KR100397469B1 - Dye Additive Composition for Improving Dyeability of Polyurethane Fiber and Synthetic Leather and Method of Preparing the Same - Google Patents

Abstract

The present invention is a polymerization composition in which a diisocyanate compound and an N-substituted ethanolamine are polymerized in a solvent, and 20 to 40% by weight of a diisocyanate compound and 5 to 5% by weight in a solvent of 40 to 70% by weight based on the total additive composition. It relates to a composition produced by polymerizing 30% by weight of N-substituted ethanolamine in the presence of a trace amount of catalyst and completing the polymerization with 0.1 to 10% by weight of reaction terminator. In the polyurethane additive composition according to the present invention, the solvent and the diisocyanate compound are added to the reaction tank and stirred while the temperature is raised to 50-80 ° C., a small amount of the catalyst is dissolved in the solvent, and the reaction mixture is added to the reaction tank at 50-80 ° C. N-substituted ethanolamine is dissolved in a solvent, added to the reactor for polymerization for 60 to 300 minutes, and a reaction terminator is dissolved in a solvent and added to the reactor to prepare a polymerization reaction.

Description

Dye Additive Composition for Improving Dyeability of Polyurethane Fiber and Synthetic Leather and Method of Preparing the Same}

Field of invention

The present invention relates to a dye additive composition capable of improving the dyeing properties of polyurethane fibers and synthetic leather. More specifically, the present invention relates to a dye additive composition which is capable of improving the dyeing properties of polyurethane fibers and synthetic leather as a polymerization composition formed by polymerizing a diisocyanate compound and N-substituted ethanolamine in a solvent. The present invention also provides a method for producing the dye additive composition.

Background of the Invention

Polyurethane has excellent whiteness, gripping force (1.8 times rubber), tear strength (double rubber), burst strength and elasticity, and is mainly used for materials such as synthetic leather, women's foundation, swimwear and gym clothes. .

However, polyurethane, which is widely used as a raw material such as synthetic leather and spandex, is poor in dyeability, and is easily deteriorated by heat or light (ultraviolet rays) as compared to fibers such as nylon or polyester, and thus, nitrogen oxides in the air ( There is a defect that discolors easily by NOx).

As a result, various dyeing additives have been developed and used for the purpose of improving the dyeing properties of polyurethane fibers and synthetic leather. However, dyeing fastness or compatibility with other additives is lowered, which leads to many problems related to product quality. It has caused. In addition, many studies have been conducted to solve these problems because of poor compatibility with UV stabilizers such as antioxidants or HALS (hindered amine light stabilizer) added for the purpose of antioxidant.

U.S. Patent No. 2,999,839 discloses a polyurethane additive that is stable to ultraviolet rays and smoke using a methacrylate polymer having a molecular weight of 280 or more, but it cannot overcome the decrease in the fastness of fibers due to chlorine bleaching.

In British Patent No. 1,104,127, hindered methacrylate was used to overcome the problems of the above-mentioned US patent, but the lowering of the fastness of the fiber could not be solved.

Therefore, the present inventors use a composition prepared by polymerizing a diisocyanate compound and N-substituted ethanolamine to overcome the drawbacks of the conventional polyurethane fiber and the dyeing additive of synthetic leather as described above. It is to develop an additive composition that improves the stability of dyeing products, and has excellent dyeing fastness, and excellent compatibility with additives such as antioxidants and UV stabilizers, as well as anti-oxidation effect and stability against UV, NOx and heat. . In addition, since the additive polymerization composition of the present invention is in a liquid phase, it is easy to use because of its good solubility.

An object of the present invention is to provide a dye additive polymerization composition that can improve the dyeing properties of polyurethane fibers and synthetic leather.

Another object of the present invention is to provide a dye additive polymerization composition which can improve the dyeing fastness of polyurethane fibers and synthetic leather products.

It is still another object of the present invention to provide a dye additive polymerization composition having good compatibility with polyurethane and additives added to prevent oxidation and stability against UV, NOx and heat.

Still another object of the present invention is to provide a dye additive polymerization composition which is easy to use because it is in a liquid state and has good solubility.

Another object of the present invention is to provide a method for producing a dye additive polymerization composition of the polyurethane.

The above and other objects of the present invention can all be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.

The present invention is a polymerization composition formed by polymerizing a diisocyanate compound and an N-substituted ethanolamine in a solvent, wherein the diisocyanate compound is contained in an amount of 20 to 40% by weight in a solvent of 40 to 70% by weight based on the total additive composition. To 30% by weight of N-substituted ethanolamine is polymerized in the presence of a trace amount of catalyst and 0.1 to 10% by weight of the reaction terminator is used to complete the polymerization reaction.

In the polyurethane additive composition according to the present invention, a solvent and a diisocyanate compound are added to a reaction tank and stirred while the temperature is raised to 50-80 ° C., a small amount of catalyst is dissolved in a solvent, and the reaction mixture is added to the reaction tank at 50-80 ° C. The N-substituted ethanolamine is dissolved in a solvent, added to the reaction tank for polymerization for 60 to 300 minutes, and the reaction terminator is dissolved in the solvent and added to the reaction tank to prepare a polymerization reaction.

