CN116875136B - Batch scraping type colorful special-purpose double-in-person cleaning scratch-resistant finishing varnish and preparation method thereof - Google Patents

Abstract

The invention relates to a batch scraping type colorful special-purpose double-personally cleaning scratch-resistant finishing varnish, which comprises the following components: the preparation method comprises the following steps of silicone-acrylic emulsion, film forming auxiliary agent, lithium magnesium silicate, nano pure silicon zeolite, auxiliary agent and water; wherein, the raw materials of the nano pure silicon zeolite are solid products obtained by blending the composition A and the composition B and reacting in a high-temperature reaction kettle; the A composition is sodium hydroxide, aluminum hydroxide and water; the composition B is TEOS, TBABr and water. The invention provides a batch scraping type colorful special-purpose double-personally-cleaning scratch-resistant finishing varnish and a preparation method thereof, which not only well solve the problem of construction and decoration, but also improve the fullness of a paint film, and the stone-like effect is more vivid, and the stain resistance and the weather-aging resistance are more excellent. It is particularly emphasized that the finish varnish provided by the technology of the invention has excellent hardness, the hardness of a paint film can reach 3H and above, and the finish varnish has excellent scratch resistance and wear resistance. The method brings omnibearing protection to the outer vertical surface of the building.

Description

A scraping type multi-colored special double-sided self-cleaning anti-scratch topcoat varnish and its preparation method

Technical Field

The invention belongs to the field of coatings, and in particular relates to a scraping-type multi-colored specially formulated double-sided self-cleaning anti-scratch topcoat varnish and a preparation method thereof.

Background technique

With the continuous development of the national economy and the improvement of people's living standards, paint, as a high-end material for interior and exterior wall decoration, is widely favored by consumers due to its advantages of simple construction, economic durability, environmental protection and safety. Water-in-water, water-in-sand and other colorful paints are the most popular products in the current coating market due to their realistic imitation stone effect and green environmental protection performance. At present, the colorful paints with matching topcoats that are widely circulated on the market are all applied by spraying and roller coating. As we all know, although spraying and roller coating are more efficient than batch scraping, they often cause the overall wall to become flowery due to uneven construction, which requires rework and consumes a lot of manpower, material resources and time costs. In addition, as the last line of defense of the facade of a building, the coating is very easy to be bumped by external forces. The common topcoat varnishes on the market now only have simple dust and stain resistance properties, but cannot protect the main glue coating from being scratched or damaged.

In addition, in the prior art, the topcoat varnish specially formulated for multi-color coatings is mainly applied by spraying and roller coating. Firstly, since the dry film of the topcoat varnish is transparent, it is often uneven in construction and causes flowery problems. Secondly, it is difficult to apply thick topcoat varnish by roller coating and spraying, and the coating of the multi-color main paint is insufficient, which easily leads to problems such as water whitening, staining and poor weather resistance. The viscosity of the multi-color specially formulated topcoat currently used for spraying and roller coating is relatively low, and in order to save costs, it is necessary to add water for application on the construction site, and application problems such as sagging and delamination often occur. Finally, the multi-color dustproof topcoat in the prior art only has the functions of dustproof and water resistance, but does not have the protective functions such as scratch resistance and wear resistance, and cannot truly meet all the performance requirements of building exterior wall decoration.

Compared with roller coating and spraying, products for batching need to have a suitable viscosity for easy loading. In addition, batching also requires products to have a moderate thixotropy and not stick to the knife. Products for batching also need a certain degree of smoothness and small resistance to scraping. However, the viscosity of the finished product of the prior art products is generally controlled between 50-70ku. On the one hand, this viscosity cannot be applied by batching. On the other hand, on the basis of the prior art products, the viscosity of the finished product is thickened to a viscosity that can be scraped, between 110-120ku, but the scraping performance is still very poor, and the phenomenon of sticking to the knife and uneven scraping occurs.

Therefore, in summary, in view of the deficiencies in the technology of existing related products, it is urgent to develop a new technical solution to solve the above defects.

Summary of the invention

Based on the above existing application technology problems, the present invention provides a batch-scratching type colorful special double-sided self-cleaning anti-scratch top varnish and its preparation method, which not only solves the construction flower problem well, but also improves the fullness of the paint film, the imitation stone effect is more realistic, and the anti-fouling and weather aging resistance are more excellent. It is particularly emphasized that the top varnish provided by the technology of the present invention has excellent hardness, the paint film hardness can reach 3H and above, and has good anti-scratch and wear resistance. It brings all-round protection to the facade of the building.

