CN116875136A - 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 kind of scratch-type multi-colored specially equipped double self-cleaning anti-scratch top varnish and its preparation method

Technical field

The invention belongs to the field of coatings, and specifically relates to a scratch-type, multi-colored, specially formulated double self-cleaning, anti-scratch finish 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, economy, durability, environmental protection and safety. Colorful coatings such as water-in-water and water-in-sand are the most popular products in the current coating market because of their realistic stone-like effects and green and environmentally friendly properties. Currently, most of the colorful paint supporting topcoats currently on the market are sprayed and roller coated. As we all know, although spraying and roller coating are more efficient than batch construction, uneven construction often leads to problems with the overall wall surface, requiring rework, which consumes a lot of manpower, material resources and time costs. In addition, as the last line of defense for building facades, coatings are easily impacted by external forces. The top varnishes currently available in the market only have simple dust-proof and stain-proof properties, but cannot protect the main coating from damage. The function of being scratched or broken.

In addition, in the existing technology, the top varnish specially used for colorful paints is mainly sprayed and roller coated. First of all, because the dry film of the top varnish is transparent, uneven application often leads to blooming problems. ; Secondly, it is difficult to achieve a thick coating of top varnish for roller coating and spraying, and the multi-colored main paint is not sufficiently covered, which can easily lead to problems such as water whitening, contamination and poor weather resistance; currently, the multi-colored special cover used for spraying and roller coating The surface viscosity is low, and in order to save costs on the construction site, it needs to be mixed with water before use, often causing application problems such as sagging and delamination. Finally, the existing colorful dust-proof topcoats are only dustproof, water-resistant, etc. Function, it does not have protective functions such as scratch resistance and wear resistance, and cannot truly meet all performance requirements for building exterior wall decoration.

Compared with roller coating and spraying construction, the product for batch scraping construction needs to have a suitable viscosity to facilitate loading; in addition, the product for batch scraping construction also needs a moderate thixotropy to avoid sticking to the knife. It also needs a certain degree of smoothness and small scraping resistance. However, the viscosity of the finished product of existing technology products is generally controlled between 50-70ku. On the one hand, this viscosity cannot be scraped for construction. On the other hand, based on the existing technology products, the viscosity of the finished product is thickened. When the scraping viscosity is reached, which is between 110-120ku, 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 shortcomings in the technology of existing related products, it is urgent to develop a new technical solution to solve the above shortcomings.

Contents of the invention

Starting from the above existing application technical problems, the present invention provides a batch-scraping type multi-colored special-fit double self-cleaning anti-scratch top varnish and a preparation method thereof, which not only solves the problem of construction blooming, but also improves the quality of the paint film. The fullness, imitation stone effect is more realistic, and the anti-staining and weathering resistance are better. It is particularly emphasized that the overcoat varnish provided by the technology of the present invention has excellent hardness, the paint film hardness can reach 3H and above, and has good scratch resistance and wear resistance. Brings all-round protection to the building's facade.

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

Auxiliary

water;

Wherein, the raw material of the nano-pure silica zeolite is a solid product obtained by blending composition A and composition B and reacting in a high-temperature reactor;

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

In the present invention, copolymerized silicone-acrylic emulsion with high cross-linking density is used as the main film-forming material, and at the same time, inorganic magnesium lithium silicate and artificially synthesized nano-zeolite are added to the formula system as functional transparent fillers. The result is a hydrophilic and lipophilic double self-cleaning anti-scratch varnish film.

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

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

a. The main film-forming substance provides a hydrophobic and lipophilic surface; b. Coating with synthetic nano-zeolite and forming a strong hydrogen bonding force; c. Provides the main properties of dustproof, water-resistant, and artificial climate aging resistance of the overcoat varnish. .

