CN116875096A - A high-impact inorganic coating and its preparation method - Google Patents

Abstract

The invention discloses a high impact resistant inorganic coating and a preparation method thereof, belonging to the technical field of inorganic coatings, wherein the inorganic coating comprises the following components in parts by weight: 51-68 parts of low-temperature inorganic powder, 1-4 parts of flaky alumina, 2-9 parts of nano zinc oxide and 25-43 parts of pigment. The invention can solve the problems of poor impact resistance, poor brightness of the surface of the coating and poor acid resistance of the inorganic coating; meanwhile, the problems of harmful raw materials to the environment, high preparation cost and the like are solved, the preparation method is efficient and environment-friendly, the cost is low, the impact resistance of the inorganic coating is effectively improved, and the method is widely applied to the fields of high impact resistance such as buildings, household appliances, automobile glass and the like.

Description

A high-impact inorganic coating and its preparation method

Technical field

The invention relates to a high-impact inorganic coating and a preparation method thereof, and belongs to the technical field of inorganic coatings.

Background technique

Inorganic coating is to evenly adhere the slurry to the surface of the object by spraying, printing or other methods, and firmly fix it on the surface of the object using high temperature, infrared or tempering. Among them, screen printing is used to print it on the glass, and is tempered at a temperature of 680 to 720°C to fuse it with the base glass. It not only has the function of decorating and covering objects behind the glass, but also has the function of For other special properties, high-impact inorganic coatings are widely used in the fields of construction, home appliances and automotive glass.

One of the main components of high-impact inorganic coating is low-temperature inorganic powder, which is used together with colorants, additives, and film-forming agents. The film-forming agent evenly disperses the low-temperature inorganic powder into a slurry and coats it on the base glass. During the tempering process, the film-forming agent gradually evaporates. Finally, the low-temperature inorganic powder firmly bonds the colorants, additives, etc. to the base glass to form an inorganic coating. At this stage, the low-temperature inorganic powder needs to have a relatively lower temperature than the base glass in order to bond other inorganic powders during tempering and present a brighter surface. If the temperature of the low-temperature inorganic powder is too low, the coating surface will be bright, but the acid resistance and impact resistance are poor, and cannot meet the impact requirements; if the temperature of the low-temperature inorganic powder is too high, the coating surface will be matte, with poor antifouling ability and poor color. It becomes dark and does not meet the aesthetics required for use. In addition, there are currently many impact-resistant inorganic coatings, but many coating formulations contain environmentally harmful halogens and lead, as well as high-cost bismuth oxide, etc., and most of the coatings have acceptable impact resistance properties. All are poor. Therefore, the present invention provides a high impact-resistant inorganic coating and a preparation method thereof, so that the coating surface has good brightness, good acid resistance, and high impact resistance.

Contents of the invention

In view of the problems existing in the above-mentioned prior art, the present invention provides a high-impact inorganic coating and a preparation method thereof, which can solve the problems of poor impact resistance of the inorganic coating, poor brightness of the coating surface, and poor acid resistance; at the same time It also solves problems such as raw materials being harmful to the environment and high preparation costs.

In order to achieve the above object, the present invention adopts the following technical solution: a high impact inorganic coating, which includes the following components and parts by weight: 51 to 68 parts of low-temperature inorganic powder, 1 to 4 parts of flaky alumina, 2 to 9 parts of nano zinc oxide and 25 to 43 parts of colorant.

Preferably, the softening point of the low-temperature inorganic powder is 450-550°C, and the expansion coefficient is 7-8×10 ^-6 /°C.

Preferably, the low-temperature inorganic powder includes the following components and parts by weight: 9 to 41 parts of quartz, 0 to 21 parts of kaolin, 0 to 28 parts of borax, 1 to 17 parts of boric acid, 0 to 17 parts of zinc oxide, and 1 part of zirconium oxide. ~6 parts, magnesium oxide 1-5 parts, barium oxide 1-6 parts, albite 2-37 parts, potassium oxide 0-14 parts, aluminum oxide 1-4 parts, titanium oxide 0-4 parts.

Preferably, the radial size of the flake alumina is 5-50 μm, and the thickness is 100-500 nm.

Preferably, the particle size of the nano zinc oxide is 10 to 500 nm.

Preferably, the coloring material is black coloring material or white coloring material.

Preferably, the black color material is one or more of ferromanganese black, iron oxide black, copper chrome black, iron chrome black, cobalt black, and carbon black.

Preferably, the white colorant is one or more of titanium white, zinc white, and zinc-barium white.

