KR20000050465A - Epoxy resin composition for road line marking and method for c0ating road line marking using the same - Google Patents

Abstract

PURPOSE: A two-component epoxy resin composition comprising a main agent and a curing agent for forming road marking and method for marking the same are provided which are excellent in thermal stability and impact resistance. CONSTITUTION: A resin composition comprises a resin composition as a main agent containing at least sulfonic acid selected from the group consisting of silicon modified epoxy resin and alkylphenyl modified sulfonic acid and alkylphenol modified sulfonic acid and a curing agent in a ratio of 1 : 0.8 - 1.2. The silicon modified epoxy resin having oxirane functional group of 2 to 10 and an epoxy equivalent of 150 to 600 is obtained by subjecting glycol having a hydroxy equivalent of 30 to 400 and liquid phase or solid phase silicon resin having a methoxy or hydroxy equivalent of 150 to 500 to condensation reaction and reacting the obtained silicon modified resin having a hydroxy equivalent of 100 to 500 with epichlorohydrin. The composition has excellent adhesiveness to glass beads, weather resistance and an excellent visibility even at night or during bad weather

Description

Epoxy resin composition for road marking and road surface marking line coating method using same {EPOXY RESIN COMPOSITION FOR ROAD LINE MARKING AND METHOD FOR C0ATING ROAD LINE MARKING USING THE SAME}

The present invention relates to an epoxy resin composition for road marking and a road road marking line coating method using the same. More specifically, the present invention relates to a two-component epoxy resin composition separated by a main agent and a curing agent for forming a road marking line having excellent weather resistance, and a method of painting a road marking line using the same.

In general, acrylic, vinyl, vinyl acrylic paints and hydrocarbon-based hard resin fusion paints manufactured using thermoplastic resins are mainly used for paints used for road marking.

Road marking paints require the following properties: First, the adhesion to road surfaces such as asphalt and concrete should be excellent, and the adhesion to glass beads that make road markings clear by reflecting light in night or dark roads should be excellent. Second, there should be no thermal change over time such as yellowing and gloss decrease by ultraviolet rays after curing and no mechanical property deterioration due to temperature change in summer and winter, and it should be excellent in impact resistance by moving objects such as automobiles. Thirdly, when painting the road, the time limiting the traffic of moving bodies and pedestrians should be short, so it must be fast-drying type that hardens within a short time.

The road marking paints used up to now have a short time to completely dry after painting, and thus have a short time limit for accompanying roads during painting. However, since the road marking paint is made of inexpensive thermoplastic resin, the adhesion to glass beads is significantly decreased with time, and after a certain period of time, Difficulty in recognition makes driving difficult.

In addition, since the cured product of the paint has a low glass transition temperature, there is a lack of thermal stability in summer and winter when the road surface temperature difference is extreme, and thus the road marking paint is cracked or cracked. Accordingly, in spite of using paints using inexpensive thermoplastic resins, the repair painting work must be frequently performed, and therefore, there is a problem in that a lot of expenses are actually required.

Accordingly, an object of the present invention is to consider the problems of the overall physical properties of the road marking paint using a thermoplastic resin, excellent adhesion to the road surface and glass beads, good thermal stability and impact resistance, after painting work It is intended to provide an epoxy resin composition for road marking, which is dried within a short time and is easy to recognize the marking on the road surface made thereof on the road during painting.

Another object of the present invention is to provide a road surface marking line coating method for easily manufacturing a variety of marks on the road surface using the paint comprising the composition for road marking.

In order to achieve the above object of the present invention, in the present invention, condensation reaction of a glycol having a hydroxy equivalent weight of 30-400 and a liquid, solid silicone resin having a methoxy or hydroxy equivalent weight of 150-500 condensation reaction results in a hydroxy equivalent of 100. Obtained a silicone modified resin of -500, obtained by reacting the silicone modified resin and epichlorohydrin obtained as described above to form 2-10 oxirane functional groups, silicone modified epoxy resin and alkyl having an epoxy equivalent of 150-600 A resin main composition comprising at least one sulfonic acid selected from the group consisting of phenyl-modified sulfonic acid and alkylphenol-modified sulfonic acid, and a liquid bisphenol-A epoxy resin and an amine having an epoxy equivalent weight of 150-250. Epoxy resin bath comprising a curing agent composed of an epoxy addition polyamine of -600, wherein the mixing ratio of the main agent and the curing agent is 1: 0.8-1.2 Provide the sacraments.

