JPH03292364A - Polyurethane composition - Google Patents

Abstract

PURPOSE:To obtain the title composition suitable for a swimsuit which is prevented from discoloring, swelling and reducing in chlorine resistance even after treatment with a tannin liquid after dyeing treatment by mixing a polyurethane with a prescribed amount of a hydrotalcite compound which has been subjected to a specific surface treatment and has a small particle diameter. CONSTITUTION:A polyurethane is mixed with 0.1-10wt.% hydrotalcite compound (e.g. compounds of formulae I and II) which has been subjected to a surface treatment with a higher fatty acid and/or silane coupling agent and has an average particle diameter of 1mum or below. The obtained polyurethane composition has such excellent properties that the excellent resistance to deterioration with chlorine is not impaired even after processing which prevents the color dyed on nylon from fading (tannin liquid treatment) after dyeing treatment, undesirable yellowing discoloration and swelling do not occur, and also yarn breakage dose not occur during spinning.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to polyurethane compositions.

More specifically, the present invention relates to a polyurethane elastic fiber composition that prevents deterioration in various chlorinated water environments.

(Prior Art and Problems of the Invention) 4. A polyurethane elastic yarn obtained from 4'-diphenylmethane diisocyanate, a polyhydroxy polymer with a relatively low degree of polymerization, and a polyfunctional active hydrogen-containing compound has a high degree of rubber elasticity, Because it has excellent mechanical properties such as tensile stress and recovery properties, and also excellent thermal behavior, it is attracting a lot of attention as a functional material for clothing such as foundations, socks, and sportswear.

However, it is known that when articles made of such long-chain synthetic elastic segmented polyurethanes are washed with chlorine bleach, a considerable reduction in the physical properties of the segmented polyurethane occurs.

In addition, swimsuits made of polyurethane elastic yarn and polyamide yarn can be used in swimming pools at active chlorine concentrations of 0.5 to 5. 3ppm
When exposed to chlorine water containing chlorine, the physical performance of the polyurethane elastic yarn deteriorates, and the dye attached to the polyamide yarn changes color and fades due to the chlorine, resulting in undesirable discoloration of swimsuits.

Therefore, for competitive swimsuits that are often used in swimming pools, we aim to improve the chlorine resistance of the polyurethane elastic system, and as a method to prevent swimsuits from discoloring and discoloring due to chlorine, we further treat them with a tannin solution after dyeing. Color fading protection treatments for dyeing are currently widely used.

Various additives have been proposed to improve the resistance of polyurethane elastic yarns to chlorine-induced degradation. As one of such improvement measures, the present applicant previously proposed a polyurethane composition in which the chlorine deterioration property was improved using a hydrotalcite compound (Japanese Patent Application Laid-Open No. 1986-13).
Publication No. 3248).

Hydrotalcite compounds have an excellent characteristic of not reducing chlorine resistance even when dyeing in an acidic state (pH=3 to 4) is carried out while dispersed in a polyurethane elastic thread.

However, when used in competitive swimwear, hydrotalcite compounds react with tannins during the tannin solution treatment process performed after dyeing to prevent polyamide yarn dye from discoloring due to chlorine, turning the yarn brown. It has been found that there are drawbacks such as discoloration, swelling of the thread in chlorinated water, and a significant reduction in the stabilizing effect on chlorine resistance.

Furthermore, it was found that thread breakage occurred during the spinning process, making it difficult to perform stable spinning over a long period of time.

(Means for Solving the Problems) The purpose of the present invention is to eliminate the above-mentioned drawbacks of polyurethane compositions containing hydrotalcite compounds, and to eliminate undesirable changes in yarns even in tannin solution treatment after dyeing. It is an object of the present invention to provide a polyurethane composition which prevents (discoloration and swelling) and a decrease in chlorine resistance performance and is excellent for use as swimwear.

A further object of the present invention is to provide a polyurethane composition that can be stably spun over a long period of time.