The invention also provides a method for preparing a high-impact inorganic coating, which includes the following steps:

(1) Preparation of low-temperature inorganic powder: mix quartz, kaolin, borax, boric acid, zinc oxide, zirconium oxide, magnesium oxide, barium oxide, albite, potassium oxide, aluminum oxide, and titanium oxide according to their raw material composition, and then heat it up Perform roasting treatment for 60 minutes to form a homogenized and cleaned melt. The melt is then quenched in deionized ice water to form inorganic slag, which is then wet ball milled for 3 hours, and then dried and screened to obtain low-temperature inorganic powder;

(2) Preparation of inorganic coating slurry: According to its raw material components, mix low-temperature inorganic powder, colorants, nano zinc oxide, flaky alumina, and film-forming agents to form a mixed material, and then coarsely grind the mixed material in sequence. Grind to obtain inorganic coating slurry;

(3) Inorganic coating preparation: Print the inorganic coating slurry on the base glass by screen printing, dry it first to form the inorganic coating semi-finished product, and then temper the inorganic coating semi-finished product for 100 to 400 seconds to obtain High impact inorganic coating.

Preferably, in step (1), the calcination temperature is 1000-1300°C.

Preferably, in step (1), the mesh screen is 300 mesh.

Preferably, in step (3), the thickness of the base glass is 2 to 8 mm.

Preferably, in step (3), the drying temperature is 150-220°C, and the tempering temperature is 680-720°C.

Beneficial effects of the present invention:

1. The low-temperature inorganic powder provided by the present invention has a lower softening point and expansion coefficient. Even after adding colorants with different expansion coefficients, the entire inorganic coating has a more appropriate expansion coefficient, thus ensuring the durability of the inorganic coating. Mechanical strength.

2. The particle size of the nano zinc oxide added in the present invention is extremely small and has a low expansion coefficient, which further improves the brightness of the coating.

3. The flaky alumina added in the present invention can greatly improve the mechanical strength of the coating and maintain a small expansion coefficient. The unique flaky structure can be embedded in the inorganic coating during the impact of the steel ball. Preventing the expansion of cracks further improves the impact resistance of the inorganic coating.

Detailed ways

The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only some of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

The experimental methods in the following examples are all conventional methods unless otherwise specified, and the experimental reagents and materials involved are conventional chemical reagents and materials unless otherwise specified.

A high-impact inorganic coating of the present invention includes the following components and parts by weight: 51 to 68 parts of low-temperature inorganic powder, 1 to 4 parts of flaky alumina, 2 to 9 parts of nano zinc oxide, and 25 to 43 parts of colorants. ; Wherein, the softening point of the low-temperature inorganic powder is 450-550°C, and the expansion coefficient is 7-8×10 ^-6 /°C; the low-temperature inorganic powder includes the following components and parts by weight: 9-41 parts of quartz, kaolin 0 to 21 parts, 0 to 28 parts of borax, 1 to 17 parts of boric acid, 0 to 17 parts of zinc oxide, 1 to 6 parts of zirconium oxide, 1 to 5 parts of magnesium oxide, 1 to 6 parts of barium oxide, 2 to 2 parts of albite 37 parts, potassium oxide 0-14 parts, aluminum oxide 1-4 parts, titanium oxide 0-4 parts; the colorant is black colorant or white colorant.

The invention provides a method for preparing a high-impact inorganic coating. The specific steps are as follows:

(1) Preparation of low-temperature inorganic powder: According to its raw material composition, accurately weigh quartz, kaolin, borax, boric acid, zinc oxide, zirconium oxide, magnesium oxide, barium oxide, albite, potassium oxide, aluminum oxide, and titanium oxide, and Mix evenly to form a mixed powder. After raising the temperature of the muffle furnace to the corresponding firing temperature, put the above mixed powder into the muffle furnace and bake for 60 minutes at the corresponding firing temperature until the solution is homogenized. , after clarification, a uniform melt is formed, and then the melt is poured into deionized ice water and quenched to form inorganic slag, and then a high-speed ball mill is used to wet-grind the inorganic slag with water for 3 hours, dried, and passed through a 300-mesh screen. That is, low-temperature inorganic powder is obtained;

(2) Preparation of inorganic coating slurry: According to its raw material composition, accurately weigh low-temperature inorganic powder, colorants, nano zinc oxide, flaky alumina and film-forming agents, stir evenly to form a mixed material, and then mix the mixed material first Pass through a sand mill for coarse grinding, and then use a three-roller grinder for fine grinding to obtain the inorganic coating slurry.

