KR101024899B1 - Paint composition for silicone release coating with high hardness - Google Patents

Abstract

The present invention relates to a coating composition for silicone release coating having a high hardness. The coating composition according to the present invention comprises a silicone polymer or a synthetic binder mixed with a silicone polymer emulsion and an organic resin to compensate for the hardness, which is the biggest disadvantage of the silicone polymer coating film, to be resistant to external impact, friction and scratches, and to improve adhesion of the coating surface. It greatly improves the pollution resistance to various contaminants, the water resistance by snow and rain, and the prevention of rain water traces when exposed to outdoor for a long time.

Description

Paint composition for silicone release coating with high hardness}

The present invention relates to a coating composition for silicone release coating having a high hardness.

In general, illegal advertisements are indiscriminately attached with various adhesives on public facilities near major roads in urban areas such as underground transformers, telephone poles, traffic light poles, street lamps, and road sign posts. These illegal advertisements are not easy to remove, which not only hurts the urban landscape, but also damages the public facilities. Therefore, there is an urgent need for measures to prevent illegal advertisements to protect the urban appearance and public facilities. Accordingly, studies on the coating composition for preventing adhesion have been actively conducted.

Conventional anti-adhesive paint was used by floating an additive such as wax or silicone oil on the surface of the coating as part of easily removing the deposit. However, these paints are not secured in durability, and can only be seen in a very short period of time to prevent adhesion, and due to long-term outdoor exposure, weather resistance and fouling resistance are deteriorated. there was.

Alternatively, in order to minimize the area where the deposit adheres to the surface of the coating film, artificial irregularities were formed by using embossing materials such as stone powder, sawdust, glass beads, or fine silicone resin powder having excellent releasability. However, this method also helps to prevent attachments at an early stage after construction, but it is easily polluted with various pollutants as the outdoor exposure period elapses, and there is a problem that contaminants are not easily removed even if they are washed. .

As another method, a technology for forming a coating film through addition reaction or condensation reaction of a silicone polymer by using a property that the silicone polymer does not adhere to an adhesive component has been developed. However, it is very difficult to apply the method to the field construction because the heat treatment is necessary for the addition reaction or the condensation reaction, and the heat treated coating film also has basic rubber properties, so that the coating film hardness is weak and the surface tacky is high. Very vulnerable to heavy pollution.

In order to overcome the above problems, it is necessary to prevent various attachments from being attached from the beginning, and at the same time, make the anti-sticking function according to the passage of the seal semipermanently. That is, by introducing the concept of anti-sticking function and self-cleaning of the facility itself, it prevents the infiltration of contaminants into the facility at the source, and it is easy to remove the contaminants and contaminants even if they are already contaminated. There is a need for development.

The inventors of the present invention, while studying a coating composition excellent in anti-sticking function, prepared a top coating composition comprising a silicone binder or a synthetic binder mixed with a silicone polymer emulsion and an organic resin, to form a coating film using the top coating composition When it was confirmed that the adhesion, hardness, transparency, room temperature dryness, accelerated weather resistance, non-pollution characteristics, anti-adhesion properties and rain water marks significantly improved, the present invention was completed.

The present invention is to provide a coating composition for silicone release coating having a high hardness that can improve the anti-sticking performance, super water-repellent and oil-repellent coating surface to significantly reduce the binding force between various lipophilic contaminants and the surface of the facility.

The present invention is 45 to 75 parts by weight of a synthetic binder of a silicone polymer or a silicone polymer emulsion represented by the following formula (1) and an organic resin, 1 to 5 parts by weight of a polysiloxane copolymer or polysiloxane copolymer emulsion represented by the formula (2), platinum It provides the coating composition for silicone mold release coating which has a high hardness containing 0.01-1 weight part of containing catalysts, and 10-50 weight part of solvents.

In Formula 1, R1 is OH, C ₁ ~ C ₄ alkyl group, C ₂ ~ C ₁₀ alkenyl group, phenyl group, carboxyl group, amino group, R2 is C ₁ ~ C ₄ alkyl group, C ₂ ~ C ₁₀ alkenyl group or phenyl group And n is a positive integer of 1 to 10,000.

Preferably, in Formula 1, R1 is a methyl group, a vinyl group, a phenyl group, a carboxyl group, an amino group, and R2 is a methyl group, a vinyl group or a phenyl group.

In Formula 2, o is a positive integer of 1-100, p is a positive integer of 1-100.

Hereinafter, the present invention will be described in detail.

Synthetic binder as a component in the coating composition for silicone release coating having a high hardness of the present invention may be prepared by hot blending or simple cold blending of a silicone polymer or a silicone polymer emulsion and an organic resin. .