The present invention is a polymerization composition obtained by polymerizing a diisocyanate compound and N-substituted ethanolamine in a solvent. Solvents usable in the present invention include dimethylacetamide and dimethylformamide. The solvent is preferably maintained in the range of 40 to 70% by weight in the total composition.

The diisocyanate compound used in the present invention includes hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, paraphenylene diisocyanate and the like. The diisocyanate compound is preferably maintained in the range of 20 to 40% by weight in the total composition. The diisocyanate compound is polymerized with the N-substituted ethanolamine to form a polymer.

N-substituted ethanolamines used in the present invention include N-methyl ethanolamine, N-propyl ethanolamine, N-methyl diethanolamine, N, N-dimethyl ethanolamine, N, N-diethyl ethanolamine, and the like. . N-substituted ethanolamine is preferably maintained in the range of 5 to 30% by weight in the total composition.

A small amount of catalyst is used to polymerize the diisocyanate compound and N-substituted ethanolamine. In the present invention, diacetate containing tin or lead can be used as the catalyst.

Reaction terminators for terminating the polymerization reaction of the diisocyanate compound and N-substituted ethanolamine include monoethylamine, diethylamine, triethyl triamine, diethyleneamine, triethylene diamine, monoethanolamine, diethanolamine, Triethanolamine, N-butylamine, dimethyl hydrazine, N-methyl hydrazine, Nt-butyl diethanolamine and the like. It is preferable to use the reaction terminator in the range of 0.1-10 weight% in the whole composition.

In order to prepare the polyurethane additive composition according to the present invention, the water in the reactor is first removed and purged with nitrogen. The solvent and the diisocyanate compound are added to the reaction tank and stirred while the temperature is raised to 50-80 ° C. A small amount of catalyst was dissolved in a solvent and introduced into the reactor at 50-80 ° C. N-substituted ethanolamine is dissolved in a solvent, added to the reactor, and polymerized for 60 to 300 minutes. The reaction terminator is dissolved in a solvent, added to the reactor, and the polymerization reaction is terminated after 60 to 300 minutes.

In addition, the polyurethane additive composition of the present invention is used together with additives to impart anti-oxidation or stability to UV, NOx and heat of urethane fibers and synthetic leather. Polyurethane additive composition of the present invention is very compatible with these additives, so that the anti-oxidation, stability to UV or NOx is increased together. That is, the polyurethane additive composition of the present invention not only overcomes the decrease in the fastness of the fiber due to the addition of the additive, but also improves the vulnerability to UV or NOx, which is a disadvantage of the urethane-based polymer.

Preferred additives added in order to prevent the oxidation or to provide stability against ultraviolet rays, NOx and heat include 1,1,1 ', 1'-tetramethyl-4,4'-(methylene-di-p-phenylene) di Semicarbazide (CAS No. 85095-61-0), 1,3,5-tris (4-t-butyl-3-hydroxy-3,6-dimethylbenzyl) 1,3,5-triazine-2, 4,6- (1H, 3H, 5H) trione, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methyl-phenyl) propionate (CAS No. 36443-68- 2), 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chloro-benzotriazole (CAS No. 3864-99-1), 2- (2-hydroxy Hydroxy-3,5, -di-tert-amyl-phenyl) benzotriazole (CAS No. 25973-55-1) is mentioned.

In addition, when the hindered phenolic antioxidant represented by the following structural formula is added to the urethane fiber and the synthetic leather, the stability against NOx and heat is significantly improved.

The present invention will be further illustrated by the following examples, which are only described for the purpose of illustrating the present invention and are not intended to limit the protection scope of the present invention.

Example 1

20 parts by weight of dimethylacetamide (DMAC) and 30 parts by weight of hexamethylene diisocyanate were added to a reaction tank purged with nitrogen, and stirred while raising the temperature to 50-80 ° C. A metal diacetate containing a trace amount of tin was dissolved in 5 parts by weight of dimethylacetamide and introduced into the reactor at 50-80 ° C. 17 parts by weight of N-methyl ethanolamine was dissolved in 15 parts by weight of dimethylacetamide, and introduced into the reactor, followed by polymerization for about 200 minutes. 3 parts by weight of monoethylamine was dissolved in 10 parts by weight of dimethylacetamide, added to the reactor, and after about 200 minutes, the reaction was terminated to prepare an additive polymerization composition.

The polymerization composition of Example 1 is 50% by weight of the polymer except for the solvent, that is, the composition is 50% by weight of solidity (solidity). Physical properties prepared according to this example are shown in Table 1 below.

Example 2

25 parts by weight of dimethylacetamide (DMAC) and 20 parts by weight of hexamethylene diisocyanate were added to the reaction tank purged with nitrogen and stirred while raising the temperature to 50-80 ° C. Metal diacetate containing a trace amount of tin was dissolved in 8 parts by weight of dimethylacetamide and introduced into the reactor at 50-80 ° C. 12 parts by weight of N-methyl ethanolamine was dissolved in 25 parts by weight of dimethylacetamide, and introduced into the reactor, followed by polymerization for about 200 minutes. 3 parts by weight of monoethylamine was dissolved in 7 parts by weight of dimethylacetamide, added to the reactor, and after about 200 minutes, the reaction was terminated to prepare an additive polymerization composition.