(3) Preparation of inorganic coating: Use screen printing to print the above-mentioned inorganic coating slurry onto the original piece of glass with a thickness of 2 to 8 mm, and dry it in a high-temperature drying tunnel of 150 to 220°C to obtain a semi-finished product of the inorganic coating. , the semi-finished glass printed with inorganic coating is tempered at 680-720°C for 100-400 seconds to obtain a high-impact inorganic coating.

Preliminary Example Preparation of Low Temperature Inorganic Powder

According to the composition, formula by weight, and firing temperature in Table 1 below, and according to the preparation method of low-temperature inorganic powder of the present invention, low-temperature inorganic powders IP-01, IP-02, IP-0103, IP-04, and IP-05 are obtained. .

Table 1

After testing, the performance parameters of low-temperature inorganic powders IP-01, IP-02, IP-0103, IP-04, and IP-05 are shown in Table 2 below.

Table 2

IP-01 IP-02 IP-03 IP-04 IP-05 Softening temperature range (℃) 496～501 530～535 461～466 477～482 434～439 Expansion coefficient (×10 ^-6 /℃) 7.02 7.29 7.86 7.35 8.44

Inorganic coating slurries prepared in Examples 1 to 4 and Comparative Examples 1 to 6

According to the composition and content in Table 3, according to the preparation method of the inorganic coating slurry of the present invention, the inorganic coating slurries of Examples 1 to 4 and Comparative Examples 1 to 6 are obtained, wherein: the black The coloring material is one or more of ferromanganese black, iron oxide black, copper chrome black, iron chrome black, cobalt black, and carbon black; according to the preparation method of the inorganic coating slurry of the present invention, the radial direction of the flake alumina The size is 5-50 μm and the thickness is 100-500 nm. The alumina used in Comparative Example 5 is spherical alumina with a particle size of 100-500 nm. The zinc oxide used in Comparative Example 6 is micron zinc oxide with a particle size of 0.5-2 μm. .

table 3

Inorganic coating slurries prepared in Examples 5 to 8 and Comparative Examples 7 to 12

According to the composition and content in Table 4 below, according to the preparation method of the inorganic coating slurry of the present invention, the inorganic coating slurries of Examples 1 to 4 and Comparative Examples 1 to 6 are obtained, wherein: the white color The color material is one or more of titanium white, zinc white, and zinc barium white; according to the preparation method of the inorganic coating slurry of the present invention, the radial size of the flake alumina is 5 to 50 μm and the thickness is 100 to 500 nm. The alumina used in Comparative Example 5 is spherical alumina with a particle size of 100 to 500 nm, and the zinc oxide used in Comparative Example 6 is micron zinc oxide with a particle size of 0.5 to 2 μm.

Table 4

Inorganic coatings corresponding to Examples 1 to 8 and Comparative Examples 1 to 12

The inorganic coating slurries prepared in Examples 1 to 8 and Comparative Examples 1 to 12 are obtained according to the preparation method of the inorganic coating of the present invention. For the inorganic coating, 10 copies of each of the inorganic coatings corresponding to Examples 1 to 8 and Comparative Examples 1 to 12 were tested.

1. Glossiness test: Test the coating surface of 1 part of each inorganic coating corresponding to Examples 1 to 48 and Comparative Examples 1 to 5 using a gloss meter (60°).

2. Acid resistance test: 1 part of each inorganic coating corresponding to Example 1 to 8 and Comparative Example 1 to 5 was soaked in 3.7% HCl at room temperature for 30 minutes, and each was compared with its corresponding 1 part of a sample that was not soaked in HCl. .

3. Impact performance layer test: 8 parts of each of the inorganic coatings corresponding to Examples 1 to 8 and Comparative Examples 1 to 4 were placed on a steel frame with a rubber pad, and a 500g steel ball was used to impact the center of the glass surface. Point position, start impacting from a height of 0.1m away from the glass. If the impact does not break once, increase the height by 0.1m and continue impacting until the glass breaks. The height at which at least 6 of the 8 pieces of glass can pass is the impact resistance of the coating. high.

1. The inorganic coating properties corresponding to Examples 1 to 4 and Comparative Examples 1 to 6 are as shown in Table 5 below.

table 5

As can be seen from Table 5 above, compared with Comparative Examples 1 to 6, the softening temperatures and expansion coefficients of the inorganic powders of Examples 1 to 4 of the present invention are within appropriate ranges, according to the given proportions of the present invention. Different amounts of nano-zinc oxide and flake aluminum oxide are added. The impact resistance height of the inorganic coating added with black pigment in the present invention is not less than 1.5m. The glossiness of the coating surface is better than 30. The coating surface is brighter and can be soaked in hydrochloric acid. No discoloration after use, good acid resistance.

