KR101461046B1 - Fusion Adhesive Type Paint Compositions for Traffic Lanes - Google Patents

Abstract

The present invention relates to a fusion adhesive type paint composition for traffic lanes consisting of a binder, a filler, and an additive, which adds a rubber-silicon modified polyurethane resin modifying with an intermediate of polybutadiene rubber and silicon resin into the paint composition to improved such as adhesion, weather resistance, wear resistance, and fouling resistance compared with an existing paint composition.

Description

Fusion Adhesive Type Paint Compositions for Traffic Lanes [0002]

More specifically, the present invention relates to a luminescent lacquer composition comprising a rubber-silicone modified polyurethane resin modified with a polybutadiene rubber and a silicone resin intermediate in a coating composition to provide a coating composition having adhesion, weatherability, abrasion resistance, Stain resistance and the like.

As for KS M 6080, the coating material for road marking is a paint used for drawing traffic marking lines, and it is used for paints using pigments, resins, glass balls, and filling materials as raw materials. Of the total.

The lane paint for marking the road can be largely divided into water and oil, and the water-based paint usually uses acrylic emulsion resin as a binder. This is a drawback that the solvent is water, which is environmentally friendly, but the drying time is slow. The oil-based paints usually use an acrylic resin containing an organic solvent as a binder, which contains an organic solvent, which causes volatilization of the solvent during drying, thereby causing air pollution.

To overcome the disadvantages mentioned above, a powder type fusion-type coating material is prepared by mixing a filler and an additive in a binder resin of a solid form and melting it in the field. Most of them use low-cost petroleum resin as a binder resin, but this has problems in performance manifestation in adhesion, weather resistance, abrasion resistance and stain resistance as mentioned above.

As a conventional technique related thereto, Korean Patent No. 10-0690277 (registered on Feb. 27, 2007) discloses a resin composition comprising a resin component containing a tackifier resin as a main component, a fluidizing agent, a pigment, a large diameter glass bead, Wherein the sepiolite-based anti-settling agent comprises a particle diameter of 0.1 to 1000 탆, wherein the sepiolite-based anti-settling agent, the sepiolite-based anti-settling agent and the synthetic wax-based anti-settling agent are mixed, Quot; and " at least 2% by weight based on the resin component and the fluidizing agent ". However, the above-mentioned invention has a difficulty because of cracking due to poor workability due to a high melting point of a thermoplastic elastomer and a phase separation due to lack of compatibility, and poor cold resistance due to the use of a thermoplastic elastomer and a plasticizer in combination, And the surface of the film is sticky, which causes the visibility defect due to the contamination.

In Korean Patent No. 10-0832922 (registered on May 21, 2008), "14 to 16 wt% of petroleum resin, 2 to 4 wt% of reinforcing resin, 2 to 6 wt% of pigment, (Fill pigment), 23 to 27% by weight of beads, 1.5 to 3% by weight of plasticizer, and 15 to 20% by weight of fumed silica, And 0.5 to 1% by weight of a thixotropic agent comprising silica (fumed silica). &Quot; However, the above-mentioned invention has the same problems as the above-mentioned invention due to the high melting point of the synthetic rubber (SEBS) by using a synthetic rubber (SEBS) and a plasticizer in combination.

The present invention has been conceived to overcome the above-mentioned problems, and it is an object of the present invention to provide a rubber composition which is superior in adhesion strength, weather resistance, abrasion resistance, And the like can be improved.

The present invention relates to a weldable lane paint composition comprising a binder, a filler and an additive, wherein the filler comprises 76 to 80 parts by weight of a mixture of the binder and aggregate, beads, colored pigment and extender pigment, And the additive comprises 2 to 6 parts by weight of a mixture of a plasticizer, a defoaming agent, a fluidizing agent, an anti-settling agent and an antioxidant.

The present invention also relates to a rubber-silicone modified polyurethane resin in which the binder is a mixture of 76 to 82% by weight of a petroleum resin and 18 to 24% by weight of a rubber-silicone modified polyurethane resin, Wherein the lacquer composition is a lacquer composition.

