CN107556832B - Coating material having water repellent and easy-to-clean characteristics and method for forming coating layer using the same - Google Patents

Abstract

The invention provides a coating material with water repellent and easy-to-clean characteristics and a method for forming a coating layer using the coating material. The coating with the water repellent easy-cleaning characteristic comprises: the polyvinyl alcohol is converted from hydrophilic property to water repellent property and is easy to clean. The steps of the method for forming a coating layer using the coating material having the water repellent easy-to-clean property are as follows. A substrate is provided. Coating the gap filler on the base material and drying. The coating of the invention is coated on the joint mixture. Finally, drying at high temperature to form a coating using the water-repellant easy-clean coating of the present invention. The invention has better durability and the characteristic of easy cleaning of water repellency.

Description

Paint with water-repellent and easy-cleaning properties and formation of coating using same method

technical field

The invention relates to a paint and a method for forming a coating using the paint, in particular to a paint with water-repellent and easy-to-clean properties and a method for forming a coating using the paint.

Background technique

In the existing water and oil repellent technologies, fluororesins or silicone resins are mostly used for surface treatment, but due to the small molecular weight and poor film-forming properties of such fluororesins or silicone resins, when the above-mentioned fluororesins or silicone resins are coated with When the cloth is placed on the surface of a porous substrate, it is easy to penetrate into the pores, so it cannot completely cover the surface of the substrate to form a continuous coating surface. In addition, due to the poor chemical reactivity of small molecule fluororesin or silicone resin, it is not easy to form a good bond with the surface of the coated substrate, so the durability is poor, and it is easy to repel water after several times of wiping. The clean characteristics will gradually disappear due to the destruction of the fluororesin or silicone resin coating. Therefore, when removing the marks caused by the oil-based pen, the ink of the oil-based pen will penetrate into the substrate from the damaged coating, causing irremovable marks. In addition, when the above-mentioned fluororesin or silicone resin is used to coat the surface of a porous substrate, it will change the touch of the surface, which is not conducive to commercial sales. In this way, it will become important in the future to provide a coating with water-repellent and easy-to-clean properties and good durability, and to process the coating on the surface of a porous substrate to form a durable, water-repellent and easy-to-clean coating. a subject.

Contents of the invention

The invention provides a coating with water-repellent and easy-to-clean properties and a method for forming a coating using the coating, which has better durability and water-repellent and easy-to-clean properties.

The invention provides a paint with water-repellent and easy-to-clean properties, which includes: full-hydrolysis polyvinyl alcohol (PVA) and hydrogen-containing silicone resin (Hydrogen silicone). The degree of polymerization of the fully hydrolyzed polyvinyl alcohol is between 300 and 2600. The weight ratio of the fully hydrolyzed polyvinyl alcohol to the hydrogen-containing silicone resin is 0.5 to 4 times. The hydrogen-containing silicone resin reacts with the fully hydrolyzed polyvinyl alcohol to make the fully hydrolyzed polyvinyl alcohol change from a hydrophilic property to a water-repellent and easy-to-clean property.

In an embodiment of the present invention, the coating with water-repellent and easy-to-clean properties further includes: a crosslinking agent and a leveling aid. The content of the crosslinking agent is 0.1-30 weight percent of the coating. The content of the leveling aid is 0.1-30% by weight of the coating.

In an embodiment of the present invention, the crosslinking agent includes glyoxal aqueous solution, glutaraldehyde aqueous solution, boric acid aqueous solution, borax aqueous solution, aqueous isocyanate or a combination thereof.

In an embodiment of the present invention, the degree of polymerization of the fully hydrolyzed polyvinyl alcohol is between 1400-2600.

The invention provides a method for forming a coating with water-repellent and easy-to-clean properties, the steps comprising:

(1) Provide the base material.

(2) selectively coating a caulking agent on the base material, and then performing a first drying treatment.

(3) Coating a coating with water-repellent and easy-to-clean properties on the caulking agent, and then performing a second drying treatment to form the coating with water-repellent and easy-to-clean properties. The paint with water-repellent and easy-to-clean properties includes: fully hydrolyzed polyvinyl alcohol and hydrogen-containing silicone resin. The degree of polymerization of the fully hydrolyzed polyvinyl alcohol is between 300 and 2600. The weight ratio of the fully hydrolyzed polyvinyl alcohol to the hydrogen-containing silicone resin is 0.5 to 4 times. The hydrogen-containing silicone resin reacts with the fully hydrolyzed polyvinyl alcohol to make the fully hydrolyzed polyvinyl alcohol change from a hydrophilic property to a water-repellent and easy-to-clean property.

