JPS60134070A - Production of modified polyester fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a modified polyester fiber, that is, a polyester fiber that has water absorption, antistatic, and antifouling properties at the same time.

For more details, please refer to the instructions for dry cleaning, washing with water,
The present invention relates to a method for producing polyester fibers that are free from darkening and reverse contamination during industrial washing and have water absorption, antistatic, and antifouling properties at the same time without deterioration in dye fastness.

Conventionally, polyester-based! 1i1ffl has excellent easy-care properties and is widely used, but because it is inherently hydrophobic, it has many problems such as lack of water absorption, poor stain resistance, and significant 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 these methods have made it possible to provide properties such as water absorption, electrical conductivity, and stain resistance, they have also resulted in a significant decrease in dye fastness, and in dry cleaning, water washing, and industrial New problems have arisen, such as re-contamination during washing, resulting in slightly dirty products, and there is a growing demand for improvements to these shortcomings.

On the other hand, regarding antistatic polyester fibers, there are methods for imparting antistatic properties in advance at the manufacturing stage of the yarn, for example,
No. 4-905, as shown in Japanese Patent Publication No. 44-911, a block polyether amide with an unmodified polyester in the core of the composite 1 and an electrostatic property in the sheath, or block polyether amide and polyamide. A technique of disposing a mixture of 11M has also been proposed, but this technique has the following problems and cannot be said to be 11M that satisfactorily satisfies practical requirements.

(1) Unwinding property becomes poor due to fusion between single yarns during spinning and fusion between fibers on the package of undrawn yarn.

(2) Since the adhesion between the polyester core component and the sheath component is poor, peeling occurs during subsequent processes such as drawing and temporary twisting, which impairs the properties of the yarn.

(3) Light fastness decreases when dyed with disperse dyes.

Against this background, the present invention aims to reduce dye fastness,
The object of the present invention is to provide a polyester fiber that does not cause re-contamination during dry cleaning, washing with water, or industrial washing, and has water absorption, electric shock, and antifouling properties at the same time.

In order to achieve this object, the present invention has the following configuration.

Terephthalic acid or/and inphthalic acid and
A method for producing a modified polyester mH, which comprises providing a sulfopolyester compound mainly composed of a dicarboxylic acid component consisting of -(alkali metal)-sulfoisophthalic acid and an alkylene glycol.

The present invention combines the above-mentioned specific core-sheath type composite IIN with a specific copolymer compound, thereby achieving for the first time three types of performance: excellent water absorption, antistatic property, and antifouling property at the same time and with good durability. At the same time, it was able to provide anti-staining properties against darkening during water washing, industrial washing, and dry cleaning.

The hydrophilic composition in the present invention is a hydrophilic polymer such as polyalkylene ether, particularly terephthalic acid, a copolymer of polyethylene glycol and ethylene glycol, or a block copolymer of polyalkylene ether and polyamide, containing an electrolyte substance. However, 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.

At that time, the mixture consisting of the block polyether amide composition and polyester is the core part, the polyester is the sheath part, the ratio occupied by the core part is 5 to 50% by weight, and the block polyether amide composition contained in the core part is The proportion of polyalkylene ether units in the composition to the total fibers is 0.
05 to 5% by weight of core-sheath type polyester composite t
LAN is particularly preferred.

The block polyether amide composition consists of an organic electrolyte,
It is a block polyether amide containing a predetermined amount of phenolic antioxidant. The organic electrolytes here are those 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 such as sodium 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. It is. The amount of this electrolyte to be blended is appropriately determined depending on the desired antistatic performance.

As a phenolic antioxidant, for example, 1°3.5
-trimethyl-2,4,6-tri(3,5-diter)
t-butyl-4-hydroxybenzyl)benzene, 2.
2'-methylenebis(4-methyl-6-tert-butylphenol), 2,6-tert-butyl-P-
Cresol, 2,2'methylenebis(4-ethyl-6-
It is a phenolic derivative containing a sterically hindered substituent at a position adjacent to a phenolic hydroxyl group, such as 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 its amount is determined by the amount of polyalkylene ether units. be done.

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 1000 or more, preferably 300
0 to 8O0O is preferable, and among them, polyethylene glycol is most suitable.

On the other hand, the polyamide constituting the block polyether amide is a homopolyamide such as nylon 6, nylon 8, nylon 12, nylon 6/6, nylon 6/10, or a copolymer containing a copolymer component of these or similar components. It is a homo- or copolyamide produced by a polycondensation reaction of polyamide-forming components.

