CN114231057A - High-environment-friendly self-cleaning batch scraping type stone-like paint and preparation method and application thereof - Google Patents
High-environment-friendly self-cleaning batch scraping type stone-like paint and preparation method and application thereof Download PDFInfo
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- CN114231057A CN114231057A CN202111469906.4A CN202111469906A CN114231057A CN 114231057 A CN114231057 A CN 114231057A CN 202111469906 A CN202111469906 A CN 202111469906A CN 114231057 A CN114231057 A CN 114231057A
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- C—CHEMISTRY; METALLURGY
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
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- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
- C09D7/44—Combinations of two or more thickening agents
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- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Abstract
The invention relates to the technical field of coatings, and particularly discloses a high-environment-friendly self-cleaning batch scraping type stone-like paint, a preparation method and application thereof, wherein the high-environment-friendly self-cleaning batch scraping type stone-like paint comprises the following components in parts by mass: 5.0-10.0 parts of self-cleaning real stone paint emulsion, 15.0-20.0 parts of modified silica sol, 55-65 parts of organic silicon modified colored sand, 0.5-0.8 part of film-forming additive, 0.6-1.5 parts of thickening agent and 0.5-1.0 part of glycerol ethoxylate; the thickening agent comprises organic modified bentonite, hydroxyethyl cellulose, a polyurethane thickening agent and a hydrophobic modified alkali swelling thickening agent; the viscosity of a 2% strength by weight aqueous mixture of hydroxyethyl cellulose at 25 ℃ is 50000-100000 mPas. The stone-like paint film disclosed by the invention is flat and compact in appearance, and has excellent construction performance, bonding strength, stain resistance, aging resistance, heat storage performance and environmental protection performance.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a high-environment-friendly self-cleaning batch scraping type stone-like paint, and a preparation method and application thereof.
Background
Along with the enhancement of the environmental protection, the limit of the exploitation of natural stones and the consideration of the control and safety of real estate companies on the cost, the natural stones are less and less used in the decoration of the outer vertical surfaces, and the natural stones are replaced by stone-like coatings, particularly stone-like paints, so that the natural stones are greatly popularized and applied, the development is still rapid in recent years, and the natural stones become one of the varieties with the maximum yield in the building coatings of the outer walls.
However, at present, urban environmental pollution is aggravated, wherein dust pollution and gas pollution are particularly serious, building outer walls serving as main landscapes of cities are eroded more and more seriously, the outer wall real stone paint is widely applied, the problems of easy contamination and incapability of self-cleaning are more and more prominent, a plurality of outer wall real stone paint projects have obvious pollution problems after 1 year, originally showy and atmospheric outer vertical surfaces become unbearable, and the use and popularization of the real stone paint are severely restricted. In addition, with the issuance and implementation of the standard of GB/T35602-2017 green product evaluation-coating, consumers increasingly pay more attention to the environmental protection performance of coating products, but the conventional real stone paint products are added with antifreeze such as ethylene glycol or propylene glycol and alcohol ethers with lower boiling points as cosolvent, and the auxiliaries contain more volatile substances, so that the environmental protection performance of the real stone paint products cannot meet the standard requirement. Meanwhile, the current real stone paint has the following three defects in the actual construction process: firstly, only a high-pressure spray gun can be adopted for spraying construction, and the construction tool is complex; secondly, large-area protection is needed in the construction process, a large amount of flying sand exists, and the construction body feeling is poor; thirdly, the sprayed stone-like paint has rough paint film surface, is easy to store ash and stain and affects the beauty. Therefore, it is necessary to improve the real stone paint in view of these disadvantages and develop a new real stone paint material.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides the high-environment-friendly self-cleaning batch scraping type stone-like paint and the preparation method thereof, and the high-environment-friendly self-cleaning batch scraping type stone-like paint film has smooth and compact appearance, and has excellent construction performance, bonding strength, stain resistance, aging resistance, heat storage performance and environmental protection performance.
