KR100883415B1 - Anti-fogging paint composition and thermosetting acrylic polymer used for it - Google Patents

Abstract

The present invention relates to an antifogging coating composition and a thermosetting acrylic polymer used therein, wherein the antifogging coating composition according to the present invention is dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, polyoxyethylene Hydrophilic monomer selected from (meth) acrylate, carboxyl group-containing monomer, N-methylol acrylamide, N-dimethyl acrylamide, N-dimethylamino propyl methacrylamide, hydroxyl-containing (meth) acrylate monomer, hydrophobic (meth) acryl A thermosetting acrylic polymer obtained by adding an initiator to a rate monomer and reacting the radical in an organic solvent; And a crosslinking agent selected from at least one of isocyanate compounds, urea compounds, and melamine compounds. Accordingly, it is possible to provide a coating composition capable of curing in a short time, excellent in anti-fogging, water resistance, and adhesion, and having excellent hot water resistance, transparency, weather resistance, chemical resistance, and heat resistance.

Description

Anti-fogging paint composition and thermosetting acrylic polymer used for it

The present invention relates to a coating composition, and more particularly, to an antifogging coating composition capable of curing in a short time and excellent in anti-fogging, water resistance and adhesion.

In general, the steaming phenomenon is caused by the condensation of water droplets due to the temperature difference between the internal temperature and the external temperature in a high temperature and humidity conditions. For example, when a person wearing glasses stays outside in a cold winter and enters a heated room, the glasses suddenly become steamy, and there is no moment at all, causing discomfort. This occurs because the wet fine particles in the air condense and adhere to the surface of the glasses due to rapid temperature changes.

In order to solve this phenomenon, conventionally, a conventional anti-fog method of spraying a coating agent using a surfactant or an antifogging agent onto the surface of glass or a general material to lower the surface tension to convert water in the form of water droplets into a water film form has been mainly used. . However, these coatings were poor in water resistance, and when applied to the surface of the material, the coating film was easily removed, and only a temporary effect could be expected, and there was a problem in that the coating had to be applied every time the fog occurred.

On the other hand, in relation to the technique for preventing the fog, Korean Patent Publication No. 1989-0005821 (Invention name: antifogging resin film-forming composition) (hereinafter referred to as 'prior art 1') and Korean Patent Publication No. 1997 -028674 (name of the invention: antifog coating composition) (hereinafter, referred to as 'prior art 2') is described. The prior art 1 discloses a technique of using at least one copolymer selected from a block copolymer and a graft copolymer with a surfactant, and the prior art 2 discloses a technique using a thermosetting polymer and a crosslinking agent. It is.

However, these prior arts 1 and 2 had the following problems.

The prior art 1 uses a surfactant, but when the composition using the surfactant is applied to the material and the time passes, the surfactant gradually flows out onto the surface, so that the initial antifogging property is excellent. There was a problem of poor water resistance. In addition, the prior art 2 uses a 2-hydroxyethyl (meth) acrylate selected from the thermosetting polymer, the use of 2-hydroxyethyl (meth) acrylate has a problem that takes a long curing time, crosslinking agent Among the organosilane compounds used, aminopropyltrimethoxy silane has good antifogging properties but adversely affects water resistance, and in case of small amount of epoxy silane, it does not have sufficient physical properties in water resistance and overcuring when used in excess. There was a problem that could not be exercised.

The present invention is to solve the above problems, can be cured in a short time, anti-fogging, water resistance, adhesion is excellent, anti-fogging for excellent water resistance, transparency, weather resistance, chemical resistance, heat resistance It is an object to provide a coating composition and a thermosetting acrylic polymer used therein.

The thermosetting acrylic polymer of the antifogging paint composition according to the present invention for achieving the above object. Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, polyoxyethylene (meth) acrylate, carboxyl group-containing monomer, N-methylol acrylamide, N-dimethyl acrylamide, N-dimethylamino propyl It is characterized by being obtained by radical reaction in an organic solvent by adding an initiator to a hydrophilic monomer selected from methacrylamide, a hydroxyl group-containing (meth) acrylate monomer and a hydrophobic (meth) acrylate monomer.

