JPH0578932A - Shape memory protein fiber yarn manufacturing method - Google Patents

Abstract

(57) [Summary] [Purpose] A method for producing a protein fiber yarn that remembers a shape. [Structure] A phosphoramide compound is attached to the protein fiber thread,
It is characterized in that a predetermined shape is given and heat treatment is performed while maintaining the shape.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art As a method of imparting a predetermined shape to a protein fiber thread and storing it, a method of adsorbing a collagen protein derivative on raw silk (Japanese Patent Publication No. 63-64550) and a method of adsorbing animal protein on wool ( Japanese Examined Patent Publication No. 1-16953).

[0003]

The methods described in the above patent publications are all methods using proteins, but these methods have complicated steps.

[0004]

[Means for Solving the Problems] The above-mentioned problem is characterized in that a protein fiber thread to which a phosphorus amide compound is attached and which has a predetermined shape is heat-treated while maintaining the shape. Invention of a method for producing a memory protein fiber yarn (hereinafter, this invention is referred to as a first invention) and heat treatment of a knitted fabric to which a phosphorus amide compound is attached, followed by unknitting, and production of a shape memory protein fiber yarn The present invention was achieved by a method invention (hereinafter, this invention is referred to as a second invention).

The first invention and the second invention will be sequentially described below. In the first invention, the protein fiber yarn to which the phosphorus amide compound is attached may be composed of the protein fiber alone, or may be composed of a mixed fiber of the protein fiber and another fiber. Examples of the protein fiber include silk,
Examples include wool, mohair, cashmere and other animal hair spun yarns, twisted yarns, sun yarns and knitted yarns.

Examples of the phosphorus amide compound attached to the protein fiber yarn include amide phosphazene compounds and phosphoric acid amide compounds, among which the amide phosphazene compounds are represented by the general formula

[0007]

[Chemical 1]

A cyclic amide phosphazene compound of the formula (1), wherein x is an integer of 3 or more, or a general formula P _n N _n (NH ₂ ) _{2n + 2} (2) (where x in the formula (2) is positive) Or a linear amide phosphazene compound of the general formula P _n N _n-1 (NH ₂ ) _{2n + 3} (3) (wherein n is a positive integer of 2 or more) Composed. 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 compound is composed of one or more kinds of phosphoric acid triamide, phosphoric acid triamide condensate and amide-substituted derivative in which a part of the amide group is substituted with other substituent. To be done. Examples of the phosphoric acid triamide condensate are imide diphosphoric tetraamide NH (PO) ₂ (NH ₂ ) ₄ , which is obtained by releasing 1 molecule of NH ₃ from 2 molecules of phosphoric acid triamide, and condensed from 3 molecules of phosphoric acid triamide. Diimide triphosphate pentaamide (NH) ₂ (PO) ₃ (NH ₂ ) ₅ , which is condensed by releasing two molecules of NH ₃ ,
Similarly, 4-molecule condensate of phosphoric acid triamide, 5-molecule condensate of phosphoric acid triamide, 6-molecule condensate of phosphoric acid triamide and the like can be mentioned.

An amide-substituted derivative may be used, for example, a part of the amide group of phosphoric amide and phosphoric acid triamide condensate is

[0011]

[Chemical 2]

[0012] There is a form that is replaced by etc. In addition, a small amount of unreacted chlorine (-Cl) remains, and unreacted chlorine (-Cl) is hydrolyzed to give a hydroxyl group (-O).
Those which have become H) also constitute amide-substituted derivatives.

These phosphorus amide compounds are preferably applied to the protein fiber yarn in the form of an aqueous solution or an organic solvent solution. As such an aqueous solution, the phosphorus amide compound is neutral water or ammonium acetate, sodium chloride, nitric acid. A neutral aqueous solution of a phosphorus amide compound dissolved in an aqueous solution of a neutral compound such as sodium or magnesium chloride; an aqueous ammonia solution of the phosphorus amide compound, an aqueous solution of sodium carbonate,
Caustic soda solution, diammonium hydrogen phosphate solution,
Alkaline aqueous solution of phosphorus amide compound dissolved in alkaline aqueous solution such as sodium phosphate aqueous solution, calcium hydroxide aqueous solution, sodium oxalate aqueous solution; and phosphorus amide compound is phosphoric acid aqueous solution, ammonium chloride aqueous solution, monosodium hydrogen phosphate aqueous solution, acetic acid aqueous solution , An acidic aqueous solution of a phosphorus amide compound dissolved in an acidic aqueous solution such as an oxalic acid aqueous solution or a succinic acid aqueous solution.

