KR20210125387A - Composition of two component type dual curing clear coat for car - Google Patents

Abstract

The present invention relates to a high-functional fine ceramic coating agent for exterior coating for vehicles, which is coated on an exterior coating surface of a vehicle and the like to form a film with high functional properties such as excellent glossiness, water repellency, and antifouling properties for a long time and provide excellent workability in car washing and the like. According to the present invention, the coating agent is a two-component ceramic coating agent used by mixing a liquid B and a liquid B in a range of 1 : 10 to 10 : 1 just before coating. The liquid A is formed by dissolving, in an organic solvent, a compound selected from trimethylsiloxy terminated methylhydrogensiloxane, dimethylvinylsiloxy terminated dimethylsiloxane, 1,3 diethenyl-1,1,3,3,-tetramethyldisiloxane complex, tetramethyldivinyldi siloxane, and organocobalt. The liquid B is formed by dissolving, in an organic solvent, a compound selected from trimethylsiloxy terminated methylhydrogensiloxane, divinylhexamethylenecyclotetrasiloxane, glycidoxypropyltrimethoxysilane, and glycidoxy & methoxy terminated methylvinylsiloxane. Accordingly, a film with excellent gloss, water repellency, and antifouling properties are formed.

Description

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

The present invention is a two-component type that can be applied to external painted surfaces such as automobiles to form a semi-permanently high-functional film such as gloss, water repellency and antifouling properties, as well as excellent workability such as car washing. Fine ceramic coating composition related technology.

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

The present invention protects the painted surfaces from external contamination by coating them on the painted surfaces of automobiles, train bodies, aircraft bodies, office furniture, and exterior walls of buildings, and can impart gloss or water repellency to the painted surfaces. It relates to a high-functional fine ceramic coating composition for automotive exterior painting.

Painted surfaces of automobiles, train bodies, aircraft bodies, office furniture, and building exterior walls are exposed to dust, fine dust, exhaust gas, asphalt or pitch, scattering dust from construction sites, acid rain or sunlight under natural environments. , for this reason, the painted surface becomes contaminated with the passage of time, and so-called deterioration such as discoloration and loss of gloss proceeds.

Therefore, as a means to prevent contamination or deterioration of such painted surfaces, 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 based on silicone oil have been proposed and used in the market.

For example, in the technology related to the surface treatment of automobile exteriors, in Patent No. 10-1671493 technology, silicon oxide, oxidation An organic/inorganic complex containing at least one selected from titanium, calcium oxide, dysprosium oxide, lanthanum oxide, erbium oxide and cerium oxide, anionic oligomers, siloxane-based resins, organic solvents, chelates, photocuring agents, rust inhibitors and UV stabilizers Including, wherein the organic/inorganic complex is 4-aminobenzoic acid, 4-chloromethyl in an inorganic precursor containing at least one selected from silicon oxide, titanium oxide, calcium oxide, dysprosium oxide, lanthanum oxide, erbium oxide and cerium oxide 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 containing organic compounds containing them A treatment agent and a vehicle exterior surface treatment method using the same are presented.

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

However, the disclosed technology is recognized as a technology that has not been settled in the field due to its low practical applicability to the price. Since the main components of automobile wax products are wax and silicone oil, the protection function for the painting itself was satisfactory, but when applied to the painted surface, the film formed on the surface forms adhesiveness, which makes it easier to attach contaminants for a long period of time. Due to the problem of not being able to exhibit the antifouling effect (antifouling property) over the course of time, as a result, effects such as glossiness and water repellency of the painted surface were inhibited, and there was a problem that the durability was 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 washing a car or coating after applying the wax to the painted surface. The operation became a very cumbersome operation, and the customer did not apply the wax, and as a result, it became a cause of hastening the deterioration of the coated surface.

Accordingly, the present inventors provide a method for resolving various problems such as loss of gloss, adhesion of contamination, and deterioration of water repellency, etc., which are seen in automobile waxes for a short period of time, by supplementing 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 fluorine 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 with respect to the room temperature curable modified silicone resin and the fluorosilane compound are prepared, and when coating on a painted surface, immediately before the coating operation, liquid A By using a two-component fine ceramic coating agent that is used by mixing Liquid B and Liquid B, it is possible to form a semi-permanently high-functional film such as excellent glossiness, water repellency and antifouling properties, and workability such as car washing can also be improved. Found and completed the present invention.