Further, based on 100 parts by weight of the solid content of the thermosetting acrylic polymer, 20 to 70 parts by weight of the hydrophilic monomer; 5 to 40 parts by weight of the hydroxyl group-containing (meth) acrylate monomer; And 20 to 60 parts by weight of the hydrophobic (meth) acrylate monomer.

Wherein the hydroxyl group-containing (meth) acrylate monomer is 4-hydroxybutyl (meth) acrylate.

Moreover, the antifogging paint composition which concerns on this invention is dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, polyoxyethylene (meth) acrylate, a carboxyl group-containing monomer, N-methylol acrylamide Obtained by adding an initiator to a hydrophilic monomer selected from N-dimethylacrylamide and N-dimethylamino propylmethacrylamide, a hydroxyl group-containing (meth) acrylate monomer, and a hydrophobic (meth) acrylate monomer, followed by radical reaction in an organic solvent. Thermosetting acrylic polymers; And a crosslinking agent selected from at least one of isocyanate compounds, urea compounds, and melamine compounds.

Wherein the hydroxyl group-containing (meth) acrylate monomer is 4-hydroxybutyl (meth) acrylate.

In addition, the hydrophobic (meth) acrylate monomers are aromatic unsaturated monomers such as styrene and vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acryl At least in the group consisting of (meth) acrylic acid alkyl esters such as tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobonyl (meth) acrylate; It is characterized by one or more selected.

The organic solvent may be an alcohol solvent such as isopropyl alcohol, isobutanol, normal butanol, diacetone alcohol or methanol, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, methyl cellosolve or ethyl cellosolve. At least one selected from the group consisting of cellosolve solvents, and the like.

Moreover, 20-70 weight part of said hydrophilic monomers with respect to 100 weight part of solid content of a thermosetting acrylic polymer; 5 to 40 parts by weight of the hydroxyl group-containing (meth) acrylate monomer; 20 to 60 parts by weight of the hydrophobic (meth) acrylate monomer; And 0.1 to 30 parts by weight of the crosslinking agent.

Here, with respect to 100 parts by weight of the solid content of the thermosetting acrylic polymer, 0.01 to 10 parts by weight of accelerator; characterized in that it further comprises.

Referring to the present invention in more detail as follows.

The present invention is dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, polyoxyethylene (meth) acrylate, carboxyl group-containing monomer, N-methylol acrylamide, N-dimethylacrylamide, N- Antifogging paint using a thermosetting acrylic polymer obtained by radical reaction in an organic solvent by adding an initiator to a hydrophilic monomer, a hydroxyl group-containing (meth) acrylate monomer, and a hydrophobic (meth) acrylate monomer selected from dimethylamino propylmethacrylamide To a composition. At this time, the thermosetting acrylic polymer is 20 to 70 parts by weight of the hydrophilic monomer, 5 to 40 parts by weight of hydroxyl group-containing (meth) acrylate monomer, and 20 to 60 parts of hydrophobic (meth) acrylate monomer based on 100 parts by weight of the solid content of the thermosetting acrylic polymer. Although it contains a weight part, the thermosetting type acrylic polymer which is excellent in antifogging property and water resistance can be manufactured by using the monomer in the said range. In addition, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate can be generally used as the hydroxyl group-containing (meth) acrylate monomer. ) Acrylate was used to improve the curing rate and increase the antifogging function.

Next will be described in more detail with respect to each composition component contained in the coating composition according to the present invention.

Antifogging paint composition according to the present invention is dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, polyoxyethylene (meth) acrylate, carboxyl group-containing monomer, N-methylol acrylamide, N- Thermosetting acryl obtained by radical reaction in an organic solvent by adding an initiator to a hydrophilic monomer selected from dimethylacrylamide and N-dimethylamino propylmethacrylamide, a hydroxyl group-containing (meth) acrylate monomer, and a hydrophobic (meth) acrylate monomer. At least one selected from polymers, isocyanate compounds, urea compounds and melamine compounds.

Hydrophilic monomers are divided into nonionic and ionic monomers, and ionic monomers can be further divided into cationic and anionic monomers. In this case, cationic and anionic monomers can be appropriately used in nonionic, ionic and ionic monomers. It should be used in combination, and it is preferable to use a functional group-containing monomer having high reactivity so that curing can be performed within a short time. Accordingly, polyoxyethylene (meth) acrylate is used as the nonionic monomer, and the ionic monomer is dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-methyl as the cationic monomer. Allacrylamide, N-dimethylacrylamide, N-dimethylamino propylmethacrylamide and a carboxyl group-containing monomer are used as the anionic monomer.