One object of the present invention is to provide a scraping type multi-colored special double-sided self-cleaning anti-scratch top varnish, which comprises the following components in parts by mass:

Additives

water;

The raw material of the nano pure silica zeolite is a solid product obtained by mixing composition A and composition B and reacting them in a high temperature reactor;

Composition A is sodium hydroxide, aluminum hydroxide and water; composition B is TEOS, TBABr and water.

The present invention adopts copolymerized high cross-linking density silicone acrylic emulsion as the main film-forming substance, and inorganic lithium magnesium silicate and artificially synthesized nano zeolite are designed to be added into the formula system as functional transparent fillers, thereby finally obtaining a hydrophilic and lipophilic self-cleaning anti-scratch topcoat varnish film.

Preferably, the mass ratio of composition A to composition B is 100:1-10:1.

The main functions of copolymerized high cross-link density silicone-acrylic emulsion include the following:

a. Main film-forming substance, providing hydrophobic and oleophilic surface; b. Coating artificially synthesized nano-zeolite and forming strong hydrogen bonding force; c. Providing main properties of topcoat varnish such as dustproof, water-resistant and resistant to artificial weathering.

The main functions of inorganic lithium magnesium silicate include: a. Providing thixotropic anti-settling properties, so that the artificially synthesized pure silicon nano zeolite will not settle in the coating system; b. Optimizing the construction performance, providing smoothness and anti-sagging performance for the scraping construction of the topcoat varnish; c. The terminal bound water hydroxyl group provides hydrophilic properties for the paint film, and has hydrogen bonding force with the emulsion, which improves the density and hardness of the paint film, thereby achieving better water resistance, anti-fouling and anti-scratch performance.

The functions of artificially synthesized nano-pure silica zeolite include: a. It is coated in a copolymerized high-crosslink density silicone-acrylic emulsion film to improve the hardness and scratch resistance of the paint film; b. It has a large number of bound water hydroxyl groups on the surface, and has a strong hydrogen bond with the emulsion, which can improve the density of the paint film; c. The large number of bound water hydroxyl groups at the end provide a hydrophilic surface for the paint film, improving the anti-fouling performance of the paint film.

Furthermore, the auxiliary agent is selected from one or more of a bactericide, an antifreeze agent, a thickener, and a defoaming agent.

The bactericide is selected from one or more of 2-methyl-4-isothiazoline-3-one and 1,2-benzisothiazolin-3-one.

The antifreeze agent is selected from one or more of propylene glycol and ethylene glycol butyl ether;

The thickener is selected from one of Dow's TT935, Wanhua Chemical's A-401 or Puwei Chemical's RS-315;

The defoaming agent is selected from one or more of polyether modified dimethylsiloxane, polysiloxane and ethylene glycol siloxane.

Furthermore, the film-forming aid is selected from one or more of alcohol ester dodecanedione, propylene glycol butyl ether, dipropylene glycol methyl ether and benzyl alcohol.

Furthermore, the size of the nano pure silica zeolite is: long diameter 5-10um; wide diameter 2-4nm.

Another object of the present invention is to provide a method for preparing the above-mentioned scraping type multi-colored special double-sided self-cleaning anti-scratch topcoat varnish, and the preparation method is as follows:

S1, pouring composition A into composition B, stirring and aging to form a seed solution;

S2, reacting the seed solution in a high temperature reactor, and then drying and filtering;

S3, calcining the obtained crude product to obtain a product.

Furthermore, in the composition A, the molar ratio of sodium hydroxide to aluminum hydroxide is 100:1-10.

Furthermore, in the B composition, the molar ratio of TEOS to TBABr is 10:3-4.

Furthermore, in step S3, the calcination temperature is 600-800°C.

Furthermore, in step S1, the aging time is 10-20 hours.

The present invention has the following beneficial effects:

1. The nano pure silica zeolite of the present invention is artificially synthesized and used in topcoat varnish for the first time. Compared with random natural zeolite, it has the advantages of rod-shaped microstructure, uniform size, regular morphology, large specific surface area, etc.; and the surface of artificially synthesized zeolite has a large number of water-binding hydroxyl groups, which form hydrogen bonds with the carboxyl groups at the end of the copolymerized silicone-acrylic emulsion, so that the emulsion is tightly coated on the surface of the nano zeolite particles, which improves the hardness of the paint film and effectively improves the scratch resistance and anti-fouling performance of the paint film.

2. The silicone-acrylic emulsion forms a hydrophobic surface, while the inorganic lithium magnesium silicate and the synthetic nano zeolite both have a large number of bound water hydroxyl groups at the ends. The two have a hydrophilic surface after being compounded. The final topcoat varnish is a hydrophilic and lipophilic surface, which has excellent self-cleaning properties in the face of complex pollution sources in the air. In addition, the thixotropy and anti-settling of nano lithium magnesium silicate make the compatibility of nano pure silica zeolite and copolymerized highly cross-linked silicone-acrylic emulsion more excellent. The three work together to make the system more stable and the effect more outstanding.