The synthetic binder by the heat mixing

1) preparing a silicone polymer liquid solution having a solid content of 5 to 30% by adding a silicone polymer or a silicone polymer emulsion represented by Chemical Formula 1 to a solvent,

2) preparing a silane-modified silicone polymer by mixing a silane coupling agent and the silicone polymer or silicone polymer emulsion represented by Formula 1 and reacting at 120 to 150 ° C. for 2 to 6 hours,

3) adding a silane coupling agent to distilled water to hydrolyze, adding a filler to it, and then adding alcohol to heat the filler at 105-110 ° C. to surface-treat the filler;

4) After adding the silicone polymer liquid solution prepared in step 1) to the surface-treated filler and mixing at 100-150 ° C., the silane-modified silicone polymer prepared in step 2) was then added to 0.5- at 100-150 ° C. Reacting for 3 hours to coat or gel the silicone polymer on the filler,

5) reacting the coated or gelled filler and the organic resin at 130 to 180 ° C. for 2 to 6 hours, and

6) is prepared by the process consisting of adding the liquid silicone polymer solution prepared in step 1) to the reaction mixture at the end of step 5) and reacting for 1 to 2 hours at 130 ~ 180 ℃.

The manufacturing method of the synthetic binder by the heat mixing will be described in detail step by step.

Step 1) is to loosen the crosslinking point of the silicone polymer or silicone polymer emulsion, and the silicone polymer or silicone polymer emulsion is added to a solvent to prepare a silicone polymer liquid solution having a solid content of 5 to 30%. The silicone polymer or silicone polymer emulsion used at this time is a straight-chain siloxane represented by Chemical Formula 1, which is terminated by a trimethylsiloxy group or two or more alkenyl groups having two or more carbon atoms and has two or more carbon atoms in the silicon atoms in a chain side chain. . The silicone polymer or silicone polymer emulsion may be, for example, polydimethylsiloxane and polymethylvinylsiloxane copolymer terminated with trimethylsiloxy, polydimethylsiloxane and polymethylvinylsiloxane copolymer terminated with dimethylvinylsiloxy, divinyl Polydimethylsiloxane and polymethylvinylsiloxane copolymers terminated with methylsiloxy, polydimethylsiloxane and polymethylvinylsiloxane copolymers terminated with trivinylsiloxy, and the like. Solvents used include, but are not limited to, n-hexane, n-heptane, n-octane, n-nonane, methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, distilled water, and the like.

Step 2) is to prepare a silane-modified silicone polymer, 30 to 50 parts by weight of the silane coupling agent, 100 to 150 parts by weight of the silicone polymer or silicone polymer emulsion represented by the formula (1), and 0.01 to 0.5 parts by weight of the catalyst is mixed And reacted for 2 to 6 hours at 120 ~ 150 ℃ to produce a silane-modified silicone polymer. The silane coupling agent used at this time includes, but is not limited to, vinyl silane, methoxy silane, ethoxy silane, and the like. Catalysts include, but are not limited to, phenol catalysts or amine catalysts such as aminopropyltriethoxysilane.

Step 3) is a step of surface treatment of the filler, hydrolyzed by adding a silane coupling agent to a small amount of distilled water, and then added to the filler and heated to 105 ~ 110 ℃. Then, the silanol of the silane coupling agent and the hydroxy group of the filler undergo a condensation reaction. At this time, the alcohol to be used is preferably added about 7 to 12 times the silane coupling agent, ethanol, propanol, isopropanol and butanol and the like can be used. It is preferable to use 0.5-3 weight part of silane coupling agents with respect to 100 weight part of fillers. The fillers include, but are not limited to, fused silica, spherical silica, alumina trihydrate, hydrosclay, talc, and the like.

Step 4) is a step of coating or gelling the silicone polymer on the surface-treated filler, by adding 50 to 150 parts by weight of the liquid silicone polymer solution prepared in step 1 to 100 parts by weight of the surface-treated filler 100 ~ 150 After mixing at 0 ° C., 5 to 20 parts by weight of the silane-modified silicone polymer prepared in step 2) was added and reacted at 100 to 150 ° C. for 0.5 to 3 hours.

Step 5) is a step of reacting the coated or gelled filler and the organic resin, 100 to 300 parts by weight of the organic resin to 100 parts by weight of the coated or gelled filler for 2 to 6 hours at 130 ~ 180 ℃. The organic resin used at this time is urethane resin, urethane dispersion, modified urethane resin, modified urethane dispersion, epoxy resin, aqueous epoxy resin, modified epoxy resin, modified aqueous epoxy resin, silicone resin, silicone emulsion, modified silicone resin, modified silicone emulsion , Phenolic resin, modified phenolic resin, thermoplastic acrylic resin, thermoplastic acrylic emulsion, modified thermoplastic acrylic resin, modified thermoplastic acrylic emulsion, alkyd resin, modified alkyd resin, polyvinyl alcohol, vinyl resin copolymer, vinyl modified resin copolymer, and the like. However, the present invention is not limited thereto.

Step 6) is a step of preparing a synthetic binder, at the time when the reaction of step 5) is finished, add 100 to 300 parts by weight of the silicone polymer liquid solution prepared in step 1) to the reaction mixture at 1 ~ 130 ~ 180 ℃ The mixture is heated and stirred for 2 hours to prepare a synthetic binder.

