KR102002832B1 - Anti-soiling coating composition - Google Patents

Abstract

상기 화학식 1 중,
R₁ 내지 R₈은 서로 독립적으로, X, 탄소수 1 내지 3의 알킬기 할로겐화된 탄소수 1 내지 3의 알킬기 및 탄소수 6 내지 20의 아릴기 중에서 선택되되, R₁ 내지 R₈ 중 적어도 1개는 반드시 X로 선택되고;
X는 아미노기, 에폭시기, 카비놀기, 디올기, 카르복실기, 페놀기 및 실란올기 중에서 선택되고;
n1은 0 내지 100의 정수이고, n1이 2이상의 정수인 경우 복수 개의

로 표시되는 모이어티는 서로 동일하거나 상이하다.Water-dispersible polyurethane resins; A siloxane-based resin represented by the following formula (1); Inorganic particles; And at least one selected from organic particles, wax-based extinction agents, and silica-based extinction agents.
[Chemical Formula 1]

In Formula 1,
R ₁ to R ₈ are independently from each other, X, doedoe selected from an aryl group having a carbon number of 1 to 3 alkyl group and having 6 to 20 carbon atoms of the halogenated C 1 -C 3, R ₁ to R at least one of ₈ necessarily X Lt; / RTI >
X is selected from an amino group, an epoxy group, a carbinol group, a diol group, a carboxyl group, a phenol group and a silanol group;
n1 is an integer of 0 to 100, and when n1 is an integer of 2 or more,

Are the same or different from each other.

Description

ANTI-SOILING COATING COMPOSITION [0001]

≪ / RTI >

Conventionally, dark-colored automotive interior materials such as natural leather and synthetic leather have been mainstream. However, due to the increase in the proportion of light-colored automotive interior materials due to the upgrading strategy, aesthetics, and design effects, The interior materials for interior use must have excellent antifouling properties and are required to exhibit properties that can be easily removed from the contaminants attached thereto.

In addition, since the automobile interior material is in direct contact with the user, the automobile interior material must have a certain level of flexibility, and the importance of a similar soft touch such as natural leather is also increasing.

One embodiment of the present invention includes a siloxane resin to ensure stain resistance and at least one selected from inorganic particle external organic particles, wax-based extinction agent, and silica-based extinction agent, To provide an antifouling coating composition.

In one embodiment of the present invention, the water dispersible polyurethane resin; A siloxane-based resin represented by the following formula (1); Inorganic particles; And at least one selected from organic particles, wax-based extinction agents, and silica-based extinction agents.

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₈ independently of each other are selected from among X, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 halogenated carbon atoms, and an aryl group having 6 to 20 carbon atoms, provided that at least one of R ₁ to R ₈ is Must be selected as X;

X is selected from an amino group, an epoxy group, a carbinol group, a diol group, a carboxyl group, a phenol group and a silanol group;

로 표시되는 모이어티는 서로 동일하거나 상이하다.n1 is an integer of 0 to 100, and when n1 is an integer of 2 or more,

Are the same or different from each other.

The siloxane-based resin may contain one or two X's.

R ₄ or R ₅ may be X, and n 1 may be an integer from 1 to 100.

_{Two of} R ₁ to R ₃ and R ₆ to R ₈ may be X.

_One selected from R ₁ to R ₃ ; And one of R ₆ to R ₈ may be X. [

The siloxane-based resin may be represented by the following formula (2) or (3).

(2)

(3)

Of the above formulas (2) and (3)

R ₂₁ to R ₂₆ and R ₃₁ to R ₄₁ independently of each other are selected from an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 20 carbon atoms;

X ₂₁ , X ₂₂ and X ₃₁ are independently selected from an amino group, an epoxy group, a carbinol group, a diol group, a carboxyl group, a phenol group and a silanol group;

n ₂₁ is an integer from 0 to 100;

n ₃₁ is an integer from 1 to 100;

m ₃₁ and m ₃₂ are each independently an integer of 0 to 100, and the sum of n ₃₁ , m ₃₁ and m ₃₂ is an integer of 1 to 100.

