TWI707013B - Resin coating - Google Patents

Abstract

A resin coating is provided, including a surface-modified carbon allotrope and a resin. The surface-modified carbon allotrope has an sp2 structure with a C:O ratio of 50:1 to 800:1, and an absorbance thereof is 0.5 to 2.5 at a wavelength of 320 nm to 750 nm.

Description

Resin coating

The present invention relates to a resin coating, and more particularly to a resin coating containing an allotrope of surface-modified carbon.

In the outdoor environment, resin coatings are usually used to coat objects and equipment (such as railings, pipes, doors and windows and other building materials) to play a protective or decorative role. However, when the resin coating is exposed to the outdoor environment for a long time, under the action of the sun, based on UV light damage to the resin, the service life may be shortened, and there are also safety risks. On the other hand, in marine coatings, storage tank coatings and laboratory reactor coatings, resin coatings are also required to have better chemical resistance and corrosion resistance to be used in harsh and highly corrosive environments.

In the existing primer-finish composite coatings, the factors that cause corrosion include environmental factors, engineering factors or other human factors. Environmental factors such as acid rain, sea breeze (salt), humidity or strong sunlight; engineering factors such as iron impact and knocking, poor paint adhesion, poor water and vapor resistance of the paint, poor weather resistance of the topcoat, insufficient primer protection, or Poor surface treatment; other human factors such as scratches, impacts, or the presence of other corrosive chemicals in the environment.

Based on the above, how to improve the chemical resistance, UV resistance, adhesion, and corrosion resistance of resin coatings is an important topic for technological development in the field.

The invention provides a resin coating which has better chemical resistance, UV resistance (increased light absorption value), corrosion resistance, high adhesion to metal substrates and reduction power, and is suitable for outdoor coatings, marine coatings, storage tanks Coatings and laboratory reactor coatings.

The resin coating of the present invention includes a first surface-modified carbon allotrope and a first resin. The allotrope of the first surface-modified carbon has an sp2 structure and a C:O ratio of 50:1 to 800:1, and an absorbance (Absorbance) of 0.5 to 2.5 at a wavelength of 320 nm to 750 nm.

In an embodiment of the present invention, based on the total weight of the resin coating, the content of the first surface-modified carbon allotrope is 0.05 wt% to 1 wt%, and the content of the first resin is 10 wt% To 25 wt%.

In an embodiment of the present invention, the first surface-modified carbon allotrope includes graphene or nanodiamond.

In an embodiment of the present invention, the first resin includes epoxy (Epoxy).

In an embodiment of the present invention, the first surface modification method of the allotrope of surface-modified carbon includes: breaking the π bond of the allotrope of carbon with a strong acid solution, and then oxidizing the The broken π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak base solution is used to carry out a reduction reaction under the reaction condition of pH 7.5 to 9, so that the first surface-modified carbon is identical The C:O ratio of the plain body is 50:1 to 800:1.

In an embodiment of the present invention, the weak base solution includes 2% to 8% sodium bicarbonate aqueous solution.

In an embodiment of the present invention, the strong acid solution includes aqueous sulfuric acid or aqueous nitric acid.

In an embodiment of the present invention, the substituent includes a carboxyl group, a hydroxyl group or an amide group.

In an embodiment of the present invention, the resin coating is used as a primer, and a topcoat is provided on the primer. The topcoat includes a second surface-modified carbon allotrope, which has an sp2 structure and a C:O ratio It is 50:1 to 800:1, and the absorbance value is 0.5 to 3 at a wavelength of 320 nm to 750 nm.

In an embodiment of the present invention, a middle paint is provided between the primer and the top paint, and the middle paint includes a third surface-modified carbon allotrope, which has an sp2 structure and a C:O ratio of 10: 1 to 300:1, the absorbance value is 0.5 to 3 at a wavelength of 320 nm to 750 nm.

In an embodiment of the present invention, the allotrope of the second surface-modified carbon includes graphene or nanodiamond.

In an embodiment of the present invention, the topcoat further includes a second resin, and the second resin includes epoxy silicone resin.

In an embodiment of the present invention, the third surface-modified carbon allotrope includes graphene or nanodiamond.

In an embodiment of the present invention, the intermediate paint further includes a third resin, and the third resin includes epoxy resin.

In an embodiment of the present invention, the surface modification method of the second surface-modified carbon allotrope includes: using a strong acid solution to break the π bond of the carbon allotrope, and then oxidizing the carbon allotrope The broken π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak base solution is used to perform a reduction reaction under the reaction condition of pH 7.5 to 9 to make the second surface-modified carbon The C:O ratio of the plain body is 50:1 to 800:1.

