KR101558876B1 - Water soluble paint composition for a road marking with improved wear resistance - Google Patents

Abstract

The present invention relates to a water-soluble paint composition for marking a road, comprising an acrylate or methacrylate repeating unit, and comprising an acrylic resin cross-linked by a hardening agent, a color pigment, and a body pigment. The paint composition for marking the road of the present invention has excellent material properties such as durability, wear resistance, and weather resistance, and excellent adhesive properties on a glass bead and stickiness.

Description

TECHNICAL FIELD [0001] The present invention relates to a water-soluble coating composition for road marking having excellent abrasion resistance,

The present invention relates to a water-soluble coating composition for road marking having excellent abrasion resistance and a process for producing the same, and more particularly to a water-soluble road marking paint which is excellent in abrasion resistance and improved adhesion to glass beads ≪ / RTI >

On the road surface, lanes are displayed for the purpose of distinguishing the direction of travel, lanes and lanes, and these lanes can be indicated by a paint for road marking.

The coating composition for road surface marking can be classified into a heating type, a room temperature, a water-soluble type, a fusion type, a two-component type, and the acrylic type, vinyl type and vinyl acrylic type coatings made by using a thermoplastic resin, And food coatings are mainly used.

The following properties are required for road marking paints.

First, it should have excellent adhesion to road surfaces such as asphalt and concrete, and should be excellent in adhesion to glass beads that reflect light at night or in dark roads and sharpen road markings.

Second, there is no change with time such as yellowing and gloss degradation due to ultraviolet ray after curing, thermal stability without mechanical property deterioration due to changes in temperature during the summer and winter, excellent impact resistance by mobile bodies such as automobiles, and the like .

Finally, since the time for restricting the passage of the moving object and the pedestrian should be short during the painting work of the road, it should be fast drying type that hardens in a short time.

However, the paint for road marking which has been used up to now has a merit that the time to complete drying after painting is short and the time limit for road passage during painting is short. However, since such a road marking paint uses an inexpensive thermoplastic resin, adhesion with glass beads remarkably deteriorates with passage of time. After a certain period of time, when the vehicle is running at night or in the rainy season, And it becomes difficult to drive the vehicle. In addition, since the cured product of the road marking paint has a low glass transition temperature, there is a problem that the thermal stability is insufficient in the summer and winter when the temperature difference on the road surface is extremely severe, and the paint for road marking is broken or cracked. Accordingly, despite the use of a coating material using an inexpensive thermoplastic resin, it is necessary to frequently carry out a repair coating operation, and therefore, it is a problem that a lot of cost is required in practice.

Of these road marking paints, room temperature curing paints are paints which are dried on the road surface by volatilization of the solvent in the product. The above-mentioned room temperature curing type coating material is one kind of KSM 6080 (oil type) and two kinds (aqueous type).

On the other hand, the conventional room temperature curable type oil paint (1 kind) and the water-soluble paint (2 kinds) are delayed in drying and can be used for a long time to pass the vehicle and can cause traffic congestion, The performance of fixing beads may be lowered. Conventional paints cause a phenomenon in which a lane is hardly visible to a driver at night or in a rainy season, which causes a traffic accident. Further, since the abrasion resistance and the durability are poor, the repair coating is performed once a year, which is a problem in that additional expenses are useless.

The water-soluble paint is a paint comprising a pigment and a squeezing agent added to a synthetic resin system and a desiccant, which are major components of a coating film. The coating is formed by physical adhesion and is applied to the road surface at room temperature or in a heated state. But it has a disadvantage that it is not applicable to environmental pollution and indication type.

In addition, its application method is applied as undiluted solution and it can be applied on vertical surface by contact type, injection type, drop type, etc., and there may be a difference in curing time depending on machine used, temperature and climate. shall.

Korean Patent No. 10-0429552 (Apr. 24, 2004) discloses a method for producing an acrylic emulsion resin, and a method for producing an acrylic emulsion resin composition of a cross-linking type at room temperature, , And as another conventional technique, there is disclosed a coating composition for road marking Korean Patent No. 10-0150625 (Oct. 15, 1998) relates to a water-soluble acrylic resin for road marking and a method for producing the same, and is a road marking which is synthesized by synthesizing a carboxylic acid- Soluble acrylic ester resin, a process for producing the same, and a water-soluble paint composition for road surface type road marking using the same.