About 1 to about 30 parts by weight of a siloxane-based resin, about 1 to about 10 parts by weight of an inorganic particle, based on 100 parts by weight of the aqueous dispersion type polyurethane resin; And from about 5 to about 30 parts by weight of at least one selected from organic particles, wax-based extinction agents, and silica-based extinction agents.

The inorganic particles may include silica particles having a particle diameter of from about 0.5 [mu] m to about 15 [mu] m.

The organic particles may include at least one selected from the group consisting of an acrylic resin, a polyurethane resin, a polystyrene resin, and a combination thereof, and may have a particle diameter of about 0.5 탆 to about 10 탆.

The wax-based light extinguishing agent may include at least one member selected from the group consisting of polyethylene, polypropylene, polytetrafluoroethylene, and combinations thereof, and may have a particle diameter of from about 0.5 [mu] m to about 100 [mu] m.

The silica-based light extinguishing agent may be at least one selected from the group consisting of silica rubber powder, silicone resin powder, silicon mixed powder, and combinations thereof.

The silicone rubber powder has a structure of a cross-linked form of linear dimethylpolysiloxane, and may have a particle diameter of about 1 [mu] m to about 30 [mu] m.

The silicone resin powder may have a structure in which siloxane bonds are crosslinked in a three-dimensional network structure, and the particle diameter may be about 0.2 um to about 8 um.

The silicon mixed powder may include organic particles having silicone resin powder protrusions formed on its surface.

The silicon mixed powder may be formed by coating the organic particles with a silicone resin powder, and the particle diameter may be about 0.5 [mu] m to about 20 [mu] m.

The above contamination-resistant coating composition can achieve a matte effect and a smooth texture effect while securing stain resistance.

The automotive interior material has improved chemical resistance, stain resistance and the like, so that it can be utilized as a bright color.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

In one embodiment of the present invention, the water dispersible polyurethane resin; A siloxane-based resin represented by the following formula (1); Inorganic particles; And at least one selected from organic particles, wax-based extinction agents, and silica-based extinction agents.

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₈ are independently from each other, X, doedoe selected from an aryl group having a carbon number of 1 to 3 alkyl group and having 6 to 20 carbon atoms of the halogenated C 1 -C 3, R ₁ to R at least one of ₈ necessarily X Lt; / RTI >

X is selected from an amino group, an epoxy group, a carbinol group, a diol group, a carboxyl group, a phenol group and a silanol group;

로 표시되는 모이어티는 서로 동일하거나 상이하다.
n1 is an integer of 0 to 100, and when n1 is an integer of 2 or more,

Are the same or different from each other.

Generally, since a fluorine-based additive is used in order to ensure antifouling property and stain resistance of the coating composition, the surface free energy of the automobile interior material is increased by using the fluorine-based additive, thereby preventing adhesion of the initial pollutant due to the water- there was. However, the effect is limited to the prevention of adhesion of contaminants on a static level, and there is a limitation in the dynamic dimension which is continuously used, such as automobile interior materials.

A cleaner such as a composition comprising an oil component such as a sorbitan fatty acid ester, a paraffinic hydrocarbon, and coconut oil may be used in order to remove contaminants in an automobile interior material contaminated already, for example, synthetic leather, It is more advantageous not to adhere.

Although it is common to use a fluorine-based additive in the water-repellent coating layer in order to ensure the stain resistance, the fluorine-based additive can be removed by wiping the pollutant with the cleaner in the contaminated state, but it is difficult to fundamentally prevent the adhesion of the pollutant .

Accordingly, the anti-fouling coating composition has excellent characteristics of preventing contamination for a long time from the beginning by including the siloxane-based resin represented by the formula (1), and can easily remove contaminants.

The siloxane-based resin may be represented by the formula (1) containing at least one X as a functional group in the siloxane bond, and the X-based siloxane resin may be a reaction type. On the other hand, when the siloxane-based resin does not contain X, it may be non-reactive.

The above contamination-resistant coating composition comprises a water-dispersible polyurethane resin as a binder. In the combination of the water-dispersible polyurethane resin and a curing agent to be added, the siloxane-based resin of Formula 1 is suitable for the reaction.

