KR101600965B1 - Antifouling paint composition and the paint comprising the same - Google Patents

Abstract

The present invention relates to a coating composition for antifouling paint containing an epoxy-modified acrylate, an unsaturated polyester, a silicone, and a curing agent, and a antifouling paint containing the antifouling coating composition. The antifouling coating composition according to the present invention, It is excellent in water repellency, antifungal property, atmospheric purification property, anti-adherence property of pollutant, adhesive property and the like, and is particularly effective in prevention of pollution in tunnels by including unsaturated polyester, silicone, And it is possible to reduce the maintenance cost for protecting the exterior appearance of the building by preventing the sticking of the sticker and the like on the outer wall of the outer wall, etc., and it has an excellent antibacterial effect and the attachment of algae such as seafood and barnacle to the marine structure It also has an excellent advantage in preventing marine pollution.

Description

TECHNICAL FIELD [0001] The present invention relates to an antifouling paint composition and a paint containing the antifouling paint composition.

More particularly, the present invention relates to a coating composition containing an epoxy-modified acrylate, an unsaturated polyester, silicone, and a curing agent, And electrostatic repulsion force is generated between the surface of the coating and the surface of the water slip off the surface shows the property of using this property to significantly reduce the adsorption of contaminants and adsorbed contaminants can be easily removed using water And a coating material containing the same.

Painting is the main purpose of protecting the surface of the object, and it can be used to give an aesthetic sense to the outside of the object or to add color to distinguish the object. Coatings used in such coating operations include solvent-type coating liquids, solvent-free coating liquids, and water-based coating liquids. Recently, environmental problems have arisen, so that a solvent-free coating solution which does not use a solvent and a water-based coating solution which uses water as a solvent are more interested than conventionally used solvent-based coating solutions.

On the other hand, the paint industry is recognized as an environmental pollution inducing business owing to the organic solvents generated during the manufacturing process or coating process of the paint. Therefore, there is a demand for a technology change to reduce such an organic solvent. As part of this effort, attempts have been made to convert existing solvent-based coatings into high-solids, water-based, and powder coatings. Of these three types of coatings, existing facilities can be used as they are, and it is high-solids paint that can utilize coating technology based on conventional solvent-based coating technology and experience accumulation. However, In recent years, water-based paints and powder coating technologies have attracted attention.

In Korea, regulations on environmental regulations, especially volatile organic compounds (VOC) emissions, have recently been enacted, but they are still weak in advanced countries, and regulations have become stricter each year. In addition to the VOC regulations, paint manufacturers are actively developing new coatings to cope with heavy metals. As a representative example, the development of tin-free antifouling paints and Pb-free electrodeposition paints .

Particularly, in recent years, attention has been focused on the development of anti-pollution coating materials, and there is a desperate need to develop paints having moisture repellency, air purification properties, and antibacterial properties.

Although a high solid type antifouling paint is disclosed in the following Patent Document 1, there is a problem that the water repellency is insufficient and contaminants are not easily removed by using water or rainwater flowing outside, and the following Patent Document 2 , There is a problem in that it is insufficient to cope with environmental pollution problem by using an excessive organic solvent.

Patent Document 1: Korean Patent Laid-Open Publication No. 2002-0068460 (Aug. 27, 2002)

Patent Document 2: Korean Patent Laid-Open Publication No. 1993-0002451 (Feb. 23, 1993)

Accordingly, in order to solve the above problems, the present invention provides an electrostatic repulsion force between water and a paint surface when coating a building or the like with a paint using a paint composition comprising an epoxy-modified acrylate, an unsaturated polyester, silicone and a curing agent It is found that the water in contact with the surface slips and falls off. Using this property, the adsorption of contaminants can be remarkably reduced and the adsorbed contaminants can be easily removed by using water. Based on this, It was completed.

Accordingly, a first aspect of the present invention is to provide a pollution-preventing coating composition having water repellency and atmospheric purification ability and capable of significantly reducing the adsorption of contaminants.

A second aspect of the present invention is to provide a paint for preventing contamination which comprises the paint composition.