The block polyether amide composition in the polyester composite fiber used in the present invention is prepared by mixing the block polyether amide composition with the polyester such that the proportion of the polyalkylene ether component in the whole is 0.05 to 5% by weight. By using a mixture of polyester as the core and polyester as the sheath, it not only has excellent durability and good antistatic properties, but also has the same 0 degree, heat resistance, light resistance, and The modified polyester fiber has dye fastness, does not cause peeling between the core and sheath, and does not suffer from quality deterioration due to fibrillation. The above-mentioned sulfopolyester compound has an extremely high affinity for the darkened modified polyester mH, and as described later, when subjected to contact processing such as in-bath treatment, it imparts water absorption and stain resistance with excellent washing durability. can.

Here, the sulfopolyester compound used in the present invention will be explained in detail.

That is, the sulfopolyester compound referred to in the present invention includes 5-(alkali metal)- in addition to terephthalic acid and/or isophthalic acid as a dicarboxylic acid component.
It requires sulfoisophthalic acid and is composed of alkylene glycol as a glycol component.

It is preferable that 5-(alkali metal)-sulfoisophthalic acid is contained in the dicarboxylic acid component in an amount of 10 to 40 mol%, and as the content m of this component increases, the hydrophilicity increases and the adhesion to ordinary polyester fibers increases. Not only does the amount decrease, but the cleaning durability of the adhered materials also tends to decrease. However, for the composite 11t according to the present invention, which has a core made of a mixture obtained by mixing a block polyether amide composition with polyester and a sheath made of ordinary polyester, the amount of the sulfopolyester compound adhered to The degree of decrease in durability and washing durability is small, and this point is also one of the major features of the present invention.

Next, the other dicarboxylic acid components, terephthalic acid and isophthalic acid, may be blended arbitrarily, but preferably terephthalic acid is contained in the acid component in an amount of 30 to 80 mol%. When terephthalic acid increases, the polymerization of processed products tends to become rough, but in this case, the texture of processed products can be improved by introducing an aliphatic dicarboxylic acid such as adipic acid in a range of 5 to 30 mol%. This is preferable because it tends to be more flexible. In this case, normal polyester type! The adhesion durability of sulfopolyester compounds into which such aliphatic dicarboxylic acids have been introduced is not very good, but the adhesion durability of composite polyester fibers according to the present invention is excellent. The decrease is small, and this point is also one of the major features of the present invention.

It should be noted that these sulfopolyester compounds are more effective in forming the core and fibers of the present invention than in ordinary polyester fibers.
Although it is not clear that sheath-type composite polyester fibers have superior adhesion and durability to washing after adhesion, it is not clear that sheath-type composite polyester fibers have better adhesion and durability when washed after adhesion. It can be estimated that the phenomenon occurred because the surface potential of the fiber changed to a direction that did not inhibit the adhesion of the sulfopolyester compound.

In addition, since the polyester compound used in the present invention does not contain polyethylene glycol units, there is no decrease in dye fastness unlike in conventional processing, and it can be used during dry cleaning, water washing, or industrial washing. It is possible to obtain a good product without darkening of the product due to recontamination.

Next, as a method for applying the above-mentioned sulfopolyester compound to the polyester fiber, any method may be employed, such as a pad-dry method, a pad-steam method, or a method of treatment in a bath. The most effective method is the bath treatment method, in which the treatment is carried out in a bath at 60 to 135°C for 2 to 60 minutes. It is better to carry out this treatment simultaneously with the staining than after the staining. The next most effective method is the pad-steam method.
A sufficient performance can be imparted by processing for 60 minutes.

The amount of the sulfopolyester compound to be used is 0.01 to 5% by weight based on the amount of fibers attached.

In addition, the forms of the objects to be processed include stable, tow, filament, and spun yarn. It may be in any form, such as knitted fabrics, woven fabrics, or webs, but knitted fabrics are the easiest to process.

Hereinafter, this will be specifically explained using examples. The evaluation methods for frictional charging voltage, water absorption, antifouling property, darkening restaining property during washing with water and dry cleaning, color fastness, etc. shown in Examples will be described in detail below.

[Frictional voltage]

Using a Kyoto University Kaken style rotary static tester (manufactured by Koa Shokai), plain cotton Kanakin No. 3 (weighing 100 G/l) was previously glued, scoured, and bleached as a friction material.
n') in an atmosphere with a rotor rotation speed of 40 OrpI11, an applied voltage of 1 oov, a temperature of 20° C., and a relative humidity of 30%.