However, in spite of the prior art including the above-mentioned prior arts, a paint composition for road marking having improved effects that can improve not only the physical properties of abrasion resistance, durability and weatherability but also adhesion and fixability to glass beads The demand for the development of the

Korean Patent No. 10-0429552 (April 29, 2004) Korean Patent No. 10-0150625 (Oct. 15, 1998)

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to improve the properties of wear resistance, durability and weatherability as well as improve adhesion and fixability with glass beads, And to provide a coating composition for road surface marking which is excellent in performance.

The present invention relates to an aqueous acrylic resin composition comprising an acrylic resin crosslinked by an aziridine curing agent containing an acrylate or methacrylate repeating unit and containing two or three aziridine groups in one molecule, A coating composition for road surface marking, wherein the aziridine curing agent used for polymerization in the crosslinked acrylic resin is used in an amount of 2 to 15 parts by weight based on the total amount of acrylic monomers.

The water-soluble road surface marking coating composition may contain 25 to 70 parts by weight of a colored pigment and 50 to 200 parts by weight of an extender pigment based on 100 parts by weight of a crosslinked acrylic resin.

In addition, the crosslinked acrylic resin may be crosslinked by ethylene imine aziridine or propylene imine aziridine curing agent.

Further, the crosslinked acrylic resin can be obtained by polymerizing acrylic acid or methacrylic acid into a comonomer.

The coating composition according to the present invention may further comprise 0.01 to 20 parts by weight of at least one of a defoaming agent, a surfactant, a dispersant, a plasticizer, a pH adjusting agent, a cryoprotectant, a water-soluble wax and a preservative based on 100 parts by weight of the coating composition can do.

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The present invention also relates to a process for the preparation of an antifogging agent comprising 10 to 40 wt% of an acrylic resin crosslinked with an ethyleneimine aziridine or propyleneimine aziridine curing agent, 8 to 30 wt% of a colored pigment, 30 to 80 wt% of an extender pigment, 0 to 5 wt 0 to 5 wt% surfactant, 0 to 5 wt% dispersant, 0 to 5 wt% plasticizer, 0 to 5 wt% pH adjuster, 0 to 5 wt% cryoprotectant, 0 to 5 wt wt. And 0 to 5 wt% of an antiseptic agent, wherein the crosslinked acrylic resin is characterized in that 2 to 15 parts by weight of an aziridine curing agent is used based on the total content of acrylic monomers Soluble coating composition for road surface marking.

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The present invention also provides a coating film for road marking obtained by mixing the coating composition for road marking with a solvent and applying the coating composition to a road surface.

INDUSTRIAL APPLICABILITY The present invention not only improves the abrasion resistance of a coating film obtained from a water-soluble road surface marking composition, but also improves adhesion and fixability with glass beads, thereby reducing the deterioration of glass beads. As a result, the maintenance period can be prolonged and the maintenance cost can be reduced, which is economical.

In addition, by reducing the deterioration of the glass bead, the ability to maintain the retroreflectivity is improved, and the visibility at night or at night is improved, thereby preventing drivers from drowsing and preventing the accident from being overspeed.

In addition, the present invention is environmentally friendly road surface marking paint which does not use petroleum resin such as thinner or gasoline, and has environmental advantage because it does not generate environmental pollutants.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the results of evaluation of wear resistance of a coating film obtained from the coating composition for water-resistant road surface marking of the present invention.

Hereinafter, preferred embodiments according to the present invention will be described in detail. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not.

The coating composition for water-soluble road surface marking according to the present invention comprises acrylate or methacrylate repeating units and is prepared by incorporating an acrylic resin crosslinked by a curing agent, a colored pigment and an extender pigment.

The acrylic resin used in the present invention is an acrylic resin comprising an acrylate or methacrylate repeating unit and crosslinked by a curing agent.

