JP2503105B2 - Elastic fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an elastic fiber excellent in dyed Kenlo degree.

(Prior Art) Japanese Patent Publication No. 61-17939 discloses dyeing a knitted fabric composed of polyester-based polyurethane elastic yarn and normal pressure cationic dye-dyeable polyester fiber with a disperse dye at 100 ° C. or lower. In addition, a knitted fabric in which polyurethane fibers and polyester fibers that can be dyed under atmospheric pressure with a disperse dye are mixed
Japanese Patent Publication No. 1-40137 discloses dyeing at 100 ° C. These are inventions aimed at using a combination of a fiber which can be dyed at a low temperature and a polyurethane fiber because the polyurethane fiber is deeply dyed at a high temperature and the light resistance to light deteriorates.

(Problems to be solved by the invention) Elastic yarns, particularly polyurethane elastic yarns, are widely used for swimsuits, pan-taste packing, and other stretchable applications that are commonly used with other fibers due to their excellent elasticity (stretchability and recovery). in use. These products are required to be dyed (colored) and at the same time have good dyeability.

Conventional stretchable products are dyed and have a good dyeing Kenro degree, but polyurethane elastic yarns are not colored and only other fibers which are main fibers are dyed in most cases.
Therefore, it is not necessary to worry about the Kenlo degree of the polyurethane elastic yarn. However, it is necessary that the polyurethane elastic yarn is also colored and has a good dyeing Kenro degree in order to prevent the polyurethane elastic yarn from having the same color as other fibers to be shared and the so-called blinding of the polyurethane elastic yarn.

On the other hand, when dyeing a stretchable fabric composed of polyurethane elastic yarn and other fibers, the polyurethane elastic yarn is not dyed with a dye other than the disperse dye. Until now, the polyurethane elastic yarn has been dyed with a disperse dye only by dyeing the polyurethane elastic yarn in a light color. This is because when the polyurethane elastic yarn is dyed in a light color with the disperse dye, there is no great problem in practical use, but when deeply dyed, the dyed Kenro degree is poor and the dye cannot be put to practical use.

As a result of intensive studies in view of the above situation, the present inventors have found an elastic yarn which is excellent in dyed Kenlo degree even when dyed.

(Means for Solving the Problems) The present invention is an elastic fiber which is made of polyurethane having the following structural unit as an essential component and which contains 0.01% by weight or more of a dyeing type disperse dye.

(In the formula, R ¹ is an alkylene group having one methyl branch and having 6 to 10 carbon atoms, and R ² is a divalent organic group having 4 to 10 carbon atoms.) Constituting the polyurethane elastic yarn used in the present invention. Polyurethane is polymer diol, organic diisocyanate,
It is obtained by polymerizing a chain extender. The polymeric diol used in the present invention is (Wherein R ¹ is an alkylene group having 1 to 10 carbon atoms and having 6 to 10 carbon atoms, and R ² is a divalent organic group having 4 to 10 carbon atoms). It is preferable that the following conditions (I) and (II) are satisfied.

5 ≦ total carbon number / (ester bond number) ≦ 11 (I) 0.015 ≦ methine group number / total carbon number ≦ 0.13 (II) (where total carbon number is included in ester bond in polymer diol) The total number of remaining carbons excluding carbons) The molecular weight of the polymer diol used in the present invention is
The range of 1000-3500 is preferred. Particularly preferably 1500
~ 3000. Less than 1000, elastic recovery, heat resistance,
Hot water resistance and cold resistance decrease, and if it exceeds 3500, elastic recovery, spinning stability and strength decrease. Examples of the compound giving an alkylene group having 1 to 10 carbon atoms and having 6 to 10 carbon atoms include 3-methyl-1,5 pentanediol (MPD)
And 2-methyl-1,8-octanediol (MOD), with 1,6-hexanediol, 1,8-octanediol, 1 being preferred diols providing other alkylene groups which can be used in combination therewith. , 9-Nonanediol, 1,
Examples include linear diols such as 10-decanediol, but are not limited thereto.

