KR20220170697A - Water dispersion composition for self healing coating - Google Patents

Abstract

The present invention relates to a water dispersion composition for self-healing coating. More specifically, the present invention relates to a water dispersion composition for self-healing coating, in which, when manufacturing a water dispersion composition for coating such as synthetic leather, by introducing a compound having a sulfone group, it is possible to impart a self-healing function to the coating layer so that scratches caused by external stimuli can be restored to their original state through heat treatment, and it is eco-friendly by not using volatile organic compounds.

Description

Water dispersion composition for self-healing coating {WATER DISPERSION COMPOSITION FOR SELF HEALING COATING}

The present invention not only allows the coating layer to have a self-healing function that allows scratches caused by external stimuli to be restored to their original state through heat treatment, but also provides an eco-friendly aqueous dispersion composition for self-healing coating without using volatile organic compounds. it's about

In general, substrates such as synthetic leather applied to various products such as uppers of shoes, bags, clothing, and furniture are scratched on the surface through external stimulation, which causes external contamination and degrades the value of the product.

In order to prevent this, a coating layer having scratch resistance is usually formed on a substrate such as synthetic leather. However, this coating layer has some effects of preventing scratches compared to a substrate on which no coating layer is formed, but once a scratch occurs, it cannot be recovered, so there is a problem in that the actual use efficiency is insufficient, and most of these coating layers are solvent-type. As a result, there are problems that cause worker's health and environmental pollution, such as emitting volatile organic compounds.

In order to solve this problem, in prior art Patent Document 1, a single molecule capable of polyhydrogen bonding is introduced at the end of a linear oligomer prepared using a polycaprolactone polymer, which is coated by melt coating or laminating on a fiber, fabric, or leather. The linear supramolecular sieve and the nonlinear supramolecular sieve equipped with a single molecule capable of polyhydrogen bonding at the end of the nonlinear oligomer prepared using the polycaprolactone polymer are mixed at a preset mixing ratio, and the linear supramolecular sieve and the nonlinear supramolecular sieve are at each end. A scratch self-healing fiber/fabric/leather coating agent characterized in that a supramolecular crosslinked product is formed by hydrogen bonding between the provided single molecules, and the mixing ratio is determined according to the number of motile points and crosslinking points of the chain. suggested.

Here, 'self-healing' refers to a function that can extend lifespan and recover physical properties by restoring the structure within the molecule itself, rather than passive repair when the structure of a material is destroyed or its physical properties are deteriorated due to external environmental factors. do.

However, in the case of Patent Document 1, there was a problem in that the expression efficiency of the actual self-healing performance was insufficient as it was not a self-healing in the molecular unit as a coating agent using a polycaprolactone polymer.

Patent Document 1: Republic of Korea Patent Registration No. 10-1906033 "Scratch self-healing fiber/fabric/leather coating agent"

The present invention is to solve the above problems, by introducing a compound having a sulfone group in the manufacture of a water dispersion composition for coating synthetic leather, etc., scratches caused by external stimuli through heat treatment An object of the present invention is to provide a water dispersion composition for self-healing coating that is environmentally friendly because it does not use volatile organic compounds and the like as well as imparts a self-healing function to the coating layer to restore it to its original state.

In the water dispersion composition of the present invention, based on 100 parts by weight of polyol or polyol mixture, 3.8 to 5.1 parts by weight of a compound having a sulfone group, 3.3 to 4.4 parts by weight of dimethylolpropionic acid and isophorone diisocyanate 24 to 33 parts by weight were mixed to prepare a polyurethane prepolymer, 2.5 to 3.4 parts by weight of triethylamine were reacted thereto, and 50 to 66 parts by weight of acetone and 315 to 340 parts by weight of water were added to prepare a polyurethane prepolymer. Dispersion and when the water dispersion is completed, 0.6 to 0.8 parts by weight of ethylenediamine are mixed and then acetone is removed to form a water dispersion composition for self-healing coating as a solution to the problem.

Here, the polyol uses poly(1,4-butanediol), and the polyol mixture contains 66 to 70% by weight of poly(1,4-butanediol) and polycarbonate diol ) 30 to 34% by weight, or 83 to 85% by weight of poly (1,4-butanediol) and 15 to 17% by weight of poly(dimethylsiloxane) bis (hydroxyalkyl) terminated It is preferable to use what consists of %.

On the other hand, the compound having a sulfone group is 2-hydroxy disulfide (2-Hydroxyethyl disulfide), 4-aminophenyl disulfide (4-Aminophenyl disulfide), 2,2'-diaminodiethyl disulfide dihydrochloride (2,2' -Diaminodiethyl disulfide dihydrochloride) or 3,3'-dihydroxydiphenyl disulfide (3,3'-Dihydroxydiphenyl disulfide) is preferably used.

