JPH10158976A - Slenderized animal hair fiber and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a fiber product having excellent physical properties, tenseness and stiffness characteristic to animal hair while keeping a slenderized state by orienting an animal hair fiber to slenderize and subsequently fixing it with a crosslinking agent. SOLUTION: Wool sliver 70 is fed to an orientation apparatus consisting of a combination of 12 steps of top rollers (31-42) and 24 steps of bottom rollers (1-24), and the sliver is oriented by multi steps. Subsequently, after the oriented sliver is impregnated with a crosslinking agent such as an aldehyde, an acetal, an epoxy compound, an active vinyl compound, an aziridyl compound, a polycarboxylic acid (acid chloride), an isocyanate compound and/or a quaternary ammonium compound, preferably a water-soluble epoxy compound in chemical baths 81-84, it is treated with a squeezing solution containing a catalyst such as magnesium perchlorate and a stabilizer such as zinc acetate, dried and subjected to a curing treatment to obtain the objective slenderized wool fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing animal hair fibers elongated by a drawing treatment, and to a fiber product obtained by using the same.

[0002]

2. Description of the Related Art Synthetic fibers are drawn after spinning to make the fibers elongated. The main purpose of this stretching is not only to make the fibers thinner, but also to orient the molecules and improve the strength. The spun fibers are continuous, at which point stretching is easy.

[0003] Recently, with the diversification of hobbies, the demand for clothing using fine-count animal hair has been increasing. However, fine-counter animal hair has traditionally only depended on natural ones, and furthermore, fine-counter animal hair has extremely low hair production and is very expensive, and a technology capable of supplying it at low cost has been desired. .

[0004] In order to reduce the length of animal hair using a common thick animal hair, for example, the surface of the animal hair fiber is dissolved or
Although it is conceivable to stretch animal hair, the former can impair the texture, characteristics, or strength of animal hair, and therefore has a limit to thinning, and can be used only in special cases.

On the other hand, in the latter method, animal hair is different from synthetic fiber, and the average fiber length, for example, Merino is usually 50 to 9%.
0 mm, and it has been difficult until recently to stretch this on an industrial scale. Recently disclosed technology is disclosed in Japanese Patent Application Publication No. Hei 5-500899. According to this technology, the driving speed difference between pulleys and the entire pulley are rotated in the direction perpendicular to the fiber axis and stretched while applying false twist to the sliver, and this advanced false twist grips short fibers and prevents slipping It is characterized by stretching. Further, according to the technology disclosed in Japanese Patent Application Laid-Open Publication No. Hei 7-3556, a feature is that short fibers are directly grasped and stretched in multiple stages using a plurality of nip rolls. The main chemical mechanism for elongation (deformation fixation) is to reduce and cut disulfide bonds (cross-linking) existing between the molecules of wool fibers, and then re-crosslink by oxidizing with steam or an oxidizing agent. It is used as a so-called "set" of wool fibers, and there is no great difference between them. Therefore, as disclosed in JP-A-7-3556, a bulky thread or a fabric having a high stretch property can be manufactured by returning to the original length after the elongation (for example, in the state of a thread, a knit, or a fabric). Has advantages. However, on the other hand, wool fibers are subjected to extremely high stress for elongation, and it is necessary to always block the -SH group expressed during the process in order to completely maintain the elongation state. That is, after the elongation, the setting involving the reduction / oxidation reaction of the disulfide bond cannot be performed again. Further, it is difficult to completely maintain the elongation even under conditions that significantly promote the swelling of the fiber, such as in an alkaline bath.

[0006] Further, the disulfide bond in the wool fiber is extremely oriented due to the elongation, and has a high setting property. In particular, it has the advantage of improving the pleating property of the woven fabric, but on the contrary, it has anti-wrinkle property and hygral expansion. (HE)
Has the disadvantage that the performance is greatly reduced as compared with the case where regular wool fibers are used. Even in the texture of the woven fabric, the original firmness / stiffness of the wool fiber is considerably reduced.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in animal hair fibers elongated by stretching. That is, it can be processed under normal conditions for producing animal hair fiber while maintaining its slender state, and it has the original physical properties of animal hair and firmness.
An object of the present invention is to provide a fiber product having stiffness and a method for producing the same.

