CN111978801A - Scraping type sand-in-water multicolor paint and preparation method thereof - Google Patents
Scraping type sand-in-water multicolor paint and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention relates to a scraping type water-coated sand multicolor paint for building exterior walls, which is characterized by being prepared from the following components in parts by mass: 55-65 parts of toning base paint; 20-30 parts of granulation protective glue; 15-25 parts of continuous phase emulsion. According to the invention, hydrophilic acrylate groups are introduced into a polyvinyl alcohol molecular chain, so that the color point strength of the batch scraping type sand-in-water multicolor coating prepared by the invention is improved; the target composition prepared by the invention also has a series of expected characteristics of complete colored dot state, high paint film hardness, no loss of adhesion force after water soaking, good heat storage stability and the like.
Description
Technical Field
The invention relates to the field of coatings, in particular to a batch scraping type sand-in-water multicolor coating and a preparation method thereof.
Background
The multi-color paint can uniformly combine the color mixing points with different colors, sizes and shapes together and achieve the texture and effect of imitating natural stones such as liquid granite, marble and the like by a one-time spraying construction mode. After decades of development in China, the colorful paint is more and more favored by people in the field of building exterior wall decoration due to high-grade decoration effect and vivid simulation degree, and is essentially different from the traditional emulsion paint; it has its own drawbacks.
The existing multicolor paint has the following defects in the actual construction process: (1) the colorful paint can be sprayed and constructed only by a high-pressure spray gun at present, the construction method is single, the pressure in a tank of the high-pressure spray gun is difficult to adjust, the pressure is too high, color points are fragile, the pressure is insufficient, the color points are difficult to spread and fuse, and the simulation degree is influenced; (2) the requirements on constructors are high, the constructors are required to have skillful spraying manipulation and gun adjusting capability, otherwise, the phenomena of uneven spraying color points and uneven color points are easy to generate; (3) the construction cost is high, and the labor cost of the current colorful construction is more than 3 times of that of real stone paint.
In the prior art, CN108504287A proposes a method for producing a multicolor paint capable of being scraped, which is to add polyvinyl alcohol and cellulose powder into a base material by grinding, and then dissolve the powder in water. However, the grinding process of the batch-scraping type multicolor paint polyvinyl alcohol prepared by the method is complex and is difficult to be applied to large-scale production in an expanding way; the polyvinyl alcohol is difficult to be fully dissolved in water under the normal temperature condition, so that the complex reaction between hydroxyl on a molecular chain and the protective adhesive is insufficient, and the toughness of the color point is not strong; in addition, the invention disclosed by the prior art uses a grinding technology to prepare the batch scraping colorful coating, can only be applied to the plane colorful coating with smaller fineness, cannot prepare the sand-in-water colorful coating by using the method, and has certain technical limitation.
Therefore, it is highly desirable to find a new multicolor paint that overcomes the above-mentioned performance deficiencies.
Disclosure of Invention
In order to solve one of the problems, the invention aims to provide a batch-scraping type water-coated sand multicolor paint for an outer wall of a building. The multicolor paint is realized by the following technical means:
the invention aims to provide a scraping type sand-in-water multicolor paint which comprises the following components in parts by mass:
55-65 parts of toning base paint
20-30 parts of granulation protective adhesive
15-25 parts of continuous phase emulsion;
the toning base paint comprises a polyvinyl alcohol derivative, wherein the polyvinyl alcohol derivative contains an olefin salt group;
the granulation protective glue contains nanoscale flaky magnesium aluminum silicate.
Further, the preparation method of the polyvinyl alcohol derivative comprises the following steps: vinyl acetate and olefine acid are polymerized under the action of catalyst to obtain intermediate product, then excess alkali is added to make alcoholysis.
Further, the molar ratio of vinyl acetate to olefinic acid is 100: 3-5.
Further, the toning base paint comprises the following components in parts by mass:
the granulation protection glue comprises the following components in parts by mass:
3-5 parts of nano flaky magnesium aluminum silicate
90-97 parts of water.