X may be selected from an amino group, an epoxy group, a carbinol group, a diol group, a carboxyl group, a phenol group and a silanol group, and the use of an amino group, an epoxy group, a carbinol group, a diol group or a carboxyl group is preferable in terms of reactivity, And it is possible to exhibit the function of preventing the adhesion of the initial pollutant due to water repellency, and wear resistance can be easily realized.

When X is a carbinol group, a diol group or a carboxyl group, it is possible to stably exhibit storage stability and compatibility in an aqueous dispersion type polyurethane resin, and to react with a carbodiimide compound, an isocyanate compound or an oxazoline compound as a curing agent, Can be continuously present in the coating layer formed of the inorganic fine particles, so that not only the initial antifouling property but also the excellent durability can be exhibited.

Specifically, the siloxane-based resin may contain one or two X's. The siloxane-based resin is blocked or graft-copolymerized with the water-dispersible polyurethane resin and the curing agent by containing at least one X. Thus, even when n1 is 0, R ₁ to R ₃ , and R ₆ to R ₈ may be one or two Xs.

R ₄ or R ₅ may be X, and n 1 may be an integer from 1 to 100. R ₄ or R ₅ in the case of X may be referred to as a side chain type reactive siloxane resin in which the siloxane resin has X in its side chain and the side chain type reactive siloxane resin may have slipperiness and abrasion resistance. In addition, due to the graft-copolymerized molecular structure, water repellency is manifested and contamination adherence can be minimized.

However, the coating may have insufficient durability in a seasonal aspect in which the temperature and humidity are changed in the long-term antifouling property, and it is difficult to satisfy flexibility as a coating composition used in an automotive interior material.

In order to overcome the disadvantages of the side chain type reactive siloxane-based resin, the siloxane-based resin may have X at both ends, and two of R ₁ to R ₃ and R ₆ to R ₈ may be X . The siloxane-based resin having X at both ends may be referred to as a horseshoe-shaped reactive siloxane-based resin. The horseshoe-shaped reactive siloxane-based resin may have flexibility, slipperiness, heat resistance, cold resistance, Can be prevented.

Specifically, one selected from R ₁ to R ₃ ; And one of R ₆ to R ₈ may be X. [ Since the molecular length of the horseshoe-type reactive siloxane-based resin varies according to n1, the elongation of the anti-fouling coating composition can be controlled according to the molecular length. Elongation is a value related to the flexibility of the coating composition, and it is possible to control the flexibility of the coating composition according to n1. For example, when n1 is 20 or more, the contamination-resistant coating composition can realize improved flexibility and stain resistance.

The siloxane-based resin may be represented by the following general formula (2) or (3).

(2)

(3)

Of the above formulas (2) and (3)

R ₂₁ to R ₂₆ and R ₃₁ to R ₄₁ independently of each other are selected from an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 20 carbon atoms;

X ₂₁ , X ₂₂ and X ₃₁ are independently selected from an amino group, an epoxy group, a carbinol group, a diol group, a carboxyl group, a phenol group and a silanol group;

n ₂₁ is an integer from 0 to 100;

n ₃₁ is an integer from 1 to 100;

m ₃₁ and m ₃₂ are each independently an integer of 0 to 100, and the sum of n ₃₁ , m ₃₁ and m ₃₂ is an integer of 1 to 100.

The siloxane-based resin represented by the above-mentioned formula (2) can impart softness to the automobile interior material such as synthetic leather, for example, by imparting flexibility with a horseshoe-shaped reactive siloxane resin, and the siloxane- The water repellency is imparted to the structure of the side chain type reactive siloxane resin, which is easy to locate on the surface of the coating layer formed of the composition, so that initial pollution can be prevented.

Dispersible polyurethane resin can be used as the binder resin. The water-dispersible polyurethane resin is formed by synthesizing a polyol compound or an isocyanate compound, and a polycarbonate diol, a mixture of isophorone diisocyanate and dimethylolpropionic acid .

