KR20030062943A - Tintable And Abrasion Resistant Coating Composition - Google Patents

Abstract

PURPOSE: A coating composition is provided, which is improved in the abrasion resistance, the dyeing property, the storage stability, the adhesive strength and the boiling resistance. CONSTITUTION: The coating composition comprises 30-50 wt% of a base resin comprising 10-30 wt% of an aqueous or alcoholic colloidal silica particle, 69.5-89.5 wt% of a hydrolyzate or partial condensate of an organic modified silane represented by R1aR2bSi(OR3)4-(a+b), 0.1-10 wt% of an aluminum chelate compound represented by AlXn(OR3)3-n, and 0.01-10 wt% of a copolymer resin of vinyl pyrrolidone and vinyl alcohol; 50-70 wt% of a solvent; and an additive, wherein R1 and R2 are independently a substituted or unsubstituted aliphatic group of C1-C20, a substituted or unsubstituted aromatic group, or an alkyl group having an epoxy functional group; a and b are an integer of 0-3; R3 and R4 are a substituted or unsubstituted aliphatic group of C1-C8; X comprises at least one ligand represented by R3COCH2COR3 and R3COCH2COOR4; and n is an integer of 1-3.

Description

Tinttable And Abrasion Resistant Coating Composition

The present invention relates to a wear resistant coating composition, and more particularly to a siloxane-based coating composition excellent in storage stability, adhesion, dyeing and the like.

Transparent plastic materials are widely used as a substitute for glass in many fields because of their light weight and good impact resistance, and are particularly applied as optical lenses, industrial safety glasses or leisure goggles. However, most plastic materials have a soft surface and are easily scratched. In order to overcome these disadvantages, a protective film is generally formed on the surface of the plastic material using an organic material or a silicone coating material.

Coating agents used for this purpose include polyurethane-based or acrylic organic materials and silicone-based coating agents.

In general, the coating composition is required to have all the basic properties such as storage stability, wear resistance, impact resistance. In addition, there is a demand for a film that can be dyed to reflect the contemporary situation that requires various personalities.

Japanese Patent Laid-Open Nos. 53-111336, 55-116764, 55-116765 and 55-116766 disclose dyeable wear resistant siloxane based coating compositions. The patents disclose that dyeing can be imparted by using a large amount of a compound having an epoxy functional group. However, such a coating composition has a disadvantage in that discoloration is severe during the curing process, poor storage stability is impossible to use for a long time, and peeling phenomenon of the coating layer occurs.

Accordingly, an object of the present invention is to provide a siloxane-based coating composition having excellent storage stability and abrasion resistance in view of the above problems, and having excellent dyeability.

In the present invention to achieve the above object

10-30% by weight of aqueous or alcoholic colloidal silica particles, 69.5-89.5% by weight of hydrolyzate or partial condensate of organic modified silane represented by formula (1), based on the total amount of the basic resin, 0.1-10% by weight 30-50% by weight of a basic resin comprising an aluminum chelate compound represented by% of the general formula (2) and a copolymer resin of 0.1-10% by weight of vinylpyrrolidone and vinyl alcohol;

R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} --- (1)

AlX _n (OR ³ ) _3-n --- (2)

R ³ COCH ₂ COR ³ --- (3)

R ³ COCH ₂ COOR ⁴ --- (4)

(Wherein R^OneAnd R²Are each independently substituted or unsubstituted C_One-C₂₀Is selected from an aliphatic group, a substituted or unsubstituted aromatic group, or an alkyl group having an epoxy functional group as a substituent, and a and b are integers of 0-3, R is³And R⁴Is substituted or unsubstituted C_One-C₈Aliphatic group of X, X comprises at least one of the ligands of the general formula (3) or (4), n is an integer of 1-3)

50-70 wt% solvent; And

It provides a coating composition comprising an additive.

In particular, in the general formula (1), R ¹ is at least one of glycidoxypropyl and β- (3,4-epoxycyclohexyl) ethyl, wherein the compound of the general formula (2) is aluminum trisethyl acetoacetate It is preferable.

In addition, the copolymer resin of vinylpyrrolidone and vinyl alcohol is preferably obtained by hydrolyzing a copolymer of vinylpyrrolidone and vinyl acetate in an alcohol solvent, and the additives include surfactants, pH adjusting agents, and the like. Can be.

