KR20120082272A - Coating composition having improved anti-microbial activity, humidity controling performance and absorbing/decomposing performance of volatile organic compounds - Google Patents

Abstract

The present invention relates to a coating composition, and to a coating composition comprising an antimicrobial compound, a silica-titania composite compound and a binder resin according to the present invention.
The coating composition according to the present invention is excellent in antimicrobial activity, humidity control and adsorptive decomposition efficacy of volatile organic compounds, and can be usefully applied to various fields requiring the above effects such as preventing sick house syndrome.

Description

COATING COMPOSITION HAVING IMPROVED ANTI-MICROBIAL ACTIVITY, HUMIDITY CONTROLING PERFORMANCE AND ABSORBING / DECOMPOSING PERFORMANCE OF VOLATILE ORGANIC COMPOUNDS}

The present invention relates to a coating composition.

Recently, with high interest in environment and hygiene and high quality of life, interest in hygiene of residential environment, indoor air of buildings, and harmfulness by bacteria have increased.

Particularly, the sealing property of buildings is emphasized for the purpose of improving the efficiency of refrigeration and the efficient use of energy. As a result, bacteria and fungi are multiplying, resulting in allergic diseases such as bronchial diseases such as asthma and atopic dermatitis. The back is increasing. In addition, volatile organic compounds (VOCs) are generated in various interior materials installed in the interior space, and new building syndrome (NBS) is emerging as a major problem.

Accordingly, the demand for functional building materials capable of adsorbing and decomposing volatile organic compounds while having antimicrobial activity is increasing, and researches on building materials having various functionalities have been actively conducted.

In the building materials, especially paints, a method of mixing an organic antimicrobial material (for example, quaternary ammonium salt, triazine, benzimidazole, triclosan, chlorohexidine, thiazole, etc.) with a binder resin is used. However, the organic antimicrobial material as described above has a problem in that the antimicrobial efficacy is reduced when exposed to light and high temperature for a long time due to its own toxicity and heat resistance.

In order to overcome the above limitations, a method of simply mixing an inorganic ceramic antimicrobial complex with a binder resin is widely used. However, this method also has a problem in that the antimicrobial activity is lowered chemically in contact with water.

On the other hand, humidity should be managed within an appropriate range according to the season. In other words, if the humidity is out of the proper range and the room is dried, the symptoms of drying of the mucous membrane of the human body causes the dust, such as microorganisms inhaled into the respiratory organs can not be sufficiently discharged out of the human body, the defense function is reduced. On the contrary, if the humidity is excessive, condensation will occur, and a good condition for mold development will be formed, which will contaminate the inside of the building.

Accordingly, a method of adding an inorganic component such as silica in order to impart autonomous humidity control to the coating composition is used, but the effect thereof is insignificant, and the situation is urgently required to compensate for this.

Accordingly, the present invention is to provide a coating composition excellent in antibacterial activity, but excellent in hygroscopicity and adsorptive decomposition efficacy of volatile organic compounds.

The present invention

At least one compound selected from the group consisting of a compound of Formula 1, a polymer compound comprising a compound of Formula 1 as a repeating unit, and a polyol compound having a compound of Formula 1;

A silica-titania composite compound having a molar ratio of silicon (Si) and titanium (Ti) 7: 3 to 9: 1; And

Binder resin

It provides a coating composition comprising:

[Formula 1]

In Formula 1,

R ¹ is 10,11-epoxy-2,6-dihydroxy-4,8-dioxoundecyl, 2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl, 2- Hydroxy-3- (4-nonylphenoxy) propyl, 3-dodecafluoro-2-hydroxy-4-oxoundecyl, 2-hydroxy-3- (methoxy) phenoxypropyl, 2-hydroxy Oxy-3- (toluene-4-sulfonyloxy) -propyl, 1-oxo-2-propenyl, or 2-methyl-1-oxo-2-propenyl;

R ² and R ³ are each independently hydrogen or methyl;

R ⁴ and R ⁵ are each independently hydrogen or fluorine;

R ⁶ is a hydrogen group, an ethyl group, a cyclopropyl group or a 2,4-difluorophenyl group;

R ⁷ is a hydrogen group, a methyl group or an amino group;

R ⁸ , R ⁹ and R ¹⁰ are each independently carbon or nitrogen.

The coating composition according to the present invention

100 parts by weight of the binder resin;

0.1 to 20 parts by weight of at least one compound selected from the group consisting of a compound of Formula 1, a polymer compound comprising a compound of Formula 1 as a repeating unit, and a polyol compound to which the compound of Formula 1 is bonded;

0.1 to 20 parts by weight of the silica-titania composite compound

It may include.

Here, the silica-titania composite compound is more preferably a molar ratio of silicon (Si) and titanium (Ti) is 7.5: 2.5 to 8.5: 1.5.

On the other hand, the compound of Formula 1 is 1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (10,11-epoxy-2,6-dihydroxy-4,8-di Oxoundecyl) -3-methyl-1-piperazinyl] -5-methyl-4-oxo-3-quinolinecarboxylic acid, 1-ethyl-6,8-difluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -3-methyl-1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, 8-ethyl -5,8-dihydro-2- {4- [2-hydroxy-3- (4-nonylphenoxy) propyl] -1-piperazinyl} -5-oxopyrido [2,3-d] Pyrimidine-6-carboxylic acid, cis-5-amino-1-cyclopropyl-6,8-difluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4- Oxa-5-oxo-6-heptenyl) -3,5-dimethyl-1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, 1- (2,4-difluorophenyl) -6-fluoro Rho-1,4-dihydro-7- [4- (2-hydroxy-5-methyl-4-oxa-5-oxo-6-heptenyl) -3-methyl-1-piperazinyl] -4 Oxo-3-quinolinecarboxylic acid, 1-cyclopropyl-6-fluoro-7- [4- (3-degree Carfluoro-2-hydroxy-4-oxoundecyl) -3-methyl-1-piperazinyl] -1,4-dihydro-5-methyl-4-oxo-3-quinolinecarboxylic acid, 1-ethyl -6,8-difluoro-1,4-dihydro-7- {4- [2-hydroxy-3- (methoxy) phenoxypropyl} -3-methyl-1-piperazinyl} -4 Oxo-3-quinolinecarboxylic acid, 1-ethyl-6-fluoro-1,4-dihydro-7- {4- [2-hydroxy-3- (toluene-4-sulfonyloxy) -propyl]- 1-piperazinyl} -4-oxo-3-quinolinecarboxylic acid, 1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4- Oxa-5-oxo-6-heptenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, 1-ethyl-6-fluoro-1,4-dihydro-7- [4- ( 2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, 8-ethyl-5,8-dihydro- 2- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1-piperazinyl] -5-oxo-pyrido [2,3-d] Pyrimidine-6-carboxylic acid, 1-ethyl-6-fluoro-1,4-dihydro-7- [4- (1-oxo-2-propene ) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, and 1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (2-methyl-1-oxo- 2-propenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid may be one or more compounds selected from the group consisting of.

In addition, the polymer compound including the compound of Formula 1 as a repeating unit may have a weight average molecular weight of 10,000 to 1,000,000 and is represented by the following Formula 2:

[Formula 2]

In Formula 2,

R ¹ to R ¹⁰ are the same as defined in Formula 1,

n is a positive integer satisfying the molecular weight.

In addition, the polymer compound including the compound of Formula 1 as a repeating unit may have a weight average molecular weight of 10,000 to 1,000,000 and a random copolymer or a block copolymer represented by Formula 3 below:

(3)

In Formula 3,

R ¹ to R ¹⁰ are the same as defined in Formula 1,

Y is a repeating unit whose main chain is vinyl alcohol, acrylonitrile, butadiene, acrylic acid, styrene, acrylimide, methylmethacrylic acid, methacrylic acid, vinyl chloride, vinyl fluoride or vinyl acetate acrylic acid,

n and m are positive integers satisfying the molecular weight.

In addition, the polymer compound including the compound of Formula 1 as a repeating unit may have a weight average molecular weight of 10,000 to 1,000,000 and a random copolymer or a block copolymer represented by Formula 4 below:

[Formula 4]

In Chemical Formula 4,

X is represented by the following formula a,

(A)

R ¹ to R ¹⁰ are the same as defined in Formula 1,

R ¹¹ and R ¹² are each independently a hydrogen group or a methyl group,

R ¹³ is a heterocyclic ring having 2 to 10 carbon atoms, sulfonyl, silane, lactone containing ester, carbonyl, amide, amine, cycloalkyl, ether, hydroxy, carboxylic acid, nitrogen (N) or oxygen (O) And an alkyl group having 1 to 18 carbon atoms containing at least one substituent selected from the group consisting of aldehyde,

n and m are positive integers satisfying the molecular weight.

In addition, the polyol compound to which the compound of Formula 1 is bonded may have a weight average molecular weight of 10,000 to 1,000,000 and is represented by the following Formula 5, Formula 6, Formula 7 or Formula 8:

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 5 to 8,

Z is represented by the following formula b,

[Formula b]

R ¹ to R ¹⁰ are the same as defined in Chemical Formula 1.

In addition, the binder resin may be one or more selected from the group consisting of an epoxy resin, a urethane resin, an acrylic resin, an alkyd resin, a urea melamine resin, and a metal silicate resin.

The coating composition according to the present invention is excellent in antimicrobial activity, heat resistance, humidity control and adsorptive decomposition efficacy of volatile organic compounds, and can be usefully applied to various fields requiring the above effects such as preventing sick house syndrome.

Hereinafter, the coating composition according to the embodiment of the present invention will be described.

Prior to that, explicit mention this one, not throughout the present specification the "silica titania, complex compounds, as silica (SiO ₂₎ and titania Ti ^{4 +} cations, not a simple mixture of (TiO _2), form a six coordination compound It is defined as a compound in which a linkage of -Si-O-Ti- is formed by substitution insertion into a Si skeleton forming a 4-coordination compound through a complexing process.

