JPS6137388B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has water absorption, antistatic, and antifouling properties at the same time,
Moreover, it relates to a modified polyester fiber having good color fastness. Conventionally, polyester fibers have been widely used due to their excellent easy care properties, but because they are inherently hydrophobic, they do not have water absorbency or stain resistance.
There were many problems, such as the generation of static electricity. Therefore, in the industry, various polyethylene glycol compounds have been applied to polyester fibers by some means to overcome these problems. However, although it has become possible to impart various properties such as water absorption, antistatic properties, and stain resistance using these methods, on the other hand, there is a significant decrease in dye fastness, recontamination during dry cleaning, and thinning. New problems have arisen, such as dirty products, and there is a strong demand for improvements in these shortcomings. With this background in mind, the present invention has been developed to provide a method that does not reduce dye fastness or cause re-contamination during dry cleaning.
The object of the present invention is to provide a polyester fiber that has water absorption, antistatic, and antifouling properties at the same time. In order to achieve this object, the present invention has the following configuration. (1) Polyester fibers containing a new aqueous composition made of a polymer having polyether segments contain 10 to 50 aliphatic or aromatic dicarboxylic acids having sulfonic acid groups or sulfonate salts in the acid component. A modified polyester fiber having a polyester polymer layer of 0.05 to 10% by weight based on the weight of the fiber. (2) The modified polyester fiber according to claim 1, wherein the polyester fiber is a polyester composite fiber containing a new aqueous composition in its core. The present invention achieves excellent water absorption and antistatic properties by combining a specific copolymer compound with the above-mentioned specific polyester fiber.
It was able to exhibit three types of antifouling properties simultaneously and with good durability. In the present invention, the hydrophilic composition comprising a polymer having a polyether segment refers to a hydrophilic composition comprising a polyalkylene ether, particularly terephthalic acid, a copolymer of polyethylene glycol and ethylene glycol, and a block copolymer of polyalkylene ether and polyamide. In order to achieve the object of the present invention, block copolymers of polyalkylene ether and polyamide (block polyether amide) are particularly preferred as such hydrophilic polymers. )
is preferred. In the present invention, the polyester fiber containing a hydrophilic composition made of a polymer having a polyether segment refers to a polyester fiber obtained by coating the surface of the fiber with the hydrophilic composition or a polyester fiber containing the hydrophilic composition. or composite fibers in which a mixture of the hydrophilic composition and polyester is arranged in the sheath and an unmodified polyester in the core; Examples include composite fibers in which a mixture of a polyester composition and a polyester are used, and an unmodified polyester is placed in the sheath. Any such polyester fiber suitably achieves the object of the present invention. Among such fibers, the former three tend to be inferior to the latter in the following respects. (1) Unfiltered property due to fusion between single yarns during spinning and fusion between fibers on the package of undrawn yarn. (2) When made into a composite fiber, the yarn quality and properties are determined by the adhesion between the core component and sheath component, as well as the peelability in subsequent processes such as drawing and temporary twisting. (3) Light fastness when dyed with disperse dyes. Therefore, in the present invention, the mixture consisting of the block polyether amide composition and polyester is the core, the polyester is the sheath, the proportion of the core is 5 to 0% by weight, and Particularly preferred is a core-sheath type polyester composite fiber in which the proportion of polyalkylene ether units in the block polyether amide composition to the total fiber is 0.05 to 5% by weight. The block polyether amide