The invention provides a stone-like paint which comprises the following components in parts by mass:
5.0-10.0 parts of self-cleaning real stone paint emulsion;
15.0-20.0 parts of modified silica sol;
55-65 parts of organic silicon modified colored sand;
0.5-0.8 part of film-forming additive;
0.6-1.5 parts of thickening agent;
0.5-1.0 part of glycerol ethoxylate;
the thickening agent comprises organic modified bentonite, hydroxyethyl cellulose, a polyurethane thickening agent and a hydrophobic modified alkali swelling thickening agent; the viscosity of the 2% strength by weight aqueous mixture prepared from hydroxyethylcellulose at 25 ℃ is 50000-100000 mPas.
In some embodiments of the present invention, the coalescing agent is an alcohol ester compound, preferably at least one of twelve alcohol esters and sixteen alcohol esters.
In some embodiments of the present invention, the self-cleaning real stone paint emulsion is a silicone modified acrylic emulsion. The natural stone paint has a relatively hydrophilic surface and a hydrophobic internal structure, and can endow the natural stone paint with excellent stain resistance and water resistance.
In some embodiments of the invention, the silicone-modified acrylic emulsion has a solids content of 40-50%, preferably badrich RS 8869.
In some embodiments of the invention, the modified silica sol is a silane coupling agent modified silica sol.
According to the invention, by a chemical modification method, firstly, a silane coupling agent is hydrolyzed, then the obtained hydrolysate is compounded and added with silica sol particles according to a certain proportion for reaction, so that bonding is formed between inorganic and organic interfaces, interface fusion is promoted, and the performance of the material is enhanced, thus the modified silica sol with better dispersibility and stability is prepared, the strength and hydrophobicity of the surface of the modified silica sol are enhanced, and finally, the modified silica sol is added into the product of the invention, so that the bonding strength and stain resistance of the stone paint can be obviously improved, the thermal storage performance is excellent, the phenomena of agglomeration and caking are prevented, and the performance is superior to that of the silica sol commonly used in the market.
In some embodiments of the invention, the silane coupling agent is gamma-glycidoxypropyltrimethoxysilane or gamma- (methacryloyloxy) propyltrimethoxysilane.
In some embodiments of the invention, the silane coupling agent is a KH560, KH570 or Michael A-187 silane coupling agent.
In some embodiments of the invention, the mass of the silane coupling agent is 3-4% of the mass of the silane coupling agent modified silica sol.
In some embodiments of the present invention, the method for preparing the silane coupling agent modified silica sol comprises the steps of: and hydrolyzing the silane coupling agent, and then reacting with silica sol.
Specifically, the preparation method of the silane coupling agent modified silica sol comprises the following steps:
s1, hydrolyzing the silane coupling agent to obtain a hydrolysate;
and S2, mixing the hydrolysate of S1 with silica sol, and reacting to obtain the product.
In some embodiments of the present invention, in the step S1, the hydrolysis manner includes, but is not limited to, stirring, when the hydrolysis is performed by stirring, the rotation speed of stirring is 100-300r/min, the stirring time is 5-10min, and the stirring temperature is 10-30 ℃.
In some embodiments of the present invention, in the step S2, the mass ratio of the hydrolysate to the silica sol is 1 to 5: 50-150, such as 2-5: 50-150, 2-5: 50-120, 3-5: 50-120, 3-5: 80-120, 3-4: 80-120.
In some embodiments of the present invention, in the step S2, the mixing manner includes, but is not limited to, stirring, when the mixing is performed by stirring, the rotation speed of stirring is 200-400r/min, the stirring time is 60-70min, and the stirring temperature is 50-70 ℃.
In some embodiments of the present invention, the amount of silicone in the silicone-modified colored sand is 2 to 8%, preferably 2 to 4% by weight of the total silicone-modified colored sand.
In some preferred embodiments of the present invention, the silicone is a methyl silicone resin; further preferably, the organic silicon is methyl organic silicon resin with 100% of solid content, so that the environment-friendly effect is better.
In some embodiments of the present invention, the silicone-modified colored sand further comprises a color master.
In some preferred embodiments of the present invention, the amount of the color masterbatch is 5 to 10% of the total weight of the silicone modified colored sand.
In some embodiments of the invention, the colored sand comprises snowflake white sand and/or quartz sand.
In some preferred embodiments of the invention, the snowflake white sand has a particle size of 20 to 100 mesh, preferably 40 to 80 mesh.
In some preferred embodiments of the present invention, the amount of the colored sand is 85 to 90% by weight based on the total weight of the silicone-modified colored sand.