On the other hand, the present inventors, in the course of repeating the study on the coating composition, when mixing the composite compound of the silicon (Si) and titanium (Ti) complex in a specific molar ratio with the antimicrobial compound according to the present invention to the binder resin, In addition to the antimicrobial activity, it was confirmed that the hygroscopicity and the adsorptive decomposition efficacy of the volatile organic compounds was excellent, the present invention was completed.

Such the present invention, according to one embodiment,

At least one compound selected from the group consisting of a compound of Formula 1, a polymer compound comprising a compound of Formula 1 as a repeating unit, and a polyol compound having a compound of Formula 1;

A silica-titania composite compound having a molar ratio of silicon (Si) and titanium (Ti) 7: 3 to 9: 1; And

Binder resin

It provides a coating composition comprising:

[Formula 1]

In Formula 1,

R ¹ is 10,11-epoxy-2,6-dihydroxy-4,8-dioxoundecyl, 2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl, 2- Hydroxy-3- (4-nonylphenoxy) propyl, 3-dodecafluoro-2-hydroxy-4-oxoundecyl, 2-hydroxy-3- (methoxy) phenoxypropyl, 2-hydroxy Oxy-3- (toluene-4-sulfonyloxy) -propyl, 1-oxo-2-propenyl, or 2-methyl-1-oxo-2-propenyl;

R ² and R ³ are each independently hydrogen or methyl;

R ⁴ and R ⁵ are each independently hydrogen or fluorine;

R ⁶ is a hydrogen group, an ethyl group, a cyclopropyl group or a 2,4-difluorophenyl group;

R ⁷ is a hydrogen group, a methyl group or an amino group;

R ⁸ , R ⁹ and R ¹⁰ are each independently carbon or nitrogen.

The coating composition according to the present invention can not only suppress bacteria, molds, and the like caused by contamination from the outside, but also can control the humidity in the room by controlling moisture or autonomously according to the humidity of the room. Volatile organic compounds (VOCs) and the like can be adsorbed and decomposed.

Hereinafter, each component contained in the coating composition of this invention is demonstrated.

First, the binder resin is a component that gives a coating property to the coating composition, and serves to stably attach the solid content included in the composition.

According to the present invention, the binder resin is preferably one or more selected from the group consisting of epoxy resins, urethane resins, acrylic resins, alkyd resins, urea melamine resins, and metal silicate resins.

In this case, the binder resin may be prevented from the peeling phenomenon by giving a minimum adhesive force in consideration of the relationship with the above-described components, while the composition within the content range to sufficiently express the effect by the above-described components Can be included.

On the other hand, the coating composition according to the present invention comprises the silica-titania composite compound. The silica-like titania, complex compounds are as defined above, silica (SiO ₂₎ and titania composite in the Si skeleton, not a simple mixture of (TiO _2), it is Ti ^{4 +} cations to form the 6 coordination compound to form a 4-coordination compound Substituted through the process to form a linkage (linkage) of -Si-O-Ti-.

In the silica-titania composite compound, the bonding distance is changed due to the substitution of the Ti cation, so that a negative charge excess occurs, and at this time, the Brentstead acid point that draws protons to maintain electrical neutrality is expressed. As a result, compared to a simple mixture of silica (SiO ₂ ) and titania (TiO ₂ ), volatile organic compounds and the like can be more efficiently adsorbed and decomposed.

In addition, the silica-titania composite compound may express excellent self-humidity as there are a myriad of micropores on the surface. That is, the silica-titania composite compound condenses water vapor in the pores when the surrounding humidity is relatively high, and when the humidity is relatively low, the condensed water is evaporated to maintain an appropriate humidity.

In addition, the silica-titania composite compound may adsorb harmful compounds, such as volatile organic compounds (VOCs), which are released from interior building interior materials through micropores. In addition, the silica-titania composite compound is activated by energy rays such as sunlight to decompose the adsorbed harmful compounds.

At this time, according to the present invention, the silica-titania composite compound preferably comprises a molar ratio of silicon (Si) and titanium (Ti) 7: 3 to 9: 1; More preferably, the molar ratio of silicon (Si) and titanium (Ti) is compounded at 7.5: 2.5 to 8.5: 1.5. That is, in view of the size, volume (porosity) of the micropores capable of expressing the effect, and the decomposition efficiency of harmful compounds, the silica-titania composite compound is preferably a compound of the molar ratio of silicon and titanium in the above range. .

In addition, the silica-titania composite compound is not particularly limited as long as the molar ratio of silicon and titanium is compounded in the above range. However, according to one embodiment of the present invention, after preparing TiOCl ₂ solution by partially hydrolyzing TiCl ₄ , mixing the aqueous solution of sodium silicate to the above molar ratio; Adjusting the mixed solution to pH 7 and reacting at a temperature of 70 to 100 ° C. for 1 to 4 hours; And after the reaction product is filtered and dried, it is preferably carried out by a method comprising the step of firing at 300 to 1100 ℃.

As such, the silica-titania composite compound may be included in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the binder resin.

That is, the silica-titania composite compound is preferably included 0.1 parts by weight or more based on 100 parts by weight of the binder resin in order to express the minimum effect by the silica-titania composite compound. In addition, when the silica-titania composite compound is added in an excessive amount, the paintability of the coating composition may be degraded and surface cracking may occur. Due to the aggregation of particles, humidity and VOCs adsorption decomposition efficiency may be deteriorated. It is preferably included in 20 parts by weight or less based on 100 parts by weight of the binder resin.

On the other hand, the coating composition according to the present invention is at least one compound selected from the group consisting of a compound of formula 1, a polymer compound comprising a compound of formula 1 as a repeating unit, and a polyol compound to which the compound of formula 1 is bonded Includes:

[Formula 1]

In Formula 1,

R ¹ is 10,11-epoxy-2,6-dihydroxy-4,8-dioxoundecyl, 2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl, 2- Hydroxy-3- (4-nonylphenoxy) propyl, 3-dodecafluoro-2-hydroxy-4-oxoundecyl, 2-hydroxy-3- (methoxy) phenoxypropyl, 2-hydroxy Oxy-3- (toluene-4-sulfonyloxy) -propyl, 1-oxo-2-propenyl, or 2-methyl-1-oxo-2-propenyl;

R ² and R ³ are each independently hydrogen or methyl;

R ⁴ and R ⁵ are each independently hydrogen or fluorine;

R ⁶ is a hydrogen group, an ethyl group, a cyclopropyl group or a 2,4-difluorophenyl group;

R ⁷ is a hydrogen group, a methyl group or an amino group;

R ⁸ , R ⁹ and R ¹⁰ are each independently carbon or nitrogen.

The compound is a component capable of imparting antimicrobial activity to the composition, even when mixed with a binder resin, it can not only maintain a continuous antimicrobial activity. Excellent heat resistance, does not elute to the outside, there is an advantage that does not affect the physical properties of the composition.

In particular, by using the compound in combination with the above-described silica-titania composite compound, the compound based on the compound of Formula 1 is bonded to the surface of the silica-titania composite compound.

Here, the above-described silica-titania composite compound may exhibit an antibacterial effect on its own, and in order for the silica-titania composite compound to exhibit antibacterial activity, the presence of light such as UV is essential.

In this regard, the coating composition according to the present invention, as the compound based on the compound of Formula 1 is bonded to the surface of the silica-titania composite compound, can exhibit antimicrobial activity regardless of the presence of light such as UV Synergy can be obtained. For example, in an environment where light is present, antimicrobial activity and humidity control can be smoothly expressed by the silica-titania composite compound and the compound based on the compound of Formula 1. In addition, even in the absence of light, airborne bacteria are adsorbed to the pores of the silica-titania composite compound by Van der Waals attraction, and the antibacterial activity is maintained by the compound based on the compound of Formula 1. It becomes possible.

In addition, in the past, the floating bacteria in the air had to be in direct contact with the coating composition to obtain the antimicrobial activity, whereas the coating composition according to the present invention is based on the silica-titania composite compound and the compound of Formula 1 By including the compound at the same time can be adsorbed suspended bacteria autonomously, it can exhibit a better antimicrobial activity.

The components included in the composition of the present invention are compounds based on the compound of Formula 1; Preferably, at least one compound selected from the group consisting of a compound of Formula 1, a polymer compound including a compound of Formula 1 as a repeating unit, and a polyol compound to which the compound of Formula 1 is bonded. Herein, the contents of the compounds include all the contents described in Korean Patent Registration No. 0536551.

Among the compounds, the compound of Formula 1 may be prepared by the method of Scheme 1 below:

[Reaction Scheme 1]

In the above Reaction Scheme 1,

R ¹ to R ¹⁰ are the same as defined in Chemical Formula 1, and A is a halogen group.

That is, the compound of Formula 1 may be prepared by reacting Compound II with Compound III- (a), as in Scheme 1, wherein the equivalent ratio of Compound III- (a) to Compound II is 1: 0.8 to It is preferable that it is 1: 1.5, and it is preferable that reaction temperature is -40 degreeC-130 degreeC.

In addition, a scavenger may be further added to remove the acid (eg hydrogen chloride) generated during the reaction. Examples of the scavenger include tetramethylguanidine, diethylamine, pyrrolidine, trimethylamine, triethylamine, pyridine or piperidine, calcium hydroxide, sodium hydroxide, calcium carbonate, potassium carbonate, and the like. It is possible to use more than one species, and it is preferable to use a skavenger in a ratio of 1: 1 to 1: 3 equivalents relative to compound II.

In addition, the compound of Formula 1 may be prepared by the method of Scheme 2:

Scheme 2

In the above Reaction Scheme 2,

R ¹ to R ¹⁰ are the same as defined in Formula 1,

R ^a is sulfonyl, halogen, nitro, hydroxy, thionyl (-SH), amine (primary, secondary, tertiary), amide, imine, carbamate, oxime, carbonyl, carboxy, epoxy, acryl , C ₁ -C ₂₀ saturated or unsaturated hydrocarbons comprising at least one functional group selected from the group consisting of esters, phenyl, vinyl and nitrile.

