JPH0660466B2 - Shape memory plant fiber manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a shape memory vegetable fiber yarn.

[Prior Art] As a method of imparting a predetermined shape to a vegetable fiber thread and storing it, a method of adsorbing animal protein on rayon and exposing it to chrome (Japanese Patent Laid-Open No. 60-259677), yarn and rayon. There is a method of adsorbing animal protein to which soy milk is added and steam-setting (Japanese Patent Publication No. 116951).

[Problems to be Solved by the Invention] Although all the methods described in the above patent publications utilize animal protein, these methods use animal protein adsorbed on cotton thread or rayon by washing or rubbing. However, there is a problem in that the shape memory property decreases with time.

[Means for Solving the Problem] The above-mentioned problem is characterized by subjecting a plant fiber to which a phosphorus amide compound is attached and having a predetermined shape to dry heat treatment while maintaining the shape. It was achieved by the invention of a method for manufacturing a memory plant fiber system.

The present invention will be described below.

In the present 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 of which include natural fibers such as cotton, ramie, and linen, and viscose rayon, polynosic, cupra, etc. Cellulose fibers may be mentioned. Further, fibers other than the base material, for example, organic synthetic fibers such as polyamide, polyester, polyacrylonitrile and spandex, inorganic fibers such as glass fibers, carbon fibers and silicone carbide fibers may be mixed.

Examples of phosphorus amide compounds attached to the plant fiber yarn include amide phosphazene compounds and phosphoric acid amide compounds. (In the formula (1), x is an integer of 3 or more), or a cyclic amide phosphazene compound or a general formula P _n N _n (NH ₂ ) _{2n + 2} (2) (wherein n is a positive number) Is an integer) or a linear amide phosphazene compound of the general formula P _n N _n-1 (NH ₂ ) _{2 n + 3} (3) (wherein n is a positive integer of 2 or more) Composed of.

In the general formulas (1), (2) and (3), a part of the amide group is an unsubstituted chloro group, a hydroxyl group obtained by hydrolysis, an alkoxy group such as a methoxy group and an ethoxy group, a phenoxy group, a mono-lower alkyl group. Those substituted with an amino group, a di-lower alkylamino group, a methylol group, a methoxymethyl group and the like are also included.

The phosphoric acid amide-based compound is composed of one or more kinds of phosphoric acid triamide, phosphoric acid triamide condensate, and an amide-substituted derivative in which a part of these amide groups is substituted with another substituent. As an example of a phosphoric acid triamide condensate, imide diphosphoric acid tetraamide NH (PO) obtained by releasing 1 molecule of NH ₃ from 2 molecules of phosphoric acid triamide and condensing
₂ (NH ₂ ) ₄ , 3 molecules of phosphoric acid triamide released from 2 molecules of NH ₃ and condensed to form diimide 3 phosphoric acid pentaamide (NH) ₂ (PO) ₃ (NH ₂ ) ₅ , and similarly phosphoric acid triamide 4-molecule condensate, 5 of phosphoric acid triamide
Examples thereof include a molecular condensate and a 6-molecule condensate of phosphoric acid triamide.

It may be used amide-substituted derivative, examples, some of the amide groups of the amide phosphate and phosphoric acid triamide _{condensates, -OCH 3, -OC 2 H 5} , -OC 3 H 7, -O
_{C 4 H 9 -OC 5 H 11} , _{-NHCH 3, -NHC 2 H 5,} -ONH 4, -CH 2
Some of them are substituted with OH, —CH ₂ OCH _3, etc.

Also, a small amount of unreacted chlorine (-C1) remaining, and a substance in which unreacted chlorine (-C1) is hydrolyzed to a hydroxyl group (-OH) also constitute an amide-substituted derivative.

These phosphorus amide compounds are preferably applied to the vegetable fiber thread in the form of an aqueous solution.
Phosphoramide compound is 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, magnesium chloride; an aqueous ammonia solution, an aqueous solution of sodium carbonate, an aqueous solution of caustic soda, an aqueous solution of diammonium hydrogen phosphate, a phosphoric acid. An alkaline aqueous solution of a phosphorus amide compound dissolved in an alkaline aqueous solution such as an aqueous sodium solution, an aqueous calcium hydroxide solution, an aqueous sodium oxalate solution; and an aqueous phosphoric acid compound, an aqueous solution of phosphoric acid, an aqueous solution of ammonium chloride, an aqueous solution of sodium hydrogen phosphate, an aqueous solution of acetic acid, shu An acidic aqueous solution of a phosphorus amide compound dissolved in an acidic aqueous solution such as an acid aqueous solution or a succinic acid aqueous solution may be used.

Since the crude phosphorus amide compound is usually obtained by a deammonification reaction of phosphorus oxychloride and ammonia,
Although it contains a large amount of by-product ammonium chloride, an aqueous solution of the 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 the phosphorus amide compound used in the present invention. Aging here means giving a chemical change to the aqueous solution of a phosphorus amide compound. The pH of the aqueous solution during aging may be acidic, neutral or alkaline. In the aqueous solution, organic compounds such as organic solvents, acids,
Inorganic compounds such as alkali and salts may be contained. 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.