In particular, the alkylphenyl-modified sulfonic acid included in the resin main composition to shorten the curing time is at least one selected from the group consisting of benzenesulfonic acid, dodecylbenzenesulfonic acid and laurylbenzenesulfonic acid, and the alkylphenol-modified sulfone The acid preferably includes at least one selected from the group consisting of phenolsulfonic acid, nonylphenolsulfonic acid, and octylphenolsulfonic acid, and the amount of the alkylphenyl-modified sulfonic acid or the alkylphenol-modified sulfonic acid added is determined by the amount of the subject composition. It is 2-5 weight% based on a reference.

In addition, it is preferable that the mixing ratio of the glycol and the silicone resin is 2: 0.5-1.9 in an equivalent ratio, and the mixing ratio of the silicone modified resin and the epichlorohydrin is 1: 1-1.1 in a molar ratio.

The glycol is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, bisphenol A, trimethylpentanediol At least one selected from the group consisting of cyclohexanedimethanol, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol and dipentaerythritol can be easily used.

In addition, the amines for preparing the curing agent include aliphatic amines including diethylenetriamine, triethylenetetraamine and tetraethylenepentaamine, cycloaliphatic amines including methylenedianiline and isophoronediamine, and metaxylenediamine and diamino. At least one selected from the group consisting of aromatic amines containing diphenylmethanol can be preferably used.

Another object of the present invention described above is a silicone-modified resin having a hydroxy equivalent weight of 100-500 by condensing a glycol having a hydroxy equivalent weight of 30-400 and a liquid or solid silicone resin having a methoxy or hydroxy equivalent weight of 150-500. Obtained by reacting the above-mentioned silicone-modified resin with epichlorohydrin to form 2-10 oxirane functional groups, and an epoxy equivalent of 150-600 silicone-modified epoxy resin and alkylphenyl-modified sulfonic acid and alkyl A resin main composition comprising at least one sulfonic acid selected from the group consisting of phenol-modified sulfonic acids, and an epoxy addition polyamine having a amine value of 200-600 by modifying a liquid bisphenol A type epoxy resin and an amine having an epoxy equivalent weight of 150-250. To prepare an epoxy resin composition by mixing the curing agent consisting of the main agent and the curing agent so that the mixing ratio is 1: 0.8-1.2. system;

Spraying a paint including the epoxy resin composition on a road; and

It is achieved by a road marking line coating method comprising the step of curing the epoxy resin composition to form a mark on the road surface.

At this time, the curing agent may further include nonylphenol and / or benzyl alcohol as a curing accelerator diluent.

Hereinafter, the present invention will be described in more detail.

The epoxy resin composition of the present invention described above is improved by a two-component high weather resistance silicone-modified epoxy paint. That is, in order to solve the problem that bisphenol A type epoxy resin has a problem of bad yellowing during outdoor coating and poor weatherability, glycol which does not form yellowing chromophore by ultraviolet rays and liquid or solid silicone resin are primarily modified. By using this to prepare an epoxy resin into which the oxirane functional group was introduced, and using this as a component of the main composition, weather resistance was improved.

In the case of the subject matter, first, a silicone modified resin having a hydroxy equivalent weight of 100-500 is condensed with a glycle having a hydroxy equivalent weight of 30-400 and a liquid or solid silicone resin having a methoxy or hydroxy equivalent weight of 150-500. Get as an intermediate.

Epichlorohydrin is reacted with the obtained intermediate to form 2-10 oxirane functional groups to obtain a silicone-modified epoxy resin having an epoxy equivalent of 150-600.

