JPH03180581A - Production of shape memory vegetable fiber yarn - Google Patents

Abstract

PURPOSE:To obtain the subject fiber yarn having resistance to lowering of shape memory properties with time due to washing, etc., by making to adhere a phosphorous amide-based compound to a vegetable fiber yarn, giving a prescribed shape thereto it and subsequently heat treating it while retaining its shape. CONSTITUTION:By immersing a vegetable fiber yarn in an aqueous solution of a phosphorous amide-based compound, making to adhere the above mentioned compound thereto, e.g. twisting the fiber yarn without drying and carrying out heat treatment while retaining its shape, or by making to adhere the phosphorous amide-based compound to a knitted fabric already having a shape and carrying out heat treatment, the objective shape memory vegetable fiber yarn free from change of the shape memory properties due to washing, friction, etc., is obtained. A vegetable fiber yarn having memory of a prescribed shape at the time of heat treatment even when the above mentioned knitted material is unknitted is obtained.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing shape memory vegetable fiber yarn.

[Prior Art] As a method of imparting and memorizing a predetermined shape to vegetable fiber yarn, there is a method of adsorbing animal protein to rayon and treating it with chrome alum (Japanese Patent Application Laid-open No. 60-259677). There is a method (Japanese Patent Publication No. 1-16951) in which soy milk is added to adsorb animal protein and steam set.

[Problems to be Solved by the Invention] All of the methods described in the above patent publications utilize animal proteins; There is a problem that the particles fall off and the shape memory properties deteriorate over time.

[Means for Solving the Problem] The above problem is a shape memory method characterized in that a plant fiber to which a phosphorus amide compound is attached and which has been given a predetermined shape is heat-treated while retaining the shape. An invention of a method for producing a vegetable fiber yarn (hereinafter referred to as the first invention), and a method for producing a shape memory vegetable fiber yarn, which is characterized in that a knitted fabric to which a phosphorus amide compound is attached is heat-treated and then unwoven. (hereinafter, this invention will be referred to as the second invention).

Hereinafter, the first invention and the second invention will be sequentially explained.

In the first invention, the base material which is the fiber base material of the vegetable fiber yarn to which the phosphorus amide compound is attached is a vegetable fiber,
Examples include natural fibers such as cotton, ramie, and linen, and regenerated cellulose fibers such as viscose rayon, polynosic, and cupro. Further, any fibers other than the base material may be mixed, such as organic synthetic fibers such as polyamide, polyester, polyacrylonitrile, and spandex, and inorganic fibers such as glass fibers, carbon fibers, and silicone carbide fibers.

Examples of phosphorus amide compounds attached to this vegetable fiber thread include amidophosphazene compounds and phosphoric acid amide compounds, among which the amidophosphazene compounds have the following formula: ), in which X is an integer of 3 or more), or a cyclic amidophosphazene compound having the general formula %formula%(2) (in formula (2), X is a positive integer) or the general formula%formula%(3) ( It is composed of a linear amidophosphazene compound of the formula (3), where n is a positive integer of 2 or more. -General formula (1)
, Among (2) and (3), a partially unsubstituted chloro group in the amide group, a hydroxyl group resulting from hydrolysis, an alkoxy group such as a methoxy group or an ethoxy group, a phenoxy group, a mono-lower alkylamino group, or a di-lower group. Also included are those substituted with alkylamino groups, methylol groups, methoxymethyl groups, etc.

The phosphoric acid amide compound is composed of one or more of phosphoric acid triamide, phosphoric acid triamide condensate, and amide-substituted derivatives thereof in which a portion of the amide group is substituted with another substituent. An example of a phosphoric acid triamide condensate is imide diphosphoric acid tetraamide NH (PO), which is condensed by releasing one molecule of NH3 from two molecules of phosphoric acid triamide.
2(NH2) 4. Diimide triphosphate pentamide (NH)t (PO)3(NH2) 5 , which is condensed by releasing 2 molecules of NH3 from 4.3 molecules of phosphoric triamide.
Similarly, examples include a 4-molecular wire compound of phosphoric acid triamide, a 5-molecular wire compound of phosphoric acid triamide, a 6-molecular wire compound of phosphoric acid triamide, and the like.

Amide-substituted derivatives may also be used, for example, phosphoric acid amide and phosphoric acid triamide condensates in which part of the amide group is -0CH3, -0C2H5.

OC3H7, OC4H? , OC5Ht+.

-NHCH3, -NHC2H5, -0NHa.