Further, the cellulose is selected from one of ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose.
Further, the continuous phase emulsion is selected from one or two of pure acrylic polymer emulsion or silicone acrylic polymer emulsion.
Further, the average particle size of the nanoscale flaky magnesium aluminum silicate is 20-50 nm.
The microstructure of the nanoscale flaky magnesium aluminum silicate is similar to that of a round coin, the surface of the coin is negatively charged, the side edge of the coin is positively charged, and a layer of 'cabin' structure film can be formed on the surface of the colored-point particles through the principle of mutual attraction of the positive charges and the negative charges, so that the effect of blocking protection is achieved.
Further, the chemical formula of the nanoscale flaky magnesium aluminum silicate is 5 MgO.18A2lO3·10SiO2·9H2O。
Further, the olefine acid is selected from acrylic acid, 3-butenoic acid or 5-hexenoic acid.
The invention also aims to provide a preparation method of the batch scraping type sand-in-water multicolor paint, which comprises the following steps: mixing the components of the granulation protective glue and the toning base paint, uniformly stirring, and standing for 3-5 h; then adding the continuous phase emulsion, and uniformly stirring to obtain a product.
Further, the stirring temperature is 25-30 ℃.
The invention has the following beneficial effects:
generally, the batch scraping type water-coated sand coating has higher requirements on strength and toughness of colored dots because the base material contains calcium sand, and the shearing force and the friction force applied to the batch scraping construction process are higher. The invention
(1) By a polymer modification method, hydrophilic acrylate groups are introduced into a polyvinyl alcohol molecular chain, so that on one hand, the polyvinyl alcohol compound modified by the acrylate is easily soluble in water at normal temperature, the addition mode that the traditional polyvinyl alcohol needs to be ground and pre-dissolved is changed, and the feeding process is simplified;
(2) the acrylate groups are introduced into the molecular chain, so that the cohesive force of the molecules can be increased, the complexing capability between the polymer molecules and the nanoscale flaky magnesium aluminum silicate is enhanced, a good synergistic effect is achieved, the stability and the wrapping property of the nanoscale flaky magnesium aluminum silicate are greatly improved, the color point strength is improved, the color points cannot be damaged in the batch scraping construction process, and the construction compatibility is improved;
(3) the batch scraping type sand-in-water multicolor paint prepared by the invention also has a series of expected characteristics of complete color point state, high paint film hardness, adhesion force of 1 grade or above after water soaking, good heat storage stability and the like.
Detailed Description
In the present specification, the term "color point" means: the water-coated sand base paint is colored by color paste and then is cut and dispersed in the granulation protection glue to form color particles.
The polyether modified dimethylsiloxane used in the examples and comparative examples was purchased from BYK, Germany, under the model number BYK 301.
The nanoscale flaky magnesium aluminum silicate used in examples 1-3 had an average particle size of 30nm and was purchased from fresh wind chemistry.
Example 1
The scraping type sand-in-water multicolor paint comprises the following components in parts by mass:
55 parts of toning base paint
Granulating protective glue 20 parts
15 parts of continuous phase emulsion.
The toning base paint comprises the following components in parts by mass:
the granulation protection glue comprises the following components in parts by weight:
5MgO·18Al2O3·10SiO2·9H2o3 part
0.1 part of chloro-methylisothiazolinone
97 parts of deionized water.
The continuous phase emulsion comprises the following components in parts by mass:
the preparation method of the polyvinyl alcohol derivative 1 comprises the following steps:
s0. purifying vinyl acetate and acrylic acid by distillation under reduced pressure;
s1, adding vinyl acetate and acrylic acid (n/n is 100:5) into a dispersion cylinder under the protection of nitrogen, adding a catalytic amount of azobisisobutyronitrile, reacting for 5 hours at 65 ℃, and then purifying by crystallization to obtain an intermediate product;
s2, dissolving the intermediate product in a methanol solution with the mass 3 times that of the intermediate product, adding excessive NaOH, heating in a water bath at 40 ℃, and reacting for 3 hours;
and S3, washing the crude product with deionized water, performing recrystallization purification by using methanol as a precipitator, and repeating the recrystallization purification twice to obtain the polyvinyl alcohol derivative 1.
