KR100513825B1 - Pollution-prevention advertisement sticker non-sticking coating compositions and the method - Google Patents

Abstract

The present invention relates to a non-fouling advertising sticker coating composition prepared by using an acrylic resin containing a tertiary amine group as a main component and epoxy silane as a curing component, and a method of manufacturing the same.

Stickers attached to street walls and power poles are not good in appearance, and do not easily fall off, which requires a lot of cost to remove the stickers. In particular, the attached advertising sticker has poor scratch resistance and weather resistance, and easily binds with street pollutants, which makes the appearance unpleasant.

In the present invention, a mixture of a tertiary amine monomer, an acrylic or methacrylic monomer having an aliphatic group, a styrene monomer, and a methacryl monomer having a hydroxyl group and a reaction initiator are added dropwise to a medium boiling point solvent for 3 to 5 hours, and the reaction temperature is reduced. Was polymerized at a temperature of 80 ° C. to 100 ° C. for 8 to 12 hours to prepare an acrylic resin composition having a solid concentration of 50%, a number average molecular weight of 16,000 to 20,000, a glass transition temperature of 30 ° C., and a viscosity of 5 to 15 cPs. The present invention provides a coating composition for preventing adhesion of non-polluting advertising stickers by mixing epoxy resin as a curing agent in a resin composition, and a method of manufacturing the same. The non-polluting advertising sticker coating composition has excellent gloss, adhesion, solvent resistance and coating hardness, and has excellent pollution prevention performance by hydrophilicity of the surface of the coating, and non-polluting characteristics and weather resistance, in which contaminants are easily removed by rain water. It forms a coating film which is difficult to adhere to an advertisement sticker having excellent smoothness.

Description

Non-polluting advertisement sticker non-sticking coating compositions and the method of manufacturing the same {Pollution-prevention advertisement sticker non-sticking coating compositions and the method}

The present invention relates to a non-polluting coating composition for preventing adhesion of a non-polluting advertisement sticker prepared using an acrylic resin containing a tertiary amine group as a main component and an epoxy silane as a curing component, and particularly, having a tertiary amine monomer and an aliphatic group. A mixture of an acrylic or methacrylic monomer, a styrene monomer, and a methacryl monomer having a hydroxyl group and a reaction initiator are added dropwise to the medium boiling point solvent for 3 to 5 hours, and the reaction temperature is 8 hours to 80 ° C to 100 ° C. The polymerization was carried out for 12 hours to prepare an acrylic resin composition having a solid content of 50%, a number average molecular weight of 16,000 to 20,000, a glass transition temperature of 30 ° C., and a viscosity of 5 to 15 cPs. It is characterized by providing a coating composition for preventing the adhesion of advertising stickers and a method of manufacturing the same. The non-polluting coating composition for the non-polluting advertisement sticker has excellent gloss, adhesion, solvent resistance, and film hardness, and has excellent pollution prevention performance by hydrophilicity of the surface of the coating, and non-polluting characteristics and weather resistance where pollutants are easily removed by rain water. The present invention relates to a two-component acrylic / silicone composition for paints, which forms a coating film that is difficult to adhere to an advertisement sticker having excellent smoothness.

The street lamps, power poles and overpasses, bridges, and electrical distribution boards installed on the streets have advertisement stickers on the streets, which make them look bad and not easy to fall off. In addition, there is a problem that the color is changed and the appearance is dirty soon after painting because it is polluted with automobile exhaust or dust on the street.

As a proper countermeasure against such a problem, there is a demand for the development of a coating composition having excellent weather resistance, non-pollution, and preventing adhesion of advertisement stickers.

Conventional anti-sticker paint has a type using wax or silicone additives on the surface of the coating film and an embossing material to form irregularities. The type using wax or silicone additives on the surface is slippery as if oil is on the surface. Sticky, scratch and weather resistance is poor and is showing a problem of easy contamination. In addition, the type using the embossing material to form irregularities on the surface of the coating film is made of wood powder (sawdust), synthetic resin (PVC) powder, stone powder, glass beads, etc. Although it is made, it looks bad and has a problem of being easily polluted.