Some are substituted with CHt OH, -CH20CH3, etc.

Further, those in which a small amount of unreacted chlorine (-CI) remains, and those in which unreacted chlorine (-CI) has become a hydroxyl group (-OH) through hydrolysis, also constitute amide-substituted derivatives.

These phosphorus amide compounds are preferably applied to the vegetable fiber threads in the form of an aqueous solution, and such aqueous solutions include:
Add phosphorus amide compounds to neutral water or ammonium acetate,
A neutral aqueous solution of a phosphorus amide compound dissolved in an aqueous solution of a neutral compound such as sodium chloride, sodium nitrate, or magnesium chloride;
An alkaline aqueous solution of a phosphoric acid compound dissolved in an alkaline aqueous solution such as ammonium aqueous solution, sodium phosphate aqueous solution, calcium hydroxide aqueous solution, sodium oxalate aqueous solution;
Examples include acidic aqueous solutions of phosphorus amide compounds dissolved in acidic aqueous solutions such as ammonium chloride aqueous solution, monosodium hydrogen phosphate aqueous solution, acetic acid aqueous solution, oxalic acid aqueous solution, and succinic acid aqueous solution.

Crude phosphorus amide compounds are usually obtained by dechlorinating ammonium reaction between phosphorus oxychloride and ammonia.
Although it contains a large amount of by-product ammonium chloride, an aqueous solution of a crude phosphorus amide compound is one of the preferred embodiments. An aqueous solution obtained by aging an aqueous solution of a phosphorus amide compound is also included in the aqueous solution of a phosphorus amide compound used in the present invention. The term "ripening" as used herein refers to imparting a chemical change to the aqueous solution of the phosphorus amide compound. The pH of the aqueous solution during aging may be acidic, neutral, or alkaline. In addition, the aqueous solution contains organic compounds such as organic solvents, acids,
Inorganic compounds such as alkalis and salts may also be included. Aqueous solutions containing ammonia and ammonium ions give particularly favorable results. The aging temperature is preferably 10 to 70°C, and the aging time varies depending on the aging temperature, but is preferably 1 hour or more, particularly preferably 5 hours or more.

The amidophosphazene compound undergoes a chemical change during ripening, and this is supported by the change in the 31P NMR curve of the amidophosphazene compound before and after ripening. Figure 1 shows a crude amidophosphazene compound (manufactured by Nippon Soda, lot No.

GB-003, purity 41.4%, ammonium chloride approximately 5
The NMR curve of 31P before ripening (8%) is shown, and the peak C
is the peak of the principal component. FIG. 2 shows an aqueous solution in which the crude amidophosphazene compound showing the 31P NMR curve in FIG.
The NMR curve of 31P after aging for 12 hours at °C is shown. According to FIG. 2, peak C seen in FIG. 1 disappears, while peaks A and B, which were not seen in FIG. 1, appear.

FIG. 3 shows the NMR curve of 3LP of a crude phosphoric acid amide compound (manufactured by Nippon Soda ■, Lot No. GL-08, purity 36.6%, ammonium chloride 63%) before ripening. Peaks D and E are the peaks of the main components. Figure 4 shows the third
The crude phosphoric acid amide compound showing the 3IP NMR curve in the figure was dissolved in a 10% ammonia aqueous solution, and 400 g/l was added.
An aqueous solution containing a crude phosphoric acid amide compound at a concentration of 5
The NMR curve of 31P after aging at 0° C. for 50 hours is shown.

According to FIG. 4, peaks D and E seen in FIG. 3 have disappeared, and most of the components have changed to peaks F and G, which were not seen in FIG.

Note that peaks F and G in FIG. 4 have approximately the same -ppm values as peaks A and B in FIG. 2, respectively, and are presumed to be the same substance.

As described above, the attachment of the phosphorus amide compound to the vegetable fiber yarn in the first invention is preferably carried out using an aqueous solution (hereinafter referred to as a processing agent solution) of a phosphorus amide compound (including an aged one), and the processing agent solution may be used alone, and acidic catalysts such as diammonium phosphate, ammonium chloride, organic amine hydrochloride, zinc chloride, magnesium chloride, zinc nitrate, zinc borofluoride, hydrochloric acid and phosphoric acid, and conventionally used Small amounts of resin processing agents, softeners, water repellents, and/or cellulose crosslinking agents may also be added as auxiliary components. Methods for attaching the processing agent solution to the yarn include a method in which the yarn is run through the processing agent solution, a method in which cheese or lint is immersed in the processing agent solution and the liquid is removed using a centrifugal dehydrator, and a method in which the processing agent solution is applied to the yarn. This can be carried out by spraying or coating the thread.