Hereinafter, the present invention will be described in detail.

The general method of preparing the coating composition of the present invention is as follows. First, an organic or inorganic acid is added to an aqueous or alcoholic silica sol to form acidic colloidal silica particles. Next, an alcoholic solvent and one or more organic modified silanes are added to proceed hydrolysis and partial condensation. Then an organic polymer solution imparting dyeability is added and an aluminum chelate solution is added. Finally, various solvents and additives are added to give an appropriate maturation period.

Hereinafter, each component included in the coating composition of the present invention will be described in detail.

(A) Colloidal silica particles

Aqueous or alcoholic colloidal silicas with a pH of 2.0-7.0 are typically organic or inorganic acids in sol or stable dispersions of amorphous silica particles having particle diameters of 5-50 nm (products such as commercially available Ludox (LUDOX, DuPont)). It is prepared by adding. The sol or dispersion of the first colloidal silica preferably has a particle size of 5-50 nm and a pH of 2.0-11.0 in terms of storage stability.

The particle content of the colloidal silica is in the range of 10-30% by weight relative to the base resin. This is because if the particle content of the colloidal silica is less than 10% by weight, the strength of the coating composition is small, and if it is more than 30% by weight, cracking is caused during the curing process. More preferably 15-25% by weight.

(B) Hydrolysates or partial condensates of organomodified silanes.

Examples of the organic modified silane represented by the general formula (1) include methyltrimethoxy silane, methyltriethoxy silane, vinyltrimethoxy silane, vinyltriethoxy silane, dimethyldimethoxy silane and phenyltrimethoxy silane. , Phenyltriethoxy silane, tetraethoxy silane, tetramethoxy silane, dimethyldimethoxy silane, dimethyldiethoxy silane, diphenyldimethoxy silane, diphenyldiethoxy silane, hexyltrimethoxy silane, butyltrimethoxy silane , β- (3,4-epoxycyclohexyl) ethyltrimethoxy silane, γ-glycidoxypropyltrimethoxy silane, γ-glycidoxypropyltriethoxy silane, γ-methacryloxypropyltrimethoxy silane , γ-methacryloxypropyltriethoxy silane, γ-methacryloxypropylmethyldimethoxy silane, γ-methacryloxypropylmethyldiethoxy silane, N-β (aminoethyl) -γ-aminopropyltrimethoxy silane , N-β (aminoethyl)- - it includes the aminopropyl triethoxysilane.

Hydrolysates or partial condensates of organo modified silanes are prepared by adding organic or inorganic acids to the organo modified silanes.

The initial dose of the organomodified silane compound is in the range of 69.5-89.5% by weight relative to the base resin. This is because if the content of the organic modified silane is less than 69.5% by weight, cracking is caused during the curing process, and if the content of the organically modified silane is more than 89.5% by weight, the strength of the composition is small. More preferably in the range 75-85% by weight.

(C) aluminum chelate compounds

The coating composition of the present invention is thermoset by a heating process. Acid and base neutralization products of organic or inorganic acids added during the process of the present invention promote the condensation reaction of silanes, but aluminum chelate compounds are required to promote the condensation reaction of silanes with organic functional groups such as epoxy functional groups or carbinol. .

Examples of aluminum chelates that can be used are as follows. Aluminum trisacetyl acetonate, aluminum trisethyl acetoacetate, aluminum diisopropoxide monoethyl acetoacetate, aluminum diisopropoxide monoacetoacetonate, aluminum dibutoxyd monoethylacetoacetate, aluminum dibutoxide monoacetoaceto Acetate, aluminum bisethylacetoacetate monoacetylacetonate, and the like.

This component should be used in the range of 0.1-10% by weight based on the base resin. This is because if the content thereof is less than 0.1 wt%, the time required for sufficient curing is long, and if it exceeds 10 wt%, discoloration of the film is caused. More preferably, it is used in the range of 0.5-5% by weight.

(D) Copolymer resin of vinylpyrrolidone and vinyl alcohol

The coating composition of the present invention comprises a copolymer resin of vinylpyrrolidone and vinyl alcohol in order to increase the dyeability of the coating. The copolymer resin of vinylpyrrolidone and vinyl alcohol used in the composition of the present invention can be obtained by hydrolyzing a copolymer of vinylpyrrolidone and vinyl acetate (trade name Luviskol, BASF) in an alcohol solvent. This component should be used in the range of 0.1-10% by weight based on the base resin. This is because if the amount thereof is less than 0.1% by weight, the time required for sufficient dyeing is long, and if it exceeds 10% by weight, the water resistance is lowered. More preferably in the range 0.5-2% by weight.