That is, the compound of Formula 1 may also be prepared through the epoxy ring-opening reaction of Compound II and Compound III- (b) as in Scheme 1, wherein the equivalent ratio of Compound III- (b) to Compound II is 1 It is preferable that it is: 0.8-1: 4, and it is preferable that reaction temperature is 35 degreeC-150 degreeC.

Both Scheme 1 and Scheme 2 can be carried out in the presence of an organic solvent. The organic solvent may be N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, xylene, tetrahydrofuran, benzene, toluene, acetonitrile, dichloromethane, ethyl acetate, butyl acetate, 1, One or more selected from the group consisting of 4-dioxane and chloroform can be used.

In addition, in Scheme 1 and Scheme 2, compound II is 1-cyclopropyl-6-fluoro-1,4-dihydro-5-methyl-7- (3-methyl-1-piperazinyl) -4 Oxo-3-quinolinecarboxylic acid, 1-ethyl-6,8-difluoro-1,4-dihydro-7- (3-methyl-1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid, 8-ethyl-5,8-dihydro-2- (1-piperazinyl) -5-oxo-pyrido [2,3-d] pyrimidine-6-carboxylic acid, (cis) -5-amino-1 -Cyclopropyl-6,8-difluoro-1,4-dihydro-7- (3,5-dimethyl-1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid, 1- (2,4 -Difluorophenyl) -6-fluoro-1,4-dihydro-7- (3-methyl-1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid, 1-ethyl-6-fluoro -1,4-dihydro-7- (1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid, 1-cyclopropyl-6-fluoro-1,4-dihydro-7- (1-pipe Razinyl) -4-oxo-3-quinolinecarboxylic acid or salts thereof.

In addition, the compound III- (a) may be a halogen compound including acryloyl chloride, methacryloyl chloride, vinyl chloride or vinyl benzyl chloride.

In addition, the compound III- (b) is glycerol diglycidyl ether, 2-methyl acrylic acid oxyranyl methyl ester, glycidyl nonyl phenyl ether, glycidyl dodecafluoroheptyl ether, glycidyl-4-meth Oxyphenyl ether, 2-methyl acrylic acid oxyranyl ester, 2,3-epoxypropyl methacrylate, 4-chlorophenyl glycidyl ether, 1-chloro-2,3-epoxypropane, glycidyl methacrylate, Glycidol, Aric acid oxyranyl methyl ester, 2-aryloxy methyl oxirane, 2-pent-4-enyl oxirane, 2-vinyl oxirane, hexadecaflorononyloxymethyl oxirane, dodecafluoroheptyl Oxymethyl oxirane, octafluoropentyloxymethyl oxirane, 2- (4-nonylphenoxymethyl) oxirane, 4-nitrobenzoic acid oxyranylmethyl ester, nitrobenzene solphonic acid oxyranyl methyl ester, toluene 4-sulfonic acid Oxiranylmethyl ester, trityloxymethyloxirane, 1, 3- ratio Oxiranyl -dihydroxy-20 2-ol may be a draw of three Rolf epoxy acrylate triglycidyl ester, epichlorohydrin or glycidoxypropyltrimethoxysilane.

Such a compound of formula 1 (compound I) is preferably 1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (10,11-epoxy-2,6-di Hydroxy-4,8-dioxoundecyl) -3-methyl-1-piperazinyl] -5-methyl-4-oxo-3-quinolinecarboxylic acid, 1-ethyl-6,8-difluoro-1 , 4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -3-methyl-1-piperazinyl] -4-oxo- 3-Quinolinecarboxylic acid, 8-ethyl-5,8-dihydro-2- {4- [2-hydroxy-3- (4-nonylphenoxy) propyl] -1-piperazinyl} -5-oxopyri Fig. [2,3-d] pyrimidine-6-carboxylic acid, cis-5-amino-1-cyclopropyl-6,8-difluoro-1,4-dihydro-7- [4- (2-hydrate Roxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -3,5-dimethyl-1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, 1- (2,4-di Fluorophenyl) -6-fluoro-1,4-dihydro-7- [4- (2-hydroxy-5-methyl-4-oxa-5-oxo-6-heptenyl) -3-methyl- 1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, 1-cycle Propyl-6-fluoro-7- [4- (3-dodecafluoro-2-hydroxy-4-oxoundecyl) -3-methyl-1-piperazinyl] -1,4-dihydro- 5-Methyl-4-oxo-3-quinolinecarboxylic acid, 1-ethyl-6,8-difluoro-1,4-dihydro-7- {4- [2-hydroxy-3- (methoxy) phenoxy Cipropyl} -3-methyl-1-piperazinyl} -4-oxo-3-quinolinecarboxylic acid, 1-ethyl-6-fluoro-1,4-dihydro-7- {4- [2-hydroxy -3- (toluene-4-sulfonyloxy) -propyl] -1-piperazinyl} -4-oxo-3-quinolinecarboxylic acid, 1-cyclopropyl-6-fluoro-1,4-dihydro-7 -[4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, 1-ethyl-6- Floro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1-piperazinyl] -4-oxo- 3-Quinolinecarboxylic acid, 8-ethyl-5,8-dihydro-2- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1-piperazinyl ] -5-oxo-pyrido [2,3-d] pyrimidine-6-carboxylic acid, 1-ethyl-6-fluoro-1,4- Hydro-7- [4- (1-oxo-2-propenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, and 1-cyclopropyl-6-fluoro-1,4-di Hydro-7- [4- (2-methyl-1-oxo-2-propenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid.

Meanwhile, the polymer compound including the compound of Formula 1 as a repeating unit may be a homopolymer or a copolymer having the compound of Formula 1 as a repeating unit. In this case, the polymer compound has a weight average molecular weight of 10,000 to 1,000,000 in consideration of reactivity and physical properties.

Here, the homopolymer of the compound of Formula 1 may be represented by the following Formula 2:

[Formula 2]

In Formula 2, R ¹ to R ¹⁰ are the same as defined in Formula 1, and n is a positive integer satisfying the molecular weight.

In addition, the copolymer comprising the compound of Formula 1 as a repeating unit may be represented by the following formula (3):

(3)

In Formula 3,

R ¹ to R ¹⁰ are the same as defined in Formula 1,

Y is a repeating unit whose main chain is vinyl alcohol, acrylonitrile, butadiene, acrylic acid, styrene, acrylimide, methylmethacrylic acid, methacrylic acid, vinyl chloride, vinyl fluoride or vinyl acetate acrylic acid,

n and m are positive integers satisfying the molecular weight.

The copolymer of Chemical Formula 3 may be prepared by radical copolymerization of the compound of Chemical Formula 1 with the Y monomer in an equivalent ratio of 1: 1 to 1: 100, and is prepared under conventional initiator and reaction conditions in the art to which the present invention pertains. Since it may be, the manufacturing method is not particularly limited.

In addition, the copolymer may be a random copolymer or a block copolymer, it is preferable that the weight average molecular weight is 10,000 to 1,000,000 in consideration of reactivity and physical properties.

In addition, the copolymer including the compound of Formula 1 as a repeating unit may be an acrylic copolymer represented by Formula 4 below:

[Formula 4]

In Chemical Formula 4,

X is represented by the following formula a,

(A)

R ¹ to R ¹⁰ are the same as defined in Formula 1,

R ¹¹ and R ¹² are each independently a hydrogen group or a methyl group,

R ¹³ is a heterocyclic ring having 2 to 10 carbon atoms, sulfonyl, silane, lactone containing ester, carbonyl, amide, amine, cycloalkyl, ether, hydroxy, carboxylic acid, nitrogen (N) or oxygen (O) And an alkyl group having 1 to 18 carbon atoms containing at least one substituent selected from the group consisting of aldehyde,

n and m are positive integers satisfying the molecular weight.

In this case, the compound of Formula 4 may be prepared by the method of Scheme 3:

Scheme 3

In Scheme 3, X, R ¹¹ , R ¹² and R ¹³ are the same as defined in Chemical Formula 4.

In Scheme 3, the compound of Formula A may be obtained by ring-opening reaction of Compound II and the epoxide compound in Scheme 2, and the epoxide compound may include glycidyl methacrylate and the like. .

In addition, in Scheme 3, the compound of Formula B may be an acrylic monomer whose main chain is a hydrocarbon chain derived from acrylic acid or methacrylic acid; Preferably, it may be a monomer having acrylic acid, alkyl acrylate, methacrylic acid or methacrylic acid alkyl ester.

As for the said acrylic acid alkyl ester and methacrylic acid alkyl ester, it is more preferable that C1-C18 alkyl is included. Examples of such alkyl acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, cyclohexyl acrylate, t-butylcyclohexyl acrylate, stearyl acrylate and lauryl acrylate.

In addition, the acrylic monomer may include a reactive functional group, and examples of the functional group include an amide group, a hydroxyl group, an epoxy group, a silanol group, or an aldehyde group. More specifically, the acrylic monomer further comprising a reactive functional group may be acrylamide, methacrylamide, N-methylacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, N-methylmethacrylamide, N Butoxymethylmethacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, γ-trimethoxysilane Methacrylate, γ-triethoxysilane methacrylate, acrolein, caprolactone modified hydroxyacrylate or caprolactone modified hydroxymethacrylate.

In addition, in Scheme 3, a known initiator may be used, and azo-bis-iso-butylnitrile (AIBN), azobisdimethylbellonitrile, benzoyl peroxide, t-butylhydroperoxide, t-butylperoxy One or more compounds selected from the group consisting of octanoate, t-butylperoxybenzoate, cumin hydroperoxide and cumyl peroxide can be used. In this case, the amount of the initiator may be 0.05 to 10 parts by weight, preferably 0.3 to 5 parts by weight based on 100 parts by weight of the total compound. In addition, the reaction temperature may be 50 ° C to 130 ° C, but is not limited thereto.