Wherein the acrylate or methacrylate repeating unit may be represented by Structural Formula A or Structural Formula A-1. Here, the substituent R 1 in the structural formula A and the structural formula A-1 may be hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

(Structure A) (Structure A-1)

More specifically, the acrylate or methacrylate repeating unit is selected from the group consisting of methyl acrylate, acrylic acid, methyl methacrylate, methacrylic acid, butyl methacrylate, hydroxypropyl methacrylate, ethylene glycol dimethacrylate, Acrylate esters such as bisphenol-A-bisphenol-A, bisphenol-A bisphenol-A diacrylate ester, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, hydroxylethyldiisocyanurate triacrylate, Alkyl ester acrylic acid, hydroxyalkyl ester methacrylic acid, butylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol dimecaacrylate, bisphenol-A dimethacrylate, ethoxylated bis N-butyrolactone dimethacrylate, nol-A dimethacrylate, pentaerythiol dimethacrylate, butylene glycol trimethacrylate, polyethylene glycol trimethacrylate, bisphenol-A trimethacrylate, ethoxylated bisphenol- Acrylate, n-octyl methacrylate, benzyl methacrylate, n-octyl methacrylate, n-octyl methacrylate, n-octyl methacrylate, , Isooctyl methacrylate, 3-vinylcyclohexyl methacrylate, 3.3.5-trimethyl cyclohexyl methacrylate, vinyl methacrylate, isobornyl methacrylate, 1-methylcyclohexyl methacrylate, propanediol di Methyl acrylate, butanediol dimethylacrylate, hexane di Acrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, , 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, Propylene-modified methacrylate, polypropylene-modified methacrylate, and ethylene-propylene-modified methacrylate. Examples of the acrylate monomer include acrylonitrile, methacrylonitrile, Glycol diglycidyl ether, n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate Acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobutyl acrylate, Acrylate, n-butyl acrylate, n-butyl acrylate, n-butyl acrylate, n-butyl acrylate,

The acrylic resin crosslinked by the curing agent is a curing agent component contained in the acrylic resin polymer, and the polymer main chains in the acrylic resin can be crosslinked to each other by functional groups other than the acrylic group.

Preferably, the acrylic resin crosslinked by the curing agent can be crosslinked by an aziridine curing agent.

For example, the aziridine curing agent is a compound containing an aziridine group, and the aziridine curing agent may include one to three aziridine groups in one molecule. Preferably, two or three such aziridine groups are used, which have two or three aziridine reactors per molecule, so that the polymer backbone in the acrylic resin can be cross-linked to each other.

The aziridine curing agent which can be used in the coating composition according to the present invention may have the structure represented by the following formulas (1) to (4), but is not limited thereto.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

The crosslinked acrylic resin of the present invention may be crosslinked by ethylene imine aziridine or propylene imine aziridine curing agent. That is, the chemical formulas 1, 2 and 4 belong to the ethylenimine-based aziridine curing agent, and the chemical formula 3 corresponds to the propyleneimine-based aziridine curing agent.

In addition, exemplary compounds of the aziridine curing agents of the present invention include tetraaziridimetaxylenediamine, tetraaziridinylmethylparaboxylenediamine, neopentylglycol di (-aziridinylpropionate), 2-methyl aziridine, 2 (2-ethyl) aziridine (HX-868), bis-iso-propyl azide, 1-methyl-aziridine (HX-752) may optionally be used to prepare a coating composition for road surface marking.

The aziridine curing agent may be used in an amount of 1 to 20 parts by weight, preferably 2 to 15 parts by weight based on 100 based on the total amount of the acrylic monomer. When the amount of the curing agent is less than 1 part by weight, When it exceeds 20 parts by weight, it is preferable to use the above range because it may increase the cost due to the excessive content of the curing agent and affect the strength, durability, water resistance and weather resistance.

In the present invention, the crosslinked acrylic resin in the coating composition for water-soluble road surface marking is an additional component other than the main monomer constituting the acrylate or methacrylate repeating unit, and is polymerized by using acrylic acid or methacrylic acid as a comonomer Can be obtained.

The acrylic acid or methacrylic acid component may react with aziridine, which is a crosslinking agent, to accelerate the crosslinking reaction.

On the other hand, in addition to the acrylic resin crosslinked by the curing agent, the present invention may include a colored pigment and an extender pigment as additional components.

The colored pigment realizes the color of the paint, has the effect of imparting coloring and hiding power to the paint, and is a powder having a color resistant to sun, not soluble in water, oil and solvent, It can be divided into inorganic pigments and organic pigments.

The inorganic pigments include metal compounds such as titanium, lead, copper, iron, chromium, and the like, and carbon black formed by incomplete combustion of petroleum or natural gas. The organic pigments are used in the form of a metal compound that is insoluble in water or a solvent And the extender pigments may be dyed with a dye so as not to dissolve in water and in a solvent.

According to the present invention, the colored pigment is prepared containing 25 to 70 parts by weight based on 100 parts by weight of the crosslinked acrylic resin. When the amount of the colored pigment is less than 25 parts by weight, the coloring and hiding power of the paint deteriorates. When the amount exceeds 70 parts by weight, wettability and adhesiveness are poor, and viscosity of the coating composition increases, .

On the other hand, the extender pigment may be selected from a mixture of fillers and extender pigments such as calcium carbonate, talc, silica, mica, kaolin and the like, and the extender pigment is used for controlling physical properties such as fluidity and viscosity of the paint, , And gloss control.

According to the present invention, the extender pigment is prepared containing 50 to 200 parts by weight based on 100 parts by weight of the crosslinked acrylic resin. When the extender pigment is less than 50 parts by weight, the effect is insignificant. When the extender pigment exceeds 200 parts by weight, the storage stability of the paint may be deteriorated.

In the present invention, the coating composition for road surface marking may further comprise at least one of a defoaming agent, a surfactant, a dispersing agent, a plasticizer, a pH adjusting agent, a cryoprotectant, a water-soluble wax and a preservative as additional components other than the crosslinked acrylic resin, colored pigment and extender pigment , And these may be included in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the coating composition.

The antifoaming agent is a silicone antifoaming agent, which removes bubbles in the paint during the production of the paint or during the work, thereby improving appearance upon drying. When the antifoaming agent is not used, bubbles are generated. On the other hand, Problems arise.

The above-mentioned surfactant is preferably an anionic surfactant. Since the content of the surfactant may affect the stability and storage stability when blended with the coating composition, it is preferable to use an appropriate range.

The dispersing agent may be at least one selected from a dispersant for organic and inorganic pigments as a wetting and dispersing agent. The dispersant improves the visual and hiding power of the coating film by improving the dispersion of the pigment and the extender pigment in the coating material, and may affect the storage stability of the coating material.

The plasticizer is used to prevent cracking of the coating composition in the winter season, and a trimethylpropanol-based plasticizer, a phthalate-based plasticizer and the like can be used, and a trimethylpropanol-based plasticizer having excellent stability is preferably used.

The pH adjusting agent Ammonia water, monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-methylpropane, 2-amino-2-methylpropane and triethylamine.

The pH should be in the range of 912. When the pH is less than 9, the viscosity of the resultant paint is increased during the storage of the paint due to the crosslinking reaction.

The water-soluble wax may be used to prevent the oxygen in the air from reacting with the acrylic monomer used in the acrylic resin, thereby preventing the drying failure and the durability from deteriorating.

The coating composition according to the present invention may further contain a cryoprotectant to prevent the coating composition from cracking at the time of winter and further include a preservative to enhance storage stability.

Examples of additives which may optionally include components such as antifoaming agents, surfactants, dispersants, plasticizers, pH adjusting agents, cryoprotectants, water-soluble waxes, preservatives and the like, which are additional components other than the crosslinked acrylic resin, colored pigments and extender pigments As the content of the water-soluble road surface marking coating composition, the composition according to the present invention comprises 10 to 40 wt% of an acrylic resin crosslinked by an ethyleneimine aziridine or propyleneimine aziridine curing agent, 8 to 30 wt% of a colored pigment, 0 to 5 wt.% Of a surfactant, 0 to 5 wt.% Of a dispersant, 0 to 5 wt.% Of a plasticizer, 0 to 5 wt.% Of a pH adjuster, 0 to 5 wt.% Of a defoamer, 30 to 80 wt.% Of a pigment, 0 to 5 wt. 0 to 5 wt%, water-soluble wax 0 to 5 wt%, and preservative 0 to 5 wt%, wherein the crosslinked acrylic resin has an aziridine curing agent based on the total content of acrylic monomers 2 to 15 parts by weight may be used.

In the present invention, the content of each of the above components can be appropriately and selectively adjusted by the user to obtain desired physical properties of the coating film.

Hereinafter, details of the process of the present invention will be described with reference to Production Examples, Examples and Comparative Examples.

Crosslinked  Acrylic resin manufacturing

Production Example 1

920 g of ion-exchanged water and 4.2 g of Hytenol BC-10 (manufactured by Cheil Pharmaceutical Co., Ltd.) as an emulsifier were placed in a five-necked flask equipped with a nitrogen inlet, a thermometer, a dropping funnel, a condenser and a stirrer. Deg.] C, 700 g of ion exchanged water, 28.2 g of Hytenol BC-10 (produced by Cheil Pharmaceutical Co., Ltd.), 4.4 g of ammonium persulfate, 800 g of methyl methacrylate, 8.11 g of acrylic acid, 720 g of butyl acrylate, 65 g of hydroxylethyl methacrylate, 33 g of acrylamide, and 30 g of trimethylolpropane-tris- (β-N-aziridinyl) propionate (CL-422, manufactured by MENADIONA, C ₂₁ H ₃₅ N ₃ O ₆ 425.24 mol / g) was preliminarily mixed with 110 g of the pre-emulsion, which was then added to the flask and maintained for 30 minutes.

When the exotherm is over, the above mixture is added dropwise at a temperature of 80 ± 2 over 3 hours. After completion of the dropwise addition, the mixture was maintained at 80 ± 2 for 2 hours and cooled to 50 ° C. or less to prepare a crosslinked acrylic resin.

Production Example 2

800 g of methyl methacrylate, 8.11 g of acrylic acid, 720 g of butyl acrylate, 65 g of 2-hydroxylethyl methacrylate, 33 g of acrylamide, 0.1 g of trimethylopropane-tris- (β-N-aziridinyl) Pianate (manufactured by MENADIONA, C ₂₁ H ₃₅ N ₃ O ₆ 425.24 mol / g) instead of 100 g, 750 g of methyl methacrylate, 8.11 g of acrylic acid, 720 g of butyl acrylate, 65 g of 2-hydroxylethyl methacrylate, 33 g of acrylamide, Except that 110 g of a pre-emulsion prepared by premixing 150 g of propene-tris- (β-N-aziridinyl) propanate (MENADIONA, CL-422) To prepare a crosslinked acrylic resin.

Manufacturing example  3: Production of acrylic resin

800 g of methyl methacrylate, 8.11 g of acrylic acid, 720 g of butyl acrylate, 65 g of 2-hydroxylethyl methacrylate, 33 g of acrylamide, 0.1 g of trimethylopropane-tris- (β-N-aziridinyl) Pianate (manufactured by MENADIONA, C ₂₁ H ₃₅ N ₃ O ₆ 425.24 mol / g) instead of 100 g, 700 g of methyl methacrylate, 8.11 g of acrylic acid, 720 g of butyl acrylate, 65 g of 2-hydroxylethyl methacrylate, 33 g of acrylamide, Except that 110 g of a pre-emulsion prepared by premixing 200 g of tris- (β-N-aziridinyl) propanate (MENADIONA, CL-422) To prepare an acrylic resin.

Preparation of coating composition

Example  One

5 g of a defoamer, 5 g of a surfactant and 10 g of a dispersant were added to 300 g of the acrylic resin binder prepared in Preparation Example 1, and the mixture was stirred for 10 to 15 minutes to uniformly mix at 1000 to 1200 rpm. Then, 150 g of a colored pigment, Add 465 g of pigment. The mixture was stirred at 2000 to 3000 rpm for 30 to 40 minutes and mixed. Then, 30 g of the pH adjusting agent, 1 g of the cryoprotectant, 3 g of the water-soluble WAX, 20 g of the plasticizer and 2 g of the preservative were added and stirred at 1000 to 1200 rpm for 20 to 30 minutes To prepare a coating composition, which was then applied to the road surface.

Example  2

5 g of a defoaming agent, 5 g of a surfactant and 10 g of a dispersant were added to 300 g of the acrylic resin binder prepared in Preparation Example 2, and stirred to uniformly mix at 1000 to 1200 rpm for 10 to 15 minutes. Then, 150 g of a colored pigment, Add 465 g of pigment. The mixture was stirred at 2000 to 3000 rpm for 30 to 40 minutes and mixed. Then, 30 g of the pH adjusting agent, 1 g of the cryoprotectant, 3 g of the water-soluble WAX, 20 g of the plasticizer and 2 g of the preservative were added and stirred at 1000 to 1200 rpm for 20 to 30 minutes To prepare a coating composition, which was then applied to the road surface.

Example  3

5 g of a defoaming agent, 5 g of a surfactant and 10 g of a dispersant were added to 300 g of the acrylic resin binder prepared in Preparation Example 3 and stirred so as to be homogeneously mixed at 1000 to 1200 rpm for 10 to 15 minutes to obtain 150 g of a colored pigment, Add 465 g of pigment. The mixture was stirred at 2000 to 3000 rpm for 30 to 40 minutes and mixed. Then, 30 g of the pH adjusting agent, 1 g of the cryoprotectant, 3 g of the water-soluble WAX, 20 g of the plasticizer and 2 g of the preservative were added and stirred at 1000 to 1200 rpm for 20 to 30 minutes To prepare a coating composition, which was then applied to the road surface.

Example  4

5 g of a defoaming agent, 5 g of a surfactant and 10 g of a dispersant were added to 350 g of the acrylic resin binder prepared in Preparation Example 1, and stirred to uniformly mix at 1000 to 1200 rpm for 10 to 15 minutes. Then, 150 g of a colored pigment, 415 g of pigment is added. The mixture was stirred at 2000 to 3000 rpm for 30 to 40 minutes and mixed. Then, 30 g of the pH adjusting agent, 1 g of the cryoprotectant, 3 g of the water-soluble WAX, 20 g of the plasticizer and 2 g of the preservative were added and stirred at 1000 to 1200 rpm for 20 to 30 minutes To prepare a coating composition, which was then applied to the road surface.

Example  5

5 g of a defoaming agent, 5 g of a surfactant and 10 g of a dispersing agent were added to 350 g of the acrylic resin binder prepared in Preparation Example 2, and stirred to uniformly mix at 1000 to 1200 rpm for 10 to 15 minutes to obtain 150 g of a colored pigment, 415 g of pigment is added. The mixture was stirred at 2000 to 3000 rpm for 30 to 40 minutes and mixed. Then, 30 g of the pH adjusting agent, 1 g of the cryoprotectant, 3 g of the water-soluble WAX, 20 g of the plasticizer and 2 g of the preservative were added and stirred at 1000 to 1200 rpm for 20 to 30 minutes To thereby prepare a coating composition and apply it on a road surface.

Example  6

5 g of a defoaming agent, 5 g of a surfactant and 10 g of a dispersant were added to 350 g of the acrylic resin binder prepared in Preparation Example 3, stirred for 10 to 15 minutes to uniformly mix at 1000 to 1200 rpm, and then 150 g of a colored pigment, 415 g of pigment is added. The mixture was stirred at 2000 to 3000 rpm for 30 to 40 minutes and mixed. Then, 30 g of the pH adjusting agent, 1 g of the cryoprotectant, 3 g of the water-soluble WAX, 20 g of the plasticizer and 2 g of the preservative were added and stirred at 1000 to 1200 rpm for 20 to 30 minutes To prepare a coating composition, which was then applied to the road surface.

The composition ratios of the coating compositions for each of the above Examples are shown in Table 1.

Comparative Example  One

As a prior art, a coating film was formed using a water-soluble road surface marking paint (Swarco , USA, colorado paint co.) Containing an acrylic binder without using an aziridine curing agent.

Comparative Example  2

An acrylic resin was prepared in the same manner as in Preparation Example 1, except that the above aziridine curing agent was not used, and a coating composition was prepared under the same conditions as in Example 1.

Comparative Example  3

A coating film was formed using a room temperature surface coating paint (KSM 6080, type 1).

Coating performance evaluation

The performance evaluation of the coating film formed by the composition obtained according to the above Examples 1 to 6 is shown in Table 2 below.

The abrasion resistance test was performed as the performance evaluation. The abrasion resistance test performance was represented by the self-conformity indication method. The white is R3 150, R4 200 and R5 300 according to the retroreflective performance (RL) can do.

For this purpose, the coated film produced according to the examples and the comparative examples was subjected to 200,000 times, 500,000 times, 1 million times, and 2,000,000 times of revolutions of the total damage such as friction and fracture by a vertical load of about 300 kg, R _L ).

Table 2 shows the evaluation results of the compositions of Examples and Comparative Examples in the present invention.

According to Table 2, the initial retroreflectivity of the examples and comparative examples of the present invention shows the highest performance as R5. However, it can be seen that the retroreflectivity decreases as the wear resistance test proceeds.

More specifically, the coating composition according to the present invention had almost no degradation in performance with a degree of retroreflectivity of R4 to R5, while the performance of Comparative Examples 1 to 3 was abruptly decreased.

That is, it can be seen that the paint composition comprising the acrylic resin binder prepared using the curing agent containing the aziridine group under the same conditions is superior to the comparative example in the retroreflective properties.