In an embodiment of the present invention, the third surface modification method of the surface-modified carbon allotrope includes: using a strong acid solution to break the π bond of the carbon allotrope, and then oxidize the carbon allotrope. The broken π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak base solution is used to carry out a reduction reaction under the reaction condition of pH 7.5 to 9 to make the third surface-modified carbon homologous The C:O ratio of the plain body is 10:1 to 300:1.

In an embodiment of the present invention, the weak base solution includes 2% to 8% sodium bicarbonate aqueous solution.

Based on the above, the resin coating of the present invention is used as a primer, has conductivity, and can increase the reduction ability of zinc powder and the adhesion of the resin. The top coat set on the primer has excellent light absorption and weather resistance, so that the resin will not powder or deteriorate, thereby effectively protecting the primer and intermediate paint. The intermediate paint set between the primer and the top coat prevents water vapor from passing through to the substrate surface smoothly.

In order to make the above-mentioned features and advantages of the present invention more obvious and understandable, the following specific embodiments are described in detail as follows.

In this article, the range represented by "a value to another value" is a general way to avoid listing all the values in the range one by one in the specification. Therefore, the record of a specific numerical range covers any numerical value in the numerical range and the smaller numerical range defined by any numerical value in the numerical range, as if the arbitrary numerical value and the smaller numerical value are clearly written in the specification The scope is the same. > Primer >

The invention provides a resin coating comprising a first surface-modified carbon allotrope and resin. The first surface-modified carbon allotrope has an sp2 structure and the C:O ratio is, for example, 50:1 to 800:1, and the absorption value (Absorbance) at a wavelength of 320 nm to 750 nm is, for example, 0.5 to 2.5 . In addition, through BET inspection, the specific surface area of the first surface-modified carbon allotrope is, for example, 10 m ² /g to 30 m ² /g; using FTIR inspection, there are functional groups such as CO, OH, COOH, etc. group. The particle size of the first surface-modified carbon allotrope is, for example, 1 μm to 20 μm, and the ID/IG ratio obtained by the Raman test is, for example, 0.0 to 0.3. In this way, when the resin coating is used as a primer, it has conductivity and cathodic protection, supplies electrons to avoid corrosion, and can increase the reduction ability of zinc powder and the adhesion of the resin.

In this embodiment, the first surface modification method of the surface-modified carbon allotrope includes: using a strong acid solution to break the π bond of the carbon allotrope, and then oxidizing the broken carbon allotrope. The π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak base solution is used to perform a reduction reaction under a reaction condition of pH 7.5 to 9, for example, to make the first surface-modified carbon allotrope The C:O ratio of the body is, for example, 50:1 to 800:1. In more detail, the weak base solution may include a 2% to 8% sodium bicarbonate aqueous solution, the strong acid solution may include an aqueous sulfuric acid solution or an aqueous nitric acid solution, and the substituent may include a carboxyl group, a hydroxyl group or an amide group.

In this embodiment, based on the total weight of the resin coating, the content of the first surface-modified carbon allotrope is, for example, 0.05 wt% to 1 wt%, and the content of the first resin is, for example, 10 wt% to 10 wt%. 25 wt%. The first surface-modified carbon allotrope may include graphene or nanodiamond, and the first resin may include epoxy resin (Epoxy). In more detail, the resin coating of the present invention can be made into an oil-based primer or a water-based primer, and the formula composition is therefore different. Regardless of whether it is an oil-based primer or a water-based primer, the formula does not use heavy metal lead, and the amount of zinc powder used is as low as possible to reduce costs.

In the oil-based primer, based on the total weight of the resin coating, the content of the first surface-modified carbon allotrope is, for example, 0.05 wt% to 1 wt% (to increase corrosion resistance). The content is, for example, 10 wt% to 15 wt% (related to film formation), the content of thickener is, for example, 0.2 wt% to 1 wt% (to increase viscosity), and the content of xylene solvent is, for example, 10 wt% to 15 wt. %, the content of isobutanol solvent is, for example, 3 wt% to 10 wt%, the content of dispersant is, for example, 0.2 wt% to 5 wt% (which can increase coating wettability), and the content of leveling agent is, for example, 0.5 wt. % To 5 wt% (to make the painting smooth), the content of zinc powder is, for example, 50 wt% to 80 wt% (reducing ability related), and the content of curing agent (crosslinking agent) is, for example, 8 wt% to 15 wt%.