(E) solvent

As a solvent used in the coating composition of the present invention, alcohol is generally preferred, which serves to significantly improve storage stability and transparency of the coating. Examples of such alcohol solvents include methanol, ethanol, isopropyl alcohol, butanol, diacetone alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetate, ethyl acetoacetate, and the like. The amount is adjusted so that the base resin in the coating composition is in the range of 30-50% by weight.

(F) various additives

Moreover, the coating composition of this invention can use various additives in the range in which the effect of this invention does not fall for the purpose of improving adhesiveness, stability, etc. with a base material. Examples thereof include epoxy resins, urea resins, melamine resins, urethane resins, ultraviolet absorbers, and the like, and various surfactants may be blended in order to improve applicability. As such surfactants, dimethylsiloxane and polyethylene oxide block copolymers, graft copolymers or fluorine-based surfactants may be used.

In addition, the coating composition of the present invention should adjust the pH in consideration of various physical properties such as storage stability, curing rate and wear resistance, and for this purpose, organic or inorganic acids are used, for example acetic acid, sulfuric acid, hydrochloric acid, para-toluenesulfo Nickic acid etc. are mentioned. These acid components may be used alone or in combination of two or more in consideration of the reaction rate according to the final pH or component of the coating solution and the adhesion to the applied substrate.

When the coating composition of the present invention as described above is applied to a plastic substrate such as a vision correcting lens and heat treated, a high hardness protective film can be obtained. In this case, a variety of commonly used methods such as silk screen, roll coating, spray coating, dip coating or spin coating may be applied without exception. Curing conditions vary slightly depending on the blending ratio and components, but in general, a protective coating having a desired hardness can be obtained by curing for 20 minutes to several hours at a temperature below the softening point of the substrate (about 60-150 ° C.).

In addition, the cured film obtained by the coating composition of the present invention can be dyed with a disperse dye, and can be arbitrarily determined conditions such as concentration, temperature, time, etc. of the disperse dye at the time of dyeing, generally dyes in the concentration range of 0.1-1% by weight An aqueous solution is used, and the dyeing is performed by dipping for 5 to 30 minutes at a temperature of 80-100 ° C.

The following presents preferred synthesis examples, comparative examples and examples to aid in understanding the invention. However, the following examples are provided only for better understanding of the present invention, and the invention is not limited only to the following examples.

Synthesis Example 1

50 g of a copolymer solution of vinylpyrrolidone and vinyl acetate (Luviskol VA 37I, BASF) was added to the reactor, followed by stirring with 200 g of methanol, 0.1 g of paratoluenesulfonic acid, and 10 g of water. Stirred for 5 hours while maintaining the temperature of the contents at 60 ℃. The obtained polymer solution (solid content 10 wt%) was used as it is without further processing.

<Example 1>

60 g of Dupont's colloidal silica Ludox HS-30 (particle size 12 nm, solid content 30% by weight) was added while maintaining the temperature inside the reactor at 30 ° C or lower. 15 g of acetic acid aqueous solution (10%) was added thereto, and a mixed solution of 60 g of methyltrimethoxy silane and 30 g of γ-glycidoxypropyltrimethoxy silane was added dropwise while stirring with a magnetic stirrer, and the temperature was raised to 60 ° C. for 5 hours. Hydrolysis. After cooling to room temperature, 2 g of aluminum trisethyl acetoacetate was added and stirred for 24 hours. 6 g of the reaction product obtained in Synthesis Example 1, 100 g of isopropanol solution, 100 g of butyl cellosolve, and 0.25 g of a silicone surfactant BYK348 (by KK) were added, and stirred well for 30 minutes to obtain a final composition. The composition was immersed in a vision correcting lens (CR-39), dried at room temperature for 5 minutes, and heated at 120 ° C. for 1 hour to obtain a cured coating.