In some embodiments of the present invention, the method for preparing the organosilicon modified colored sand comprises the following steps:
mixing and calcining the colored sand and the organic silicon; and optionally, adding the color master batch to mix before calcining.
In some preferred embodiments of the present invention, the temperature of the calcination is 300-400 ℃, and the time of the calcination is 15-30 min.
According to the invention, the organic silicon resin and the color master are coated on the white sand with the size of 40-80 meshes by a calcination process at the temperature of 300-400 ℃, so that the white sand becomes modified colored sand, and after calcination and stirring, the particle size of the organic silicon modified colored sand particles is uniform and the surface is smooth, and the hydrophobicity of the surface of the organic silicon modified colored sand is enhanced, so that the smoothness, stain resistance and bonding strength of the product construction are improved, and in addition, the flatness and compactness of a paint film can be ensured.
In some embodiments of the invention, the thickener comprises the following components in parts by mass:
0.15-0.4 part of organic modified bentonite;
0.1-0.3 part of hydroxyethyl cellulose;
0.3-0.6 part of polyurethane thickener;
0.05-0.15 part of hydrophobic modified alkali swelling thickener.
In some embodiments of the invention, the organically modified bentonite is a non-metallic mineral and is prepared by taking bentonite as a raw material and utilizing the layered structure of montmorillonite in the bentonite and the characteristic that the montmorillonite can be swelled and dispersed into colloidal clay particles in water, and inserting an organic covering agent by using an ion exchange technology. The organic modified bentonite provided by the invention can ensure that materials do not fall off in the construction process, obvious layering does not occur after 15 days of thermal storage, and the organic modified bentonite has excellent stain resistance.
In some embodiments of the invention, the polyurethane thickener is a polyether polyurethane thickener and/or a hydrophobically modified polyurethane thickener. Which is helpful to improve the stain resistance and the scraping smoothness of the real stone paint.
In some embodiments of the invention, the hydrophobically modified alkali swellable thickener is an alkali soluble acrylic emulsion. The stone-like paint has the advantages that the stone-like paint is beneficial to improving the constructability of the stone-like paint, sand running and material falling in the construction process are prevented, the appearance of the paint film is smoother, and gaps are prevented.
In some embodiments of the invention, the glycerol ethoxylate is selected from clariant Polyglykol G300.
In some embodiments of the present invention, the stone-like paint further comprises water and/or other auxiliary agents.
In some embodiments of the invention, the water is present in an amount of 7.5 to 16 parts by mass and/or the further auxiliary agent is present in an amount of 0.5 to 1.2 parts by mass.
In some embodiments of the invention, the other auxiliary agents include at least one of pH adjusting agents, wetting agents, dispersing agents, antifoaming agents, preservatives.
In some embodiments of the invention, the pH adjuster is 0.1 to 0.2 parts by mass; and/or 0.05-0.15 parts by mass of a wetting agent; and/or 0.2 to 0.3 part by mass of the dispersant; and/or the defoaming agent is 0.1-0.15 parts by mass; and/or 0.1-0.2 parts by mass of the preservative.
In some embodiments of the invention, the wetting agent is at least one of sodium alkyl sulfosuccinate, alkyl polyoxyethylene ether, polyethoxy nonylphenol;
and/or the dispersant is a sodium polycarboxylate salt, preferably a sodium polycarboxylate salt dispersant having a hydrophobically modified structure, which has excellent water resistance and extremely high dispersion efficiency;
and/or the defoaming agent is at least one of polydimethylsiloxane and mineral oil;
and/or the preservative is at least one of zinc pyrithione and 1, 2-benzisothiazolin-3-one.
In some embodiments of the invention, the pH adjusting agent is 2-amino-2 methyl-1-propanol.
In a second aspect of the present invention, there is provided a method for preparing the above stone-like paint, comprising the steps of:
and mixing the self-cleaning real stone paint emulsion, the modified silica sol, the organic silicon modified colored sand, the thickening agent, the film forming auxiliary agent and the glycerol ethoxylate to obtain the self-cleaning real stone paint.