The water dispersible polyurethane resin is different in properties depending on the combination of polyol components and can realize physical properties required for automobile interior materials such as heat resistance, cold resistance, abrasion resistance, flexibility, workability, flexibility, chemical resistance and durability. The water-dispersible polyurethane resin is excellent in adaptability to various processing methods and is used for producing films, sheets and various molded articles as binders for synthetic artificial leather materials, various coating agents, inks, paints and the like.

Based resin may include about 1 to about 30 parts by weight of the siloxane-based resin per 100 parts by weight of the water-dispersible polyurethane resin. When the amount of the siloxane-based resin is less than about 1 part by weight, there is a fear that the effect of preventing the adhesion of contaminants and the effect of abrasion resistance may not be exhibited. When the amount exceeds about 30 parts by weight, It is advantageous in that the above range is maintained to realize the anti-fouling effect simultaneously with the matting effect.

Generally, when the siloxane-based resin is mixed with an aqueous dispersion type polyurethane resin, the gloss of the coating composition is increased according to the content of the siloxane-based resin, and when the gloss is increased, the stain resistance is lowered, , For example, it is difficult to realize smooth texture such as natural leather and synthetic leather.

Wherein said antifouling coating composition comprises inorganic particles; And at least one selected from the group consisting of organic particles, wax-based extinction agents, and silica-based extinction agents, thereby lowering the gloss and maintaining the stain resistance improved by the siloxane-based resin.

Also, the anti-fouling coating composition can reduce the content of inorganic particles and replace the reduced inorganic particles with at least one selected from organic particles, wax-based extinction agents and silica-based extinction agents, The quenching effect due to the extinction interference phenomenon of light is improved by the difference in refractive index between the inorganic particles, the organic particles and the quencher, thereby realizing a matte surface. In addition, a smooth texture can be maintained by reducing the inorganic particle content.

Conventional anti-fouling coating compositions contain about 15 to 20 parts by weight of inorganic particles per 100 parts by weight of the water-dispersible polyurethane resin. However, in this case, since the inorganic particles can not express a smooth texture, I could not feel it.

On the other hand, the anti-fouling coating composition contains about 1 part by weight to about 10 parts by weight of the inorganic particles with respect to 100 parts by weight of the water-dispersible polyurethane resin, so that the soft texture is not impaired and the light- . In particular, when the inorganic particles are contained in an amount of less than about 1 part by weight, anti-blocking properties may be impaired. When the inorganic particles are contained in an amount exceeding about 10 parts by weight, soft texture may be impaired and surface friction may increase, .

The inorganic particles may be extinguished by diffused reflection of the inorganic particles themselves as a quencher. For example, as the inorganic particles, barium sulfate, silicon dioxide, calcium carbonate, titanium dioxide, talc, antimony trioxide, silica particles and the like can be used.

The use of silica particles is advantageous in that it can economically exert a quenching effect, and the inorganic particles may include silica particles having a particle diameter of about 0.5 [mu] m to about 15 [mu] m. 'Particle diameter' refers to the 'average particle diameter', which means the average value of the diameter measured in any region of the particle. Specifically, when the particle diameter of the silica particles is less than about 0.5 μm, the thickness of the coating layer formed by the composition may not be sufficient, and the anti-blocking property may be impaired. When the particle diameter is more than about 15 μm, May rise.

Based on 100 parts by weight of the water-dispersible polyurethane resin, about 5 to about 30 parts by weight of at least one selected from organic particles, wax-based extinction agents and silica-based extinction agents. The anti-fouling coating composition may contain at least one selected from the organic particles, wax-based extinction agent and silica-based extinction agent in place of the reduced inorganic particles. When the amount of the at least one selected from the organic particles, the wax-based extinction agent, and the silica-based extinction agent is more than about 30 parts by weight, the dispersibility of the particles may deteriorate. When the content is less than about 5 parts by weight There is a problem that it is difficult to express the matte.

For example, it is preferable that at least about 7 parts by weight to about 15 parts by weight of at least one selected from the organic particles, the wax-based extinction agent and the silica-based extinction agent is contained, It is advantageous.