The preparation method of the toning base paint comprises the following steps: sequentially adding deionized water, ethyl hydroxyethyl cellulose, polyether modified dimethyl silane, alcohol ester dodeca and ethylene glycol monobutyl ether in a dispersion cylinder according to the mass parts, and stirring for 10min at the rotating speed of 500 rpm; then the rotating speed is increased to 1000rpm, rutile type titanium dioxide, calcined kaolin, 2-amino-2-methyl-1-propanol and polyvinyl alcohol derivative 1 are added in sequence according to the mass parts, and the mixture is continuously stirred for 25 min; and then, reducing the rotating speed to 600rpm, sequentially adding the pure acrylic emulsion, TT-935 and 80-120 mesh calcium sand according to the mass parts, and continuously stirring for 10min to obtain the toning base paint.
The preparation method of the granulation protective glue comprises the following steps: in a dispersion cylinder, deionized water and 5MgO 18Al are added in sequence according to the mass parts2O3·10SiO2·9H2O, adjusting the dispersing speed to 1200rpm, and continuously stirring for 25min until no particles visible to naked eyes exist; adjusting the rotating speed to 450rpm, slowly dripping chlorine-methylisothiazolinone according to the mass parts, and continuously stirring for 3 min; and then placing the mixed solution in a thermostatic chamber with the temperature of 25 ℃ for standing for 24 hours for later use to obtain the granulation protection glue.
The preparation method of the continuous phase emulsion comprises the following steps: sequentially adding deionized water, silicone-acrylic emulsion, benzyl alcohol, 2-amino-2-methyl-1-propanol, polyether modified dimethyl siloxane, propylene glycol and chloro-methylisothiazolinone in the dispersion cylinder according to the mass parts, adjusting the rotating speed to 400rpm, and dispersing for 15 min; and adjusting the rotating speed to 800rpm, mixing TT-935 and deionized water according to the mass parts, slowly dripping the mixture into a dispersion cylinder, continuously stirring for 10min, and standing for later use to obtain the continuous phase emulsion of the batch scraping type sand-in-water multicolor paint.
The preparation method of the batch scraping type sand-in-water multicolor paint comprises the following steps: after the toning base paint is toned into different colors by using inorganic color paste, adding 55 parts by mass of toning base paint (the parts are all referred to as mass parts) into a dispersion cylinder filled with 20 parts of protective glue, shearing color points to the size of 1cm in diameter by using a special multicolor granulator, and rapidly transferring the color points into a thermostatic chamber at 25 ℃ for standing for 3 hours to ensure that a protective glue solution fully reacts with the polyvinyl alcohol derivative 1 in the toning base paint; and accurately weighing and adding 15 parts of continuous phase emulsion, and uniformly stirring to obtain the batch scraping type water-coated sand multicolor paint.
Example 2
A batch-scraping type sand-in-water multicolor paint for building exterior walls is prepared from the following components in parts by mass:
65 portions of toning base paint
30 portions of granulation protective glue
25 parts of continuous phase emulsion;
the toning base paint comprises the following components in parts by mass:
the granulation protection glue comprises the following components in parts by mass:
5MgO·18Al2O3·10SiO2·9H2o5 portion
0.3 part of chloro-methylisothiazolinone
And 95 parts of deionized water.
The continuous phase emulsion comprises the following components in parts by mass:
the preparation method of the polyvinyl alcohol derivative 2 is the same as that of the polyvinyl alcohol derivative 1, only acrylic acid is changed into 3-butenoic acid, and the molar ratio of vinyl acetate to 3-butenoic acid is 100: 3.
The preparation method of the toning base paint comprises the following steps: sequentially adding deionized water, ethyl hydroxyethyl cellulose, dimethyl siloxane, propylene glycol butyl ether and ethylene glycol butyl ether in a dispersion cylinder according to the mass parts, and stirring for 10min at the rotating speed of 500 rpm; then the rotating speed is increased to 1200rpm, rutile type titanium dioxide, calcined kaolin, diethanolamine and polyvinyl alcohol derivative 2 are added in sequence according to the above mass parts, and the mixture is continuously stirred for 25 min; then the rotating speed is reduced to 600rpm, and pure acrylic emulsion, TT-615 and 80-120 mesh calcium sand are added in sequence according to the mass parts; and continuously stirring for 10min to obtain the toning base paint.
The preparation method of the granulation protective glue comprises the following steps: in a dispersion cylinder, deionized water and 5MgO 18Al are added in sequence according to the mass parts2O3·10SiO2·9H2O, adjusting the dispersing speed to 1200rpm, and continuously stirring for 30min until no visible particles exist; adjusting the rotating speed to 450rpm, slowly dripping chlorine-methylisothiazolinone according to the mass parts, and continuously stirring for 3 min; and then placing the mixed solution in a thermostatic chamber with the temperature of 25 ℃ for standing for 24 hours for later use to obtain the granulation protection glue.
The preparation method of the continuous phase emulsion comprises the following steps: sequentially adding deionized water, alcohol ester dodeca, 2-amino-2-methyl-1-propanol, polyether modified dimethyl siloxane, glycerol and chloro-methylisothiazolinone in the dispersion cylinder according to the mass parts, adjusting the rotating speed to 400rpm, and dispersing for 15 min; and adjusting the rotating speed to 800rpm, mixing TT-935 and deionized water uniformly according to the mass parts, slowly dropping the mixture into a dispersion cylinder, continuously stirring for 10min, and standing for later use to obtain the continuous phase emulsion.
The preparation method of the batch scraping type sand-in-water multicolor paint comprises the following steps: after the toning base paint is toned into different colors by using inorganic color paste, 65 parts by mass (the parts are all referred to as mass parts) of toning base paint is added into a dispersion cylinder filled with 30 parts of protective glue, a special multicolor granulator is used for shearing color points to the size of 1cm in diameter, and the color points are rapidly transferred into a thermostatic chamber at 25 ℃ for standing for 3 hours, so that the protective glue solution and the polyvinyl alcohol derivative 2 in the toning base paint are fully reacted; and then accurately weighing and adding 25 parts of continuous phase emulsion, and uniformly stirring to obtain the batch scraping type water-coated sand multicolor paint.
Example 3
A batch-scraping type sand-in-water multicolor paint for building exterior walls is prepared from the following components in parts by mass:
60 parts of toning base paint
Granulating protective glue 25 parts
20 parts of continuous phase emulsion;
the toning base paint comprises the following components in parts by mass:
the granulation protection glue comprises the following components in parts by weight:
5MgO·18Al2O3·10SiO2·9H2o4 portion
0.2 part of chloro-methylisothiazolinone
90 parts of deionized water.
The continuous phase emulsion comprises the following components in parts by mass:
wherein, the preparation method of the polyvinyl alcohol derivative 3 is the same as that of the polyvinyl alcohol derivative 1, only acrylic acid is changed into octadecenoic acid, and the molar ratio of vinyl acetate to octadecenoic acid is 100: 4.
The preparation method of the toning base paint comprises the following steps: sequentially adding deionized water, ethyl hydroxyethyl cellulose, chlorine-methyl isothiazolinone, ethylene glycol siloxane, dipropylene glycol methyl ether and ethylene glycol butyl ether in the dispersing cylinder according to the mass parts, and stirring at the rotating speed of 500rpm for 10 min; then the rotating speed is increased to 1000rpm, rutile type titanium dioxide, calcined kaolin, 2-amino-2-methyl-1-propanol and polyvinyl alcohol derivative 3 are added in sequence according to the mass parts, and the mixture is continuously stirred for 25 min; then the rotating speed is reduced to 600rpm, and pure acrylic emulsion, TT-935 and 80-120 mesh calcium sand are added in sequence according to the mass parts; and continuously stirring for 10min to obtain the toning base paint.
The preparation method of the granulation protective glue comprises the following steps: in thatAdding deionized water and 5MgO 18Al into a dispersion cylinder in sequence according to the mass parts2O3·10SiO2·9H2O, adjusting the dispersing speed to 1200rpm, and continuously stirring for 30min until no visible particles exist; adjusting the rotating speed to 450rpm, slowly dripping chlorine-methylisothiazolinone according to the mass parts, and continuously stirring for 3 min; and then placing the mixed solution in a thermostatic chamber with the temperature of 25 ℃ for standing for 24 hours for later use to obtain the granulation protection glue.
The preparation method of the continuous phase emulsion comprises the following steps: sequentially adding deionized water, silicone-acrylic emulsion, dipropylene glycol methyl ether, ammonia water, polyether modified dimethyl siloxane, ethylene glycol butyl ether and chloro-methylisothiazolinone in the dispersion cylinder according to the mass parts, adjusting the rotating speed to 400rpm, and dispersing for 15 min; and adjusting the rotating speed to 800rpm, mixing TT-615 and deionized water uniformly according to the mass parts, slowly dropping the mixture into a dispersion cylinder, continuously stirring for 10min, and standing for later use to obtain the continuous phase emulsion.
The preparation method of the batch scraping type sand-in-water multicolor paint comprises the following steps: after the toning base paint is toned into different colors by using inorganic color paste, 60 parts by mass (the parts are all referred to as mass parts) of toning base paint is added into a dispersion cylinder filled with 25 parts of protective glue, a special multicolor granulator is used for shearing color points to the size of 1cm in diameter, and the color points are rapidly transferred into a thermostatic chamber at 25 ℃ for standing for 3 hours, so that the protective glue solution and the polyvinyl alcohol derivatives 3 in the toning base paint are fully reacted; and then accurately weighing and adding 20 parts of continuous phase emulsion, and uniformly stirring to obtain the batch scraping type water-coated sand multicolor coating.
Example 4
Example 4 the formulation, amounts and preparation were the same as in example 1, except that the magnesium aluminum silicate used in example 4 had an average particle size of 10 nm.
Example 5
Example 5 the formulation, content and preparation method of example 1 are the same, with the only difference that the molar ratio of vinyl alcohol and acrylic acid in example 5 is 100: 10.
comparative example 1
Comparative example 1 was the same as example 1 in formulation components, contents and preparation method, except that comparative example 1 did not contain polyvinyl alcohol derivative 1.
Comparative example 2
Comparative example 1 the formulation, content and preparation method of example 1 were the same, except that in comparative example 2, polyvinyl alcohol derivative 1 was replaced by equal parts by mass of unmodified polyvinyl alcohol (purchased from Shanghai Aladdin Biotech Co., Ltd., model 1799).
Comparative example 3
Comparative example 3 has the same formulation, content and preparation method as example 1, except that the granulated protective colloid composition of comparative example 3 does not contain nanoscale flaky magnesium aluminum silicate.
Test example
A series of performance tests were performed on the batch-scraped sand-in-water multicolor paints prepared in examples 1 to 5 and comparative examples 1 to 3, and the results are shown in table 1 below.
The specific test method is as follows:
the test method of the color point state after batch scraping comprises the following steps: uniformly coating the batch-scraping type sand-in-water finished paint on the surface of 40-30 cm calcium silicate at room temperature, performing batch scraping back and forth for 10 times at a constant speed by using a batch knife, and observing the color point state.