The animal hair fibers used in the present invention include, for example, wool, alpaca, mohair, angora, and camel, but are not limited thereto. Hereinafter, animal hair fibers are sometimes referred to as wool fibers.

[0009]

The significance of disulfide bonds (crosslinking) in wool fibers is that they do not dissolve in polar solvents and have only limited swelling in the transverse direction. It is a characteristic feature of a natural protein fiber, such as relatively strong wet strength, reversible cross-linking and setability. However,
Maintaining the shape of the wool fiber elongated by drawing only by the inherent disulfide bond makes the handling delicate and limits the subsequent processing conditions. This is probably because extremely high stress was generated in the fiber axis direction by the drawing. For this reason, the light reduction treatment used for the set processing and the treatment in a weak alkaline bath for washing cannot be generally performed because the elongation cannot be maintained. Further, the disulfide bonds existing between and within the molecules are highly oriented due to the elongation, so that the physical properties or texture of wool fibers are changed.

[0010] In order to solve this problem, the present invention is to introduce a new chemically stable cross-link between wool fiber molecules. In addition, since disulfide bonds are greatly involved in the setting properties of wool fibers, it is important to introduce other cross-linking bonds. The method of introducing such cross-linking between fiber molecules has been studied in detail for cellulosic fibers in addition to wool fibers, and is already known.However, an example applied to wool fibers elongated by drawing has been found so far. Without
It has been achieved as a result of intensive studies.

As a possible crosslinking agent, aldehyde R
CHO (including N-methylol compounds as derivatives),
Acetal RCHCOR ', epoxy compound

[0012]

Embedded image Active vinyl compound R (CH = CH ₂ ) ₂ , aziridyl compound

[0013]

Embedded image Polycarboxylic acid, R (COOH) ₂ , its acid chloride R
(COCl) ₂ , isocyanate R (NCO) ₂ , quaternary ammonium compound

[0014]

Embedded image And the like.

Note that R and R 'used in the above chemical formulas 1 to 3 are used.
Represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
R and R 'may be the same or different.

In the case of an aromatic hydrocarbon group, a benzene ring,
Alternatively, a compound in which a methyl group and / or a hydroxyl group are bonded to a naphthalene ring, and in the case of an aliphatic hydrocarbon group, CnH2n or CnH2n + 1 (n is a positive integer)
It is. Although it cannot be said unconditionally depending on the compound, n is at most up to 18, usually 1 to 5, preferably 1 to 3.
It is.

However, water-soluble epoxy compounds are preferred in view of the fact that they can be treated in an aqueous system, that they are highly safe, and that they do not damage wool fibers when cross-linking is introduced. That is, the epoxy compound that can be preferably used in the present invention is:

[0018]

Embedded image It has a chemical structure exemplified by Among them, particularly preferred epoxy compounds are diglycidyl ether and those wherein R is -O- (CHOCHO) n- and n = 1 to 5.

The above compounds can also form crosslinks between fiber molecules by treatment in a bath in the presence of an alkali agent, but are not preferred in the present invention as described above. In the present invention, it is essential to carry out the reaction on the acidic side, but there is no problem since the above compound can be cross-linked by using an acidic catalyst by padding, drying and heat treatment. Further, since the above compounds have low self-condensability, hardening of the texture is kept to a minimum. This means that it can be processed with raw cotton such as sliver without any trouble in the spinning process.

The introduction of a new cross-link by the epoxy compound can be carried out by a known method. The epoxy compound and the acidic catalyst may be added to water or an aqueous solution of isopropyl alcohol, and the resulting mixture may be applied to fibers, dried, and heat-treated. What is necessary is just to apply uniformly to the wool fiber thinned by drawing, and the fiber may have any shape in principle, such as sliver, yarn, knitting and woven fabric. However, since the crosslinking treatment is not completed in the bath, processing with a sliver and a fabric is generally easy. A wide variety of application methods such as spraying and putting can be employed. In the processing using a sliver, a dip and a nip may be performed by continuously providing a bath to a known stretching device (for example, Japanese Patent Application Laid-Open No. 7-3556). In addition, treatment by a back washer may be performed independently after stretching. In the case of treatment with fabric, normal padding treatment is advantageous.
Generally, it is better to carry out this processing before dyeing. (Good elongation maintenance during dyeing).