Korean Patent Laid-Open Publication Nos. 2001-0087777 and 2002-0089664 disclose coating compositions for preventing ad sticker adhesion using silicone resins and silica powders, silicone resins and curing agents, respectively, in order to solve the problems described above. However, both of the invention has a good anti-sticker function, but the non-pollution characteristics have a problem that the appearance looks poor.

In order to fundamentally improve the fouling resistance, the surface of the coating is replaced with a hydrophilic component to weaken the binding strength with lipophilic substances such as exhaust gas and soot, which are the main causes of pollution, and it is difficult to penetrate the contaminants by increasing the crosslinking density of the coating. However, even if it is contaminated, it is absolutely necessary to develop a non-polluting advertisement sticking prevention coating that has a function of easily removing attached contaminants by rainwater.

The present invention has been made to solve the above problems, the object of the present invention is to impart non-pollution and anti-sticker properties at the same time, and to introduce a high-elasticity when cross-linking by introducing a functional group of the tertiary amine in the acrylic resin structure It exhibits high durability and expands elastic area of coating and expresses great breakage energy. It has excellent scratch resistance, and adjusts glass transition temperature by using acrylic or methacrylic monomer and styrene monomer with aliphatic group. Increasing the crosslinking density by combining acrylic resin and epoxy silane by introducing hydroxy group to increase adhesion, improving drying speed, surface hardness, solvent resistance, etc., while maintaining high surface energy and contact angle of water due to hydrophilicity of coating film Two-component acrylic / excellent in weatherability and smoothness and imparting non-pollution properties It is a silicone resin composition and a non-staining advertising stickers for preventing paint composition using the same to provide.

An object of the present invention as described above is a mixture of a tertiary amine monomer, an acrylic or methacrylic monomer having an aliphatic group, a styrene monomer, a methacrylic monomer having a hydroxyl group and a reaction initiator is added dropwise to the middle boiling point solvent for 3 to 5 hours. In addition, the reaction temperature was polymerized at a temperature of 80 to 100 ℃ for 8 to 12 hours to prepare an acrylic resin composition having a solid content concentration of 50%, number average molecular weight of 16,000 to 20,000, glass transition temperature of 30 ℃, viscosity of 5 to 15 cPs In addition, by mixing an epoxy silane as a curing agent to the prepared acrylic resin composition is achieved by providing a non-polluting coating composition for preventing the adhesion of advertising stickers and a method of manufacturing the same.

The acrylic resin composition containing the tertiary amine group introduces the functional group of the tertiary amine to express high elasticity and high durability at the time of crosslinking, and expands the elastic region of the coating film and expresses great breakage energy, and is excellent in gloss and scratch resistance. The glass transition temperature is adjusted by using an acrylic or methacrylic monomer having an aliphatic group or a styrene monomer, and the crosslinking density of the acrylic resin and epoxy silane which increases the adhesiveness by introducing a methacryl monomer having a hydroxyl group is increased. It improves the drying speed, surface hardness, solvent resistance, etc., and maintains high surface energy and water contact angle increase due to the hydrophilicity of coating film, and it has excellent weather resistance and smoothness and imparts non-pollution characteristics.

Hereinafter, a non-polluting coating composition for preventing adhesion of an advertisement sticker according to the present invention and a manufacturing method thereof will be described in detail.

The acrylic resin composition containing the tertiary amine group according to the present invention is prepared by radical polymerization of various types of monomers having a vinyl double bond using a pyrolysis initiator. The radical polymerization is according to the solution polymerization method.

As a raw material used in the acrylic resin composition containing the tertiary amine group, both acrylic ester and methacrylic ester may be used. Monomers having a vinyl double bond include 3 to 15 wt% of tertiary amine-containing monomers, 60 to 80 wt% of acrylic or methacrylic monomers having aliphatic groups, 15 wt% of styrene monomers, and 2 to 10 methacrylic monomers having hydroxyl groups. Used in proportions by weight.