In some embodiments of the invention: s1, dissolving organic modified bentonite and hydroxyethyl cellulose in water, and then simultaneously or sequentially adding a film-forming aid, a self-cleaning real stone paint emulsion, modified silica sol, a polyurethane thickener, a hydrophobic modified alkali swelling thickener and glycerol ethoxylate for mixing; and S2, adding organic silicon modified colored sand, and mixing to obtain the paint.
In some embodiments of the present invention, in the step S1, the mixing manner includes, but is not limited to, stirring, and when the mixing is performed by stirring, the rotation speed of stirring is 600-.
In some embodiments of the present invention, in the step S2, the mixing manner includes, but is not limited to, stirring, and when the mixing is performed by stirring, the rotation speed of stirring is 1000-.
In a third aspect of the invention, the application of the real stone paint in the decoration field is provided.
In a fourth aspect of the invention, a coating is provided, which is formed by curing the above stone-like paint.
The stone-like paint and the preparation method thereof according to the embodiment of the invention have at least the following beneficial effects:
(1) according to the invention, the modified silica sol and the self-cleaning real stone paint emulsion are used as main film forming substances, the interface binding force of the modified silica sol and the self-cleaning real stone paint emulsion is enhanced by virtue of the covalent bond effect, an interface film can be formed between the surface of the real stone paint and pollutants, and the pollutants fall off under the action of gravity, water flow and the like to achieve the self-cleaning effect;
(2) according to the invention, a thickening system formed by combining organic modified bentonite, hydroxyethyl cellulose, a polyurethane thickener and a hydrophobic modified alkali swelling thickener is adopted, and organic silicon modified colored sand with uniform particle size is matched for use, so that the product has excellent thixotropy, water resistance, storage property and constructability;
(3) according to the invention, inorganic modified silica sol and high-environmental-protection self-cleaning stone-like paint emulsion are selected as film forming substances, formaldehyde and VOC are not contained, glycerol ethoxylate is selected as a moisturizing wetting agent of the system, glycol, propylene glycol or low molecular weight alcohol ether auxiliary agents which can generate volatile substances in the prior art are replaced, and a formaldehyde-free preservative system is selected, so that the product is further endowed with green and environment-friendly performance, and the volatile organic matter content and the formaldehyde content are both lower than the standard detection limit according to the detection of harmful substance inspection standard in GB/T35602 plus 2017 green product evaluation coating;
(4) compared with the traditional real stone paint, the high-environment-friendly self-cleaning real stone paint provided by the invention can be constructed in a batch scraping manner, the surface of a paint film constructed in the batch scraping manner is flat and compact, ash is not easy to accumulate, and the stain resistance and the self-cleaning property of a coating can be remarkable.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The component information used in the examples of the present invention is as follows, wherein the organically modified bentonite is mesh MZ organically modified bentonite; the hydroxyethyl cellulose is Danisco SK200 hydroxyethyl cellulose, and the rotational viscosity of a 2 wt% water mixture prepared from the hydroxyethyl cellulose at 25 ℃ is 100000 mPa.s; the alkyl polyoxyethylene ether adopts a colain LCN070 wetting agent; the hydrophobically modified polycarboxylic acid sodium salt adopts a Dow chemical 731A dispersant; 2-amino-2-methyl-1-propanol adopts a Dow chemical AMP95 multifunctional auxiliary agent; the alcohol ester twelve adopts Eschmann texanol ester alcohol; zinc pyrithione adopts a brown sterilization and mildew prevention agent; the organosilicon modified acrylic emulsion adopts Badfei RS8869 organosilicon modified acrylic emulsion; the modified silica sol is self-made from Foshan family condensed KN-1430B silica sol; polyether polyurethane adopts a Dow chemical RM-8W polyurethane thickener; the alkali soluble acrylic emulsion adopts a Dow chemical TT-615 hydrophobic alkali soluble swelling thickener; the glycerol ethoxylate adopts colain Polyglykol G300 glycerol ethoxylate; the polydimethylsiloxane adopts a Pasf chemical 2410 antifoaming agent; the organic silicon modified colored sand is prepared by self-made snowflake white sand with 40-80 meshes of New Guangxi Huafa; the silicone resin adopts the belief chemical KR-510 silicone resin (KR-510 silicone resin is a methyl silicone resin).