On the other hand, the polyol compound to which the compound of Formula 1 is bonded as the compound of Formula 1 is combined with a linker, and then reacted with the polyol; In this case, the polyol compound preferably has a weight average molecular weight of 10,000 to 1,000,000 in consideration of reactivity and physical properties; It may be represented by the following formula (5):

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 5 to 8,

Z is represented by the following formula b,

[Formula b]

R ¹ to R ¹⁰ are the same as defined in Chemical Formula 1.

In this case, as the linker bonded to the compound of Formula 1, one or more selected from the group consisting of compounds containing isocyanate (-N = C = O), haloacyl halides and acid anhydrides may be used. Preferably, the linker is an isocyanate, selected from the group consisting of toluene diisocyanate (TDI), dodecyl diisocyanate (DDI), hexamethylene diisocyanate (HDI) and trihexamethylene isocyanurate triisocyanate (HMTI). It may be one or more compounds.

In addition, the polyol may be used as conventional in the art to which the present invention belongs; Preferably, acrylic polyols, alkyd polyols or mixtures thereof can be used. In addition, according to one embodiment of the present invention, the polyol is more preferably OH value of 15 to 80 mol%, glass transition temperature of 70 to 130 ℃, and non-volatile content of 40 to 60% by weight.

In addition, the polyol compound may be prepared in the presence of a solvent, preferably N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, xylene, tetrahydrofuran, benzene, toluene, aceto It may be one or more selected from the group consisting of nitrile, dichloromethane, ethyl acetate, butyl acetate, 1,4-dioxane and chloroform.

 As such, at least one compound selected from the group consisting of a compound of Formula 1, a polymer compound including the compound of Formula 1 as a repeating unit, and a polyol compound to which the compound of Formula 1 is bonded is 100 wt% of the binder resin. 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on the parts.

That is, the compound is preferably included 0.1 parts by weight or more based on 100 parts by weight of the binder resin in order to express the minimum effect by the compound. In addition, when the compound is added in an excessive amount, the physical properties of the composition may be deteriorated, and thus the physical properties of the coating film may be inferior, such that the coating film is hardened more than necessary. In order to prevent this, 20 parts by weight based on 100 parts by weight of the binder resin may be used. It is preferable to be contained in parts or less.

On the other hand, the coating composition according to the present invention may further include an additive commonly used in the art, in addition to the above-described components.

For example, the coating composition may further include additives such as thickeners, stabilizers, and dispersants, depending on the use of the composition, the place of application, and the like. At this time, the content of the additive can be determined within various ranges that do not lower the physical properties of the composition according to the present invention, it is not particularly limited.

Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

Manufacturing example  1-1

Preparation of Silica-Titania Composites

: An aqueous sodium silicate solution was added to a TiOCl ₂ solution (strongly acidic) obtained by partial hydrolysis by adding TiCl ₄ to distilled water. At this time, the molar ratio of Si and Ti was added so that it was 8: 2. The mixture was adjusted to pH 7 using NH ₄ OH and HCl, and then reacted at 80 to 95 ° C. for 2 hours. The reaction product was filtered and dried, and then fired in a heating furnace at 900 ° C. to prepare a silica-titania composite.

Manufacturing example  1-2

Preparation of Silica-Titania Composites

: An aqueous sodium silicate solution was added to a TiOCl ₂ solution (strongly acidic) obtained by partial hydrolysis by adding TiCl ₄ to distilled water. At this time, the molar ratio of Si and Ti was added so that it was 7: 3. The mixture was adjusted to pH 7 using NH ₄ OH and HCl, and then reacted at 80 to 95 ° C. for 2 hours. The reaction product was filtered and dried, and then fired in a heating furnace at 900 ° C. to prepare a silica-titania composite.

Manufacturing example  1-3

Preparation of Silica-Titania Composites

: An aqueous sodium silicate solution was added to a TiOCl ₂ solution (strongly acidic) obtained by partial hydrolysis by adding TiCl ₄ to distilled water. At this time, the molar ratio of Si and Ti was added so that it was 9: 1. The mixture was adjusted to pH 7 using NH ₄ OH and HCl, and then reacted at 80 to 95 ° C. for 2 hours. The reaction product was filtered and dried, and then fired in a heating furnace at 900 ° C. to prepare a silica-titania composite.

Manufacturing example  1-4

Preparation of Silica-Titania Composites

: An aqueous sodium silicate solution was added to a TiOCl ₂ solution (strongly acidic) obtained by partial hydrolysis by adding TiCl ₄ to distilled water. At this time, the molar ratio of Si and Ti was added to be 6.5: 3.5. The mixture was adjusted to pH 7 using NH ₄ OH and HCl, and then reacted at 80 to 95 ° C. for 2 hours. The reaction product was filtered and dried, and then fired in a heating furnace at 900 ° C. to prepare a silica-titania composite.

Manufacturing example  1-5

Preparation of Silica-Titania Composites

: An aqueous sodium silicate solution was added to a TiOCl ₂ solution (strongly acidic) obtained by partial hydrolysis by adding TiCl ₄ to distilled water. At this time, the molar ratio of Si and Ti was added so that it was 9.5: 0.5. The mixture was adjusted to pH 7 using NH ₄ OH and HCl, and then reacted at 80 to 95 ° C. for 2 hours. The reaction product was filtered and dried, and then fired in a heating furnace at 900 ° C. to prepare a silica-titania composite.

Manufacturing example  2-1

{1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (10,11-epoxy-2,6-dihydroxy-4,8-dioxoundecyl) -3- Methyl-1-piperazinyl] -5-methyl-4-oxo-3-quinolinecarboxylic acid}

: A 50 ml round three-necked flask was equipped with a thermometer and a stirring facility, 15.0 ml of N, N-dimethylformamide was added thereto, and then 1-cyclopropyl-6-fluoro-1,4-dihydro-5 at room temperature. 30.4 mg of -methyl-7- (3-methyl-1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid was added and stirred slowly at room temperature for 10 minutes. 17.2 mg of glycerol diglycidyl ether was added thereto and stirred. The reaction was washed with 1.2 ml of N, N-dimethylformamide and the temperature was adjusted to 60 ° C., followed by reaction for 5 hours. It was then cooled and stirred at 20 ° C for 10 minutes. The reaction was obtained in crystallized state in the water layer and dried to give 35.0 mg of 1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (10,11-epoxy-2,6-di Hydroxy-δ4,8-dioxoundesyl) -3-methyl-1-piperazinyl] -5-methyl-4-oxo-3-quinolinecarboxylic acid was obtained.

¹ H-NMR (DMSO-d ₆ ) δ1.05 (3H, d), 1.20-1.44 (4H, m), 2.40 (3H, s), 2.50-3.00 (7H, m), 3.10-4.00 (16H, m), 7.39 (1 H, d), 8.81 (1 H, s).

Manufacturing example  2-2

(1-ethyl-6,8-difluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -3 -Methyl-1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid}

: 1-ethyl-6,8-difluoro-1,4-dihydro-7- (3-methyl-1-piperazinyl) in 10.0 ml of 2,6-dimethylpiperazine after installing a 50 ml round flask 39.4 mg of 4-oxo-3-quinolinecarboxylic acid were mixed and stirred slowly at room temperature for 10 minutes. 22.0 mg of glycidyl methacrylate was added thereto, the mixture was stirred at room temperature, and the reaction was washed with 2.0 ml of 2,6-dimethylpiperazine. After reacting for 8 hours at 40 ℃ and cooled to room temperature again and stirred for 8 hours. Obtained crystallized reactant in water layer and dried to give 25 mg of 1-ethyl-6,8-difluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa -5-oxo-6-heptenyl) -3-methyl-1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid was obtained.

¹ H-NMR (DMSO-d ₆ ) δ 1.10 (3H, d), 1.58 (3H, t), 1.93 (3H, s), 2.52-3.00 (5H, m), 3.23-3.41 (4H, m) , 3.90-4.38 (5H, m), 5.58 (1H, d), 6.15 (1H, d), 7.72 (1H, s), 8.62 (1H, s)

Manufacturing example  2-3

{8-ethyl-5,8-dihydro-2- {4- [2-hydroxy-3- (4-nonylphenoxy) propyl] -1-piperazinyl} -5-oxopyrido [2, 3-d] pyrimidine-6-carboxylic acid}

: 8 ml of 8-ethyl-5,8-dihydro-5-oxo-2- (1-piperazinyl) pyrido®2,3-dpyrimidine- in 12.0 ml of dimethyl sulfoxide after installing a 50 ml round flask. 38.0 mg of 6-carboxylic acid was mixed and stirred slowly at room temperature for 10 minutes. 18.0 mg of glycidylnonylphenyl ether was added thereto, and the mixture was stirred at room temperature and washed with 12 ml of dimethyl sulfoxide. After standing at 50 ° C. for 11 hours, the mixture was stirred at 20 ° C. for 10 minutes. The reaction product was crystallized from methylene chloride, an aqueous layer, isopropyl alcohol, filtered and dried, and then 37.2 mg of 8-ethyl-5,8-dihydro-2- {4- [2-hydroxy-3- (4) was obtained. -Nonylphenoxy) propyl] -1-piperazinyl} -5-oxopyrido [2,3-d] pyrimidine-6-carboxylic acid was obtained.

¹ H-NMR (DMSO-d ₆ ) δ0.88 (3H, t), 1.10 to 1.70 (17H, m), 2.45 to 3.05 (10H, m), 3.35 to 3.55 (4H, m), 3.92 to 4.12 ( 3H, m), 6.76, 7.05 (4H, ABq), 8.58 (1H, s), 8.87 (1H, s).