It is an object of the present invention to be coated on an exterior painted surface of a vehicle to form a semi-permanently high-functional film such as excellent gloss, water repellency and antifouling properties, as well as providing excellent effects in workability such as car washing. To provide a high-functional fine ceramic coating composition for painting.

The present invention relates to a two-component, high-functionality fine ceramic coating agent that is used by mixing immediately before the coating operation when coating a painted surface. They are stable as they are not reactive in each state, but when the two solutions A and B are mixed, they are gradually polymerized through a block copolymerization reaction by a complex reaction of a crosslinking agent and a curing agent. The solvent is volatilized while coating on the surface, and the remaining siloxane polymer functions to terminate the reaction by growing into a large-molecular silicate-based fine ceramic.

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

Therefore, the present application is a high-functional fine ceramic coating composition for painting that forms a film with excellent gloss, water repellency and antifouling properties by being coated on an external coating surface. To provide a two-part ceramic coating agent that is mixed and used, but the liquid A is trimethyl-siloxy terminated Methylhydrogen Siloxane, dimethylvinylsiloxy terminated dimethyl siloxane (Dimethylvinylsiloxy terminated Dimethyl Siloxane), 1,3 diethenyl-1,1,3,3,-tetramethyldisiloxane complexes (1,3-Diethenyl-1,1,3,3-Tet -ra methyldisiloxane Complexes), tetramethyldivinyldisiloxane -thyldivinyldisiloxane), a compound selected from organic cobalt is dissolved in an organic solvent, and solution B is trimethylsiloxy?terminated MethylhydrogenSiloxane, divinylhexamethylcyc-lotetrasiloxane. , Glycidoxypropyltrimethoxysilane, Glycidoxy & methoxy terminated Methylvinylsiloxane is used by dissolving in an organic solvent for excellent gloss, water repellency and It features a highly functional fine ceramic coating composition for external painting provided to form an antifouling film.

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

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

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

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

When the content of Trimethylsiloxy terminated MethylhydrogenSiloxane in solution A and solution B of the coating composition of the present application is 1.0 wt% or less, respectively, the reaction is accelerated, so that the curing reaction is accelerated in the mixing process of solution A and solution B. coating cannot be performed, and on the contrary, if the content is 30.0 wt% or more, the reaction is too slow and ultra-high molecular weight is not formed. It is not possible to obtain a coating film with very excellent properties of coating, high water repellency, heat resistance, weather resistance, and antifouling properties, and, conversely, the content of other components except for Trimethylsiloxy terminated MethylhydrogenSiloxane is the lowest. In this case, since the content of Trimethylsiloxy terminated MethylhydrogenSiloxane shows opposite results in the highest and lowest cases, the purpose can only be achieved when used within the range presented herein.

Therefore, the purpose of this application can be achieved only by observing the compounding ratio presented in the application in order to obtain the optimum effect of difficult reactivity, economical cost, practicality, and physical properties according to the raw material used according to the technical idea of the present invention and a specific mixing ratio.

In addition, the solvent on the side of solution A and the solvent on the side of solution B may be the same as each other or may be applied differently as long as the conditions of solution A and solution B are satisfied. Regarding the quantitative ratio of the two liquids when composing the coating liquid, the composition of the coating liquid obtained by mixing these two liquids needs to have an appropriate composition as a protective varnish for the painted surface, so depending on the composition of these liquids A and B, However, in consideration of the packaging type and handling characteristics of Liquid A and Liquid B, the component composition of Liquid A and Liquid B is designed so that the volume mixing ratio of Liquid A and Liquid B is in the range of 1:10 to 10:1. it is preferable

Regarding the method of using the two-component protective varnish made according to the technical idea of the present application, first, immediately before the application operation, solution A and solution B are mixed in a predetermined ratio, and the obtained coating solution is used with a towel, sponge, non-woven fabric, tissue, etc. It is applied to the painted surface of automobiles, etc., and then the solvent of the applied coating liquid is evaporated and dried, and then unnecessary components on the painted surface are wiped off with a non-injury such as towel, non-woven fabric, wool, etc. It is a technological invention.