Since the crude phosphorus amide compound is usually obtained by a deammonium chloride reaction of phosphorus oxychloride and ammonia, it contains a large amount of by-product ammonium chloride, but an aqueous solution of the crude phosphorus amide compound is one of the preferred embodiments. Is one. 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. The aqueous solution may contain an organic compound such as an organic solvent and an inorganic compound such as an acid, an alkali or a salt. Aqueous solutions containing ammonia and ammonium ions give particularly favorable results. Aging temperature is 10
The temperature is preferably 70 ° C., and the aging time varies depending on the aging temperature, but is preferably 1 hour or longer, particularly preferably 5 hours or longer.

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 ³¹ P NMR curve of a crude amidophosphazene compound (purity: 41.4%, ammonium chloride: about 58%) before aging, and peak C is a main component peak. FIG. 2 shows a solution of a crude amide phosphazene compound having a ³¹ P NMR curve shown in FIG. 1 dissolved in 14% aqueous ammonia to a concentration of 400 g / l of the crude amide phosphazene compound at 50 ° C. The ³¹ P NMR curve after aging for 12 hours is shown. 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.

FIG. 3 shows ³¹ P of a crude phosphoric acid amide compound (purity: 36.6%, ammonium chloride: 63%) before aging.
The NMR curve of the is shown. Peaks D and E are main component peaks. FIG. 4 shows a crude phosphoric acid amide compound having a ³¹ P NMR curve shown in FIG. 3 dissolved in a 10% aqueous ammonia solution to give an aqueous solution having a concentration of the crude phosphoric acid amide compound of 400 g / l at 50 ° C. ³¹ P shows the NMR curve of ³¹ P after aging for 50 hours. According to FIG. 4, the peaks D and E seen in FIG. 3 disappear and the peak F not seen in FIG.
And G are almost the same. Note that peaks F and G in FIG. 4 are peaks A and B in FIG. 2, respectively.
Is almost the same as the ppm value and is presumed to be the same substance.

As described above, when the phosphorus amide compound is attached to the protein fiber yarn in the first invention by using an aqueous solution of the phosphorus amide compound (including aged one), the aqueous solution may be used alone. Well, diammonium phosphate, ammonium chloride, organic amine hydrochloride, zinc chloride, magnesium chloride, zinc nitrate, zinc borofluoride, acid catalysts such as hydrochloric acid and phosphoric acid, and a small amount of resin processing agents that have been conventionally used. , A softening agent, a water repellent, and / or a cellulose cross-linking agent may be added as an auxiliary component. Particularly phosphates such as triammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium dihydrogen phosphate, tripotassium phosphate, sodium dihydrogen phosphate, dihydrogen phosphate. Sodium, trisodium phosphate, sodium ammonium hydrogen phosphate, calcium dihydrogen phosphate and the like are preferred adjunct ingredients. These auxiliary components promote the reaction between the silk and the phosphorus amide compound during the heat treatment. The organic solvent solution of the phosphorus amide compound of the present invention is obtained by dissolving and / or suspending the phosphorus amide compound in an organic solvent. Any organic solvent may be used as long as it dissolves and / or suspends the phosphorus amide compound, and examples thereof include aprotic polar solvents such as dimethyl sulfoxide ((CH ₃ ) ₂ SO), sulfolane and dimethyl sulfone, and ethylene. Polyhydric alcohols such as glycol, polyethylene glycol and glycerin can be mentioned.

A small amount of water, ammonium chloride, organic amine hydrochloride, zinc chloride, magnesium chloride, zinc borofluoride and other acidic catalysts in a solution of a phosphorus amide compound in an organic solvent and a small amount of resin processing conventionally used. Agent, softener,
Penetrants, water repellents and the like can also be added as auxiliary components. Particularly phosphates such as triammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium dihydrogen phosphate, tripotassium phosphate, sodium dihydrogen phosphate, dihydrogen phosphate. Sodium, trisodium phosphate, sodium ammonium hydrogen phosphate, calcium dihydrogen phosphate and the like are preferred adjunct ingredients. These auxiliary components promote the reaction between the silk and the phosphorus amide compound during the heat treatment. The crude amide compound contains a large amount of by-product ammonium chloride, and a solution of the crude amide compound in an organic solvent is one of the preferred embodiments. (Hereinafter, an aqueous solution of a phosphorus amide compound and /
(Or an organic solvent solution is called a processing agent solution) As a method of attaching the processing agent solution to the thread, a method of running the thread in the processing agent solution, immersing cheese or ridges in the processing agent solution, and using a centrifugal dehydrator, etc. It can be carried out by a method of deliquoring, a method of spraying and applying a processing agent solution on the yarn, or the like.