<Example 2>

While maintaining the temperature inside the reactor at 30 ° C. or less, 60 g of Dupont's colloidal silica Ludox HS-30 (particle size 12 nm, solid content 30 wt%) was added thereto. 15 g of acetic acid aqueous solution (10%) was added thereto, and a mixed solution of 60 g of methyltrimethoxysilane and 30 g of γ-glycidoxypropyltrimethoxy silane was added dropwise while stirring with a magnetic stirrer, and the temperature was raised to 60 ° C. for 5 hours. Hydrolysis. After cooling to room temperature, 2 g of aluminum trisethyl acetoacetate was added and stirred for 24 hours. 3 g of the reaction product obtained in Synthesis Example 1, 100 g of isopropanol solution, 100 g of butyl cellosolve, and 0.25 g of a silicone surfactant BYK348 (by KK) were added and stirred well for 30 minutes to obtain a final composition. The composition was immersed in a vision correcting lens (CR-39), dried at room temperature for 5 minutes, and heated at 120 ° C. for 1 hour to obtain a cured coating.

<Example 3>

While maintaining the temperature inside the reactor at 60 ° C or less, 60 g of Dupont's colloidal silica Ludox HS-30 (12 nm particle size, 30 wt% solids) was added thereto, and 15 g of an aqueous acetic acid solution (10%) was added thereto, followed by a magnetic stirrer. While stirring, a mixed solution of 30 g of methyltrimethoxy silane and 60 g of γ-glycidoxypropyltrimethoxy silane was added dropwise, and heated to 60 ° C. for hydrolysis for 5 hours. After cooling to room temperature, 2 g of aluminum trisethyl acetoacetate was added and stirred for 24 hours. 6 g of the reaction product obtained in Synthesis Example 1, 100 g of isopropanol solution, 100 g of butyl cellosolve, and 0.25 g of a silicone surfactant BYK348 (by KK) were added, and stirred well for 30 minutes to obtain a final composition. The composition was immersed in a vision correcting lens (CR-39), dried at room temperature for 5 minutes, and heated at 120 ° C. for 1 hour to obtain a cured coating.

<Example 4>

While maintaining the temperature inside the reactor at 30 ° C. or less, 60 g of Dupont's colloidal silica Ludox HS-30 (particle size 12 nm, solid content 30 wt%) was added thereto. 15 g of acetic acid aqueous solution (10%) was added thereto, and a mixed solution of 60 g of methyltrimethoxy silane and 30 g of γ-glycidoxypropyltrimethoxy silane was added dropwise while stirring with a magnetic stirrer, and the temperature was raised to 60 ° C. for 5 hours. Hydrolysis. After cooling to room temperature, 5 g of aluminum trisethyl acetoacetate was added and stirred for 24 hours. 6 g of the reaction product obtained in Synthesis Example 1, 100 g of isopropanol solution, 100 g of butyl cellosolve, and 0.25 g of a silicone surfactant BYK348 (by KK) were added, and stirred well for 30 minutes to obtain a final composition. The composition was immersed in a vision correcting lens (CR-39), dried at room temperature for 5 minutes, and heated at 120 ° C. for 1 hour to obtain a cured coating. The composition was immersed in a vision correcting lens (CR-39), dried at room temperature for 5 minutes, and heated at 120 ° C. for 1 hour to obtain a cured coating.

Example 5

While maintaining the temperature inside the reactor at 30 ° C. or less, 60 g of Dupont's colloidal silica Ludox HS-30 (particle size 12 nm, solid content 30 wt%) was added thereto. 15 g of acetic acid aqueous solution (10%) was added thereto, and a mixed solution of 60 g of methyltrimethoxy silane and 30 g of γ-glycidoxypropyltrimethoxy silane was added dropwise while stirring with a magnetic stirrer, and the temperature was raised to 60 ° C. for 5 hours. Hydrolysis. After cooling to room temperature, 0.5 g of aluminum trisacetylacetonate was added and stirred for 24 hours. 10 g of the reaction product obtained in Synthesis Example 1, 100 g of isopropanol solution, 100 g of butyl cellosolve, and 0.25 g of a silicone surfactant BYK348 (by KK) were added, followed by stirring for 30 minutes to obtain a final composition. The composition was immersed in a vision correcting lens (CR-39), dried at room temperature for 5 minutes, and heated at 120 ° C. for 1 hour to obtain a cured coating.

Comparative Example 1

A coating composition was obtained in the same manner as described in Example 1 except that the reaction product obtained in Synthesis Example 1 was not used. The composition was immersed in a vision correcting lens (CR-39), dried at room temperature for 5 minutes, and heated at 120 ° C. for 1 hour to obtain a cured coating.