By using a diol having one methyl branch, both elastic recovery and heat resistance are improved. Use of a diol having two or more methyl branches or a long side chain such as an ethyl group, a propyl group or a butyl group reduces the overall performance such as heat resistance, elastic recovery and cold resistance. When the diol has less than 5 carbon atoms, elastic recovery, heat resistance, hot water resistance and the like are deteriorated. If it is more than 10, elasticity recovery and transparency are deteriorated.

Examples of the compound that provides the organic group (R ² ) of the polymeric diol include dicarboxylic acids. Among them, aliphatic dicarboxylic acids having 6 to 12 carbon atoms or aromatic dicarboxylic acids are preferable, and fatty acid dicarboxylic acids are particularly preferable.

Furthermore, the polymeric diol of the present invention is
It is preferable to satisfy the regulation represented by the formula (I). When the total carbon number / (ester bond number) in the formula (I) is less than 5, hot water resistance and cold resistance are lowered, and when it is more than 11, elastic recovery is lowered. It is preferably 6-10. In the formula (II), when the number of methine groups / total carbon number is smaller than 0.015, elastic recovery is lowered, and when it is larger than 0.13, heat resistance and elastic recovery are reduced. A more preferable range is 0.03 to 0.10.
Is.

The methine group referred to in the present invention is bonded to three different atoms (which may be the same element) other than a hydrogen atom. Is.

As the polymer diol used in the present invention, another polymer diol may be used as long as it does not impair the effects of the present invention.

Above all, polyurethane elastic yarn, which has an excellent elastic recovery property even at a low temperature of -10 ° C, is used as a diol component.
Number of methylene such as azelaic acid (AZ), sebacic acid (SA) and 1,10-decanedicarboxylic acid (DA) as dicarboxylic acid component using diol containing 50 mol% or more of -methyl-1,5-pentanediol Are obtained from polyurethanes with polyester diols obtained by using 7-10 aliphatic dicarboxylic acids.

The polyurethane constituting the present invention is a chain extender having at least two hydrogen atoms capable of reacting with the polymer diol thus obtained, an organic diisocyanate having a molecular weight of 500 or less, and a diol having a molecular weight of 400 or less, an isocyanate such as a diamine. It is obtained by polymerizing.

Other polymers may be used in the polyurethane used in the present invention within a range that does not impair the effects of the present invention.

In particular, when an elastic yarn is produced from thermoplastic polyurethane by a melt spinning method, 4,4′-diphenylmethane diisocyanate (MDI) is used as an organic diisocyanate used in the synthesis of thermoplastic polyurethane and 1,4-butane is a chain extender. By selecting the diol (BD) and / or 1,4-bis (hydroxyethoxy) benzene (BHEB), excellent performance in heat resistance, elastic recovery and elongation can be obtained.

Regarding the ratio (B) / (A) of the organic diisocyanate (B) to the polymer diol (A), a molar ratio of 1.5 to 4.5 is excellent in terms of overall performance such as elastic recovery, heat resistance, and cold resistance.

Furthermore, in the composition ratio of the polymer diol (A), the organic diisocyanate (B), and the chain extender (C), (B) /
The molar ratio of {(A) + (C)} is in the range of 0.9 to 1.2, especially 0.1.
The range from 95 to 1.15 is preferred. With this range, heat resistance,
A polyurethane elastic yarn excellent in elastic recovery and elongation can be obtained.

Regarding the molar ratio of (B) / {(A) + (C)}, the melt polymerization temperature that can be controlled during polyurethane polymerization or during spinning is not particularly limited, but 200 ° C or higher 2
60 ° C or lower is preferable.

The polyurethane used in the present invention is substantially a. A divalent group (soft segment) obtained by removing two hydrogen atoms from hydroxyl groups at both ends of a polymer diol molecule; b. formula A group represented by the formula (in the formula, R ³ represents a divalent organic group); c. A divalent form in which two hydrogen atoms capable of reacting with an isocyanate of a low-molecular compound (chain extender) molecule are removed. It is considered that the group is composed of a structural unit of.