The present invention not only has the effect of imparting a self-healing function to the coating layer to recover scratches caused by external stimuli to its original state through heat treatment, but also has an eco-friendly advantage because it does not use volatile organic compounds or the like.

1 is a real photograph of a test piece for confirming the self-healing effect for Examples and Comparative Examples of the present invention

The present invention to achieve the above effect relates to a water dispersion composition for self-healing coating, and only parts necessary for understanding the technical configuration of the present invention are described, and descriptions of other parts are omitted so as not to distract from the gist of the present invention. It should be noted that it will be

Hereinafter, the aqueous dispersion composition for self-healing coating according to the present invention will be described in detail.

The aqueous dispersion composition for self-healing coating according to the present invention contains 3.8 to 5.1 parts by weight of a compound having a sulfone group, 3.3 to 4.4 parts by weight of dimethylolpropionic acid and isophorone diisocyanate (with respect to 100 parts by weight of polyol or polyol mixture). 24 to 33 parts by weight of isophorone diisocyanate is mixed to prepare a polyurethane prepolymer, 2.5 to 3.4 parts by weight of triethylamine is reacted thereto, 50 to 66 parts by weight of acetone and 315 to 340 parts by weight of water After the water dispersion is completed, 0.6 to 0.8 parts by weight of ethylenediamine are mixed and then acetone is removed.

Here, the polyol uses poly(1,4-butanediol), and the polyol mixture contains 66 to 70% by weight of poly(1,4-butanediol) and polycarbonate diol ) 30 to 34% by weight, or 83 to 85% by weight of poly (1,4-butanediol) and 15 to 17% by weight of poly(dimethylsiloxane) bis (hydroxyalkyl) terminated % is used.

Here, if the content of each composition is out of the above range, there is a concern that the aqueous dispersion may not be properly prepared or workability may deteriorate.

On the other hand, the compound having a sulfone group is added to allow scratches caused by external stimuli to be restored to their original state through heat treatment, and more specifically, to have a disulfide bond in the water dispersion.

That is, since the disulfide bond has a molecular unit self-healing function through chain exchange with adjacent atoms when damaged, the self-healing function is imparted by applying a compound having a sulfone group as described above.

To this end, the compound having a sulfone group is 2-hydroxyethyl disulfide, 4-aminophenyl disulfide, 2,2'-diaminodiethyl disulfide dihydrochloride (2,2' -Diaminodiethyl disulfide dihydrochloride) or 3,3'-dihydroxydiphenyl disulfide (3,3'-Dihydroxydiphenyl disulfide) can be used, and if the content is less than 7.7 parts by weight, self-healing function may not be properly implemented, , If it exceeds 8.7 parts by weight, there is a concern that the physical properties of the water dispersion composition may deteriorate.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited by the examples.

1. Preparation of water dispersion composition

(Comparative Example 1)

A thermometer, stirrer, and reflux condenser were installed in a three-necked reactor, and 100 parts by weight of poly(1,4-butanediol) (Poly(1,4-butanediol), Aldrich, Mw=2,000) was completely dissolved at 85° C. and then stirred for 1 hour. Water is removed under reduced pressure over Thereafter, 3.1 parts by weight of dimethylolpropionic acid (Aldrich) was added and stirred for 30 minutes under a nitrogen stream. Then, 14.8 parts by weight of isophorone diisocyanate (Aldrich) was added dropwise for an hour and a half and reacted at 85 ° C until the NCO value reached 4.5 to 5% to prepare a polyurethane prepolymer. Next, the temperature was lowered to 65 ° C., and 2.3 parts by weight of triethylamine (Triethylamine, Junsei) was added and stirred for 30 minutes under a nitrogen stream. At this time, the increased viscosity was adjusted by adding 33 parts by weight of acetone (Acetone, Samchun chem.). Thereafter, the temperature of the reactant is lowered to 40° C. or less, and 283 parts by weight of water is slowly added while stirring at high speed to disperse the mixture in water. When the water dispersion is completed, 0.6 parts by weight of ethylenediamine (Ethylenediamine, Junsei) is dissolved in a small amount of water, added dropwise over 30 minutes, further stirred, and the reaction is terminated after confirming the complete disappearance of NCO using FT-IR. Finally, the final polyurethane water dispersion is obtained by removing residual acetone using an evaporator. The prepared polyurethane water dispersion had a solid content of 30.2% and a viscosity of 5,025 cps. (Brookfield, DV-II+, LV Spindle 64).