In addition, the synthetic binder by the simple cold and hot mixing, by adding a silicone polymer or silicone polymer emulsion represented by the formula (1) to a solvent to prepare a silicone polymer liquid solution of 5 to 30% solid content, 100 weight of the silicone polymer liquid solution 50 to 200 parts by weight of an organic resin is added to the part and prepared by stirring for 1 to 2 hours.

The polysiloxane copolymer or polysiloxane copolymer emulsion as a component in the coating composition for silicone release coating having a high hardness of the present invention is a polymethylhydrogen siloxane copolymer represented by Formula 2, which is directly bonded to a silicon atom in one molecule. It contains two or more hydrogen atoms and there is no limit to the combined position. The organic functional group bonded to the silicon atom except the hydrogen atom is a functional group without an aliphatic unsaturated bond, preferably a methyl group. The polysiloxane copolymer or polysiloxane copolymer emulsion is, for example, a copolymer of polydimethylsiloxane and polymethylhydrogensiloxane terminated with trimethylsiloxy, polydimethylsiloxane and polymethylhydrogen terminated with dimethylhydrogensiloxy. Copolymers of siloxanes, or mixtures thereof, including but not limited to. Polysiloxane copolymers or polysiloxane copolymer emulsions are used as crosslinking agents of silicone polymers or silicone polymer emulsions of formula (1).

Platinum-containing catalyst as a component in the coating composition for silicone release coating having a high hardness of the present invention serves as a catalyst for the addition reaction of the silicone polymer and the crosslinking agent.

The solvent which is a component in the coating composition for silicone release coating which has the high hardness of this invention is aromatic hydrocarbons, such as toluene and xylene; esters such as n-butyl acetate, ethyl acetate and methoxypropyl acetate; Ketones such as methyl isobutyl ketone and methyl amyl ketone; Alcohols such as methanol, ethanol and isopropanol; Glycol ethers such as ethylene glycol monomethyl ether and propylene glycol monoethyl ether; And distilled water may be used alone or in combination.

In addition to the above components, the coating composition for silicone release coating having high hardness of the present invention may further include other additives such as silicone-based surface modifiers, material wetting agents, and antifoaming agents, ultraviolet absorbers, 15 micron urethane beads, or 16 nm hydrophobic fumed silica. have.

The 16 nm hydrophobic fumed silica was treated with dimethyldichlorosilane to have a hydrophobic surface to provide a water and oil repellent surface. Therefore, it helps to remove various contaminants and to prevent rain marks when left outdoors.

The coating composition according to the present invention may be used by removing dust and foreign matter on the surface of the adherend material by using alcohol washing and air pressure, and then using a brush, a roller, a brush, or a spray. Specifically, after coating the undercoat composition with a dry coating thickness (DFT) of 20 ~ 30㎛ using an air spraying method on the surface of the adherend material, it is left at room temperature for 1 to 3 hours, and then the top coat composition of the present invention This was applied to the undercoating film with a dry coating thickness (DFT) of 20 ~ 30㎛ using an air spray method, and then dried at room temperature for 2 to 5 hours.

The deposition material may include a concrete wall, a concrete structure, a steel structure, a wooden structure, a wooden wall, road facilities such as a roadside tree, and an anti-sticking facility applied to a plate metal, wood, and plastic. In addition, the coating composition of the present invention is applied to a plate- or sheet-shaped molded article, and then cured by applying heat. It is also possible. At this time, the release paper can also use a sheet of paper printed on the pattern. Therefore, the coating composition according to the present invention can be applied to almost any facility without being limited to the applied material.

The coating composition for silicone release coating having a high hardness according to the present invention includes a silicone polymer or a synthetic binder in which a silicone polymer emulsion and an organic resin are mixed to compensate for the hardness, which is the biggest disadvantage of the silicone polymer coating film, against external impact, friction, and scratches. It strengthens, eliminates the adhesiveness of the coating film surface, and significantly improves the pollution resistance to various contaminants, the water resistance due to snow and rain, rainwater prevention, etc., during long-time outdoor exposure. Therefore, it is possible to prevent the attachment of various illegal advertisement stickers or unauthorized attachments in advance, and it is possible to remove contaminants even by an easy washing method such as rainwater, thereby greatly reducing the time and expense required for maintenance of the city's aesthetics, and at room temperature. It can be cured and can be applied directly to existing public facilities with a brush or roller coating, which can satisfy the conditions that can significantly expand the scope of application expansion.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.

Manufacture example 1-4  : Manufacture of paint coating composition

Gas paints, crosslinking agents, additives and organic solvents commonly used in the paint field were mixed in a stirring vessel and stirred for 10 minutes with a 300 rpm stirrer to prepare a paint composition. The composition components used in the undercoat are shown in Table 1 below.