In the water-based primer, based on the total weight of the resin coating, the content of the first surface-modified carbon allotrope is, for example, 0.05 wt% to 0.8 wt% (to increase corrosion resistance). The content is, for example, 15 wt% to 25 wt%, the content of dispersant is, for example, 5 wt% to 10 wt% (can increase the wettability of the coating), and the content of leveling agent is, for example, 0.5 wt% to 2 wt% (to make Brushing smoothly), the content of zinc powder is, for example, 50 wt% to 85 wt% (reducing ability related), the content of anti-settling agent is, for example, 5 wt% to 10 wt% (to avoid precipitation), curing agent (crosslinking agent) The content of is, for example, 5 wt% to 15 wt%. > Topcoat >

The resin coating of the present invention is used as a primer, and a topcoat can be provided on the primer. The topcoat includes a second surface-modified carbon allotrope and a second resin. The allotrope of the second surface-modified carbon has an sp2 structure and the C:O ratio is, for example, 50:1 to 800:1, and the absorbance at a wavelength of 320 nm to 750 nm is, for example, 0.5 to 3. In addition, through BET inspection, the specific surface area of the second surface-modified carbon allotrope is, for example, 5 m ² /g to 30 m ² /g; using FTIR inspection, there are functional groups such as CO, OH, COOH, etc. group. The particle size of the second surface-modified carbon allotrope is, for example, 1 μm to 20 μm, and the ID/IG ratio obtained by Raman inspection is, for example, 0.0 to 0.3. In this way, the top coat of the present invention has strong light absorption and weather resistance, which can prevent the resin from powdering or deterioration, thereby effectively protecting the primer and middle coat.

In this embodiment, the second surface modification method of the surface-modified carbon allotrope includes: using a strong acid solution to break the π bond of the carbon allotrope, and then oxidizing the broken carbon allotrope. The π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak alkaline solution is used to perform a reduction reaction under a reaction condition of pH 7.5 to 9, for example, to make the second surface-modified carbon allotrope The C:O ratio of the body is, for example, 50:1 to 800:1. In more detail, the weak base solution may include a 2% to 8% sodium bicarbonate aqueous solution, the strong acid solution may include an aqueous sulfuric acid solution or an aqueous nitric acid solution, and the substituent may include a carboxyl group, a hydroxyl group or an amide group.

In this embodiment, the second surface-modified carbon allotrope may include graphene or nanodiamond, and the second resin may include epoxy silicone resin. Based on the total weight of the topcoat composition, the content of the second surface-modified carbon allotrope is, for example, 0.1 wt% to 1 wt% (to increase corrosion resistance), and the content of the second resin is, for example, 25 wt% to 32 wt% (related to film formation), the content of thickener is, for example, 0.1 wt% to 5 wt% (increasing viscosity), the content of xylene solvent is, for example, 10 wt% to 20 wt%, isobutyl The content of alcohol solvent is, for example, 3 wt% to 8 wt%, the content of dispersant is, for example, 0.5 wt% to 2 wt% (which can increase the wettability of the coating), and the content of leveling agent is, for example, 0.5 wt% to 1.5 wt. % (To make the painting smooth), the content of titanium dioxide is, for example, 5 wt% to 10 wt% (weather-resistant UV white pigment), the content of barium sulfate filler powder is, for example, 8 wt% to 15 wt%, zinc phosphate filler powder The content is, for example, 1 wt% to 3 wt%, the content of silica filler powder is, for example, 20 wt% to 30 wt%, and the content of anti-settling agent is, for example, 3 wt% to 10 wt% (to avoid precipitation), crosslinking agent The content of is, for example, 3 wt% to 10 wt%. > Intermediate paint >

In the present invention, an intermediate paint can be arranged between the primer and the top paint, and the intermediate paint includes a third surface-modified carbon allotrope and a third resin. The allotrope of the third surface-modified carbon has an sp2 structure and the C:O ratio is, for example, 10:1 to 300:1, and the absorbance at a wavelength of 320 nm to 750 nm is, for example, 0.5 to 3. In addition, through the BET test, the specific surface area of the third surface-modified carbon allotrope is, for example, 10 m ² /g to 50 m ² /g; using FTIR test, there are functional groups such as CO, OH, COOH, etc. group. The particle size of the third surface-modified carbon allotrope is, for example, 1 μm to 20 μm, and the ID/IG ratio obtained by the Raman test is, for example, 0.0 to 0.3. In this way, the intermediate paint can effectively prevent moisture from passing through to the surface of the substrate.

