KR101430652B1 - Resin composition for road coating - Google Patents

Abstract

The present invention relates to a resin composition for road coating, which comprises an acrylic mixture comprising at least two monomer mixtures selected from acrylate monomers and an acrylic polymer soluble in said monomer mixture, and liquid phase paraffin, a crosslinking agent and a polymerization promoter The resin composition for road coating according to the present invention can be rapidly cured at room temperature and can maintain high viscosity even when applied by using a high-pressure spray, and does not cause cob webbing, , A sufficient and uniform film thickness can be ensured.

Description

Resin composition for road coating "

The present invention relates to a resin composition for road coating. More particularly, the present invention relates to a resin composition for road covering comprising an acrylic mixture containing liquid phase paraffin, a crosslinking agent and a polymerization accelerator.

Recently, many bicycle routes have been constructed nationwide to reduce greenhouse gases to prevent global warming. In the case of bicycle-only roads, various road-covering products are used for prevention of vehicle entry and visibility, as bicycles having a relatively low load are mainly used as compared with general roads.

Such a coated product is widely used as an acrylic reaction type resin having excellent durability and high visibility as in Korean Patent No. 10-0987340. A variety of high pressure spray devices are used in these resins since it is very important to ensure rapid application and sufficient thickness of the coating. However, in general, in order to secure a sufficient film thickness while reducing the number of coatings, it is desirable that the viscosity of the resin composition is high, but in such a case, cobwebbing occurs in the same manner as a general paint when using a spraying apparatus.

When cob webbing is sprayed with a high molecular weight polymer, the paint emits in a thread shape to cause a spider-like defect on the surface of the coating film, and when scattered by the wind, it causes contamination to nearby vehicles and buildings. Generally, in order to solve this problem, the viscosity of the coating material should be lowered. However, when the viscosity is lowered, the number of application times increases in order to secure sufficient film thickness for durability. In addition, It becomes difficult to cause defects.

Korean Patent No. 10-0987340 (October 06, 2010)

An object of the present invention is to provide a resin composition for an acrylic resin film capable of securing excellent workability and film thickness without cob webbing without lowering the viscosity of the composition for road coating.

The present invention relates to a resin composition for road coating.

One aspect of the present invention relates to a resin composition for road coating comprising an acrylic mixture comprising a mixture of two or more kinds of monomers selected from acrylate monomers and an acrylic polymer soluble in the monomer mixture and a liquid phase paraffin, Wherein the resin composition for road coating comprises 0.5 to 5 parts by weight of liquid phase paraffin, 0.1 to 5 parts by weight of a crosslinking agent, and 1 to 10 parts by weight of a polymerization accelerator, based on 100 parts by weight of the acrylic mixture.

Another embodiment of the present invention is a process for the preparation of the acrylic mixture, wherein the acrylic mixture comprises 20 to 40% by weight of methyl methacrylate and 30 to 45% by weight of an acrylate monomer excluding methyl methacrylate and 20 to 40% And a resin composition for road surface coating.

In another embodiment of the present invention, the acrylic polymer comprises 30 to 80% by weight of methyl methacrylate, 20 to 70% by weight of one or more of a methacrylate monomer, an acrylate monomer or a comonomer, Wherein the methacrylate monomer is selected from the group consisting of ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate And 2-ethylhexyl methacrylate, and the acrylate monomer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate And the comonomer is at least one selected from the group consisting of methacrylic acid, acrylic acid, It relates to the sacred.

Hereinafter, the resin composition for road coating according to the present invention will be described in detail.

Generally, cobwebbing means that when a paint using a high molecular weight polymer as a vehicle is sprayed, the paint emits in a thread shape, resulting in a defect such as a spider web attached to the drawing. In order to solve this problem, it is possible to improve the solubility of the thinner or increase the amount of the thinner to lower the absolute viscosity of the coating composition, lower the molecular weight of the resin composition, or improve the use of the monomer having low volatility. However, when the viscosity is lowered, it is difficult to uniformly obtain the thickness of the coating film. When the molecular weight of the monomer or resin composition having a low volatility is lowered, it is difficult to secure desired physical properties of the coating film.

