KR102483440B1 - Composition of two component type dual curing clear coat for car - Google Patents

Abstract

The present application is coated on the exterior painting surface of automobiles to form a film with high functionality such as excellent gloss, water repellency and antifouling property for a long time, as well as high functionality for automobile exterior painting that provides excellent workability such as car washing. It is a technology related to fine ceramic coating agents.
The coating composition of the present application is a two-component ceramic coating that is used by mixing liquid A and liquid B in the range of 1:10 to 10:1 immediately before coating operation.
Liquid A is trimethylsiloxy-terminated methylhydrogensiloxane, dimethylvinylsiloxy-terminated dimethylsiloxane, 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex, tetramethyldivinyldi A compound selected from siloxane and organic cobalt is dissolved in an organic solvent and liquid B is trimethylsiloxy-terminated methylhydrogensiloxane, divinylhexamethylenecyclotetrasiloxane, glycidoxypropyltrimethoxysilane, glycidoxy & A compound selected from methoxy-terminated methylvinylsiloxane is used by being dissolved in an organic solvent, so that it is implemented as a fine ceramic coating composition for external painting provided to form a film with excellent glossiness, water repellency and antifouling property.

Description

Two component type fine ceramic coating composition for exterior painting of automobiles {Composition of two component type dual curing clear coat for car}

The present invention is a two-component type that is applied to the exterior painted surface of an automobile to form a coating having high functionality such as excellent gloss, water repellency and antifouling property semi-permanently, as well as excellent workability such as car washing. It is a fine ceramic coating composition related technology.

The coating agent composition of the present application can be applied as a two-component fine ceramic coating agent used by mixing liquid A and liquid B immediately before coating when coating on a painted surface, and contains a room temperature curable modified silicone resin and a fluorosilane compound as active ingredients It is a high-functional fine ceramic coating composition for automobile exterior painting that can be used and composed of Liquid A and Liquid B containing a reaction catalyst having a catalytic action on the room temperature curable modified silicone resin and fluorosilane compound as active ingredients.

The present invention can protect the painted surface from external contamination and at the same time impart gloss or water repellency to the painted surface by coating the painted surface of automobiles, train bodies, aircraft fuselages, office furniture, and outer walls of buildings. It relates to a highly functional fine ceramic coating composition for exterior painting of automobiles.

Paint surfaces of automobiles, train bodies, aircraft bodies, office furniture, and exterior walls of buildings are exposed to dust, fine dust, exhaust gas, asphalt or pitch, scattering dust from construction sites, acid rain, or sunlight in the natural environment. As a result, the painted surface becomes contaminated with the passage of time, and so-called deterioration such as discoloration and loss of luster progresses.

Therefore, as a means to prevent contamination or deterioration of the painted surface, for example, in the case of automobiles, wax (beeswax) that forms a film to give gloss and fluidizes the wax and imparts water repellency to the film formed at the same time Various automobile waxes containing silicone oil as a main component have been proposed and used in the market.

For example, as a technology related to surface treatment of automobile exteriors, the technology registered in Patent No. 10-1671493 has excellent gloss during surface treatment of automobile exteriors to maintain high gloss for a long period of time, and is a surface treatment agent with excellent water repellency and scratch resistance. An organic/inorganic complex containing at least one selected from titanium, calcium oxide, dysprosium oxide, lanthanum oxide, erbium oxide, and cerium oxide, anionic oligomer, siloxane-based resin, organic solvent, chelate, photocuring agent, rust inhibitor, and UV stabilizer 4-aminobenzoic acid, 4-chloromethyl A surface composed of benzoic acid, 4-bromomethylbenzoic acid, 4-aminomethylbenzoic acid, 4-phenylazobenzoic acid, 4-methylsulfonylbenzoic acid, 4-chlorosulfonylbenzoic acid, or an organic/inorganic complex in which organic compounds containing these are mixed. A treatment agent and an automobile exterior surface treatment method using the same are presented.