[70 sting]: Fibrillation phenomenon caused by abrasion. On a friction table with sandpaper attached, attach a wet sample (preferably a sample dyed in navy blue, etc.) to the head, and set the load to 7500. After adjusting the head, lower the head onto the friction table and fix it.
After rotating eccentrically with a ROM and rubbing for 15 minutes, the sample is removed and the degree of fibrillation is visually determined. When fibrillation occurs, the rubbed area looks whiter than the unrubbed area.

[Water absorption]

Based on JTS L-1079 Injection Kenpo.

[Stain resistance]

Using a method compliant with AATCCl 30-69, a 20 cm x 20 cm sample was placed on a piece of paper, and 3 drops of motor oil and Daphnitronic Oil 5EA (manufactured by Idemitsu Kosan) were dripped onto the same spot from a height of 3 cm, and left for one day and night. After cleaning, wash with household detergent 'ILL'S containing 10/ff of neutral detergent.
Wash at 0°C for 10 minutes, then wash with water and dry. The sample thus obtained is compared with a 5ta1n standard plate.

[Washing durability]

After washing the sample in a household washing machine in a 40°C washing liquid containing 1q/α of neutral detergent, the frictional charging voltage, water absorption,
Evaluate stain resistance, etc. Lo is no washing, 10 in a row
The case of washing for 0 minutes is defined as LtQ.

[Dry cleaning recontamination]

A staining agent consisting of 25% by weight of stearic acid, 25% by weight of olive oil, 25% by weight of solid paraffin, and 25% by weight of carbon black was added to 0.0%. '5Q/71-Perkleen, viscosity 5
A staining agent consisting of 0% by weight, 20% by weight of Portland cement, 15% by weight of silica gel, and 15% by weight of n-decane was added to O, 2o/Q-percrene and a neutral detergent to 2a/7.
1- Percrene solution 20 formulated to be percrene
Put 0cc into the rounder meter pot, 5cm x 5c
Insert 6 +n samples, rotate and treat at 40°C for 20 minutes, evaluate recontamination with the naked eye or use a photoelectric reflectance meter, measure the reflectance before and after treatment, and calculate the recontamination rate using the following formula. .

Recontamination rate (%) = [(Ro-R1) /Ro] ・
100 where Ro is the reflectance before treatment (%) R1 is the reflectance after treatment (%) [Water washing restainability] Stearic acid 17.5% by weight, oleic acid 17.5% by weight, hardened oil 17. 5% by weight, olive oil 17.5% by weight
, A staining agent consisting of 23% by weight of solid paraffin, 17% by weight of carbon black and B consisting of a viscosity of 58% by weight, 15% by weight of Portland cement, 15% by weight of silica gel, 10% by weight of n-decane, and 92% carbon bluff. A staining agent is mixed at a ratio of 3:1, and the mixed staining agent and anionic detergent [Super Zabu (Kao Soap Co., Ltd.)] are ground in a weighing mortar at a weight ratio of 7:3. Water is added to the solution to prepare a diluted solution containing the contaminant to a concentration of 0.2%. A test fabric (5 c
mx 10cn+) was placed in the sample, and treated with a rounder meter type tester at 40°C for 20 minutes to judge the darkening and reverse contamination properties.

Example 1, Comparative Examples 1 to 4 60 parts by weight of a 45% aqueous polyethylene glycol diammonium adipate solution, 35 parts by weight of an 85% aqueous caprolactam solution, and 5 parts by weight of a 40% aqueous hexamethylene diammonium isophthalate solution. Sodium dodecylbenzenesulfonate and 1,5°5-trimedel-2,4,6-tri(3
, 5 di-tert-butyl 4-hydroxybenzyl) benzene in an amount of 5% by weight, respectively, and a block polyether amide composition obtained by adding 5% by weight of each of di-tert-butyl 4-hydroxybenzyl) benzene was mixed with 7.0% of polyethylene terephthalate having an intrinsic viscosity of 0.63. The core component is polyethylene terephthalate, which has an intrinsic viscosity of 0.63, and the sheath component is polyethylene terephthalate, with a composite ratio of core to sheath of 10:9.
A concentric composite yarn of 0 (weight) was spun into a drawn yarn of 150 denier and 48 filaments.

