than 0.1, the weather resistance and adhesion of the coating film will deteriorate, and it will not be possible to form a thickness Ht with good coating performance.On the other hand, if this ratio is greater than l In this case, the adhesion of the In2 film is poor, it tends to sag due to the influence of the solvent in the solvent-based acrylic resin coating composition TB), and it lacks hardness, making it impossible to form a thick film.

The coating composition (4) used in the present invention is prepared by blending 30 to 300 parts by weight of water to 100 parts of the above mixture (a) to give a coating viscosity of 5 to 3 o voids. This is because cement hardening and painting workability are good within this range.

Next, as the resin used in the solvent-type acrylic resin coating composition (B) used as the top coating in the present invention, acrylic acid or methacrylic acid ester copolymer resin (ester is an alkyl group having 1 to 8 carbon atoms) or the above-mentioned A copolymer resin of acrylic acid or methacrylic acid ester and styrene (styrene content is 30% by weight or less) is used. However, since the resin is used for top coating, it is preferable that the glass transition temperature g) is 20 to 55°C. T
.

If the temperature is lower than 20°C, contamination such as adhesion of dust during the summer season will be significant, whereas if it is higher than 55°C, the coating film will be too hard and cracks will easily occur, which is not suitable.

The resin has a solid content of 55 to 9 in the mixture (c).
It is blended in a proportion of 5% by weight.

As the filler used in the solvent-based acrylic resin coating composition (B), extender pigments such as carnoum carbonate, barium sulfate, magnesium carbonate, talc, and clay can be used. The filler is blended in the mixture (c) in a proportion of 0 to 15% by weight.

(9) As the coloring pigment, inorganic pigments and organic pigments similar to those used in the above coating composition (4) can be used. The coloring pigment is blended in the mixture (c) in an amount of 3 to 20% by weight.

If the amount of the filler or color pigment exceeds the above range, the gloss of the finished coating film will decrease and the efflorescence prevention effect of the coating film will also decrease, which is not preferable.

The solvent-type acrylic resin coating composition (B) may further contain additives such as a dispersant, a surface conditioner, a fungicide, an ultraviolet absorber, an antifoaming agent, and a film-forming aid, if necessary.

The solvent-type acrylic resin coating composition (B) used in the present invention is a round composition containing 60 to 200 parts by weight of a solvent to 100 parts by weight of the mixture (c).

The solvent is not limited in terms of percentage as long as it dissolves the resin, but ester solvents such as ethyl acetate and butyl acetate;
Ketone-based solvents such as methyl ethyl ketone and methyl imbutyl ketone; in light, to improve compatibility with the undercoat film, the solvent width is about 3 to 15% by weight ethanol, isopropyl alcohol, phthanol, ethylene glycol monoethyl ether, ethylene glycol It is desirable to blend a hydrophilic alcoholic solvent such as monobutyl ether. In addition, if the hydrophilic alcohol solvent becomes excessive,
It is better to avoid uncured cement tiles and water oozing into the base coat, which tends to lack the moisture necessary for cement hardening.

The coating composition (4) as described above is applied to the surface of a cement tile by a conventional coating method such as spray coating, roller coating, flow coating, etc. The film thickness is approximately 4011 to 10 in dry film thickness.
0o#, preferably 80 to 300μ. Cement tiles to be coated include tiles immediately after press molding and uncured tiles that have been temporarily cured for demolding, and it is important to provide a good coating to these tiles. This is because the above coating composition (4) applied to the uncured cement tile is cured simultaneously with the cement composition of the tile during curing of the cement tile, and the above coating composition (B) is cured simultaneously with the above coating composition (4). 4) Preventing the evaporation of water necessary for hardening of the cement component in the paint composition (4), thereby making the undercoat film stronger, and the resin component in the paint composition (4) providing good adhesion to the top coat film; This is because it provides excellent adhesion of the coating film. 9th item 4 & 10 which is conventionally impossible to prevent the surface evaporation of water in the undercoat film at the same time.
Even with a film thickness of about 00 μm, a thick film can be formed without causing cracks, cracks, etc.