(식 1)

(Equation 1)

(In the above formula 1,

R: a silicone resin intermediate represented by the following formula

R ': a glycol chain or polybutadiene chain having straight and branched chains,

R ": phenylene, metaxylene, hexylene, diphenylmethane chain,

n is an integer of 3 to 5)

(식 2)

(Equation 2)

(In the above formula 2,

n is an integer of 3 to 5,

r is a lower alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or isopropyl group,

ph: phenyl group)

Also, the present invention provides a fusible lane coating composition, wherein the filler is mixed with 47 to 52 wt% of aggregate, 29 to 32 wt% of beads, 9 to 12 wt% of colored pigment, and 10 to 15 wt% of extender pigment do.

Finally, the present invention is characterized in that the additive comprises 3 to 9 parts by weight of a plasticizer, 2 to 4 parts by weight of a defoamer, 3 to 6 parts by weight of a fluidizing agent, 0.1 to 0.5 parts by weight of an antioxidant, And 1 to 3 parts by weight of an anti-settling agent, based on the total weight of the composition.

The luminescent lane coating composition according to the present invention can improve adhesion, weather resistance, abrasion resistance, stain resistance and the like by adding rubber-silicone modified polyurethane resin which is a soft solid state at room temperature, It has an advantage of excellent workability in construction.

The fusing lane coating composition according to the present invention will be described in detail below.

The lint type lining paint composition according to the present invention is characterized by comprising 18 to 22 parts by weight of a binder, 76 to 80 parts by weight of a filler and 2 to 6 parts by weight of an additive in a lint type lining paint composition comprising a binder, a filler and an additive .

Hereinafter, the binder, filler, and additive constituting the fusing type lane coating composition of the present invention will be described in detail.

(1) Binders

1) Petroleum resin

Generally, the melt-lane lacquer compositions use low-cost petroleum resin as a main binder, which has a good crumbling characteristic and shows weak adhesion, weak abrasion resistance and weak weather resistance. The blending amount of the binder in the luminescent lane paint composition is 18 to 22 parts by weight and the appropriate amount of the petroleum resin in the total binder components is 76 to 82% by weight. If the amount is less than 76% by weight, , And when it exceeds 82% by weight, the viscosity is lowered and the settling of the aggregate becomes severe.

The petroleum resin is a C ₅ to have the usual polymerization of a mono-olefin or diolefin is obtained as a by-product in the production process of ethylene and aliphatic C ₉ aromatic. The physical properties are a softening point of 70 to 150 ° C, a molecular weight of 600 to 2000, an acid value of 1 or less, a specific gravity of 0.96 to 1.08, a color of 4 to 13 (Gardner) and a flash point of 240 ° C. Petroleum resins are soluble in benzene, toluene, and xylene. Compatibility with secondary elastomers such as rubber elastomers and rubber-silicone modified polyurethane resins is better than aromatic ones.

In order to compensate for these poor properties, most manufacturers use synthetic rubber and plasticizer in the manufacture of welded lane paints. However, the use of a synthetic rubber and a plasticizer imparts flexibility to the coating film, but it has a disadvantage that the strength of the coating film is weakened and the surface of the coating film becomes sticky. This prescription also creates pollution on the lane of the road caused by the wheels of the moving cars, which makes the roads messy and the roads become soiled quickly so that the visibility is getting worse, making drivers' safe driving difficult.

In addition, because the petroleum resin is a non-polar resin, the adhesive strength to the substrate is weak, and when used, the coating film is torn off because of low adhesive strength and abrasion resistance. Therefore, in the case of the fusing lane paint, epoxy resin or alkyd resin And a primer of a primer is used. In addition, the petroleum resin contains an unsaturated double bond or a residual metal powder in the resin, so that the petroleum resin is easily discolored or broken by ultraviolet rays.

2) Rubber-silicone modified polyurethane resin

The present inventors have conducted extensive research to overcome the shortcomings of adhesion, weather resistance, abrasion resistance and stain resistance in the prior art. As a result, the rubber-silicone modified polyurethane resin as shown in the following formula 1 was added as an auxiliary binder, And the physical properties were improved so as to have excellent compatibility with petroleum resin and other plasticizers.