In order to solve the above problems, the present inventors have carried out studies to prevent volatilization of monomers while improving the mobility while maintaining a high viscosity. When liquid paraffin was added, absolute viscosity did not change and mobility And the liquid paraffin is distributed on the surface of the composition to prevent volatilization. Thus, the present invention has been completed.

The resin composition for road coating according to the present invention comprises a liquid phase paraffin, a crosslinking agent and a polymerization accelerator in an acrylic mixture containing at least two monomer mixtures selected from acrylate monomers and an acrylic polymer soluble in the monomer mixture .

First, the acrylic mixture may include 20 to 40% by weight of methyl methacrylate, 30 to 45% by weight of an acrylate monomer excluding methyl methacrylate, and 20 to 40% by weight of an acrylic polymer.

The methyl methacrylate is preferably used in an amount of 20 to 40% by weight. When the content is less than 20% by weight, the curing is delayed. When the content is more than 40% by weight, it is difficult to exhibit sufficient elongation after curing.

In the present invention, the acrylate monomers other than methyl methacrylate may be selected from the group consisting of ethylacrylate, n-butylacrylate, n-butylmethacrylate, t-butyl acrylate (t-butylacrylate), and 2-ethylhexylacrylate (2-ethylhexylacrylate).

The acrylate monomer excluding the methyl methacrylate is preferably used in an amount of 30 to 45% by weight. When the content is less than 30% by weight, the low-temperature characteristics after curing deteriorates. When the content exceeds 45% by weight, the curing is delayed.

It is preferable that the acrylic polymer is copolymerized with 30 to 80% by weight of methyl methacrylate and 20 to 70% by weight of one or more of a methacrylate monomer, an acrylate monomer or a comonomer.

The methacrylate monomer may be selected from the group consisting of ethylmethacrylate, n-butylmethacrylate, i-butylmethacrylate, t-butylmethacrylate, , Laurylmethacrylate, and 2-ethylhexylmethacrylate. These may be used alone or in combination of two or more.

The acrylate monomer may be selected from the group consisting of methylacrylate, ethylacrylate, n-butylacrylate, t-butylacrylate and 2-ethylhexyl acrylate -ethylhexylacrylate) may be used.

The comonomer is preferably methacrylic acid, acrylic acid or a mixture thereof.

The acrylic polymer may first be subjected to suspension polymerization at 70 to 90 ° C and then further reacted at 110 to 130 ° C for copolymerization. When the polymerization temperature is lower than 70 ° C, the reaction time is significantly slowed to make complete polymerization difficult. When the polymerization temperature exceeds 90 ° C, there is a problem that the polymerization stability is impaired by an abrupt reaction. Further, the addition reaction is carried out for the purpose of reducing the unreacted residual monomer, and when the temperature exceeds 130 ° C, the already formed polymer may aggregate. In the suspension polymerization reaction, distilled water, stabilizer, polymerization initiator or the like which can be generally used in the art may be further added to proceed the reaction.

The polymerization initiator causes a curing reaction and it is preferable to use an organic peroxide. As the polymerization initiator, it is preferable to use one or two or more organic peroxides selected from the group consisting of ketone peroxides, diacyl peroxides, azo peroxides, dialkyl peroxides, and peroxides. Cumene hydroperoxide, diisopropyl benzene hydroperoxide and dibenoxyl peroxide are particularly preferred from the viewpoints of hardenability and pot life. It is also preferable to use it in the form of a paste, a powder or a diluted solution in an inert liquid or solid concentration of about 25 to 50% for handling safety.

The polymerization initiator is preferably added in an amount of 1 to 20 parts by weight based on 100 parts by weight of the acrylic mixture. When the content of the polymerization initiator is less than 1 part by weight, the reaction rate is low and rapid curing is difficult to occur. When the content is more than 20 parts by weight, flexibility is low.

It is preferable that the prepared acrylic polymer has a glass transition temperature in the range of -20 to 60 占 폚. When the glass transition temperature is lower than -20 ° C, it is difficult to completely remove the unreacted residual monomer. Thus, when used in a resin composition for coating, a change over time may occur over time, The sufficient ductility can not be secured due to the lack of ductility.

The acrylic polymer is preferably used in an amount of 20 to 40% by weight. If less than 20% by weight is added, the viscosity of the composition is lowered, causing a problem of shrinkage upon curing, and it is difficult to secure a sufficient thickness of the coating film when the road is inclined. When it is added in an amount exceeding 40% by weight, the viscosity becomes too high, and the workability is remarkably lowered, and self-leveling becomes impossible.

In addition to preventing the coving webbing effect, the liquid paraffin in the liquid phase is a substitute for the solid paraffin wax used to prevent the problem that the surface of the coating film is uncured by contacting with oxygen in the methacrylate-based reactive resin composition Effect. The liquid paraffin is preferably paraffin oil having kinetic viscosity of 1 to 100 cSt at 40 캜. If the kinematic viscosity of the paraffin oil exceeds 100 cSt, the kinematic viscosity during the extrusion process is high, which may lead to problems such as load increase, defective surface of the sheet and film, difficulty in extraction in the extraction process, And problems such as reduced permeability may occur. If the kinematic viscosity of the paraffin oil is less than 1 cSt, kneading becomes difficult during extrusion due to the viscosity difference with the composition in the extruder.

The liquid phase paraffin preferably comprises 0.5 to 5 parts by weight based on 100 parts by weight of the acrylic mixture. When the content is less than 0.5 parts by weight, the effect of preventing cork webbing is deteriorated. When the content is more than 5 parts by weight, elongation and tensile strength of the coating film after curing are deteriorated.

In the present invention, the crosslinking agent plays a role of improving the chemical resistance by cross-linking during the curing of the monomer. The crosslinking agent may be a (meth) acrylate monomer having two or more (meth) acrylate groups or a crosslinking agent having two or more anilyl groups or allyl groups, for example, ethylene glycol diacrylate, Ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, Butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol diacrylate (1,4-butylene glycol diacrylate, butanediol diacrylate and 1,4-butylene glycol dimethacrylate. These may be used singly or in combination of two or more thereof.

The crosslinking agent is preferably used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the acrylic mixture. When the content of the crosslinking agent is less than 0.1 part by weight, the curability is impaired. When the amount is more than 5 parts by weight, the flexibility may be lowered after curing and the coating film may be broken.

The polymerization accelerator may be an amine compound or a metal catalyst. The amine compound may be selected from the group consisting of N, N-di (2-hydroxypropyl) -p-toluidine, tri-n-butylamine N-dimethyl-p-toluidine, N-ethyl-N-hydroxyethylanyline and N, N-dimethylaniline N, N-dimethylaniline), and the metal catalyst may be cobalt naphthalate, cobalt octylate, cobalt acetacetate, or the like. These may be used alone or in combination of two or more.

The polymerization promoter may be added immediately before curing the resin composition, or may be added together with other compositions. The polymerization promoter is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic mixture. When the content of the polymerization accelerator is less than 0.1 parts by weight, the curing reaction is retarded at a low temperature. When the content is more than 10 parts by weight, a curing reaction does not occur at a high temperature.

The present invention may further include functional additives such as a coloring agent, a colorant, a polymerization inhibitor, and an oxidation stabilizer, if necessary, and may be mixed with ordinary aggregates and other fillers according to a construction method.

The coloring agent or coloring agent is preferably an oily coloring agent such as a universal coloring agent commonly used in the art, and the amount of the coloring agent to be added can be freely adjusted according to the method and purpose of the resin composition.

The polymerization inhibitor may be added in order to improve the storage stability of the resin composition according to the present invention, preferably hydroquinone, hydroquinone monoethyl ether, 2,4-dimethyl- polymerization such as 2,4-dimethyl-t-butyl phenol or 2,6-di-t-butyl-4-methyl phenol Preference is given to adding an inhibitor and 2,4-dimethyl-t-butylphenol and 2,6-di-t-butyl-4-methylphenol are preferred for the prevention of yellowing during storage.

The polymerization inhibitor is preferably used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the acrylic mixture. When the content of the polymerization inhibitor is less than 0.001 parts by weight, it is difficult to obtain desired storage stability. When the content of the polymerization inhibitor exceeds 1 part by weight, curing does not occur or the curing time becomes long, and the amount of the curing agent to be added at the time of curing increases, not.

The oxidizing stabilizer serves to stabilize the curing property of the resin composition according to the present invention, and is preferably selected from the group consisting of tributylphosphate, tri (2-ethylhexyl) phosphate and tridecylphosphate it is preferable to use phosphates such as tridecylphosphate, tri stearyl phosphate, tris (nonylphenyl) phosphate, and triphenyl phosphate.

Examples of the aggregate and the filler include sand, silica sand, quartz sand or their coloring materials, calcined rocks such as quartz and silica sand, calcined crushed materials such as colored ceramics and ceramics, calcium carbonate, alumina and glass beads The amount of the aggregate and the filler to be added can be adjusted freely according to the method and purpose of the resin composition.

In addition to the additives listed above, various additives such as a plasticizer, an ultraviolet absorber, an antistatic agent, a thickener, a thixotropic agent, and a leveling agent may be further added as needed in order to improve various properties of the resin composition.

INDUSTRIAL APPLICABILITY The resin composition for road coating according to the present invention can be rapidly cured at room temperature, and even when applied by using a high-pressure spray, it is possible to maintain a high viscosity and to avoid the occurrence of cobwebbing, A uniform film thickness can be ensured.

Hereinafter, the resin composition for road coating according to the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are provided for illustrating the present invention, and the present invention is not limited thereto.

The properties of the following examples and comparative examples were evaluated as follows.

(Viscosity)

The viscosity of the resin composition was measured at 25 캜 using a Brookfield viscometer (BROOKFIELD LV type, DV-II + pro).

(Thermal analysis residue ratio)

10 to 15 mg of the prepared resin composition was prepared and heated from room temperature to 100 ° C using a thermogravimetric analyzer (PerkimElmer Pyris 6 TGA), and the temperature was slowly lowered to determine the weight to be volatilized.

(Cove webbing)

The resin composition thus prepared was applied by using a two-fluid high-pressure piston sprayer.

[Manufacturing Example]

0.15 parts by weight of azobisisobutyronitrile as an initiator and 200 parts by weight of water were added to 100 parts by weight of an acrylic mixture containing 60% by weight of methyl methacrylate, 20% by weight of ethyl acrylate and 20% by weight of butyl acrylate, 0.84 part by weight of a polyvinyl alcohol solution (POVAL PVA217 manufactured by Kuraray) as a dispersant at a concentration of 5% and 0.36 part by weight of normal-octylmercaptan as a chain transfer agent were subjected to suspension polymerization at 80 DEG C for 90 minutes. After the reaction, additional reaction was carried out at 120 ° C for 15 minutes in order to remove the residual monomer. After completion of the reaction, the polymerized beads were washed with a dehydrator and dried in a drier for 24 hours to prepare an acrylic polymer having a weight average molecular weight of 65,000 g / mol, an average particle size of 250 μm and a glass transition temperature of 45 ° C.