In order to achieve the first aspect of the present invention, a coating composition for preventing contamination according to an embodiment of the present invention comprises 30 to 50 wt% of an epoxy-modified acrylate, 20 to 30 wt% of an unsaturated polyester, 1 to 10 wt% To 35% by weight.

In another embodiment of the paint composition, the epoxy-modified acrylate may be prepared using 55 to 75% by weight of monomers, 10 to 35% by weight of solvent, 3 to 10% by weight of initiator and 1 to 5% by weight of chain transfer agent have.

In another embodiment of the coating composition, the monomer comprises 30 to 45% by weight of i-butylacrylate, 25 to 40% by weight of methylmethacrylate, 2-hydroxypropyl acrylate 10 to 20% by weight of hydroxypropylacrylate, 5 to 10% by weight of hydroxyl-functional acrylate and 5 to 10% by weight of glycidylmethacrylate.

In another embodiment of the coating composition, the solvent is selected from the group consisting of acetone, methylethylketone, cyclohexanone, methylcellusolve, ethylcellusolve, butylcellosolve, ethylcellulose, butylcellosolve, ethylacetate, butylacetate, and mixtures thereof.

In yet another embodiment of the coating composition, the initiator may be 1,1,3,3-tetramethyl peroxy 2-ethylhexanoate (1,1,3,3-tetramethyl peroxy 2-ethylhexanoate) have.

In another embodiment of the coating composition, the epoxy-modified acrylate may have a structure of the following formula (1).

[Chemical Formula 1]

In still another embodiment of the coating composition, the unsaturated polyester may include a structure represented by the following formula (2).

(2)

Here, x is an integer of 1 to 10, and n is an integer of 1 to 20.

In still another embodiment of the coating composition, the silicone may comprise a structure represented by the following formula (3).

(3)

Here, c is an integer of 1 to 10, and d is an integer of 1 to 15.

In order to achieve the second aspect, the antifouling paint according to an embodiment of the present invention includes the antifouling paint composition according to the various embodiments of the first invention.

The anti-fouling coating composition and the coating material containing the same according to the present invention are excellent in water repellency (hydrophobic), antimicrobial property, atmospheric purification property, and anti-adsorption property by including epoxy-modified acrylate, unsaturated polyester, silicone and curing agent It has excellent effects such as prevention of pollution in tunnels, and has an excellent advantage of being able to reduce the maintenance cost for protecting the exterior of the building by preventing the graffiti on the outer wall of buildings and the like. In addition, such paints are excellent in adhesion to materials such as polypropylene, polyethylene terephthalate, or olefin without primer, have excellent antimicrobial effect, and prevent marine pollution such as seafood and shellfish from adhering to marine structures, And has an advantage of preventing stickers and the like from being attached to the outer wall of the building.

Before describing the invention in more detail, it is to be understood that the words or words used in the specification and claims are not to be construed in a conventional or dictionary sense, It should be interpreted as meaning and concept consistent with the technical idea of the present invention. Therefore, the constitution of the embodiments described in the present specification is merely a preferred example of the present invention, and does not represent all the technical ideas of the present invention, so that various equivalents and variations And the like.

Hereinafter, preferred embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

The antifouling paint composition according to one embodiment of the present invention basically comprises an epoxy-modified acrylate, an unsaturated polyester, a silicone and a curing agent.

When a paint is prepared using such a paint composition for preventing contamination, it has excellent chemical resistance, abrasion resistance, light resistance, and weather resistance, and has excellent adhesion to the outer wall of a building or the like.

The paint using the coating composition for anti-fouling according to the present invention can be used mainly on the outer wall of a building or the like, but the application field is not necessarily limited to a building or the like, and is applied to various fields such as a ship, an aircraft, It is possible.

Conventional paints were a form in which a simple acrylate not modified with an epoxy group was mixed with silicon or a saturated polyester was mixed with silicon. However, a simple acrylate which is not denatured with an epoxy group fails to exert sufficient moisture repellency, and thus, when used in an outer wall of a building or the like, the antifouling performance is not sufficiently exhibited. As described above, the present invention is characterized in that, unlike the conventional coating compositions, acrylate and unsaturated polyester modified with an epoxy group are mixed at a certain ratio and used simultaneously to exhibit excellent antifouling performance.