The organic particles may include at least one member selected from the group consisting of an acrylic resin, a polyurethane resin, a polystyrene resin, and a combination thereof, and the particle diameter may be about 0.5 [mu] m to about 100 [mu] m.

The organic particles are advantageous in the smooth texture realization in the form of a spherical shape. However, when the organic particles are used singly, they have limitations in achieving a matte finish and can be easily mixed with silica inorganic particles to form a coating layer on a matte surface.

For example, the acrylic resin particles may exhibit a light extinction effect due to light diffusion due to a difference in refractive index from an aqueous polyurethane resin, but they may be disadvantageous in securing soft feeling and abrasion resistance due to insufficient elasticity. On the other hand, the polyurethane resin particles are excellent in elastic force, and can realize moist touch feeling like natural leather, and can be used in automobile interior materials in which natural leather and synthetic leather are used.

The wax-based light extinguishing agent may include at least one member selected from the group consisting of polyethylene, polypropylene, polytetrafluoroethylene, and combinations thereof, and may have a particle diameter of from about 0.5 [mu] m to about 100 [mu] m.

Specifically, when the particle size of the wax-based light extinguishing agent is less than about 0.5 탆, particles which do not contribute to the matting in the coating layer formed by the composition increase, and an excessive amount of the wax-based light extinguishing agent has to be added. In this case, the wax-based light extinguishing agent tends to flocculate, the dispersibility is lowered, the smoothness of the surface of the coating layer is impaired, and the viscosity of the coating composition may be increased. On the other hand, when it exceeds about 100 μm, the smoothness of the coating layer is lowered, and the wax-based light-extinguishing agent tends to settle during the coating process, so that a uniform coating layer can not be obtained.

When the wax-based light extinguishing agent is used alone, the light-extinguishing property may be deteriorated. However, when the wax-based light extinguishing agent is mixed with the inorganic particles or organic particles, the surface slip property and the solvent resistance are improved and the stain resistance is improved. . Further, when the above-mentioned content is maintained, the flowability of the contaminated coating composition is improved, which is advantageous in coating work.

The specific gravity may vary depending on each constitution of the wax-based light extinguishing agent, but may have an average specific gravity of about 0.7 to about 2.3, specifically about 0.8 to about 1.2.

In addition, the softening point of the wax-based quencher may vary depending on the constitution, but the average softening point may be about 70 ° C to about 320 ° C. When the softening point of the wax-based light-quenching agent is less than about 70 ° C, the wax-based light-extinguishing agent tends to soften during the drying process to reduce the matting effect of the coating layer. When the softening point exceeds about 250 ° C, It is difficult to realize a matte effect.

The silica-based light extinguishing agent may be at least one selected from the group consisting of silica rubber powder, silicone resin powder, silicon mixed powder, and combinations thereof.

The silica-based quencher is mainly composed of silica (SiO ₂ ). When the silica-based quencher is used in a large amount, it is possible to realize a matte, but it has a disadvantage in that the surface thereof becomes coarse, By including the above silica-based quenching agent, stain resistance can be exhibited.

The silicone rubber powder has a structure of a cross-linked form of linear dimethylpolysiloxane, and may have a particle diameter of about 1 [mu] m to about 30 [mu] m. The silicone rubber powder has weatherability, heat resistance, and cold resistance as compared with ordinary rubber, and elasticity is maintained over a wide temperature range, so that a smooth and moist feel can be achieved.

When the particle diameter is too small, the cohesive force is increased and it is difficult to disperse. It is more advantageous to realize slippery property and smooth texture to maintain the particle diameter within the above range.

The silicone resin powder may have a structure in which siloxane bonds are crosslinked in a three-dimensional network structure, and the particle diameter may be about 0.2 um to about 8 um.

Specifically, the silicone resin powder is a powder of polymethylsilsesquioxane. The silicone resin powder is excellent in heat resistance as compared with a general silicone resin, and has a structure in which a siloxane bond is crosslinked in a three-dimensional network structure. Thus, It does not dissolve or expand in an ester-based organic solvent and is excellent in solvent resistance.

In addition, by keeping the particle diameter of the silicone resin powder within the above-mentioned range, it is possible to realize a matte property, a slip property and an abrasion resistance.

