KR102258881B1 - Preparing method of coating composition for artificial leather having improved durability and the coating composition for artificial leather having improved durability - Google Patents

Abstract

상기 식에서,
a 및 b는 각각 독립적으로 1 내지 300의 정수이고,
c 및 d는 각각 독립적으로 1 내지 12의 정수이다.
[화학식 2]

상기 식에서,
e는 1 내지 100의 정수이다.The present invention comprises the steps of preparing an emulsion solution by reacting, mixing, and stirring an amino-modified polysiloxane represented by the following formula (1) with a nonionic surfactant; 1st distilled water mixing step of reacting, mixing, and stirring the emulsion solution with distilled water; A second distilled water mixing step of reacting, mixing, and stirring the emulsion solution in which the first distilled water is mixed with distilled water; A pH adjustment step of reacting, mixing, and stirring the emulsion solution in which the secondary distilled water is mixed with distilled water and an acid to adjust the pH to a range of 6 to 7; A polydimethylsiloxane mixing step of reacting, mixing, and stirring the emulsion solution in which the pH is adjusted with polydimethylsiloxane and nonionic (C11 to C15) secondary alcohol ethoxylate surfactants represented by the following formula (2); And an additive mixing step of reacting, mixing, and stirring the emulsion solution in which the polydimethylsiloxane is mixed with an additive; by including, a method for preparing a coating composition for artificial leather having excellent durability such as abrasion resistance and stain resistance, and durability produced therefrom It relates to this excellent coating composition for artificial leather.
[Formula 1]

In the above formula,
a and b are each independently an integer of 1 to 300,
c and d are each independently an integer of 1 to 12.
[Formula 2]

In the above formula,
e is an integer from 1 to 100.

Description

Preparation method of a coating composition for artificial leather having excellent durability, and a coating composition for artificial leather having excellent durability prepared therefrom and having improved durability and the coating composition for artificial leather having improved durability}

The present invention relates to a method for producing a coating composition for artificial leather having excellent durability such as abrasion resistance and stain resistance, and a coating composition for artificial leather having excellent durability prepared therefrom.

Recently, artificial leather has been developed that can obtain a texture and unique appearance similar to that of natural leather with a synthetic resin fabric, and is easy to process at an inexpensive price. It is widely used in various fields such as interior and exterior materials for electronic products. As such artificial leather, many types of artificial leather such as nylon leather, polyvinyl chloride leather (PVC leather), and polyurethane dry type leather are on the market, and the development of such artificial leather is a substitute for natural leather. Since it can complement the shortcomings of natural leather as well as its uses, its demands and areas are rapidly expanding, such as being applied to high-end fashion materials.

Artificial leather is required to have excellent physical properties, such as having excellent abrasion resistance or activity, and sufficient resistance to contamination.

Thus, in order to improve the above-described physical properties, a polyurethane-based coating composition was mainly used on the surface of the conventional artificial leather. However, such a polyurethane-based coating composition contains a large amount of an organic solvent such as dimethylformamide or methyl ethyl ketone in order to improve film-forming properties, and thus there is a problem that is harmful to the human body or the environment.

Therefore, instead of organic solvents, water-based polyurethane resins dispersed in water have been developed and used, but the water-based polyurethane resins are unstable in distribution, molecular size, and dispersion conditions in water, and are coated by heat generated by mechanical friction. There were problems such as hardening of the polyurethane resin. In addition, polyurethane has poor solvent resistance and is easily soluble in polar solvents such as dimethylformamide and methyl ethyl ketone, so it may damage the product. It has poor hydrolysis resistance to water, so it is hydrolyzed when exposed to moisture for a long period of time. There was a problem that could happen. In addition, the process of adjusting the touch through an additional surface milling process in order to satisfy the sense of mass of the artificial leather is complicated, and the final production of artificial leather is produced by the generation of residues such as fiber powder generated through the above process. There was a problem of poor quality.

Therefore, in order to solve the above problems that occur during the manufacture of conventional artificial leather, it is not harmful during manufacturing, is stable against temperature changes, and has excellent durability such as solvent resistance, moisture decomposition resistance, abrasion resistance and contamination resistance. There is a need to develop a coating composition.

Korean Patent Registration No. 10-1536848 Korean Patent Registration No. 10-2027323 Korean Patent Registration No. 10-2175133

The present invention was conceived to solve the above-described problems, and an embodiment of the present invention replaces the conventional polyurethane-based coating composition, and is not harmful during manufacture, is stable to changes in temperature, solvent resistance, moisture decomposition resistance. It is intended to provide a method of manufacturing a coating composition for artificial leather with improved wear resistance and stain resistance, and in particular, excellent durability such as abrasion resistance and stain resistance.

In addition, another embodiment of the present invention is to provide a coating composition for artificial leather having excellent durability prepared from the method for preparing a coating composition for artificial leather having excellent durability.