The composition ratio of the antifouling paint composition according to one embodiment of the present invention will be described below.

The epoxy-modified acrylate is contained in an amount of 30 to 50% by weight based on the total composition, the unsaturated polyester is contained in an amount of 20 to 30% by weight based on the total composition, the silicone is contained in an amount of 1 to 10% . On the other hand, the curing agent is contained in an amount of 15 to 35% by weight based on the total composition.

When the composition ratio of the epoxy-modified acrylate is less than 30% by weight, there is a problem that the weather resistance and the crack-preventing effect of the paint are deteriorated. When the composition is more than 50% by weight, the addition amount of the remaining components is limited.

The unsaturated polyester is characterized by excellent weather resistance, light resistance, scratch resistance and high crosslinking density. Therefore, when the composition ratio of the unsaturated polyester is less than 20% by weight, the weatherability, light resistance, scratch resistance and crosslinking density are lowered, and the durability of the coating is lowered. When the composition is more than 30% by weight, .

In addition, the silicone is hydrophobic and exhibits an excellent reflecting structure by increasing the repulsive force against water and extending to the surface and the inside of the coating film in the form of a long chain. Therefore, when the composition ratio of silicon is less than 1% by weight, the repulsive force of water in contact with the surface is lowered and the durability of the paint is lowered. When the composition ratio exceeds 10% by weight, there is a problem.

On the other hand, when the curing agent is added in an amount of less than 15% by weight based on the total composition, the curing efficiency of the coating is lowered. When the curing agent is more than 35% by weight, the coating operation is not efficient due to excessive curing.

The epoxy-modified acrylate may be prepared using a monomer, a solvent, a reaction initiator, and a chain transfer agent.

Each of these components will be specifically described below.

The monomer is added in an amount of 55 to 75% by weight. The monomer may be selected from the group consisting of i-butylacrylate (i-BA), methylmethacrylate (MMA), hydroxypropylacrylate (2-HPA), hydroxyl functional acrylate hydroxyl-functional acrylate (Tone-100) and glycidylmethacrylate (GMA). The composition ratio of the monomers used in the preparation of the epoxy-modified acrylate according to the present invention is i-butyl acrylate 30 to 45% by weight of i-butylacrylate I-BA, 25 to 40% by weight of methylmethacrylate (MMA), 10 to 20% by weight of hydroxypropylacrylate (2-HPA) 5 to 10% by weight of a hydroxyl-functional acrylate (Tone-100), and 5 to 10% by weight of glycidylmethacrylate (GMA).

 If the addition amount of the total monomer is less than 55% by weight, there is a problem that defoaming property, flexural resistance, weather resistance and scratch resistance are deteriorated. When the addition amount exceeds 75% by weight, addition amount of other components is limited and there is an uneconomical problem.

The i-butyl acrylate has bubble resistance, bending resistance and lipophilicity, and methyl methacrylate has weather resistance. In addition, the 2-hydroxypropyl acrylate has a hydroxyl group exhibiting a low steric hindrance effect and is related to postcurement control and hydrophilicity. On the other hand, the hydroxyl functional acrylate has a hydroxyl group exhibiting a high steric hindrance effect and is related to the pre-curing control and the moisture repellency. In addition, the above glycidyl methacrylate has the effect of maximizing the crosslinking density of the coating material and preventing cracking. Therefore, when the composition ratio of the above monomers is used, the characteristics of each of these monomers can be best exhibited.

The solvent is added in an amount of 10 to 35% by weight. When the amount of the solvent is less than 10% by weight, the dispersibility of the components constituting the epoxy-modified acrylate decreases. When the amount of the solvent is more than 35% by weight, an excessively long time is required to prepare the epoxy-modified acrylate A problem arises.

The solvent may be selected from the group consisting of acetone, methylethylketone, cyclohexanone, methylcellusolve, ethylcellusolve, butylcellusolve, ethylacetate, And butylacetate. However, the scope of the present invention is not limited to these solvents, and various solvents can be used in addition to these solvents.