In addition, Patent Publication No. 10-2015-0071907 discloses a two-component non-ferrous metal coating agent consisting of an undercoating composition containing a polyester resin and a top-coating composition containing an acrylic polyol resin, a cellulose acetate butyrate resin, and a polyethylene and/or polyethylene-propylene copolymer. As suggested, a primer composition containing (A1) polyester resin as the main resin component, (B1) acrylic polyol resin, (B2) cellulose acetate butyrate resin, and (B3) polyethylene and polyethylene-propylene copolymer as the main resin component. A two-component non-ferrous metal coating agent consisting of a top coat composition containing a resin selected from

However, the disclosed technology is identified as a technology that has not been established in the field due to its low practical applicability to the price, and has been used in the prior art as a means to increase gloss and water repellency and prevent contamination during surface treatment of automobile exteriors in addition to the above technology. Since the main components of car wax products are wax and silicone oil, the protective function for the paint itself was satisfactory. Due to the problem that the antifouling effect (antifouling) cannot be exerted over the period, as a result, the effect of glossiness and water repellency of the painted surface is inhibited, and the durability is short.

In addition, since the film formed in the conventional car wax has adhesiveness, it takes a lot of time and effort to remove unnecessary wax when applying the wax to the painted surface and then washing the car or coating, etc. The work has become a very cumbersome task, and the consumer has not applied the wax, resulting in hastening the deterioration of the coated surface.

Therefore, the present inventors are directed to a method for solving various problems such as loss of gloss in a short period of time, adhesion of stains, and deterioration in water repellency, which are seen in car waxes, and complement the problems of poor field applicability of the prior art as described above. As a result of long-term research, a room temperature curable modified silicone resin that forms a film with excellent gloss and antifouling properties by curing at room temperature in the presence of a predetermined reaction catalyst, and a fluorophore that reacts in the presence of a predetermined reaction catalyst to form a film with excellent water repellency and antifouling properties Liquid A containing a silane compound and liquid B containing a reaction catalyst having a curing or catalytic action on the room temperature curable modified silicone resin and fluorosilane compound are prepared, and when coating on a painted surface, liquid A immediately before the coating operation By using a two-component fine ceramic coating agent mixed with liquid B and liquid B, it is possible to form a film with high functionality such as excellent gloss, water repellency and antifouling property semi-permanently, and to improve workability such as car washing. discovered and completed the present invention.

An object of the present invention is to form a film with high functionality such as excellent gloss, water repellency and antifouling property semi-permanently by being coated on the exterior paint surface of a car, etc., and to provide excellent workability such as car washing. It is to provide a highly functional fine ceramic coating composition for painting.

The present invention relates to a two-component, high-functional fine ceramic coating agent that is mixed and used immediately before the coating operation when coating on a painted surface, and is composed of Liquid A composed of a reactive siloxane curing agent and Liquid B composed of a reactive siloxane crosslinking agent, These are stable because they are not reactive in their respective states, but when the two liquids A and B are mixed, ultra-polymerization is achieved by block copolymerization by the complex reaction of the crosslinking agent and the curing agent. While coating on the surface, the solvent volatilizes, and the remaining siloxane polymer grows into macromolecular silicate-based fine ceramics and functions to terminate the reaction.

The physical properties of the coating film to which the present technology is applied provide excellent adhesion to the painted surface, and very excellent functionality such as high gloss, high hardness, high water repellency, heat resistance, weather resistance, and antifouling.

Therefore, the present application is a highly functional fine ceramic coating composition for painting that is coated on an external painted surface to form a film with excellent gloss, water repellency and antifouling properties, and liquid A and liquid B are mixed in the range of 1:10 to 10:1 immediately before coating. Provides a two-component ceramic coating agent that is mixed and used, but liquid A is trimethyl-siloxy terminated methylhydrogen siloxane, dimethylvinylsiloxy terminated dimethylsiloxane, 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes (1,3-Diethenyl-1,1,3,3-Tet-ra methyldisiloxane Complexes), tetramethyldivinyldisiloxane (Tetrame -thyldivinyldisiloxane), a compound selected from organic cobalt is dissolved in an organic solvent, and liquid B is trimethylsiloxy-terminated methylhydrogensiloxane, divinylhexamethylenecyclotetrasiloxane (Divinylhexamethylcyc -lotetrasiloxane) , Glycidoxypropyltrimethoxysilane, and glycidoxy & methoxy terminated methylvinylsiloxane (Glycidoxy & methoxy terminated methylvinylsiloxane) is used by dissolving it in an organic solvent, so it has excellent gloss, water repellency and It is characterized by a highly functional fine ceramic coating composition for external painting provided to form an antifouling film.

