KR0129113B1 - Process for making composition of polyurethan resin haring improved - Google Patents

Abstract

Title additive comprises; 1)organic diisocyanates selected from aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, aliphatic diisocyanate such as 1,6-hexamethylene diisocyanate, alicyclic diisocyanate such as isophorone diisocyanate, bis-(4-diisocyanate cyclohexyl)-methane, 2)a lower molecular diol such as N-methyldiethanolamine containing tertiary nitrogen atom, 3-dimethylamino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 3) 10-90% (based on the total weight of the composition) of any organic solvent for polyurethane. Polyurethane having excellent dyeabilities was prepared by mixing polyurenthane resin solution used nitrogen-free lower molecular diol as a chain extender and title additive.

Description

Method for producing polyurethane resin composition with improved dyeability

The present invention relates to a method for producing a polyurethane resin composition with improved dyeability, and more specifically, it is possible to improve dyeing properties without bringing down the physical properties such as elasticity and softness of polyurethane, and to mix it with a polyurethane resin solution. It relates to a method for producing a polyurethane resin composition.

As a general technique for improving the dyeability of polyurethanes used in the manufacture of artificial leather, spandex and the like, 1) a method of introducing a tertiary nitrogen atom into a polyurethane polymer chain (Japanese Patent Publication 62-23097), 2) A method of introducing a salt of an organic acid or an inorganic acid and a tertiary amine into a polyurethane polymer chain (Japanese Patent Publication 75-17520), 3) introducing a tertiary or quaternary nitrogen atom to the terminal of the polyurethane polymer chain. Methods (Japanese Patent Publication 69-16386), 4) a method of using a low molecular diamine as a chain extender (Japanese Laid-Open Patent Publication No. 59-108021), and the like.

However, methods 1) and 2) tend to become gels during the reaction, and method 3) has a problem that it is difficult to control the amount of nitrogen atoms introduced. In addition, method 4) using a low molecular weight diamine as a chain extender may improve dyeing property, but has a problem of lowering softness and elasticity.

In addition, in the prior art (Application No. 93-9904, name of the invention: Polyurethane resin composition with improved dyeability), organic diisocyanate, high molecular diol, low molecular diol containing no nitrogen, high molecular triol, organic solvent Although the above problems have been partially compensated by synthesizing polyurethane by injecting a low molecular diol containing nitrogen atoms into the resin, in order to improve dyeing property, when a certain amount of a low molecular diol containing nitrogen atoms is added, a decrease in physical properties is caused. There was a difficulty in sufficiently improving the dyeability of polyurethane. These problems arise because of the fact that nitrogen atoms are present in the polyurethane polymer chain.

Therefore, the inventors of the present invention have studied to solve the above problems, and when a separate preparation of a material containing a nitrogen atom that leads to the improvement of dyeability, mixed with a polyurethane resin solution containing no nitrogen atom, the nitrogen atom is a polyurethane polymerization Since it exists outside the chain, it was found that the physical properties and dyeing properties can be improved at the same time.

That is, an object of the present invention is to provide a method for producing a polyurethane resin composition that can improve dyeing properties without bringing a general decrease in physical properties, and a low molecular diol containing an organic diisocyanate, a tertiary nitrogen atom, and An additive consisting of an organic solvent is first prepared, and then mixed with a polyurethane resin solution prepared using a low molecular diol having no nitrogen atom as a chain extender.

The content of the present invention will be described in detail as follows.

The organic diisocyanate used in the additive of the present invention is generally used 4,4-diphenylmethane diisocyanate, aromatic diisocyanate including toluene diisocyanate and aliphatic diisocyanate including 1,6-hexamethylene diisocyanate, and It is optionally used among alicyclic diisocyanates including isophorone diisocyanate, bis- (4-diisocyanatocyclohexyl) -methane. The number of moles of the organic diisocyanate is 0.5X to 1.0X when the number of moles of the low molecular diol containing nitrogen atoms is X.

In addition, as a low molecular diol containing a tertiary nitrogen atom having a molecular weight of 300 or less, the number of carbons present in the chain directly connecting the two groups is two or more, and at least one of the three groups linked to the nitrogen atom is a methyl group or a butyl group. In the case where a nitrogen atom is included in the substituted structure, a methyl group may be used. Use of a different structure results in lowered physical properties. Low molecular diols having such a structure include N-methyl diethanolamine, N-butyl diethanolamine, 3-dimethylamino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, and the like. Most preferred is N-methyldiethanolamine having good dyeability and general physical properties.

Any organic solvent can be used as the organic solvent used in the present invention, but the amount of the solvent is 10 to 90% by weight based on the total composition.

By using the above-mentioned materials presented in the present invention to prepare a polyurethane participant and mixed with the polyurethane resin solution, it is possible to produce a polyurethane with improved dyeing properties without bringing down the physical properties.

Examples and comparative examples of the present invention are as follows.

Example 1

The additives were synthesized by using a raw material of the additive as shown in Table 1 while maintaining the polymerization at a temperature of 60 revolutions per minute while maintaining 5 ° C in a reactor blocked from the outside.

Into the 12 wt% solution in which the polyurethane liquid resin for artificial leather impregnation was dissolved in 4,4-dimethylformamide, the additive solids were added so as to be 5 wt% with respect to the polyurethane resin solids, and then made of nylon 0.05 denier microfiber. Table 2 shows the results of dyeing the physical and acid dyes after impregnating the bubbles and coagulating them in water.

Example 2

It is the same as that of Example 1 except having used the weight% of the added additive solid content 10weight% with respect to the polyurethane resin solid content. The results are shown in Table 2.

Example 3

It was the same as Example 1 except that t-butyl diethanolamine was used instead of N-metal diethanolamine for the synthesis | combination of the added additive.

The results are listed in Table 2.

Comparative Example 1

Same as Example 1 except that no additive was added.

The evaluation results are shown in Table 3.

Comparative Example 2

It is the same as that of Example 1 except the polyurethane resin synthesize | combined using the final nitrogen atom content of the low molecular weight diol containing a tertiary nitrogen atom the same as Example 1, and the additive was not used.

The evaluation results are shown in Table 3.

TABLE 1

TABLE 2

TABLE 3

Claims (2)

In the preparation of the polyurethane resin, an additive consisting of an organic diisocyanate, a low molecular diol containing a tertiary nitrogen atom, and an organic solvent is first prepared, and then the additive is prepared using a low molecular diol having no nitrogen atom as a chain extender. A method for producing a polyurethane resin composition with improved dyeability, characterized by mixing in one polyurethane resin solution. The method for producing a polyurethane resin composition with improved dyeability according to claim 1, wherein the content of the organic diisocyanate is 0.5-1.0 molar ratio of the number of moles of low molecular weight diol containing nitrogen atoms.