Example 1
The embodiment provides a real stone paint and a preparation method thereof, and the steps are as follows:
weighing the following raw materials in parts by mass:
11.75 parts of deionized water;
0.15 part of organic modified bentonite;
0.3 part of hydroxyethyl cellulose;
0.1 part of alkyl polyoxyethylene ether;
0.25 part of hydrophobically modified sodium polycarboxylate;
0.15 part of 2-amino-2-methyl-1-propanol;
twelve 0.65 parts of alcohol ester;
0.2 part of zinc pyrithione;
7.5 parts of organic silicon modified acrylic emulsion;
17.5 parts of modified silica sol;
0.45 part of polyether polyurethane;
0.1 part of alkali-soluble acrylic emulsion;
0.75 part of glycerol ethoxylate;
0.15 part of polydimethylsiloxane;
60 parts of organic silicon modified colored sand.
The preparation method of the modified silica sol comprises the steps of firstly adding deionized water into a round-bottom flask, adding a Michael diagram A-187 silane coupling agent at normal temperature and at the rotating speed of 200r/min, adding the mixture according to the weight ratio of 1:1 of water to the silane coupling agent, stirring for 5-10 minutes, and obtaining a hydrolysate after hydrolysis when the solution becomes transparent from turbidity and the temperature returns to the initial value; and secondly, adding the hydrolysate obtained in the first step into a 150mL round-bottom flask, then adding a certain amount of silica sol, adding the hydrolysate and the silica sol according to the weight ratio of 3.5:100, controlling the reaction temperature to 60 ℃, controlling the rotation speed to be 300r/min, stirring for 60min, and filtering to obtain the modified silica sol.
The preparation method of the organic silicon modified colored sand comprises the steps of mixing 100 parts of 50-mesh snowflake white sand, 2 parts of organic silicon resin and 5 parts of color master according to the weight ratio, calcining the mixture at 400 ℃ for 15-30min, and finally cooling to room temperature to obtain the organic silicon modified colored sand.
Then, 11.75 parts of deionized water and 0.15 part of organically modified bentonite are mechanically stirred for 4min at the rotating speed of 500r/min, then 0.3 part of hydroxyethyl cellulose is added, and the mechanical stirring is carried out for 4min at the rotating speed of 500r/min until the materials are completely dissolved. Then, sequentially adding 0.1 part of alkyl polyoxyethylene ether, 0.25 part of hydrophobically modified sodium polycarboxylate, 0.15 part of 2-amino-2 methyl-1-propanol, 0.65 part of alcohol ester dodeca and 0.2 part of zinc pyrithione, continuously stirring for 5min at the rotating speed of 700r/min, then sequentially adding 7.5 parts of organic silicon modified acrylic emulsion and 17.5 parts of modified silica sol at the rotating speed of 700r/min, and continuously stirring for 9 min; and continuing to add 0.45 part of polyether polyurethane, 0.1 part of alkali-soluble acrylic emulsion mixed with water in advance according to a ratio of 1:2, 0.75 part of glycerol ethoxylate and 0.15 part of polydimethylsiloxane in sequence at the rotating speed of 700r/min, and continuously stirring for 9 min. And finally, increasing the rotating speed to 1200r/min, adding 60 parts of organic silicon modified colored sand, and continuously stirring for 17.5min to obtain the stone-like paint.
Example 2
The embodiment provides a real stone paint and a preparation method thereof, and the steps are as follows:
weighing the following raw materials in parts by mass:
7.5 parts of deionized water;
0.2 part of organic modified bentonite;
0.2 part of hydroxyethyl cellulose;
0.15 part of sodium alkyl sulfosuccinate;
0.2 part of hydrophobically modified sodium polycarboxylate;
0.1 part of 2-amino-2-methyl-1-propanol;
sixteen (0.5) parts of alcohol ester;
0.1 part of 1, 2-benzisothiazolin-3-one;
5 parts of organic silicon modified acrylic emulsion;
20 parts of modified silica sol;
0.3 part of hydrophobic modified polyurethane;
0.15 part of alkali-soluble acrylic emulsion;
0.5 part of glycerol ethoxylate;
0.1 part of mineral oil;
and 65 parts of organic silicon modified colored sand.
The preparation methods of the modified silica sol and the organic silicon modified colored sand are the same as example 1.