Next, the filament is made into a temporarily twisted thread,
A twill fabric with a mesh size of 200 Q/m2 was used.

On the other hand, the dicarboxylic acid component consists of 30 mol% of 5-sodium sulfoisophthalic acid, 50 mol% of terephthalic acid, and 20 mol% of isophthalic acid, and the alcohol component consists of 80 mol% of ethylene glycol and 20 mol% of diethylene glycol. The sulfopolyester resin is 1
A 0% solution is used, 10% by weight is used for the above-mentioned twill fabric, and the temperature is gradually raised from normal humidity in a solution with a bath ratio of 1:3O.
Soaked at 130°C for 30 minutes) Heat treated (Example 1)
.

This twill fabric contained 0.21% of the above-mentioned sulfopolyester compound. Table 1 shows the frictional charging voltage, water absorption, antifouling properties, restainability when washed with water, restainability during dry cleaning, and color fastness (washing and wet abrasion) of the fabric thus obtained.

For comparison, the block polyether amide composition of this example was mixed with polyethylene terephthalate with an intrinsic viscosity of 0163 at 1.4% by weight as the sheath component, and polyethylene terephthalate with an intrinsic viscosity of 0.63 was used as the core component. In this example, the composite ratio of core to sheath was 50:50 (Comparative Example 1), and in this example, the block polyether amide composition was added to the polyethylene prephthalate at 1.0%.
Fibers spun by uniformly mixing the weight percentage (Comparative Example 2) were used, and the rest was treated in the same manner as in this example. These results are also summarized in Table 1.

Next, instead of the sulfopolyester compound in this example, a non-sulfopolyester compound copolymerized with polyethylene glycol of 1 u3000 molecules (Comparative Example 3), a non-sulfopolyester compound not copolymerized with polyethylene gelcol ( Comparative Example 4) was used, and the application was started on the twill fabric in the same manner as in this example. These results are also summarized in Table 1.

In addition, fibrillation and dye fastness marked with * in the table are c, r,
These are the results of measurement on a dyed product stained with Disperse Blue 257 3% owfk-.

Example 2, Comparative Example 5 A twill fabric made of the same polyester composite yarn as in Example 1 was treated with the following compound. That is, the dicarboxylic acid component consists of 30 mol% of 5-sodium sulfoisophthalic acid, 30 mol% of terephthalic acid, 10 mol% of isophthalic acid, and 10 mol% of adipic acid, and the glycol component consists of 80 mol% of ethylene glycol and 20 mol% of diethylene glycol. A 10% solution of sulfopolyester resin consisting of 10% by weight was applied to the above-mentioned twill fabric, and the temperature was gradually raised from room temperature to 130°C for 30 minutes in a solution with a bath ratio of 1:30. Immersion and heat treatment <Example 2>
). This twill fabric had 0.23% of the sulfopolyester compound attached thereto. Table 2 shows the frictional charging voltage, water absorption, antifouling property, restaining property when washed with water, and restaining property during dry cleaning of the fabric thus obtained.

For comparison, a twill fabric similar to that in this example was prepared using ordinary polyester fiber (150 denier, 48 filaments), and the rest was treated in the same manner as in this example (
Comparative Example 5). This product had 0.14% of the sulfopolyester compound attached.

Example 3 7.0% by weight of a hydrophilic polyether ester obtained by block copolymerizing 70 parts of polyethylene glycol having a molecular weight of 13,000 with 30 parts of polynysdel of open buds and having an intrinsic viscosity of 0.63.
The core component is a mixture of polyethylene terephthalate of A twill fabric similar to that of Example 1 was obtained.

After that, the same processing and treatment as in Example 2 was performed, and Example 2
obtained similar results.

Example 4 A twill fabric made of the same polyester composite yarn as in Example 1 was made of C, 1, Disperse Red 3232% owf.
After dyeing with 20q/α (solid content: 2Q/Q>) of the same sulfopolyester compound as in Example 2, it was blotted with an aqueous solution of 2Q/Q>, and then treated with saturated steam at 100°C for 3 minutes.

When the obtained fabric was subjected to the same test as in Example 1, the same results as in Example 1 were obtained.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] Terephthalic acid or/and isophthalic acid and 5
A method for producing a modified polyester fiber, which comprises applying a sulfopolyester compound mainly composed of an alkylene glycol and a dicarboxylic acid component consisting of -(alkali metal)-sulfoisophthalic acid.