The main functions of inorganic lithium magnesium silicate include: a. Providing thixotropic anti-settling properties so that the synthetic pure silicon nanozeolite will not settle in the coating system; b. Optimizing construction performance and providing a solution for the scraping construction of top varnish. Smoothness and anti-sag performance; c. The water-bound hydroxyl group at the end provides hydrophilic properties to the paint film, and has a hydrogen bonding force with the emulsion to improve the density and hardness of the paint film, thereby achieving better water resistance and Anti-stain and anti-scratch properties.

The functions of artificially synthesized nano-pure silica zeolite include: a. Coating in a copolymerized high-crosslinking-density silicone-acrylic emulsion film to improve the hardness and scratch resistance of the paint film; b. The surface has a large number of bound water hydroxyl groups, which interact with There are extremely strong hydrogen bonding forces between emulsions, which can improve the density of the paint film; c. A large number of water-binding hydroxyl groups at the ends provide a hydrophilic surface for the paint film and improve the anti-fouling performance of the paint film.

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

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

The antifreeze is selected from one or more types 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 silicone.

Further, the film-forming assistant is selected from one or more of the alcohol ester dodecanol, propylene glycol butyl ether, dipropylene glycol methyl ether and benzyl alcohol.

Further, 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 preparation method for the above-mentioned batch-scraping multi-color special-fit double self-cleaning anti-scratch finish varnish. The preparation method is as follows:

S1. Pour composition A into composition B, stir and age to form a seed crystal solution;

S2. React the seed crystal solution in a high-temperature reactor, then dry and filter;

S3. Calculate the crude product to obtain the product.

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

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

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

Further, in step S1, the aging time is 10-20h.

The invention has the following beneficial effects:

1. The nanometer pure silicalite zeolite of the present invention is artificially synthesized and is used in top varnish for the first time. Compared with random natural zeolites, it has the advantages of rod-like microstructure, uniform size, regular morphology, and large specific surface area; and the surface of synthetic zeolites has a large number of water-bound hydroxyl groups, which is consistent with the copolymerized silicone acrylic emulsion. The terminal carboxyl groups form hydrogen bonds, allowing the emulsion to tightly coat the surface of the nanozeolite particles, which not only improves the hardness of the paint film, but also 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 nanozeolite have a large number of water-bound hydroxyl groups at the ends. After the two are combined, they have a hydrophilic surface. The final top varnish is The hydrophilic and lipophilic surface has excellent self-cleaning properties in the face of complex pollution sources in the air; and the thixotropy and anti-sedimentation of nano-magnesium lithium silicate make nano-pure silica zeolite and copolymerized highly cross-linked silica acrylic The compatibility of the two emulsions is better, and the three of them work together to make the system more stable and the effect more prominent.

3. The present invention obtains a top varnish that can be applied by scraping, and the hardness of the paint film can reach 3H and above, with excellent wear resistance and scratch resistance; secondly, the paint film has hydrophilic and lipophilic properties. On the surface, according to the HG/T5065-2016 standard test, the stain resistance can reach within 5%, which is much higher than the 15% required by the standard; further, compared with the large circulation cover varnish on the market, this technical solution uses The scraping construction method avoids the risk of missed 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 used in top varnish and has an ideal viscosity range (~120-130ku), so that its construction method changes from traditional roller coating and spraying to scraping construction, with excellent applicability. prospect.

Detailed ways

In order to illustrate the technical solution of the present invention more clearly, the following examples are enumerated. The raw materials, reactions and post-treatment methods appearing in the examples, unless otherwise stated, are all common raw materials on the market, as well as technical means 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 Bardford Company. This 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 form of the emulsion particles, thus giving The paint film has high hardness and toughness;

The inorganic magnesium lithium silicate in the embodiment of the present invention is selected from HSJA966HH of Haoshijia New Material Technology Co., Ltd. HSJA 966HH is a powder-type rheology additive screened by a special process and activated and modified. The amount added in water At a concentration of 3-5wt%, a colorless translucent pseudoplastic slurry can be formed. In the formula system, it can not only prevent sinking 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 magnesium lithium silicate, which can form a large number of hydrogen bonds with the carboxylates at the terminals of the copolymerized silicone acrylic emulsion, which not only improves the density, hardness and scratch resistance of the paint film, but also has a positive effect on the entire The water resistance and anti-fouling properties of the coating system have also been qualitatively improved.