As a result of intensive research to achieve this objective, the present inventors have found that by using hydrotalcite compounds with an average particle size of lμ or less that have been treated with higher fatty acids and/or coupling agents, the reaction with tannins can be improved. Surprisingly, we have found that these treatments further improve the chlorine resistance of hydrotalcite compounds and further reduce the occurrence of yarn breakage during the spinning process.

That is, the present invention has been made based on the above findings, and is based on the present invention, in which a hydrotalcite compound having an average particle diameter of 1 μm or less that has been treated with at least a higher fatty acid and/or a silane camping agent is added to polyurethane. ．．
It is a polyurethane composition containing 1 to 10% by weight.

The hydrotalcite compounds mentioned here are
Alz(OH)zx, 6-ax(A”-)z・elH
2O (wherein, gate 2' represents at least one metal element selected from the group consisting of Mg and Zn, and A"- is: 0H-2F-CI-, BrNO3-, Co3"-,
SC2”-, Fe (CN) 6'CH, COO-
, oxalate ion, salicylate ion, etc., n represents the valence of the anion, and x, z, and m each represent a number that satisfies the following conditions.

A positive number of X≧2, a positive number of Z≦2, m is a positive number, or a fired product thereof.

Preferred representative examples include Mg, 2Al□(OH), □, CO3Mga, ,A
Iz (OH)13CCh-3,5H20MgyA
Iz (OH)+oCO3・1.7 Hz○ etc. can be mentioned.

The higher fatty acid used in the present invention has carbon atoms ranging from 0 to 3.
It is a mono- or dicarboxylic acid having 0 straight-chain or branched hydrocarbon groups.

Specific examples include dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, and oleic acid, and particularly preferred are octadecanoic acid and oleic acid.

(Higher Fatty Acids and Hydrotalcite) [As for the treatment method with the compound, for example, there is a method of coating the surface of particles of hydrotalcite a compound with higher fatty acids, but various other known methods can be used. To give one specific example, a hydrotalcite compound is dispersed in water or an appropriate organic solvent (e.g. alcohol), and 0.01 to 20% by weight of higher fatty acid is added to the hydrotalcite compound. A method of adding and stirring while heating and melting, and then removing the solvent, or adding 0.01 to 20% by weight of higher fatty acids to the hydrotalcite compound and stirring or, in some cases, heating and stirring. This can be done by

After the treatment, by measuring the weight change of the hydrotalcite a compound before and after the higher fatty acid treatment, the treated amount (adhesion amount) of the higher fatty acid can be determined.

As a preferable treatment method, in the process of producing a hydrotalcite compound, if the hydrotalcite compound is not yet used. It is preferable to process the higher fatty acids in a moist, undried state.

The silane coupling agent used in the present invention is generally represented by the following chemical formula.

Y-3i (OR).

Here, the alkoxy group represented by OR is hydrolyzed to form a silanol group (SiOH) by moisture in an aqueous solution, in the air, or by moisture in a hydrotalcite compound.
It is thought that this reacts with the surface of the hydrotalcite compound, modifying the surface and making it inert to tannins.

Y is an organic residue that increases the affinity for polyurethane or is capable of bonding to the polyurethane, and is an alkyl group, an alkoxy group,
Examples include vinyl group, allyl group, methacrylic group, amino group, and mercapton group.

Representative examples of specific compounds include pages 121 to 1 of “Latest Technology of Polymer Additives” published by CMC Co., Ltd.
It is described on page 33.

The amount of the treatment agent attached or reacted can be determined by measuring the weight change before and after the treatment of the hydrotalcite compound with the silane coupling agent. Can be done.

Various known silane coupling reactions are used as a treatment method for the hydrotalcite compound and the silane coupling agent, but as a specific example, 0.01 ~20% by weight of the alkylsilane compound (0.5-10% by weight of hydrotalcin) in a suitable solvent, e.g. alcohol solution)
I! After keeping the compound completely wet, 100~
A method of heat treatment at a temperature of 150"C under normal pressure or vacuum for 10 minutes to 5 hours can be used. In addition, the smaller the particle size of the hydrotalcite compound, the more effective it is in chlorine resistance. It is necessary that the average particle size is 1 μm or less.