composition is a block polyether amide containing a predetermined amount of an organic electrolyte and a phenolic antioxidant. The organic electrolyte mentioned here is formed from sulfonic acids such as dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, nonylbenzenesulfonic acid, hexadecylsulfonic acid, and dodecylsulfonic acid, and alkali metals such as sodium, potassium, and lithium. There are alkali metal salts of sulfonic acid, alkali metal salts of phosphoric acid such as sodium distearyl phosphate, and alkali metal salts of other organic carboxylic acids, among which metal salts of sulfonic acid such as sodium dodecylbenzenesulfonate are good. be. The amount of this electrolyte to be blended is appropriately determined depending on the desired antistatic performance. Examples of phenolic antioxidants include:
1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,2'-methylenebis(4-
methyl-6-tert-butylphenol), 2.6
-di-tert-butyl-P-cresol, 2,2'-
It is a phenolic derivative having a sterically hindered substituent at a position adjacent to a phenolic hydroxyl group such as methylenebis(4-ethyl-6-tert-butylphenol). This antioxidant is blended as a stabilizer for the block polyether amide, and is blended to the extent that it can withstand the heat during melt spinning, but the amount depends on the amount of polyalkylene ether units. will be determined. The polyether constituting the block polyether amide is a polyalkylene ether, which is a polymerization product of ethylene oxide and/or propylene oxide such as polyethylene ether, polypropylene ether, and polyethylene propylene ether. The molecular weight of these polyethers is preferably 1,000 or more, preferably 3,000 to 8,000, and among them, polyethylene glycol is most suitable. On the other hand, the polyamide constituting block polyetheramide is homopolyamide such as nylon 6, nylon 8, nylon 12, nylon 6/6, nylon 6/10, or a copolyamide containing these or other copolymer components. It is a homo- or copolyamide produced by a polycondensation reaction of polyamide-forming components. Particularly suitable polyester fibers for the present invention are those containing such a block polyether amide composition, for example, in which the proportion of polyalkylene ether segments in the entire fiber is
By using a mixture of a block polyether amide composition mixed with polyester at a concentration of 0.05 to 5% by weight as the core and polyester as the sheath, it has excellent durability and good antistatic properties. It is a polyester fiber that has the same whiteness, heat resistance, light resistance, and dyeing fastness as ordinary polyester yarn, does not cause peeling of the core and sheath, and does not deteriorate in quality due to fibrillation. It can be done. Next, a polyester polymer (hereinafter referred to as sulfopolyester polymer) in which an aliphatic or aromatic dicarboxylic acid having a sulfonic acid group or a sulfonate salt accounts for 10 to 50 mol% of the acid component used in the present invention will be explained. . Sulfo means _-SO3X group. However, X
is hydrogen or an alkali metal cation such as sodium, potassium and lithium, an alkaline earth metal cation, a tertiary or quaternary nitrogen cation such as ammonium, N-methylpyridinium, methylammonium, triethylammonium, tetraethylammonium. be. The sulfo-substituted dicarboxylic acids referred to in the present invention include sulfo-substituted aliphatic dicarboxylic acids such as sulfosuccinic acid, 2-sulfoglutaric acid, and 3-sulfoglutaric acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 5-sulfonaphthalene. It means a sulfo-substituted aromatic dicarboxylic acid such as -1,4-dicarboxylic acid. Non-sulfo-substituted dicarboxylic acids other than such sulfo-substituted dicarboxylic acids include succinic acid, adipic acid, maleic acid, glutaric acid, suberic acid, 1.4
-Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-
Examples of the diol component of the polyester polymer include aromatic dicarboxylic acids such as pyridine dicarboxylic acid, and examples of the diol component of the polyester polymer include ethylene glycol, propylene glycol, 1,4-butanediol, 1.
Examples include 5-pentanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol. The sulfopolyester polymer of the present invention contains 10 to 50 mol% of the above sulfo-substituted dicarboxylic acid in the total acid component.