In an embodiment of the present invention, the substrate includes wallpaper, fabric, glass, wall or a combination thereof.

In an embodiment of the present invention, the caulking agent includes a water-soluble polymer, an aqueous emulsion, the paint with water-repellent and easy-to-clean properties, or a combination thereof.

In an embodiment of the present invention, the water-soluble polymer includes polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) or a combination thereof. The aqueous emulsion includes polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), acrylic resin (Acrylic resin) emulsion, polyurethane (PU) emulsion or a combination thereof.

In one embodiment of the present invention, the step of coating the caulking agent on the substrate includes coating one or more layers of the caulking agent.

In an embodiment of the present invention, the temperature of the second drying treatment is between 130° C. and 170° C., and the time of the second drying treatment is between 3 minutes and 10 minutes.

Based on the above, the present invention provides a coating, which utilizes fully hydrolyzed polyvinyl alcohol and hydrogen-containing silicone resin to react and bond, so that the fully hydrolyzed polyvinyl alcohol changes from hydrophilic property to water-repellent and easy-to-clean property. Due to the chemical bond between the fully hydrolyzed polyvinyl alcohol and the hydrogen-containing silicone resin, the coating to which it belongs has better durability, and also has the property of repelling water and being easy to clean. In addition, polyvinyl alcohol is inherently resistant to oily solvents and has better adhesion to most substrate surfaces, thus providing additional durability and easy-cleaning properties. In addition, the present invention also provides a method for forming a coating layer using the paint. In the forming method, the caulking agent is first coated on the base material, and then the paint is coated on the caulking agent. Since the caulk fills the pores in the substrate, it allows subsequently applied paint to form a continuous surface. In this way, the present invention can prevent the ink of the oil-based pen from penetrating into the pores of the base material in the prior art, thereby improving the water-repelling and easy-cleaning ability of the coating.

In order to make the above-mentioned features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail with reference to the accompanying drawings.

Description of drawings

Fig. 1 is a schematic cross-sectional view of a coating according to an embodiment of the present invention.

Reference signs:

100: substrate;

102: caulking agent;

104: Coating.

Detailed ways

An embodiment of the present invention provides a paint with water-repellent and easy-to-clean properties, which includes fully hydrolyzed polyvinyl alcohol and hydrogen-containing silicone resin. Since polyvinyl alcohol is rich in hydroxyl groups (ie, OH functional groups), it can undergo a dehydration reaction with the hydrogen-containing silicone resin and bond to the main chain of the hydrogen-containing silicone resin. The so-called fully hydrolyzed polyvinyl alcohol means that the hydrophobic acetic acid groups in polyvinyl alcohol acetate are hydrolyzed into hydrophilic hydroxyl groups to form polyvinyl alcohol, and the degree of hydrolysis of polyvinyl alcohol acetate is greater than or equal to 95% molar ratio . Because the hydroxyl group in the fully hydrolyzed polyvinyl alcohol is hydrophilic, it itself has the characteristics of oily solvent resistance, and has better adhesion with most substrate surfaces, therefore, oily ink (such as oil-based pen or other oily stains) will not penetrate into paints composed of fully hydrolyzed polyvinyl alcohol. In this way, it can improve the durability and easy-cleaning properties of the paint. In addition, because the fully hydrolyzed polyvinyl alcohol reacts with the hydrogen-containing silicone resin to bond, it makes the fully hydrolyzed polyvinyl alcohol change from a hydrophilic property to a water-repellent and easy-to-clean property. Therefore, compared with the small molecule fluororesin or silicone resin in the prior art, the coating of this embodiment has better durability, and also has the characteristics of water repellency and easy cleaning. The so-called durability means that the coating will not reduce its water-repellent and easy-to-clean properties due to wiping. The descriptions of the various components included in the coating of this embodiment are as follows, and the examples and contents of the various components listed are only for illustrative purposes, and are not intended to limit the present invention.

The weight ratio of the fully hydrolyzed polyvinyl alcohol and the hydrogen-containing silicone resin in this embodiment is 0.5-4 times. The fully hydrolyzed polyvinyl alcohol refers to polyvinyl alcohol with a degree of hydrolysis greater than or equal to 95%, and its degree of polymerization may be, for example, 300-2600. In one embodiment, the degree of polymerization of the fully hydrolyzed polyvinyl alcohol may be, for example, 1400-2600.