Here, as the carboxyl group-containing monomer which is an anionic monomer, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, maleic acid monomethyl, maleic acid monobutyl, itaconic acid monoethyl, itaconic acid mono At least one selected from butyl and unsaturated acid-containing modified acids is used.

The use of such hydrophilic monomers has the effect of producing a polymer having sufficient antifogging properties, and it is preferable to use at least two hydrophilic monomers. The hydrophilic monomer is used in the coating composition, 20 to 70 parts by weight based on 100 parts by weight of the solid content of the thermosetting acrylic polymer, when used less than 20 parts by weight is less anti-fogging and when used in excess of 70 parts by weight Increased hydrophilicity can increase the anti-fogging function, but the water resistance is poor. Therefore, it is to be used within the above range (preferably 20 to 60 parts by weight). On the other hand, it is preferable to use the carboxyl group-containing monomer which is an anionic monomer also in a hydrophilic monomer at 40 weight part or less. When the carboxyl group-containing monomer is used in excess of 40 parts by weight, the reactivity with the crosslinking agent can be increased, but the amount of other hydrophilic monomers and hydrophobic (meth) acrylate monomers is relatively reduced, resulting in a decrease in antifogging and water resistance.

As the hydroxyl group-containing (meth) acrylate monomer, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) ylate can generally be used, but the antifogging function can be significantly improved, the curing is fast and the reactivity is excellent. It is preferable to use 4-hydroxybutyl (meth) acrylate which can bring about the effect which can harden | cure a paint within 10 minutes even at the temperature of 120 degreeC. The hydroxyl group-containing (meth) acrylate monomer is included in the coating composition in an amount of 5 to 40 parts by weight based on 100 parts by weight of the solid content of the thermosetting acrylic polymer, but when used less than 5 parts by weight, the reactivity with the crosslinking agent is insufficient. If the crosslinking density is lowered and used in excess of 40 parts by weight, the amount of the hydrophilic monomer and the hydrophobic (meth) acrylate monomer is relatively insufficient, and thus the desired antifogging property and water resistance cannot be obtained. Therefore, it is to be used within the above range (preferably 5 to 30 parts by weight).

Hydrophobic (meth) acrylate monomers have the effect of producing a polymer having excellent water resistance. As hydrophobic (meth) acrylate monomer, aromatic unsaturated monomers, such as styrene and vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, At least one selected from (meth) acrylic acid alkyl esters such as tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate is used. . The hydrophobic (meth) acrylate monomer described above is used in the coating composition in an amount of 20 to 60 parts by weight based on 100 parts by weight of the solid content of the thermosetting acrylic polymer, but when used less than 20 parts by weight, the hydrophobic portion is less in the structure of the polymer. If the water resistance is lowered and used in excess of 60 parts by weight, the hydrophobic portion is increased, the hydrophilicity is insufficient and the anti-fogging property is poor. Therefore, it is to be used within the above range (preferably 20 to 50 parts by weight).

The crosslinking agent is used by selecting at least one of isocyanate compound, urea compound, and melamine compound.The isocyanate compound is highly reactive with thermosetting acrylic polymer at room temperature, so the pot life of the paint can be shortened. It is preferable to use blocked isocyanate compounds to control the pot life of the. The crosslinking agent is used in the coating composition in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the solid content of the thermosetting acrylic polymer. When used, the crosslinking density increases, so the anti-fogging property of the coating film is sharply degraded, and the transparency is also degraded. Therefore, it is to be used within the above range (preferably 0.1 to 20 parts by weight).

On the other hand, an accelerator may be used to control the curing reaction. When an isocyanate compound is used as a crosslinking agent, a carboxyl group-containing monomer may act as a catalyst, but an accelerator may not be used. However, when using a urea compound and a melamine compound, a short time is required. It is preferably used to react with the thermosetting acrylic polymer to cure. In this case, phosphates such as para-toluene sulfonic acid, dodecyl benzene sulfonic acid, dinonyl naphthalene sulfonic acid, dinonyl naphthalene disulfonic acid, sulfonic acid such as alkyl acid phosphate, and phenyl acid phosphate can be used. It is preferable to use a block type accelerator to increase the reaction stability at room temperature and to control the pot life of the paint. The accelerator is used in the coating composition in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the solid content of the thermosetting acrylic polymer. When the accelerator is not used, curing is not performed within a short time, so that the water resistance is poor and 10 parts by weight. If used in excess, water resistance is degraded by excessive acid component, and transparency of coating film is also reduced. Therefore, it is to be used within the above range (preferably 0.01 to 5 parts by weight).