The glycol monomers used in the above subjects are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, bisphenol A , Trimethylpentanediol, cyclohexanedimethanol, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, dipentaerythrol, and the like can be used.

In addition, as the liquid or solid silicone resin modified with the glycol monomer, Dow Corning's silicone intermediates Z-6018 and DC-3037 may be used. The mixing ratio of glycol and silicone intermediate is equivalent ratio of 2: 0.5-1.9. If the proportion of silicone intermediate is less than 0.5, it is difficult to expect improvement of weather resistance and thermal stability when applying the paint because the silicone content in the main resin is small. If the proportion of silicone intermediate is more than 1.9, the viscosity of the main resin is high and the epoxy equivalent is too high. Since there is a problem that the workability of the coating material is deteriorated, the ratio thereof is within the above range.

Silicone-modified resin, a polyol obtained by condensation of glycol and silicone intermediate, is reacted with epichlorohydrin to form a silicone-modified epoxy resin. At this time, the mixing ratio of silicone-modified resin and epichlorohydrin is in an equivalent ratio of 1: 1. The ratio is 1.1. The sodium hydroxide used to remove the chloride component reacts the molar ratio with epichlorohydrin at 1: 1 to 1.1 to minimize the hydroxy unreacted of the glycol and to remove the chloride component of epichlorohydrin to the maximum.

In addition, when mixing the obtained silicone-modified epoxy resin with a curing agent having a primary or secondary amine, alkylphenyl is added to the silicone-modified epoxy resin to shorten the curing time by forming a ″ strong salt ″ and increasing the latent heat of the mixed paint. A strong acid such as modified sulfonic acid, alkylphenol modified sulfonic acid is introduced to obtain the subject composition. The amount of sulfonic acid added is to be 2-5% by weight based on the subject. If the amount of sulfonic acid is less than 2% by weight it is difficult to obtain the effect of shortening the curing time, if the amount exceeds 5% by weight of the curing time is too short, the workability is lowered, so the amount of sulfonic acid added Within one range.

The curing agent was synthesized with bisphenol A epoxy-added polyamine to improve the adhesion between the road surface and the glass beads, and the curing accelerator and the reactive diluent were introduced to accelerate the curing, and the optimum viscosity was maintained to spray the coating. It was made possible.

Specifically, the curing agent denatures the liquid bisphenol A epoxy resin having an epoxy equivalent weight of 150-250 and an aliphatic, cycloaliphatic or aromatic amine, and synthesizes an epoxy addition polyamine having an amine value of 200-600 to a polyamine. It shortens and improves the adhesion between the road surface and glass beads.

Examples of the amines used in the preparation of the curing agent include aliphatic amines such as diethylenetriamine, triethylenetetraamine, and detraethylenepentaamine, alicyclic amines such as methylenedianiline and isophoronediamine, methaxylenediamine, and diamino. Aromatic amines such as diphenylmethane and the like. Liquid bisphenol A-type epoxy resin is added to the amine to improve adhesion between the road surface and glass beads, and nonylphenol or benzyl alcohol is mixed as a curing accelerator diluent to shorten the drying speed and allow spraying. .

The main composition obtained as mentioned above and a hardening | curing agent are mixed, and the epoxy resin composition for road markings which concerns on this invention is obtained. At this time, the mixing ratio of the main composition and the curing agent is 1: 0.8 to 1.2. If their mixing ratio is out of the above range, it is not easy to paint it on the road and it is not easy to work because it does not have an appropriate drying speed.

Hereinafter, the present invention will be described in detail through specific examples. In the following examples, the main composition and the curing agent are prepared separately.