[Example 1]

The stirrer was heated to 60 DEG C, and 38 wt% of methyl methacrylate, 22 wt% of butyl acrylate and 10 wt% of 2-ethylhexyl acrylate were added to a stirrer, and 30 wt% of the acrylic polymer prepared in the above- And dissolved. To 100 parts by weight of the acrylic mixture were added 1.0 part by weight of liquid paraffin (kinetic viscosity 80 cSt), 3 parts by weight of 1,4-butanediol diacrylate, 0.4 parts by weight of bis (2-hydroxyethyl methacrylate) -Butylamine were added and dissolved, and the mixture was warmed to room temperature to prepare a resin composition for coating. The properties of the prepared compositions were evaluated and are shown in Table 1 below.

[Example 2]

The composition was prepared in the same manner as in Example 1, except that the liquid paraffin having a kinematic viscosity of 30 cSt was used. The properties of the prepared compositions were evaluated and are shown in Table 1 below.

[Comparative Example 1]

The composition was prepared by the same composition and method as in Example 1 except that no liquid paraffin was used. The properties of the prepared compositions were evaluated and are shown in Table 1 below.

[Comparative Example 2]

Except that 20% by weight of the acrylic polymer of the above-mentioned production example, 40% by weight of methacrylate, 20% by weight of butyl acrylate and 20% by weight of 2-ethylhexyl acrylate were used and liquid paraffin was not used. The compositions were made with the same composition and method. The properties of the prepared compositions were evaluated and are shown in Table 1 below.

[Table 1]

Comparative Example 1 in which liquid paraffin was not used as shown in Table 1 shows that cove webbing is generated. Also, in the case of Comparative Example 2 in which the composition ratio of the composition was changed, it was found that the cob webbing did not occur but the volatilization of the monomer was relatively increased as compared with the examples.

Claims (12)

Acrylate monomer and an acrylic polymer which is soluble in the monomer mixture, and a liquid phase paraffin having a kinematic viscosity of 1 to 100 cSt, a crosslinking agent and a polymerization accelerator, wherein the acrylic polymer comprises a mixture of two or more kinds of monomers selected from acrylate monomers, Resin composition. The method according to claim 1,
Wherein the resin composition for road coating comprises 0.5 to 5 parts by weight of liquid phase paraffin, 0.1 to 5 parts by weight of a cross-linking agent, and 1 to 10 parts by weight of a polymerization promoter, based on 100 parts by weight of the acrylic mixture. The method according to claim 1,
Wherein the acrylic mixture comprises 20 to 40% by weight of methyl methacrylate and 20 to 40% by weight of a monomer mixture comprising 30 to 45% by weight of an acrylate monomer excluding methyl methacrylate and an acrylic polymer Resin composition. The method of claim 3,
The acrylate monomer except for the methyl methacrylate is at least one selected from the group consisting of ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate and 2-ethylhexyl acrylate Resin composition for coating. The method according to claim 1,
Wherein the acrylic polymer is a copolymer of 30 to 80% by weight of methyl methacrylate and 20 to 70% by weight of one or more of a methacrylate monomer, an acrylate monomer or a comonomer; Composition. 6. The method of claim 5,
Wherein the methacrylate monomer is selected from the group consisting of ethyl methacrylate, n-butyl methacrylate, I-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate and 2-ethylhexyl methacrylate. One or two or more thereof. 6. The method of claim 5,
Wherein the acrylate monomer is any one or two or more selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate. 6. The method of claim 5,
Wherein the comonomer is methacrylic acid, acrylic acid, or a mixture thereof. The method according to claim 1,
Wherein the acrylic polymer is subjected to suspension polymerization at 70 to 90 占 폚, followed by further reaction at 110 to 130 占 폚 to copolymerize. delete The method according to claim 1,
The crosslinking agent is selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 3-butylene glycol dimethacrylate, 1,4-butanediol diacrylate, and 1,4-butylene glycol dimethacrylate. The method according to claim 1,
The polymerization accelerator may be selected from the group consisting of N, N-di (2-hydroxypropyl) -p-toluidine, tri-n-butylamine, N, N- , N-dimethylaniline, and the like.