Particles with an average diameter larger than 1 μm, or those that have not been treated with a higher fatty acid and/or a silane coupling agent as in the present invention, not only do not have sufficient chlorine resistance effects, but also have poor chlorine resistance during the spinning process. This causes filter clogging and thread breakage in the spinning tube.

This is because hydrotalcite compounds have poor affinity with polyurethane and the slagging agents (dimethylacetamide, dimethylformamide, dimethyl sulfoxide, etc.) used in polyurethane, and hydrotalcite compounds in polyurethane or the above-mentioned organic solvents of polyurethane. This is due to the aggregation of similar compounds, but when a hydrotalcite compound subjected to the treatment described in the present invention was used, surprisingly no aggregation was observed and stable spinning became possible.

The polyurethane used in the present invention (hereinafter sometimes referred to as segmented polyurethane) is a substantially linear polymer having hydroxyl groups at both ends and having a molecular weight of 600 to 4,000, such as a homopolymer. or a copolymer of polyester, polylactone, polyether, polyester amide, polycarbonate, polythioether, polyhydrocarbon, or a mixture thereof, or a copolymer of these, an organic diisonate, and a polyfunctional active hydrogen atom. The main component is a chain extender such as hydrazine, polyhydrazide, polysemicarbazide, polyol, polyamine, hydroxylamine, water, or a mixture thereof.

In the present invention, polyurethane contains 0.1 to 10% by weight, preferably 0.5 to 3% by weight of treated hydrotalcite compounds having an average particle size of 1 μm or less; Addition of more than % by weight has an adverse effect on the physical performance of the fibers, so it is preferable to keep the amount added to the minimum necessary. However, if the amount added is less than 0.1% by weight, the effect of preventing chlorine deterioration is insufficient.

The treated hydrotalcite compounds of the present invention may be combined with other compounds commonly used in polyurethane elastic yarns, such as ultraviolet absorbers, antioxidants, light stabilizers, gas stabilizers,
It may be used in combination with colorants, matting agents, fillers, etc.

Further, the treated hydrotalcite compound of the present invention is usually added to a polyurethane polymer solution in which a polyurethane prepolymer, a chain extender, and a solvent are reacted, but it may be added to each of these agents in advance or Alternatively, it can be added during the polymerization.

The elastic fiber obtained from the polyurethane composition of the present invention is
The polyurethane elastic yarn has excellent resistance to chlorine-induced deterioration, and even when treated with tannin solution, the polyurethane elastic yarn does not change color or swell in chlorinated water, making it highly resistant to chlorine deterioration. Tolerance is maintained.

The polyurethane elastic yarn according to the present invention does not lose its chlorine-resistant stabilizing effect even if it is further treated with a tannin solution after dyeing. It is extremely useful as a material.

Furthermore, the polyurethane composition of the present invention can be used not only for elastic fibers but also for films, elastomers, and foam materials.

In addition, various measurement methods and various pretreatments of the fibers were performed using the methods described below.

(Measurement of available chlorine concentration) Weigh out 25ad of chlorine water sample into a 100ml Erlenmeyer flask, add 2g of dried potassium iodide, and shake. Add 10-acetic acid diluted with the same volume of ion-exchanged water and mix. Titrate with 1/100N sodium thiosulfate solution, and when the solution changes from orange to light yellow, add the starch solution. 1 until the blue color due to iodine starch reaction disappears.
/100N sodium thiosulfate solution.

Separately, 25 samples of ion-exchanged water were sampled and titrated by the same procedure as above to determine the titration amount. The effective chlorine concentration is calculated using the following formula.

Vs H: Effective chlorine concentration (ppm) Vs: Titration amount of 1/100N sodium thiosulfate when titrating chlorine water (d) vb: Titration amount of 1/100N sodium thiosulfate when titrating ion exchange water (〆) f: Factor Ws of 1/100N sodium thiosulfate: Weight of chlorine water (g) (Dyeing condition treatment) Boiling the test yarn adjusted to acidity (PH 3, 5) with acetic acid and sodium acetate under 50% elongation. It was immersed in water for a predetermined time (1 hour). Then, after this acidic treatment, it is washed under running water for 10 minutes.

(Tannin solution treatment) Next, the test yarn was added to a solution prepared by adding 4.5 g of special tannic acid manufactured by Dainippon Pharmaceutical ■ and 2.7 g of acetic acid to 62 mL of ion-exchanged water when the treatment solution reached 25°C. Thereafter, the temperature of the treatment liquid is raised to 50° C., and immersion treatment is performed for 30 minutes.

(Chlorine resistance performance evaluation test) After the above treatment, sodium hypochlorite e (manufactured by Sasaki Yakuhin ■) was diluted with ion-exchanged water to determine the effective chlorine concentration (
(See measurement method below) 3 ppm, P)i is 7 with HCI.
The samples were immersed in water/l at 130°C under 50% elongation in a solution adjusted to
S/TS, x 100%, TS, Ni blank strong, Ts
: strength after treatment) was determined.

The results are shown in Tables 1-3.

(Yarn swelling test) Untreated test yarn of initial length foam was stretched by 50%, dyed, then treated with tannin solution, and then subjected to the above conditions of effective chlorine concentration of 3 ppm and water temperature of 30°C for 48 hours. When the thread length measured in chlorinated water after being left standing was 42 cm,
The degree of swelling of the yarn is expressed by the following formula.

The grade was determined based on the standard.

That is, 1st class indicates the whiteness of the untreated system, 2nd class means slightly colored, 3rd class means slightly colored, 4th class means colored, and 5th class means strongly colored.

(Measurement of average particle size of hydrotalcite) The average particle size was determined using an automatic image analyzer set on an optical microscope.

0 (Discoloration degree test in tannin solution treatment) Test yarn (40
After bundling 200 denier threads with a skein winding machine, approximately 10C
After cutting the pieces to the same length as I and tightly binding them in the center with cotton string), the pieces were dyed under the above-mentioned dyeing conditions, then washed under running water for 10 minutes, and then dyed with the above-mentioned tannin solution. After the treatment was carried out in a vacuum chamber, the substrate was treated with running water for 10 minutes, and then air-dried at 20° C. day and night.

This test yarn was evaluated as follows. That is, the chromaticity after treatment with a tannin solution will be explained below in more detail with reference to the following examples, but the present invention is not limited to these examples.

In addition, the part in the following side means a part by weight, and % means the weight% with respect to the total weight of fiber.

Example 1 133.3 parts (parts by weight, same hereinafter) of polytetramethylene glycol with an average molecular weight of 1,600 and 4.4° -
31.2 parts of diphenylmethane diisocyanate was reacted with stirring at 95°C in a nitrogen gas stream for 90 minutes to obtain a prepolymer having a residual incy 2-to group. Next, after cooling this to room temperature, 270 parts of dry dimethylformamide was added and dissolved to obtain a prepolymer solution.

On the other hand, 2.34 parts of ethylenediamine and 0537 parts of diethylamine were dissolved in 157 parts of dry dimethylformamide, and the prepolymer solution was added thereto at room temperature.
A polyurethane solution with a viscosity of 1.500 poise (30°C) was obtained.

Titanium dioxide 4 was added to the viscous polymer solution thus obtained.
% (weight %, same hereinafter), 4.4"-butylidene-bis(3-methyl-6-t-butylphenol) 2%, 2-
(2°-Hydroxy-3"L-butyl-5"-methylphenyl)-5-chloro-benzotriazole 0.7%
And the chlorine deterioration inhibitor shown in Table 1 was added.

This polymer solution was dry spun at a spinning speed of 400 m/min to obtain a 6-filament, 40-denier yarn.

At this time, comparative examples B-1, B-4, 5, and 6 each suffered yarn breakage 20, 25, 18, and 14 times in the spindle during spinning for 30 minutes, but All of the talcite compounds did not break even once during spinning for 30 minutes.

Example 2 125 parts of polyester diol with a molecular weight of 1.500 obtained from ethylene glycol and adipic acid and 4,
31.2 parts of 4°-diphenylmethane diisocyanate were reacted with stirring at 95°C in a nitrogen gas stream for 90 minutes to obtain a prepolymer having residual isocyanate groups.

Next, after cooling this to room temperature, 281 parts of dry dimethylformamide was added and dissolved to obtain a prepolymer solution.

Meanwhile, 2.34 parts of ethylenediamine and 0.37 parts of diethylamine were dissolved in 185 parts of dry dimethylformamide, and the prepolymer solution was added thereto at room temperature.
A polyurethane solution with a viscosity of 1,510 poise (30° C.) was obtained.

The viscous polymer solution thus obtained was
2% butylidene-bis (3-methyl-6-butylphenol) and the chlorine deterioration inhibitor shown in Table 2 were added.

This polymer solution was dry spun in the same manner as in Example 1, and
I got a denier thread. Table 2 shows the results of the color change and swelling degree after dyeing and tannin solution treatment and chlorine water immersion test on this yarn in the same manner as in Example 1.

Example 3 Copolycarbonate diol with hydroxyl groups at both ends, CJOCHzCHzCHzCHzCHzOC+: 55
.

I -JCHICH2CH2CHICI (2CH20G-)
-: 1 at a ratio of 45 and a number average molecular weight of 3,00031500 g.

4.240g of 4'-diphenylmethane diisocyanate
, 1.150 g of N,N'-dimethylacetamide,
The prepolymer was reacted with stirring at 40°C in a nitrogen gas stream for 3 hours.

A N"-dimethylacetamide solution was obtained.

Next, after cooling this to room temperature, dry N, N'
- 1,900 g of dimethylacetamide was added and dissolved with stirring at room temperature to obtain a uniform prepolymer solution.

Separately, 26.9 g of ethylenediamine, 3.13 g of diethylamine, 1 g of N,N"-dimethylacetamide
A solution consisting of 780 g is prepared, to which the prepolymer solution is added dropwise with vigorous stirring. The viscosity gradually increased at the same time as the dropwise addition, and after stirring for about 30 minutes after the completion of the dropwise addition,
1 at °C. A viscous liquid of 600 poise was obtained.

The viscous polymer solution thus obtained was
2% butylidene-bis(3-methyl-6t-butylphenol) and the chlorine deterioration inhibitor shown in Table 3 were added.

This polymer solution was dry spun in the same manner as in Example 1 to obtain a 40 denier thread. This yarn was subjected to dyeing treatment and tannin solution treatment in the same manner as in Example 1, and the results of the degree of discoloration, degree of swelling of the yarn, and chlorine water immersion test are shown in Table 3.

(Effects of the Invention) From the results in Tables 1 to 3, it can be seen that the surface-treated hydrotalcite-containing polyurethane composition of the present invention with an average particle size of 1 μm or less can be treated with nylon dye fading prevention treatment (tannin liquid treatment) after dyeing treatment. ), it does not impair its excellent resistance to chlorine degradation, does not cause undesirable discoloration or swelling of polyurethane, and does not cause yarn breakage in the spinning cylinder during the spinning process. It is clear that it has certain characteristics.

(1 other person)

Claims (1)

[Claims] The polyurethane (A) is characterized by containing 0.1 to 10% by weight of a hydrotalcite compound (B) having an average particle size of 1 μ or less treated with at least a higher fatty acid and/or a silane coupling agent. A polyurethane composition.