More specifically, the liquid A contains 1.0 to 30.0% by weight of trimethylsiloxy-terminated methylhydrogensiloxane, 0.2 to 5.0% by weight of dimethylvinylsiloxy-terminated dimethylsiloxane, 1,3 diethenyl-1,1,3, 0.1-4.0% by weight of 3,-tetramethyldisiloxane complex, 0.1-4.0% by weight of tetramethyldivinyldisiloxane, 0.01-0.5% by weight of organic cobalt, and the rest is filled with an organic solvent to make 100.0% by weight, and liquid B is trimethyl Siloxy terminated methylhydrogensiloxane 1.0 - 30.0% by weight, divinylhexamethylenecyclotetrasiloxane 0.3 - 3.5% by weight, glycidoxypropyltrimethoxysilane 0.1 - 2.0% by weight, glycidoxy & methoxy terminators Tide methylvinylsiloxane 0.02 - 2.0% by weight, the rest may be filled with an organic solvent to make 100.0% by weight.

In another embodiment, the liquid A contains 0.2 to 5.0% by weight of dimethylvinylsiloxy terminated dimethylsiloxane, 0.1 to 4.0% by weight of 1,3 diethenyl-1,1,3,3,-tetramethyldisiloxane complex, 0.1-4.0% by weight of tetramethyldivinyldisiloxane, 0.01-0.5% by weight of organic cobalt, and the rest being filled with an organic solvent to make up 100.0% by weight, or the liquid B is 0.3-3.5% by weight of divinylhexamethylenecyclotetrasiloxane , 0.1 - 2.0% by weight of glycidoxypropyltrimethoxysilane, 0.02 - 2.0% by weight of glycidoxy & methoxy-terminated methylvinylsiloxane, and the remainder filled with an organic solvent to be applied as a coating composition consisting of 100.0% by weight. .

In addition, the organic solvent used in the liquid A and liquid B in the coating composition of the present application is petroleum naphtha, solvent naphtha, petroleum ether, isoparaffin, n-paraffin, liquid paraffin, methanol, ethanol, n-propanol, isopropyl alcohol , ethylene glycol, organic solvents selected from cellocells may be used alone or as a mixed solvent in which two or more are mixed, and in a more preferred form, 5-20% by weight of ethylene glycol, 5 isopropyl alcohol -20% by weight, 5-20% by weight of ethylcellosolve, and the rest can be applied as a mixed solvent consisting of 100% by weight by filling with C9-13 isoalkane (isoparaffin oil).

In addition, the organic cobalt used in liquid A of the coating composition of the present application may be selected from among cobalt octoate and cobalt naphthenate.

When the content of trimethylsiloxy terminated methylhydrogensiloxane in Liquid A and Liquid B of the coating composition of the present application is 1.0% by weight or less, respectively, the reaction is accelerated, so that the curing reaction occurs in the mixing process of Liquid A and B. On the contrary, if the content is more than 30.0% by weight, the reaction is too slow and the formation of ultra-high molecular is not possible, so the adhesion to the painted surface, which is the effective part of the present invention, is excellent, high gloss, high hardness It is not possible to obtain a coating film with excellent functionality such as water repellency, high water repellency, heat resistance, weather resistance, and antifouling, and on the contrary, the content of other components except for trimethylsiloxy terminated methylhydrogensiloxane is the lowest. In this case, since the content of trimethylsiloxy terminated methylhydrogensiloxane (Trimethylsiloxy terminated MethylhydrogenSiloxane) shows the opposite results in the case of the highest and lowest, the purpose can be achieved only when used within the range presented herein.