(Unit: parts by weight) Raw material Preparation Example 1 Production Example 2 Production Example 3 Preparation Example 4 Polyester polyol resin 45 - - - Thermosetting acrylic resin - 60 - - Thermoplastic acrylic resin - - 65 - Bisphenol A type epoxy resin 40 Hexamethylene diisocyanate resin (HDI) 25 9 - - Polyamide resin - 20 Organic solvent
(Toluene / xylene / n-butylacetate = 30/30/40) 26 27 31 36 Other additives 2 2 2 2 Tinuvin 292 2 2 2 2

Four types were used as the gas resin: 1) Polyester polyol resin (king industry product, hydroxyl group 200-400 mg KOH / g, acid group 1-20 mg KOH / g, solid content 50-100 %], 2) Thermosetting acrylic resin [Aekyung Chemical, 41 mg KOH / g hydroxyl group, 2.3-3.3 mg KOH / g acidic acid, 50% solid content], 3) Thermoplastic acrylic resin [Aekyung Chemical, 2-5 mg acid value] KOH / g, solid content 45%, Tg 35 ℃], 4) bisphenol A epoxy resin [Kukdo Chemical, equivalent 300 to 600, softening point 70 ℃, 2,500 ~ 4,000 cps viscosity at 25 ℃] was used.

-Polyamide resin was used as epoxy resin curing agent. [Amine value is 200 ~ 300, 50,000 ~ 70,000cps viscosity at 20 ℃, and the content ratio is 1: 1 in consideration of epoxy equivalent ratio of epoxy resin and active hydrogen equivalent ratio of curing agent. Adjust the content of the formulation so that

-Yellowing type hexamethylene diisocyanate was used as a crosslinking agent [Aekyung Chemical, 50-100% of solid content, NCO 15-25%, Gardner viscosity X-Z2].

The organic solvent was used by mixing toluene / xylene / n-butyl acetate in a weight ratio of 30/30/40.

-As other additives, a silicone-based surface modifier, a material wetting agent, and an antifoaming agent manufactured by BYK were used.

As a UV absorber, HALS (Hindered amine light stablizer) Tinuvin 292 manufactured by Ciba-Geigy was used.

Experimental Example 1  : Physical Properties Test of Coating Film Using Undercoat Coating Composition

In order to evaluate the physical properties of the coating film using the undercoat composition prepared in Preparation Examples 1 to 4, the following method was performed.

Stainless steel 304 species (SUS 304) and PVC sheets were used for the specimens, and the specimens were prepared in a size of 10 cm (width) x 15 cm (length). The specimens were pretreated using simple alcohol cleaning and air pressure to remove dust and debris. The primer coating composition prepared in Preparation Examples 1 to 4 was coated on the pre-treated specimens with a dry coating thickness (DFT) of 20 to 30 μm using an air spraying method, and then dried at room temperature for 3 hours.

Test items and test evaluation method of coating film are as follows.

1.adhesive

The upper part of the specimen was cut horizontally and vertically at intervals of 1 mm using a knife, and then the cellophane adhesive tape was attached thereto, and then removed, and the adhesiveness was evaluated by the number of remaining pieces of the coating film separated into 100 pieces on the coating film. And this experiment was performed immediately after the test specimens and experiments performed after 7 days left at room temperature.

2. Coating Hardness

The coating hardness was used the pencil hardness method of JISK-5400. Specifically, the degree of scratches at the time of drawing a 45 degree angle for each kind of pencil to the dried coating film using the pencil hardness tester was visually determined.

3. Transparency

After forming a coating film with a thickness of 30㎛ on a transparent PET film and heat-treated for about 5 minutes in a 60 ℃ drying furnace, the degree of transparency was visually observed.

4. Room temperature dryness

After spray coating, the mixture was left at room temperature and the drying time was checked to determine the completion point.

The physical properties of the coating film using the undercoat composition are shown in Table 2.

Test Items Preparation Example 1 Production Example 2 Production Example 3 Preparation Example 4 Initial Adhesion (%) SUS 304 40 75 60 92 PVC sheet 90 95 95 100 Adhesiveness after 7 days SUS 304 85 95 78 100 PVC sheet 100 100 100 100 Coating hardness (pencil hardness) SUS 304 HB H H HB PVC sheet 2B HB H HB Transparency PET film ◎ ◎ ◎ ◎ Room temperature drying (touch drying) SUS 304 3 hours 30 minutes 15 minutes 50 minutes

As shown in Table 2, Preparation Example 2 (Thermosetting Acrylic Resin) and Preparation Example 4 (Epoxy Resin) showed generally good physical properties in almost all test items in SUS 304 and PVC sheets. On the contrary, in Preparation Example 1 (polyester polyol resin), the initial adhesiveness and room temperature dryness were weak in SUS 304. In addition, in Preparation Example 3 (thermoplastic resin), the coating film hardness and room temperature dryness was excellent, but the adhesion to SUS 304 was poor.

Therefore, in the subsequent top coat composition, the adhesive resin to the base material of the bottom coat was considered as the top priority, and the resin of the epoxy resin of Preparation Example 4 and the polyamide-based crosslinking agent were used.