The reaction initiator is preferably added in an amount of 3 to 10% by weight. When the addition amount of the reaction initiator is less than 3% by weight, the production yield of the epoxy-modified acrylate is markedly decreased. When the addition amount exceeds 10% by weight, the problem of remaining initiator not participating in the reaction and uneconomical problems arise.

As the reaction initiator, 1,1,3,3-tetramethyl peroxy 2-ethylhexanoate (1,1,3,3-tetramethyl peroxy 2-ethylhexanoate) may be used.

The chain transfer agent is contained in an amount of 1 to 5% by weight. As the chain transfer agent, 2-mercaptoethanol (2-hydroxyethanethio) may be used. The chain transfer agent may be used as a chain transfer agent for various monomer The chain polymerization of one monomer is stopped and the polymerization of the other monomer is promoted in the radical polymerization reaction using the radical polymerization initiator. That is, by controlling the addition amount of the chain transfer agent, the repeating units of various kinds of monomers can be controlled . When the amount of the chain transfer agent added is less than 1 wt% or exceeds 5 wt%, there is a problem that the epoxy-modified acrylate used in the present invention is not produced.

On the other hand, the epoxy-modified acrylate may include the following formula (1).

[Chemical Formula 1]

Moisture repulsive force is generated by the hydroxyl group (-OH) and the epoxy group (-COC-) contained in the above formula (1), and when a curing reaction is performed using a curing agent described later, a dense three-dimensional network structure is formed by the functional group, Is given. Due to such a water repelling force, the paint exhibits a hydrophobic property. On the other hand, the hydrophobicity of such paints, i.e., water repellency, is directly related to the antifouling performance and contaminant removal performance of the paint. That is, in general, contaminants such as dust and the like become hydrophilic. When such a hydrophilic contaminant approaches the hydrophobic surface of the paint in which the paint of the present invention is used, a repulsive force is generated between them, so that the contaminants do not adhere easily, and the adhered contaminants are removed from the surface of the paint It is easily removed.

In addition, the unsaturated polyester may include a compound represented by the following general formula (2).

(2)

In Formula 2, x is an integer of 1 to 10, and n is an integer of 1 to 20.

The unsaturated polyester has excellent weather resistance, light resistance, scratch resistance and high crosslinking density, which is attributable to the hydroxyl group (-OH) present at the end of the above formula (2).

In addition, the silicon may include a compound represented by the following formula (3).

(3)

In Formula 3, c is an integer of 1 to 10, and d is an integer of 1 to 15.

The silicone is hydrophobic and has an increased repulsive force against water and is dispersed to the surface and the inside of the coating film in a long chain to realize excellent antireflective property. This action is caused by the hydroxyl group (-OH) present at the end of Formula 3, .

On the other hand, when epoxy-modified acrylates, unsaturated polyesters and silicones each containing the above-described formulas (1) to (3) are mixed together with a urethane-based curing agent to cure them into a three-dimensional network structure to maximize the dense three- Whereby the silicone is semi-permanently applied to the coating film. As the urethane-based curing agent, it is possible to use HDI-trimer of Bayer Leverkusen.

When the coating composition according to the present invention is used, the water contact angle becomes very large when moisture is in contact with the surface of the coated paint. Even if the inclination of the coated object is very low due to such a high water contact angle, moisture easily flows down.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to the following examples.

Synthesis Example 1 - Synthesis of epoxy-modified acrylate

(butyl acetate), 16.46 g of a solvent (1,1,3,3-tetramethylperoxy-2-hydroxypropyl) acetate, 21.41 g of i-BA, 18.83 g of MMA, 9.06 g of 2-HPA, 4.70 g of Tone- Ethylhexanoate) and 2.63 g of a chain transfer agent (2-mercaptoethanol (2-hydroxyethanethio)) were mixed and maintained at 120 ° C for 5 hours to perform dropping, (Tg = 15 ° C., Nv = 70%, Mw = 24,000, Mn = 9100, PDI = 2.63, Vis = 3800) through aging with maintaining the temperature at 120 ° C. for 2 hours. Were synthesized.