(Preparation of Topical Composition)

Example 1

A 2-liter four-necked flask was equipped with a thermometer, condenser, stirrer, moisture removal condenser and temperature raising device. Here, 265 g of Z-6018 (Dow Corning) and 104 g of neopentyl glycol were mixed as a silicone intermediate having a hydroxy equivalent weight of 265, and the temperature was raised to 100 ± 5 ° C. while gradually stirring. After mixing 0.7 g of triisopropyl titanate as a reaction catalyst at 100 ° C., the temperature was raised to 180 ± 3 ° C. to obtain a silicone-modified polyol having a hydroxyl equivalent weight of 350 ± 10 by condensation reaction. The obtained polyol 350g, epichlorohydrin 102g, and toluene 200g were mixed, and it heated up at 80 +/- 5 degreeC. 8.2 g of 40% aqueous sodium hydroxide solution was added dropwise as a reaction catalyst, and then maintained for 20 minutes. Again 113 g of 40% aqueous sodium hydroxide solution was added dropwise over 2 hours and maintained for 30 minutes.

The resulting product was washed three times with 600 g of water. After the washing process, the mixture was distilled under reduced pressure to completely remove toluene, thereby obtaining 409 g of a silicone-modified epoxy resin having an epoxy equivalent of 400 ± 50 and a silicone resin content of 65%. To the obtained epoxy resin, 8 g of phenolsulfonic acid, which would generate latent heat during the curing reaction, was added and mixed to obtain a main composition.

Example 2

A 2-liter four-necked flask was equipped with a thermometer, condenser, stirrer, moisture removal condenser and temperature raising device. Here, 265 g of Z-6018 (Dow Corning) and 90 g of trimethylolpropane were mixed as a silicon intermediate having a hydroxy equivalent weight of 265, and the temperature was raised to 100 ± 5 ° C. while gradually stirring. After mixing 0.7 g of tetraisopropyl titanate as a reaction catalyst at 100 ° C., the temperature was raised to 180 ± 3 ° C. to obtain a silicone-modified polyol having a hydroxy equivalent of 335 ± 10 by condensation reaction. 330 g of obtained polyol, 102 g of epichlorohydrin and 200 g of toluene were mixed and heated to 80 ± 5 ° C. 8.2 g of 40% aqueous sodium hydroxide solution was added dropwise as a reaction catalyst, and then maintained for 20 minutes. Again 113 g of 40% aqueous sodium hydroxide solution was added dropwise over 2 hours and maintained for 30 minutes.

The resulting product was washed three times with 600 g of water. After the washing process was completed, distillation under reduced pressure completely removed toluene to obtain 386 g of a silicone-modified epoxy resin having an epoxy equivalent weight of 380 ± 50 and a silicone resin content of 68%. To the obtained epoxy resin, 8 g of phenolsulfonic acid, which would generate latent heat during the curing reaction, was added and mixed to obtain a main composition.

Example 3

A 2-liter four-necked flask was equipped with a thermometer, condenser, stirrer, moisture removal condenser and temperature raising device. Here, 265 g of Z-6018 (Dow Corning) and 70 g of pentaerythritol were mixed as a silicon intermediate having a hydroxy equivalent weight of 265, and the temperature was raised to 100 ± 5 ° C. while gradually stirring. 0.6 g of tetraisopropyl titanate as a reaction catalyst was mixed at 100 ° C., and then heated to 180 ± 3 ° C. to obtain a silicone-modified polyol having a hydroxyl equivalent of 310 ± 10 by condensation reaction. 310 g of the obtained polyol, 102 g of epichlorohydrin and 200 g of toluene were mixed and heated to 80 ± 5 ° C. 8.2 g of 40% aqueous sodium hydroxide solution was added dropwise as a reaction catalyst, and then maintained for 20 minutes. Again 113 g of 40% aqueous sodium hydroxide solution was added dropwise over 2 hours and maintained for 30 minutes.

The resulting product was washed three times with 600 g of water. After the washing process, the mixture was distilled under reduced pressure to completely remove toluene, thereby obtaining 366 g of a silicone-modified epoxy resin having an epoxy equivalent weight of 330 ± 50 and a silicone resin content of 72%. To the obtained epoxy resin, 7 g of benzylsulfonic acid which would generate latent heat during the curing reaction was added and mixed to obtain a main composition.