(식 1)

(Equation 1)

(In the above formula 1,

R: a silicone resin intermediate represented by the following formula

R ': a glycol chain or polybutadiene chain having straight and branched chains,

R ": phenylene, metaxylene, hexylene, dimethanemethane chain,

n is an integer of 3 to 5)

(식 2)

(Equation 2)

(In the above formula 2,

n: an integer from 3 to 5

r: a lower alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or isopropyl group

ph: phenyl group)

The rubber-silicone modified polyurethane resin was prepared by first synthesizing a rubber-modified polyurethane resin and then reacting with a silicone intermediate, and hereafter, a method of producing a rubber-silicone modified polyurethane resin Will be described in detail.

a) Production process of rubber-modified polyurethane resin

The rubber-modified polyurethane resin includes a polybutadiene rubber having at least two hydroxyl groups (-OH) in the molecule, a polyfunctional glycol having at least two hydroxyl groups (-OH) in the molecule, at least two isocyanate groups (-NCO) was added to the reactor to carry out an addition reaction at 40 to 60 ° C, and the structure of the product was as shown in the following formula 3. embedded image

(식 3)

(Equation 3)

(In the above formula 3,

R ': a straight or branched chain or polybutadiene chain

R ": phenylene, metaxylene, hexylene, diphenylmethane chain

n is an integer of 4-5.)

The polybutadiene rubber as a raw material of the rubber-modified polyurethane resin having a molecular weight of 500-2000 was used. The appropriate amount used is 20-48 wt% of the total reactants. If the molecular weight is too high or the amount is too large, phase separation occurs in the composite and the product becomes less uniform. Examples of usable polybutadiene rubber include POLY BD R-45HT from DuPont Petroleum, Nisso PB G-1000 from Japan Soda Co., and HTE-4001 from Hypro ^TM .

As the polyfunctional glycol, di- or tri-valent glycols such as ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), triethylene glycol (TEG), polyethylene glycol ), Polypropylene glycol (PPG), and the like. Examples of trivalent glycols include trimethylol propane (TMP), hexanetriol, and glycerin. The appropriate amount used is 22-50 wt% of the total reactants, and if the glycol is used too much during the reaction, compatibility with the petroleum resin is poor when mixed.

As the polyfunctional isocyanate (NCO) compound, those having a valence of 2 or more are used. Examples of the polyfunctional isocyanate (NCO) compound include 2,4 or 2,6-trilene diisocyanate (TDI), 4,4'- diphenylmethane diisocyanate Diisocyanate (HMDI), and meta-xylene diisocyanate (MXDI). The amount thereof is 30-58 wt% of the total reactants. If the amount is too small, compatibility with the petroleum resin is poor. If the amount is too much, the viscosity of the reactant is increased.

In the rubber-modified polyurethane resin, a glycol and a polybutadiene rubber were charged into a reactor, and the temperature was elevated while stirring to maintain the temperature at 40 ° C. After the isocyanate compound was uniformly dropped for 3 hours at this temperature, the temperature was raised to 60 ° C The reaction is stopped when the temperature is raised to 600 to 800 cps (25 ° C) and the hydroxyl value (-OH) is increased to 60 to 90 at a constant temperature for 2 to 5 hours at this temperature. .

The equivalent ratio of OH / NCO of the initial hydroxyl group compound to the isocyanate compound is 1.1 to 2.5. The content of active isocyanate groups (free NCO) remaining unreacted after the reaction is less than 0.1%. The final state of the reaction was determined by viscosity and hydroxyl group (-OH) content, where the important value is the hydroxyl group value. This is because the silanol group (-Si-OH) of the silicone resin intermediate must be reacted with the unreacted hydroxyl group (-OH) in the next step. Examples of reaction catalysts that can be used include DBTDL (di-butyl tin di-laurate), DBTDA (di-butyl tin di-acetate), tin octoate and tri- ethyl amine (TEA) The amount used is 0.01 to 0.03 phr for the reactants. Depending on the catalyst and temperature during the reaction, biuret or allophanate bonds may be formed, which do not pose a problem in achieving the object of the present invention.

b) Manufacturing process of rubber-silicone modified polyurethane resin

A rubber-modified polyurethane resin was synthesized by reacting a silicone resin intermediate having the same structure as R in Fig. 2 with a rubber-modified polyurethane resin as shown in Formula 3 previously prepared. The silicone resin intermediate has at least one reactive silanol group (-Si-OH) in the molecule as shown in R in Fig. 2, which can undergo a dehydration condensation reaction with another hydroxyl group (-OH).

Silicone resin intermediates which can be used include Z-6018, DC-3017 from Dow Corning, and SH-6018 from Tori Silicones, Japan. The appropriate amount is 30-50% of the total reactants.