Therefore, the purpose of the present application can be achieved only when the mixing ratio presented in the application is followed in order to obtain the optimum effect of practicality and physical properties of difficult reactivity and economic cost according to the raw material and specific mixing ratio used according to the technical idea of the present invention.

In addition, the solvent on the liquid A side and the solvent on the liquid B side may be the same as each other, as long as the conditions of the liquid A and liquid B are satisfied, and may be applied differently. In the present application, liquid A and liquid B are mixed Regarding the quantitative ratio of the two liquids in the composition of the coating liquid, the composition of the coating liquid obtained by mixing these two liquids needs to be appropriate as a protective polishing agent for the painted surface. However, considering the packaging form and handling of liquids A and B, the component composition of liquids A and B is designed so that the volume mixing ratio of liquids A and B is in the range of 1:10 to 10:1. it is desirable

Regarding the method of using the two-component protective polish made according to the technical idea of the present application, first, immediately before the application, liquid A and liquid B are mixed in a predetermined ratio, and the obtained coating liquid is used with a towel, sponge, non-woven fabric, tissue, etc. After applying it to the painted surface of a car, etc., and then volatilizing and drying the solvent of the applied coating liquid, unnecessary components on the painted surface are wiped off with a towel, non-woven fabric, wool, etc. It is an invention of technological thought.

The present application is a coating for exterior painting of automobiles that can be coated on the exterior painting surface of automobiles to form a film with high functionality such as excellent gloss, water repellency and antifouling property semi-permanently, as well as providing excellent workability such as car washing. It has the effect of providing a functional fine ceramic coating composition.

When the coating agent composition of the present application is coated on the exterior painted surface of a car, etc., it provides the effect of forming a film with high functionality such as excellent gloss, water repellency and antifouling property, and the workability such as car washing is also easy, reducing car washing and washing time while washing car And it provides the effect of lasting the cleaning effect for a long time.

The present application is a coating for exterior painting of automobiles that can be coated on the exterior painting surface of automobiles to form a film with high functionality such as excellent gloss, water repellency and antifouling property semi-permanently, as well as providing excellent workability such as car washing. A specific embodiment for providing a functional fine ceramic coating composition is presented as an example of the invention.

Hereinafter, by presenting comparative examples for comparison with manufacturing examples and examples of specific embodiments of the present invention, in order to specifically describe suitable embodiments of the present invention and analyze the results, A solution in the ratio shown in Table 1 and liquid B were prepared.

2 component Liquid A Liquid B material name A-1 A-2 A-3 A-4 A-5 A-6 A-7 B-1 B-2 B-3 B-4 B-5 Example 1 0.0 0.2 0.1 0.1 0 0.01 99.59 30 0.3 0.1 0.02 69.58 Example 2 1.0 1.0 1.0 1.0 0.1 0.20 95.70 15.0 1.0 0.5 0.5 83.00 Example 3 15.0 3.0 3.0 2.0 0.15 0.10 76.75 1.0 2.5 1.0 1.0 94.50 Example 4 30.0 5.0 4.0 4.0 0.5 0.00 56.50 0.0 3.5 2.0 2.0 92.50 Comparative Example 1 30.0 1.0 1.0 1.0 0.1 0.10 66.80 30.0 1.0 0.5 0.5 68.00 Comparative Example 2 0.0 3.0 3.0 2.0 0.15 0.00 91.85 0.0 2.5 1.0 1.0 95.5

amount A

*A-1=B-1: Trimethyl-siloxy terminated MethylhydrogenSiloxane,

*A-2: Dimethylvinylsiloxy terminated Dimethyl Siloxane,

*A-3: 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes (1,3-Diethenyl-1,1,3,3-Tet-ra methyldisiloxane Complexes),

*A-4: Tetramethyldivinyldisiloxane (Tetrame-thyldivinyldisiloxane),

*A-5: Organic cobalt (Cobalt Octoate)

*A-6: Organic cobalt (Cobalt Naphthenate)