The overall solid content of the water-repellent and easy-to-clean coating of this embodiment may be, for example, 1%˜30%. In one embodiment, the overall solid content of the water-repellent and easy-to-clean paint may be, for example, 10%-20%. The hydrogen-containing silicone resin refers to a silicone resin having Si-H chemical bonds in the silicone resin structure. The position of the Si-H chemical bond in the hydrogen-containing silicone resin can be a terminal group, a side group, or both, but the present invention is not limited thereto. The terminal group means that the Si-H chemical bond is located at the end of the hydrogen-containing silicone resin polymer chain; and the side group means that the Si-H chemical bond is located at the side of the hydrogen-containing silicone resin polymer chain. In one embodiment, the hydrogen-containing silicone resin may be, for example, methyl hydrogen silicone, ethylhydrogen silicone or a combination thereof.

In addition, the water-repellent and easy-to-clean coating of this embodiment may optionally include a crosslinking agent and a leveling aid. The content of the crosslinking agent is 0.1-30 weight percent of the coating. A cross-linking agent can be mixed with the fully hydrolyzed polyvinyl alcohol aqueous solution, which can be cross-linked with the fully hydrolyzed polyvinyl alcohol after drying, so as to improve the water resistance and strength of the coating. In addition, when not cross-linked, part of the cross-linking agent can also be used as an antibacterial agent. In one embodiment, the crosslinking agent can be, for example, glyoxal aqueous solution, glutaraldehyde aqueous solution, boric acid aqueous solution, borax aqueous solution, aqueous isocyanate or a combination thereof, as long as the crosslinking agent capable of crosslinking polyvinyl alcohol can be used. The crosslinking agents can be used alone or in combination, and the present invention is not limited thereto. The content of the leveling aid is 0.1-30% by weight of the coating. Leveling aids can be used to make the coating self-leveling evenly and covering the surface of the substrate after being coated on the substrate. In one embodiment, the leveling aid can be, for example, isopropyl alcohol, ethylene glycol, butylene glycol, dipropylene glycol monomethyl ether, modified silicone resin (such as BYK-333), acrylic copolymer (such as BYK- 3440) or other suitable materials, as long as the leveling aid can help the coating to level. The leveling aids can be used alone or in combination, and the present invention is not limited thereto.

FIG. 1 is a schematic cross-sectional view of the manufacturing process of a coating according to an embodiment of the present invention.

The present invention provides a method for forming the coating layer 104 using the paint, the steps of which are as follows. First, a substrate 100 is provided. In one embodiment, the substrate 100 can be, for example, wallpaper, fabric, glass, wall or a combination thereof. But the present invention is not limited thereto, as long as the coating can be coated thereon, the type of the substrate 100 can be selected according to requirements.

Next, the caulking agent 102 can be selectively coated on the substrate 100, and a first drying process is performed. The function of the caulking agent 102 is to fill the pores in the substrate 100 , so as to prevent the continuous coating 104 from being formed on the surface of the substrate 100 due to the leakage of the pores during subsequent coating. In one embodiment, the step of coating the sealant 102 on the substrate 100 may be, for example, coating one layer or multiple layers of the sealant 102 . The caulking agent 102 can be, for example, a water-soluble polymer, an aqueous emulsion, the paint with water-repellent and easy-to-clean properties, or a combination thereof. In one embodiment, the water-soluble polymer may be, for example, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) or a combination thereof. The aqueous emulsion can be, for example, polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), acrylic resin (Acrylic resin) emulsion, polyurethane (PU) emulsion or combinations thereof. The caulking agent 102 can be used depending on the characteristics of different substrates. It can be used alone or in combination with a variety of caulking agents 102, as long as the compatibility of the ingredients in the caulking agent 102 allows, The present invention is not limited thereto. In other embodiments, the caulking agent 102 can also be, for example, a water-insoluble molecule, a non-aqueous emulsion, or a combination thereof. In one embodiment, the temperature of the first drying treatment is between 130°C and 170°C. The time for the first drying treatment is between 3 minutes and 10 minutes.

In addition, additives can also be optionally added to the caulking agent 102 to adjust the surface tension of the caulking agent 102 , so that the caulking agent 102 has a smooth surface. In one embodiment, the additive may include a silicone-based material. The silicone-based material may be, for example, polyether-modified dimethyl silicone resin, polyether-modified phenylmethyl silicone resin, polyether-modified polysiloxane, or a combination thereof. But the present invention is not limited thereto, as long as the surface tension of the caulking agent 102 can be adjusted, the types of additives can be selected according to requirements.