However, it is preferable that the content is further within the range of 15 to 30 mol%. That is, if the sulfo-substituted dicarboxylic acid in the acid component is less than 10 mol%, the sulfopolyester polymer exhibits excellent adhesion to the polyester fiber of the present invention, which is easy to wash and has excellent durability. If the desired water absorption and antifouling properties are insufficient, and on the other hand, if the sulfo-substituted dicarboxylic acid exceeds 50 mol% in the acid component, the water absorption and antifouling properties, which are one of the objectives of the present invention, may be excellent. , it becomes less durable when washed. Such sulfopolyester polymers may be water-soluble, water-dispersible close to water-soluble, or capable of taking the form of an emulsion, but from the standpoint of fully achieving the purpose of the present invention, it is preferable to use an emulsion form or a water-dispersion form. Those that can be used are preferable from the viewpoint of adhesion to the polyester fiber of the present invention and durability to wash the adhered materials. Such sulfopolyester polymers have a characteristic that they have better adhesion durability to the polyester fibers referred to in the present invention than ordinary regular polyester fibers, and have excellent durability in water absorption and antifouling performance. It is characterized by a tendency to improve. Although the cause of these characteristics is not clear, the polyester fibers of the present invention have greater hydrophilicity and water swelling properties than ordinary regular polyester fibers, and have a higher affinity with the sulfopolyester polymer. It is surmised that the high fiber resistance and the ease with which the polymer penetrates into the fibers lead to improved durability. In addition, it can be inferred that the fact that the sulfopolyester polymer tends to have a low interfacial potential (jeeter potential) in water is also a reason for the increased affinity with the polyester fiber of the present invention. The high compatibility between the polyester fiber and the sulfopolyester polymer is that
This is a major feature of the present invention. In the present invention, an adhesion layer made of such a sulfopolyester polymer is provided on a polyester fiber containing a hydrophilic composition made of a polymer having polyether segments. In order to achieve the object of the present invention, the adhesion is preferably 0.05 to 10% by weight, or even 0.1 to 2% by weight. Although such an adhesion layer may be provided in any form, it usually takes the form of a film on the polyester fiber of the present invention, and in some cases, it is at least partially retained within the fiber. The advantage of the present invention is that certain polyester fibers (such as JP-A-48-27066 and JP-A-52-150392, which have water-absorbing, antistatic, and antifouling fibers having a polymer layer having a polyalkylene glycol segment on the fiber surface) )
Decreased color fastness and darkening due to recontamination during dry cleaning have been extremely difficult to overcome even with the use of various processing agents, as the performance may be offset or other defects may occur. The problem could have been improved by easy means. In addition to various other performances, clothing fibers are considered to have antistatic properties as an extremely important and essential performance. Electricity could not be obtained, and there was a problem that the application to the clothing field had to be severely restricted. The present inventors have discovered that such sulfopolyester polymers act synergistically with polymers having polyalkylene glycol segments without canceling out their respective properties, and have also achieved color fastness that was unexpected in the prior art. This study revealed the fact that the problems of dry cleaning and dry cleaning recontamination can be solved all at once. The modified polyester fiber of the present invention not only has excellent washability and durability, and has high levels of water absorption, antistatic, and antifouling properties, but also has low recontamination during dry cleaning, and has excellent color fastness. It exhibits excellent performance. Next, the method for producing the modified polyester fiber of the present invention will be described below by giving one example. Polyester fibers containing a hydrophilic composition made of a polymer having a polyether segment of the present invention can be produced by a conventional method of coating a polyester fiber with the composition or a mixed spinning method of mixing the composition and polyester. It is formed by methods such as , composite spinning method, etc. When such a fiber is provided with a sulfopolyester polymer layer, it is treated with a treatment solution containing 0.1 to 100 g/g of the polymer. If it is less than 0.1 g/, the object of the present invention cannot be achieved, and if it exceeds 100 g/, the object of the present invention can be sufficiently achieved, but the effect reaches equilibrium. Therefore, further use will only increase the cost and is industrially disadvantageous. If necessary, 0.1 to 10 g of a water-soluble inorganic salt may be added to the treatment liquid. The water-soluble inorganic salt as used herein means sodium sulfate, sodium chloride, ammonium sulfate, diammonium phosphate, calcium chloride, magnesium chloride, subsalt chloride, and the like. By using these inorganic salts in combination, the adhesion of the sulfopolyester polymer to the polyester fibers can be further improved. Further, the pH of the treatment liquid is preferably neutral or acidic, and preferably PH 3 to 6 from the viewpoint of improving adhesion and durability. Any method may be used to form the polymer layer on the polyester fiber using the liquid, such as a pad-dry method, a pad-steam method, or a bath treatment method. However, the most effective method is the bath treatment method, which involves treatment in a bath at 60 to 135°C for 2 to 60 minutes.