Examples 1-4 and Comparative Examples 1-4  : Production of Top Coating Composition

The composition components shown in Table 3 were sequentially added to the stirring vessel, followed by stirring for 10 minutes with a 300 rpm stirrer to prepare a top coat composition.

(Unit: parts by weight) Raw material Comparative example Example One 2 3 4 One 2 3 4 Silicone Polymer (Rubber) 50 50 50 50 - - - - Synthetic binder - - - - 50 50 50 50 15 micron urethane beads - 5 - - - 5 - 5 16nm Hydrophobic Fumed Silica - - - - - - 5 - Polysiloxane copolymer 5 5 10 0.5 2.5 2.5 2.5 - Polysiloxane copolymer emulsion - - - - - - - 2.5 Platinum-containing catalyst 0.5 0.5 1.0 0.1 0.2 0.2 0.2 0.2 menstruum 42.5 37.5 37.0 47.4 45.3 40.3 37.3 37.3 Other additives 2 2 2 2 2 2 2 2 Sunscreen - - - - - - 3 3

The silicone polymer was a polydimethylsiloxane terminated with dimethylvinyl and a polymethylvinylsiloxane copolymer (50% solids, Dow Corning, viscosity 15,000 cps).

The polysiloxane copolymer was a polydimethylsiloxane terminated with trimethylsiloxy and a methylhydrogensiloxane copolymer (Dow Corning, 100% solids, viscosity 20 cps).

Polysiloxane Copolymer Emulsions were made of polydimethylsiloxane terminated with dimethylvinyl and cyclotetrasiloxane copolymer (Dow Corning, 40% active ingredient).

Platinum-containing catalysts were used (a Dow Corning company) catalyst with a platinum content of 5,000 ppm, a viscosity of 400 cps and a specific gravity of 0.96.

In Examples 1 to 3, a solvent obtained by mixing toluene / xylene / n-butyl acetate in a weight ratio of 30/30/40 was used, and in Example 4, ethanol / ethylene glycol monomethyl ether / distilled water was used. The solvent mixed in the weight ratio of 20/30/50 was used.

-As other additives, a silicone-based surface modifier, a material wetting agent, and an antifoaming agent manufactured by BYK were used.

-As a UV absorber, HALS (Hindered amine light stablizer) Tinuvin manufactured by Ciba-Geigy was used.

16 nm hydrophobic fumed silica was used Degussa products treated with dimethyldichlorosilane to have a hydrophobic surface providing a water and oil repellent surface.

-Synthetic binders used in Examples 1 to 3 were prepared by the following method. First, 200 parts by weight of n-hexane was added to 100 parts by weight of polydimethylsiloxane and polymethylvinyl siloxane copolymer (Dow Corning Co., 50% solids, viscosity 15,000 cps), which were terminated with dimethylvinyl, a silicone polymer. A polymer liquid solution was prepared. 40 parts by weight of vinyltrimethoxysilane (manufactured by Dow Corning), a silane coupling agent, polydimethylsiloxane and polymethylvinylsiloxane copolymer terminated with dimethylvinyl, a silicone polymer (manufactured by Dow Corning, 50% solids, viscosity 15,000 cps) 130 parts by weight, 0.1 parts by weight of aminopropyltriethoxysilane (manufactured by Dow Corning), an amine catalyst, was mixed and reacted at 140 ° C. for 4 hours to prepare a silane-modified silicone polymer. Subsequently, a small amount of distilled water was added to vinyltrimethoxysilane, which is a silane coupling agent, to hydrolyze the alkoxy group of vinyltrimethoxysilane in distilled water to produce a silanol group. A spherical silica (average particle size of 5 microns, manufactured by KGCHEM) was added thereto as a filler, and isopropanol was added 8 times to the silane coupling agent and then heated at 110 ° C. By heating, the spherical silica was surface treated with a silane coupling agent. 100 parts by weight of the silicone rubber liquid solution prepared above was added to 100 parts by weight of the surface-treated spherical silica and mixed uniformly at 130 ° C. 10 parts by weight of the silane-modified silicone polymer was added thereto, followed by heating and stirring at 130 ° C. for 1.5 hours to coat or gel the silicone polymer on spherical silica. To 100 parts by weight of the coated or gelled spherical silica was added 200 parts by weight of a thermoplastic acrylic resin (manufactured by Rohm & Haas, 30% solids, Tg 105 ° C., molecular weight 120,000), followed by reaction at 150 ° C. for 4 hours. At the end of the reaction, 200 parts by weight of the silicone rubber liquid solution prepared above was added to the reaction mixture, and stirred at 150 ° C. for 1.5 hours to prepare a synthetic binder.