The amount of the processing agent solution attached to the yarn is 2 to 7% of the active ingredient of the phosphorus amide compound to the yarn during drying (before heat treatment).
The amount that adheres by weight is preferable.

The weight of processing agent fixed on the finished yarn is proportional to the phosphorus content of the yarn. The preferred content is 0.1 to 1.5% by weight, particularly preferably 0.5 to 1.2% by weight. This is because if the amount of adhesion is small, the shape memory effect will be small, and if the amount of adhesion is large, the strength and white skin will decrease depending on the material.

After the processing agent solution has been applied, drying methods to remove moisture include hot air, infrared rays, far infrared rays, microwave,
This can be carried out using methods such as radiation, electric heating, and convection using heat sources such as water vapor and electricity. Note that the subsequent heat treatment step can also be performed in an undried state without drying.

Giving a predetermined shape to the vegetable fiber yarn in the first invention is as follows:
This can be carried out by twisting, wrapping around a rod, sandwiching with a jig, etc.

When using the twisting method, 8
It is preferable to have a twisted shape of 00 to 3.5007/M.

The attachment of the phosphorus amide compound to the vegetable fiber yarn and the imparting of a predetermined shape to the vegetable fiber yarn in the first invention may be carried out first, and then the latter may be carried out later, or the latter may be carried out first,
The former may then be performed later. The former and the latter may be performed at the same time.

Methods for heat treatment while retaining the shape or at the same time as imparting the shape include methods using hot air, methods using infrared rays, far infrared rays, microwaves, and methods using a hot plate. The heat treatment may be performed once or twice or more. The preferred heat treatment temperature is 130 to 220°C, and the preferred heat treatment time is 1 second to 10 minutes. The temperature and time may be appropriately selected so as not to damage the yarn. The processing agent is hardened and fixed to the thread by heat treatment,
The yarn remembers its shape during heat treatment. After the heat treatment, it is preferable to wash the yarn with hot water or the like to remove water-soluble components attached to the yarn.

This heat treatment results in a shape memory vegetable fiber yarn having a predetermined shape, which shape memory vegetable fiber yarn has a ratio of at least 2 crimps/cm.

Further, when the yarn is untwisted in the opposite direction to the twisting direction after heat treatment, crimp occurs due to untwisting because the twisted state is stored in shape memory.

The shape memory vegetable fiber yarn obtained in the first invention has a remarkable advantage that the shape memory property does not change due to washing or friction because the phosphorus amide compound has good adhesion properties.

Next, the second invention will be explained. This second invention differs from the first invention only in that a knitted fabric that has already been given a shape is used and that it is unwoven after heat treatment, and that a phosphorus compound is attached. The heat treatment is the same as in the first invention. Therefore, the explanation will focus on the points that are different from the first invention.

The knitted fabric used in the second invention is obtained by hand-knitting or machine-knitting yarn, and examples thereof include tricot fabric, jersey fabric, milled fabric, smooth fabric, fleece fabric, kanoko fabric, teleco fabric, and pile fabric. Examples include fabrics. The knitted fabric used in the second invention has already been given a shape, so unlike the vegetable fiber yarn in the first invention,
There is no need to provide a separate shape.

For the unraveling after the heat treatment performed in the second invention, an appropriate unraveling method is adopted depending on the type of the above-mentioned various knitted fabrics, but this point is well known in the technical field, and detailed explanation is not provided. Omitted. By this unraveling, a vegetable fiber yarn having a predetermined shape upon heat treatment is obtained. In the second invention, the amount of the processing agent solution to be deposited on the knitted fabric is preferably 2 to 7 weight, similar to the case of the yarn of the first invention. As with the first invention, the preferable phosphorus content after disassembly is 0.
．． 1 to 1.5% by weight, particularly preferably 0.5 to 1.2%
Weight%.

The shape memory fiber yarn obtained in the second invention also has a remarkable advantage that the phosphorus amide compound has good adhesion properties, so that the shape memory property does not change due to washing or friction.

[Example] Examples of the present invention will be described below.