Examples of the method for producing a polyurethane elastic yarn from the polyurethane thus obtained include a melt spinning method, a dry spinning method, and a wet spinning method. In the case of the melt spinning method, the wound yarn is heat-treated in the range of +20 to -50 ° C against the glass transition temperature (Tg) of the hard segment under low humidity to sufficiently perform the phase separation of the hard and soft segments. Preferably.

The polyurethane elastic yarn thus obtained has R ≧ 7800 / T (R: hot water resistance retention rate (%) T: hot water treatment temperature <140 ° C.) HD _100% ≧ 155 ° C. (HD _100% : 100% elongation Cutting drying temperature) Elongation: 300% or more, which has excellent properties.

 Next, the dye used in the present invention will be described.

The dye used in the present invention is a disperse dye. As described above, when nylon and polyurethane elastic yarns are dyed with acid dyes, cationic dyeable yarns and polyurethane elastic yarns are dyed with cationic dyes, etc. Polyurethane elastic yarns are dyed with dyes other than disperse dyes. There is nothing.

The reason for using the disperse dye is to obtain the same color property as that of the other fibers that are commonly used, and to prevent the blinding and enhance the color reproducibility. Quinone yarn and azo yarn are known as disperse dyes.

The dyeing type disperse dye used in the present invention means 2% owf of any one kind of polyurethane elastic yarn used in the present invention.
40% by weight (measured from weight loss) after reducing and washing the dye dyed when dyed at 130 ° C for 60 minutes.
This is the remaining dye. That is, for any one type of polyurethane elastic yarn, dyeing is performed on the elastic yarn to determine whether or not it is a dyeing type disperse dye.

Reduction cleaning conditions Hydrosulfaid 3g / soda ash 2g / amylazine 1g / bath ratio 1:30 Temperature 80 ° C × 20 minutes On the other hand, polyurethane elastic threads can be roughly classified into ester polyurethane elastic threads and ether polyurethane elastic threads.
At least the currently available ester-based polyurethane elastic yarns that are commercially available cannot withstand high temperature and high pressure dyeing at 110 ° C or higher, and cannot be used together with polyesters that require high temperature and high pressure dyeing at least at 110 ° C or higher. If it is less than 110 ° C, it may be difficult to sufficiently deepen the dyeing or the dyeing degree may be poor. The fact that there is no material that can withstand high-temperature and high-pressure dyeing at 110 ° C or higher means that it melts or loses stretchability at high-temperature and high-pressure dyeing at 110 ° C or higher.

In this respect, the ester-based polyurethane elastic yarn used in the present invention can be dyed at a high temperature and a high temperature of 110 ° C. or higher as described above.

Further, although the reason is not clear, when the ester polyurethane elastic yarn used in the present invention is dyed with a dyeing type disperse dye at a dyeing temperature of 110 ° C. or higher, the dyeing Kenlo degree is good (3rd grade or higher). .

(Effect of the present invention) The present invention is a polyurethane elastic fiber excellent in dyeability by dyeing a specific polyurethane elastic yarn with a dyeing type disperse dye.

Further, by dyeing the polyester fiber and the polyurethane elastic yarn with a dyeing type disperse dye, a stretchable cloth or a product having the same color property and an excellent dyeing Kenlo degree can be obtained. By performing the present invention and the dyeing depending on the other fibers used in the stretchable fabric or the product at the same time or separately, there is a possibility that the same color property with all other fibers can be realized. For example, when cotton is used as the other fiber, the polyurethane elastic yarn may be first dyed according to the present invention, and then the cotton may be dyed with a reactive dye or the like.

The present invention will be further described with reference to the following examples. The measuring method adopted in the present invention is as follows.

(Strength and Elongation) Measured according to JIS-1013.