 In order to synthesize | combine a thermosetting acrylic polymer using said hydrophilic monomer, a hydroxyl-containing (meth) acrylate monomer, and a hydrophobic (meth) acrylate monomer, the initiator which carries out a radical reaction with an organic solvent is used. The organic solvent is also used to adjust the viscosity by diluting the paint in addition to the manufacturing of the thermosetting acrylic polymer. The organic solvent used here is sufficiently diluted with the thermosetting acrylic polymer and the crosslinking agent since the thermosetting acrylic polymer exhibiting antifogging properties is polarized. It is preferable to use a polar organic solvent so that it can be. Accordingly, the polar organic solvents used may be alcohol solvents such as isopropyl alcohol, isobutanol, normal butanol, diacetone alcohol and methanol, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, methyl cellosolve, and ethyl. There are cellosolve solvents such as cellosolve, and at least one or two or more thereof are used in combination. In addition, the initiator for the radical reaction is 2,2-azobisisobutyronitrile, 2,2-azobis- (2-methylbutyronitrile), 2,2-azobis- (2,4-dimethylvalero Azo compounds such as nitrile), benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butylper oxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate and the like can be used. have.

The coating composition according to the present invention may be added an antioxidant, an ultraviolet stabilizer, an ultraviolet absorber, a leveling agent, an antifoaming agent, or the like as necessary. Each amount is suitably 0.01 to 5 parts by weight with respect to 100 parts by weight of the solid content of the thermosetting acrylic polymer in the coating composition, and more than that may reduce the adhesion and water resistance of the coating.

Such paint compositions are polyvinyl chloride (PVC), acrylic, polycarbonate

It can be used by roller coating, brushing, bar coat or spraying on the surface of glass or metal material.

As described in detail above, the coating composition according to the present invention has the following effects.

First, thermosetting acrylic polymers prepared using hydrophilic monomers to increase the antifogging property, hydrophobic monomers to increase the water resistance, and (meth) acrylate monomers having excellent reactivity were reacted with a crosslinking agent and the curing reaction rate was increased by the accelerator. It is fast and antifogging and water resistance is excellent.

Second, because of its excellent anti-fog and water resistance, no steaming occurs even when it is exhaled at 0 ℃, and it is excellent in adhesion and hot water resistance of coating film even when soaked in hot water at 40 ℃ for more than 240 hours, and has transparency, weather resistance, chemical resistance, and heat resistance. Also excellent

Third, because the curing is fast, it can be cured within 10 minutes even at a temperature of 120 ℃.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

Manufacturing Example 1 Thermosetting  Acrylic Polymer A)

Put 100 parts by weight of butyl cellosolve into the reaction vessel, replace the vessel with nitrogen gas, and maintain the temperature in the vessel at 80 ° C., 35 parts by weight of methyl (meth) acrylate, and 30 parts by weight of dimethylaminoethyl (meth) acrylate. , 5 parts by weight of 4-hydroxybutyl (meth) acrylate, 20 parts by weight of polyoxyethylene (meth) acrylate, 10 parts by weight of a carboxyl group-containing monomer, 2 parts by weight of azobisisobutyronitrile as a reaction initiator The added mixture was added dropwise for 3 hours, reacted for 1 hour, and then 0.5 parts by weight of azobisisobutyronitrile was further added for 3 hours to continue the reaction. .

Manufacturing Example 2 Thermosetting  Acrylic polymer B)

Put 100 parts by weight of butyl cellosolve into the reaction vessel, replace the vessel with nitrogen gas, and maintain the temperature in the vessel at 80 ° C. 35 parts by weight of methyl (meth) acrylate and 30 parts by weight of diethylaminoethyl (meth) acrylate Parts, 5 parts by weight of 4-hydroxybutyl (meth) acrylate, 20 parts by weight of polyoxyethylene (meth) acrylate, 10 parts by weight of a carboxyl group-containing monomer, and 2 parts by weight of azobisisobutyronitrile as a reaction initiator. 3 parts by weight of the mixture was added dropwise, the reaction was carried out for 1 hour, and then 0.5 parts by weight of azobisisobutyronitrile was added and the reaction continued for 3 hours. It was.