Examples of tertiary amine-containing monomers used in the present invention include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and the like, and examples of the acrylic or methacrylic monomer having an aliphatic group include normal butyl acrylate and 2- Ethylhexyl acrylate, ethyl acrylate, normal butyl methacrylate, normal propyl methacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, glycidyl methacrylate , Lauryl methacrylate, isobonyl methacrylate, and the like, and examples of the methacryl monomer having a hydroxyl group include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxy. Butyl methacrylate, and the like, and one or more of these may be selected to adjust the glass transition temperature. The glass transition temperature of the acrylic resin and in the range of 0 ℃ to 50 ℃, preferably 20 ℃ to 40 ℃.

The content of the tertiary amine-containing monomer used in the present invention is used to be 3 to 15% by weight, based on the solid content of the acrylic resin in consideration of crosslinking with the epoxysilane used as a curing agent, preferably 5 to 10% by weight to be. If the content of the tertiary amine group is too low, the crosslinking density with the epoxy silane, which is a curing agent, is low, resulting in deterioration of coating properties. If the content is too high, the coating film is hardened, poor storage stability and yellowing are caused by excessive increase in the crosslinking density. Symptoms may occur.

Acrylic or methacrylic monomers used in the present invention is to adjust the glass transition temperature by appropriately adjusting the flexible monomer and the hard monomer. Their content is used to 60 to 80% by weight based on the solid content of the acrylic resin, preferably 70 to 78% by weight. These functions adjust the hardness of the coating film, impart gloss and smoothness, and contribute to improving scratch resistance.

Styrene monomer used in the present invention is a hard monomer serves to improve the coating hardness, give gloss and lower the price. If the content of these is more than 20% by weight based on the solid content of the acrylic resin, the weather resistance of the coating film may be lowered and yellowing may occur. Therefore, 15 wt% was used in the present invention.

The methacryl-based monomer containing a hydroxyl group used in the present invention is used to be 2 to 10% by weight based on the solid content of the acrylic resin, since the viscosity increase is severe when used in excess of them, preferably 2 to 5% by weight. Their function contributes to the enhancement of the hardness of the coating film and the adhesion with the workpiece.

As the radical polymerizable initiator used in the present invention, benzoyl peroxide, tertiary butyl peroxy benzoate, tertiary butyl peroxy-2-ethyl hexanoate, tertiary mil peroxy-2-ethyl hexanoate, azobisiso Butyronitrile and the like. Such radically polymerizable initiators may be used alone or in combination of two or more thereof. The amount of the initiator is used to be 1 to 3% by weight based on the total weight of the monomer composition, preferably 1 to 2% by weight. If the content of the radical initiator is too small, the viscosity and molecular weight is increased to generate a slip phenomenon, poor spray workability, if too large can cause a decrease in the coating properties due to excessive molecular weight decrease.

The solvent used in the present invention is aromatic hydrocarbons such as toluene, xylene, esters such as normal butyl acetate, ethylene glycol ethyl ether acetate, ketones such as methyl isobutyl ketone, methyl normal amyl ketone, isopropanol, normal butanol and iso Alcohols such as butanol and glycol ethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether may be used, and these solvents may be used alone or in combination in consideration of the effect of reaction temperature on the molecular weight and final viscosity of the synthetic resin. In consideration of synthesis temperature, solubility parameter, evaporation rate, etc., a solvent having a boiling point of 100 ° C. to 160 ° C. is used, and preferably, a boiling point has a range of 110 ° C. to 150 ° C.

In the resin composition synthesis method, the mixed solution containing the monomers and the initiators listed above is added to the solvent solution in the reactor at a uniform rate for 3 to 5 hours, and dropped therein, for 8 to 12 hours at a temperature of 80 ° C to 100 ° C. The polymerization proceeds. By stably inducing the reaction conditions as described above, it is possible to obtain a tertiary amine-containing acrylic resin composition having excellent gloss, good smoothness, and good scratch resistance.