3. The present invention obtains a topcoat varnish that can be applied by scraping, and the hardness of the paint film can reach 3H or above, with excellent wear resistance and scratch resistance; secondly, the paint film has a hydrophilic and lipophilic surface, and according to the HG/T5065-2016 standard test, the stain resistance can reach less than 5%, which is far higher than the standard requirement of 15%; further, compared with the widely circulated topcoat varnish on the market, the technical solution adopts a scraping construction method, which avoids the risk of missing coating and blooming, and the construction thickness is higher, providing stronger protection for the main coating.

4. The technical solution of the present invention is applied to topcoat varnish and has an ideal viscosity range (~120-130ku), which changes its construction method from traditional roller coating and spraying to batch coating, and has excellent application prospects.

Detailed ways

In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

The silicone-acrylic emulsion in the embodiment of the present invention is selected from RS-8680 of Badful Company. The emulsion adopts a new generation of LIPN polymerization technology, which is an efficient connection between the core and the shell, and accurately controls the structural morphology of the emulsion particles, thereby giving the paint film high hardness and toughness;

The inorganic lithium magnesium silicate in the embodiment of the present invention is selected from HSJA966HH of Haoshijia New Material Technology Co., Ltd. HSJA 966HH is a powdered rheological additive screened by a special process and activated and modified. When added to water at a concentration of 3-5wt%, it can form a colorless, translucent pseudoplastic slurry. In the formulation system, it can not only prevent sedimentation and sagging, but also greatly improve the smoothness of scraping construction. In addition, there are a large number of terminal hydroxyl groups on the surface of inorganic lithium magnesium silicate, which can form a large number of hydrogen bonds with the carboxylates at the ends of the copolymer silicone acrylic emulsion, which not only improves the density, hardness and scratch resistance of the paint film, but also has a qualitative improvement in the water resistance and anti-fouling properties of the entire coating system.

In the embodiment of the present invention, the bactericide is 2-methyl-4-isothiazoline-3-one; the antifreeze agent is propylene glycol; the thickener is Dow's TT935; and the defoaming agent is polyether-modified dimethylsiloxane.

In the embodiment of the present invention, the preparation method of nano pure silica zeolite is as follows: A composition is sodium hydroxide, aluminum hydroxide and water (sodium hydroxide: aluminum hydroxide: water = 2: 1: 420, n/n/n); B composition is TEOS and TBABr (TEOS: TBABr = 10: 30, n/n/n); then 4500g of A composition is poured into 130g of B composition, stirred for 3h, and aged for 12h to form a seed solution; then the seed solution is placed in a high temperature reactor, reacted at 150°C for 3 days, then transferred to an oven for drying, dried at 100°C, and filtered to obtain a white powder; the white powder is calcined at 600°C for 12h to obtain nano pure silica zeolite. Wherein the nano pure silica zeolite is a rod-like structure with an average long diameter of 5-10um and a wide diameter of 2-4nm.

Example 1

A batch-scraping type multi-colored special double-sided self-cleaning anti-scratch top varnish, comprising the following components in parts by weight:

The preparation method of the above-mentioned scraping-type colorful, specially formulated, double-sided, self-cleaning, scratch-resistant topcoat varnish is as follows: deionized water is added to the reactor according to the above-mentioned mass fractions, and lithium magnesium silicate is added thereto at a rotation speed of 1000 rpm and dispersed for 8 minutes; then, at 600 rpm, the bactericide, antifreeze agent, silicone-acrylic emulsion, film-forming aid and defoaming agent are added to the reactor respectively, stirred for 5 minutes, and then nano-pure silica zeolite is added and dispersed for 8 minutes; finally, the thickener is added, stirred thoroughly, and then the bottom of the reactor is discharged to obtain the product.

Example 2

A batch-scraping type multi-colored special double-sided self-cleaning anti-scratch top varnish, comprising the following components in parts by weight:

The preparation method of the above-mentioned scraping-type colorful, specially formulated, double-sided, self-cleaning, scratch-resistant topcoat varnish is as follows: deionized water is added to the reactor according to the above-mentioned mass fractions, and lithium magnesium silicate is added thereto at a rotation speed of 1200rpm and dispersed for 8 minutes; then, at 800rpm, the bactericide, antifreeze agent, silicone-acrylic emulsion, film-forming aid and defoaming agent are added to the reactor respectively, stirred for 5 minutes, and then nano-pure silica zeolite is added and dispersed for 8 minutes; finally, the thickener is added, stirred thoroughly, and then the material is discharged from the bottom of the reactor to obtain the product.

