JPS583498B2 - Anti Casareta Polyurethane Elastomer Soseibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyurethane composition with improved whiteness retention, and is particularly intended to make polyurethane resistant to discoloration due to light or combustion gas.

Polyurethane provides a wide range of useful materials such as foams, elastomers, elastic threads, leather, adhesives, and paints due to its functional characteristics, but it has the disadvantage that it discolors due to sunlight and combustion gas when exposed to the atmosphere. is known to have.

The present invention aims to overcome these drawbacks of polyurethane and provide a polyurethane that is stable and has excellent whiteness retention.

Conventionally, in order to prevent discoloration of polyurethane having urea bonds and urethane bonds, it is known to add antioxidants, ultraviolet absorbers, and aliphatic amines.

However, even among the conventional stabilizers for polyurethane, there is not one that satisfies both light resistance and gas resistance, and those that have a light resistance effect are polluting with gas, and conversely, those that have a gas resistance effect promote photodeterioration. There were many cases where I would do something like that.

Furthermore, in the case of fibers, there has been a phenomenon in which stabilizers are removed during scouring, dyeing processes, or when products are washed repeatedly, resulting in loss of white retention.

It is an object of the present invention to provide a polyurethane composition with outstanding white color retention.

It is also an object to provide stabilizers that can be added to conventional polyurethane compositions to produce compositions that are more stable and of higher quality than conventional polyurethane compositions.

That is, as a result of extensive studies on the whiteness retention properties of polyurethane, the present inventors have discovered an excellent stabilizer that retains the whiteness of polyurethane, and have accomplished the present invention.

In other words, what does the present invention mean? In the formula, Rlt R2 is a C1-2 alkyl group, aralkyl group, phenyl group, pyridyl group, amino group, -RCO
OH, -RCOOR' (here R is Cl
~10 alkylene groups, phenylene groups, or may be absent.

R' represents a C1-1o alkyl group.

) The nucleus of the phenyl group, aralkyl group, or pyridyl group may be substituted with a hydroxyl group, a C1-18 alkoxy group, or a C1-4 alkyl group.

R3, R4 are groups selected from the same group as the group defined for R, X1, X2 are 0, S, NH1, 1, m are 0 or 1, and cannot be 0 at the same time, and 1 or more 20
Represents the following integer.

An object of the present invention is to provide a polyurethane elastomer composition which retains an acid hydrazide derivative represented by the formula of the group consisting of the following formula and has improved whiteness retention.

The method for producing the acid hydrazide derivative represented by the general formula used in the present invention can be carried out, for example, by reacting a common acylating agent (e.g., acid chloride, acid anhydride) with hydrazide, or by reacting an ester with hydrazide. .

Examples of the compounds of the present invention include: It has also been found that the whiteness retention effect of the compounds of the present invention varies greatly depending on the degree of polymerization n.

That is, with compounds where n=1 to 3, the whiteness retention effect was not so expected, but as n increases,
Completely contrary to our expectations, it has become clear that it has an outstanding effect.

Furthermore, it has been found that as n increases, the tendency for the light resistance strength retention rate to decrease after washing is also suppressed.

However, as n increases, the molecular weight increases and solubility in polymers or solvents decreases, so n is 20
The number below is particularly preferably 12 or less.

The amount of stabilizer added in the present invention is 0.1 to 10% by weight based on the polyurethane.

Even if a large amount of stabilizer is added, the stabilizing effect will not be affected, but from an economic point of view or the mechanical properties of polyurethane, it is desirable that the total amount added is 5% or less.

Furthermore, various stabilizers are conveniently added by stirring after the polyurethane synthesis reaction is completed.

The polyurethane to which the present invention is applied and whose whiteness retention property is significantly improved is a polymer having a melting point of 60°C or lower, active hydrogen at both ends, and a molecular weight of 600 to 4,000, an organic diisocyanate, an organic diamine, hydrazine, Products obtained by adding a chain extender such as dihydrazide, glycol, or water, and in some cases monofunctional alcohol, amine, etc., and reacting in one step or in multiple steps in the presence or absence of a solvent. It is.

In preparing the composition of the present invention, conventionally known ultraviolet absorbers, antioxidants and other additives can also be used in combination.

Furthermore, the compound represented by the general formula of the present invention has little contaminating property and can be incorporated into various known polymer materials.