Manufacturing example 3 Thermosetting  Acrylic polymer C)

Put 100 parts by weight of butyl cellosolve into the reaction vessel, replace the vessel with nitrogen gas, and maintain the temperature in the vessel at 80 ° C., 35 parts by weight of methyl (meth) acrylate, 30 parts by weight of N-dimethylacrylamide, 4- 5 parts by weight of hydroxybutyl (meth) acrylate, 20 parts by weight of polyoxyethylene (meth) acrylate, 10 parts by weight of a carboxyl group-containing monomer, and 2 parts by weight of azobisisobutyronitrile were added as a reaction initiator. After the mixture was added dropwise for 3 hours and reacted for 1 hour, 0.5 parts by weight of azobisisobutyronitrile was further added, and the reaction was continued for 3 hours. After completion of the reaction, the mixture was diluted with butyl cellosolve to obtain a concentration of 40%.

Manufacturing Example 4 Thermosetting  Acrylic Polymer D)

100 parts by weight of butyl cellosolve was placed in the reaction vessel, and then the inside of the vessel was replaced with nitrogen gas, and the temperature in the vessel was maintained at 80 ° C., 25 parts by weight of methyl (meth) acrylate and 40 parts by weight of diethylaminoethyl (meth) acrylate. Parts, 5 parts by weight of 4-hydroxybutyl (meth) acrylate, 20 parts by weight of polyoxyethylene (meth) acrylate, 10 parts by weight of a carboxyl group-containing monomer, and 2 parts by weight of azobisisobutyronitrile as a reaction initiator. 3 parts by weight of the mixture was added dropwise, the reaction was carried out for 1 hour, and then 0.5 parts by weight of azobisisobutyronitrile was added and the reaction continued for 3 hours. It was.

Manufacturing example 5 Thermosetting  Acrylic Polymer E)

Put 100 parts by weight of butyl cellosolve into the reaction vessel, replace the vessel with nitrogen gas, and maintain the temperature in the vessel at 80 ° C. 55 parts by weight of methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate 5 Parts by weight, 30 parts by weight of dimethylaminoethyl (meth) acrylate, 10 parts by weight of a carboxyl group-containing monomer, and a mixture of 2 parts by weight of azobisisobutyronitrile as a reaction initiator were added dropwise for 3 hours, followed by reaction for 1 hour. After the reaction, 0.5 parts by weight of azobisisobutyronitrile was further added, and the reaction was continued for 3 hours, and diluted with butyl cellosolve so that the concentration of the obtained polymer was 40% after completion of the reaction.

Manufacturing Example 6 Thermosetting  Acrylic Polymer F)

Put 100 parts by weight of butyl cellosolve into the reaction vessel, replace the vessel with nitrogen gas, and maintain the temperature in the vessel at 80 ° C. 55 parts by weight of methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate 5 Part by weight, 30 parts by weight of polyoxyethylene (meth) acrylate, 10 parts by weight of a carboxyl group-containing monomer, and a mixture of 2 parts by weight of azobisisobutyronitrile as a reaction initiator were added dropwise for 3 hours, followed by reaction for 1 hour. After the reaction, 0.5 parts by weight of azobisisobutyronitrile was further added, and the reaction was continued for 3 hours, and diluted with butyl cellosolve so that the concentration of the obtained polymer was 40% after completion of the reaction.

Manufacturing example 7 Thermosetting  Acrylic polymer G)

Put 100 parts by weight of butyl cellosolve into the reaction vessel, replace the vessel with nitrogen gas, and maintain the temperature in the vessel at 80 ° C., 35 parts by weight of methyl (meth) acrylate, and 30 parts by weight of dimethylaminoethyl (meth) acrylate. , 5 parts by weight of 2-hydroxyethyl (meth) acrylate, 20 parts by weight of polyoxyethylene (meth) acrylate, 10 parts by weight of a carboxyl group-containing monomer, 2 parts by weight of azobisisobutyronitrile as a reaction initiator The added mixture was added dropwise for 3 hours, reacted for 1 hour, and then 0.5 parts by weight of azobisisobutyronitrile was further added for 3 hours to continue the reaction. .