The synthetic binder used in Example 4 was added with 100 parts by weight of ethylene glycol monoethyl ether to 100 parts by weight of a dimethylvinylmethylsiloxane copolymer (40% active ingredient manufactured by Dow Corning) terminated with dimethylvinyl as a silicone polymer emulsion. A 20% silicone polymer liquid solution was prepared. 100 parts by weight of polyurethane dispersion (Chemine Co., Ltd., self-crosslinking type, solid content 40%) was added thereto, and stirred for 1 hour using a 300 rpm stirrer to prepare a synthetic binder.

Experimental Example 2  : Physical Properties Test of Coating Film Using Top Coating Composition

In order to evaluate the physical properties of the coating film using the top coat composition prepared in Examples 1 to 4 and Comparative Examples 1 to 4, the following method was performed.

Stainless steel 304 species (SUS 304) and PVC sheets were used for the specimens, and the specimens were prepared in a size of 10 cm (width) x 15 cm (length). The specimens were pretreated using simple alcohol cleaning and air pressure to remove dust and debris. The prepainted coating composition prepared in Preparation Example 4 was coated with a dry coating thickness (DFT) of 20 to 30 μm using an air spraying method and then left at room temperature for 2 hours. Subsequently, the top coat composition prepared in Examples 1 to 4 and Comparative Examples 1 to 4 was coated on the undercoat coating specimen with a dry coating thickness (DFT) of 20 to 30 μm using an air spray method, followed by 3 at room temperature. It was dried at room temperature for time.

Test items and test evaluation method of coating film are as follows.

1. Paint initial properties and paint stability

In the initial phase test of the paint, the phase separation and the haze state were visually determined immediately after the top coat compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4, and the paint stability test was performed for 8 hours after preparation of the top coat composition. After the passage, appearance states such as phase separation and haze were determined.

2. Adhesiveness, transparency, room temperature drying

Adhesiveness, transparency, room temperature dryness experiment was the same as the method of Experimental Example 1.

3. Coating Hardness

The coating hardness test measured the presence or the like of peeling or sliding of the coating film by hand at 25 ° C., and a phenomenon that the coating film surface became cloudy.

4. Promote weather resistance

The QUV Accelerated Weathering Test item used ASTM G-53's QUV Accelerated Weathering Tester. Specifically, as for the ultraviolet fluorescent lamp, gloss preservation value and color difference were evaluated for each of 148 hours (7 days) and 720 hours (30 days) using a UV-B313 lamp (280-315 nm).

The gloss retention value was calculated by the following equation (1) using a glossmeter (BYK) company.

Gloss Preservation Value (%) = [60 ° Mirror Polish / Initial 60 ° Mirror Polish after Experiment] × 100

In addition, the color difference used the spectrocolorimeter which is a diffuse reflectance measuring apparatus. Specifically, the difference between the two colors is expressed from the visual concept to the numerical concept. That is, the geometric distance of the two colors in the color space coordinates was expressed numerically, and was calculated by Equation 2 below.

Color difference (△ E) = [(△ L) ² + (△ a) ² + (△ b) ²] ½

In Equation 2, L is a brightness index of the Hunter color display system, and a and b represent the chromatic coefficients of the Hunter color display system.

5. Promote pollutant

After spraying a 10 parts by weight of carbon black solution in water to the specimen, and dried for 5 hours in a 30 ± 2 ℃ constant temperature oven, water washing and rubbing test was performed. These experiments were performed immediately after the specimen was prepared and after 60 days in the open air. The water washability was determined by visual inspection of the remaining state after washing down naturally with the surface coated with carbon solution in running water, and the rubability was determined visually by wiping the surface of the coating film with gauze or tissue.

6. Attachment Release

After attaching various stickers, oriented polypropylene (OPP) tapes, blue tapes, etc. on the coating film, rub them to be in close contact with each other, and then store them in a thermostatic bath at 60 ° C for 30 minutes, and then cool them down to room temperature and remove them easily. Determined. This experiment was also performed immediately after specimen preparation and repeated experiments were performed after leaving for 60 days outdoors.

7. Rain mark prevention

The appearance of the surface of the coating film was visually observed after 24 hours after directly pouring the water in the form of rainwater using the washing hose.

Physical properties of the coating film using the top coat composition are shown in Table 4.