Various problems to be solved by the present invention are not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

In one embodiment of the present invention, 100 parts by weight of an amino-modified polysiloxane represented by the following Formula 1 is reacted with 10 to 70 parts by weight of a nonionic surfactant for 50 to 150 minutes at a temperature of 35 to 45° C., mixed, and stirred, and an emulsion solution Manufacturing a; 1st distilled water mixing step of reacting, mixing, and stirring the emulsion solution with 5 to 45 parts by weight of distilled water for 50 to 150 minutes at a temperature of 35 to 45 °C; A second distilled water mixing step of reacting, mixing, and stirring the emulsion solution in which the first distilled water is mixed at 80 to 110 parts by weight of distilled water at a temperature of 40 to 60°C for 50 to 150 minutes; The second-distilled water-mixed emulsion solution was reacted with 60 to 90 parts by weight of distilled water and 0.1 to 5 parts by weight of acid and 40 to 60° C. for 50 to 150 minutes, mixed, and stirred to bring the pH to the range of 6 to 7 Adjusting the pH adjustment step; The pH-adjusted emulsion solution is 80 to 130 parts by weight of polydimethylsiloxane represented by the following formula (2) and 60 to 100 parts by weight of a nonionic (C11 to C15) secondary alcohol ethoxylate surfactant and a temperature of 40 to 60°C. Polydimethylsiloxane mixing step of reacting, mixing, and stirring for 220 to 300 minutes at; And an additive mixing step of reacting, mixing and stirring the emulsion solution in which the polydimethylsiloxane is mixed with 1 to 20 parts by weight of an additive at a temperature of 40 to 60° C. for 50 to 150 minutes; It provides a method for preparing the composition.

[Formula 1]

In the above formula,

a and b are each independently an integer of 1 to 300,

c and d are each independently an integer of 1 to 12.

[Formula 2]

In the above formula,

e is an integer from 1 to 100.

The nonionic surfactant is one or more selected from the group consisting of polyoxyethylene alkyl ether, fatty acid sorbitan ester, fatty acid diethanolamine, alkyl monoglyceryl ether, and mixtures thereof; The acid may be one or more selected from the group consisting of acetic acid, lactic acid, citric acid, formic acid, nitric acid, glycolic acid, hypophosphorous acid, and mixtures thereof.

The additive is polyether-modified polysiloxane 45 to 65% by weight, cellulose alkyl ether 30 to 50% by weight, ethoxylated fatty (C6 to C22) alcohol 1 to 5% by weight, alkylphosphonic acid represented by the following formula (3) It may include 0.01 to 1% by weight of the compound and 0.01 to 1% by weight of silicoaluminophosphate.

[Formula 3]

In the above formula,

R ¹ is a linear or branched C1 to C4 alkyl group,

x is 0 or 1.

Synthesizing a first template solution by dissolving a block copolymer of polyethylene oxide and polypropylene oxide in an organic solvent containing alcohol in the silicoaluminophosphate; Dissolving piperidine and tetramethylammonium chloride (TMACl) in distilled water to synthesize a second template solution; Sodium silicate, pseudo-bohemite, and triethyl phosphate were respectively 50 to 80 parts by weight of 100 parts by weight of a mixed template solution obtained by mixing the first template solution and the second template solution in a ratio of 1: 2 to 5 by weight. Preparing a hydration gel by mixing 20 to 50 parts by weight of the source mixture mixed in a content range of weight %, 15 to 45 weight %, and 1 to 10 weight %; The prepared hydration gel is aged by stirring for 2 to 24 hours at a temperature of 30 to 90° C., and then stirred at a temperature of 150 to 200° C. for 5 to 48 hours to form a solid product by hydrothermal reaction; And sintering the obtained solid product at a temperature of 800 to 1000° C. for 1 to 5 hours at a temperature increase rate of 0.2 to 2° C./min and then slowly cooling.

In addition, another embodiment of the present invention provides a coating composition for artificial leather having excellent durability, which is prepared from the method for preparing a coating composition for artificial leather having excellent durability.

According to a method for preparing a coating composition for artificial leather having excellent durability and a coating composition for artificial leather having excellent durability prepared therefrom according to an embodiment of the present invention, including amino-modified polysiloxane and polydimethylsiloxane, conventional polyurethane-based It has the effect of replacing the coating composition. As a result, it is environmentally friendly because it is not harmful during manufacture, is stable to changes in temperature, and improves solvent resistance, moisture decomposition resistance, abrasion resistance and contamination resistance, and in particular, durability such as abrasion resistance and fouling resistance is excellent. Thereby, by coating the surface of artificial leather used as interior materials such as automobiles, the touch, uniform surface and quality of the artificial leather can be realized or improved as it is, and there is an effect that the surface protection effect of such artificial leather can last a long time. .

1 shows a process chart of a method of manufacturing a coating composition for artificial leather having excellent durability according to an embodiment of the present invention.
FIG. 2 shows an actual image after performing fouling resistance evaluation with respect to specimens for testing artificial leather coated with the coating composition prepared in Example 2 and Comparative Example 1. FIG.
3 shows an actual image after performing abrasion resistance evaluation (abrasion 1000 times) with respect to the specimens for testing the artificial leather coated with the coating composition prepared in Example 2 and Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