Manufacturing example  2-4

{Cis-5-amino-1-cyclopropyl-6,8-difluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo- 6-heptenyl) -3,5-dimethyl-1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid}

: 50 ml round flask was installed, and 5.0 ml of N, N-dimethylacetamide was added to cis-5-amino-1-cyclopropyl-6,8-difluoro-1,4-dihydro-7- (3,5 43.7 mg of -dimethyl-1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid were mixed and stirred slowly at room temperature for 10 minutes. 17.5 mg of glycidyl methacrylate was added thereto, stirred at room temperature, and washed with 3.1 ml of N, N-dimethylacetamide. It left for 6 hours at 75 degreeC, and stirred for 10 minutes at 20 degreeC. The reaction was then crystallized from methylene chloride, an aqueous layer, isopropyl alcohol, filtered and dried to give 29.3 mg of cis-5-amino-1-cyclopropyl-6,8-difluoro-1,4-dihydro-7 -[4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -3,5-dimethyl-1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid Obtained.

¹ H-NMR (DMSO-d ₆ ) δ1.07 (6H, d), 1.20-1.45 (4H, m), 1.96 (3H, s), 2.50-3.00 (4H, m), 3.20-3.60 (5H, m), 4.00-4.40 (3H, m), 5.67 (1H, s), 6.20 (1H, s), 8.60 (1H, s).

Manufacturing example  2-5

{1- (2,4-Difluorophenyl) -6-fluoro-1,4-dihydro-7- [4- (2-hydroxy-5-methyl-4-oxa-5-oxo-6 -Heptenyl) -3-methyl-1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid}

: A 50 ml round flask was placed in 10.0 ml of N, N-dimethylformamide and 1- (2,4-difluorophenyl) -6-fluoro-1,4-dihydro-7- (3-methyl- 49.2 mg of 1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid was mixed and stirred at room temperature for 10 minutes. 14.3 mg of glycidyl methacrylate was added thereto, stirred at room temperature, and washed with 5.0 ml of N, N-dimethylformamide. After standing at 80 ° C. for 9 hours, the mixture was stirred at 20 ° C. for 10 minutes. The reaction was filtered through a methylene chloride, an aqueous layer, isopropyl alcohol, crystalline form, dried, and then 41.0 mg of 1- (2,4-difluorophenyl) -6-fluoro-1,4-dihydro-7- [ 4- (2-hydroxy-5-methyl-4-oxa-5-oxo-6-heptenyl) -3-methyl-1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid was obtained.

¹ H-NMR (DMSO-d ₆ ) δ1.06 (3H, d), 1.95 (3H, s), 2.50-3.00 (5H, m), 3.20-3.40 (4H, m), 4.00-4.40 (3H, m), 5.58 (1H, s), 6.15 (1H, s), 6.45-6.85 (4H, m), 7.89 (1H, d), 8.62 (1H, s).

Manufacturing example  2-6

{1-cyclopropyl-6-fluoro-7- [4- (3-dodecafluoro-2-hydroxy-4-oxoundecyl) -3-methyl-1-piperazinyl] -1,4 -Dihydro-5-methyl-4-oxo-3-quinolinecarboxylic acid}

: 1 ml cyclopropyl-6-fluoro-5-methyl-1,4-dihydro-7- (3-methyl-1-piperazine) in 12.2 ml of N, N-dimethylformamide after installing a 50 ml round flask. 39.4 mg of 1) -4-oxo-3-quinolinecarboxylic acid was added thereto and stirred slowly at room temperature for 10 minutes. To this was administered 37.3 mg of glycidyl dodecafluoroheptyl ether, stirred at room temperature, and washed with 12.2 ml of N, N-dimethylformamide. After standing at 70 ° C. for 6 hours, the mixture was stirred at 20 ° C. for 10 minutes. The reaction was crystallized from ether, aqueous layer, isopropyl alcohol, filtered, washed with hexane and dried to give 43.1 mg of 1-cyclopropyl-6-fluoro-7- [4- (3-dodecafluoro-2 -Hydroxy-4-oxoundecyl) -3-methyl-1-piperazinyl] -1,4-dihydro-5-methyl-4-oxo-3-quinolinecarboxylic acid was obtained.

¹ H-NMR (DMSO-d ₆ ) δ1.06 (3H, d), 1.20-1.45 (4H, m), 2.40 (3H, s), 2.50-3.00 (5H, m), 3.20-4.10 (10H, m), 5.80-6.30 (1 H, m) 7.40 (1 H, d), 8.82 (1 H, s).

Manufacturing example  2-7

{1-ethyl-6,8-difluoro-1,4-dihydro-7- {4- [2-hydroxy-3- (methoxy) phenoxypropyl} -3-methyl-1-piperazine Preparation of -4--4-oxo-3-quinolinecarboxylic acid}

: 1-ethyl-6,8-difluoro-1,4-dihydro-7- (3-methyl-1-piperazinyl) in 13.0 ml of N, N-dimethylformamide after installing a 50 ml round flask. 30.4 mg of 4-oxo-3-quinolinecarboxylic acid were mixed and stirred slowly at room temperature for 10 minutes. 19.7 mg of glycidyl4-methoxyphenylether was added thereto, stirred at room temperature, and washed with 10.2 ml of N, N-dimethylformamide. After standing at 80 ° C. for 7 hours, the mixture was stirred at 15 ° C. for 5 minutes. After filtration with dioxane, an aqueous layer and ethyl alcohol, crystallization, washing with hexane, drying, and 17.3 mg of 1-ethyl-6,8-difluoro-1,4-dihydro-7- {4- [2 -Hydroxy-3- (methoxy) phenoxypropyl} -3-methyl-1-piperazinyl} -4-oxo-3-quinolinecarboxylic acid was obtained.

¹ H-NMR (DMSO-d ₆ ) δ1.06 (3H, d), 1.58 (3H, t), 2.50-3.00 (5H, m), 3.20-3.40 (4H, m), 3.70 (3H, s) , 3.90-4.40 (5H, m), 6.60-6.80 (4H, m), 7.68 (1H, s), 8.60 (1H, s).

Manufacturing example  2-8

{1-ethyl-6-fluoro-1,4-dihydro-7- {4- [2-hydroxy-3- (toluene-4-sulfonyloxy) -propyl] -1-piperazinyl}- 4-oxo-3-quinolinecarboxylic acid}

: 100 ml round flask was installed, and 50 ml of 1, ethyl-6-fluoro-1,4-dihydro-7- (1-piperazinyl) -4-oxo-3- in 50 ml of N, N-dimethylformamide. 39.4 mg of quinolinecarboxylic acid were mixed and slowly stirred at room temperature for 20 minutes. 14.4 mg of glycidyl tosylate was added thereto, stirred at room temperature, and washed with 30.0 ml of N, N-dimethylformamide. After standing at 80 ° C. for 5 hours, the mixture was stirred at 25 ° C. for 10 minutes. The reaction was crystallized by passing through column chromatography (20 gm silica, 10% ethyl acetate / hexane), and then filtered and dried to obtain 1-ethyl-6-fluoro-1,4-dihydro-7- {4-. 11.2 mg of [2-hydroxy-3- (toluene-4-sulfonyloxy) -propyl] -1-piperazinyl} -4-oxo-3-quinolinecarboxylic acid was obtained.

¹ H-NMR (DMSO-d ₆ ) δ 1.60 (3H, t), 2.40 (3H, s), 2.50-2.85 (6H, m), 3.20-3.40 (4H, m), 3.90-4.40 (5H, m), 6.82 (1 H, d), 7.40-7.85 (5 H, m), 8.60 (1 H, s).

Manufacturing example  2-9

(1-Cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1-pipe Razinyl] -4-oxo-3-quinolinecarboxylic acid}

: 100 ml round flask was placed in 50 ml of N, N-dimethylacetamide and 1-cyclopropyl-6-fluoro-1,4-dihydro-7- (1-piperazinyl) -4-oxo-3 39.4 mg of quinolinecarboxylic acid were mixed and stirred slowly at room temperature. 17.5 mg of glycidyl methacrylate was added thereto, stirred at room temperature, and washed with 1.2 ml of N, N-dimethylacetamide. Thereafter, the mixture was left at 80 ° C. for 19 hours, stirred at 25 ° C. for 30 minutes, crystallized from methylene chloride, an aqueous layer and isopropyl alcohol, and filtered. It was dried to yield 1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1 53.3 mg of piperazinyl] -4-oxo-3-quinolinecarboxylic acid were obtained.

¹ H-NMR (CDCl ₃ ) δ1.20-1.41 (4H, m), 2.05 (3H, s), 2.51 (2H, d), 2.59 (2H, t), 2.85 (2H, d), 3.25-3.60 (5H, m), 4.05 (2H, m), 4.30 (1H, m), 5.58 (1H, s), 6.15 (1H, s), 7.28 (1H, d), 8.05 (1H, d), 8.80 ( 1H, s)

Manufacturing example  2-10

{1-ethyl-6-fluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1-piperazine Production] -4-oxo-3-quinolinecarboxylic acid}

: 100 ml round flask was placed in 50 ml of N, N-dimethylacetamide and then 1-ethyl-6-fluoro-1,4-dihydro-7- (1-piperazinyl) -4-oxo-3- 39.4 mg of quinolinecarboxylic acid was added thereto and stirred slowly at room temperature for 10 minutes. 17.5 mg of glycidyl methacrylate was added thereto, stirred at room temperature, and washed with 11.2 ml of N, N-dimethylacetamide. After standing at 80 ℃ for 15 hours and then stirred at 25 ℃ for 1 hour. The reaction was passed through column chromatography (20 gm silica, 10% ethyl acetate / hexane), crystallized from methylene chloride, an aqueous layer, and isopropyl alcohol, and filtered. The filtrate was dried to give 1-ethyl-6-fluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl)- 36 mg of 1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid were obtained.