The amount of the processing agent solution adhered to the yarn is preferably such that the active ingredient of the phosphorus amide compound adheres to the yarn during drying (before heat treatment) in an amount of 1 to 20% by weight. The weight of the processing agent fixed to the finished thread is proportional to the phosphorus content of the thread. The preferred phosphorus content is 0.01 to 1.5% by weight, particularly preferably 0.05 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 whiteness are reduced depending on the material. As a drying method for removing water 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. it can. The subsequent heat treatment step may be performed in an undried state without drying.

The predetermined shape is imparted to the vegetable fiber yarn in the first invention by a twisting method, a winding method on a rod,
It can be carried out by a method of sandwiching with a jig. When using the twisting method, 800 in the S or Z direction
The twisted shape is preferably about 3,500 T / M.
In the first invention, the attachment of the phosphorus amide compound to the vegetable fiber thread and the imparting of a predetermined shape may be performed by the former, then the latter, or the latter.
The former may then be performed later. The former and the latter may be performed at the same time.

As a method of 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. The heat treatment may be performed once, may be performed twice or more, may be performed in an open state, or may be performed in a sealed state. If the yarn is hermetically sealed in a wet state, water or solvent remains in the yarn after heat treatment. A preferable heat treatment temperature is 50 to 180 ° C., and a preferable heat treatment time is 1 second to 60 ° C.
Minutes. The temperature and the time may be appropriately washed under the condition that the yarn is not damaged. By the heat treatment, the processing agent hardens and is fixed to the yarn, and the yarn remembers the shape at the time of the heat treatment. After the heat treatment, it is preferable to wash with hot water to remove the water-soluble components attached to the yarn. By this heat treatment, a shape memory protein fiber yarn having a predetermined shape is obtained, and the shape memory protein fiber yarn has at least 2 crimps / cm. When the yarn is untwisted in the direction opposite to the twisting direction after the heat treatment, the twisted state is stored in the shape memory, and thus crimping occurs due to the untwisting. The shape memory protein fiber yarn obtained in the first invention has a good fixing property of the phosphorus amide compound, and thus has the remarkable advantage that the shape memory property does not change due to washing or rubbing, and the process is extremely simple.

Next, the second invention will be described. The second invention differs from the first invention only in that a knitted fabric having a shape is already used and the knitting is performed after heat treatment.
The point of attaching the phosphorus amide compound and the point of heat treatment are the same as in the first invention. Therefore, the points different from the first invention will be mainly described. The knitted fabric used in the second invention is obtained by hand-knitting or machine-knitting yarns, and examples thereof include tricot fabric, tenjiku fabric, milling fabric, smooth fabric, fleece fabric, kanoko fabric, teleco fabric, pile. For example, dough. Since the knitted fabric used in the second invention has already been given a shape, unlike the protein fiber yarn in the first invention, it is not necessary to give a shape separately.

The unraveling after the heat treatment performed in the second invention is
An appropriate unraveling method is adopted depending on the type of each of the above-mentioned various knitted fabrics, but this is a matter well known in the art, and detailed description thereof will be omitted. By this unraveling, a protein fiber yarn having a predetermined shape during heat treatment can be obtained. In the second invention, the amount of the processing agent solution attached to the knitted fabric is preferably 1 to 20% by weight as in the case of the yarn of the first invention. The phosphorus content after disintegration is also preferably 0.01 to 1.5% by weight, particularly preferably 0.05 to 1.2% by weight, as in the first invention. The shape-memory fiber yarn obtained in the second invention also has a good adhering property of the phosphorus amide-based compound, and thus has the remarkable advantage that the shape-memory property does not change due to washing or rubbing, and the process is simple.

[0024]

EXAMPLES Examples of the present invention will be described below. Examples 1 to 4 (Examples of the first invention) As the protein fiber yarn, raw silk 31d was used, which was dipped in a phosphoric acid amide 100 g / l aqueous solution as a processing agent solution, squeezed to a pickup 105%, and dried. Without using the jig, the wood rod having a diameter of 2 mm was wound in one row to give a shape, and then heat-treated at 120 ° C. for 20 minutes to obtain the shape memory protein fiber yarn of Example 1 (measured by the sulfuric acid / colorimetric method). A phosphorus content of 0.2%) was obtained. The crimp a (pieces / cm) of the obtained shape memory protein fiber yarn of Example 1 and the number of crimps b (pieces / cm) after being immersed in water at 20 ° C. for 30 minutes and dried were measured, and the shape was maintained by the following formula. The rate R (%) was calculated. In addition, the shape memory protein fiber thread of Example 1 was put in a net and J
The crimp number c (pieces / cm) after washing 5 times was also measured according to IS L 0213103. The results are summarized in Table 1.