This application is coated on the exterior paint surface of automobiles to form a semi-permanently high-functional film such as excellent gloss, water repellency and antifouling properties, as well as excellent workability such as car washing. It has the effect of providing a functional fine ceramic coating composition.

When the coating composition of the present application is coated on an exterior painted surface of a vehicle, it provides the effect of forming a film with high functional properties such as excellent glossiness, water repellency and antifouling properties, and it is easy to work in car washing, etc. And it provides an effect that the cleaning effect lasts for a long time.

This application is coated on the exterior paint surface of automobiles to form a semi-permanently high-functional film such as excellent gloss, water repellency and antifouling properties, as well as 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, in order to provide a comparative example for contrast with the preparation examples and examples of specific embodiments of the present invention, to specifically describe suitable embodiments of the present invention and to analyze the results, solution A in the proportions shown in Table 1 and solution B was prepared.

2-component A liquid B liquid 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

A liquid

*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/Cobalt Octoate)

*A-6: Organic cobalt (Cobalt Naphthenate/Cobalt Naphthenate)

*A-7=B-5 : Solvents

B liquid

*B-1=A-1: Trimethylsiloxy terminated MethylhydrogenSiloxane,

*B-2: Divinylhexamethylcyc lotetrasiloxane,

*B-3: Glycidoxypropyltrimethoxysilane,

*B-4: Glycidoxy & methoxy terminated Methylvinylsiloxane

*B-5=A-7 : Solvents

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

[Evaluation of workability to wipe off after application]

Regarding the wiping property after application, spray the mixed solution on the painted surface of a black car, wipe the surface lightly using a nonwoven fabric to apply the surface, volatilize the solvent, and then wipe with a clean dry towel (melt) to see the painted surface visually. The workability of wiping was evaluated by setting the following criteria while performing a light wiping operation until a certain state was reached.

◎: It is lightly finished without unevenness.

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

(triangle|delta): Non-uniformity remains and does not complete cleanly.

×: It is not wiped off and there is a slight unevenness.

was evaluated in 4 stages.

[Evaluation of glossiness, water repellency and antifouling properties]

Make a square test area of a certain size (10cm×10cm) with a masking tape on the painted surface of a white or black car, spray the mixed solution and lightly wipe the surface using a nonwoven fabric to apply the surface, and volatilize the solvent After cleaning, wipe it off with a clean dry towel (melted), then leave it outdoors, drive about 100 km or more in units of 1 week, wash it with water at the rate of 1 per unit, and luster, water repellency and contamination in each unit. As a means of visually observing the prevention properties, the glossiness immediately after application is evaluated.

◎: Very good gloss.

○: Very glossy.

△: There is gloss.

×: There is little luster

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

(double-circle) : It is equal to the initial stage.

○: Almost good.

(triangle|delta): It lags slightly.

x: There is little glossiness.

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

(double-circle) : There is almost no water drop.

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

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

×: not clean due to water,

was evaluated in 4 stages, and the water repellency after 1 month

(double-circle) : It is equal to the initial stage.

○: Almost good.

(triangle|delta): It lags slightly.

x: There is almost no water repellency.

was evaluated in 4 stages.

In addition, regarding the anti-pollution properties,

◎: same as initial,

○: slightly contaminated,

△: slightly dirty, and

×: It was evaluated in 4 stages of considerable contamination.

[Evaluation of surface hardness (scratch resistance)]

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

For reference, the pencil hardness of a general automobile painted surface not painted 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 ◎ ◎ ◎ ◎ × ◎ Glossiness immediately after application ◎ ◎ ◎ ◎ ○ ○ Glossiness after 1 month ○ ◎ ◎ ○ ○ ◎ Water repellency immediately after application ○ ◎ ◎ ○ ○ ○ Water repellency after 1 month ◎ ◎ ◎ ◎ △ ◎ anti-pollution ○ ◎ ◎ ○ ◎ ○ 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 in Table 2 above, the coating composition provided by applying the technical idea of the present application has high surface hardness when coated on an external painted surface such as a car, etc. It was possible to confirm the effect of maintaining the functionality for a long time, and it was possible to confirm the effect of maintaining the car washing and washing effect for a long time while shortening the washing and washing time due to the ease of workability such as car washing, which led to a patent application.