7.5 parts of deionized water and 0.2 part of organically modified bentonite are mechanically stirred for 3min at the rotating speed of 400r/min, then 0.2 part of hydroxyethyl cellulose is added, and the mixture is mechanically stirred for 3min at the rotating speed of 400r/min until the mixture is completely dissolved. Then sequentially adding 0.15 part of sodium alkyl sulfosuccinate, 0.2 part of hydrophobically modified polycarboxylic acid sodium salt, 0.1 part of 2-amino-2 methyl-1-propanol, 0.5 part of hexadecanol ester and 0.1 part of 1, 2-benzisothiazolin-3-one, continuously stirring for 4min at the rotating speed of 600r/min, then sequentially adding 5 parts of organic silicon modified acrylic emulsion and 20 parts of modified silica sol at the rotating speed of 600r/min, and continuously stirring for 8 min; and continuously adding 0.3 part of hydrophobic modified polyurethane, 0.15 part of alkali-soluble acrylic emulsion which is mixed with water in advance according to the ratio of 1:2, 0.5 part of glycerol ethoxylate and 0.1 part of mineral oil in sequence at the rotating speed of 600r/min, and continuously stirring for 8 min. And finally, increasing the rotating speed to 1400r/min, adding 65 parts of organic silicon modified colored sand, and continuously stirring for 20min to obtain the stone-like paint.
Example 3
The embodiment provides a real stone paint and a preparation method thereof, and the steps are as follows:
weighing the following raw materials in parts by mass:
16 parts of deionized water;
0.4 part of organic modified bentonite;
0.1 part of hydroxyethyl cellulose;
0.05 part of polyethoxy nonyl phenol;
0.3 part of hydrophobically modified sodium polycarboxylate;
0.2 part of 2-amino-2-methyl-1-propanol;
twelve 0.8 parts of alcohol ester;
0.1 part of 1, 2-benzisothiazolin-3-one;
0.1 part of zinc pyrithione;
10 parts of organic silicon modified acrylic emulsion;
15 parts of modified silica sol;
0.6 part of polyether polyurethane;
0.05 part of alkali-soluble acrylic emulsion;
1.0 part of glycerol ethoxylate;
0.1 part of polydimethylsiloxane;
0.1 part of mineral oil;
55 parts of organic silicon modified colored sand.
The preparation methods of the modified silica sol and the organic silicon modified colored sand are the same as example 1.
Mechanically stirring 16 parts of deionized water and 0.4 part of organically modified bentonite for 5min at the rotating speed of 600r/min, then adding 0.1 part of hydroxyethyl cellulose, and mechanically stirring for 5min at the rotating speed of 600r/min until the materials are completely dissolved. Then, sequentially adding 0.05 part of polyethoxy nonyl phenol, 0.3 part of hydrophobically modified polycarboxylic acid sodium salt, 0.2 part of 2-amino-2 methyl-1-propanol, 0.8 part of alcohol ester dodeca, 0.1 part of 1, 2-benzisothiazolin-3-one and 0.1 part of zinc pyrithione, continuously stirring for 6min at the rotating speed of 800r/min, then sequentially adding 10 parts of organic silicon modified acrylic emulsion and 15 parts of modified silica sol at the rotating speed of 800r/min, and continuously stirring for 10 min; and continuously adding 0.6 part of polyether polyurethane, 0.05 part of alkali-soluble acrylic emulsion mixed with water in advance according to a ratio of 1:2, 1.0 part of glycerol ethoxylate, 0.1 part of polydimethylsiloxane and 0.1 part of mineral oil in sequence at the rotating speed of 800r/min, and continuously stirring for 10 min. And finally, increasing the rotating speed to 1000r/min, adding 55 parts of organic silicon modified colored sand, and continuously stirring for 15min to obtain the stone-like paint.
Comparative example 1
The preparation process of example 1 was referenced, except that the glycerol ethoxylate in example 1 was replaced with propylene glycol.
Comparative example 2
The preparation method of example 1 was followed, except that the modified silica sol of example 1 was replaced with a commercially available silica sol (i.e., a commercially available silica sol in which no silane coupling agent was used to modify the silica sol).
Comparative example 3
The preparation method of example 1 is referred to, except that the organic silicon modified colored sand in example 1 is replaced by a commercially available natural colored sand.