Example 1

5.0 parts by weight of a melamine compound (trade name: cymel 303, manufactured by CYTEC) is stirred and mixed with the thermosetting acrylic polymer A to 100 parts by weight of the thermosetting acrylic polymer A to obtain a coating composition. The resulting coating composition was diluted to 10% by weight using a butyl cellosolve, and 2 parts by weight of para-toluene sulfonic acid (NACURE 2530, 25% solids, manufactured by King Industries, Inc.) as a promoter was added. Spray and apply | coated to a carbonate plate, it is made to dry-cure for 10 minutes in the drier set to the temperature of 120 degreeC, and a coating film is formed. The thickness of the cured coating film was 5 to 7 µm.

Example 2

5.0 parts by weight of a melamine compound (trade name: cymel 303, manufactured by CYTEC) is stirred and mixed with the thermosetting acrylic polymer B to 100 parts by weight of the thermosetting acrylic polymer B to obtain a coating composition. The resulting coating composition was diluted to 10% by weight using a butyl cellosolve, and 2 parts by weight of para-toluene sulfonic acid (NACURE 2530, 25% solids, manufactured by King Industries, Inc.) as a promoter was added. It sprays and apply | coats to a carbonate plate, it is made to dry harden for 10 minutes in the dryer set to the temperature of 120 degreeC, and a coating film is formed. The thickness of the cured coating film was 5 to 7 µm.

Example 3

5.0 parts by weight of a melamine compound (trade name: cymel 303, manufactured by CYTEC) is stirred and mixed with the thermosetting acrylic polymer C to 100 parts by weight of the thermosetting acrylic polymer C to obtain a coating composition. The resulting coating composition was diluted to 10% by weight using a butyl cellosolve, and 2 parts by weight of para-toluene sulfonic acid (NACURE 2530, 25% solids, manufactured by King Industries, Inc.) as a promoter was added. It sprays and apply | coats to a carbonate plate, it is made to dry harden for 10 minutes in the dryer set to the temperature of 120 degreeC, and a coating film is formed. The thickness of the cured coating film was 5 to 7 µm.

Example 4

5.0 parts by weight of a melamine compound (trade name: cymel 303, manufactured by CYTEC) is stirred and mixed with the thermosetting acrylic polymer D based on 100 parts by weight of the thermosetting acrylic polymer D to obtain a coating composition. The resulting coating composition was diluted to 10% by weight using a butyl cellosolve, and 2 parts by weight of para-toluene sulfonic acid (NACURE 2530, 25% solids, manufactured by King Industries, Inc.) as a promoter was added. It sprays and apply | coats to a carbonate plate, it is made to dry harden for 10 minutes in the dryer set to the temperature of 120 degreeC, and a coating film is formed. The thickness of the cured coating film was 5 to 7 µm.

Example 5

5.0 parts by weight of a melamine compound (trade name: cymel 303, manufactured by CYTEC) is stirred and mixed with the thermosetting acrylic polymer E to 100 parts by weight of the thermosetting acrylic polymer E to obtain a coating composition. The resulting coating composition was diluted to 10% by weight using a butyl cellosolve, and 2 parts by weight of para-toluene sulfonic acid (NACURE 2530, 25% solids, manufactured by King Industries, Inc.) as a promoter was added. It sprays and apply | coats to a carbonate plate, it is made to dry harden for 10 minutes in the dryer set to the temperature of 120 degreeC, and a coating film is formed. The thickness of the cured coating film was 5 to 7 µm.

Example 6

5.0 parts by weight of a melamine compound (trade name: cymel 303, manufactured by CYTEC) is stirred and mixed with the thermosetting acrylic polymer F to 100 parts by weight of the thermosetting acrylic polymer F to obtain a coating composition. The resulting coating composition was diluted to 10% by weight using a butyl cellosolve, and 2 parts by weight of para-toluene sulfonic acid (NACURE 2530, 25% solids, manufactured by King Industries, Inc.) as a promoter was added. It sprays and apply | coats to a carbonate plate, it is made to dry harden for 10 minutes in the dryer set to the temperature of 120 degreeC, and a coating film is formed. The thickness of the cured coating film was 5 to 7 µm.