In addition, it can be seen that the reduced retroreflectivity of Comparative Examples 1 to 3 is much lower than the average value of the reduced retroreflectivity of Examples 1 to 3 according to the present invention.

Further, it can be seen that the coating composition obtained by using the acrylic resin binder produced according to the present invention is superior in adhesion to glass beads as compared with those obtained from the coating compositions according to Comparative Examples 1 to 3.

It is to be understood that this is by way of example only and is not intended to limit the scope of the invention in any way.

Claims (11)

Acrylate or methacrylate repeating unit, which is crosslinked by an aziridine curing agent containing two or three aziridine groups in one molecule, a water-soluble road surface marking agent containing a colored pigment and an extender pigment As a coating composition,
Wherein the aziridine curing agent used for polymerization in the crosslinked acrylic resin is used in an amount of 2 to 15 parts by weight based on the total amount of the acrylic monomer. The water-borne road marking paint composition according to claim 1, wherein the coating composition for water-soluble road surface marking comprises 25 to 70 parts by weight of a colored pigment and 50 to 200 parts by weight of an extender pigment based on 100 parts by weight of a crosslinked acrylic resin Composition. The method according to claim 1,
The acrylate or methacrylate repeating unit may be selected from the group consisting of methyl acrylate, acrylic acid, methyl methacrylate, methacrylic acid, butyl methacrylate, hydroxypropyl methacrylate, ethylene glycol dimethacrylate, ethoxylated bisphenol- A diacrylate ester, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, hydroxylethyl diisocyanate triacrylate, alkyl ester acrylic acid, hydroxyalkyl ester acrylic acid, Hydroxyalkyl ester methacrylic acid, butylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol dimecacrylate, bisphenol-A dimethacrylate, ethoxylated bisphenol-A dimethacrylate, Arc Acrylate, pentaerythritol dimethacrylate, butylene glycol trimethacrylate, polyethylene glycol trimethacrylate, bisphenol-A trimethacrylate, ethoxylated bisphenol-A trimethacrylate, pentaacrylic diol tri Acrylate, methacrylate, alkyl methacrylate, cycloalkyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, benzyl methacrylate, isooctyl methacrylate , 3-vinylcyclohexylmethacrylate, 3.3.5-trimethylcyclohexylmethacrylate, vinylmethacrylate, isobonylmethacrylate, 1-methylcyclohexylmethacrylate, propanediol dimethylacrylate, butanediol di Methyl acrylate, hexanediol dimethyl acrylate Trimethylolpropane trimethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, Hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, kadura acrylate, But are not limited to, lactone acrylate, caprolactone methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, polypropylene modified acrylate, polypropylene modified methacrylate, and ethylene glycol diglyme Cidyl ether, normal butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate Acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, And cyclohexyl acrylate. The coating composition for water-resistant road marking according to claim 1, delete The method according to claim 1,
Wherein the crosslinked acrylic resin is crosslinked with an ethylene imine aziridine or propylene imine aziridine curing agent. The method according to claim 1,
Wherein the crosslinked acrylic resin is obtained by polymerizing acrylic acid or methacrylic acid with a comonomer. The method according to claim 1,
Wherein the coating composition further comprises 0.01 to 20 parts by weight of at least one of a defoaming agent, a surfactant, a dispersant, a plasticizer, a pH adjuster, a cryoprotectant, a water-soluble wax and a preservative based on 100 parts by weight of the coating composition Coating composition for water - soluble road surface marking. delete 10 to 40 wt% of an acrylic resin crosslinked with an ethyleneimine aziridine or propyleneimine aziridine curing agent, 8 to 30 wt% of a colored pigment, 30 to 80 wt% of an extender pigment, 0 to 5 wt% of a defoaming agent, 0 to 5 wt%, 0 to 5 wt% dispersant, 0 to 5 wt% plasticizer, 0 to 5 wt% pH adjuster, 0 to 5 wt% cryoprotectant, 0 to 5 wt% water soluble wax, To 5 wt% based on the total amount of the acrylic monomer, wherein the crosslinked acrylic resin is used in an amount of 2 to 15 parts by weight, based on the total amount of the acrylic monomer, of an aziridine curing agent / RTI > delete A coating film for road marking obtained by mixing the coating composition for road marking according to any one of claims 1 to 3, 5 to 7, and 9 with a solvent and applying the coating composition to a road surface.

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