Epoxysilane used as a curing agent in the present invention can be used directly by using 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, or by polymerizing them, the amount of the curing agent used According to the amine content in the tertiary amine-containing acrylic resin, the equivalent of amine and epoxy is used at 1: 1. If the tertiary amine group or the epoxy group does not participate in the crosslinking reaction, it does not form a dense crosslinking, resulting in a decrease in coating properties.

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples.

<Examples 1 to 4 and Comparative Examples>

In a four-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer, 140 g of xylene and 60 g of normal butanol were added thereto, and the temperature was increased to 90 ° C. while being replaced with nitrogen gas. Thereafter, while maintaining the temperature of the solvent, a mixed solution of 4 g of azobisisobutyronitrile was added dropwise at a uniform rate over 3 to 5 hours with the monomer and initiator described below. After completion of the dropping, the mixture was further aged for 3 hours, and then 0.5 g of azobisisobutyronitrile was dissolved in 50 g of xylene as an initiator, added dropwise over 30 minutes, and the reaction was terminated by removing unreacted monomer with stirring for 3 hours. 86.8 g of xylene and 58.7 g of normal butanol were added thereto to dilute to obtain a tertiary amine-containing acrylic resin having a glass transition temperature of 30 ° C. and a solid content of 50%.

<Table 1>

Normal Butyl Acrylate Methyl methacrylate Normal Butyl Methacrylate Styrene 2-hydroxyethyl methacrylate Dimethylaminoethyl methacrylate Viscosity (cPs) Number average molecular weight Polydispersity (Mw / Mn) Nonvolatile matter (%) Example 1 95.1 144.9 80 60 - 20 6.27 18000 2.0 49.5 Example 2 90.9 129.1 80 60 20 20 10.7 17700 2.1 49.8 Example 3 82.6 117.4 80 60 20 40 12.9 17600 2.1 49.6 Example 4 74.4 105.6 80 60 20 60 14.0 17100 2.1 49.7 Comparative example 99.1 140.9 80 60 20 - 8.84 17700 2.0 49.7

<Film Property Evaluation>

In order to determine the properties of the coating film formed from the composition comprising the acrylic resin of Examples 1 to 4 and Comparative Examples as shown in the following table, the amine and epoxy equivalent ratio of the acrylic resin and the curing agent epoxysilane as 1: 1, the transparent paint and After preparing the white paint, the general physical properties, weather resistance, and non-pollution test of the coating film and the adhesion prevention of the advertising sticker were compared and examined. On the other hand, the coating material was prepared as an acrylic / urethane paint using Bayer's Desmodur N-3600, a polyisocyanate, as a curing agent, was prepared with an equivalent ratio of NCO / OH of 1: 1.

Coating performance test specimens were prepared as follows.

First, tin plate was polished with abrasive paper # 220, then the surface washer was spray-coated to a dry coating thickness (DFT) of 50 μm and dried, then polished with abrasive paper # 600, and the base coat white coating was 20 to 25 μm. It was spray-coated to a film thickness and dried. Thereafter, the paint prepared by the above formulation was naturally dried for 7 days after spray coating with DFT 50 µm to obtain a test coating film, and then the coating performance was examined.

Coating performance test was evaluated according to the general coating properties evaluation method as follows.

<Table 2>

Drying time was coated on a glass plate with a doctor film applicator (0.004 inch) so that the wet coating film thickness was 0.05 ㎜ according to the drying time test method of paint of KS M 5000-2512, and then dried naturally. The evaluation method measured the drying time using the dry-hard method.

Gloss measurement is a 60 ^o mirror gloss test method of the paint of KS M 5000-3312, and the reflectance is measured by the glossmeter when the angle of incidence and the horizontal angle are 60 ^o , respectively, and the percentage when the mirror surface gloss of the standard glass surface is 100 The average value measured 5 times was expressed as.

Adhesion test is done according to ISO 2409 paint test method by drawing 11 lines horizontally and vertically on the specimen so that the gap is 1mm, attaching cellophane adhesive tape on it, and then peeling it off. Adhesiveness was evaluated by the number of pieces remaining.