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

[0026]

[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 protein fiber yarn obtained after the treatment are shown in Table 1. According to Table 1, Example 1
Shape memory protein fiber yarns of ~ 4 have crimp number a after processing
The shape retention rate R calculated from the number of crimps b after water immersion drying is as high as 40 to 55%, and the number of crimps c after 5 times of washing is almost the same as the number of crimps b after being immersed in water. After that, it was revealed that the shape memory property was retained. On the other hand, in Comparative Example 1, the shape retention rate R was 33%, and the crimp number c after washing 5 times was 2.0, which was inferior to Example 1.

Example 5 (First Invention and Example) As a protein fiber yarn, after dipping raw silk 30d twin yarn in a processing agent solution, squeezing liquid, twisting and heat treatment were simultaneously carried out, and finally the twisting direction was changed. Untwisted in the opposite direction. See Table 2 for details of the processing agent solution and processing conditions used in this example.

[0029]

[Table 2]

As is clear from Table 2, the number of crimps a after processing of the protein fiber yarn of this Example 5 obtained after untwisting is 20.5 / cm, but the number of crimps after immersion in water is dried. b
Was 27.5 pieces / cm, and the number of crimps increased. The number of crimps c after washing 5 times was 26.0 pieces / cm, and almost no deterioration in shape memory property due to washing was observed.

Examples 6 to 7 (Examples of the Second Invention) As shown in Table 3, various kinds of knitted fabrics were used, which were dipped in a processing agent solution, squeezed, dried, heat-treated, and unknitted to form Example 6 ~ 7
The shape memory protein fiber yarn of was obtained. The physical properties of the obtained shape memory protein fiber yarn are shown in Table 3.

[0032]

[Table 3]

Comparative Example 2 Treatment was carried out under substantially the same conditions as in Example 6 except that no processing agent solution was used. Table 3 shows the physical property values of the obtained vegetable fiber yarn. As is clear from Table 3, in the shape memory protein fiber yarns of Examples 6 to 7, the shape retention rate R calculated from the clamp number a after processing and the crimp number b after immersion in water was 110 to 129%. It was also high, and the crimp number c after washing 5 times was almost the same as the crimp b after soaking in water, and it was revealed that the shape memory property was maintained even after washing. On the other hand, in the comparative example, the shape retention ratio R is 82.
%, The crimp number c after washing 5 times was 6.0, which was inferior to that in Example 6.

Example 8 As the protein fiber thread, raw thread 31d was used, and this was dipped in a dimethyl sulfoxide solution containing 200 g / l of crude phosphoric acid amide as a processing agent solution and 40 g / l of triammonium phosphate as an auxiliary component. After squeezing the liquid on the pickup 100, and without drying it, it is wrapped in a row on a wood rod with a diameter of 1 mm, which is a jig, to give a shape, and then it is sealed at 120 ° C. for 2 times.
Heat treatment was performed for 0 minutes to obtain a shape memory protein fiber yarn. Table 1 shows the physical properties of the obtained shape memory protein fiber yarn.

[0035]

As described above, according to the present invention, it is possible to obtain a shape-memory vegetable fiber yarn which has a simple processing step and whose shape-memory property is less likely to deteriorate with time due to washing or rubbing.

[Brief description of drawings]

FIG. 1 is an NMR spectrum diagram of an amide phosphazene compound used as a phosphorus amide compound in the present invention before aging.

FIG. 2 is an NMR spectrum diagram of an amide phosphazene compound used as a phosphorus amide compound in the present invention after aging at 50 ° C. for 12 hours.

FIG. 3 is an NMR spectrum diagram of a phosphoramide compound used as a phosphoramide compound in the present invention before aging.

FIG. 4 is an NMR spectrum diagram of a phosphoramide compound used as a phosphoramide compound in the present invention after aging at 50 ° C. for 50 hours.

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Claims (3)

[Claims] 1. A method for producing a shape memory protein fiber yarn, which comprises heat-treating a protein fiber yarn having a phosphorus amide compound attached thereto and having a predetermined shape, while maintaining the shape. 2. A predetermined shape is imparted by twisting,
The method for producing a shape memory protein fiber yarn according to claim 1, wherein the shape-memory protein fiber yarn is heat-treated at the same time as or after the twisting, and then untwisted in a direction opposite to the twisting direction. 3. A method for producing a shape memory protein fiber yarn, which comprises heat-treating a knitted fabric having a phosphorus amide compound attached thereto, and then deknitting the knitted fabric.