Comparative Example 1

5.0 parts by weight of a melamine compound (trade name: cymel 303, manufactured by CYTEC) is stirred and mixed with the thermosetting acrylic polymer G based on 100 parts by weight of the thermosetting acrylic polymer G to obtain a coating composition. The resulting paint composition was diluted to 10% by weight using a butyl cellosolve, and 2 parts by weight of para-toluene sulfonic acid (NACURE 2530, 25% solids, manufactured by King Industries) was added as a promoter, and then 70 mm × 150 mm poly It sprays and apply | coats to a carbonate plate, it is made to dry harden for 10 minutes in the dryer set to the temperature of 120 degreeC, and a coating film is formed. The thickness of the cured coating film was 5 to 7 µm.

Comparative Example 2

5.0 parts by weight of an organosilane compound (epoxy silane, KBM 403, manufactured by Shin Etsu) is stirred and mixed with the thermosetting acrylic polymer A based on 100 parts by weight of the thermosetting acrylic polymer A to obtain a coating composition. The resulting paint composition was diluted to 10% by weight using a butyl cellosolve, and 2 parts by weight of para-toluene sulfonic acid (NACURE 2530, 25% solids, manufactured by King Industries) was added as a promoter, and then 70 mm × 150 mm poly Spraying is applied to a carbonate plate and dried for 20 minutes in a drier set at a temperature of 120 ° C. to form a coating film. The thickness of the cured coating film was 5 to 7 µm.

Comparative Example 3

5.0 parts by weight of an organosilane compound (aminopropyltrimethoxy silane, KBE 903, manufactured by Shin Etsu) is stirred and mixed with the thermosetting acrylic polymer A based on 100 parts by weight of the thermosetting acrylic polymer A to obtain a coating composition. The resulting paint composition was diluted to 10% by weight using a butyl cellosolve, and 2 parts by weight of para-toluene sulfonic acid (NACURE 2530, 25% solids, manufactured by King Industries) was added as a promoter, and then 70 mm × 150 mm poly Spraying is applied to a carbonate plate and dried for 20 minutes in a drier set at a temperature of 120 ° C. to form a coating film. The thickness of the cured coating film was 5 to 7 µm.

The physical properties of the cured coating films of Examples and Comparative Examples as described above were measured by the following experiments, and the results are shown in Table 1 below.

Experimental Method

(1) Appearance: Visually inspect the transparency and smoothness of the cured coating film.

(2) Adhesion: A hardened coating film is drawn by 11 rows of widths of 1 mm each, attached with a 25 mm width cellophane tape and pulled out to test.

(3) Aerobic: After the cured coating film is left at 0 ° C for 10 seconds, an aerobic test is performed.

0: No Kim Seorim

△ disappears immediately after the rainbow phenomenon

X: There is Kim Seo Rim

(4) Heat resistance: After leaving the cured coating film in an atmosphere of 120 ° C. for 240 hours, the appearance, aerobicity, and adhesion are tested by the same method as described above at room temperature. The yellowness is measured as follows.

 0 for yellowness: △ YI <3

               △: △ YI <5

                x: △ YI ＞ 5

(5) Water resistance: The cured coating film was immersed in an atmosphere of 40 ° C for 240 hours, dried at room temperature for 1 hour, and then tested for appearance, aerobicity, and adhesiveness by the same method as described above.

0 for yellowness: △ YI <3

              △: △ YI <5

               x: △ YI ＞ 5

(6) Light resistance: The cured coating film is exposed to 1,050 KJ / m ² at 90 ° C. and 50% RH for 240 hours, and then tested for appearance, aerobicity, and adhesion at room temperature in the same manner as described above. Measure together.