In the embodiment of the present invention, the fungicide is 2-methyl-4-isothiazolin-3-one; the antifreeze is propylene glycol; the thickener is Dow's TT935; the defoaming agent is polyether modified dimethyl Silicone.

In the embodiment of the present invention, the preparation method of nano-pure silicalite is as follows: Composition A 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 pour 4500g of A composition into 130g of B composition, stir for 3h, and age for 12h , to form a seed crystal solution; then put the seed crystal solution into a high-temperature reaction kettle, react at 150°C for 3 days, then transfer to an oven to dry, dry at 100°C, and filter to obtain a white powder; The white powder was calcined at 600°C for 12 hours to obtain nano-pure silicalite. Among them, nano-pure silicalite zeolites are all rod-shaped structures, with an average long diameter of 5-10um and a wide diameter of 2-4nm.

Example 1

A batch-scraping type multi-colored specially formulated double self-cleaning anti-scratch top varnish, which includes the following ingredients in parts by mass:

The preparation method of the above-mentioned batch-scraping type multi-colored special double self-cleaning anti-scratch varnish is as follows: according to the above mass parts, add deionized water to the reaction kettle, and add magnesium lithium silicate at a rotation speed of 1000 rpm. Among them, disperse for 8 minutes; then add the fungicide, antifreeze, silicone-acrylic emulsion, film-forming aid and defoaming agent to the reactor at 600 rpm, stir for 5 minutes, then add the nano-pure silicalite and disperse for 8 minutes; finally Add the thickener, stir thoroughly, and then discharge the material from the bottom of the kettle to obtain the product.

Example 2

A batch-scraping type multi-colored specially formulated double self-cleaning anti-scratch top varnish, which includes the following ingredients in parts by mass:

The preparation method of the above-mentioned batch-scraping multi-color specially formulated double self-cleaning anti-scratch varnish is as follows: according to the above mass parts, add deionized water to the reaction kettle, and add magnesium lithium silicate at a rotation speed of 1200 rpm. Among them, disperse for 8 minutes; then add the fungicide, antifreeze, silicone-acrylic emulsion, film-forming aid and defoaming agent to the reactor at 800 rpm, stir for 5 minutes, then add the nano-pure silicalite and disperse for 8 minutes; finally Add the thickener, stir thoroughly, and then discharge the material from the bottom of the kettle to obtain the product.

Example 3

A batch-scraping type multi-colored specially formulated double self-cleaning anti-scratch top varnish, which includes the following ingredients in parts by mass:

The preparation method of the above-mentioned batch-scraping multi-color specially formulated double self-cleaning anti-scratch varnish is as follows: according to the above mass parts, add deionized water to the reaction kettle, and add magnesium lithium silicate at a rotation speed of 1200 rpm. Among them, disperse for 8 minutes; then add the fungicide, antifreeze, silicone-acrylic emulsion, film-forming aid and defoaming agent to the reactor at 900 rpm, stir for 10 minutes, then add the nano-pure silicalite and disperse for 10 minutes; finally Add the thickener, stir thoroughly, and then discharge the material from the bottom of the kettle to obtain the product.

Comparative example 1

The component types, mass fractions and preparation methods of Comparative Example 1 are the same as those of Example 1. The only difference is that the zeolite in Comparative Example 1 is natural zeolite (brand name: 4A zeolite powder) instead of nanopure in equal mass fractions. Silicalite.

