JPH02133613A - Polyamide spun-dyed yarn having excellent stain resistance - Google Patents

Abstract

PURPOSE:To obtain the subject spun-dyed yarn hardly stained with acidic dust material and thus undyed yarn after mixing weaving with the aimed yarn is able to be dyed without anxiety of staining or dyeing of the aimed yarn containing cation-soluble polymer as constituting polyamide in multifilament. CONSTITUTION:The aimed spun-dyed yarn is composed of cation-soluble polyamide multifilament. Besides, preferably amino group concentration of terminal group of said polyamide is <=10g equiv./10<6>g and sulfonic acid salt is contained in the other terminal group. Furthermore, 100-700ppm copper compound (preferably cuprous halide) is preferably added.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a spun-dyed polyamide yarn with excellent stain resistance.
More specifically, the present invention relates to a spun-dyed polyamide yarn that is not easily contaminated by acidic stains.

[Conventional technology]

Conventionally, dope-dyed yarns have been widely used for general clothing and industrial materials because of the advantage that the dyeing process can be omitted. In addition, since dyed yarns are superior in terms of weather resistance and fastness, demand from the market has been increasing in recent years.

However, polyamide spun-dyed yarn is rarely used in a single color for general clothing or in the industrial material field. For this reason, it is necessary to manufacture dyed yarn in various colors, but this is disadvantageous in terms of productivity.
Usually, polyamide spun-dyed yarn is produced in large quantities in colors that are used in large quantities.

In addition, for multicolored patterns, yarn dyeing or post-dying is performed using acid dyes.

However, in the case of spun-dyed polyamide yarn, there is a drawback that the spun-dyed polyamide may be colored by acid dyes, or may be stained or slightly dyed by acid dyes in the post-dyeing process.

In addition, even if the product is colored only by dyeing without dyeing, products such as carpets may be contaminated with stains such as colored beverages, coffee, wine, soy sauce, etc. when used in daily life. In particular, the problem arises that acid stains cause stains and coloration, making it impossible to maintain the initial color tone.

[Problem to be solved by the invention]

The present invention was made against the background of the problems of the prior art, and an object of the present invention is to provide a spun-dyed polyamide yarn that is neither dyed by acid dyes nor contaminated by acidic stains.

[Means to solve the problem]

The present invention provides a spun-dyed polyamide yarn consisting of multifilaments, characterized in that the polyamide constituting the ff4 filaments is a cationically dyeable polymer, and has excellent stain resistance.

The polyamides constituting the polyamide spun-dyed yarn of the present invention include nylon 6, nylon 6.6, nylon 12,
It is made of a polymer having an amide bond such as fron 4, 6, or a copolymer or blend thereof.

Further, as the pigment used for the raw material in the present invention, any pigment can be used as long as it has weather resistance and washing resistance.For example, inorganic In material such as carbon black,
Examples include organic pigments such as phthalocyanine green and perylene red.

The amount of coloring pigment added to the polyamide multifilament is not particularly limited, but it is usually an amount that provides a practically sufficient color depth, for example, 0.01 to 2.0% by weight.
is used.

In the spun-dyed polyamide yarn of the present invention, the polyamide constituting the multifilament is composed of cationically dyeable polyester.

The cationic dyeable polymer is not particularly limited;
Examples include those having fl/10''g or less and containing a sulfonate as the other terminal group.

Ordinary polyamide multifilament has an amino group concentration of 50 g equivalent/lohg or more in the terminal group.

The amino group concentration of the terminal group of polyamide is 10g/lo
Doppin-dyed yarn exceeding bg may be dyed in the post-processing process, or
This is undesirable as it will be contaminated with acidic substances. Also,
This dyed yarn cannot avoid contamination by acidic dyes and acidic substances simply because it has a small number of amino terminal groups, and it is cationically dyeable, which prevents acidic substances from approaching in an ionic manner. end groups, such as sulfonate salts as described above. Examples of compounds containing such sulfonate salts include sodium 3,5-dicarboxybenzenesulfonate.