In one embodiment of the present invention, 100 parts by weight of an amino-modified polysiloxane represented by the following Formula 1 is reacted with 10 to 70 parts by weight of a nonionic surfactant for 50 to 150 minutes at a temperature of 35 to 45° C., mixed, and stirred, and an emulsion solution Manufacturing a; 1st distilled water mixing step of reacting, mixing, and stirring the emulsion solution with 5 to 45 parts by weight of distilled water for 50 to 150 minutes at a temperature of 35 to 45 °C; A second distilled water mixing step of reacting, mixing, and stirring the emulsion solution in which the first distilled water is mixed at 80 to 110 parts by weight of distilled water at a temperature of 40 to 60°C for 50 to 150 minutes; The second-distilled water-mixed emulsion solution was reacted with 60 to 90 parts by weight of distilled water and 0.1 to 5 parts by weight of acid and 40 to 60° C. for 50 to 150 minutes, mixed, and stirred to bring the pH to the range of 6 to 7 Adjusting the pH adjustment step; The pH-adjusted emulsion solution is 80 to 130 parts by weight of polydimethylsiloxane represented by the following formula (2) and 60 to 100 parts by weight of a nonionic (C11 to C15) secondary alcohol ethoxylate surfactant and a temperature of 40 to 60°C. Polydimethylsiloxane mixing step of reacting, mixing, and stirring for 220 to 300 minutes at; And an additive mixing step of reacting, mixing and stirring the emulsion solution in which the polydimethylsiloxane is mixed with 1 to 20 parts by weight of an additive at a temperature of 40 to 60° C. for 50 to 150 minutes; It provides a method for preparing the composition.

[Formula 1]

In the above formula,

a and b are each independently an integer of 1 to 300,

c and d are each independently an integer of 1 to 12.

[Formula 2]

In the above formula,

e is an integer from 1 to 100.

Fig. 1 shows a process chart of a method for producing a coating composition for artificial leather having excellent durability according to an embodiment of the present invention.

According to a method for preparing a coating composition for artificial leather having excellent durability and a coating composition for artificial leather having excellent durability prepared therefrom according to an embodiment of the present invention, including amino-modified polysiloxane and polydimethylsiloxane, conventional polyurethane-based It has the effect of replacing the coating composition. As a result, it is environmentally friendly because it is not harmful during manufacture, is stable to changes in temperature, and improves solvent resistance, moisture decomposition resistance, abrasion resistance and contamination resistance, and in particular, durability such as abrasion resistance and fouling resistance is excellent. Thereby, by coating the surface of artificial leather used as interior materials such as automobiles, the touch, uniform surface and quality of the artificial leather can be realized or improved as it is, and there is an effect that the surface protection effect of such artificial leather can last a long time. .

First, 100 parts by weight of the amino-modified polysiloxane represented by Formula 1 is reacted with 10 to 70 parts by weight of a nonionic surfactant for 50 to 150 minutes at a temperature of 35 to 45° C., mixed, and stirred to prepare an emulsion solution. Carry out.

The amino-modified polysiloxane represented by Formula 1 functions to provide excellent stain resistance.

Conventionally, a fluorine-based additive was used to secure contamination resistance. These fluorine-based additives were able to prevent the adhesion of pollutants in the initial stage, but their effect is limited to preventing the adhesion of pollutants in a static dimension, and there was a limitation in dynamic dimensions that are continuously used such as interior materials for automobiles. In addition, the fluorine-based additive makes it possible to remove contaminants by wiping them with a cleaner in a contaminated state, but there is a limitation in fundamentally preventing the adhesion of contaminants.

In comparison, the amino-modified polysiloxane represented by Chemical Formula 1 is excellent in preventing contamination for a long time from the beginning and has the effect of easy removal of contaminants.

More preferably, in Formula 1, when a is an integer of 1 to 150, and b is an integer of 250 to 300, the above-described effect can be further improved, and the soft texture of the leather can be effectively maintained.

In addition, the amino-modified polysiloxane represented by Chemical Formula 1 may preferably have a viscosity of 100 to 5,000 cP in order to prevent the above-described improvement effect and agglomeration during the emulsion solution manufacturing process.

On the other hand, the nonionic surfactant functions to improve dispersion stability and transparency of the emulsion solution by reducing the interfacial tension.

The nonionic surfactant may preferably be one or more selected from the group consisting of polyoxyethylene alkyl ether, fatty acid sorbitan ester, fatty acid diethanolamine, alkyl monoglyceryl ether, and mixtures thereof.

The nonionic surfactant is preferably contained in an amount of 10 to 70 parts by weight based on 100 parts by weight of the amino-modified polysiloxane. When the content of the nonionic surfactant is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the nonionic surfactant is too large, there is a problem that the fouling resistance may be rather lowered.

In addition, the emulsion solution further contains 0.1 to 10 parts by weight of decamethylcyclopentasiloxane based on 100 parts by weight of the amino-modified polysiloxane in order to maintain dispersion stability by inhibiting re-aggregation during dispersion and to improve durability such as abrasion resistance. can do. If the content of the decamethylcyclopentasiloxane is too large, there is a problem in that the fouling resistance may be rather lowered.

In addition, the reaction, mixing, and agitation may be performed at a temperature of 35 to 45 °C for 50 to 150 minutes in order to prevent aggregation during dispersion to maintain dispersion stability, and to improve durability such as contamination resistance and abrasion resistance as a result. have. More specifically, the stirring is preferably carried out with a relatively low-speed stirring of 30 to 70 rpm.

Then, the first distilled water mixing step of reacting, mixing, and stirring the emulsion solution with 5 to 45 parts by weight of distilled water for 50 to 150 minutes at a temperature of 35 to 45 °C; And a second distilled water mixing step of reacting, mixing, and stirring the emulsion solution in which the first distilled water is mixed at 80 to 110 parts by weight of distilled water at a temperature of 40 to 60° C. for 50 to 150 minutes.

The distilled water functions to stably disperse the emulsion solution.

When a large amount of distilled water is mixed with the emulsion solution at one time, an emulsification phenomenon or agglomeration phenomenon may occur. Therefore, by performing the first distilled water mixing step and the second distilled water mixing step, distilled water is mixed with the emulsion solution step by step to provide a composition having excellent transparency, and as a result, durability such as excellent stain resistance and abrasion resistance can be provided. It can be.