This treatment may be carried out simultaneously with staining. The next most effective method is the pad steam method, which can provide sufficient performance if treated at 80°C or higher for 2 to 60 minutes. In addition, the forms of the objects to be processed include staples,
It may be in any form such as tow, filament, spun yarn, knitted fabric, woven fabric, or web, but knitted fabric is the easiest to process. Hereinafter, this will be specifically explained using examples. The evaluation methods for frictional charging voltage, water absorption, antifouling property, restaining property during dry cleaning, color fastness, etc. shown in Examples will be described in detail below. [Frictional electrification voltage] Using a Kyoto University Kaken type rotary static tester (manufactured by Koa Shokai), plain weave cotton Kanakin 3, which had been previously glued, scoured, and bleached, was used as the friction target fabric.
(Weight: 100g/m ² ), rotor rotation speed
400rpm, applied voltage 100V, temperature 20℃, relative humidity 30
This is a value measured in a % atmosphere. [Water absorption] According to JIS L-1079 needle method. [Anti-fouling property] Applied to paper using a method compliant with AATCC 130-69.
Place a 20cm x 20cm sample on top and add 3 coats of motor oil and Daph Nitronic Oil SEA (manufactured by Idemitsu Kosan).
A drop was placed on the same spot from a height of 3 cm, left for a day and night, then washed in a household washing machine containing 1 g of neutral detergent at 40°C for 10 minutes, then washed with water and dried. The thus obtained sample is compared with a 5tain standard plate. [Washing durability] After washing the sample in a household washing machine in a 40°C washing solution containing 1 g of neutral detergent, the frictional charging voltage, water absorption, stain resistance, etc. described above were evaluated. No laundry
Let L be ₀ , and let L be ₁₀ when washing for 100 minutes continuously. [Dry cleaning restainability] Stearic acid 25% by weight, olive oil 25% by weight,
0.5 g of a staining agent consisting of 25% by weight of solid paraffin and 25% by weight of carbon black/0.2g of a staining agent consisting of 25% by weight of perchlorine, 50% by weight of clay, 20% by weight of Portland cement, 15% by weight of silica gel, and 15% by weight of n-decane. Pour 200 c.c. of perc.c. of perc.c., which is a combination of g/- percrene and a neutral detergent to give 2g/- perc., into a rounder meter pot, add 6 samples of 5 cm x 5 mm, and rotate at 40℃ for 20 minutes. The recontamination rate is determined with the naked eye or using a photoelectric reflectance meter, and the reflectance before and after treatment is measured, and the recontamination rate is calculated using the following formula. Recontamination rate (%) = R ₀ - R ₁ / R ₀ × 100 where R ₀ is the reflectance before treatment (%) R ₁ is the reflectance after treatment (%) [Dyeing fastness: washable] JIS L -0844(A-). [Dye fastness: wet friction] According to JIS L-0849. Example 1, Comparative Examples 1 to 7 Obtained by polymerizing 60 parts by weight of 45% polyethylene glycol diammonium adipate aqueous solution, 35 parts by weight of 85% caprolactam aqueous solution, and 5 parts by weight of 40% hexamethylene diammonium isophthalate aqueous solution. Obtained by adding 5% by weight each of sodium dodecylbenzenesulfonate and 1,5,5-trimethyl-2,4,6-tri(3,5di-tert-butyl-4-hydroxybenzyl)benzene to block polyetheramide. A mixture of 7.0% by weight of a block polyether amide composition in polyethylene terephthalate with an intrinsic viscosity of 0.63 was used as the core component, while a normal polyethylene terephthalate with an intrinsic viscosity of 0.63 was used as the sheath component, and the composite ratio of core to sheath was 10.