The polymerization composition of Example 2 is 35% by weight of the polymer except for the solvent, that is, a composition having a solidity of 35% by weight. Physical properties prepared according to this example are shown in Table 1 below.

Example 1 Example 2 color Pale yellow Pale yellow Moisture content 0.002% or less 0.002% or less water 99.9% or more 99.9% or more Solid components 50% 35% condition Transparent liquid Transparent liquid Viscosity 2,000-5,000 cps 30-80 cps

Table 2 shows a comparison result of the stability against UV with time when the polymerization composition of the present invention is used and when it is not used. Example 3 uses the polymerization composition prepared in Example 1 together with the antioxidant, and Comparative Example is a case where only the antioxidant is used without using the polymerization composition of the present invention.

Yellow index White index 0 hours 72 hours 144 hours 288 hours 0 hours 72 hours 144 hours 288 hours Example 3 0.0 5.5 8.7 15.3 0.0 -15.4 -25.4 -44.8 Comparative Example 0.0 8.5 9.4 29.4 0.0 -22.9 -27.3 -96.4

As shown in Example 3 and Comparative Example 2, it can be seen that in the case of using the dyeing additive composition of the present invention, the change in the color index over time is much less than in the comparative example. Therefore, the dye additive composition of the present invention was found to increase with the effect of stability to UV when used with antioxidants.

In addition, the comparison results of the stability of the NOx gas with and without the polymerization composition of the present invention are shown in Table 3 below.

Yellow index White index Before exposure Post-exposure result Before exposure Post-exposure result Example 3 1.98 5.81 3.83 68.1 56.8 -11.3 Comparative Example 7.03 12.88 5.85 57.3 37.9 -19.4

As shown in Example 3 and Comparative Example of Table 3, it can be seen that when using the dye additive composition of the present invention, the change in color index before and after exposure is much more relaxed than in Comparative Example. That is, when the dye additive composition of the present invention is used with an antioxidant, it was found that the effect of stability on the NOx gas was accompanied.

As a result of the experiment, it was found that the use of the dye additive composition of the present invention with the antioxidant is more stable against UV and NOx than when using only the antioxidant. In addition, the dye additive polymerization composition of the present invention is in a liquid state, and has a good solubility and is easy to use.

The present invention can improve the dyeing properties of polyurethane fibers and synthetic leather, improve the dyeing fastness of polyurethane products, and is compatible with additives added to prevent oxidation and stability against UV, NOx and heat. It has the effect of the invention to be excellent to provide a dye additive polymerization composition having improved antioxidant and stability against UV and NOx.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (6)

Polymerization composition obtained by polymerizing diisocyanate compound and N-substituted ethanolamine in dimethylacetamide or dimethylformamide solvent, 20-40% by weight of diisocyanate in 40-70% by weight of the solvent based on the total additive composition. Polyurethane fiber, which is produced by polymerizing 5-30% by weight of N-substituted ethanolamine to a system compound in the presence of a diacetate catalyst and completing the polymerization using 0.1 to 10% by weight of a reaction terminator. And a dye additive composition for improving dyeability of synthetic leather. The polyurethane fiber according to claim 1, wherein the diisocyanate compound is selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, 1,5 to naphthalene diisocyanate, and paraphenylene diisocyanate. Dye additive composition for improving the dyeability of synthetic leather. According to claim 1, wherein the N-substituted ethanolamine is N-methyl ethanolamine, N-propyl ethanolamine, N-methyl diethanolamine, N, N-dimethyl ethanolamine, and N, N-diethyl ethanolamine A dye additive composition for improving the dyeability of polyurethane fibers and synthetic leather, characterized in that it is selected from the group consisting of. The method of claim 1, wherein the reaction terminator is monoethylamine, diethylamine, triethyl triamine, diethyleneamine, triethylene diamine, monoethanolamine, diethanolamine, triethanolamine, N-butylamine, dimethyl hydrazine , N-methyl hydrazine, and Nt- butyl diethanolamine selected from the group consisting of a dye additive composition for improving the dyeability of polyurethane fibers and synthetic leather. The dye additive composition of claim 1, wherein the diacetate-based catalyst is a tin diacetate-containing metal diacetate. In a dimethylacetamide or dimethylformamide solvent, a diisocyanate compound was added to a reaction tank and stirred while the temperature was raised to 50-80 ° C. A small amount of catalyst was dissolved in a solvent, and the reaction mixture was charged at 50-80 ° C. N-substituted ethanolamine is dissolved in a solvent and added to the reactor for polymerization for 60 to 300 minutes, and the reaction terminator is dissolved in a solvent and added to the reactor to produce a polymerization reaction. The manufacturing method of the dye additive composition which improved the dyeing property of the polyurethane fiber and synthetic leather.