  0 for yellowness: △ YI <3

                △: △ YI <5

                 x: △ YI ＞ 5

(7) Acid resistance: 5 drops of 0.1 mol / L sulfuric acid is added to the cured coating film, which is left at room temperature for 24 hours, washed with water and dried at room temperature for 1 hour.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Exterior 0 0 0 0 0 0 0 0 0 Adhesion 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 Aerobic 0 0 0 0 △ △ 0 x 0  Heat resistance Exterior 0 0 0 0 0 0 0 x x Adhesion 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 Aerobic 0 0 0 0 x x 0 x x Yellowing degree △ △ △ △ △ 0 △ x x  Water resistance Exterior 0 0 0 0 0 0 x x x Adhesion 100/100 100/100 100/100 70/100 100/100 100/100 0/100 0/100 0/100 Aerobic 0 0 0 x x x x x x Yellowing degree 0 0 0 0 0 0 x x x  Light resistance Exterior 0 0 0 0 0 0 0 0 x Adhesion 100/100 100/100 100/100 100/100 100/100 100/100 0/100 0/100 0/100 Aerobic 0 0 0 0 x x x x x Yellowing degree △ △ △ x △ 0 0 0 x Acid resistance 0 0 0 x 0 0 x x x

As can be seen in Table 1, Comparative Example 1 using 2-hydroxyethyl (meth) acrylate has poor curing resistance compared to other examples, and thus has low water resistance, and Comparative Example using epoxy silane and aminopropyltrimethoxy silane as crosslinking agents. 1 and Comparative Example 2 can be confirmed that the physical properties are inferior to other embodiments as well as water resistance.

Claims (9)

Polyoxyethylene (meth) acrylate monomers; Carboxyl group-containing monomers; Hydrophilic monomers selected from dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-methylol acrylamide, N-dimethylacrylamide, and N-dimethylamino propylmethacrylamide; Hydroxyl-containing (meth) acrylate monomers; And Hydrophobic (meth) acrylate monomers; A thermosetting acrylic polymer of an antifogging paint composition, which is obtained by adding an initiator to a radical reaction in an organic solvent. The method of claim 1, To 100 parts by weight of the solid content of the thermosetting acrylic polymer The polyoxyethylene (meth) acrylate monomer; 20 to 70 parts by weight of a hydrophilic monomer comprising a carboxyl group-containing monomer; 5 to 40 parts by weight of the hydroxyl group-containing (meth) acrylate monomer; And 20 to 60 parts by weight of the hydrophobic (meth) acrylate monomer; thermosetting acrylic polymer of the antifogging paint composition comprising a. The method according to claim 1 or 2, The hydroxyl group-containing (meth) acrylate monomer is 4-hydroxybutyl (meth) acrylate; Thermosetting acrylic polymer of the antifogging coating composition, characterized in that. Polyoxyethylene (meth) acrylate; Carboxyl group-containing monomers; Hydrophilic monomers selected from dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-methylol acrylamide, N-dimethyl acrylamide, and N-dimethylamino propylmethacrylamide; Hydroxyl-containing (meth) acrylate monomers; And hydrophobic (meth) acrylate monomers; A thermosetting acrylic polymer obtained by adding an initiator to the radical reaction in an organic solvent; And At least one crosslinking agent selected from blocked isocyanate compounds, urea compounds and melamine compounds; Anti-fog coating composition comprising a. The method of claim 4, wherein The hydroxyl group-containing (meth) acrylate monomer is 4-hydroxybutyl (meth) acrylate; Antifogging paint composition, characterized in that. The method of claim 4, wherein The hydrophobic (meth) acrylate monomers include aromatic unsaturated monomers such as styrene and vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, at least one or more from the group consisting of (meth) acrylic acid alkyl esters such as tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate Antifogging paint composition, characterized in that selected. The method of claim 4, wherein The organic solvent may be an alcohol solvent such as isopropyl alcohol, isobutanol, normal butanol, diacetone alcohol or methanol, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, methyl cellosolve or ethyl cellosolve. Anti-fog coating composition, characterized in that at least one selected from the group consisting of cellosolve solvents. The method of claim 4, wherein To 100 parts by weight of the solid content of the thermosetting acrylic polymer The said polyoxyethylene (meth) acrylate; 20 to 70 parts by weight of a hydrophilic monomer comprising a carboxyl group-containing monomer; 5 to 40 parts by weight of the hydroxyl group-containing (meth) acrylate monomer; 20 to 60 parts by weight of the hydrophobic (meth) acrylate monomer; And Anticorrosive coating composition comprising a; 0.1 to 30 parts by weight of the crosslinking agent. The method of claim 8, 0.01 to 10 parts by weight of the accelerator, based on 100 parts by weight of the solid content of the thermosetting acrylic polymer.