Test Items Comparative example Example One 2 3 4 One 2 3 4 Paint initial appearance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Paint stability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ Initial Adhesion (%) 20 20 25 5 100 100 100 90 Adhesiveness after 7 days 40 40 50 10 100 100 100 85 Coating hardness (rubbing property) × (film peeling) × (film peeling) × (film peeling) × (film peeling) ◎ ◎ ◎ ○ Transparency ◎ □ ◎ ◎ ◎ □ ○ ○ Room temperature drying (touch drying) 15th 15th 7 days N / A 2 hours 1 hours 1 hours 3 hours Accelerated weathering (QUV) 148 hours Glossy Preservation Value (%) 95 96 96 N / A 93 95 97 95 Color difference (△ E) 3.8 4.2 3.9 N / A 4.7 4.8 2.5 2.1 720 hours Glossy Preservation Value (%) 91 93 92 N / A 91 93 95 93 Color difference (△ E) 6.5 6.8 6.7 N / A 7.8 6.9 3.2 2.8 Promote pollution Immediately after specimen preparation Water washability × × × N / A □ □ ○ □ Rub × × △ N / A ○ ○ ◎ ○ After 60 days Water washability N / A N / A N / A N / A ○ □ ○ □ Rub N / A N / A N / A N / A ◎ ◎ ◎ ○ Attachment Release Immediately after specimen creation sticker ◎ ◎ ◎ N / A ◎ ◎ ◎ ○ OPP tape for packaging ◎ ◎ ◎ N / A ◎ ◎ ◎ ○ Blue tape ○ ◎ ◎ N / A ○ ◎ ◎ ○ After 6 days sticker ◎ ◎ ◎ N / A ◎ ◎ ◎ □ OPP tape for packaging ◎ ◎ ◎ N / A ◎ ◎ ◎ ○ Blue tape ○ ◎ ◎ N / A ○ ◎ ◎ ○ Rainwater mark prevention Immediately after specimen creation △ △ △ N / A □ ○ ○ □ After 6 days □ □ □ N / A ○ ○ ◎ ○

※ ◎: Very good, ○: Good, □: Normal, △: Insufficient, ×: Poor

As shown in Table 4, the coating composition (Examples 1 to 4) according to the present invention includes a synthetic binder in which a silicone polymer or a silicone polymer emulsion and an organic resin are mixed to compensate for the hardness of the silicone polymer coating film. It is resistant to impact, friction, and scratches, and eliminates adhesiveness on the surface of coatings, and significantly improves pollution resistance to various contaminants during long-term exposure to the outdoors, water resistance due to snow and rain, and rainwater mark prevention. In particular, the physical properties of the coating composition of Example 3 was the best, which uses 16nm hydrophobic fumed silica to form a water repellent and oil-repellent coating surface, which greatly helps to remove various contaminants and to prevent rainwater marks when left outdoors. It seems to be.

On the other hand, in the coating compositions of Comparative Examples 1 to 4 containing silicone polymer alone, there is no problem in the appearance or stability of the paint, but in the case of the addition reaction in which heat is not accompanied during the curing process, curing is not performed at all. Could not get In particular, in the case of Comparative Example 4 using a small amount of the polysiloxane copolymer and the catalyst, addition reaction itself did not occur, so that not only the appearance of the coating film but also the phenomenon that the coating film was dropped by a slight rubbing occurred.

The coating composition for silicone release coating having a high hardness according to the present invention includes a silicone polymer or a synthetic binder in which a silicone polymer emulsion and an organic resin are mixed to compensate for the hardness, which is the biggest disadvantage of the silicone polymer coating film, against external impact, friction, and scratches. It strengthens, eliminates the adhesiveness of the surface of the coating film, and has the effect of remarkably improving pollution resistance to various contaminants, water resistance due to snow and rain, rainwater prevention, etc., during long-time outdoor exposure. Therefore, it is possible to prevent the attachment of various illegal advertisement stickers or unauthorized attachments in advance, and it is possible to remove contaminants even by an easy washing method such as rainwater, thereby greatly reducing the time and expense required for maintenance of the city's aesthetics, and at room temperature. It can be cured and can be applied directly to existing public facilities with a brush or roller coating, which can satisfy the conditions that can significantly expand the scope of application expansion.

Claims (11)

45 to 75 parts by weight of a silicone binder represented by the formula (1) or a synthetic binder mixed with a silicone polymer emulsion and an organic resin, 1 to 5 parts by weight of a polysiloxane copolymer or a polysiloxane copolymer emulsion represented by the formula (2), and a platinum-containing catalyst 0.01 Coating composition for a silicone release coating having a high hardness, comprising ~ 1 part by weight and 10-50 parts by weight of a solvent: <Formula 1>

In Formula 1, R1 is OH, C ₁ ~ C ₄ alkyl group, C ₂ ~ C ₁₀ alkenyl group, phenyl group, carboxyl group, amino group, R2 is C ₁ ~ C ₄ alkyl group, C ₂ ~ C ₁₀ alkenyl group or phenyl group And n is a positive integer of 1 to 10,000. <Formula 2>

In Formula 2, o is a positive integer of 1-100, p is a positive integer of 1-100. The method of claim 1, wherein the synthetic binder 1) preparing a silicone polymer liquid solution having a solid content of 5 to 30% by adding a silicone polymer or silicone polymer emulsion represented by Formula 1 to a solvent, 2) preparing a silane-modified silicone polymer by mixing a silane coupling agent and a silicone polymer or silicone polymer emulsion represented by the following Formula 1 and reacting at 120 to 150 ° C. for 2 to 6 hours, 3) adding a silane coupling agent to distilled water to hydrolyze, adding a filler to it, and then adding alcohol to heat the filler at 105-110 ° C. to surface-treat the filler; 4) After adding the silicone polymer liquid solution prepared in step 1) to the surface-treated filler and mixing at 100-150 ° C., the silane-modified silicone polymer prepared in step 2) was then added to 0.5- at 100-150 ° C. Reacting for 3 hours to coat or gel the silicone polymer on the filler, 5) reacting the coated or gelled filler and the organic resin at 130 to 180 ° C. for 2 to 6 hours, and 6) is prepared through the process consisting of adding a liquid solution of the silicone polymer prepared in step 1) to the reaction mixture at the end of step 5) and reacting for 1 to 2 hours at 130 ~ 180 ℃ A coating composition for coating a silicone release coating having high hardness: <Formula 1>