The reactants were obtained by dehydration condensation reaction of the above rubber modified polyurethane resin, silicone resin intermediate and organic acid catalyst at a reaction temperature of 140 to 150 ° C for 3 to 7 hours. In the reaction, a suitable equivalent ratio of (-OH) / (-Si-OH) of the rubber-modified urethane resin to the silicone resin intermediate is 1.2 to 1.5.

The reaction can be carried out using a catalyst. As the catalyst, organic acids such as octanoic acid and benzoic acid can be used. The amount of the organic acid to be used can be 1 to 5 phr. The final state of the reaction is when the compound has a viscosity of Z ₃ to Z ₅ (Gardner, 60 ° C) and a hydroxyl group (-OH) content of 10 or less.

A suitable amount of the rubber-silicone modified polyurethane resin is preferably 18 to 24% by weight of the entire binder component. When the rubber-silicone modified polyurethane resin is used in an amount of less than 18% by weight, there is no reinforcing effect. When the rubber-silicone modified polyurethane resin is used in an amount exceeding 24% by weight, the coating film is rather weak.

(2) Fillers

In the fusible lane paint composition according to the present invention, the blending amount of the filler is preferably from 76 to 82 parts by weight, and the filler comprises 47 to 52% by weight of aggregate, 29 to 32% by weight of beads, 9 to 12% by weight of colored pigments, To 15% by weight. In the following, each component will be described in detail.

1) Aggregate

Generally, dolomite of silica-based dolomite or kaolin-based dolomite powder is used as the aggregate, and the physical properties required in the aggregate are the compatibility with the resin and the physical strength. The aggregate is present on the surface of the film, making the surface rough and forming irregularities. It provides slip-proof function and grinds the ore to make it 0.7 ~ 1.2mm in size or it can be used directly by using silicone resin It is possible. Importantly, the strength and hardness should not be broken when the coating is subjected to a vertical load, and the aggregate must remain rigid to exhibit its anti-slip properties. When the amount is less than 47% by weight, there is no slip-preventing function. When the amount is more than 52% by weight, the viscosity of the mixture is increased to deteriorate the fluidity and sedimentation of the aggregate. There are FS-W-05 (white), FS-B-05 (blue), FS-Y-05 (yellow) and FS-R-05 (red) of FILSTONE CO., LTD.

2) Beads

In order to improve the visibility of the bead, the transparent bead was used. In the lane paint, the use of the glass bead is essential. By using the glass bead, reflections of refracted light are used to improve the visibility and visibility of the lane to be. In the present invention, beads having a diameter of 0.15 to 1.7 mm are used, and the amount of beads used is preferably 29 to 32% by weight of the filler. As the content of beads increases, clarity and visibility increase. However, when the content of beads is more than 32% by weight, sedimentation occurs largely in a mixing tank before lane construction, and uniform application becomes difficult.

3) colored pigments

A suitable amount of the colored pigment in the filler is 9 to 12% by weight of the filler. The current lanes are white, yellow, blue, and red. White is used as a cruise line, yellow is used as a separation line, blue is used as a bus lane, and red is used as a crosswalk.

As the white pigment, titanium oxide or zinc oxide was used. Examples of usable products include KA-100 of Cosmo Co., R-902 of DuPont, R-720 of Hans Chemical, THR-218 of Polymer World Co., . Yellow 605, Moly orange, MH-300 of Interchem Co., Y-5000 of Sambo Fine Chemical Co., Ltd., etc. were used as the yellow pigment, and chrome yellow or yellow pigments were used. . Cobalt was used as a blue pigment, and Blue-214 and Blue 7300 of Daesung Pigment Co., Ltd. are available. As the red pigment, iron oxide was used. Examples of usable products are Oxide-Red-110, Red-2R, Oxide Red-130 of Samyang Fine Co.,

4) Extention pigments

An extender pigment is used as an extender of the colored pigment, and calcium carbonate, silica, glass powder, talc and the like can be used. A suitable amount used is 10-15% by weight in the filler. When an appropriate amount of extender pigment is used, it has some strength and hardness reinforcing effect due to the filling effect, but when it is used in excess of 15% by weight, the flowability is deteriorated due to the viscosity increase. It is recommended that calcium carbonate be used in combination with 50-60 mesh or 325mesh. WT-800, WSP-70, SHF-T and SHC-300 of Sungshin Chemical Co., Ltd. . As the silica, 50-300 mesh can be used as well as calcium carbonate. Glass powder having a size of 0.1-1.7 mm of Yu Jung Industrial Co., Ltd. can be used. Talc is SK-325 from Kumkang Chemical Co., Ltd. and KT-325 from Dawon Chemical Co., Ltd.