(Example 1)

A thermometer, stirrer, and reflux condenser were installed in a three-necked reactor, and 100 parts by weight of poly(1,4-butanediol) (Poly(1,4-butanediol), Aldrich, Mw=2,000) was completely dissolved at 85° C. and then stirred for 1 hour. Water is removed under reduced pressure over Then, after lowering the temperature to 65°C, 3.8 parts by weight of 2-hydroxyethyl disulfide (Aldrich) was added and stirred for 1 hour under a nitrogen stream, and then 3.3 parts by weight of dimethylolpropionic acid (Aldrich) was added and stirred under a nitrogen stream. Stir for an additional 1 hour. Then, 24 parts by weight of isophorone diisocyanate (Aldrich) was added dropwise at 65° C. for an hour and a half, and the mixture was raised to 85° C. and aged for 3 hours to prepare a polyurethane prepolymer. Then, the temperature was lowered to 65 ° C., and 2.5 parts by weight of triethylamine (Triethylamine, Junsei) was added and stirred for 30 minutes under a nitrogen stream. At this time, the increased viscosity was adjusted by adding 50 parts by weight of acetone (Acetone, Samchun chem.). Thereafter, the temperature of the reactant is lowered to 40° C. or less, and 315 parts by weight of water is gradually added while stirring at high speed to disperse the mixture in water. When the water dispersion is completed, 0.6 parts by weight of ethylenediamine (Ethylenediamine, Junsei) is dissolved in a small amount of water, added dropwise over 30 minutes, further stirred, and the reaction is terminated after confirming the complete disappearance of NCO using FT-IR. Finally, the final polyurethane water dispersion is obtained by removing residual acetone using an evaporator. The prepared polyurethane water dispersion had a solid content of 30.9% and a viscosity of 60 cps. (Brookfield, DV-II+, LV Spindle 64).

(Example 2)

A thermometer, stirrer, and reflux condenser were installed in a three-neck reactor, and 85% by weight of poly(1,4-butanediol) (Poly(1,4-butanediol), Aldrich, Mw = 2,000) and poly(1,4-butanediol) (Poly (1,4-butanediol), Aldrich, Mw = 1,000) 100 parts by weight of polyol consisting of 15% by weight was completely dissolved at 85 ° C, and then water was removed under reduced pressure for 1 hour. Then, after lowering the temperature to 65° C., 4.4 parts by weight of 2-hydroxyethyl disulfide (Aldrich) was added and stirred for 1 hour under a nitrogen stream, and then 3.8 parts by weight of dimethylolpropionic acid (Aldrich) was added and stirred under a nitrogen stream. Stir for an additional 1 hour. Then, 27 parts by weight of isophorone diisocyanate (Aldrich) was added dropwise at 65° C. for an hour and a half, and the mixture was raised to 85° C. and aged for 3 hours to prepare a polyurethane prepolymer. Then, the temperature was lowered to 65 ° C., and 2.9 parts by weight of triethylamine (Triethylamine, Junsei) was added and stirred for 30 minutes under a nitrogen stream. At this time, the increased viscosity was adjusted by adding 57 parts by weight of acetone (Acetone, Samchun chem.). Thereafter, the temperature of the reactant is lowered to 40° C. or lower, and 325 parts by weight of water is slowly added while stirring at high speed to disperse the mixture in water. When the water dispersion is completed, 0.6 parts by weight of ethylenediamine (Ethylenediamine, Junsei) is dissolved in a small amount of water, added dropwise over 30 minutes, further stirred, and the reaction is terminated after confirming the complete disappearance of NCO using FT-IR. Finally, the final polyurethane water dispersion is obtained by removing residual acetone using an evaporator. The prepared polyurethane water dispersion had a solid content of 30.5% and a viscosity of 150 cps. (Brookfield, DV-II+, LV Spindle 64).