The amount of the epoxy compound to be used cannot be determined unconditionally depending on the type of the catalyst, the properties of the elongated wool fiber and the fabric, etc., but is preferably 0.01 mol or more in consideration of the epoxy equivalent per 100 g of the elongated wool fiber. Is 0.01 ~
What is necessary is just to use 0.2 mol. The heat treatment conditions also vary depending on the type of the catalyst used, but generally from 110 to 150 ° C, from 3 to 150 ° C.
When the temperature is 150 ° C. or more for 10 minutes, the wool fiber turns yellow, which is not preferable.

The product made of the thinned wool fiber subjected to the above-mentioned cross-linking treatment is fine and soft, and has the natural firmness of wool,
Has a stiffness.

Hereinafter, the present invention will be described in detail with reference to embodiments.

Example 1 A pure wool sliver for spinning having an average fiber diameter of 20.97 μm and a fiber length (average 74 mm, maximum length 143 mm) was adjusted to a sliver density of about 18 g / m using a rotary gil.
This adjusted sliver was stretched at a nip pressure of 160 kg and a supply speed of 30 cm / min using the stretching apparatus shown in FIG. An aqueous solution (adjusted to pH 8.0 with 20% sodium hydroxide) containing 30 g / l of sodium bisulfite and 2 g / l of monoethanolamine as a wetting liquid was heated to 80 ° C.

The specifications of the stretching device are as follows. Bottom roller: 24 steps, stainless steel, diameter 20 mm, working width 200 mm, concave width 2 mm, convex width 1.45 mm, depth 1 m
m. Up to 12 of the 24 bottom rollers were immersed in the wetting liquid. Bottom rollers (1, 2); (3, 4);
(5,6); (7,8); (9,10); (11,1)
The distance between the shafts in each combination of 2) was 28 mm, and each pair was rotated at the same speed. Stretching is a bottom roller (2,3); (4,5); (6,7); (8,9)
The distance between the axes was 24 mm.
The rotation speed of the bottom roller 1 is 0.8 rpm,
(2, 3); Each speed ratio up to (12, 13) is increased in six steps by 1.05 times as compared with the front and rear. Bottom rollers 14 to 24 are also steps of fixing while stretching, and are heated at a vapor pressure of 2 kg / cm ₂ .

Bottom rollers (14, 15);
(17); (18, 19); (20, 21); (22, 2)
3) The speed ratio between each is 1.15 times, 1.10 times,
It is 1.10 times, 1.05 times, and 1.02 times, and between them, it is stretched 1.49 times.

The top roller was made of rubber having a hardness of 80, the diameter was 50 mm, and the interval between the rolls was 52 mm between the axes.

After stretching, bath A (81) is used for fixing.
Chemical treatment was performed in bath B (82), bath C (83), and bath D (84). The baths A and B were heated with 3% hydrogen peroxide at 80 ° C., and the bath C was washed with water at 40 ° C. Bath D contains 20% (w / v) of a water-soluble epoxy compound (Denacol EX-850, manufactured by Nagase Kasei Kogyo), 2.0% (w / v) of magnesium perchlorate as an acidic catalyst, and zinc acetate as a stabilizer. 0.2% (w / v) was padded at room temperature. The pickup rate at that time was 70%.

The stretched sliver thus obtained was air-dried at 80 ° C. After air drying, a curing treatment was performed at 130 ° C. for 10 minutes to react the epoxy compound. Thereafter, the unreacted epoxy compound was washed with a back washer and dried at 80 ° C.

The average diameter (average fineness) of the single fibers of the obtained sliver was 17.43 μm and the average fiber length (JIS)
L1083 5.2 Hauteur system) was 93.0 mm, and the longest part was 233 mm.

Using this sliver, spinning was performed in a normal process to obtain a spun yarn (meter count: 1/48 Z480). Steam the yarn at 90 ° C for 25 minutes, and twist
After twining at 0, the yarn was steamed at 90 ° C. for 25 minutes. This spun yarn became an extremely shiny knitted yarn.