The color point strength test method comprises the following steps: and (3) uniformly smearing the finished paint on a glass plate at room temperature, smearing the colored dots at a constant speed and constant pressure back and forth by using a paint mixing knife until the colored dots are broken, and recording the back and forth smearing times.
The test method of the hardness of the paint film comprises the following steps: the measurement was carried out by the B method-manual method in GB/T6739-1996 Pencil test method for hardness of paint film.
The method for testing the adhesive force after soaking in water comprises the following steps: after a sand-in-water paint film is soaked in deionized water at 25 ℃ for 96 hours, water stains on the surface of the paint film are wiped off by a paper towel, and then the adhesive force of the paint film after soaking is measured according to a lattice drawing method in GB/T9286-1998 grid drawing test of paint films of colored paint and varnish.
The test method of the thermal storage stability comprises the following steps: the sample is filled in a 200ml glue pot, a cover is screwed and sealed, then the glue pot is placed in a constant temperature drying oven, the sample is stored for 30 days under the acceleration condition of 50 +/-2 ℃, and then the can is cooled to the room temperature, and the can state of the finished paint is observed.
TABLE 1 results of testing technical effects of examples 1 to 5 and comparative examples 1 to 3
The above technical effect tests fully demonstrate that, compared with examples 1 to 5, especially examples 1 to 3, comparative examples 1 to 3 do not have the polyvinyl alcohol derivatives of the present invention, and thus cannot generate synergistic effect with nanoscale flaky magnesium aluminum silicate, so that the related technical effects are far inferior to those of examples 1 to 3. Therefore, examples 1 to 3 are more advanced in technical effect than comparative examples 1 to 3.
Claims (10)
1. The scraping sand-in-water multicolor paint is characterized by comprising the following components in parts by mass:
55-65 parts of toning base paint
20-30 parts of granulation protective adhesive
15-25 parts of continuous phase emulsion;
the toning base paint comprises a polyvinyl alcohol derivative, wherein the polyvinyl alcohol derivative contains an olefin salt group;
the granulation protective glue contains nanoscale flaky magnesium aluminum silicate.
2. The batch-scraping sand-in-water multicolor paint as claimed in claim 1, wherein the polyvinyl alcohol derivatives are prepared by the following steps: vinyl acetate and olefine acid are polymerized under the action of catalyst to obtain intermediate product, then excess alkali is added to make alcoholysis.
3. The batch-doctored sand-in-water multicolor paint according to claim 2, wherein the molar ratio of vinyl acetate to alkenoic acid is 100: 3-5.
4. The batch-scraping type sand-in-water multicolor paint as claimed in claim 1, wherein the toning base paint comprises the following components in parts by mass:
the granulation protection glue comprises the following components in parts by mass:
3-5 parts of nano flaky magnesium aluminum silicate
90-97 parts of water.
5. The batch-scraping sand-in-water multicolor paint according to claim 4, wherein the cellulose is selected from one of ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose.
6. The batch-doctored sand-in-water multicolor coating according to claim 1, wherein said continuous phase emulsion is selected from one or both of a pure acrylic polymer emulsion or a silicone acrylic polymer emulsion.
7. The batch-scraping sand-in-water multicolor paint as claimed in claim 1, wherein the nano-scale flaky magnesium aluminum silicate has an average particle size of 20-50 nm.
8. The batch-scraping sand-in-water multicolor paint as claimed in claim 1, wherein the nano-scale flaky magnesium aluminum silicate has a chemical formula of 5 MgO-18A2lO3·10SiO2·9H2O。
9. The method for preparing the batch-scraping sand-in-water multicolor paint according to the claims 1 to 8, which is characterized by comprising the following steps: mixing the components of the granulation protective glue and the toning base paint, uniformly stirring, and standing for 3-5 h; then adding the continuous phase emulsion, and uniformly stirring to obtain a product.
10. The method of claim 9, wherein the stirring temperature is 25-30 ℃.
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| CN111978801B (en) | 2021-09-21 |
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