In the first mixing step of distilled water, the distilled water is preferably contained in the range of 5 to 45 parts by weight based on 100 parts by weight of the amino-modified polysiloxane. In addition, in the secondary distilled water mixing step, the distilled water is preferably contained in the range of 80 to 110 parts by weight based on 100 parts by weight of the amino-modified polysiloxane. When the content of distilled water is too small, the above-described improvement effect may be insufficient, and when the content of distilled water is too large, there is a problem in that dispersion stability or fouling resistance may be rather decreased.

In addition, in the first mixing step of distilled water, the reaction, mixing, and stirring are preferably performed at a temperature of 35 to 45° C. for 50 to 150 minutes. In addition, in the second distilled water mixing step, the reaction, mixing, and stirring are preferably performed at a temperature of 40 to 60° C. for 50 to 150 minutes. That is, by performing sufficient dispersion while gradually increasing the temperature, aggregation can be prevented during dispersion to maintain dispersion stability, and as a result, durability such as stain resistance and abrasion resistance can be improved.

More specifically, it is preferable that the agitation is performed at a speed of 30 to 70 rpm in the first mixing step of distilled water and the second mixing step of distilled water.

Thereafter, the second-distilled water-mixed emulsion solution was reacted with 60 to 90 parts by weight of distilled water and 0.1 to 5 parts by weight of acid and 40 to 60° C. for 50 to 150 minutes, mixed and stirred, and the pH was adjusted to 6 to 7 Perform a pH adjustment step to adjust to the range.

The distilled water functions to stably disperse the emulsion solution as in the first distilled water mixing step and the second distilled water mixing step.

In addition, the acid can improve transparency and provide excellent dispersion stability by neutralizing the basified composition by the amino group of the amino-modified polysiloxane. In this case, the acid may preferably be one or more selected from the group consisting of acetic acid, lactic acid, citric acid, formic acid, nitric acid, glycolic acid, hypophosphorous acid, and mixtures thereof. More preferably, by using a mixture of acetic acid and lactic acid in a weight ratio of 1: 0.1 to 0.5, there is an effect of providing the composition with better storage stability at room temperature and high temperature.

The acid is preferably contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the amino-modified polysiloxane. When the content of the acid is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the acid is too high, the pH of the composition becomes too acidic, and the fouling resistance may be rather lowered. have.

In addition, the reaction, mixing, and agitation may be performed at a temperature of 40 to 60° C. for 50 to 150 minutes in order to prevent aggregation during dispersion to maintain dispersion stability and, as a result, to improve durability such as stain resistance and abrasion resistance. have. More specifically, the stirring is preferably performed at a speed of 30 to 70 rpm.

Thereafter, the pH-adjusted emulsion solution is 80 to 130 parts by weight of polydimethylsiloxane represented by the following formula (2) and 60 to 100 parts by weight of a nonionic (C11 to C15) secondary alcohol ethoxylate surfactant and 40 to 60°C. Polydimethylsiloxane mixing step of reacting, mixing, and stirring at a temperature of 220 to 300 minutes is performed.

The polydimethylsiloxane represented by Chemical Formula 2 is used together with the amino-modified polysiloxane to provide excellent wear resistance.

The polydimethylsiloxane represented by Formula 2 is preferably contained in an amount of 80 to 130 parts by weight based on 100 parts by weight of the amino-modified polysiloxane. When the content of the polydimethylsiloxane is too small, the above-described improvement effect may be insufficient, and when the content of the polydimethylsiloxane is too large, there is a problem that the soft touch of the leather may be deteriorated.

The nonionic (C11 to C15) secondary alcohol ethoxylate surfactant functions to improve dispersion stability and transparency of the emulsion solution by reducing the interfacial tension. In particular, by improving the miscibility of the polydimethylsiloxane and the additive, it functions to improve durability such as stain resistance and abrasion resistance.

The nonionic (C11 to C15) secondary alcohol ethoxylate surfactant is preferably contained in an amount of 60 to 100 parts by weight based on 100 parts by weight of the amino-modified polysiloxane. If the content of the nonionic (C11 to C15) secondary alcohol ethoxylate surfactant is too small, the above-described improvement effect may be insufficient, and the nonionic (C11 to C15) secondary alcohol ethoxylate If the content of the surfactant is too large, there is a problem in that durability such as contamination resistance and abrasion resistance may be rather deteriorated.

In addition, the reaction, mixing, and stirring may be performed at a temperature of 40 to 60° C. for 220 to 300 minutes in order to prevent aggregation during dispersion to maintain dispersion stability and, as a result, to improve durability such as stain resistance and abrasion resistance. have. More specifically, the stirring is preferably performed at a speed of 30 to 70 rpm.

Thereafter, an additive mixing step of reacting, mixing and stirring the emulsion solution in which the polydimethylsiloxane is mixed with 1 to 20 parts by weight of an additive at a temperature of 40 to 60° C. for 50 to 150 minutes is performed.

The additives are generally used in the art, and the type is not particularly limited, but for example, one or more selected from the group consisting of antifoaming agents, preservatives, leveling agents, and mixtures thereof may be used.