Comparative example 2

The component types, mass parts, and preparation methods of Comparative Example 2 are the same as those of Example 1. The only difference is that Comparative Example 2 does not contain magnesium lithium silicate.

test case

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

The test results are shown in Table 1.

It can be seen from Table 1 that Examples 1-3, a batch-scraping multi-color specially formulated double self-cleaning anti-scratch top varnish, have very excellent storage stability and construction performance, especially in terms of paint film hardness. In terms of washing resistance and stain resistance, it is obviously better than Comparative Example 1 and Comparative Example 2. Comparative Example 1: The artificially synthesized nano-pure silica zeolite of the present invention is replaced with commercially available natural 4A zeolite in equal amounts, which has a significant impact on the storage stability of the product and the hardness, stain resistance, and wash resistance of the paint film. Furthermore, in Comparative Example 2, the magnesium lithium silicate in the solution of the present invention was removed, and the finished paint was significantly worse in terms of construction and storage stability. Overall, this formula technology has achieved excellent application and performance results.

It is obvious to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, and that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention. Therefore, the embodiments should be regarded as illustrative and non-restrictive from any point of view, and the scope of the present invention is defined by the appended claims rather than the above description, and it is therefore intended that all claims falling within the claims All changes within the meaning and scope of equivalent elements are included in the present invention.

In addition, it should be understood that although this specification is described in terms of implementations, not each implementation only contains an independent technical solution. This description of the specification is only for the sake of clarity, and those skilled in the art should take the specification as a whole. , the technical solutions in each embodiment can also be appropriately combined to form other implementations that can be understood by those skilled in the art.

Claims (9)

1. A batch-scraping type multi-colored special-matched double self-cleaning anti-scratch finish varnish, characterized in that the batch-scraping type multi-color special-matched double self-cleaning anti-scratch finish varnish includes the following mass parts: Wherein, the raw material of the nano-pure silica zeolite is a solid product obtained by blending composition A and composition B and reacting in a high-temperature reactor; Composition A is sodium hydroxide, aluminum hydroxide and water; composition B is TEOS, TBABr and water. 2. The batch-scraping type multi-colored special-matched double self-cleaning anti-scratch varnish according to claim 1, characterized in that the auxiliary agent is selected from a bactericide, an antifreeze agent, a thickener, and a defoaming agent. or more. 3. The batch-scraping type multi-colored special-matched double self-cleaning anti-scratch varnish according to claim 1, characterized in that the film-forming assistant is selected from the group consisting of alcohol ester dodecyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether and One or more types of benzyl alcohol. 4. The batch-scraping type multi-colored special-matched double self-cleaning anti-scratch varnish according to claim 1, characterized in that the size of the nano-pure silicalite is: long diameter 5-10um; wide diameter 2-4nm. 5. The preparation method of the batch-scraping type multi-colored specially formulated double self-cleaning anti-scratch varnish according to any one of claims 1 to 4, characterized in that the preparation method of the nano-pure silicalite is as follows: S1. Pour composition A into composition B, stir and age to form a seed crystal solution; S2. React the seed crystal solution in a high-temperature reactor, then dry and filter; S3. Calculate the crude product to obtain the product. 6. The preparation method of the batch-scraping type multi-colored special-matched double self-cleaning anti-scratch varnish according to claim 5, characterized in that in the A composition, the molar ratio of sodium hydroxide and aluminum hydroxide is 100 :1-10. 7. The preparation method of the batch-type multi-colored special-matched double-hand-cleaning anti-scratch varnish according to claim 5, characterized in that in the B composition, the molar ratio of TEOS and TBABr is 10:3-4 . 8. The preparation method of the batch-type multi-colored special-matched double-hand-cleaning anti-scratch varnish according to claim 5, characterized in that in step S3, the calcination temperature is 600-800°C. 9. The preparation method of the batch-type multi-colored special-matched double-hand-cleaning anti-scratch varnish according to claim 5, characterized in that in step S1, the aging time is 10-20 h.