(Example 3)

A thermometer, stirrer, and reflux condenser were installed in a three-necked reactor, and poly(1,4-butanediol) (Poly(1,4-butanediol), Aldrich, Mw = 2,000) 66% by weight and polycarbonate diol, Needfil: T6001, Mw = 1,000) 100 parts by weight of a polyol mixture composed of 34% by weight was completely dissolved at 85° C., and then water was removed under reduced pressure for 1 hour. Thereafter, after lowering the temperature to 65° C., 5.1 parts by weight of 2-hydroxyethyl disulfide (Aldrich) was added and stirred for 1 hour under a nitrogen stream, and then 4.4 parts by weight of dimethylolpropionic acid (Aldrich) was added and stirred under a nitrogen stream. Stir for an additional 1 hour. Then, 33 parts by weight of isophorone diisocyanate (Aldrich) was added dropwise at 65° C. for an hour and a half, and the mixture was raised to 85° C. and aged for 3 hours to prepare a polyurethane prepolymer. Then, the temperature was lowered to 65 ° C., and 3.4 parts by weight of triethylamine (Triethylamine, Junsei) was added and stirred for 30 minutes under a nitrogen stream. At this time, the increased viscosity was adjusted by adding 66 parts by weight of acetone (Acetone, Samchun chem.). Thereafter, the temperature of the reactant is lowered to 40° C. or less, and 340 parts by weight of water is slowly added while stirring at high speed to disperse the mixture in water. When the water dispersion is completed, 0.8 parts by weight of ethylenediamine (Ethylenediamine, Junsei) is dissolved in a small amount of water, added dropwise over 30 minutes, further stirred, and the reaction is terminated after confirming the complete disappearance of NCO using FT-IR. Finally, the final polyurethane water dispersion is obtained by removing residual acetone using an evaporator. The prepared polyurethane water dispersion had a solid content of 30.5% and a viscosity of 470 cps. (Brookfield, DV-II+, LV Spindle 64).

(Example 4)

A thermometer, stirrer, and reflux condenser were installed in a three-necked reactor, and 66% by weight of poly(1,4-butanediol) (Poly(1,4-butanediol), Aldrich, Mw = 2,000) and poly(1,4-butanediol) (Poly (1,4-butanediol), Aldrich, Mw = 1,000) 100 parts by weight of polyol consisting of 34% by weight was completely dissolved at 85 ° C, and then water was removed under reduced pressure for 1 hour. Thereafter, after lowering the temperature to 65° C., 5.1 parts by weight of 2-hydroxyethyl disulfide (Aldrich) was added and stirred for 1 hour under a nitrogen stream, and then 4.4 parts by weight of dimethylolpropionic acid (Aldrich) was added and stirred under a nitrogen stream. Stir for an additional 1 hour. Then, 33 parts by weight of isophorone diisocyanate (Aldrich) was added dropwise at 65° C. for an hour and a half, and the mixture was raised to 85° C. and aged for 3 hours to prepare a polyurethane prepolymer. Then, the temperature was lowered to 65 ° C., and 3.4 parts by weight of triethylamine (Triethylamine, Junsei) was added and stirred for 30 minutes under a nitrogen stream. At this time, the increased viscosity was adjusted by adding 66 parts by weight of acetone (Acetone, Samchun chem.). Thereafter, the temperature of the reactant is lowered to 40° C. or less, and 340 parts by weight of water is slowly added while stirring at high speed to disperse the mixture in water. When the water dispersion is completed, 0.8 parts by weight of ethylenediamine (Ethylenediamine, Junsei) is dissolved in a small amount of water, added dropwise over 30 minutes, further stirred, and the reaction is terminated after confirming the complete disappearance of NCO using FT-IR. Finally, the final polyurethane water dispersion is obtained by removing residual acetone using an evaporator. The solid content of the prepared polyurethane water dispersion was 32.4% and the viscosity was 8,210 cps. (Brookfield, DV-II+, LV Spindle 64).

(Example 5)

A thermometer, stirrer, and reflux condenser were installed in a three-neck reactor, and 55% by weight of poly(1,4-butanediol) (Poly(1,4-butanediol), Aldrich, Mw = 2,000) and poly(1,4-butanediol) (Poly (1,4-butanediol), Aldrich, Mw = 1,000) 28% by weight and polydimethylsiloxane bishydroxyalkylterminated (Poly (dimethylsiloxane) bis (hydroxyalkyl) terminated, Aldrich) Polyol mixture consisting of 17% by weight 100 parts by weight of the mixture was completely dissolved at 85° C., and then water was removed under reduced pressure over 1 hour. Then, after lowering the temperature to 65 ° C, 4.5 parts by weight of 4-Aminophenyl disulfide (Aldrich) was added and stirred for 1 hour under a nitrogen stream, and then 3.9 parts by weight of dimethylolpropionic acid (Aldrich) was added and stirred under a nitrogen stream. Stir for an additional 1 hour. Then, 29 parts by weight of isophorone diisocyanate (Aldrich) was added dropwise at 65° C. for an hour and a half, and the mixture was raised to 85° C. and aged for 3 hours to prepare a polyurethane prepolymer. Then, the temperature was lowered to 65 ° C., and 2.9 parts by weight of triethylamine (Triethylamine, Junsei) was added and stirred for 30 minutes under a nitrogen stream. At this time, the increased viscosity was adjusted by adding 59 parts by weight of acetone (Acetone, Samchun chem.). Thereafter, the temperature of the reactant is lowered to 40° C. or less, and 328 parts by weight of water is slowly added while stirring at high speed to disperse the mixture in water. When the water dispersion is completed, 0.7 parts by weight of ethylenediamine (Ethylenediamine, Junsei) is dissolved in a small amount of water and added dropwise over 30 minutes, followed by additional stirring, and after confirming the complete disappearance of NCO using FT-IR, the reaction is terminated. Finally, the final polyurethane water dispersion is obtained by removing residual acetone using an evaporator. The solid content of the prepared polyurethane water dispersion was 31.6% and the viscosity was 2,580 cps. (Brookfield, DV-II+, LV Spindle 64).