In particular, the additives not only further improve stain resistance and abrasion resistance, but also improve storage stability, temperature stability, flexibility, slip resistance, heat resistance and cold resistance performance, polyether-modified polysiloxane 45 to 65% by weight, cellulose alkyl Ether 30 to 50 wt%, ethoxylated fatty (C6 to C22) alcohol 1 to 5 wt%, alkylphosphonic acid compound represented by the following formula (3) 0.01 to 1 wt% and silicoaluminophosphate 0.01 to 1 wt% It may be to include.

[Formula 3]

In the above formula,

R ¹ is a linear or branched C1 to C4 alkyl group,

x is 0 or 1.

The polyether-modified polysiloxane implements excellent stain resistance, has excellent foaming properties and anti-foaming persistence, so that a large foaming effect is obtained with small additions, and by suppressing re-aggregation of the composition, it maintains dispersion stability, storage stability and temperature stability. Functions.

The polyether-modified polysiloxane is preferably contained in the range of 45 to 65% by weight based on the additive. If the content of the polyether-modified polysiloxane is too small, the above-described improvement effect may be insufficient, and if the content of the polyether-modified polysiloxane is too large, the fouling resistance of the composition may be rather lowered. There is this.

The cellulose alkyl ether functions to improve dispersion stability, storage stability and temperature stability by inhibiting re-aggregation of the composition together with the polyether-modified polysiloxane.

The cellulose alkyl ether may preferably be one or more selected from the group consisting of ethyl cellulose, propyl cellulose, butyl cellulose, pentyl cellulose, hexyl cellulose, heptyl cellulose, octyl cellulose, nonyl cellulose, decyl cellulose, and mixtures thereof. .

The cellulose alkyl ether is preferably contained in the range of 30 to 50% by weight based on the additive. When the content of the cellulose alkyl ether is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the cellulose alkyl ether is too large, there is a problem that the fouling resistance of the composition may be rather lowered.

The ethoxylated fatty (C6 to C22) alcohol has a function of reducing the interfacial tension, improving dispersion stability and transparency of the emulsion solution, and improving flexibility and slip properties.

The ethoxylated fatty (C6 to C22) alcohol is preferably contained in an amount of 1 to 5% by weight based on the additive. If the content of the ethoxylated fatty (C6 to C22) alcohol is too small, there is a problem that the above-described improvement effect may be insufficient, and the content of the ethoxylated fatty (C6 to C22) alcohol is too large There is a problem in that the contamination resistance of the composition may be rather lowered.

The alkylphosphonic acid compound represented by Formula 3 not only further improves abrasion resistance, but also functions to improve storage stability, temperature stability, heat resistance, and cold resistance performance.

The alkylphosphonic acid compound represented by Formula 3 is preferably contained in an amount of 0.01 to 1% by weight based on the additive. When the content of the alkylphosphonic acid compound is too small, the above-described improvement effect may be insufficient, and when the content of the alkylphosphonic acid compound is too large, the flexible texture of the leather may be rather reduced. There is this.

The silicoaluminophosphate not only further improves stain resistance and abrasion resistance, but also functions to improve storage stability, temperature stability, flexibility, slip resistance, heat resistance and cold resistance.

In particular, the silicoaluminophosphate is a step of dissolving a block copolymer of polyethylene oxide and polypropylene oxide in an organic solvent containing alcohol to synthesize a first template solution; Dissolving piperidine and tetramethylammonium chloride (TMACl) in distilled water to synthesize a second template solution; Sodium silicate, pseudo-bohemite, and triethyl phosphate were respectively 50 to 80 parts by weight of 100 parts by weight of a mixed template solution obtained by mixing the first template solution and the second template solution in a ratio of 1: 2 to 5 by weight. Preparing a hydration gel by mixing 20 to 50 parts by weight of the source mixture mixed in a content range of weight %, 15 to 45 weight %, and 1 to 10 weight %; The prepared hydration gel is aged by stirring for 2 to 24 hours at a temperature of 30 to 90° C., and then stirred at a temperature of 150 to 200° C. for 5 to 48 hours to form a solid product by hydrothermal reaction; And sintering the obtained solid product at a temperature of 800 to 1000° C. for 1 to 5 hours at a temperature increase rate of 0.2 to 2° C./min and then slowly cooling the obtained solid product. Can be further improved.

At this time, the step of synthesizing the first template solution by dissolving the block copolymer of polyethylene oxide and polypropylene oxide in the organic solvent containing alcohol is to include polyethylene oxide and polypropylene oxide in 100 parts by weight of the organic solvent containing the alcohol. It can be carried out by dissolving 1 to 10 parts by weight of the block copolymer.

In addition, the organic solvent containing the alcohol is generally used in the art, and its kind is not particularly limited, but for example, an alkyl alcohol having 1 to 15 carbon atoms may be used.

In addition, the block copolymer of polyethylene oxide and polypropylene oxide has an effect of providing a first template having excellent strength even at a high porosity by using a polyethylene oxide/polypropylene oxide molar ratio of 0.9 to 1.1. .

Meanwhile, the step of dissolving piperidine and tetramethylammonium chloride (TMACl) in the distilled water to synthesize a second template solution includes 0.1 to 5 parts by weight of piperidine and tetramethylammonium chloride (TMACl) in 100 parts by weight of the distilled water. It can be carried out by dissolving 1 to 10 parts by weight.

Accordingly, by using a mixed template in which the first template and the second template having different porosities from each other are used, the above-described effect can be greatly improved.