Comparative example 4
Reference is made to the preparation process of example 1, except that the organically modified bentonite in example 1 is replaced with ordinary bentonite.
Comparative example 5
The manufacturing method of example 1 was referenced except that the hydroxyethyl cellulose in example 1 was replaced with hydroxyethyl cellulose having a viscosity of 5000mpa.s at 25 ℃.
Comparative example 6
The preparation method of example 1 was referenced except that 0.15 parts of organically modified bentonite in example 1 was replaced with 0.05 parts of hydroxyethyl cellulose, 0.05 parts of polyether urethane, and 0.05 parts of alkali-soluble acrylic emulsion.
Comparative example 7
The production method of example 1 was referenced except that 0.3 parts of hydroxyethyl cellulose in example 1 was replaced with 0.1 parts of organically modified bentonite, 0.1 parts of polyether urethane, and 0.1 parts of alkali-soluble acrylic emulsion.
Comparative example 8
The production method of example 1 was referenced except that 0.45 parts of polyether urethane in example 1 was replaced with 0.1 parts of organically modified bentonite, 0.1 parts of hydroxyethyl cellulose and 0.25 parts of alkali-soluble acrylic emulsion.
Comparative example 9
The production method of example 1 was referenced except that 0.1 part of the alkali-soluble acrylic emulsion in example 1 was replaced with 0.02 part of organically modified bentonite, 0.04 part of hydroxyethyl cellulose and 0.04 part of polyether urethane.
Comparative example 10
The preparation process of example 1 is referred to with the difference that the silicone-modified acrylic emulsion of example 1 is replaced by a conventional acrylic emulsion (which is not silicone-modified).
Comparative example 11
Comparative example 11 is a prior art stone-like paint product, consisting of the following ingredients:
the components are as follows: 13 parts of pure acrylic emulsion, 0.2 part of hydroxyethyl cellulose, 1.0 part of film-forming additive, 0.1 part of defoaming agent, 0.1 part of bactericide, 0.1 part of multifunctional additive, 0.5 part of propylene glycol, 75 parts of natural colored sand and 10 parts of water.
In the components, the pure acrylic emulsion is BLJ-9975 pure acrylic paint emulsion; the hydroxyethyl cellulose adopts Samsung B30K hydroxyethyl cellulose; the film forming auxiliary agent adopts the twelve alcohol ester of Runtai chemical; the defoaming agent is NXZ defoaming agent of Nopochaceae; the bactericide is Turkel EG-CLF bactericide; the multifunctional additive adopts Australian chemical AR95 multifunctional additive; the natural color sand adopts 40-80 mesh natural color sand of Fucheng mineral industry in Henan province.
Test example
Workability, adhesive strength, stain resistance and heat storage property in examples 1 to 3, comparative examples 1 to 10 and comparative example 11 of the prior art product were measured in accordance with the regulation of JG/T24-2018; VOC and formaldehyde content are detected according to the standard regulation of GB 18582-2020; in addition, the stain resistance after 200 hours of artificial weathering resistance is carried out according to the cycle A regulation in GB/T1865-2009, the evaluation of the result is characterized according to the value of the reflection coefficient reduction rate calculated according to the stain resistance of the outer wall coating in GB/T9780-2013, and the smaller the obtained value is, the better the stain resistance is. The specific pollutant is fly ash, and the specific evaluation standard is as follows: level 1: very slight, barely perceptible color differences; and 2, stage: slight, have more obvious chromatic aberration; and 3, level: moderate, with obvious chromatic aberration; 4, level: severe, severe color difference; the stain resistance of the paint film surface after 3 months of outdoor exposure was characterized by visual inspection, and the results of the relevant tests are shown in tables 1 and 2.
Table 1: technical indices of examples 1 to 3
As can be seen from the test results in Table 1, examples 1 to 3 provided by the present invention are excellent in workability, paint film appearance, adhesive strength, stain resistance, heat storage property and environmental protection property.