The spun yarn described above was used in accordance with JIS L-1095.
The hot water shrinkage was measured by the 7.24A method. Further, using an aqueous alkaline solution (pH 10 with soda ash) and an aqueous solution containing a reducing agent (sodium bisulfite 30 g / l),
After boiling for 0 minutes, the shrinkage was measured in the same manner as the hot water shrinkage. The average fineness after the measurement of the shrinkage was also measured. Table 1 shows the results.

Furthermore, the above-mentioned knitted yarn was made into a skein of 250 g, and dyed red with a normal skein dyeing using a gold-containing dye.
Sweater using this yarn (12k-2
P). The sweater was very soft and had the swelling inherent in wool fibers while having a drape.

Comparative Example 1 An untreated sliver of the same lot as in Example 1 was subjected to a stretching treatment in the same manner. However, baths A, B and C were the same in terms of immobilization conditions, but bath D used normal-temperature water and did not use a water-soluble epoxy compound.

This stretched sliver (average fineness 17.41)
(μm, average fiber length 92.8 mm), the same yarn as in Example 1 was spun, and the same shrinkage test was performed. Table 1 shows the results. Further, a red sweater was produced from the knitted yarn in the same manner as in Example 1. The dyeing was performed in the same bath as in Example 1.

Although it had drape properties, it did not have the original swelling of wool fibers. The red color was lighter than that of Example 1.

As shown in Table 1, in Example 1 using a water-soluble epoxy compound, water, an aqueous alkaline solution,
The shrinkage under any conditions of the aqueous solution to which the reducing agent was added hardly shrank, and no significant change in fineness was observed. However, Comparative Example 1 was significantly shrunk by the alkaline aqueous solution and the aqueous solution to which the reducing agent was added. In addition, the fineness is also a large value, and it can be said that the elongation is unstable compared to the first embodiment.

Therefore, in the present invention, since the elongation is stable, there is no fear even in a process using an alkaline aqueous solution and an aqueous solution to which a reducing agent is added. For example, it is possible to use an alkaline agent in the scouring step. In addition, in the trouble in the dyeing process, decoloring with a reducing agent is also possible to some extent, so that restaining is possible without affecting the elongation.

Example 2 An average fiber diameter of 19.49 μm, an average fiber length of 66.5 mm,
A pure hair sliver for spinning having an elongated portion of 134.1 mm was subjected to a stretching treatment in the same manner as in Comparative Example 1. This drawn sliver (average fiber diameter 16.24 μm, average fiber length 90.4 m)
m, a slender part 204.8 mm) using a spun yarn for textiles (2
/ 72, Z760 x S800).

The spun yarn is used as a warp and a weft, and
/ 1 gabber (warp density 42 yarns / cm, weft yarn density 24 yarns / c
m, a basis weight of 310 g / m 2), and were subjected to rope washing and continuous boiling in a usual process. After drying, a water-soluble epoxy compound (Denacol EX-810, manufactured by Nagase Kasei Kogyo Co., Ltd.) was treated as a 10% (w / v) acidic catalyst with 0.8% zinc borofluoride.
% (W / v) and 0.1% (w / v) zinc acetate as a stabilizer.
/ V) was padded with one dip and one nip. The pickup rate at that time was 70%. After drying, curing was performed at 130 ° C. for 5 minutes. After treatment,
Washing solution (Peletex NC.57, Miyoshi Oil & Fat Co., Ltd.) at 70 ° C. for 10 minutes using a circular dyeing machine.
Soaping was performed at 3 g / l. After washing with water, the dyeing was carried out with a chromium dye and dyed dark blue. After dyeing, a normal finishing step was performed to obtain a woven product. The obtained product is soft, while having drape, wool product original swelling,
It had a tactile feeling of firmness and firmness. The Hygral expansion (IWS method), wrinkle resistance test (IWS method), tensile cooperation (JIS 1096 6.12 labeled strip method) and tear strength (JIS 1096 6.15 D method) of this woven product were measured. Table 2 shows the results.

Comparative Example 2 An untreated sliver of the same lot as in Example 2 was similarly subjected to a stretching treatment. Using this drawn sliver, the same yarn as in Example 2 was spun to produce a similar woven fabric. This woven fabric was subjected to the same steps as in Example 2 to obtain a woven product. However, the treatment of the water-soluble epoxy compound was not performed. The dyeing was performed in the same bath as in Example 1. The resulting product was soft and drapeable, but did not have the swelling, firmness, or firmness of wool products.