The silicoaluminophosphate is preferably contained in an amount of 0.01 to 1% by weight based on the additive. When the content of the silicoaluminophosphate is too small, the above-described improvement effect may be insufficient, and when the content of the silicoaluminophosphate is too large, there is a problem in that the flexible texture of the leather may be rather reduced. .

On the other hand, the additive is preferably contained in the range of 1 to 20 parts by weight based on 100 parts by weight of the amino-modified polysiloxane. When the content of the additive is too small, there is a problem that the desired improvement effect may be insufficient, and when the content of the additive is too large, there is a problem that the fouling resistance and abrasion resistance may be rather deteriorated.

In addition, the reaction, mixing, and agitation may be performed at a temperature of 40 to 60° C. for 50 to 150 minutes in order to prevent aggregation during dispersion to maintain dispersion stability and, as a result, to improve durability such as stain resistance and abrasion resistance. have. More specifically, the stirring is preferably performed at a speed of 30 to 70 rpm.

In addition, another embodiment of the present invention provides a coating composition for artificial leather having excellent durability, which is prepared from the method for preparing a coating composition for artificial leather having excellent durability.

In particular, the excellent durability coating composition for ^{artificial leather is coated on the surface of high-density artificial leather with an apparent density of 0.7 to 0.9 g/cm 3} , so that the excellent effects of the present invention can be more effectively implemented.

According to a method for preparing a coating composition for artificial leather having excellent durability and a coating composition for artificial leather having excellent durability prepared therefrom according to an embodiment of the present invention, including amino-modified polysiloxane and polydimethylsiloxane, conventional polyurethane-based It has the effect of replacing the coating composition. As a result, it is environmentally friendly because it is not harmful during manufacture, is stable to changes in temperature, and improves solvent resistance, moisture decomposition resistance, abrasion resistance and contamination resistance, and in particular, durability such as abrasion resistance and fouling resistance is excellent. Thereby, by coating the surface of artificial leather used as interior materials such as automobiles, the touch, uniform surface and quality of the artificial leather can be realized or improved as it is, and there is an effect that the surface protection effect of such artificial leather can last a long time. .

Above, the preferred embodiment of the present invention has been described in detail, but the present invention is not limited to the above embodiment, and various modifications by those of ordinary skill in the relevant field within the scope of the technical idea of the present invention This is possible.

<Example 1>

100 parts by weight of the amino-modified polysiloxane represented by the following Formula 1-1 is reacted with 50 parts by weight of a nonionic surfactant (polyoxyethylene alkyl ether) at a temperature of 40° C. at a rate of 60 rpm for 120 minutes, mixed, and stirred for emulsification. The solution was prepared.

[Formula 1-1]

Wherein a is 135; b is 178; c is 3; d is 2.

Thereafter, the emulsion solution was reacted with 27 parts by weight of distilled water at a temperature of 40° C. at a rate of 60 rpm for 120 minutes, mixed, and stirred.

Thereafter, the emulsion solution in which the first distilled water was mixed was reacted with 83 parts by weight of distilled water at a temperature of 50° C. at a rate of 60 rpm for 120 minutes, followed by mixing and stirring.

Thereafter, the emulsion solution in which the secondary distilled water was mixed was reacted with 73 parts by weight of distilled water and 0.8 parts by weight of acetic acid at a temperature of 50° C. at a rate of 60 rpm for 120 minutes, mixed and stirred, and the pH was adjusted to a range of 6.5.

Thereafter, the pH-adjusted emulsion solution was mixed with 100 parts by weight of polydimethylsiloxane represented by the following Formula 2-1 and 67 parts by weight of a nonionic (C11 to C15) secondary alcohol ethoxylate surfactant and 60 at a temperature of 50°C. Reaction, mixing, and stirring were performed for 240 minutes at a speed of rpm.

[Formula 2-1]

In the above formula, e is an integer of 57.

Thereafter, the emulsion solution in which the polydimethylsiloxane was mixed was reacted with 7 parts by weight of an additive at a rate of 40 rpm at a temperature of 50° C. for 120 minutes, mixed, and stirred to prepare a coating composition for artificial leather having excellent durability.

At this time, the additives are polyether-modified polysiloxane 48% by weight, cellulose alkyl ether (ethylcellulose) 47% by weight, ethoxylated fatty (C13) alcohol 3.4% by weight, alkylphosphonic acid represented by the following formula 3-1 One containing 0.8% by weight of the compound and 0.8% by weight of silicoaluminophosphate was used.

[Chemical Formula 3-1]

In the above formula, R ¹ is an ethyl group and x is 1.

At this time, the silicoaluminophosphate is dissolved 7 parts by weight of a block copolymer of polyethylene oxide and polypropylene oxide (the molar ratio of polyethylene oxide / polypropylene oxide is 1.1) in 100 parts by weight of ethanol to synthesize a first template solution. step; Dissolving 3 parts by weight of piperidine and 7 parts by weight of tetramethylammonium chloride (TMACl) in 100 parts by weight of distilled water to synthesize a second template solution; To 100 parts by weight of the mixed template solution obtained by mixing the first template solution and the second template solution in a ratio of 1: 3 by weight, sodium silicate, pseudo-bohemite, and triethyl phosphate were added at 77% by weight, 21, respectively. Preparing a hydration gel by mixing 45 parts by weight of the source mixture mixed in a content range of 2% by weight and 2% by weight; Stirring the prepared hydration gel for 12 hours at a temperature of 60° C. for aging, followed by stirring at a temperature of 190° C. for 35 hours to hydrothermal reaction to form a solid product; And sintering the obtained solid product at a temperature of 1000° C. for 3 hours at a heating rate of 1.5° C./min and then slowly cooling it.

<Example 2>

100 parts by weight of amino-modified polysiloxane represented by the following Formula 1-2 reacted with 50 parts by weight of a nonionic surfactant (polyoxyethylene alkyl ether) at a rate of 60 rpm at a temperature of 40° C. for 120 minutes, mixed, and stirred to emulsify The solution was prepared.

[Formula 1-2]

Wherein a is 75; b is 290; c is 3; d is 2.

Thereafter, the emulsion solution was reacted with 27 parts by weight of distilled water at a temperature of 40° C. at a rate of 60 rpm for 120 minutes, mixed, and stirred.

Thereafter, the emulsion solution in which the first distilled water was mixed was reacted with 83 parts by weight of distilled water at a temperature of 50° C. at a rate of 60 rpm for 120 minutes, followed by mixing and stirring.

Thereafter, the second-distilled water-mixed emulsion solution was reacted with 73 parts by weight of distilled water and 0.8 parts by weight of acid (acetic acid and lactic acid in a weight ratio of 1: 0.2) and reacted at a temperature of 50° C. at a rate of 60 rpm for 120 minutes and By mixing and stirring, the pH was adjusted to the range of 6.5.

Thereafter, the pH-adjusted emulsion solution was mixed with 100 parts by weight of polydimethylsiloxane represented by Formula 2-1 and 67 parts by weight of a nonionic (C11 to C15) secondary alcohol ethoxylate surfactant and 60 at a temperature of 50°C. Reaction, mixing and stirring were performed for 240 minutes at a speed of rpm.

Thereafter, the emulsion solution in which the polydimethylsiloxane was mixed was reacted with 7 parts by weight of an additive at a rate of 40 rpm at a temperature of 50° C. for 120 minutes, mixed, and stirred to prepare a coating composition for artificial leather having excellent durability.

At this time, the additives were the same as those used in Example 1.

<Comparative Example 1>

100 parts by weight of the amino-modified polysiloxane represented by the following Formula 1-3 reacted with 50 parts by weight of a nonionic surfactant (polyoxyethylene alkyl ether) at a rate of 60 rpm at 40° C. for 120 minutes, mixed, and stirred to emulsify. The solution was prepared.

[Formula 1-3]

Thereafter, the emulsion solution was reacted with 27 parts by weight of distilled water at a temperature of 40° C. at a rate of 60 rpm for 120 minutes, mixed, and stirred.

Thereafter, the emulsion solution in which the first distilled water was mixed was reacted with 83 parts by weight of distilled water at a temperature of 50° C. at a rate of 60 rpm for 120 minutes, followed by mixing and stirring.

Thereafter, the emulsion solution in which the secondary distilled water was mixed was reacted with 73 parts by weight of distilled water at a temperature of 50° C. at a speed of 60 rpm for 120 minutes, followed by mixing and stirring.

Thereafter, the pH-adjusted emulsion solution was reacted with 7 parts by weight of an additive and at a temperature of 50° C. at a rate of 40 rpm for 120 minutes, mixed, and stirred to prepare a comparative coating composition.

At this time, the additive was used to contain 49% by weight of polyether-modified polysiloxane, 47% by weight of cellulose alkyl ether (ethylcellulose), and 4% by weight of ethoxylated fatty (C13) alcohol.

<Test Example>

Emulsion stability evaluation

The coating composition prepared in Examples and Comparative Examples was allowed to stand for 2 months in a constant temperature state of 4°C, 40°C and 45°C and cycling conditions in which the temperature is changed twice a day to -4°C to 40°C to evaluate the separation state. Emulsion stability was tested, and the results are shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Remark Room temperature 1 month ○ ○ ○ ○: Good
△: Normal
×: Separation 2 months ○ ○ ○ 4℃ 1 month ○ ○ × 2 months ○ ○ × 40℃ 1 month ○ ○ ○ 2 months ○ ○ × 45℃ 1 month ○ ○ ○ 2 months ○ ○ × Cycling (-4℃ to 40℃ twice a day) 1 month ○ ○ ○ 2 months ○ ○ ×

As can be seen from the results of Table 1, it can be confirmed that the coating composition for artificial leather having excellent durability prepared in the Example of the present invention has excellent emulsion stability compared to the comparative coating composition prepared in Comparative Example. there was.

Pollution resistance evaluation

A test specimen was prepared by coating the coating composition prepared in the above Examples and Comparative Examples on the surface of the artificial leather having an apparent density of about 0.8 g/cm ^{3 and high density.} For the test specimen prepared above, the contamination test cloth (general ¹⁾ , denim ²⁾ was moved 100 mm at a speed of 30 times/min, and the degree of contamination was measured in gray scale after reciprocating 100 times with a load of 500gf (Grey scale, KSK 0910). ) Was judged as a grade, and the results are shown in Table 2 below. At this time, it was marked as "5th grade: no pollution, 3rd grade: normal, 2nd grade: with pollution".

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)

In addition, the actual image after performing the stain resistance evaluation on the artificial leather test specimen coated with the coating composition prepared in Example 2 and Comparative Example 1 is shown in FIG.

Example 1 Example 2 Comparative Example 1 General ¹⁾ 5 5 2 Denim ²⁾ 3 5 2

As can be seen from the results of Table 2 and FIG. 2, the coating composition for artificial leather having excellent durability prepared in the Example of the present invention has excellent stain resistance compared to the comparative coating composition prepared in Comparative Example. I could confirm that.

Wear resistance evaluation

A test specimen was prepared by coating the coating composition prepared in the above Examples and Comparative Examples on the surface of the artificial leather having an apparent density of about 0.8 g/cm ^{3 and high density.} For the test specimen prepared above, abrasion resistance was evaluated based on the point when the surface was peeled off when abrasion was performed more than 2,000 times with a friction wear wheel having a load of KG, and the results are shown in Table 3 below.

In addition, the actual image after performing abrasion resistance evaluation (abrasion 1000 times) for the artificial leather test specimen coated with the coating composition prepared in Example 2 and Comparative Example 1 is shown in FIG.

Example 1 Example 2 Comparative Example 1 Wear resistance (number of times) 2300 2700 800

As can be seen from the results of Table 3 and FIG. 3, the coating composition for artificial leather having excellent durability prepared in the Example of the present invention has excellent wear resistance compared to the comparative coating composition prepared in Comparative Example. I could confirm.

As described above, those skilled in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features thereof. Therefore, all of the embodiments described above are illustrative and should be understood as non-limiting. The scope of the present invention should be construed as including all changed or modified forms derived from the meaning and scope of the claims to be described later rather than the above detailed description, and equivalent concepts thereof.

Claims (5)

Reacting, mixing and stirring 100 parts by weight of an amino-modified polysiloxane represented by the following Formula 1 with 10 to 70 parts by weight of a nonionic surfactant for 50 to 150 minutes at a temperature of 35 to 45° C. to prepare an emulsion solution;
1st distilled water mixing step of reacting, mixing, and stirring the emulsion solution with 5 to 45 parts by weight of distilled water for 50 to 150 minutes at a temperature of 35 to 45 °C;
A second distilled water mixing step of reacting, mixing, and stirring the emulsion solution in which the first distilled water is mixed at 80 to 110 parts by weight of distilled water at a temperature of 40 to 60° C. for 50 to 150 minutes;
The second-distilled water-mixed emulsion solution was reacted with 60 to 90 parts by weight of distilled water and 0.1 to 5 parts by weight of acid and 40 to 60° C. for 50 to 150 minutes, mixed, and stirred to bring the pH to the range of 6 to 7 Adjusting the pH adjustment step;
The pH-adjusted emulsion solution is 80 to 130 parts by weight of polydimethylsiloxane represented by the following formula (2) and 60 to 100 parts by weight of a nonionic (C11 to C15) secondary alcohol ethoxylate surfactant and a temperature of 40 to 60°C. Polydimethylsiloxane mixing step of reacting, mixing, and stirring for 220 to 300 minutes at; And
Including an additive mixing step of reacting, mixing, and stirring the emulsion solution in which the polydimethylsiloxane is mixed with 1 to 20 parts by weight of an additive and at a temperature of 40 to 60° C. for 50 to 150 minutes,
The additives are polyether-modified polysiloxane 45 to 65% by weight, cellulose alkyl ether 30 to 50% by weight, ethoxylated fatty (C6 to C22) alcohol 1 to 5% by weight, alkylphosphonic acid represented by the following formula (3) A method for producing a coating composition for artificial leather having excellent durability, comprising 0.01 to 1% by weight of the compound and 0.01 to 1% by weight of silicoaluminophosphate.
[Formula 1]

In the above formula,
a and b are each independently an integer of 1 to 300,
c and d are each independently an integer of 1 to 12.
[Formula 2]

In the above formula,
e is an integer from 1 to 100.
[Formula 3]

In the above formula,
R ¹ is a linear or branched C1 to C4 alkyl group,
x is 0 or 1.
The method of claim 1,
The nonionic surfactant is one or more selected from the group consisting of polyoxyethylene alkyl ether, fatty acid sorbitan ester, fatty acid diethanolamine, alkyl monoglyceryl ether, and mixtures thereof;
The acid is at least one selected from the group consisting of acetic acid, lactic acid, citric acid, formic acid, nitric acid, glycolic acid, hypophosphorous acid, and mixtures thereof.
delete The method of claim 1,
The silicoaluminophosphate is
Synthesizing a first template solution by dissolving a block copolymer of polyethylene oxide and polypropylene oxide in an organic solvent containing alcohol;
Dissolving piperidine and tetramethylammonium chloride (TMACl) in distilled water to synthesize a second template solution;
Sodium silicate, pseudo-bohemite, and triethyl phosphate were respectively 50 to 80 parts by weight of 100 parts by weight of the mixed template solution obtained by mixing the first template solution and the second template solution in a ratio of 1: 2 to 5 by weight. Preparing a hydration gel by mixing 20 to 50 parts by weight of the source mixture mixed in a content range of weight%, 15 to 45% by weight and 1 to 10% by weight;
The prepared hydration gel is aged by stirring for 2 to 24 hours at a temperature of 30 to 90° C., and then stirred at a temperature of 150 to 200° C. for 5 to 48 hours to form a solid product by hydrothermal reaction; And
The obtained solid product is calcined at a temperature of 800 to 1000° C. for 1 to 5 hours at a temperature increase rate of 0.2 to 2° C./min and then slowly cooled. Method for producing a coating composition for leather.
A coating composition for artificial leather having excellent durability, characterized in that it is prepared from the method of manufacturing a coating composition for artificial leather having excellent durability according to any one of claims 1, 2 and 4.

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