In this embodiment, the third surface modification method of the surface-modified carbon allotrope includes: using a strong acid solution to break the π bond of the carbon allotrope, and then oxidizing the broken carbon allotrope The π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak alkaline solution is used to perform a reduction reaction under a reaction condition of pH 7.5 to 9 to make the third surface-modified carbon allotrope The C:O ratio of the body is, for example, 10:1 to 300:1. In more detail, the weak base solution may include a 2% to 8% sodium bicarbonate aqueous solution, the strong acid solution may include an aqueous sulfuric acid solution or an aqueous nitric acid solution, and the substituent may include a carboxyl group, a hydroxyl group or an amide group.

In this embodiment, the third surface-modified carbon allotrope may include graphene or nanodiamond, and the third resin may include epoxy resin. Based on the total weight of the middle coating composition, the content of the third surface-modified carbon allotrope is, for example, 0.1 wt% to 2 wt%, and the content of the third resin is, for example, 20 wt% to 30 wt% ( Related to film formation), the content of thickener is, for example, 3 wt% to 5 wt% (increasing viscosity), the content of xylene solvent is, for example, 5 wt% to 10 wt%, and the content of isobutanol solvent is, for example, 3. wt% to 10 wt%, the content of the methyl isobutyl ketone (MIBK) solvent is, for example, 3 wt% to 10 wt%, and the content of the dispersant is, for example, 0.1 wt% to 2 wt% (which can increase the coating wettability ), the content of leveling agent is, for example, 0.1 wt% to 2 wt% (to make the painting smooth), the content of Al/Zr surface treatment TiO _{2 is} , for example, 3 wt% to 8 wt% (as toner and filler), sulfuric acid The content of barium filler powder is, for example, 5 wt% to 10 wt%, the content of zinc phosphate filler powder is, for example, 1 wt% to 5 wt%, and the content of functional filler is, for example, 5 wt% to 20 wt%. Crosslinking agent The content of is, for example, 5 wt% to 15 wt%.

In the primer, middle coat and top coat composite coating system of the present invention, the total coating thickness of the primer, middle coat and top coat is, for example, 240 μm. The thickness of the primer is, for example, 80 μm to 120 μm, the thickness of the middle coating is, for example, 0 μm to 80 μm, and the thickness of the top coat is, for example, 60 μm to 120 μm. When the thickness of the top coat is thick enough, the middle coat can be omitted. For example, when the thickness of the primer is 120 μm and the thickness of the top paint is, for example, 120 μm, the thickness of the intermediate paint is, for example, 0 μm, that is, the intermediate paint may not be applied.

The primer, middle coat and top coat composite coating system of the present invention has good weather resistance, and the test result ΔE is 0.061. The adhesion evaluation method adopts the 100-grid adhesion test. The test method is to use a 100-grid knife to draw 10×10 (100) 1 mm×1 mm grids on the surface of the test sample (glass material), each of which is deep And the bottom layer of the paint. After that, use a brush to clean the debris in the test area, then use 3M 600 adhesive tape or equivalent adhesive tape to firmly stick the small grid to be tested, and wipe the tape with an eraser to enlarge the tape and the tested area. Contact area and intensity of the area. Then, grab one end of the tape with your hand, quickly pull off the tape in the vertical direction (90°), and perform the same test twice at the same position. The 100-grid adhesion test result of the primer, middle coat and top coat composite coating system of the present invention is 4B, which has good adhesion.

Hereinafter, experimental examples are used to describe in detail the primer, middle coat and top coat composite coating systems proposed in the above embodiments. However, the following experimental examples are not intended to limit the present invention. Experimental example

In order to prove that the primer, midcoat and topcoat composite coating system of the present invention has excellent chemical resistance, UV resistance (increased absorbance), corrosion resistance, adhesion to metal substrates and reducing power, the following special This experimental example. Salt water anti-rust test

The primer, midcoat, and topcoat composite coating systems of the present invention were coated with different thicknesses, and then subjected to a 720-hour salt spray accelerated test to evaluate the anti-rust ability. The experimental results are listed in Table 1 below. As shown in Table 1 below, the results of the 720-hour salt spray accelerated test of the primer, midcoat and topcoat composite coating system of the present invention show no rust test results. Therefore, it can be seen that the primer of the present invention The lacquer, middle coat and top coat composite coating system has a good anti-rust effect. Table 1 coating Example 1 Example 2 Example 3 Example 4 Primer thickness (μm) 120 120 100 80 Middle paint thickness (μm) 0 60 60 80 Topcoat thickness (μm) 120 60 80 80 Total thickness (μm) 240 240 240 240 Test Results Does not rust Does not rust Does not rust Does not rust

In summary, the resin coating of the present invention is used as a primer, has conductivity, and can increase the reduction ability of zinc powder and the adhesion of the resin. The top coat set on the primer has excellent light absorption and weather resistance, so that the resin will not powder or deteriorate, thereby effectively protecting the primer and intermediate paint. The intermediate paint set between the primer and the top coat prevents water vapor from passing through to the substrate surface smoothly. In addition, the results of the 100 grid adhesion test verify that the primer, midcoat and topcoat composite coating systems of the present invention have good adhesion, and the salt water anti-rust test results further verify the primer, midcoat and topcoat of the present invention. The top coat composite coating system has excellent anti-rust ability.