The silicone rubber powder maintains soft touch due to its elasticity. On the other hand, the silicone resin powder can be improved in slipperiness with a rigid material having no elasticity. Further, since the refractive index differs from that of the binder resin, the light diffusing property is imparted to improve the extinction effect.

The silicon mixed powder may include organic particles having silicone resin powder protrusions formed on its surface.

The silicon mixed powder is formed by coating the organic particles with a silicone resin powder. For example, by coating the polyurethane resin particles with polymethylsilsesquioxane, the surface of the polyurethane resin particles can be coated with a polymeric silsesquioxane A projection may be formed.

In addition, the particle diameter of the silicon mixed powder may be about 0.5 um to about 20 um, and it is advantageous in that the particle diameter of the range is able to realize a matting effect, an anti-blocking property, and a wear resistance.

The silicone mixed powder is a mixed form of the organic resin and the silicone resin powder. The silicone mixed powder is not easily agglomerated among the powders, so that the dispersibility is excellent and a soft touch can be realized.

In addition, the antifouling coating composition may further include conventional additives such as an isocyanate curing agent, an epoxy curing agent, a viscosity adjusting agent, a defoaming agent, and a leveling agent. The content of the additive is not limited as long as it does not affect the properties of the composition. For example, the amount of the additive may be 0.1 to 10 parts by weight based on 100 parts by weight of the binder resin.

The anti-fouling coating composition contains a siloxane-based resin to ensure stain resistance. The content of the inorganic particles is reduced, and the reduced inorganic particles are selected from organic particles, wax-based extinction agents, and silica- It is possible to realize a matte effect and a soft texture effect and at the same time to maintain the stain resistance due to the siloxane resin.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

< Example  And Comparative Example >

Example  One

10 parts by weight of a siloxane-based resin represented by the following formula (1), 8 parts by weight of silica particles having a particle diameter of 5 탆, 10 parts by weight of a silicon mixed powder having a particle diameter of 5 탆, 100 parts by weight of a crosslinking agent 5 parts by weight of an isocyanate compound as a leveling agent, 1 part by weight of Hydrophobically modified polyethylene oxide urethane (HEUR) as a viscosity modifier, and 0.5 part by weight of a silicone resin as a defoaming agent were mixed to form an antifouling coating composition.

[Chemical Formula 1]

The R ₁ , R ₃ To R ₇ are -CH ₃ , R ₂ and R ₈ are carbinol groups, and n 1 is 20 or more.

Example 2

An antifouling coating composition was prepared in the same manner as in Example 1 except that the above-mentioned formula (1) was the following formula (1).

[Chemical Formula 1]

R ₁ to R ₃ , R ₅ To R ₈ are -C ₂ H ₅ , R ₄ is a carbinol group, and n 1 is 20 or more.

Example 3

An antifouling coating composition was prepared in the same manner as in Example 1, except that [Formula 1] of Example 1 and [Formula 1] of Example 2 were mixed at a ratio of 6: 4.

Comparative Example  One

10 parts by weight of a tetrafluoroethylene (TFE) copolymer dispersion (Lanxess, Aquaderm X-Shield L) relative to 100 parts by weight of an aqueous dispersion type polyurethane resin other than the siloxane- , An antifouling coating composition was prepared in the same manner as in Example 1 above.

Comparative Example  2

Except for containing 10 parts by weight of a fluorinated polyurethane aqueous dispersion (3M, SRC-220) relative to 100 parts by weight of an aqueous dispersion type polyurethane resin in addition to the siloxane-based resin represented by the above formula (1) To prepare an antifouling coating composition.

Comparative Example  3

An antifouling coating composition was prepared in the same manner as in Example 1 except that the above-mentioned formula (1) was the following formula (1).

[Chemical Formula 1]

The R ₁ To R ₈ is -CH _3, n1 is at least 20.

< Experimental Example > - Pollution  Stain resistance of coating compositions

The antifouling coating compositions of the above Examples and Comparative Examples were applied to a polyvinyl chloride resin layer to a thickness of 10 mu m and dried to prepare an automotive interior material having an antifouling coating layer formed thereon.