¹ H-NMR (CDCl ₃ ) δ 1.48 (3H, t), 1.93 (3H, s), 2.51 (2H, d), 2.59-2.82 (4H, m), 3.10-3.40 (4H, t), 3.45 (2H, m), 3.90-4.28 (4H, m), 5.58 (1H, d), 6.05 (1H, d), 6.75 (1H, S), 7.62 (1H, d), 8.58 (1H, s)

Manufacturing example  2-11

{8-ethyl-5,8-dihydro-2- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1-piperazinyl] -5- Preparation of oxo-pyrido [2,3-d] pyrimidine-6-carboxylic acid}

: 100 ml round flask was placed in 50 ml of N, N-dimethylacetamide and 8-ethyl-5,8-dihydro-5-oxo-2- (1-piperazinyl) -pyrido [2,3- d] 38.2 mg of pyrimidine-6-carboxylic acid was mixed and stirred slowly at room temperature for 50 minutes. 15.0 mg of glycidyl methacrylate was added thereto, stirred at room temperature, and washed with 10 ml of N, N-dimethylacetamide. After standing at 70 ℃ for 15 hours and then stirred at 20 ℃ for 1 hour. The reaction was passed through column chromatography (20 gm silica, 10% ethyl acetate / hexane), crystallized from methylene chloride, an aqueous layer and isopropyl alcohol, filtered and dried, and then 8-ethyl-5,8-dihydro- 2- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1-piperazinyl] -5-oxo-pyrido [2,3-d] 27 mg of pyrimidine-6-carboxylic acid was obtained.

¹ H-NMR (DMSO-d ₆ ) δ 1.58 (3H, s), 1.95 (3H, s), 2.50 to 2.85 (6H, m), 3.20 to 3.50 (4H, m), 3.90 to 4.40 (5H, m), 5.60 (1 H, s), 6.14 (1 H, s), 8.62 (1 H, s), 8.87 (1 H, s).

Manufacturing example  2-12

Preparation of {1-ethyl-6-fluoro-1,4-dihydro-7- [4- (1-oxo-2-propenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid}

: 500 mg (1.567 mmol) of 1-ethyl-6-fluoro-1,4-dihydro-7- (1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid under nitrogen conditions after installing a 50 ml round flask 30 ml of chloroform was added thereto, and 0.436 ml (3.134 mmol) of triethylamine was added thereto, followed by stirring at room temperature for 10 minutes. 0.127 ml (1.567 mmol) of acryloyl chloride was slowly added dropwise while maintaining the temperature inside the vessel at -10 ° C. The mixture was reacted at -10 DEG C for 3 hours under nitrogen, distilled water was added, followed by extraction with dichloromethane. This was concentrated and chromatographed (20gm silica, 7% MeOH / CH ₂ Cl ₂ ) to give 1-ethyl-6-fluoro-1,4-dihydro-7- [4- (1-oxo-2- Propenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid was obtained.

¹ H-NMR (CDCl ₃ ) δ 1.48 (3H, t), 3.20 (4H, t), 3.42 (4H, t), 4.32 (2H, q), 5.55 (1H, t), 6.12 (1H, t ), 6.62 (1H, t), 7.02 (1H, s), 7.75 (1H, s), 8.85 (1H, s)

Manufacturing example  2-13

{1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (2-methyl-1-oxo-2-propenyl) -1-piperazinyl] -4-oxo-3 -Quinolinecarboxylic acid}

: 700 mg (2.024) of 1-cyclopropyl-6-fluoro-1,4-dihydro-7- (1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid under a stream of nitrogen in a 50 ml round three-necked flask mmol) was added, and 30 ml of chloroform and 0.491 ml (3 mmol) of pyridine were added and stirred at room temperature for 10 minutes. 0.197 ml (2.024 mmol) of methacryloylchloride was slowly added dropwise while maintaining the temperature inside the vessel at −10 ° C. After reaction for 3 hours, distilled water was added, extracted with dichloromethane, concentrated, and then subjected to chromatography (20gm silica, 7% MeOH / CH ₂ Cl ₂ ) to 1-cyclopropyl-6-fluoro-1,4-dihydro. -7- [4- (2-methyl-1-oxo-2-propenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid was obtained.

¹ H-NMR (CDCl ₃ ) δ 1.20 (2H, m), 1.41 (2H, m), 2.00 (3H, s), 3.30 (4H, t), 3.35 (1H, m), 3.50 (1H, m ), 3.95 (2H, d), 5.20 (2H, d) 7.42 (1H, d), 8.00 (1H, d), 8.90 (1H, s)

Manufacturing example  2-14

Preparation of {1-ethyl-6-fluoro-1,4-dihydro-7- [4- (4-vinylbenzyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid}

: 400 mg (1.252 mmol) of 1-ethyl-6-fluoro-1,4-dihydro-7- (1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid under nitrogen stream after installing a 50 ml round flask ) Was mixed with 30 ml of chloroform, and 0.349 ml (2.505 mmol) of triethylamine were added and stirred at room temperature for 10 minutes. 0.177 ml (1.252 mmol) of vinylbenzylchloride was slowly added dropwise while maintaining the temperature inside the vessel at -10 ° C. The mixture was reacted for 3 hours while maintaining the temperature at −10 ° C. under a nitrogen stream, and distilled water was added thereto, followed by extraction with dichloromethane. The extract was concentrated and chromatographed (20gm silica, 5% MeOH / CH ₂ Cl ₂ ) to give 1-ethyl-6-fluoro-1,4-dihydro-7- [4- (4-vinylbenzyl) 501 mg (91.9%) of 1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid were obtained.

NMR (CDCl ₃ ) δ 1.48 (3H, t), 3.20 (4H, t), 3.42 (4H, t), 4.55 (2H, q), 5.18 (2H, s), 5.61 (2H, d), 6.63 (1H, m) 7.01 (2H, d), 7.10 (1H, d), 7.18 (2H, d), 7.81 (1H, d), 8.87 (1H, s)

Manufacturing example  2-15

Preparation of Polymer of Formula 2 (Homopolymer of Compound 1)

: 1-ethyl-6-fluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-hep after installing a 50 ml round flask Tenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid 750 mg was dissolved in 30 ml of N, N-dimethylacetamide and stirred at room temperature for 10 minutes. 20 mg of AIBN was added thereto, reacted at 70 ° C. for 4 hours, and then cooled to room temperature. The reaction solution was slowly added to 100 ml of cold water prepared in advance, stirred at room temperature for 30 minutes, and then filtered to obtain crystals. It was dried to obtain a polymer of formula (2).

Manufacturing example  2-16

Preparation of Polymer of Formula 3 (Copolymer Using Compound of Formula 1 as Monomer)

: 1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6- after installing a 50 ml round flask Heptenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid 0.5 g (1.251 mmol) was dissolved in 30 ml of N, N-dimethylformamide and stirred at room temperature for 10 minutes. 10 g (138.77 mmol) of acrylic acid was added thereto, stirred at room temperature for 10 minutes, and 0.05 g of benzoyl peroxide was slowly added dropwise. Then, the mixture was heated up to 80 ° C. for 4 hours, and cooled to room temperature. The reaction solution was slowly added while stirring 100 ml of previously prepared cold water, and the solid was filtered and dried to obtain a compound.

Manufacturing example  2-17 to 2-20

Preparation of Polyol Compound Incorporating Compound of Formula 1

: 1-ethyl-6-fluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6- after installing a 50 ml round three-necked flask 0.840 mg of heptenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid was added to 30 ml of benzene, dissolved at 50 ° C, and then 0.635 mg of 2,4-toluenediisocyanate and dibutyltindiolate ( DBTDL) 0.01 mg was added and stirred at 60 ° C. for 2 hours. 0.213 mg of isopropyl alcohol was added to the reaction, followed by stirring at 60 ° C. for 5 hours to complete the reaction. After the reaction temperature was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure, and chromatographed (20 mg silica, 10% ethyl acetate / hexane) was carried out to obtain an antimicrobial compound.

Then, the compound was mixed with the polyol and reacted to prepare a polyol compound. At this time, the polyol is a commercial article BURNOCK (acrylic polyol, manufacturer: Aekyung Chemical, OH value: 17.5 mol%, Tg: 126 ℃, non-volatile content: 50% by weight), ALKYLATE (acrylic polyol, manufacturer: Aekyung Chemical, OH Value: 25 mol%, Tg: 79 ° C., non-volatile content: 50 weight%), 045-093 (alkyd polyol, manufacturer: Aekyung Chemical, OH value: 80 mol%, Tg: 97 ° C., non-volatile content: 55 weight%) And acrylic (acrylic polyol, manufacturer: Kukdo Chemical, OH value: 23 mol%, Tg: 89 ° C., nonvolatile content: 50 wt%).

Example  One

5 parts by weight of the silica-titania composite compound according to Preparation Example 1-1, and 1 weight of Compound according to Preparation Example 2-1 based on 100 parts by weight of the metal silicate-based binder resin (manufacturer: Youngil Chemical, product name: ECO-100) The parts were mixed. To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Example  2

To 100 parts by weight of an acrylic binder resin (manufacturer: World Industries, Product Name: Platop), 5 parts by weight of the silica-titania composite compound according to Preparation Example 1-1 and 1 part by weight of the compound according to Preparation Example 2-2 were mixed. . To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Example  3

To 100 parts by weight of epoxy binder resin (manufacturer: swallow paint, product name: Epomax), 5 parts by weight of the silica-titania composite compound according to Production Example 1-1, and 1 part by weight of the compound according to Production Example 2-3 were mixed. It was. To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Example  4

To 100 parts by weight of the urethane-based binder resin (manufacturer: roe deer paint, product name: Greenness), 5 parts by weight of the silica-titania composite compound according to Preparation Example 1-1 and 1 part by weight of the compound according to Preparation Example 2-4 were mixed. . To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Example  5

To 100 parts by weight of an alkyd binder resin (manufacturer: roe deer paint, product name: enamel), 5 parts by weight of the silica-titania composite compound according to Preparation Example 1-1, and 1 part by weight of the compound according to Preparation Example 2-5 were mixed. . To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Example  6

To 100 parts by weight of urea melamine-based binder resin (manufacturer: Aekyung Chemical, product name: Au-171-65), 5 parts by weight of the silica-titania composite compound according to Preparation Example 1-1, and the compound according to Preparation Example 2-6 1 part by weight was mixed. To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Example  7

To 100 parts by weight of an acrylic binder resin (manufacturer: World Industries, Product Name: Platope), 5 parts by weight of the silica-titania composite compound according to Preparation Example 1-2, and 1 part by weight of the compound according to Preparation Example 2-1 were mixed. . To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Example  8

To 100 parts by weight of an acrylic binder resin (manufacturer: World Industries, Product Name: Platop), 5 parts by weight of the silica-titania composite compound according to Production Examples 1-3 and 1 part by weight of the compound according to Production Example 2-1 were mixed. . To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Comparative example  One

To 100 parts by weight of an acrylic binder resin (manufacturer: World Industries, Product Name: Platop), 5 parts by weight of the silica-titania composite compound according to Preparation Example 1-4 and 1 part by weight of the compound according to Preparation Example 2-1 were mixed. . To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Comparative example  2

To 100 parts by weight of an acrylic binder resin (manufacturer: World Industries, Product Name: Platope), 5 parts by weight of the silica-titania composite compound according to Preparation Example 1-5, and 1 part by weight of the compound according to Preparation Example 2-1 were mixed. . To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Comparative example  3

8 parts by weight of silica (SiO ₂ ), 2 parts by weight of titania (TiO ₂ ) and 1 part by weight of the compound according to Preparation Example 2-1 were mixed with 100 parts by weight of the acrylic binder resin (manufacturer: World Industry, Product Name: Platope). It was. To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Comparative example  4

1 part by weight of the compound according to Production Example 2-1 was mixed with 100 parts by weight of the acrylic binder resin (manufacturer: World Industry, Product Name: Platope). To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Comparative example  5

10 parts by weight of a silver nano compound (manufactured by E & B Korea, product name: NSSE) was mixed with 100 parts by weight of an acrylic binder resin (manufacturer: World Industries, product name: platop). To the 100 parts by weight of the binder resin, 5 parts by weight of an additive such as a thickener, a stabilizer, and a dispersant were added thereto, followed by stirring for 1 hour to prepare a coating composition.

Experimental Example  One

Antifungal and antibacterial tests were carried out using ASTM G21 method (Inhibition Zone Test) using the respective coating compositions according to Examples 1, 2, 3, 4, 6 and Comparative Example 5. It carried out, and the results are shown in Table 1 below.

sample A. Niger
Yeast mold
(KCTC6942) P. citrinum
Blue mold
(KCTC6549) E. coli
Escherichia coli
(KCTC1682) S. typhimurium
Salmonella
(KCTC1925) S. aureus
Staphylococcus aureus
(KCTC1916) Example 1 14 ± 1 13 ± 1 11 ± 1 12 ± 1 13 ± 1 Example 2 13 ± 1 11 ± 1 10 ± 1 12 ± 1 13 ± 1 Example 3 13 ± 1 12 ± 1 10 ± 1 12 ± 1 12 ± 1 Example 4 12 ± 1 12 ± 1 11 ± 1 11 ± 1 12 ± 1 Example 6 12 ± 1 13 ± 1 11 ± 1 11 ± 1 11 ± 1 Comparative Example 5 - - - - -

Experimental Example  2

Using the respective paint compositions according to Examples 1 to 6 and Comparative Example 5, the antifungal test and the antibacterial test were carried out by ASTM G22 method (Shake Flask method), and the results are shown in Table 2 below. Indicated.

Strain sample Immediately after inoculation 24 hours later % Reduction E. coli Example 1 6.32 Х 10 ⁵ 2.63 Х 10 ³ 99.99 Example 2 1.5 Х 10 ⁵ 1.46 Х 10 ³ 99.99 Example 3 4.71 Х 10 ⁵ 1.1 Х 10 ³ 99.99 Example 4 5.14Х 10 ⁵ 3.14 Х 10 ³ 99.99 Example 5 1.0 Х 10 ⁵ 4.12 Х 10 ³ 99.99 Example 6 2.8 Х 10 ⁵ 3.94 Х 10 ³ 99.99 Comparative Example 5 4.81 Х 10 ⁵ 2.79 Х 10 ⁷ - S. aureus Example 1 7.47 Х 10 ⁵ 1.7 Х 10 ³ 99.99 Example 2 3.78 Х 10 ⁵ 3.07 Х 10 ⁴ 99.99 Example 3 6.87 Х 10 ⁵ 2.56 Х 10 ³ 99.99 Example 4 5.36 Х 10 ⁵ 3.34 Х 10 ³ 99.99 Example 5 4.31 Х 10 ⁵ 2.19 Х 10 ³ 99.99 Example 6 1.84 Х 10 ⁵ 1.35 Х 10 ³ 99.99 Comparative Example 5 5.34 Х 10 ⁵ 3.40 Х 10 ⁷ -

Strain sample Immediately after inoculation 24 hours later % Reduction B. subtilis Example 1 9.07 Х 10 ⁵ 7.62Х 10 ³ 99.99 Example 2 2.5 Х 10 ⁵ 6.45 Х 10 ³ 99.99 Example 3 4.79 Х 10 ⁵ 7.13 Х 10 ³ 99.99 Example 4 7.17 Х 10 ⁵ 5.91 Х 10 ³ 99.99 Example 5 8.74 Х 10 ⁵ 3.94 Х 10 ³ 99.99 Example 6 9.16 Х 10 ⁵ 5.87 Х 10 ³ 99.99 Comparative Example 5 1.61 Х 10 ⁵ 7.65 Х 10 ⁷ - M. luteus Example 1 6.14 Х 10 ⁵ 6.80 Х 10 ³ 99.99 Example 2 7.03 Х 10 ⁵ 5.71 Х 10 ³ 99.99 Example 3 6.52 Х 10 ⁵ 6.44 Х 10 ³ 99.99 Example 4 5.94 Х 10 ⁵ 5.19 Х 10 ³ 99.99 Example 5 7.19 Х 10 ⁵ 4.72 Х 10 ³ 99.99 Example 6 6.31 Х 10 ⁵ 5.93 Х 10 ³ 99.99 Comparative Example 5 3.25 Х 10 ⁵ 6.81 Х 10 ⁷ -

Experimental Example 3

The autonomous humidity characteristics of each coating composition according to Examples 1, 7, 8 and Comparative Examples 1, 2 and 4 were evaluated.

At this time, the test piece for measuring the physical properties of the coating on the glass plate of 10cmХ10cm using a bar coater (bar coater) to 150 ㎛, and then prepared by a method of curing by leaving at room temperature for 12 hours, the specimen 40 The weight was measured after standing for 24 hours in a thermo-hygrostat that maintains% humidity.

Thereafter, the specimen was placed in a constant temperature and humidity chamber maintained at 80% humidity for 24 hours, and then the moisture absorption was measured. Then, the specimen was kept in a constant temperature and humidity chamber maintained at 40% humidity for 24 hours and then measured for moisture resistance.

Here, the moisture absorption amount refers to the moisture absorption amount based on the start specimen (that is, moisture absorption amount = [(moisture absorption specimen-starting specimen) / unit area), and the moisture absorption amount means moisture absorption amount based on the moisture absorption specimen. (I.e. moisture proof amount = [(moisture-absorbent specimen-moisture-proof specimen) / unit area).

Sample Moisture absorption Moisture proof Example 1 250 g / m ² 215.4 g / m ² Example 7 200 g / m ² 174 g / m ² Example 8 290 g / m ² 258 g / m ² Comparative Example 1 120g / m ² 86 g / m ² Comparative Example 2 300 g / m ² 263 g / m ² Comparative Example 4 70 g / m ² 40 g / m ²

As can be seen in Table 4, the coating compositions of Examples 1, 7, and 8, and Comparative Examples 1 and 2, including the silica-titania composite, did not add the silica-titania composite. Compared with the moisture absorption and moisture proof effect was excellent. In addition, in the case of Comparative Example 1 in which the molar ratio of Si: Ti in the silica-titania composite was 6.5: 3.5, it was found that the moisture absorption and moisture damping effect was not good. It can be seen that it must be above a certain level. In addition, in the case of Comparative Example 2 in which the molar ratio of Si: Ti in the silica-titania composite was 9.5: 0.5, the Si content was high, so that the moisture absorption and moistureproof effect was excellent. Adsorption and decomposition efficiency of volatile organic compounds was found to be inferior.

Experimental Example  4

Adsorption and decomposition characteristics of volatile organic compounds were evaluated for the respective coating compositions according to Examples 1, 7, 8 and Comparative Examples 1, 2, and 4. At this time, the samples were prepared by coating the prepared paint on a glass plate of 10cmХ10cm using a bar coater (bar coater) at 150 μm and then curing them by standing at room temperature for 12 hours, and preparing 500 ppm of formaldehyde and a specimen in a sealed chamber. After the reduction of formaldehyde was measured, the results are shown in Table 5 below.

sample Formaldehyde Reduction (%) Example 1 99.5 Example 7 99.9 Example 8 90.5 Comparative Example 1 99.9 Comparative Example 2 58.7 Comparative Example 4 43.1

As can be seen in Table 5, the coating compositions of Examples 1, 7, and 8 containing silica-titania composites were compared with those of Comparative Example 4 without the addition of silica-titania composites of volatile organic compounds. Adsorption and decomposition effects were excellent. In addition, in Comparative Example 2 in which the molar ratio of Si: Ti in the silica-titania composite was 9.5: 0.5, the moisture absorption and moisture damping effect was excellent (see Table 4), but the adsorption and decomposition effect of the volatile organic compound had a silica-titania composite. It is shown that it is not so good that there is no difference with Comparative Example 4 not added, it can be seen that the Ti content in the silica-titania composite must be a certain level or more in order to obtain the adsorption and decomposition effect of the excellent volatile organic compounds. In addition, in Comparative Example 1 in which the molar ratio of Si: Ti in the silica-titania composite was 6.5: 3.5, the Ti content was high, so that the adsorption and decomposition effects of volatile organic compounds were excellent, but as shown in Experimental Example 3, The low content was found to be ineffective in absorbing moisture and moisture.