Afterwards, the paint is coated on the caulking agent 102 . In one embodiment, the step of coating the paint on the caulk 102 may be, for example, coating one layer or multiple layers of paint. The paint includes fully hydrolyzed polyvinyl alcohol and hydrogen-containing silicone resin. The degree of polymerization of the fully hydrolyzed polyvinyl alcohol in this embodiment is between 300-2600. In one embodiment, the degree of polymerization of the fully hydrolyzed polyvinyl alcohol is between 1400-2600. The weight ratio of the fully hydrolyzed polyvinyl alcohol to the hydrogen-containing silicone resin is 0.5 to 4 times. In one embodiment, the hydrogen-containing silicone resin may be, for example, methyl hydrogen silicone resin, ethyl hydrogen silicone resin or a combination thereof.

In addition, the coating of this embodiment may optionally include a cross-linking agent and a leveling aid. The content of the crosslinking agent is 0.1-30 weight percent of the coating. In one embodiment, the crosslinking agent may be, for example, glyoxal aqueous solution, glutaraldehyde aqueous solution, boric acid aqueous solution, borax aqueous solution, aqueous isocyanate or a combination thereof. The content of the leveling aid is 0.1-30% by weight of the coating. In one embodiment, the leveling aid can be, for example, isopropyl alcohol, ethylene glycol, butylene glycol, dipropylene glycol monomethyl ether, modified silicone resin (such as BYK-333), acrylic copolymer (such as BYK- 3440) or other suitable materials.

Next, a second drying treatment is performed, so that the fully hydrolyzed polyvinyl alcohol reacts with the hydrogen-containing silicone resin to form a coating 104 with water-repellent and easy-to-clean properties on the caulking agent 102 . In one embodiment, the temperature of the second drying treatment is between 130°C and 170°C. The time for the second drying treatment is between 3 minutes and 10 minutes. In one embodiment, the temperature of the second drying treatment may be between 150° C. and 170° C.

In order to specifically illustrate the coating of the present invention and the coating 104 using the coating, experimental examples and comparative examples are listed below to illustrate the preparation method of the coating of the present invention and the formation method and characteristics of the coating 104 using the coating, wherein The content of each component and the production steps are for illustration only, and should not be used to limit the present invention.

"Experimental Example 1~4"

Material Description

1. PVA1: 10% by weight fully hydrolyzed resin with a degree of polymerization of 1700.

2. PVA2: 20% by weight fully hydrolyzed resin with a polymerization degree of 300.

3. PVA3: 10% by weight of partially hydrolyzed resin, with a degree of polymerization of 500.

4. Acrylic emulsion: the one selected in Table 1 is a styrene-acrylic copolymer resin emulsion with a solid content of 47±1%.

5. Water-based PU resin: water-based PU resin with a solid content of 35±1%.

6. Hydrogen-containing silicone resin: silicone resin emulsion with 50% active ingredient.

7. Fluororesin: It is a C6 fluorocarbon copolymer with a solid content of 20±1%.

Implementation

The compositions in Experimental Examples 1-4 and Comparative Examples 1-4 were coated on 50mm×150mm plain glass with a #14 wire bar by the wire bar coating method, and then heated in a hot air drying oven at 150°C for 5 minutes. Dry under the same conditions, which is the test piece.

Evaluation method

A. Water drop angle: Use a water drop contact angle measuring instrument to measure the water drop angle of the sample coating film.

B. Water resistance: Wipe the surface of the coating film with a damp cloth to observe whether there are defects on the surface of the coating film, such as sticky surface, loss of gloss on the surface, lack of material on the surface, etc. The qualified product should be the same as before the test.

C. Ease of wiping: Use an oil-based pen to scratch the surface of the sample, and then wipe the surface with 70% alcohol after drying. The qualified product must not leave oil-based ink marks on the surface.

D. Easy-to-wipe durability: Repeat the easy-to-wipe test three times, and wait for the alcohol to dry before applying.

It can be seen from the above Table 1 that the water resistance, easy-to-wipe property and easy-to-wipe durability of Experimental Examples 1-4 are all better than Comparative Examples 1-4.

"Experimental Example 5-7"

Implementation

Coat the composition of Experimental Example 1 with a #14 wire bar on a 130mm x 160mm wallpaper by the wire bar coating method, and then use a hot air drying oven to dry it at 150°C x 5 minutes to complete the applied layer Count one layer (i.e. Experimental Example 5). Afterwards, the second layer (ie Experimental Example 6) and the third layer (ie Experimental Example 7) can be repeatedly produced according to the required number of layers.

Evaluation method

Use an oil-based pen to graffiti on the wallpaper sample, spray it with 70% alcohol after drying, use toilet paper to wipe off the traces of the oil-based pen, observe the leakage of the oil-based pen ink (that is, leakage) and the degree of residual ink traces of the oil-based pen ( Ease of cleaning) to be evaluated.