Specifically, compared with Example 3, Comparative Example 1 has different low-temperature inorganic powder ratios, but both have relatively low softening temperatures. When the inorganic powders are added in the same ratio, due to the IP- 05 The expansion coefficient of inorganic powder is too large and it does not have a good impact resistance effect. Therefore, the impact resistance height and acid resistance of the inorganic coating in Comparative Example 1 or Comparative Example 7 are significantly reduced. On this basis, Comparative Example 2 adds oxidation With the addition of aluminum, the impact resistance and acid resistance of the inorganic coating in Comparative Example 2 are significantly improved, but the surface gloss of the coating is very poor.

Comparative Example 3 Compared with Example 1, in Comparative Example 1, the nano-zinc oxide was removed from the inorganic coating raw material, and the impact resistance was slightly reduced but not significantly, indicating that zinc oxide provides a part of the impact resistance effect, but the entire inorganic coating coating The surface gloss is significantly reduced, indicating that the addition of nano-zinc oxide makes a greater contribution to the surface brightness of the inorganic coating.

Comparative Example 4 Compared with Example 1, the inorganic coating of Comparative Example 4 removes the flake alumina, the acid resistance is slightly reduced, and the impact resistance is greatly reduced, but it is still relatively slightly higher, indicating that IP-01 with a suitable expansion coefficient has It has a certain impact resistance effect, but the addition of flake alumina greatly improves its impact resistance.

Comparative Example 5 Compared with Example 1, the inorganic coating of Comparative Example 5 uses spherical alumina, which cannot maintain its high impact resistance. Moreover, due to the high melting temperature and large particle size of spherical alumina, it affects other local powders. The heating and leveling of the material results in poor glaze gloss.

Comparative Example 6 Compared with Example 1, the inorganic coating of Comparative Example 5 uses micron zinc oxide, which cannot maintain its high impact resistance. Moreover, due to the high melting temperature and large particle size of micron zinc oxide, it affects other parts of the local area. The heating and leveling of the powder lead to poor glaze gloss.

2. The corresponding inorganic coating properties of Examples 5 to 8 and Comparative Examples 7 to 12 are as shown in Table 6 below.

Table 6

As can be seen from Table 6 above, compared with Comparative Examples 7 to 12, the softening temperatures and expansion coefficients of the inorganic powders of Examples 1 to 4 of the present invention are within appropriate ranges, according to the given proportions of the present invention. Different amounts of nano zinc oxide and flake aluminum oxide are added. The impact resistance height of the inorganic coating added with white pigment in the present invention is not less than 1.7m, the surface gloss of the coating is better than 20, there is no powdering after immersion in hydrochloric acid, and it is acid resistant. better.

Specifically, compared with Example 7, Comparative Example 7 has different low-temperature inorganic powder ratios, but both have relatively low softening temperatures. When the inorganic powders are added in the same ratio, due to the IP- 05 The expansion coefficient of inorganic powder is too large and it does not have a good impact resistance effect. Therefore, the impact resistance height and acid resistance of the inorganic coating in Comparative Example 7 are significantly reduced. On this basis, Comparative Example 2 or Comparative Example 8 adds oxidation With the addition of aluminum, the impact resistance and acid resistance of the inorganic coating in Comparative Example 8 are significantly improved, but the surface gloss of the coating is very poor.

Comparative Example 9 Compared with Example 5, the inorganic coating raw material in Comparative Example 9 removes nano-zinc oxide, and the impact resistance is slightly reduced but not significantly, indicating that zinc oxide provides a part of the impact resistance effect, but the entire inorganic coating The surface gloss of the layer is significantly reduced, indicating that the addition of nano-zinc oxide makes a greater contribution to the surface brightness of the inorganic coating.

Comparative Example 10 Compared with Example 5, the inorganic coating of Comparative Example 4 removes the flake alumina, the acid resistance is slightly reduced, and the impact resistance is greatly reduced, but it is still relatively slightly higher, indicating that IP-01 with a suitable expansion coefficient has It has a certain impact resistance effect, but the addition of flake alumina greatly improves its impact resistance.

Comparative Example 11 Compared with Example 5, the inorganic coating of Comparative Example 11 uses spherical alumina, which cannot maintain its high impact resistance. Moreover, due to the high melting temperature and large particle size of spherical alumina, it affects other local powders. The heating and leveling of the material results in poor glaze gloss.