According to the results of Table 4 and Table 5, the molar ratio between Si and Ti in the silica-titania composite is appropriate in order to simultaneously achieve the excellent self-regulating ability and the adsorption and decomposition efficiency of the volatile organic compound by using the silica-titania composite. And the molar ratio between them is shown in Example 1 (Si: Ti = 8: 2), Example 7 (Si: Ti = 7: 3), and Example 8 (Si: Ti = 9) of the present invention. In the case of the range (1), it can be seen that it is possible to simultaneously achieve excellent self-humidifying ability and excellent volatile organic compound adsorption and decomposition efficiency.

Experimental Example  5

For each coating composition according to Example 1 comprising a silica-titania composite compound and Comparative Example 3 comprising a simple mixture of silica and titania, self-humidifying properties and adsorption and decomposition properties of volatile organic compounds were evaluated.

At this time, the test piece for measuring the physical properties of the coating on the glass plate of 10cmХ10cm using a bar coater (bar coater) to 150 ㎛, and then prepared by a method of curing by leaving at room temperature for 12 hours, the specimen 40 The weight was measured after standing for 24 hours in a thermo-hygrostat that maintains% humidity.

Thereafter, the specimen was placed in a constant temperature and humidity chamber maintained at 80% humidity for 24 hours, and then the moisture absorption was measured. Then, the specimen was kept in a constant temperature and humidity chamber maintained at 40% humidity for 24 hours and then measured for moisture resistance. Here, the moisture absorption amount refers to the moisture absorption amount based on the start specimen (that is, moisture absorption amount = [(moisture absorption specimen-starting specimen) / unit area), and the moisture absorption amount means moisture absorption amount based on the moisture absorption specimen. (I.e. moisture proof amount = [(moisture-absorbent specimen-moisture-proof specimen) / unit area).

In addition, after the formaldehyde 500 ppm and the specimen in a closed chamber was measured the reduction rate of formaldehyde, the results are shown in Table 6 below.

Sample Moisture absorption Moisture proof Formaldehyde Reduction (%) Example 1 250 g / m ² 215.4 g / m ² 99.5 Comparative Example 3 200 g / m ² 150 g / m ² 92

As shown in Table 1 to Table 6, Comparative Example 1 and Comparative Example 2 in which the molar ratio of silicon and titanium is out of the preferred range even though the silica-titania composite compound is included in the comparative examples; Comparative Example 3 comprising a simple mixture of silica and titania; Comparative Example 4, which does not contain a silica-titania composite compound, was found to be inferior in antimicrobial activity, humidity control, and adsorptive decomposition efficiency of volatile organic compounds.

On the contrary, the coating composition according to Examples 1 to 8 includes a composite compound in which silicon (Si) and titanium (Ti) are combined at a specific molar ratio together with the antimicrobial compound according to the present invention, compared to Comparative Examples 1 to 5 In addition, the antimicrobial activity was excellent, the humidity was excellent, and the adsorption and decomposition efficiency of volatile organic compounds was also excellent.

Claims (9)

At least one compound selected from the group consisting of a compound of Formula 1, a polymer compound comprising a compound of Formula 1 as a repeating unit, and a polyol compound having a compound of Formula 1;
A silica-titania composite compound having a molar ratio of silicon (Si) and titanium (Ti) 7: 3 to 9: 1; And
Binder resin
Coating composition comprising:
[Formula 1]

In Chemical Formula 1,
R ¹ is 10,11-epoxy-2,6-dihydroxy-4,8-dioxoundecyl, 2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl, 2- Hydroxy-3- (4-nonylphenoxy) propyl, 3-dodecafluoro-2-hydroxy-4-oxoundecyl, 2-hydroxy-3- (methoxy) phenoxypropyl, 2-hydroxy Oxy-3- (toluene-4-sulfonyloxy) -propyl, 1-oxo-2-propenyl, or 2-methyl-1-oxo-2-propenyl;
R ² and R ³ are each independently hydrogen or methyl;
R ⁴ and R ⁵ are each independently hydrogen or fluorine;
R ⁶ is a hydrogen group, an ethyl group, a cyclopropyl group or a 2,4-difluorophenyl group;
R ⁷ is a hydrogen group, a methyl group or an amino group;
R ⁸ , R ⁹ and R ¹⁰ are each independently carbon or nitrogen. The method of claim 1,
100 parts by weight of the binder resin;
0.1 to 20 parts by weight of at least one compound selected from the group consisting of a compound of Formula 1, a polymer compound comprising a compound of Formula 1 as a repeating unit, and a polyol compound to which the compound of Formula 1 is bonded; And
0.1 to 20 parts by weight of the silica-titania composite compound
Coating composition comprising a. The method of claim 1,
The silica-titania composite compound has a molar ratio of silicon (Si) and titanium (Ti) of 7.5: 2.5 to 8.5: 1.5. The method of claim 1,
The compound of Formula 1 is 1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (10,11-epoxy-2,6-dihydroxy-4,8-dioxone Sil) -3-methyl-1-piperazinyl] -5-methyl-4-oxo-3-quinolinecarboxylic acid, 1-ethyl-6,8-difluoro-1,4-dihydro-7- [4 -(2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -3-methyl-1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, 8-ethyl-5 , 8-dihydro-2- {4- [2-hydroxy-3- (4-nonylphenoxy) propyl] -1-piperazinyl} -5-oxopyrido [2,3-d] pyrimidine -6-carboxylic acid, cis-5-amino-1-cyclopropyl-6,8-difluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa- 5-oxo-6-heptenyl) -3,5-dimethyl-1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, 1- (2,4-difluorophenyl) -6-fluoro- 1,4-dihydro-7- [4- (2-hydroxy-5-methyl-4-oxa-5-oxo-6-heptenyl) -3-methyl-1-piperazinyl] -4-oxo 3-quinolinecarboxylic acid, 1-cyclopropyl-6-fluoro-7- [4- (3-dodecapel Luoro-2-hydroxy-4-oxoundecyl) -3-methyl-1-piperazinyl] -1,4-dihydro-5-methyl-4-oxo-3-quinolinecarboxylic acid, 1-ethyl- 6,8-difluoro-1,4-dihydro-7- {4- [2-hydroxy-3- (methoxy) phenoxypropyl} -3-methyl-1-piperazinyl} -4- Oxo-3-quinolinecarboxylic acid, 1-ethyl-6-fluoro-1,4-dihydro-7- {4- [2-hydroxy-3- (toluene-4-sulfonyloxy) -propyl] -1 -Piperazinyl} -4-oxo-3-quinolinecarboxylic acid, 1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (2-hydroxy-6-methyl-4-oxa -5-oxo-6-heptenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, 1-ethyl-6-fluoro-1,4-dihydro-7- [4- (2 -Hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid, 8-ethyl-5,8-dihydro-2 -[4- (2-hydroxy-6-methyl-4-oxa-5-oxo-6-heptenyl) -1-piperazinyl] -5-oxo-pyrido [2,3-d] pyri Midine-6-carboxylic acid, 1-ethyl-6-fluoro-1,4-dihydro-7- [4- (1-oxo-2-propenyl) -1-pi Ferrazinyl] -4-oxo-3-quinolinecarboxylic acid, and 1-cyclopropyl-6-fluoro-1,4-dihydro-7- [4- (2-methyl-1-oxo-2-propenyl) -1-piperazinyl] -4-oxo-3-quinolinecarboxylic acid is a coating composition which is at least one compound selected from the group consisting of. The method of claim 1,
A high molecular weight compound comprising the compound of Formula 1 as a repeating unit has a weight average molecular weight of 10,000 to 1,000,000 and is represented by the following Chemical Formula 2:
(2)

In Formula 2,
R ¹ to R ¹⁰ are the same as defined in Formula 1,
n is a positive integer satisfying the molecular weight. The method of claim 1,
A polymer composition comprising the compound of Formula 1 as a repeating unit has a weight average molecular weight of 10,000 to 1,000,000 and is a random copolymer or a block copolymer represented by Formula 3 below:
(3)

In Chemical Formula 3,
R ¹ to R ¹⁰ are the same as defined in Formula 1,
Y is a repeating unit whose main chain is vinyl alcohol, acrylonitrile, butadiene, acrylic acid, styrene, acrylimide, methylmethacrylic acid, methacrylic acid, vinyl chloride, vinyl fluoride or vinyl acetate acrylic acid,
n and m are positive integers satisfying the molecular weight. The method of claim 1,
A polymer composition comprising the compound of Formula 1 as a repeating unit has a weight average molecular weight of 10,000 to 1,000,000 and is a random copolymer or a block copolymer represented by Formula 4 below:
[Chemical Formula 4]

In Chemical Formula 4,
X is represented by the following formula a,
(A)

R ¹ to R ¹⁰ are the same as defined in Formula 1,
R ¹¹ and R ¹² are each independently a hydrogen group or a methyl group,
R ¹³ is a heterocyclic ring having 2 to 10 carbon atoms, sulfonyl, silane, lactone containing ester, carbonyl, amide, amine, cycloalkyl, ether, hydroxy, carboxylic acid, nitrogen (N) or oxygen (O) And an alkyl group having 1 to 18 carbon atoms containing at least one substituent selected from the group consisting of aldehyde,
n and m are positive integers satisfying the molecular weight. The method of claim 1,
The polyol compound to which the compound of Formula 1 is bonded has a weight average molecular weight of 10,000 to 1,000,000 and is represented by the following Chemical Formula 5, Chemical Formula 6, Chemical Formula 7 or Chemical Formula 8:
[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In Chemical Formulas 5 to 8,
Z is represented by the following formula b,
[Formula b]

R ¹ to R ¹⁰ are the same as defined in Chemical Formula 1. The method of claim 1,
The binder resin is at least one coating composition selected from the group consisting of epoxy resins, urethane resins, acrylic resins, alkyd resins, urea melamine resins, and metal silicate resins.