A concentric composite yarn of 90 (weight ratio) was spun to obtain a drawn yarn of 150 denier 48 filaments. Next, the filament was made into ordinary false twisted yarn to make a twill fabric with a basis weight of 200 g/m ² . On the other hand, a sulfopolyester polymer consisting of a dicarboxylic acid component consisting of 20 mol% of 5-sulfoisophthalic acid sodium salt, 80 mol% of terephthalic acid, and a diol component of 100 mol% of ethylene glycol was prepared in a 10% aqueous dispersion. I did it. 5 g/10% aqueous dispersion of such sulfopolyester polymer
(active ingredient 0.5g/
), C.I. Disperse Red
57 5% owf, diammonium phosphate salt 3
The above-mentioned twill fabric was immersed in the added solution at a bath ratio of 1:50, and the temperature was raised from room temperature; heat treatment was performed in the bath at 130° C. for 60 minutes. Next, after cooling, washing with water, drying, and finishing setting at 180°C for 1 minute are performed, as shown in the following table, to achieve a smooth, dry-touch texture that is easy to wash, with excellent water absorption, antistatic, and antifouling properties. A woven fabric made of a modified polyester fiber having a good color fastness and not causing darkening due to dry cleaning was obtained (this example). Next, as a comparison, instead of the sulfopolyester polymer in this example, 20 moles of ethylene oxide was added to dimethacrylate of Bis-Phale A (Comparative Example 1), 10% by weight of terephthalic acid, and 20% by weight of ethylene glycol. , a polyethylene glycol-modified polyester polymer (Comparative Example 2) consisting of 70% by weight of polyethylene glycol with a molecular weight of 4000 was used in the same amount as the sulfopolyethylene polymer in this example, and the rest was treated in the same manner as in this example. However, all of them were inferior to this example in terms of darkening during dry cleaning and color fastness. The following table also shows the performance of an unprocessed product of the modified polyester fabric in this example that was not treated with a sulfopolyester polymer (Comparative Example 3). Furthermore, as a comparison, a twill fabric made of ordinary polyester fibers was processed in the same manner as in this example with the same sulfopolyester polymer as in this example (Comparative Example 4). In addition, twill fabrics made of ordinary polyester fibers were treated with the same polymers as in Comparative Examples 1 and 2 (Comparative Examples 5 and 6), and woven fabrics made of ordinary polyester fibers were not treated at all (Comparative Examples 5 and 6). Regarding 7), the performance of each is shown in the table below.

[Table] Example 2 The same modified polyester fabric as in Example 1 was used as C.I. Disperse Blue 120, 5% owf.
Dyeing was carried out at 130°C for 60 minutes in a bath ratio of 1:50. Next, after washing with water and drying, a sulfopolyester polymer consisting of a dicarboxylic acid component consisting of 75 mol% of dimethyl terephthalate, 5 mol% of isophthalic acid, and 20 mol% of sodium 5-sulfoisophthalate, and 100 mol% of ethylene glycol. 20%
The polymer was made into an aqueous dispersion at a concentration of 50 g/water, and a mangle with a 60° shore was used to make the polymer into an aqueous dispersion.
It is squeezed under mangle pressure of Kg/cm ² so that the pick-up is 80%, and then steamed for 10 minutes in a high-pressure steamer at 130℃ to create a dry-touch texture with excellent water absorption, anti-static, and antifouling properties. A product with good color fastness without darkening during dry cleaning was obtained (this example). Next, as a comparison, melamine resin and acrylic ester resin (Comparative Examples 8 and 9) were used instead of the sulfopolyester polymer in this example, and the rest was treated under the same conditions as in this example. However, all of them had poor antifouling properties and antistatic properties, and the product aimed at by the present invention could not be obtained.

Claims (1)

[Scope of Claims] 1 Polyester fibers containing a hydrophilic composition made of a polymer having polyether segments contain an aliphatic or aromatic dicarboxylic acid having a sulfonic acid group or a sulfonate in the acid component. ,
A modified polyester fiber made by adhering 0.05 to 10% by weight of a polyester polymer that accounts for 10 to 50 mol% based on the weight of the fiber. 2. The modified polyester fiber according to claim 1, wherein the polyester fiber contains the hydrophilic composition in its core.