The coating film hardness is a 45 ^o angle according to the type of pencil (B, HB, F, H, 2H, 3H, etc.) drawn on a coating film dried using a pencil hardness tester according to the pencil hardness method of JIS K-5400. The degree of scratches was visually determined.

Solvent resistance was observed in appearance after the methyl ethyl ketone (MEK) was sufficiently immersed in the cloth, and the coating film was peeled off with the number of times to rub the coating film.

Accelerated fouling was carried out by spraying the specimen with carbon black dispersed in water and a solvent (mineral spirits) at 20% for 5 hours at 80 ± 2 ° C., drying and evaluating water washing and rubbing.

The water washing property visually determined the state remaining after the carbon-washed surface was washed down naturally with flowing water.

Rubbing property visually determined the degree of wiping off the surface when the surface of the coating film was wiped off with gauze or toilet paper.

The accelerated weather resistance test was conducted by two tests of SWO and QUV. The SWO test uses sunshine weather-Ometer (Atlas Electric Devices Co., Ci65A type) according to the accelerated weather resistance test method of paint of KS M 5000-3231. The test was conducted using a QUV accelerated weathering tester (The Q-Panel Co.) according to ASTM G-53, and UV fluorescent lamps were UV-B313 lamps (280-315 nm) and cold rolled steel sheets 1,000, 2,000, And the glossiness preservation value and color difference were evaluated at 3,000 time periods.

Gloss preservation value was calculated by the following formula using a Glossmeter (Pacific Scientific Co., Glossgard Type II).

 [Equation 1]:

Color difference expresses the difference between two colors from visual to numerical concept. In other words, the geometric distance of two colors from the color space coordinates is displayed numerically. Spectro Color Meter (Dippon Denshoku Kogyo Co., SZ-∑ 80 type), which is a diffuse reflectance measuring device, was used for measurement. The color difference was calculated by the following equation.

[Equation 2]: color difference (ΔE) = [(ΔL) ² + (Δa) ² + (Δb) ² ] ^1/2

     Where L = Hunter color indicator

              a, b = chromaticity coefficients of the Hunter colorimeter

Non-stick property was determined by adhering the advertising sticker, packaging cloth, and OPP adhesive tape on the coating film, rubbing it to be in perfect contact, heating at 60 ° C. for 30 minutes, and then cooling it to room temperature and removing it easily.

<Table 3>

    Test Items Example 1 Example 2 Example 3 Example 4 Comparative example  60 ° gloss 87 88 87   89 85  Pencil hardness F H H 2H HB  Dry-hard, hrs 5.5. 5 4.5 4 5  Solvent resistance (MEK rub / times) 20 50 < 50 < 50 < 3 Adhesiveness (%) aluminum 100 100 100 100 50 Tin 100 100 100 100 100 Glass 100 100 100 100 30 Glass enamel 100 100 100 100 0 tile 100 100 100 100 20 Accelerated weathering (QUV) 1000 (hrs) Glossiness Preservation Value (%) 96 99 98 98 97 Color difference (△ E) 0.18 0.17 0.29 0.35 0.32 2000 (hrs) Glossiness Preservation Value (%) 79 81 86 91 52 Color difference (△ E) 0.42 0.44 0.53 0.71 0.66 3000 (hrs) Glossiness Preservation Value (%) 63 65 78 83 37 Color difference (△ E) 0.60 0.58 0.62 0.91 0.86 Accelerated Weather Resistance (SWO) 1000 (hrs) Glossiness Preservation Value (%) 100 100 100 100 98 Color difference (△ E) 0.22 0.21 0.31 0.39 0.38 2000 (hrs) Glossiness Preservation Value (%) 85 84 89 96 62 Color difference (△ E) 0.48 0.50 0.59 0.80 0.79 3000 (hrs) Glossiness Preservation Value (%) 72 73 83 88 44 Color difference (△ E) 0.63 0.61 0.69 1.09 0.98 Accelerated pollution water Water washability Good Good Good Good Bad Rub Good Good Good Good Bad menstruum Water washability Good Good Good Good Bad Water washability Good Good Good Good Bad Non-stick property Advertising stickers Not glued Not glued Not glued Not glued Not glued Cloth for packing (blue tape) Not glued Not glued Not glued Not glued Good adhesion Opp Adhesive Tape for Packaging Not glued Not glued Not glued Not glued Good adhesion