Example 4

Performed in the same manner as in Example 2, using 222 g of DC-3037 (Dow Corning) silicone intermediate having a methoxy equivalent weight of 222 instead of the silicone intermediate of the hydroxy functional group to obtain a silicone-modified polyol having an epoxy equivalent of 280 ± 10 Using 280 g of the obtained silicone-modified polyol, 333 g of a silicone-modified epoxy resin having an epoxy equivalent of 330 ± 50 and a silicone resin content of 67% was obtained. To the obtained epoxy resin, 7 g of phenolsulfonic acid, which would generate latent heat during the curing reaction, was added and mixed to obtain a main composition.

(Production of Hardeners)

Example 5

A 2-liter four-necked flask was equipped with a thermometer, condenser, stirrer, moisture removal condenser and temperature raising device. 75 g of a liquid bisphenol A epoxy resin having a epoxy equivalent weight of 150-250, 100 g of diethylenetriamine, and 200 g of nonylphenol were mixed and reacted at 80 ° C. for 1 hour while slowly stirring. Thereafter, the temperature was raised to 100 ° C. to completely react the unreacted epoxy resin to obtain a curing agent that was a liquid resin having an amine value of 450 ± 50, an active hydrogen equivalent of 65 ± 5, and a Gardner viscosity of Z3-Z4.

Example 6

The reaction was carried out in the same manner as in Example 5, but using 150 g of triethylenetetraamine, 200 g of nonylphenol, and 40 g of benzyl alcohol instead of diethylenetriamine. A curing agent which was a liquid resin having an amine number of 450 ± 50 and a Gardner viscosity of Z5 was obtained.

In order to examine the properties of the final cured physical properties of the main composition and the curing agent obtained in each of the above-mentioned examples, an epoxy composition for road marking including the main composition obtained in Examples 1-4 and the hardener obtained in Example 5 was prepared, and The paint was obtained as shown in Table 1 below. Table 1 shows the mixing ratio of the main agent and the curing agent and the composition ratio of the white TiO ₂ pigment and CaCO ₃ .

At this time, since the main agent and the curing agent are mixed beforehand, they cannot be hardened to perform the painting work on the road. Therefore, they must be stored in different containers and mixed at the same time and sprayed at a constant rate during the painting work. In other words, using a _two- component fluid handling equipment that contains the main composition in one container and the curing agent, benzyl alcohol, TiO ₂ and CaCO ₃ in the other container, the continuous operation can be carried out at an appropriate mixing ratio. It is to form a mark on the surface.

For comparison, the fusion coating used for fusion lane coating using a thermoplastic resin, which is a conventional road marking method, was prepared as shown in Table 2, and the content of each component was used as a comparative example.

In order to find out the properties of each coating composition shown in Table 1 and Table 2, the properties of the cured product were tested and the results are shown in Table 3.

In Table 3, the evaluation items indicating the characteristics of each paint means the following. In the drying evaluation, ◎ means drying within 5 minutes, ○ means drying within 10 minutes, △ means drying within 15 minutes and × means drying within 30 minutes. In the glass transition temperature, ◎ means 150 ° C or more, ○ means 100-150 ° C, △ means 50-100 ° C and × means 50 ° C or less. In the remaining items, ◎ is very good, ○ is good, △ is normal and × means poor.

In addition, each characteristic in Table 3 was measured by the following method. First, drying property compares room temperature dryness, melt | dissolves each coating material, spray-paints, and confirms room temperature dryness visually.

Adhesion to asphalt and concrete is obtained by coating the coating composition on the upper part of the body and then carrying out a cut-off peel test. The adhesion to the glass bead is attached to the surface of the glass bead by measuring the weight, and then the tire is attached. After the shock was applied to the automatic roller for 1 hour, the weight was measured and the relative weight change was compared.

The weatherability was compared with the change in color difference in the yellowing degree of UV using a weather resistance meter, the hardness was measured using a Barcole hardness tester, the impact resistance was measured by comparing relatively using an impact test (Impact test).

As shown in the table, the production of the paint using the epoxy resin composition according to the present invention has the following distinct advantages.