The coating composition (4) is applied, and while the undercoat film is wet, it is preferable to apply a spray-type acrylic resin coating composition (odor) to the round areas. Paint using the same method as for item (4).

In the method of the invention, the coated substrate is then cured and cured. There are nine curing methods, such as the following, and any one of these methods may be used or they may be used in combination. (1) Natural curing (natural curing and curing in atmospheric atmosphere)
, (2) Underwater curing (immersion in water at a temperature of 5 to 30°C for 2 hours or more, and further natural curing as necessary) , (3
) Steam curing (steam curing for 2 hours or more in an atmosphere with a temperature of 40 to 60°C and a humidity of 95 to 100%, and further curing by natural curing or autoclave curing as necessary).

Although the pretreatment for these curing methods in the method of the present invention is not necessarily necessary in the case of natural curing, the following low-temperature heat treatment is suitable.

That is, paint compositions (4) and (8) are applied to uncured cement roof tiles.
After applying and drying to the touch, heat at 5 to 20℃ in an atmosphere of 30 to 60℃.
Appropriate methods include heating and drying for a period of time, followed by water curing or steam curing as described above. The heating drying time is 2 when the ambient temperature is 60℃ or higher.
If the time exceeds 0 hours, the amount of water required for curing the cement will be significantly reduced, and the adhesion of the coating will be significantly reduced. Furthermore, if the ambient temperature is less than 30° C. and the heating drying time is less than 5 hours, the coating will not be formed sufficiently, so if the coating is cured in water or in steam, the coating will flow. In addition, it is not preferable to naturally cure uncured cement tiles, to roll them up by curing them in water, or to stack the tiles vertically, as this will cause blocking.

Note that, if the coated object is left for a long time before entering the curing process, low-temperature heat treatment is not necessarily necessary.

In the above-mentioned Yomaiki invention method, since the coating composition (4) contains epoxy resin and cement as the constituent components, it is possible to obtain a dense and hard coating film with excellent adhesion to the cement tile to be coated. The coating film does not flow and has good adhesion even under summer sunshine conditions. Furthermore, in the method of the present invention, the resin component of the coating composition (4) is sufficiently dispersed in the filler to densify the coating film, improve durability against water, heat and ultraviolet rays, and prevent discoloration and coating film. Prevents peeling. Furthermore, it has been considered difficult to directly apply a solvent-based paint over an uncured cement roof tile or an uncured emulsion/paint film, but in the present invention, the specific above-mentioned paint composition (4) is used. By doing so, it is possible to apply the solvent-based coating composition (6) over and over again, and the surface evaporation of water in the rounded base coat film can be prevented. No rounding cracks or cracks occur due to moisture retention. 9. The method of the present invention not only has good properties of the coating film formed by coating, but also cures the coating film by applying it to uncured cement tiles and curing the coating film at the same time as the cement tiles itself. It also has the advantage of shortening the manufacturing process for cement tiles.

The present invention will be explained below with reference to Examples. In the examples, parts and % are parts by weight and % by weight, respectively.

The 19th undercoat paint composition is spray-coated on the surface of an uncured cement tile to a dry film thickness of 300 μm, and then the top coat composition shown in Table 2 is immediately spray-coated to a dry film thickness of 30 μm; After heating at 35°C for 10 hours, the cement tiles and coating were cured using the curing method shown in Table 3.

In addition, in Table 3, natural curing is left in the air for 10 days, underwater curing is immersed in water at 20°C for one day and then left in the air for one week, and steam curing is at a temperature of 40°C and humidity of 98% for 12 hours. This was done under abandoned conditions.

The results of the adhesion, accelerated efflorescence test, freeze-thaw cycle test, and accelerated weather resistance test of the obtained colored cement tiles are shown in the lower part of Table 3.9. The test method and evaluation were performed as follows.