(HD _100% ) The polyurethane elastic yarn is put into the dry heat treatment layer while being stretched 100%, the temperature is raised from 110 ° C to 5 ° C / 1 minute, and the temperature at which the yarn is broken is measured.

(Holding resistance to hot water resistance) Polyurethane elastic fibers were combined with polyester fibers having a denier of 2 to 5 times that of the fibers to form a tubular knit (circular knit) fabric, and the relax treatment was performed in hot water at 95 to 98 ° C for 10 minutes. Done,
After air-drying this knitted fabric, preset (180 ° C x 1 minute, hot air)
Then, after dyeing with hot water at a specified temperature (any temperature from 120 to 135 ° C) under pressure for 60 minutes under disperse dye dyeing conditions, air-drying and releasing the knitted fabric, only polyurethane elastic fiber is released. The retention rate was obtained by measuring the strength of the yarn that was taken out and released from the tubular knit before treatment and the yarn from which the tubular knit after treatment was released.

Example 1 Total carbon number consisting of MPD and AZ / ester bond number is 6.93,
A mixture of polyester and BD having a methine group number / total carbon number of 0.0825 and a number average molecular weight of 1985 and heated to 30 ° C.
Melt polymerization was carried out by charging MDI heated and melted at 50 ° C into a twin-screw extruder in an amount such that the molar ratio of polyester / MDI / BD used was 1 / 3.15 / 2. The resulting polyurethane (PU) was continuously extruded in the form of strands into a water column and then formed into pellets with a pelletizer. This pellet
It was vacuum dried at 80 ° C for 10 hours, and spun (using a straight oil agent) at a spinning temperature of 230 ° C and a spinning speed of 500 m / min using a spinning machine of a single screw extruder to obtain a 40dr-2f polyurethane elastic yarn. This yarn has a strength of 1.4 g / dr, an elongation of 530%, an elastic recovery rate at 20 ° C of 98%, and HD.
_100% was 163 ° C and R at 130 ° C was 85%.

Next, this polyurethane elastic yarn was knitted by a 20 gauge tubular knitting machine and dyed under the following conditions.

Scouring Relax: 80 ° C x 1 minute Dyeing machine: Drum dyeing machine Dye: Sumikaron Red E-RPD (Quinone Sumitomo Chemical Co., Ltd.)
2.0% owf Dispersion aid: Disper TL (manufactured by Meisei Chemical Industry Co., Ltd.) …… 1g / pH adjuster: ammonium sulfate ………… 1g / acetic acid 1g / bath ratio: 1:30 Temperature: 40 ℃ up to 130 ℃ over 30 minutes And then at 130 ° C for an additional 3
Hold for 0 minutes.

Reduction washing: Hydrosulfide: 3g / Soda ash: 2g / Amylazine (Daiichi Pharmaceutical Co., Ltd.): 1g / Bath ratio: 1:30 Temperature: 80 ℃ × 20 minutes Successively well washed with water and dried to observe the dyed state However, there was almost no color difference between the polyester and the polyurethane elastic yarn, and they were dyed, and the color uniformity was excellent. When only the polyurethane elastic yarn was dyed and reduced and washed under the same conditions, the residual ratio of the dye before the reduction and washing was 85%.

When the dyed Kenlo degree of the knitted fabric after the reduction washing was measured, it was as follows.

Washing Kenro degree (JIS L-0844A2 method): 4 to 5 grade (contamination) Water Kenro degree (JIS L-0846B method): 4 to 5 grade (contamination) Sweat Kenlo degree (JIS L-0848A method) (acid, alkali Together) 4
~ 5th grade (contamination) Light resistance (JIS L-0842 carbon arc third exposure method): 4th-5th grade (discoloration) Chlorine resistance (JIS L-0856 strong test method): 4th-5th grade (alteration) (Discoloration) All the dyed Kenlo degrees measured above were good, and all of the grade 3 required for ordinary clothing were cleared.