Note that as the amino terminal Wi4 degree decreases, the dyeability deteriorates, but in the case of the present invention, since coloring is performed with a stock solution,
There is no need to worry about dyeability.

In the present invention, in order to make the amino group concentration of the terminal group of the polyamide constituting the spun-dyed yarn 10 g equivalent/10 hg or less, sodium 3,5-dicarboxybenzenesulfonate, thorium 3-carboxybenzenesulfonate, etc. A sulfonic acid compound, such as sulfonic acid compound, may be added to the polyamide to adjust the amino terminal group to a predetermined 4 degrees.

In addition, in order to improve the weather resistance of the polyamide multifilament itself or the coloring material 61, copper iodide,
Copper bromide, I14 chloride, etc. and cuprous J genide; or copper compounds such as copper sulfate, copper acetate, etc., especially copper halogenated halides from the viewpoint of less corrosion, 50 to 00ppm.
It is preferable to add about 100 to 700 ppm. If the amount is less than 50 ppl, the color will be dull or the polymer will tend to deteriorate, while if it exceeds 1,000 ppm, copper will precipitate and the spinning property will deteriorate.

At this time, as an agent for preventing precipitation or coloring of ff1i+1, an iodine compound such as copper iodide, a 2-mercaptohencyimidazole compound or a diol compound, pentaerythritol, and triphenyl phosphite are used, for example, 11 It is preferable to add a polycondensate or the like reacted at a molar ratio of 2 to 5 times the amount of the copper compound.

Furthermore, the polyamide spun-dyed yarn of the present invention may be added with a 15 water/oil repellent containing a fluorine compound, such as an acrylic ester or perfluoroalkyl group containing a perfluoroalkyl group.
The amount of trimellitic acid ester containing I badle group is 0.3 to 1. It is preferable from the viewpoint of preventing stains that it is possible to further prevent acidic stains by coating the fibers by coating the fibers to form a film of a fluorine compound on the surface of the fibers.

(Example〕 Hereinafter, the present invention will be explained in more detail with reference to Examples.

Incidentally, the spinning properties, acid stains and weather resistance were measured by straining as follows.

When drawing 1,000 kg of M-based polyamide multifilament, the number of times defects such as yarn breakage occurred was evaluated, and 1 time or less was evaluated as 012, 4 times as Δ, and 5 times or more as ×.

The method used to determine the extent to which carpets are stained by a commercially available beverage composition containing Red Dye No. 40 (acid dye) was applied.

That is, the beverage formulation is in dry solid form dissolved in deionized water to contain FD&C Red Dye No. per liter of water.
, 40 was set to 0.1 g. Sufficient wetting agent (DuPont, Morpol SE, nonionic ethylene oxide condensate) was added to the dye solution to provide 0.5 g of wetting agent per 11 parts of dye solution. The test sample was without a second lining;
It is a 3 inch by 3 inch square of undyed 25 oz level loop nylon 6.6 tufted to spunbond polypropylene.

The test sample (test curved piece) was red dye N.

Place Tough [-side down] in a shallow pool of 40EE of 40 Dirt Mixture. Normally, the soil mixture soaks into the Zube C specimen. After an immersion period of 2 to 2 minutes, the test piece is removed and placed in a shallow dish with the tufted side facing up in a wet state. The specimens were then placed in a circulating air oven for 20 minutes at 121°C.
Heat to °C. The specimen does not need to be dried at the end of this heating period. In many cases, it is extremely humid. The specimen is then rinsed with warm water, and the sample is manually squeezed for a 2 to 3 minute rinse to remove as much leta as possible. The rinsed samples are then dried at 12 BiC for 15 minutes. 15 samples
If not dry after minutes, heat at 121"C for an additional 15 minutes or until dry.

The degree of staining was evaluated using an unstained carpet as a standard sample, with no rips at all marked as O, those discolored due to dirt as ×, slight -ll in the middle, and △ for cracks. .