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Claims (18)

A resin coating comprising: a first surface-modified carbon allotrope, which has an sp2 structure and a C:O ratio of 50:1 to 800:1, and the absorbance at a wavelength of 320nm to 750nm (Absorbance) And a first resin, wherein the resin coating is used as a primer, a topcoat is provided on the primer, and the topcoat includes a second surface-modified carbon allotrope, which It has an sp2 structure and a C:O ratio of 50:1 to 800:1, and the absorbance value at a wavelength of 320nm to 750nm is 0.5 to 3. The resin coating as described in item 1 of the scope of patent application, wherein based on the total weight of the resin coating, the content of the first surface-modified carbon allotrope is 0.05wt% to 1wt%, so The content of the first resin is 10wt% to 25wt%. The resin coating according to item 1 of the scope of patent application, wherein the first surface-modified carbon allotrope includes graphene or nanodiamond. The resin coating according to the first item of the scope of patent application, wherein the first resin includes an epoxy resin (Epoxy). The resin coating according to the first item of the scope of the patent application, wherein the first surface-modified carbon allotrope surface modification method includes: using a strong acid solution to break the π bond of the carbon allotrope , And then oxidize the broken π bond to bond the substituent that can form a hydrogen bond with water; and A weak base solution is used to perform the reduction reaction under the reaction conditions of pH 7.5 to 9, so that the C:O ratio of the first surface-modified carbon allotrope is 50:1 to 800:1. The resin coating according to item 5 of the scope of patent application, wherein the weak alkali solution includes 2% to 8% sodium bicarbonate aqueous solution. The resin coating according to item 5 of the scope of patent application, wherein the strong acid solution includes an aqueous sulfuric acid solution or an aqueous nitric acid solution. The resin coating according to item 5 of the scope of patent application, wherein the substituent includes a carboxyl group, a hydroxyl group or an amide group. The resin coating according to item 1 of the scope of patent application, wherein an intermediate paint is provided between the primer and the topcoat, and the intermediate paint includes a third surface-modified carbon allotrope, which It has an sp2 structure and a C:O ratio of 10:1 to 300:1, and the absorbance value is 0.5 to 3 at a wavelength of 320nm to 750nm. The resin coating according to item 1 of the scope of patent application, wherein the allotrope of the second surface-modified carbon includes graphene or nanodiamond. The resin coating according to item 1 of the scope of patent application, wherein the topcoat further includes a second resin, and the second resin includes an epoxy silicone resin. The resin coating according to item 9 of the scope of patent application, wherein the allotrope of the third surface-modified carbon includes graphene or nanodiamond. The resin coating according to item 9 of the scope of patent application, wherein the intermediate paint further includes a third resin, and the third resin includes an epoxy resin. The resin coating as described in item 1 of the scope of the patent application, wherein the second surface-modified carbon allotrope surface modification method includes: using a strong acid solution to break the π bond of the carbon allotrope , And then use oxidation to bond the substituents that can form hydrogen bonds with water on the broken π bond; and use a weak base solution to perform a reduction reaction under the reaction conditions of pH 7.5 to 9 to make the first The C:O ratio of the surface-modified carbon allotrope is 50:1 to 800:1. The resin coating according to item 9 of the scope of patent application, wherein the third surface modification method of the surface-modified carbon allotrope includes: using a strong acid solution to break the π bond of the carbon allotrope , And then use oxidation to bond the substituents that can form hydrogen bonds with water on the broken π bond; and use a weak base solution to perform a reduction reaction under the reaction conditions of pH 7.5 to 9 to make the first The C:O ratio of the allotrope of three-surface modified carbon is 10:1 to 300:1. The resin coating according to item 14 or item 15 of the scope of patent application, wherein the weak alkali solution includes 2% to 8% sodium bicarbonate aqueous solution. The resin coating according to item 14 or item 15 of the scope of patent application, wherein the strong acid solution includes an aqueous sulfuric acid solution or an aqueous nitric acid solution. The resin coating according to item 14 or item 15 of the scope of the patent application, wherein the substituent includes a carboxyl group, a hydroxyl group or an amide group.