Comparative Example 1 Dyeing, reduction washing, washing with water and drying were performed in the same manner as in Example 1, except that the polyurethane elastic yarn was a commercially available ether polyurethane elastic yarn. The polyurethane elastic yarn was dyed to the same extent as polyester and no scoring was observed, but the dyed Kenlo degree was as follows.

Washing Kenro degree (JIS L-0844A2 method): Grade 2 (contamination) Water Kenro degree (JIS L-0846B method): Grade 2 to 3 (contamination) Sweat Kenro degree (JIS L-0848A method) (acid, alkali) 2-3 grade (contamination) Light resistance (JIS L-0842 carbon arc third exposure method): 2-3 grade (discoloration) Chlorine resistance (JIS L-0856 strong test method) 2-3 grade (alteration) Discoloration) The color density was reduced as a whole as compared with Example 1, and there were grades 3 and below which were unsuitable for clothing.

Example 2 A warp knitted fabric was knitted from the polyurethane elastic yarn of Example 1 and the polyester multifilament stretched yarn 50d-36f. The conditions are as follows.

Warp draft: 2 times Knitting machine: 28 gauge tricot made by Karl Mayer Organization: Half thread Front: Polyester 50d-36f Buck: Polyurethane 40d Braiding length: Front 160cm / 480 course: Back 82cm / 480 course Number of on-board courses : 60 courses / in This greige machine was scoured under the same conditions as in Example 1 and then pre-set at 180 ° C for 1 minute, dyed, reduced washed, washed with water under the same conditions as in Example 1 and finished under the following conditions (the scouring was a relaxer , Use a pin tenter for the preset).

Finishing Cut: 150 ℃ x 1 minute (pin tenter) Finishing Density: 100 courses / inch x 60 wales / inch The elongation of this finishing fabric is 120% warp, 110% weft (2.25kg /
Inch load), and the instantaneous elastic recovery rate at 50% elongation was 93% for warp and 91% for weft (measured at 20%), indicating good stretchability.

On the other hand, the dyed state was observed, but there was almost no color difference between the polyester and the polyurethane elastic yarn, and the dyeing was excellent, and the color uniformity was excellent. The dyed Kenro degree was as follows.

Washing Kenro degree (JIS L-0844A2 method): 4 to 5 grade (contamination) Water Kenro degree (JIS L-0846B method): 4 to 5 grade (contamination) Sweat Kenlo degree (JIS L-0848A method) (acid, alkali Together) 4
~ 5 grade (contamination) Light resistance (JIS L-0842 carbon arc third exposure method): 4-5 grade (discoloration) Chlorine resistance (JIS L-0856 strong test method) 4-5 grade (discoloration) ) All the dyed Kenro's measured above were good, and all of the grade 3 required for ordinary clothing were cleared.

Comparative Example 2 The fabric of Example 2 is a non-dyed Sumikaron Red
It dye | stained like Example 2 except using S-BDF.

The cloth before reduction washing had the polyurethane elastic yarn dyed to the same extent as polyester, and there was no eye bleeding, but the washing Kenro degree: grade 1, water Kenlo degree: grade 1, sweat Kenlo degree: grade 1. The light resistance was 2nd grade, and the chlorine resistance was 1st grade. When reduction washing was performed, 80% or more of the dye was desorbed and the color disappeared.

Claims (1)

(57) [Claims] 1. A polyurethane comprising, as a component, a polymeric diol which essentially contains the following structural units and satisfies the following conditions (I) and (II), and contains 0.01% by weight or more of a dyeing type disperse dye. Elastic fiber to do. (In the formula, R ¹ is an alkylene group having one methyl branch and having 6 to 10 carbon atoms, and R ² is a divalent organic group having 4 to 10 carbon atoms.) 5 ≦ total carbon number / (number of ester bonds) ) ≤ 11 ...... (I) 0.015 ≤ number of methine groups / total carbon number ≤ 0.13 ...... (II) (Here, the total number of carbons is the total of the remaining carbons excluding the carbons contained in the ester bond in the polymeric diol. number)