During the aging, the amide phosphazene compound undergoes a chemical change, which is supported by the change in the ³¹ P NMR curve of the amide phosphazene compound before and after aging. Fig. 1 shows a crude amide phosphazene compound (Lot No. GB-003 manufactured by Nippon Soda Co., Ltd., pure 41.4).
%, Ammonium chloride approx. 58%) before aging ³¹ P NM
The R curve is shown, and the peak C is the peak of the main component. Second
The figure shows that the crude amide phosphazene compound showing the ³¹ P NMR curve was first dissolved in 14% aqueous ammonia and
Fig. 3 shows a ³¹ P NMR curve after aging an aqueous solution having a concentration of a crude amide phosphazene compound of 00 g / at 12 hours at 50 ° C. According to FIG. 2, the peak C seen in FIG. 1 disappears, while the occurrence of peaks A and B not seen in FIG. 1 is seen.

3 shows a ³¹ P NMR curve of a crude phosphoric acid amide compound (Lot No. GL-08, manufactured by Nippon Soda Co., Ltd., pure content: 36.6%, ammonium chloride: 63%, before aging. Peak D And E are the main component peaks, and Fig. 4 shows that the crude phosphoric acid amide-based compound whose ³¹ P NMR curve is shown in Fig. 3 is dissolved in a 10% aqueous ammonia solution to give 400 g / crude phosphoric acid amide-based compound. Aqueous solution with compound concentration of 50 ° C
The NMR curve of ³¹ P after aging for 50 hours is shown. According to FIG. 4, the peaks D and E seen in FIG. 3 have disappeared, and the components shown in the peaks F and G not seen in FIG. 3 have almost been changed. Note that peaks F and G in FIG. 4 have almost 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 plant fiber yarn in the present invention is preferably performed using an aqueous solution of a phosphorus amide compound (including aged one) (hereinafter referred to as a processing agent solution). , May be used alone, diammonium phosphate, ammonium chloride, organic amine hydrochloride, zinc chloride, magnesium chloride, zinc nitrate,
An acidic catalyst such as zinc borofluoride, hydrochloric acid and phosphoric acid, and a small amount of a resin processing agent, a softening agent, a water repellent and / or a cellulose cross-linking agent which have been conventionally used can be added as an auxiliary component. As a method of attaching the processing agent solution to the thread, a method of running the thread in the processing agent solution, a method of immersing cheese or ridges in the processing agent solution and deliquoring with a centrifugal dehydrator, etc. It can be carried out by a method of spraying or coating the same.

Regarding the amount of the processing agent solution deposited on the yarn, the active ingredient of the phosphorus amide compound is 2 to the dried yarn (before heat treatment).
An amount of 7% by weight is preferable. The weight of the processing agent fixed to the as-processed 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 is also small, and if the amount of adhesion is large, the strength and self-dependence are reduced depending on the material. As a drying method for removing moisture after the processing agent solution is attached, it can be carried out by a method such as radiation using a heat source such as hot air, infrared rays, far infrared rays, microwaves, steam, and electricity, electric heating, convection, etc. . The subsequent dry heat treatment step may be performed in an undried state without drying.

The imparting of a predetermined shape to the plant fiber yarn in the present invention can be carried out by a twisting method, a winding method around a rod, a sandwiching method with a jig, or the like. When adopting the twisting method, 800-3,500T in the S or Z direction
/ M twisted shape is preferable.

In the present invention, the attachment of the phosphorus amide compound to the plant fiber yarn and the imparting of a predetermined shape may be performed by the former, then the latter may be performed later, or the latter may be performed first, and then the former may be performed later. Good. The former and the latter may be performed at the same time.

As a method of dry heat treatment while maintaining the shape or simultaneously with imparting the shape, there are a hot air method, an infrared ray, a far infrared ray, a microwave method, a hot plate method and the like. 1
The heat treatment may be performed once, or the dry heat treatment may be performed twice or more. A preferable dry heat treatment temperature is 130 to 220 ° C., and a preferable dry heat treatment time is 1 second to 10 minutes. Regarding the temperature and time, it is appropriate to appropriately select the conditions that do not damage the yarn. By the dry heat treatment, the processing agent is hardened and fixed to the yarn, and the yarn remembers the shape at the time of the dry heat treatment. It is preferable to remove the water-soluble components attached to the yarn by washing with hot water after the dry heat treatment.

By this dry heat treatment, a shape memory vegetable fiber yarn having a predetermined shape is obtained, and this shape memory vegetable fiber yarn has crimps at a rate of at least 2 pieces / cm.

When the yarn is untwisted in the direction opposite to the twisting direction after the dry heat treatment, crimping occurs due to the untwisting because the twisted state is stored in the shape memory.