Claims (7)

In the high-functional fine ceramic coating composition for painting, which is coated on an external coating surface to form a film of excellent gloss, water repellency and antifouling properties,
It is a two-component ceramic coating agent that is used by mixing solution A and solution B in the range of 1:10 to 10:1 just before coating.
Liquid A contains Trimethyl-siloxy terminated Methylhydrogen Siloxane, Dimethylvinylsiloxy terminated Dimethyl Siloxane, 1,3 diethenyl-1,1,3, A compound selected from 3,-tetramethyldisiloxane complexes (1,3-Diethenyl-1,1,3,3-Tet-ra methyldisiloxane Complexes), tetramethyldivinyldisiloxane (Tetrame-thyldivinyldisiloxane), and organocobalt is organic It is dissolved in a solvent and used.
Solution B is Trimethylsiloxy?terminated MethylhydrogenSiloxane, Divinylhexamethylcyc -lotetrasiloxane, Glycidoxypropyltrimethoxysilane, Glycidoxy & Methoxysilane A high-functionality fine for external painting, characterized in that a compound selected from Glycidoxy & methoxy terminated Methylvinylsiloxane is dissolved in an organic solvent and used to form a film with excellent gloss, water repellency and antifouling properties Ceramic coating composition. According to claim 1,
The liquid A is trimethylsiloxy terminated methylhydrogensiloxane 1.0 - 30.0 wt%, dimethylvinylsiloxy terminated dimethylsiloxane 0.2 - 5.0 wt%, 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 remainder is filled with an organic solvent to make up 100.0% by weight,
The liquid B is trimethylsiloxy terminated methylhydrogensiloxane 1.0 - 30.0 wt%, divinylhexamethylenecyclotetrasiloxane 0.3-3.5 wt%, glycidoxypropyltrimethoxysilane 0.1 - 2.0 wt%, glycidoxy & Methoxy-terminated methylvinylsiloxane 0.02 - 2.0 wt%, the balance is filled with an organic solvent to 100.0 wt% High-functional fine ceramic coating composition for automotive exterior painting, characterized in that it consists of. 3. The method of claim 2,
The liquid A is dimethylvinylsiloxy terminated dimethylsiloxane 0.2 - 5.0% by weight, 1,3 diethenyl-1,1,3,3,-tetramethyldisiloxane complex 0.1 -4.0% by weight, tetramethyldivinyldi Siloxane 0.1-4.0% by weight, organic cobalt 0.01-0.5% by weight The remainder is filled with an organic solvent to make up 100.0% by weight of a high-functional fine ceramic coating composition for automotive exterior painting 3. The method of claim 2,
The liquid B contains 0.3-3.5 wt% of divinylhexamethylenecyclotetrasiloxane, 0.1-2.0 wt% of glycidoxypropyltrimethoxysilane, 0.02-2.0 wt% of glycidoxy & methoxy terminated methylvinylsiloxane, the remainder High-functional fine ceramic coating composition for automotive exterior painting, characterized in that it is filled with an organic solvent and composed of 100.0 wt% According to any one of claims 1 or 2,
The organic solvents used in the A and B solutions are petroleum naphtha, solvent naphtha, petroleum ether, isoparaffin, n-paraffin, liquid paraffin, methanol, ethanol, n-propanol, isopropyl alcohol, ethylene glycol, cellocell. A high-functionality fine ceramic coating composition for automotive exterior painting, characterized in that the organic solvent selected from brew is used alone or as a mixed solvent in which two or more are mixed. 6. The method of claim 5,
The organic solvent used in solution A and solution B is ethylene glycol 5-20% by weight, isopropyl alcohol 5-20% by weight, Ethylenglycolmonoethylether 5-20% by weight, the rest is High functional fine ceramic coating composition for automotive exterior painting, characterized in that it is filled with C9-13 isoalkane (isoparaffin oil) and used as a mixed solvent comprising 100% by weight. According to any one of claims 1 or 2,
The organocobalt used in the liquid A is selected from cobalt octoate and cobalt naphthenate. A high-functional fine ceramic coating composition for automotive exterior painting, characterized in that it is used