Comparative Example 2

A coating composition was prepared in the same manner as described in Example 1 except that polyvinylpyrrolidone (Luviskol K 30, BASF Co., Ltd.) was dissolved in methanol at 5% by weight instead of the reaction product obtained in Synthesis Example 1. Got it. The composition was immersed in a vision correcting lens (CR-39), dried at room temperature for 5 minutes, and heated at 120 ° C. for 1 hour to obtain a cured coating.

Hereinafter, the physical properties of the immersion-cured coating were examined by the following method.

(1) storage stability

The viscosity change at the time of storage at 25 degreeC for 1 month was evaluated, and when the change of viscosity was insignificant, it was represented by (double-circle), when the change was small, it represented by (circle) and when there was a significant change, it represented by (triangle | delta).

(2) wear resistance

After tying # 0000 steel wool to a hammer of 1.5 kg and rubbing the cured film 30 times, the scratches were 1, the scratches were 2, and the severe scratches were 3.

(3) adhesion

According to ASTM D3359, 100 squares of 1 mm2 were made by drawing the squares at 1 mm intervals on the film, and then 5 times peeling tests were performed using 3 mm wide cellophane tape of 3M Korea. It was determined by counting the number of spaces present.

(4) Hot water resistance

The coated vision correcting lens was immersed in 80 ° C. brine (10 wt% brine) for 30 minutes and then subjected to an adhesion test.

(5) Dyeing

A lens coated on a 10 wt% aqueous solution of BPI Sun Brown, manufactured by Brain Powder Inc., was deposited at 90 ° C. for 5 minutes, and then the transmittance of the lens was measured.

Coating property check table after coating using composition Storage stability Wear resistance Adhesion Hot water resistance Dyeability (%) Example 1 ◎ 2 100 100 65 Example 2 ◎ 2 100 100 85 Example 3 ◎ 2 100 100 60 Example 4 ◎ One 90 100 70 Example 5 ◎ 2 70 90 90 Comparative Example 1 ◎ One 100 100 90 Comparative Example 2 ◎ 2 90 50 90

Through the results shown in Table 1, the coating composition according to the present invention can be confirmed that the storage stability, abrasion resistance, adhesion, hot water resistance, etc. are very good and in particular, dyeing is excellent.

The wear-resistant coating composition of the present invention as described above is excellent in storage stability and can be used for long-term storage, and exhibits excellent wear resistance, excellent adhesion, hot water resistance of high hardness and excellent dyeing property.

Although the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the present invention without departing from the spirit and scope of the invention described in the claims below. I can understand that you can.

Claims (5)

10-30% by weight of aqueous or alcoholic colloidal silica particles, 69.5-89.5% by weight of hydrolyzate or partial condensate of organic modified silane represented by formula (1), based on the total amount of the basic resin, 0.1-10% by weight 30-50% by weight of a basic resin comprising an aluminum chelate compound represented by% of the general formula (2) and a copolymer resin of 0.1-10% by weight of vinylpyrrolidone and vinyl alcohol; R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} --- (1) AlX _n (OR ³ ) _3-n --- (2) R ³ COCH ₂ COR ³ --- (3) R ³ COCH ₂ COOR ⁴ --- (4) (Wherein R^OneAnd R²Are each independently substituted or unsubstituted C_One-C₂₀Is selected from an aliphatic group, a substituted or unsubstituted aromatic group, or an alkyl group having an epoxy functional group as a substituent, and a and b are integers of 0-3, R is³And R⁴Is substituted or unsubstituted C_One-C₈Aliphatic group of X, X comprises at least one of the ligands of the general formula (3) or (4), n is an integer of 1-3) 50-70 wt% solvent; And Coating composition comprising an additive. The coating composition according to claim 1, wherein in formula (1), R ¹ is at least one of glycidoxypropyl and β- (3,4-epoxycyclohexyl) ethyl. The coating composition according to claim 1, wherein the compound of formula (2) is aluminum trisethyl acetoacetate. The coating composition of claim 1, wherein the copolymer resin of vinylpyrrolidone and vinyl alcohol is obtained by hydrolyzing a copolymer of vinylpyrrolidone and vinyl acetate in an alcohol solvent. The coating composition of claim 1, wherein the additive comprises a surfactant and a pH adjuster.