The shape memory vegetable fiber yarn obtained in the present invention has a good adhering property of the phosphorus amide compound, and thus has a remarkable advantage that the shape memory property is not changed by washing or rubbing.

According to the present invention, as will be apparent from the examples described later, 45-
A shape memory plant fiber having a shape retention of 150% is obtained.

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

Examples 1 to 4 As the plant fiber yarn, 100% 30 count single yarn was used, and this was dipped in 100 g of phosphoric acid amide which is a processing agent solution / aqueous solution, squeezed to a pickup of 95%, and dried without jig. A wire rod having a diameter of 2 mm is wound in a row to give a shape, and then a dry heat treatment is performed at 150 ° C. for 3 minutes.
The shape-memory vegetable fiber yarn (having a phosphorus content of 1.2% measured by a sulfuric acid / colorimetric method) was obtained.

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

In addition, the shape memory plant fiber thread of Example 1 was put in a net to obtain JI.
According to SL 0213 103, the number of crimps after washing 5 times c (pieces /
cm) was also measured.

Furthermore, the length L ₁ under a load of 100 mg and the length L under a load of 1000 mg were measured on the shape memory vegetable fiber yarn of Example 1,
The expansion ratio (%) was calculated by the following formula.

The results are summarized in Table 1.

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

Comparative Example 1 Treatment was carried out under substantially the same conditions as in Example 1 except that the phosphorus amide compound was not used. The physical properties of the vegetable fiber yarn obtained after the treatment are shown in Table 1.

Comparative Example 2 As the processing agent, industrial collagen was used instead of the phosphorus amide compound, and the treatment was performed under substantially the same conditions as in Example 1. Table 1 shows the physical properties of the vegetable fiber yarn obtained after the treatment.

Comparative Example 3 As a processing agent, a shrink-proofing processing agent and a glyoxal resin were used instead of the phosphorus amide compound, and the treatment was performed under substantially the same conditions as in Example 1. 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
Number of crimps a after processing and number of crimps b after immersion in water
The shape retention rate R calculated from is as high as 50 to 60%, and the crimp number c after washing 5 times does not change at all from the crimp number b after soaking and drying, and the shape memory property is retained even after washing. It became clear. Further, the shape memory plant fiber yarns of Examples 1 to 4 have a high expansion and contraction rate of 45 to 53%. On the other hand, in Comparative Example 1 in which the phosphorus amide compound is not used, the shape retention rate R is 39%, and the crimp number c after 5 times washing is c
Was 1.3 and the expansion / contraction rate was 15%, which was inferior to that of Example 1.

Also, instead of phosphorus amide compounds, industrial collagen,
In Comparative Examples 2 and 3 in which the glyoxal resin was used, the shape retention rate, the crimp number c after 5 times washing, and the expansion / contraction rate were inferior to those in Example 1.

Example 5 As a vegetable fiber yarn, 100% cotton 20th count twin yarn was dipped in a processing agent solution, and then squeezed, twisted and dry heat treated at the same time, and finally untwisted in the direction opposite to the twisting direction. See Table 2 for details of the processing agent solution used in this example, processing conditions, and the like.

As is clear from Table 2, the processed crimp number a of the plant fiber yarn of Example 5 obtained after untwisting was 10 / c.
However, the number of crimps b after immersion in water was 15.0 pieces / cm, and the number of crimps increased. Further, the crimp number c after washing 5 times was 14.5 pieces / cm, and almost no deterioration in shape memory property due to washing was observed. The expansion / contraction rate was 131%, which was extremely high.

[Effects of the Invention] As described above, according to the present invention, a shape memory vegetable fiber yarn in which the shape memory property is less likely to decrease with time due to washing or rubbing was obtained.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1, FIG. 2, FIG. 3 and FIG. 4 are NMR spectrum diagrams of amide phosphazene compounds and phosphoric acid amide compounds used as phosphorus amide compounds in the present invention.

Claims (4)

[Claims] 1. A method for producing a shape memory vegetable fiber yarn, which comprises subjecting a vegetable fiber yarn having a phosphorus amide compound attached thereto and having a predetermined shape to dry heat treatment while maintaining the shape. . 2. The shape according to claim 1, wherein a predetermined shape is imparted by twisting, a dry heat treatment is performed simultaneously with the twisting or after the twisting, and then untwisting is performed in a direction opposite to the twisting direction. Memory plant fiber yarn manufacturing method. 3. A shape memory plant having a shape retention rate of 45-150% by subjecting a plant fiber thread having a phosphorus amide compound attached thereto and having a predetermined shape to dry heat treatment while maintaining the shape. A method for producing a shape memory vegetable fiber yarn, which comprises obtaining a fiber yarn. 4. The shape memory according to claim 3, wherein a predetermined shape is imparted by twisting, dry twisting is performed simultaneously with twisting or after twisting, and then untwisted in a direction opposite to a twisting direction. A method for producing a vegetable fiber thread.