As a coating composition prepared from the tertiary amine-containing acrylic resin and epoxy silane of the present invention, the cured coating film of the coating composition is excellent in fouling resistance and weather resistance as well as excellent adhesion to various materials as compared to the conventional cured coating film. . In particular, it has excellent non-sticking properties, so it can be applied to prevent sticking of advertising stickers. In addition, the paints prepared using the tertiary amine-containing acrylic resins of Examples 1 to 4 and using epoxy silane as a curing agent satisfy all of the above properties, thereby preventing the adhesion of advertising stickers and contributing to environmental protection. useful. Non-polluting advertising sticker coating composition has excellent gloss, adhesiveness, solvent resistance, and film hardness, and has excellent pollution prevention performance by hydrophilicity of coating surface, and non-polluting property, weather resistance, and smoothness that pollutants are easily removed by rain water. It is a two-component acryl / silicone composition for paints which forms a coating film which is difficult to adhere this excellent advertisement sticker.

Claims (12)

delete delete delete delete delete delete 3 to 15 wt% of a tertiary amine monomer of any one of dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate; Normal butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, normal butyl methacrylate, normal propyl methacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate 60 to 80 wt% of an acrylic or methacrylic monomer having any aliphatic group selected from the group consisting of glycidyl methacrylate, lauryl methacrylate, and isobornyl methacrylate; 15% by weight of styrene monomer; 2 to 10% by weight of a methacryl-based monomer having any one hydroxyl group selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate; With a mixture of Selected from the group consisting of benzoyl peroxide, tertiary butyl peroxy benzoate, tertiary butyl peroxy-2-ethyl hexanoate, tertiary mil peroxy-2-ethyl hexanoate, and azobisisobutyronitrile 1-3 wt% of any one or more radical polymerizable initiators; A tertiary amine-containing acrylic resin composition characterized by radical polymerization in a middle boiling point solvent, having a solid content concentration of 50%, a number average molecular weight of 16,000 to 20,000, a glass transition temperature of 30 ° C, and a viscosity of 5 to 15 cPs. delete 3 to 15 wt% of a tertiary amine monomer of any one of dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate; Normal butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, normal butyl methacrylate, normal propyl methacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate 60 to 80 wt% of an acrylic or methacrylic monomer having any aliphatic group selected from the group consisting of glycidyl methacrylate, lauryl methacrylate, and isobornyl methacrylate; 15% by weight of styrene monomer; 2 to 10% by weight of a methacryl-based monomer having any one hydroxyl group selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate; Mixing; With the above monomer mixture and benzoyl peroxide, tertiary butyl peroxy benzoate, tertiary butyl peroxy-2-ethyl hexanoate, tertiary mil peroxy-2-ethyl hexanoate, and azobisisobutyronitrile 1 to 3% by weight of any one or more radically polymerizable initiators selected from the group consisting of: dripping 3 to 5 hours in a medium boiling point solvent; And Preparing an acrylic resin composition by radically polymerizing the dropped composition at a reaction temperature of 80 ° C. to 100 ° C. for 8 to 12 hours; Method for producing a tertiary amine-containing acrylic resin composition, characterized in that consisting of. It is prepared by mixing the tertiary amine-containing acrylic resin composition of claim 7 and the epoxy silane which is a curing agent in which the equivalent ratio of amine and epoxy is adjusted to 1: 1 according to the amine content of the tertiary amine-containing acrylic resin. Non-polluting advertising sticker coating composition. The method of claim 10, Epoxysilane used as the curing agent is composed of 3-glycidoxypropyltriethoxysilane or 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane and 3-glycidoxypropyltri Non-polluting advertising sticker coating composition, characterized in that consisting of a polymer of methoxysilane. delete