(3) Additives

In the fusible lane paint composition according to the present invention, the blending amount of the additive is 2 to 6 parts by weight. As the additive, a plasticizer, a defoaming agent, a fluidizing agent, an anti-settling agent and an antioxidant may be mixed. Hereinafter, each component will be described in detail.

1) Plasticizer

Since the petroleum resin used as a binder is extremely brittle, the plasticizer can be used to improve the workability of the work by adding a liquid plasticizer. The amount of the plasticizer is preferably 3-9 parts by weight per 100 parts by weight of the total binder to be. Dibutyl phthalate (DBP), dioctyl phthalate (DOP), and tricresyl phthalate (TCP). Alternatively, solventless alkyd resins, low molecular weight polyester resins, and process oils can be used. Too little plasticizer will have little effect, too much plastic will reduce strength, plasticizer will migrate and surface stickiness will occur.

2) Defoamer

The antifoaming agent is used for destroying bubbles floating on the surface of a paint and a coating film by surface tension. The amount of antifoaming agent used is 2 to 4 parts by weight per 100 parts by weight of the total binder. Examples of antifoaming agents that can be used include KF-96, KP-357 from Shin-Etsu K.K., B-111F and B-211F from Adeka Chemical Co.,

3) The fluidizing agent

The fluidizing agent may be polyethylene wax, amide wax, or the like, which improves the fluidity of the coating material to provide gloss to the surface of the coating film and also serves as an anti-settling agent for the filler. An appropriate amount to be used is 3-6 parts by weight based on 100 parts by weight of the total binder. If the amount of wax is too low, the fluidity is not good. If it is too much, the strength is low. The melting point range of the usable product is 90 to 120 ° C. When the melting point is too low, it volatilizes during heating.

4) Anti-settling agent

The anti-settling agent is a substance that prevents precipitation of large particles such as aggregate and large diameter, and an appropriate amount is 1-3 parts by weight with respect to 100 parts by weight of the total filler. As the kind of the anti-settling agent, it is possible to use fine particle silica, hemp stone, amine compound, or the like. Too little of an anti-settling agent has no effect, and if it is used too much, the viscosity increases and the workability is deteriorated due to thixotropy.

5) Antioxidant

Since lane paints are exposed to intense sunlight after being applied on asphalt or cement roads, the paints can easily be oxidized by ultraviolet rays, heat, and ozone, so that the antifouling agent may be added to improve durability good. An appropriate amount to be used is 0.1-0.5 parts by weight based on 100 parts by weight of the total binder. Examples of usable products include tertiary butyl hydroquinone (TBHQ), phenylbetanaphthylamine (PNA), dibutylhydroxytoluene (BHT), and butylhydroxyanisole (BHA). However, it should be noted that even if a large amount of an antioxidant is added, the physical properties of a resin excellent in oxidation resistance can not be surpassed.

(Production Example 1) Production of rubber-silicone modified polyurethane resin

First, 22 g of diethylene glycol, 10 g of trimethylolpropane and 26 g of polybutadiene rubber (R-45HT) were placed in a reactor and heated with stirring to prepare a rubber-modified polyurethane resin. When the temperature reached 40 ° C, 42 g of 2,4-TDI was added dropwise over 3 hours under constant temperature reaction at this temperature. The temperature was raised again and the reaction was allowed to proceed at 60 ° C for 2 hours to obtain a rubber-modified polyurethane resin having a hydroxyl value (-OH) value of 80.

Subsequently, 100 g of the rubber-modified polyurethane resin prepared above, 96 g of silicone resin intermediate (Z-6018 from Dow Corning) and 3 g of benzoic acid were put into a reactor to prepare a rubber-silicone modified polyurethane resin, To obtain a rubber-silicone modified polyurethane resin having a hydroxyl value of 8.6 and a viscosity of Z ₄ (Gardner, 60 캜).

(Production Example 2) Production of rubber-silicone modified polyurethane resin

First, 26 g of ethylene glycol, 10 g of trimethylolpropane and 30 g of polybutadiene rubber (G-1000, manufactured by Nippon Soda Co., Ltd.) were added to the reactor and heated with stirring to prepare a rubber-modified polyurethane resin. When the temperature reached 40 占 폚, 48 g of 2,4-TDI was added dropwise over 3 hours under constant temperature reaction at this temperature. The temperature was raised again and the reaction was allowed to proceed at 60 캜 for 3 hours to obtain a rubber-modified polyurethane resin having a hydroxyl value (-OH) value of 68.