In Formula 1, R1 is OH, C ₁ ~ C ₄ alkyl group, C ₂ ~ C ₁₀ alkenyl group, phenyl group, carboxyl group, amino group, R2 is C ₁ ~ C ₄ alkyl group, C ₂ ~ C ₁₀ alkenyl group or phenyl group And n is a positive integer of 1 to 10,000. The method of claim 1, wherein the synthetic binder is prepared by adding a silicone polymer or silicone polymer emulsion represented by Formula 1 to a solvent to prepare a silicone polymer liquid solution having a solid content of 5 to 30%, and then, to 100 parts by weight of the silicone polymer liquid solution. 50 to 200 parts by weight of an organic resin is added, characterized in that it is prepared by stirring for 1 to 2 hours, the coating composition for silicone release coating having a high hardness: <Formula 1>

In Formula 1, R1 is OH, C ₁ ~ C ₄ alkyl group, C ₂ ~ C ₁₀ alkenyl group, phenyl group, carboxyl group, amino group, R2 is C ₁ ~ C ₄ alkyl group, C ₂ ~ C ₁₀ alkenyl group or phenyl group And n is a positive integer of 1 to 10,000. 4. The silicone polymer or silicone polymer emulsion according to any one of claims 1 to 3, wherein the silicone polymer or silicone polymer emulsion is polydimethylsiloxane terminated with trimethylsiloxy and polymethylvinylsiloxane copolymer, polydimethyl terminated with dimethylvinylsiloxy. Consisting of siloxane and polymethylvinylsiloxane copolymer, polydimethylsiloxane and polymethylvinylsiloxane copolymer terminated with divinylmethylsiloxy, and polydimethylsiloxane and polymethylvinylsiloxane copolymer terminated with trivinylsiloxy Paint composition for silicone release coating having a high hardness, characterized in that it comprises one or more selected from the group. The organic resin according to any one of claims 1 to 3, wherein the organic resin is a urethane resin, urethane dispersion, modified urethane resin, modified urethane dispersion, epoxy resin, aqueous epoxy resin, modified epoxy resin, modified aqueous epoxy resin, silicone Resin, silicone emulsion, modified silicone resin, modified silicone emulsion, phenolic resin, modified phenolic resin, thermoplastic acrylic resin, thermoplastic acrylic emulsion, modified thermoplastic acrylic resin, modified thermoplastic acrylic emulsion, alkyd resin, modified alkyd resin, polyvinyl alcohol, A vinyl resin copolymer, a vinyl modified resin copolymer, characterized in that it comprises one or more selected from the group consisting of, a coating composition for silicone release coating having a high hardness. The method of claim 2 or 3, wherein the solvent is n-hexane, n-heptane, n-octane, n-nonane, methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, propylene glycol monoethyl ether and distilled water Paint composition for silicone release coating having a high hardness, characterized in that it comprises one or more selected from the group. The method of claim 2, wherein the silane coupling agent in step 2) and 3) comprises at least one member selected from the group consisting of vinyl silane, methoxy silane and ethoxy silane, having a high hardness Coating composition for silicone release coating. The method of claim 2, wherein the filler in step 3) is characterized in that it comprises at least one selected from the group consisting of fused silica, spherical silica, alumina trihydrate, hydrosclay and talc, silicon release having high hardness Coating composition for coating. 2. The polysiloxane copolymer or polysiloxane copolymer emulsion of claim 1 is a copolymer of polydimethylsiloxane and polymethylhydrogensiloxane terminated with trimethylsiloxy, polydimethylsiloxane and poly terminated with dimethylhydrogensiloxy. A coating composition for silicone release coating having high hardness, comprising at least one selected from the group consisting of a copolymer of methylhydrogensiloxane, or a mixture thereof. The method of claim 1, wherein the solvent is toluene, xylene, n-butyl acetate, ethyl acetate, methoxypropyl acetate, methyl isobutyl ketone, methyl amyl ketone, methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, propylene glycol mono A coating composition for silicone release coating having a high hardness, characterized in that it comprises one or more selected from the group consisting of ethyl ether and distilled water. The method of claim 1, wherein the coating composition further comprises at least one member selected from the group consisting of silicone surface modifiers, material wetting agents, defoamers, ultraviolet absorbers, 15 micron urethane beads and 16 nm hydrophobic fumed silica, Coating composition for silicone release coating having a high hardness.