The present invention will be described below with reference to Examples, but the present invention is not limited to the scope of these Examples.

Furthermore, in the examples, parts refer to parts by weight.

[Reference example]

Synthesis of (I)-1 0.01 mol of adipic acid diminal ester and 0.01
2 mol of nicotinic acid hydrazide and 0.01 mol of carbodihydrazide in a 500 ml autoclave.
After heating at 00° C. for 4 hours, the mixture was allowed to cool to room temperature, and 0.01 mol of stearic acid chloride was added.

Although the reaction product was slightly colored, it was decolorized and purified by recrystallization with ethanol, and the elemental analysis value was C: 57.98%.
H: 8.50% N: 18.96% (calculated value C: 58
．． 01%, H: 8.46%, N: 1903%).

Similarly, hydrazide derivatives with different molecular weights were synthesized by changing the molar ratio of starting materials.

Synthesis of (I)-2 to [■]-5 Condensates were synthesized in the same manner as in Compound [I]-1 by changing the starting materials and their charging ratios.

Example 1 100.0 parts of polytetramenalene glycol having an average molecular weight of 1,200 and 31.2 parts of 4,4'-diphenylmethane diisocyanate were reacted with stirring at 85°C in a nitrogen gas stream for 120 minutes to form incyanate. A group-terminated intermediate polymer was obtained.

Then, after cooling to room temperature, dry dimethylformamide 1
83.7 parts were added and dissolved.

This was mixed with 2.40 parts of ethylenediamine and 0 parts of diethylamine.
．． 30 parts were added to a solution of 122.4 parts of dimethylformamide at room temperature.

The mixed solution reacted quickly and a highly viscous solution was obtained.

In the polymer solution thus obtained, predetermined amounts of the additives shown in Table 1 and 4% titanium oxide based on the polymer were dissolved in dimethylformamide in an amount such that the final polymer solution was 25%. The additive solution was added to the polymer solution and stirred well.

Each solution was poured onto a glass plate, stretched to a thickness of 1.0 mm, and dried under reduced pressure at 80° C. and 2 mmHg to obtain a film.

These films were subjected to an ultraviolet irradiation resistance test using a fade meter to measure discoloration and strength retention.

Furthermore, a fastness test using nitrogen oxide gas was conducted using AATOC2.
3-1962.

The coloring property was determined visually using a gray scale, and was ranked 1st grade, 2nd grade, 5th grade, based on the coloring of dogs.

Example 2 According to the method of Example 1, an intermediate polymer was obtained from 1,500.0 parts of polycaprolactone having an average molecular weight of 1,500 and 45 parts of 4,4'-diphenylmethane diisocyanate.

After dissolving in dimethylformamide, a dimethylformamide solution containing 8.7 parts of 1,4-cyclohexanediamine and 0.5 parts of N,N-dienalaminopropylamine was added to react.

To the thus obtained polymer solution were added an amount of titanium oxide equivalent to 4% based on the fixed amount of the polymer and a predetermined amount of the additive shown in the second coating, and the mixture was thoroughly stirred.

This was dry-spun using a conventional method to obtain an elastic yarn of 210 denier.

A light fastness test and a nitrogen oxide gas fastness test were conducted on each yarn in the same manner as in Example 1.

Furthermore, the threads were treated in a MiBeads bath of 5 h/l for 5 minutes, washed with water, and then subjected to a light fastness test after drying to examine changes in strength retention due to washing.

Claims (1)

[Scope of Claims] 1 General formula [wherein R1 and R2 are C1 to C2, an alkyl group, an aralkyl group, a phenyl group, a pyridyl group, an amino group, one RCO
OH, -RCOOR' (where R represents a C1-1o alkylene group, phenylene group, or may be absent. R' represents a C1-1o alkyl group), and the phenyl group, aralkyl group, The core of the pyridyl group is a hydroxyl group, a C1-I8 alkoxy group, C, -. The alkyl group may be unsubstituted. R3 and R4 are groups selected from the same group as the group defined for R, and X1,
2 is C, S, NH, 1 and m are 0 or 1 and cannot be O at the same time, and n represents an integer from 1 to 20. ] A polyurethane elastomer composition characterized by retaining an acid hydrazide derivative represented by the formula of the group consisting of: