JPH0524246B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION The present invention relates to dry cleaning stable polyurethane elastic fibers. More specifically, the present invention relates to polyurethane elastic fibers that are stabilized against deterioration and discoloration when exposed to sunlight, chlorine bleach, combustion gas, heat, etc. after dry cleaning. Polyurethane elastic fibers can be mixed and woven with other synthetic fibers such as nylon, natural fibers such as cotton, and recycled fibers such as rayon to provide materials with rich elastic properties, and are used in a wide range of products from innerwear to outerwear. is being done. According to the present invention, it is possible to improve the durability and whiteness retention of the elastic function of these materials, and furthermore, it is possible to maintain the performance even when dry cleaning outerwear, and as a result, the product value is significantly improved. It became possible to do so. Prior Art Products using polyurethane elastic fibers are required to have sufficient stability against deterioration and discoloration. Conventionally, various compounds have been added for this purpose, such as hindered phenolic antioxidants, hindered amine compounds, benztriazole-based, benzophenone-based or salicylic acid-based ultraviolet absorbers, and even acid hydrazide compounds. Some proposals have been made, but none have been fully satisfactory. In addition, compounds that exhibit some degree of effectiveness, such as stabilizers with a molecular weight of about 1000 or less, as described in JP-A-56-11948, are easily extracted by dry cleaning, and their resistance to deterioration and coloring is significantly impaired. It will be done. In addition, special public service
No. 6510 describes a compound that is a condensate of p-cresol and divinylbenzene and has a molecular weight of about 1500 or more. This compound is difficult to extract with dry cleaning solvents, but its color stability against combustion gas is not fully satisfactory. Furthermore, Japanese Patent Publication No. 14099/1989 discloses an isobutylene reaction product of a condensate obtained by condensing a phenol compound and dicyclopentadiene at a molar ratio of 1.7 to 1.5:1. It has the disadvantage that it is small and easily extracted from perchlorethylene. Problems to be Solved by the Invention Polyurethane elastic fibers must have resistance to deterioration and gas coloring, so a stabilizer that satisfies both of these properties and does not adversely affect physical properties is required. . Furthermore, when polyurethane elastic fibers conventionally used in the clothing field are dry-cleaned, the stabilizer is extracted by perchlorethylene, a dry-cleaning solvent, and the resistance to deterioration and discoloration is greatly reduced. It was something to do. The object of the present invention is to make polyurethane elastic fibers that are sufficiently stabilized against deterioration and discoloration after dry cleaning by making the stabilizers in polyurethane elastic fibers difficult to extract into perchlorethylene. The purpose is to provide elastic fibers. Means for Solving the Problems Already known stabilizers did not exhibit a sufficient stabilizing effect on polyurethane elastic fibers against deterioration and discoloration after being treated with a perchlorethylene solution. This was due to the high solubility of low molecular weight stabilizers in perchlorethylene. In addition, even if the stabilizer has a high molecular weight, it is not compatible with polyurethane, and the stabilizer may fall off or change in quality during processing steps such as scouring and heat treatment, and in some cases, the stabilizer itself becomes significantly colored. . Therefore, the present inventors have determined that the molecular weight is at least about 1500 or more, has good compatibility with polyurethane, is difficult to dissolve into perchlorethylene from polyurethane elastic fibers, and is resistant to deterioration compared to polyurethane elastic fibers. As a result of extensive research into the development of polyurethane elastic fibers containing a compound having excellent color resistance, the inventors have invented a polyurethane elastic fiber that is stable for dry cleaning according to the present invention. That is, according to the present invention, the following general formula [] (However, in the formula, R ₁ is an alkyl group having 1 to 6 carbon atoms, R ₂ is an alkyl group, cycloalkyl group, or aralkyl group having 4 to 9 carbon atoms, R ₃ ,
R ₄ represents a hydrogen atom or a methyl group, and n represents the number of repeating units and represents a positive integer from 5 to 20. ) There is provided a polyurethane elastic fiber which is stable to dry cleaning and contains a phenolic compound represented by the following formula. The fiber is a polyurethane elastic fiber that exhibits an excellent stabilizing effect against deterioration and discoloration after repeated dry cleaning. Furthermore, the phenolic compound according to the present invention can be used in combination with a urethane compound having an aliphatic tertiary amino group in its molecule and co-incorporated in polyurethane elastic fibers to prevent deterioration and coloring after dry cleaning. It is possible to exhibit an even more excellent stabilizing effect. The molecular weight of the phenolic compound described in the present invention is at least about 1,500 or more and about 5,000 or less, that is,
In the structure represented by the general formula [],
It is effective that n is a positive integer from 5 to 20, more preferably from 6 to 15. The polyurethane elastic fiber containing the phenolic compound is
The stabilizing effect is maintained even after repeated dry cleaning. If the molecular weight is less than about 1,500, it will easily elute in perchlorethylene, and if it is more than about 5,000, the compatibility with polymers and solubility in polar solvents such as dimethylacetamide will decrease. The compound is 0.1% by weight based on polyurethane.
As mentioned above, the effect is exhibited by preferably containing 0.5% by weight or more. However, even if it is added in an amount of 10% by weight or more, the effect equivalent to increasing the amount cannot be obtained, which is uneconomical. Further, the effects of the present invention are further enhanced when the phenol compound and a polyurethane compound having an aliphatic tertiary amino group in the molecule are used in combination. The polyurethane used in the present invention has hydroxyl groups at both ends and has a molecular weight of 600.
~5000, such as polyesters, polylactones, polyethers, polyesteramides, polythioethers, polyhydrocarbons, or mixtures thereof, and chains having organic diisocyanates and polyfunctional active hydrogen atoms. It is a fibrous material of an elastic polymer having a urethane group in the molecule obtained by reacting an extender such as hydrazine, polyhydrazide, polysemicarbazide, polyol, polyamine, hydroxylamine, water, etc. A general synthesis example of the phenolic compound used in the present invention will be given. An example of synthesis of a condensate of a p-alkyl-phenol compound and dicyclopentadiene, and an example of reaction of the condensate with isobutylene gas. Adding about 1.0 mol to 1.2 mol of p-alkylphenol to 1 mol of dicyclopentadiene,
Furthermore, BF ₃ .(C ₂ H ₅ ) ₂ O is added to the
Add only 3% by weight, heat up while stirring in nitrogen gas,
After being kept at about 90°C to about 150°C for 5 hours, the basic substances such as diethylamine, triethylamine, ammonia are dissolved in 50-80% in an inert hydrocarbon solvent such as toluene or hexane alone or in a mixed solvent. Organic compounds such as Na ₂ CO ₃ , Ca
Add a solid or aqueous solution of an inorganic compound such as (OH) ₂ , NaOH, KOH or a basic ion exchange resin, and BF ₃
After removing enough water, add H ₂ SO ₄ or acidic ion exchange resin. This mixture is heated from about 60℃ to 80℃.
Heat to °C and gradually add isobutylene gas until no isobutylene reacts. Adding the above-mentioned inorganic compound or its aqueous solution to this,
Decompose H ₂ SO ₄ or separate acidic ion exchange resin. Thereafter, when the temperature of the reaction solution is gradually lowered, powder is precipitated. The desired phenolic compound is obtained by collecting and drying it. At this time, since low molecular weight compounds are dissolved in the liquid, they can be easily separated. The molecular weight can be adjusted by adjusting the molar ratio of dicyclopentadiene and p-alkylphenol. To obtain a high molecular weight, the ratio should be close to 1:1, and to obtain a low molecular weight, the ratio should be close to 1:1.2. By this method, condensates of various p-alkylphenols and dicyclopentadiene or methylcyclopentadiene dimer were reacted with isobutylene, styrene, α-methylstyrene, and cyclohexene to produce the compounds shown in Table 1.

[Table] In the present invention, the following compounds are listed as examples of urethane compounds having a tertiary amino group in the molecule that exhibits an excellent synergistic effect when used in combination with a phenolic compound.

【table】

[Table] Here, the urethane compound having a tertiary amino group has -R ₃ -R ₁ N -R ₂ - (where R ₁ is an alkyl group having 3 to 10 carbon atoms, R ₂ and R ₃ represent an alkylene group having 2 to 20 carbon atoms, and R ₂ and R ₃
is bonded to the urethane group. ). The above compound is used in an amount of 0.3 to 10 times the weight of the phenol compound, preferably 1 to 6 times the weight, and the total amount of the phenol compound and the urethane compound having a tertiary amino group in the molecule. is based on 100 parts by weight of polyurethane solids,
Preferably, it is 0.5 to 15 parts by weight. Furthermore, the polyurethane elastic fiber of the present invention includes:
In addition to the above-mentioned phenolic compound and urethane compound having a tertiary amino group, known stabilizers, pigments, inorganic compounds, dyes, etc. may be added and contained. Examples include the following compounds. 1 Benztriazole ultraviolet absorbers, examples of which include the compounds listed in Table 3 below.

【table】

[Table] Hindered amine light stabilizer In addition, hindered amine compounds can be selected from the known ones shown in Table 4 below.

[Table] The composition of the present invention can be added to polyurethane at any stage of polyurethane production. is preferable. The solution or molten polyurethane composition containing the phenolic compound and the urethane compound having an aliphatic tertiary amino group in the molecule described in the present invention can be made into fibers through a dry, wet or melt spinning process. I can do it. Examples Specific examples of the present invention will be explained by the following examples. Synthesis of polyurethane polymer 1000 parts by weight of polytetramethylene glycol having an average molecular weight of 2000 and 250 parts by weight of 4,4'-diphenylmethane diisocyanate were reacted with stirring at 85°C for 2 hours in a nitrogen gas stream to form isocyanate groups. A prepolymer was obtained that had at both ends. 1800 parts by weight of dimethylformamide was added to this and dissolved to form a homogeneous solution. Separately, when 22.2 parts by weight of ethylenediamine and 4.4 parts by weight of diethylamine were dissolved in 1900 parts by weight of dimethylformamide and the above intermediate polymer solution was added thereto at room temperature, the mixed solution reacted rapidly and reached a high temperature of 2100 poise at 30°C. A viscous solution was obtained. In addition, 57.45 parts by weight of titanium oxide and dimethylformamide, including a small amount of blue-tinged pigment.
After adding 163.6 parts by weight and thoroughly dispersing it, it was gradually added to the previous solution and stirred thoroughly.
It became a high viscosity solution of 1500 poise. This is called A dope. Molding into polyurethane fiber Add various phenolic compounds used in the present invention (listed in Table 1 above) and a urethane compound having a tertiary amino group (listed in Table 2 above) to the A dope to make it uniform. After stirring as described above, vacuum defoaming was performed to remove air bubbles from the solution. This solution is discharged from a hole orifice into an atmosphere of approximately 200℃, and subjected to spinning, drying, false twisting, and oiling.
A fiber of 40 denier was obtained by winding at a speed of m/min. The strength and elongation properties of these elastic systems were excellent. Light resistance and yellowing resistance test The 40 denier fiber obtained above was stretched by 50%,
Soak in perchlorethylene solution at 30°C for 3 hours. After that, after drying with warm air at 45℃ for 10 minutes, irradiation with ultraviolet rays for 30 hours using a fade-o-meter.
A color degree test for combustion gas exposure was conducted according to AATCC-23. The light resistance test was carried out using a Tensilon measuring machine to measure the breaking strength of the yarn before and after irradiation with ultraviolet rays using a fade-ometer, and the results were expressed as the retention rate after irradiation. Furthermore, yellowing resistance was expressed by dividing the degree of coloration of combustion gas into the following five ranks. 1st grade...yellow and colored 2nd grade...yellow 3rd grade...pale yellow 4th grade...slightly colored 5th grade...uncolored In addition, as a comparative example, yarns that were not immersed in perchloroethylene were also tested at the same time. These results are shown in Table 5. The symbols of the additives shown in Table 5 are shown using the symbols described in the detailed description of the invention. Furthermore, the amount added is
It is expressed in parts by weight based on 100 parts by weight of polyurethane solid content. In addition, as a comparative example of a known stabilizer, a p-cresol and divinylbenzene condensate with a molecular weight of about
3000 was used as a comparative example of the isobutylene reaction product of the condensate of p-cresol and dicyclopentadiene under the trade name of Gutdeyer's "Wingstay L" (the molecular weight of this product was 750).
(However, A represents a yarn not treated with perchlorethylene, and B represents a yarn treated with perchlorethylene.)

【table】

[Table] Effects of the Invention Table 5 shows the photodeterioration of polyurethane elastic fibers containing the phenol compound of the present invention or a phenol compound and a urethane compound having an aliphatic tertiary amine before and after immersion in perchlorethylene. and the effect on coloring. The polyurethane elastic fiber containing the phenolic compound of the present invention is much more resistant to deterioration and discoloration than elastic fibers containing other known compounds. Furthermore, it is found that by using the phenolic compound of the present invention in combination with a urethane compound having an aliphatic tertiary amino group, it is possible to obtain a polyurethane elastic fiber that is significantly resistant to photodeterioration and coloring.

Claims (1)

[Claims] 1. The following general formula [] (However, in the formula, R ₁ is an alkyl group having 1 to 6 carbon atoms, R ₂ is an alkyl group, cycloalkyl group, or aralkyl group having 4 to 9 carbon atoms, R ₃ ,
R ₄ represents a hydrogen atom or a methyl group, and n represents the number of repeating units and represents a positive integer from 5 to 20. )
A dry cleaning-stable polyurethane elastic fiber containing the phenolic compound shown below. 2. The dry cleaning-stable elastic polyurethane fiber according to claim 1, wherein the content of the phenolic compound is from 0.1 to 10 parts by weight per 100 parts by weight of the polyurethane. 3 General formula below [] (However, in the formula, R ₁ is an alkyl group having 1 to 6 carbon atoms, R ₂ is an alkyl group, cycloalkyl group, or aralkyl group having 4 to 9 carbon atoms, R ₃ ,
R ₄ represents a hydrogen atom or a methyl group, and n represents the number of repeating units and represents a positive integer from 5 to 20. ) and a urethane compound having an aliphatic tertiary amino group in the molecule, which is a polyurethane elastic fiber that is stable to dry cleaning. 4 The content of the phenolic compound is 0.1 to 5 parts by weight per 100 parts by weight of polyurethane, and the total amount of the phenol compound and the urethane compound having an aliphatic tertiary amino group in the molecule is 0.5 to 15 parts by weight. The polyurethane elastic fiber according to claim 3, which is a polyurethane elastic fiber.