2. Evaluation of water dispersion composition

(1) Self-healing effect

In order to confirm the self-healing effect, the aqueous dispersion compositions of Comparative Example 1 and Examples 1 to 5 were prepared into films, cut, and heat-treated in an oven at a constant temperature to confirm the self-healing effect. The results are shown in FIG. was

(2) strength recovery rate (%)

In order to confirm the recovery rate of the self-healing resin, the water dispersion compositions of Comparative Example 1 and Examples 1 to 5 were prepared into films, and then the initial tensile strength and the tensile strength after self-healing were measured, and the following [Equation 1 The recovery rate was calculated by ], and the results are shown in [Table 1] below.

[Equation 1]

Here, the initial tensile strength was measured after making the water dispersion composition into a film, and the tensile strength after self-healing was measured after cutting the film, Examples 1 to 3 at 70 degrees for 2 hours, Examples 4 to 5 measured the tensile strength of the self-healing film after treatment at 90 degrees for 2 hours. Tensile strength was measured using UTM (DTU-900MHA) at a cross-head speed of 200 mm/min, and a total of 5 specimens were measured, and the average value was recorded.

division comparative example
One Example
One Example
2 Example
3 Example
4 Example
5 Seal
robbery
(kg/cm2) before self healing 3.15 1.03 2.11 1.15 1.14 1.65 after self healing - 0.95 2.12 0.91 1.17 1.66 Strength recovery rate (%) 0 92.2 100.5 79.1 102.6 100.6

As shown in Figure 1 and [Table 1], it can be seen that the examples according to the present invention are environmentally friendly because they do not use volatile organic compounds, etc., and have excellent self-healing effect and strength recovery rate compared to the comparative examples.

As described above, the aqueous dispersion composition for self-healing coating according to a preferred embodiment of the present invention has been described according to the above description and drawings, but this is only an example and various variations within the scope of the technical idea of the present invention have been described. It will be appreciated by those skilled in the art that variations and modifications are possible.

Claims (3)

In the water dispersion composition,
Based on 100 parts by weight of polyol or polyol mixture, 3.8 to 5.1 parts by weight of a compound having a sulfone group, 3.3 to 4.4 parts by weight of dimethylolpropionic acid, and 24 to 33 parts by weight of isophorone diisocyanate are mixed to make polyurethane. After preparing a prepolymer, reacting 2.5 to 3.4 parts by weight of triethylamine therein, adding 50 to 66 parts by weight of acetone and 315 to 340 parts by weight of water to disperse the water, and when the water dispersion is completed, ethylene A water dispersion composition for self-healing coating, characterized in that it is formed by mixing 0.6 to 0.8 parts by weight of diamine (Ethylenediamine) and then removing acetone.
According to claim 1,
The polyol uses poly(1,4-butanediol) (Poly(1,4-butanediol),
The polyol mixture consists of 66 to 70% by weight of poly(1,4-butanediol) and 30 to 34% by weight of polycarbonate diol, or 83 to 85% by weight of poly(1,4-butanediol) and polycarbonate diol. An aqueous dispersion composition for self-healing coating, characterized by using 15 to 17% by weight of dimethylsiloxane bishydroxyalkylterminated (Poly (dimethylsiloxane) bis (hydroxyalkyl) terminated).
According to claim 1,
The compound having the sulfone group,
2-hydroxyethyl disulfide, 4-aminophenyl disulfide, 2,2'-diaminodiethyl disulfide dihydrochloride, or 3, A water dispersion composition for self-healing coating, characterized in that it is 3'-dihydroxydiphenyl disulfide (3,3'-Dihydroxydiphenyl disulfide).

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