*A-7=B-5: Solvents

Liquid B

*B-1=A-1: Trimethylsiloxy terminated methylhydrogensiloxane (Trimethylsiloxy terminated MethylhydrogenSiloxane),

*B-2: Divinylhexamethylenecyclotetrasiloxane (Divinylhexamethylcyc lotetrasiloxane),

*B-3: Glycidoxypropyltrimethoxysilane,

*B-4: Glycidoxy & methoxy terminated methylvinylsiloxane

*B-5=A-7: Solvents

As a means for evaluating the glossiness, antifouling property, and water repellency after application of the composition obtained through the manufacturing examples shown in Table 1 above, it is indicated by the A solution and the B solution obtained above just before the application operation is performed on the painted surface. The coating solutions of Examples 1 to 4 and Comparative Examples 1 to 2 were prepared by mixing in the ratio shown in 1, respectively, wiping property after application, gloss immediately after application, gloss after 1 month, antifouling property, coating The water repellency immediately after and the water repellency after 1 month were evaluated, respectively, and the evaluation results are shown in Table 2.

[Evaluation of wiping workability after application]

Regarding the property of wiping after application, spray the mixed solution on the painted surface of a black car, apply the surface by lightly wiping the surface using a non-woven fabric, evaporate the solvent, and then wipe it off with a clean dry towel (melting) so that the painted surface can be visually inspected. , and lightly wiping was performed until a certain state was reached, and the wiping workability was evaluated by setting the following criteria.

◎: Finished lightly and cleanly without unevenness.

○: It is finished cleanly without unevenness, but it is difficult to wipe off.

(triangle|delta): Unevenness remains and is not finished cleanly.

x: It is not wiped off and there is a little unevenness.

was evaluated in 4 stages.

[Evaluation of glossiness, water repellency and stain resistance]

Make a rectangular test area with a certain size (10cm×10cm) on the painted surface of a white or black car with masking tape, spray the mixed solution, lightly wipe the surface using a non-woven fabric, apply the surface, and volatilize the solvent After that, wipe it off with a clean dry towel (Yung), then leave it outdoors, drive about 100 km or more per week, wash with water at a rate of once per unit, and improve gloss, water repellency and contamination for each unit. As a means of visually observing the anti-corrosion property, for glossiness, the gloss immediately after application

◎: Excellent gloss.

○: Very glossy.

△: There is gloss.

×: almost no gloss

It was evaluated in 4 stages, and at the same time, the gloss after 1 month

◎: Equivalent to the initial stage.

○: Almost good.

△: Slightly inferior.

x: There is almost no gloss.

It was evaluated in 4 steps, and for water repellency, the formation distribution of water droplets formed by spraying water with a hose was observed, and the water repellency immediately after application was evaluated.

◎: There are almost no water droplets.

○: Water droplets are small and formed between 5 and 10,

△: Water droplets are very small, and more than 10 are formed.

×: It is stained with water and is not clean.

was evaluated in 4 stages of , and the water repellency after one month

◎: Equivalent to the initial stage.

○: Almost good.

△: Slightly inferior.

x: There is almost no water repellency.

was evaluated in 4 stages.

In addition, for anti-fouling

◎: Equivalent to initial,

○: slightly contaminated,

△: slight contamination, and

x: Evaluated as 4 levels of significant contamination.

[Evaluation of surface hardness (scratch resistance)]

In addition, the surface hardness of the painted surface after the above application workability test was measured for pencil hardness using a pencil for measuring pencil hardness from 1H to 7H.