Table 2

From Table 2 above, it can be seen that the leakage and easy-to-clean performance of layers with more applied layers (such as Experimental Example 7) are better than those applied with fewer layers (such as Experimental Example 5).

In summary, the present invention provides a coating, which utilizes fully hydrolyzed polyvinyl alcohol and hydrogen-containing silicone resin to react and bond, so that the fully hydrolyzed polyvinyl alcohol changes from hydrophilic properties to water-repellent and easy-to-clean properties . Due to the chemical bond between the fully hydrolyzed polyvinyl alcohol and the hydrogen-containing silicone resin, the coating to which it belongs has better durability, and also has the property of repelling water and being easy to clean. In addition, the present invention also provides a method for forming a coating layer using the paint. In the forming method, the caulking agent is first coated on the base material, and then the paint is coated on the caulking agent. Since the caulk fills the pores in the substrate, it allows subsequently applied paint to form a continuous surface. In this way, the present invention can prevent the ink of the oil-based pen from penetrating into the pores of the base material in the prior art, thereby improving the water-repelling and easy-cleaning ability of the coating.

Although the present invention has been disclosed above with the embodiments, it is not intended to limit the present invention. Any person skilled in the art may make some changes and modifications without departing from the spirit and scope of the present invention. within the scope of the present invention.

Claims (10)

1. A coating with water-repellent and easy-to-clean characteristics, comprising: Fully hydrolyzed polyvinyl alcohol with a degree of polymerization between 300 and 2600; and Hydrogen-containing silicone resin, having Si-H chemical bonds, the weight ratio of the fully hydrolyzed polyvinyl alcohol to the hydrogen-containing silicone resin is 0.5 to 4 times, wherein the hydrogen-containing silicone resin reacts with the fully hydrolyzed polyvinyl alcohol Bonding, so that the fully hydrolyzed polyvinyl alcohol changes from hydrophilic properties to water-repellent and easy-to-clean properties. 2. coating according to claim 1, is characterized in that, also comprises: crosslinking agent, the content of which is 0.1 to 30 weight percent of the coating; and The content of the leveling aid is 0.1-30% by weight of the coating. 3. The coating according to claim 2, wherein the crosslinking agent comprises glyoxal aqueous solution, glutaraldehyde aqueous solution, boric acid aqueous solution, borax aqueous solution, aqueous isocyanate or a combination thereof. 4. The coating according to claim 1, characterized in that the degree of polymerization of the fully hydrolyzed polyvinyl alcohol is between 1400 and 2600. 5. A method for forming a coating with water-repellent and easy-to-clean properties, comprising: Provide the substrate; selectively coating a caulking agent on the substrate, followed by a first drying treatment; Coating a coating with water-repellent and easy-cleaning properties on the caulking agent, and then performing a second drying treatment to form the coating with water-repellent and easy-cleaning properties, wherein the coating with water-repellent and easy-cleaning properties Including: fully hydrolyzed polyvinyl alcohol and hydrogen-containing silicone resin with Si-H chemical bonds, the degree of polymerization of the fully hydrolyzed polyvinyl alcohol is between 300 and 2600, and the fully hydrolyzed polyvinyl alcohol The weight ratio of the hydrogen-containing silicone resin is 0.5 to 4 times, wherein the fully hydrolyzed polyvinyl alcohol reacts and bonds with the hydrogen-containing silicone resin, so that the fully hydrolyzed polyvinyl alcohol changes from a hydrophilic property to a Water-cleaning properties. 6. The method for forming a coating according to claim 5, wherein the substrate comprises wallpaper, fabric, glass, wall or a combination thereof. 7 . The coating forming method according to claim 5 , wherein the caulking agent comprises a water-soluble polymer, an aqueous emulsion, the coating having water-repellent and easy-to-clean properties, or a combination thereof. 8. The formation method of coating according to claim 7, is characterized in that, described water-soluble polymer comprises polyvinyl alcohol, polyvinylpyrrolidone or its combination, and described aqueous emulsion comprises polyvinyl acetate, polymethyl Methyl acrylate, acrylic emulsion, polyurethane emulsion or combinations thereof. 9 . The method for forming a coating according to claim 5 , wherein the step of coating the caulking agent on the substrate comprises coating one or more layers of the caulking agent. 10. The coating forming method according to claim 5, characterized in that, the temperature of the second drying treatment is between 130°C and 170°C, and the time of the second drying treatment is between 3 minutes to 10 minutes.