Comparative Example 12 Compared with Example 5, the inorganic coating of Comparative Example 12 uses micron zinc oxide, which cannot maintain its high impact resistance. Moreover, due to the high melting temperature and large particle size of micron zinc oxide, it affects other parts of the local area. The heating and leveling of the powder lead to poor glaze gloss.

In summary, the low-temperature inorganic powder prepared by the present invention has a relatively low expansion coefficient, and the addition of flaky alumina and nano-zinc oxide further reduces the expansion coefficient of the coating and increases the matching degree between the coating and the base glass. ; Flake alumina has high hardness and mechanical strength, and its unique morphology prevents crack expansion during impact; Nano-zinc oxide greatly increases the gloss of the inorganic coating. The preparation process of the present invention is efficient, environmentally friendly, and low-cost, can effectively ensure the acid resistance of the inorganic coating, has excellent coating surface brightness, and effectively improves the impact resistance of the inorganic coating. After printing the inorganic coating and tempering Use a 500g steel ball to impact the glass surface, which can meet the impact of at least 1.5m height without breaking.

Finally, it should be noted that the above embodiments are only used to illustrate rather than limit the technical solutions of the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that the present invention can still be modified or equivalently substituted. , any modification or partial replacement without departing from the spirit and scope of the present invention shall be covered by the claims of the present invention.

Claims (10)

1. The high impact resistance inorganic coating is characterized by comprising the following components in parts by weight: 51-68 parts of low-temperature inorganic powder, 1-4 parts of flaky alumina, 2-9 parts of nano zinc oxide and 25-43 parts of pigment.

2. The high impact inorganic coating according to claim 1, wherein the low temperature inorganic powder has a softening point of 450 to 550 ℃ and an expansion coefficient of 7 to 8 x 10 ^-6 /℃。

3. The high impact inorganic coating according to claim 1, wherein the low temperature inorganic powder comprises the following components in parts by weight: 9-41 parts of quartz, 0-21 parts of kaolin, 0-28 parts of borax, 1-17 parts of boric acid, 0-17 parts of zinc oxide, 1-6 parts of zirconium oxide, 1-5 parts of magnesium oxide, 1-6 parts of barium oxide, 2-37 parts of albite, 0-14 parts of potassium oxide, 1-4 parts of aluminum oxide and 0-4 parts of titanium oxide.

4. The high impact inorganic coating according to claim 1, wherein the radial dimension of the flaky alumina is 5-50 μm and the thickness is 100-500 nm; the particle size of the nano zinc oxide is 10-500 nm.

5. A high impact inorganic coating according to claim 1, wherein the colorant is a black colorant or a white colorant.

6. The high impact inorganic coating according to claim 5, wherein the black pigment is one or more of manganese iron black, iron oxide black, copper chromium black, iron chromium black, cobalt black, and carbon black.

7. The high impact inorganic coating according to claim 5, wherein the white pigment is one or more of titanium white, zinc white, lithopone.

8. A process for the preparation of a high impact resistant inorganic coating according to any one of claims 1 to 7, characterized in that it comprises the following steps:

(1) Preparing low-temperature inorganic powder: mixing quartz, kaolin, borax, boric acid, zinc oxide, zirconium oxide, magnesium oxide, barium oxide, albite, potassium oxide, aluminum oxide and titanium oxide according to the raw material composition, heating and roasting for 60min to form homogenized and washed molten liquid, placing the molten liquid into deionized ice water for water quenching to form inorganic slag, wet ball grinding for 3h, drying and screening to obtain low-temperature inorganic powder;

(2) Preparing inorganic coating slurry: mixing low-temperature inorganic powder, pigment, nano zinc oxide, flaky alumina and a film forming agent according to raw material components to form a mixed material, and sequentially carrying out coarse grinding and grinding on the mixed material to obtain inorganic coating slurry;

(3) And (3) preparing an inorganic coating: printing the inorganic coating slurry on the base glass in a screen printing mode, firstly drying to form an inorganic coating semi-finished product, and then tempering the inorganic coating semi-finished product for 100-400 s to obtain the high impact resistance inorganic coating.

9. The method for producing a high impact-resistant inorganic coating according to claim 8, wherein in the step (1), the baking temperature is 1000 to 1300 ℃; the mesh screen was 300 mesh.

10. The method for producing a high impact-resistant inorganic coating according to claim 8, wherein in the step (3), the thickness of the base glass is 2 to 8mm; the drying temperature is 150-220 ℃, and the tempering temperature is 680-720 ℃.