Table 2: each of the technical indices of comparative examples 1 to 10 and comparative example 11
As can be seen from the results in Table 2, comparative example 1, in which the glycerol ethoxylate of the present invention is not added, greatly reduces the environmental protection performance of the product, and detects significant volatile substances. From the test results of comparative example 2, it is understood that the product has a remarkably reduced stain resistance without using the modified silica sol of the present invention, and the product has a coagulation and agglomeration phenomenon in heat storage property, and the viscosity strength is inferior to that of the product of the present invention when using the silica sol commonly used in the market. From the experimental result of comparative example 3, it can be seen that the stain resistance of the product is remarkably reduced without using the organic silicon modified colored sand of the present invention, which is far inferior to that of example 1, and the smoothness of construction, the compactness of paint film and the bonding strength are also negatively affected to a certain extent.
As can be seen from comparative examples 6 to 9 in Table 2, when any one or two of hydroxyethylcellulose, organically modified bentonite, polyurethane and hydrophobically modified alkali swellable thickeners are absent as thickeners, the prepared coating is affected to various degrees in terms of construction smoothness, sand running, material falling, heat storage and adhesive strength, and thus it can be seen that the four thickeners of the present invention are absent and play a crucial role in the stability of the entire coating. Further, as can be seen from comparative examples 4 to 5, the organically modified bentonite and the hydroxyethyl cellulose with the viscosity of 50000-. As is clear from the experimental results of comparative example 10, when a conventional acrylic emulsion was used, the stain resistance of the product was greatly affected and the stain resistance was remarkably lowered.
Compared with the prior art product comparative example 11, the examples 1-3 of the invention have very obvious advantages from the aspects of workability, stain resistance and bonding strength of the product and environmental protection performance, and successfully overcome the problems of poor stain resistance, general environmental protection and incapability of batch scraping construction of the prior art product.
Claims (10)
1. The stone-like paint is characterized by comprising the following components in parts by mass:
5.0-10.0 parts of self-cleaning real stone paint emulsion;
15.0-20.0 parts of modified silica sol;
55-65 parts of organic silicon modified colored sand;
0.5-0.8 part of film-forming additive;
0.6-1.5 parts of thickening agent;
0.5-1.0 part of glycerol ethoxylate;
the thickening agent comprises organic modified bentonite, hydroxyethyl cellulose, a polyurethane thickening agent and a hydrophobic modified alkali swelling thickening agent;
the viscosity of the 2% strength by weight aqueous mixture prepared from hydroxyethylcellulose at 25 ℃ is 50000-100000 mPas.
2. The stone-like paint as claimed in claim 1, wherein the self-cleaning stone-like paint emulsion is an organosilicon modified acrylic emulsion, and the solid content of the organosilicon modified acrylic emulsion is 40-50%.
3. The stone-like paint as claimed in claim 1, wherein the modified silica sol is a silane coupling agent modified silica sol; further, the silane coupling agent is gamma-glycidoxypropyltrimethoxysilane or gamma- (methacryloyloxy) propyltrimethoxysilane; the mass of the silane coupling agent accounts for 3-4% of that of the modified silica sol of the silane coupling agent.
4. The stone-like paint as claimed in claim 3, wherein the preparation method of the silane coupling agent modified silica sol comprises the following steps: and hydrolyzing the silane coupling agent, and then reacting with silica sol.
5. The stone-like paint as claimed in claim 1, wherein the amount of the organic silicon in the organic silicon modified colored sand is 2-8% of the total weight of the organic silicon modified colored sand; the organic silicon is methyl organic silicon resin.
6. The stone-like paint as claimed in claim 5, wherein the organosilicon modified color sand further comprises a color master; the amount of the color master is 5-10% of the total weight of the organic silicon modified color sand.
7. The stone-like paint as claimed in claim 1, wherein the polyurethane thickener is a polyether polyurethane thickener and/or a hydrophobically modified polyurethane thickener; further, the hydrophobic modified alkali swelling thickener is alkali soluble acrylic emulsion.
8. The method for preparing the stone-like paint as claimed in any one of claims 1 to 7, comprising the steps of:
and mixing the self-cleaning stone-like paint emulsion, the modified silica sol, the organic silicon modified colored sand, the thickening agent, the film forming auxiliary agent and the glycerol ethoxylate to obtain the stone-like paint.
9. Use of the stone-like paint according to any one of claims 1 to 7 in the field of decoration.
10. A coating layer, characterized in that the coating layer is formed by curing the stone-like paint as claimed in any one of claims 1-7.
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