Was prepared in the automobile interior for the specimens of 25mm (width) X220mm (h), the common contamination siheompo the specimen ^1), denim ²⁾ 100mm sikyeotgo go to 30 times / min, 100 times under a load of 500gf The degree of pollution after the round trip was graded according to the gray scale (KSK 0910). At this time, "5 grade: No pollution, 3 grade: Normal, 2 grade: There is contamination" was marked.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Reactive siloxane resin Fluorine additive Unreactive
Siloxane resin General ^{1 )} 5 3 5 2 2 2 Denim ^{2 )} 3 3 3 2 2 2

1) Testfabrics EPMA 106 (Cotton soiled with IEC carbon black / mineral oil)

2) Testfabrics EPMA 128/1 (Cotton Jeans, indigo / sulfur black, soil with carbon black / olive oil)

Referring to Table 1, Examples 1 to 3 containing a reactive siloxane-based resin were found to have excellent stain resistance as compared with Comparative Examples 1 and 2 containing a fluorine-based additive and Comparative Example 3 containing a non-reactive siloxane-based resin I could.

Claims (15)

100 parts by weight of a water-dispersible polyurethane resin;
1 to 30 parts by weight of a siloxane-based resin represented by the following formula (1);
0.1 to 10 parts by weight of a curing agent;
1 to 10 parts by weight of inorganic particles; And
Silicon mixed powder of 7 to 15 parts by weight,
The aqueous dispersion type polyurethane resin is formed by polymerization of polycarbonate diol, isophorone diisocyanate and dimethylol propionic acid,
The curing agent is selected from the group consisting of carbodiimide compounds, isocyanate compounds, oxazoline compounds, and combinations thereof,
Wherein the inorganic particles are silica particles having a particle diameter of from 0.5 mu m to 15 mu m,
Wherein the silicon mixed powder comprises organic particles having a silicone resin powder protrusion formed on the surface thereof and the organic particles are coated with a silicone resin powder, the particle diameter of the silicon mixed powder is 0.5 um to 20 um,
Wherein the organic particles comprise at least one member selected from the group consisting of an acrylic resin, a polyurethane resin, a polystyrene resin, and a combination thereof, wherein the organic particles have a particle diameter of 0.5 to 10 mu m
&Lt; / RTI &gt;

[Chemical Formula 1]

In Formula 1,
R ₁ to R ₈ independently of each other are selected from among X, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 halogenated carbon atoms, and an aryl group having 6 to 20 carbon atoms, provided that at least one of R ₁ to R ₈ is Must be selected as X;
X is selected from a carbinol group, a diol group and a carboxyl group;
n1 is an integer of 0 to 100, and when n1 is an integer of 2 or more,

Are the same or different from each other.
The method according to claim 1,
The siloxane-based resin may contain one or two X
&Lt; / RTI &gt;
The method according to claim 1,
R ₄ or R ₅ is X, and n 1 is an integer of 1 to 100
&Lt; / RTI &gt;
The method according to claim 1,
_{Two of} R ₁ to R ₃ and R ₆ to R ₈ are X
&Lt; / RTI &gt;
The method according to claim 1,
_One selected from R ₁ to R ₃ ; And
One selected from R ₆ to R ₈ is X
&Lt; / RTI &gt;
The method according to claim 1,
The siloxane-based resin is represented by the following formula (2) or
Contamination coating composition:
(2)

(3)

Of the above formulas (2) and (3)
R ₂₁ to R ₂₆ and R ₃₁ to R ₄₁ independently of each other are selected from an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 20 carbon atoms;
X ₂₁ , X ₂₂ and X ₃₁ are independently selected from a carbinol group, a diol group and a carboxyl group;
n ₂₁ is an integer from 0 to 100;
n ₃₁ is an integer from 1 to 100;
m ₃₁ and m ₃₂ are each independently an integer of 0 to 100, and the sum of n ₃₁ , m ₃₁ and m ₃₂ is an integer of 1 to 100. delete delete delete delete delete delete delete delete delete