Examples 1 to 4 (Example of the first invention) A 100% 30 count single yarn was used as the vegetable fiber yarn, and this was immersed in a 100 g/l aqueous solution of phosphoric acid amide, which was a processing agent solution, and the pick-up was reduced to 90%. The shape-memory vegetable fiber yarn of Example 1 (sulfuric acid/colorimetric A phosphorus content of 1.2% was obtained.

Crimp a of the obtained shape memory plant fiber yarn of Example 1 (
The number of crimp b (pieces/cm) after immersion in 20° C. water for 30 minutes and drying was measured, and the shape retention rate R (%) was determined by the following formula.

In addition, the shape-memory plant fiber yarn of Example 1 was put into the net and J
The number of crimps C (pieces/cm) after washing 5 times was also measured according to IS L 0213103.

These results are summarized in Table 1.

Further, shape memory vegetable fiber yarns of Examples 2 to 4 were obtained in the same manner as in Example 1 using the vegetable fiber yarns, processing agent solutions, and processing methods shown in Table 1. The physical properties of these shape memory vegetable fiber yarns are also shown in Table 1.

Comparative Example 1 The treatment was carried out under almost the same conditions as in Example 1, except that no phosphorus amide compound was used. Table 1 shows the physical properties of the vegetable fiber yarn obtained after the treatment.

According to Table 1, the shape memory vegetable fiber yarns of Examples 1 to 4 are:
The shape retention rate R calculated from the number of crimps after processing and the number of crimps after immersion drying in water is as high as 50 to 60%, and the number of crimps after washing five times C is also the same as the number of crimps after immersion drying in water. It became clear that there was no change at all, and that the shape memory property was maintained even after washing. On the other hand, Comparative Example 1 had a shape retention rate R of 39% and a crimp number C after 5 washes of 1.3, which was inferior to Example 1.

Example 5 (Example of the first invention) As a vegetable fiber yarn, 100% cotton 20 count twin yarn was given a predetermined shape by twisting with a false twisting machine, then immersed in a processing agent solution, and then squeezed. Further, twisting and heat treatment were performed at the same time, and finally untwisting was performed in the opposite direction to the twisting direction. Please refer to Table 2 for details of the processing agent solution and processing conditions used in this example.

As is clear from Table 2, the number a of crimps after processing of the vegetable fiber yarn of Example 5 obtained after untwisting is 10/
cm, but the number of crimp after soaking and drying in water is 15.
0 pcs/am, and the number of crimps increased. Also 5
The number of crimps C after washing was also 14.5/cm, and almost no deterioration in shape memory was observed due to washing.

Examples 6 to 9 (Example of the second invention) As shown in Table 3, various knitted fabrics were dipped in a processing agent solution, squeezed, dried, heat treated, and unwoven to produce Examples 6 to 9.
A shape memory plant fiber yarn was obtained. The physical properties of the obtained shape memory vegetable fiber yarn are shown in Table 3.

Comparative Example 2 Processing was carried out under almost the same conditions as in Example 6, except that no processing agent solution was used. Table 3 shows the physical properties of the obtained vegetable fiber yarn.

As is clear from Table 3, the shape memory vegetable fiber yarns of Examples 6 to 9 have a shape retention rate R of 110, which is calculated from the crimp number a after processing and the crimp number after water immersion and drying.
~167%, which is high, and the crimp number C after washing 5 times is also equal to or higher than crimp B after soaking and drying in water.
It became clear that the shape memory property was maintained even after washing.

On the other hand, the comparative example had a shape retention rate R of 80%. Crimp number C after 5 washes is 8° O, It was inferior to Example 6.

(Hereinafter, blank space) [Effects of the Invention] As described above, according to the present invention, a shape memory vegetable fiber yarn whose shape memory properties are not easily deteriorated over time due to washing or friction was obtained.

[Brief explanation of drawings]

FIG. 1, FIG. 2, FIG. 3, and FIG. 4 are NMR spectra of amidophosphazene compounds used as phosphorus amide compounds in the present invention.

Claims (3)

[Claims] (1) A method for producing a shape memory vegetable fiber yarn, which comprises heat-treating a vegetable fiber yarn to which a phosphorus amide compound has been attached and which has been given a predetermined shape while maintaining the shape. (2) The shape memory vegetable fiber according to claim (1), wherein the predetermined shape is imparted by twisting, heat-treated at the same time as or after the twisting, and then untwisted in the opposite direction to the twisting direction. How to make yarn. (3) A method for producing a shape memory vegetable fiber yarn, which comprises heat-treating a knitted fabric to which a phosphorus amide-based compound is attached, and then unraveling it.