Example 3

A batch-scraping type multi-colored special double-sided self-cleaning anti-scratch top varnish, comprising the following components in parts by weight:

The preparation method of the above-mentioned scraping-type colorful, specially formulated, double-sided, self-cleaning, scratch-resistant topcoat varnish is as follows: deionized water is added to the reactor according to the above-mentioned mass fractions, and lithium magnesium silicate is added thereto at a rotation speed of 1200rpm and dispersed for 8 minutes; then, at 900rpm, the bactericide, antifreeze agent, silicone-acrylic emulsion, film-forming aid and defoaming agent are added to the reactor respectively, stirred for 10 minutes, and then nano-pure silica zeolite is added and dispersed for 10 minutes; finally, the thickener is added, stirred thoroughly, and then the bottom of the reactor is discharged to obtain the product.

Comparative Example 1

The types of ingredients, mass fractions and preparation methods of Comparative Example 1 are the same as those of Example 1, with the only difference being that the zeolite in Comparative Example 1 is natural zeolite (brand: 4A zeolite powder) in equal mass fractions instead of nano pure silica zeolite.

Comparative Example 2

The types of ingredients, mass fractions and preparation methods of Comparative Example 2 are the same as those of Example 1, with the only difference being that Comparative Example 2 does not contain lithium magnesium silicate.

Test Case

Performance tests were performed on Examples 1-3 and Comparative Examples 1-2.

The test results are shown in Table 1.

As can be seen from Table 1: Examples 1-3, a batch-scratching type multi-colored specially formulated double-sided self-cleaning anti-scratch topcoat varnish, all have very excellent storage stability and construction performance, especially in terms of paint film hardness, scrub resistance and stain resistance, which are significantly better than Comparative Examples 1 and 2. Comparative Example 1 replaces an equal amount of the artificially synthesized nano-pure silicon zeolite of the present invention with commercially available natural 4A zeolite, which has a significant effect on the storage stability of the product and the hardness, stain resistance, scrub resistance and other properties of the paint film. Furthermore, Comparative Example 2 removes the lithium magnesium silicate in the solution of the present invention, and the finished paint has a significant deterioration in construction and storage stability. Overall, this formulation technology has achieved excellent application and performance effects.

It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims (7)

1. A scraping type multi-color special double-sided self-cleaning anti-scratch top varnish, characterized in that the scraping type multi-color special double-sided self-cleaning anti-scratch top varnish comprises the following components in parts by mass: Silicone acrylic emulsion 55.0-65.0 parts Film-forming aid 1.5-2.0 parts Lithium magnesium silicate 3.0-5.0 parts Nano pure silica zeolite 0.5-1.0 parts Additives water; The raw material of the nano pure silica zeolite is a solid product obtained by mixing composition A and composition B and reacting them in a high temperature reactor; Composition A is sodium hydroxide, aluminum hydroxide and water; Composition B is TEOS, TBABr and water; In the composition A, the molar ratio of sodium hydroxide to aluminum hydroxide is 100:1-10; In the B composition, the molar ratio of TEOS to TBABr is 10:3-4; The mass ratio of the composition A to the composition B is 100:1-10:1. 2. The scraping type colorful special double-sided self-cleaning anti-scratch top varnish according to claim 1 is characterized in that the auxiliary agent is selected from one or more of a bactericidal agent, an antifreeze agent, a thickener, and a defoaming agent. 3. The scraping type colorful special double-sided self-cleaning anti-scratch top varnish according to claim 1, characterized in that the film-forming aid is selected from one or more of alcohol ester dodecahydrate, propylene glycol butyl ether, dipropylene glycol methyl ether and benzyl alcohol. 4. The scraping type colorful special double-sided self-cleaning anti-scratch top varnish according to claim 1, characterized in that the size of the nano pure silica zeolite is: long diameter 5-10um; wide diameter 2-4nm. 5. The method for preparing the batch-scratching type multi-color special double-sided self-cleaning anti-scratch topcoat varnish as claimed in any one of claims 1 to 4, characterized in that the preparation method of the nano pure silica zeolite is as follows: S1, pouring composition A into composition B, stirring and aging to form a seed solution; S2, reacting the seed solution in a high temperature reactor, and then drying and filtering; S3, calcining the obtained crude product to obtain a product. 6. The method for preparing the scraping type multi-color double-sided self-cleaning anti-scratch top varnish according to claim 5, characterized in that in step S3, the calcination temperature is 600-800°C. 7. The method for preparing the scraping-type multi-color special double-sided self-cleaning anti-scratch top varnish according to claim 5, characterized in that in step S1, the aging time is 10-20 hours.