Subsequently, 100 g of the rubber-modified polyurethane resin prepared above, 80 g of a silicone resin intermediate (Z-6018, manufactured by Dow Corning Incorporated) and 3 g of octanoic acid were added to prepare a rubber-silicone modified polyurethane resin and dehydrated and condensed at 150 ° C. for 3 hours To obtain a rubber-silicone modified polyurethane resin having a hydroxyl group (-OH) value of 6.2 and a viscosity of Z ₅ (Gardner, 60 ° C).

Each raw material was prepared in various ratios as shown in the following Table 1, put into a melting furnace and heated and melted to 200 DEG C with sufficient stirring to prepare each sample. The colored hard aggregate is produced by blending a titanium dioxide pigment with clay, firing and pulverizing.

Thereafter, the adhesive strength, weather resistance, abrasion resistance and stain resistance were tested under the following conditions, and the results are shown in Table 2 below. The colored hard aggregate is produced by blending a titanium dioxide pigment with clay, firing and pulverizing.

Note) Auxiliary binder 1: The rubber-silicone modified polyurethane resin obtained in Production Example 1

Secondary binder 2: The rubber-silicone modified polyurethane resin obtained in Production Example 2

<Test Method>

1) Adhesive strength

The samples of Examples 1 to 6 and Comparative Examples 1 and 2 in Table 1 were measured for bonding strength of the test pieces according to ASTM D 1002.

2) Weatherability

The paint mixture was heated to 220 DEG C and poured into a metal mold having a mold release agent to prepare a disk-shaped test piece having a diameter of 10 cm and a thickness of 3 mm, followed by drying at 60 DEG C for 3 days and ultraviolet irradiation at a wavelength of 250 nm for 2 days. Were compared.

3) Abrasion resistance

According to the quality standard of KS M 6080, the abrasion resistance shall be less than 500mg per 100 revolutions.

4) Contamination resistance

The coating mixture was heated to 220 ° C in accordance with KS F 3111 and poured into a metal mold with a mold release agent to prepare a disk-shaped test piece having a diameter of 10 cm and a thickness of 3 mm. The test piece was then dried at 60 ° C for 3 days. , 2 cm in length, left for 4 hours, and then erased with a neutral detergent to judge whether or not the letters were erased.

<Analysis of Test Results>

From Table 2, it can be seen that Examples 1 and 2 according to the preferred raw material blend ratio of the present invention are superior to those of Examples 3 to 6 and Comparative Examples 1 and 2 which do not follow the preferred blending ratio of the present invention, , Weatherability, abrasion resistance and stain resistance.

Claims (4)

delete Wherein the filler comprises 76 to 80 parts by weight of a mixture of an aggregate, a bead, a colored pigment and an extender pigment, the additive is a plasticizer, a filler, and an additive, , A defoaming agent, a fluidizing agent, an anti-settling agent, and an antioxidant in an amount of 2 to 6 parts by weight,
Wherein the binder is a mixture of 76 to 82 wt% of a petroleum resin and 18 to 24 wt% of a rubber-silicone modified polyurethane resin, wherein the rubber-silicone modified polyurethane resin is a compound represented by the following formula Gt;

(Equation 1)
(In the above formula 1,
R: a silicone resin intermediate represented by the following formula
R ': a glycol or polybutadiene chain having straight and branched chains,
R ": phenylene, metaxylene, hexylene, diphenylmethane chain,
n is an integer of 3 to 5)

(Equation 2)
(In the above formula 2,
n is an integer of 3 to 5,
r is a lower alkyl group which is any one of methyl, ethyl and isopropyl groups,
ph: phenyl group)
The method of claim 2,
Wherein the filler is a mixture of 47 to 52% by weight of aggregate, 29 to 32% by weight of beads, 9 to 12% by weight of colored pigments and 10 to 15% by weight of extender pigments.
The method of claim 3,
3 to 6 parts by weight of an antioxidant, 0.1 to 0.5 parts by weight of an antioxidant, and 3 to 9 parts by weight of an anti-settling agent 1 to 100 parts by weight of the filler, based on 100 parts by weight of the binder, &Lt; / RTI &gt; to 3 parts by weight, respectively, based on the total weight of the composition.