Synthesis Example 2 - Synthesis of unsaturated polyester

45.13 g (5.45 mol) of fumaric acid, 15.11 g (4.22 mol) of ethylene glycol, and 15.11 g (2.46 mol) of diethylene glycol were mixed and heated to 150 DEG C, To increase the reaction temperature. Thereafter, water (H ₂ O) was removed and the reaction was maintained so that the acid value was 80 mg / KOH. The reaction product thus obtained was cooled to 130 ° C., and 24.43 g (1.97 mol) of trimethylol diallylether and 0.12 g of 4-methoxyphenol were added. The reaction temperature was elevated to 130 ° C. And the acid value of the unsaturated polyester was adjusted to 19.5 mg / KOH for 4 hours to 170 ° C.

Example 1

80.0 g of the acrylate oligomer synthesized above and 50.0 g of the unsaturated polyester were mixed with 10.0 g of silicone and 40.0 g of HDI-trimer (Bayer Leverkusen) to prepare a coating composition for preventing contamination.

Comparative Example 1

130.0 g of an acrylate oligomer not modified with an epoxy group was mixed with 10.0 g of silicone and 40.0 g of HDI-trimer (Bayer Leverkusen) to prepare a coating composition for preventing contamination.

Comparative Example 2

130.0 g of saturated polyester was mixed with 10.0 g of silicone and 40.0 g of HDI-trimer (Bayer Leverkusen) to prepare a coating composition for preventing contamination.

Comparative Example 3

80.0 g of an acrylate oligomer not modified with an epoxy group and 50.0 g of a saturated polyester were mixed with 10.0 g of silicone and 40.0 g of HDI-trimer (Bayer Leverkusen) to prepare a coating composition for preventing contamination.

Comparative Example 4

80.0 g of an acrylate oligomer not modified with an epoxy group and 50.0 g of an unsaturated polyester were mixed with 10.0 g of silicone and 40.0 g of HDI-trimer (Bayer Leverkusen) to prepare a coating composition for preventing contamination.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown.

The paint prepared using the coating composition prepared in Example 1 and Comparative Examples 1 to 4 was sprayed onto a concrete wall of 1 m x 1 m and dried for 3 days. Using the concrete samples coated with the above paints, the anti-fouling performance was tested by dividing the paints into three categories: hydrophobicity (water repellency), antifouling property, and antimicrobial property.

Hydrophobic (water repellency) test - Removal of contaminants from water

The paint of Example 1 and Comparative Examples 1 to 4 was tested for hydrophobicity, i.e., water repellency.

After the concrete samples were exposed for 3 months around the road where pollution such as dust and car exhaust gas was severe, the degree of removal of pollutants was measured by using a constant pressure hose and running water, And 10 were classified into 10 states and 1 state where no state was completely removed. The results are shown in Table 1 below. As the water repellency (smallness) of the paint becomes stronger, the contaminants attached to the surface of the paint are easily removed by moisture. That is, contaminants such as dust and the like are usually hydrophilic and contaminants are contacted with and mixed with moisture and are easily removed from the surface of the hydrophobic coating.

Using a constant water pressure hose Running water Example 1 (Sample 1) 8 6 Example 1 (Sample 2) 7 5 Example 1 (Sample 3) 7 5 Comparative Example 1 3 2 Comparative Example 2 4 3 Comparative Example 3 4 4 Comparative Example 4 5 3

As can be seen from Table 1, Samples 1 to 3 according to Example 1 of the present invention exhibited comparatively good pollutant removal performance with a measured value of 7 to 8 when water was sprayed using a hose having a constant water pressure However, in Comparative Examples 1 and 2 in which conventional coating materials were used, it was confirmed that the measurement values were 3 and 4, respectively, and the removal of contaminants was not good. In Comparative Examples 3 and 4, And 5 show that the removal of contaminants is not good.

In addition, as a result of evaluating the pollutant removal performance by using water flowing naturally, samples 1 to 3 according to Example 1 of the present invention exhibited relatively good pollutant removal performance with a measured value of 5 to 6 , It can be confirmed that the contaminants are hardly removed in Comparative Examples 1 and 2 in which the conventional paint is used, and in Comparative Examples 3 and 4, the contaminants are hardly removed.