(1) Adhesion test method: 2wm cellophane tape test evaluation of coating film: ◎...50150, ○...49150-26
150,

Evaluation: ◎... No abnormalities at all: ○... Very few abnormalities, X... Total abnormalities (3) Freeze-thaw cycle test Test method: [-20°C x 16 hours freezing → Room temperature x 8 time〕
35 cycle evaluation 20: No abnormality at all, ○: Only a few abnormalities, ×: Fully abnormal (with cracks) (4) Accelerated weathering test E111 method: Sunshine carbon irradiation for 2000 hours Evaluation: ◎... No abnormality at all, ○... Only a few abnormalities were observed, ×... Fully abnormal (with chalking). The temperature was 15°C.

Note 2) A mixture consisting of a dispersing agent, an antifoaming agent, a film forming aid, and a preservative and antifungal agent.

Claims (1)

[Scope of Claims] (1) (1) (1) Acrylic acid or methacrylic acid ester copolymerized emulsion carbon IIJ& (ester is an alkyl group having 1 to 8 carbon atoms) or the acrylic acid or methacrylic ester and styrene. O copolymer emulsion resin (styrene content is 30% by weight or less) Solid content: 2-40% by weight (IQ
Hisphenol phosphor epoxy emulsion resin solid content
...0.5-5% by weight filler...
...10-85% by weight (-cement ...
...5-60% by weight (V) Coloring raw material ...
...0.1-15% by weight and 0.8-1.2m of the epoxy emulsion resin! Bolioid resin hardening steel of 11 ml, an aliphatic polyvalent hardening agent, and a small amount of various additives as necessary, the weight ratio of pl and [(1) + (30) / stem) is (0,1 ~ l) 100 parts by weight of a mixture in the range of 1), and (b) 30 to 300 parts by weight of water with a viscosity of 5 to 30 voids 0
(1) Copolymer resin of acrylic acid or memethacrylic acid ester (ester is an alkyl group having 1 to 8 carbon atoms) or copolymer of acrylic acid or methacrylic acid ester and styrene (styrene). Content is 30% by weight
Below) t! ! Form content: 55-95% by weight (If) Filler: 0-15% by weight It) Coloring pigment: 3-20% by weight, and various additions as necessary Mixture 10 consisting of a small amount of agent
0 parts by weight, and (d) a solvent-based acrylic resin paint composition consisting of 60 to 200 parts by weight of solvent (B) to a dry thickness of approximately 15 to 50 sK1. A method for procuring colored cement roof tiles characterized by simultaneously curing and hardening the tiles. (2) Molten M lid acrylic resin material composition (colored cement tile according to claim 11, characterized in that the copolymer resin constituting the bird has a glass transition temperature of 20 to 55°C) Oml manufacturing method. (3) The above-mentioned solvent constituting the solvent-lid acrylic resin coating composition (1) has a hydrophilic alcohol content of about 3 to 1
Tested to contain 5% by weight, Claim 8 (1)
) The method for producing colored cement roof tiles as described in section 2. (4) 11ml acrylic 11 [r coating Nm acid (n)t
jlk6 After stacking, it is dried for 5 to 20 hours in an atmosphere of 30 to 60°C. A method for producing colored cement tiles. (5) The patented OI is characterized by curing and hardening using a natural curing method of leaving it under the atmosphere! lllth (1)
The method for manufacturing colored cement roof tiles as described in item (4) or item (4). (Claim 4) Curing and hardening by soaking in water at 5 to 30°C for 2 hours or more, and further curing by natural curing if necessary, Claim No. 4
) How to procure colored cement tiles as described in section. (7) IIJ [W at 40-60℃, humidity 95-lθO%
- Curing and hardening using the steam curing method where it is left in the air for more than 2 hours, and is even more essential! Claim 11(
Item 41: Method for producing soft O-colored cement tiles.