For reference, the pencil hardness of the painted surface of a general vehicle not coated with the product of the present invention was measured based on 1H, and the evaluation results are shown in Table 2.

division Example comparative example One 2 3 4 One 2 Workability after application ◎ ◎ ◎ ◎ × ◎ Gloss immediately after application ◎ ◎ ◎ ◎ ○ ○ Gloss after 1 month ○ ◎ ◎ ○ ○ ◎ Water repellency immediately after application ○ ◎ ◎ ○ ○ ○ Water repellency after 1 month ◎ ◎ ◎ ◎ △ ◎ Pollution prevention ○ ◎ ◎ ○ ◎ ○ Pencil hardness immediately after application 2H 3H 3H 2H 3H 1H Pencil hardness after 1 month 4H 5H 5H 4H 5H 4H

As shown in the analysis results of Table 2, the coating composition provided by applying the technical idea of the present application has high surface hardness and high functional properties such as excellent glossiness, water repellency and antifouling property when coated on the exterior painted surface of automobiles. It was possible to confirm the effect of maintaining functionality for a long time, and it was also possible to confirm the effect of maintaining the car washing and cleaning effect for a long time while reducing the car washing and cleaning time due to the easy workability of car washing, which led to a patent application.

Claims (7)

High functionality for automotive painting that forms a film with excellent glossiness, water repellency and antifouling properties by mixing liquid A and liquid B at a volume mixing ratio of 1:10 to 10:1 (volume) immediately before coating and coating on the exterior painting surface In the fine ceramic coating composition,
Liquid A contains 1.0 to 30.0% by weight of trimethylsiloxy-terminated methylhydrogensiloxane, 0.2 to 5.0% by weight of dimethylvinylsiloxy-terminated dimethylsiloxane, 1,3 diethenyl-1,1,3,3,- 0.1-4.0% by weight of tetramethyldisiloxane complex, 0.1-4.0% by weight of tetramethyldivinyldisiloxane, 0.01-0.5% by weight of organic cobalt, the rest being petroleum naphtha, solvent naphtha, petroleum ether, isoparaffins, n-paraffins, liquid It is filled with an organic solvent selected from paraffin, methanol, ethanol, n-propanol, isopropyl alcohol, ethylene glycol, and cello cells and used at 100.0% by weight,
The liquid B is trimethylsiloxy-terminated methylhydrogensiloxane 1.0 - 30.0% by weight, divinylhexamethylenecyclotetrasiloxane 0.3-3.5% by weight, glycidoxypropyltrimethoxysilane 0.1 - 2.0% by weight, glycidoxy & methoxy terminated methylvinylsiloxane 0.02 - 2.0% by weight, the balance being petroleum naphtha, solvent naphtha, petroleum ether, isoparaffin, n-paraffin, liquid paraffin, methanol, ethanol, n-propanol, isopropyl alcohol, ethylene glycol A highly functional fine ceramic coating composition for exterior painting of automobiles, characterized in that it is filled with an organic solvent selected from lycol and cellocells and used to form an excellent gloss, water repellency and antifouling film. delete According to claim 1,
The liquid A contains 0.2 to 5.0% by weight of dimethylvinylsiloxy-terminated dimethylsiloxane, 0.1 to 4.0% by weight of 1,3-diethenyl-1,1,3,3,-tetramethyldisiloxane complex, and tetramethyldivinyldi High-functional fine ceramic coating composition for exterior painting of automobiles, characterized in that it is applied after being modified to consist of 0.1-4.0% by weight of siloxane, 0.01-0.5% by weight of organic cobalt, and 100.0% by weight of the rest filled with an organic solvent. According to claim 1,
The liquid B contains 0.3 to 3.5% by weight of divinylhexamethylenecyclotetrasiloxane, 0.1 to 2.0% by weight of glycidoxypropyltrimethoxysilane, 0.02 to 2.0% by weight of glycidoxy & methoxy terminated methylvinylsiloxane, and the rest. Is a high-functional fine ceramic coating composition for exterior painting of automobiles, characterized in that applied after being filled with an organic solvent and modified to consist of 100.0% by weight. delete According to claim 1,
The organic solvents used in the A and B solutions are 5-20% by weight of ethylene glycol, 5-20% by weight of isopropyl alcohol, 5-20% by weight of ethylcellosolve, and the rest is C9-13 A high-functional fine ceramic coating composition for automobile exterior painting, characterized in that it is used as a mixed solvent filled with isoalkane (isoparaffin oil) to form 100% by weight. According to claim 1,
The organic cobalt used in the liquid A is selected from among cobalt octoate and cobalt naphthenate.