Pollution prevention test

Pollution prevention test was conducted using the paints of Example 1 and Comparative Examples 1 to 4. The concrete samples were exposed to the surrounding roads and tunnels with severe pollution such as dust and vehicle exhaust gas for 3 months and then the degree of contamination on the surface was measured. The results are shown in Table 2 below. [Table 2] < tb > < TABLE >

Around the road tunnel Example 1 (Sample 1) 4 7 Example 1 (Sample 2) 5 5 Example 1 (Sample 3) 4 6 Comparative Example 1 8 10 Comparative Example 2 8 9 Comparative Example 3 7 8 Comparative Example 4 6 8

As shown in Table 2, samples 1 to 3 according to Example 1 of the present invention are comparatively low in contamination degree from 4 to 5 in the case of the roads around and 5 to 7 in the case of tunnels, It can be seen that the degree of contamination is very high in Comparative Examples 1 and 2 where 8 to 10 are used and in Comparative Examples 3 and 4 the degree of contamination is relatively severe.

Antibacterial test

The antibacterial properties of the coating compositions of Example 1 and Comparative Examples 1 to 4 were tested. The concrete samples were exposed to the surrounding roads and tunnels with severe pollution such as dust and vehicle exhaust gas for 3 months, and microorganisms present on the surface contaminants were measured. The results are shown in Table 3 below.

Around the road (cfu / ㎡) Tunnel (cfu / ㎡) Example 1 (Sample 1) 120 280 Example 2 (Sample 2) 70 180 Example 3 (Sample 3) 110 210 Comparative Example 1 630 720 Comparative Example 2 580 640 Comparative Example 3 480 630 Comparative Example 4 620 710

As shown in Table 3, Samples 1 to 3 according to Example 1 of the present invention exhibited relatively excellent antimicrobial activity at 70 to 120 (cfu / m 2) in the case of a road and 180 to 280 (cfu / Able to know. However, in the case of Comparative Examples 1 and 2 in which conventional paints were used, it was 630 and 580 (cfu / m 2) in the case of the road periphery and 720 and 640 (cfu / And the antimicrobial activity was significantly lowered in Comparative Examples 3 and 4 as well.

Claims (9)

30 to 50 wt% of an epoxy-modified acrylate, 20 to 30 wt% of an unsaturated polyester, 1 to 10 wt% of silicon, and 15 to 35 wt% of a curing agent,
The epoxy-modified acrylate is prepared using 55 to 75% by weight of monomer, 10 to 35% by weight of solvent, 3 to 10% by weight of initiator and 1 to 5% by weight of chain transfer agent. delete The method according to claim 1,
Wherein the monomer comprises 30 to 45% by weight of i-butylacrylate, 25 to 40% by weight of methyl ylmethacrylate, 10 to 20% by weight of 2-hydroxypropylacrylate, 5 to 10% by weight of a hydroxyl-functional acrylate, and 5 to 10% by weight of glycidylmethacrylate. The method according to claim 1,
The solvent may be selected from the group consisting of acetone, methylethylketone, cyclohexanone, methylcellusolve, ethylcellusolve, butylcellusolve, ethylacetate, butyl Butylacetate, and mixtures thereof. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
Wherein the initiator is 1,1,3,3-tetramethylperoxy 2-ethylhexanoate (1,1,3,3-tetramethyl yl peroxy 2-ethylhexanoate). The method according to claim 1,
Wherein the epoxy-modified acrylate comprises a structure represented by the following formula (1).
[Chemical Formula 1]

The method according to claim 1,
Wherein the unsaturated polyester comprises a structure represented by the following formula (2).
(2)

Here, x is an integer of 1 to 10, and n is an integer of 1 to 20. The method according to claim 1,
Wherein the silicone comprises a structure represented by the following formula (3).
(3)

Here, c is an integer of 1 to 10, and d is an integer of 1 to 15. A paint for preventing contamination, comprising the paint composition according to any one of claims 1 to 9.