The above-mentioned test car vent piece was treated with a sunshine weather meter at 83°C for 500 hours while spraying water for 1 minute every 5 hours. Visually observe the state of deterioration. If the color has completely changed or deteriorated to a tattered state, mark it as ×. If the color has not changed and the strength is maintained as 5, mark it as 0. If the state is in between, Δ.
It was evaluated as

Examples 1-4, Comparative Examples 1-5 Amino end groups were end-capped with 3.5 dicarboxylbenzenesulfonate sodium as end-capping agent A.
Nylon 6 (intrinsic viscosity [η] - about 1.34) with various amino end group concentrations shown in Table 1 was prepared, 1.0% by weight of phthalocyanine green was added as a dyed pigment, and further Copper iodide Q4 to improve weather resistance
It was added in a proportion not shown in 1k in terms of atoms.

Next, the carpet was spun, stretched, and compressed to a tuft of 2,000 denier/L24 ft to form a carpet. After that, the carpet was evaluated for acid run and weather resistance. For comparison, Table 1 also shows the case where acetic acid was used as the terminal [, 1-chain agent B to lower the amino group.

As is clear from Table 1, the polyamide spun-dyed yarn of the present invention using a cationically dyeable polymer as the polyamide is particularly excellent against acidic stains, which is the object of the present invention.

On the other hand, with spun-dyed yarn using acetic acid as the end-blocking agent,
It can be seen that even if the amino concentration of the terminal group is less than Log equivalent/10 bg, both acidic staining and weather resistance are poor (Comparative Examples 1 to 3).
2). Furthermore, even in polyamides using thorium 3,5-dicarboxylbenzenesulfonate as an end-capping agent, the amino concentration of the terminal ◇t1 groups is ffi/1 per 10 g.
It can be seen that when the weight exceeds 0.06 g (Comparative Example 3), both acidic staining and weather resistance are poor.

Furthermore, the amino group concentration of the terminal group is log equivalent/106g
If the amount of the compound 5 (compound 51) added exceeds 1,000 ppm (comparative example 4), even if the polyamide contains a sodium sulfonic acid salt in the other end group, the spinning property may decrease. I understand.

(Effect of the invention) According to the present invention, the cation 6■
By using a dyeable polyamide multifilament, it is possible to expand the applications of the obtained spun-dyed yarn in woven and knitted fabrics.

In addition, it is possible to mix and knit the spruce-dyed yarn of the present invention and ordinary differently dyed yarn, and after mixing and knitting the sprue-dyed yarn of the present invention and ordinary undyed yarn, the latter It is possible to dye yarns without worrying about lθ dyeing or dyeing of spun-dyed yarns, and this has the advantage that woven or knitted fabrics can be made into multiple brands in the post-processing dyeing process.

Furthermore, it is reasonable and eliminates the trouble of post-processing such as so-called acid-resistant staining treatment (fix treatment with polyhydric phenols, tannins, etc.) that is performed on dyed products, and it also prevents yellowing caused by acid-resistant stains. Does not occur.

Furthermore, even if acidic stains are spilled during use, such as drinks containing synthetic colorants (food additives), the product will not be contaminated and will maintain its new color for a long time.

Claims (4)

[Claims] (1) A spun-dyed polyamide yarn consisting of multifilaments and having excellent stain resistance, characterized in that the polyamide constituting the filaments is a cationically dyeable polymer. (2) The spun-dyed polyamide yarn with excellent stain resistance according to claim 1, wherein the amino group concentration of the terminal group of the polyamide is 10 g equivalent/10^6 g or less, and the other terminal group contains a sulfonate. (3) 50 to 1,000 ppm of copper compound in polyamide
The spun-dyed polyamide yarn having excellent stain resistance according to claim 1 or 2. (4) The spun-dyed polyamide yarn with excellent stain resistance according to claim 3, wherein the copper compound is cuprous halide.