It has excellent adhesion to glass beads, which reflects light on asphalt, concrete, and night roads or dark roads, and makes road markings clear, especially weather resistance. In addition, it has good impact resistance and high glass transition temperature, so it is excellent in thermal stability.Therefore, there is almost no departure or crack due to the change of temperature, the change of temperature according to the change of season, the impact, etc. Recognition is very easy.

As mentioned above, although the present invention has been described and illustrated in detail by the preferred embodiments, the present invention is not limited thereto, and it is possible for a person skilled in the art to modify or improve the present invention within a conventional range. .

Claims (8)

Condensation reaction of a glycol having a hydroxy equivalent weight of 30-400 and a liquid or solid silicone resin having a methoxy or hydroxy equivalent weight of 150-500 yields a silicone-modified resin having a hydroxy equivalent weight of 100-500. In the group consisting of a silicone-modified epoxy resin, alkylphenyl-modified sulfonic acid and alkylphenol-modified sulfonic acid, obtained by reacting a modified resin with epichlorohydrin and having 2-10 oxirane functional groups formed thereon, and an epoxy equivalent of 150-600. A resin subject composition comprising at least one sulfonic acid selected; and A liquid bisphenol A epoxy resin having an epoxy equivalent weight of 150-250 and a curing agent composed of an epoxy addition polyamine having an amine value of 200-600 by modifying an amine. The epoxy resin composition whose mixing ratio of the said subject and said hardening | curing agent is 1: 0.8-1.2. The method of claim 1, wherein the alkylphenyl-modified sulfonic acid to be included in the resin main composition to shorten the curing time is at least one selected from the group consisting of benzenesulfonic acid, dodecylbenzenesulfonic acid and laurylbenzenesulfonic acid, The alkylphenol-modified sulfonic acid is at least one selected from the group consisting of phenolsulfonic acid, nonylphenolsulfonic acid and octylphenolsulfonic acid, and the amount of the alkylphenyl-modified sulfonic acid or the alkylphenol-modified sulfonic acid added is based on the amount of the subject composition. The epoxy resin composition, characterized in that 2 to 5% by weight. The epoxy resin composition according to claim 1, wherein the mixing ratio of the glycol and the silicone resin is 2: 0.5-1.9 in an equivalent ratio. The epoxy resin composition according to claim 1, wherein the mixing ratio of the silicone-modified resin and the epichlorohydrin is 1: 1-1.1 in molar ratio. The method of claim 1, wherein the glycol is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, Epoxy resin composition, characterized in that at least one glycol selected from the group consisting of bisphenol A, trimethyl pentanediol, cyclohexane dimethanol, trimethylol propane, trimethylol ethane, glycerin, pentaerythritol and dipentaerythrol. The method of claim 1, wherein the amines are aliphatic amines including diethylenetriamine, triethylenetetraamine and tetraethylenepentaamine, cycloaliphatic amines including ethylenedianiline and isophoronediamine and metaxylenediamine and diaminodi Epoxy resin composition, characterized in that at least one selected from the group consisting of an aromatic amine containing phenylmethane. Condensation reaction between a glycol having a hydroxy equivalent weight of 30-400 and a liquid and solid silicone resin having a methoxy or hydroxy equivalent weight of 150-500 yields a silicone-modified resin having a hydroxy equivalent weight of 100-500. In the group consisting of 2-10 oxirane functional groups formed by reacting a modified resin with epichlorohydrin and an epoxy equivalent of 150-600, a silicone-modified epoxy resin and an alkylphenyl-modified sulfonic acid and an alkylphenol-modified sulfonic acid A resin main composition comprising at least one sulfonic acid selected, and a curing agent composed of a liquid bisphenol A type epoxy resin having an epoxy equivalent weight of 150-250 and an epoxy addition polyamine having an amine value of 200-600, by modifying an amine, Preparing an epoxy resin composition by mixing so that the mixing ratio of the curing agent is 1: 0.8-1.2; Spraying a paint including the epoxy resin composition on a road; and A road surface marking line coating method comprising the step of hardening the epoxy resin composition to form a mark on a road surface. The method of claim 7, wherein the curing agent further comprises nonylphenol and / or benzyl alcohol as a curing accelerator diluent.