The same test as in Example 2 was performed on this woven product. Table 2 shows the results.

Comparative Example 3 Using untreated wool of the same lot as in Example 2, a yarn similar to that of Comparative Example 2 was obtained without stretching. Using the obtained yarn,
A fabric product similar to that of Comparative Example 2 was produced. Dyeing was carried out in the same bath as in Example 2 and Comparative Example 2. The resulting woven product had the firmness and firmness of the wool fiber product, but the softness and drapability were far from those of Example 2 and Comparative Example 2. Table 2 shows the physical properties of the fabric in the same manner as in Example 2 and Comparative Example 2.

As is evident from Table 2, the woven product obtained in Example 1 of the present invention is superior to Comparative Example 2 in hygral expansion, anti-wrinkle properties and tear strength.

The dye adsorbed amounts of the textile products of Example 2, Comparative Example 2 and Comparative Example 3 were in the following order.

(Light) Comparative Example 2 <Comparative Example 3 <Example 2
(Dark) From these results, Example 2 is advantageous in terms of dye cost,
There was no problem with regard to spots and color fastness as compared with Comparative Example 3.

Example 4 Average fiber diameter 25.66 μm, average fiber length 80.6 mm,
A stretch treatment was performed on the mohair sliver having the longest fiber of 161.3 mm in the same manner as in Comparative Example 1. Using this drawn sliver (average fiber diameter 22.21 μm, average fiber length 102.4 mm, longest fiber portion 291.3 mm), a spun yarn for woven fabric (織物)
0 Z540).

The spun yarn for woven fabric is used for the weft yarn, and the 2/72 yarn of Comparative Example 3 is used for the warp yarn, and a plain woven fabric (warp density: 23 / cm, weft density: 23 / cm, basis weight: 210 g / cm2) m
) Was produced. Rope washing and continuous washing were performed in the usual process. After drying, a water-soluble epoxy compound (Denacol EX-313, manufactured by Nagase Kasei Kogyo) was added at 10% (w /
v), 1.0% of magnesium borofluoride as an acidic catalyst
(W / v), and 0.1% zinc acetate as a stabilizer
(W / v) was padded with one dip and one nip. The pickup rate at that time was 70%.
After drying, curing was performed at 130 ° C. for 5 minutes. Using a circular dyeing machine, soaping was performed at 70 ° C. for 10 minutes with 0, 3 g / l of a detergent (Peletex NC-57, Miyoshi Oil & Fat Co., Ltd.). After the washing with the renewed solution, the product was dyed black with a chromium dye and subjected to a finishing process by a usual method to obtain a black woven product. The obtained product was blacker than ordinary wool / mohair products, and was at a level that could be sufficiently used as a formal black.

By stretching the mohair fiber and cross-linking it with a water-soluble epoxy compound, a woven product having unprecedented softness, drape and gloss can be obtained.

Example 5 The sliver of the elongated wool fiber obtained in Example 1 was dyed brown with a top dyeing machine in a conventional manner. The dye was a chromium dye and treated at 98 ° C. for 30 minutes.

The average fineness after dyeing is 17.41 μm.
No change was observed before staining.

Comparative Example 4 The sliver of the elongated wool fiber obtained in Comparative Example 1 was dyed brown with a top dyeing machine in the same manner as in Example 5. The average fineness after dyeing was 18.83 μm, which was a large value as compared to that before dyeing, and it was found that the shrinkage was apparent.

Comparing Example 5 with Comparative Example 4, Comparative Example 4 (elongated wool sliver obtained in Comparative Example 1) shows that
In the top dyeing process, in which wet heat is applied vigorously without tension, the fibers shrink and the elongation cannot be fixed. On the other hand, in Example 5 of the present invention (elongated sliver obtained in Example 1), no change in fineness was observed even by top dyeing, indicating that elongation was fixed and stable. .

Example 6 An untreated sliver of the same lot as in Example 1 was drawn in the same manner. However, thioglycolic acid 3
% (W / w) (adjusted to pH 8.0 with 20% sodium hydroxide) was used heated to 80 ° C.

For fixing after stretching, the same treatment as in Example 1 was performed. The average fineness of the obtained sliver is 17.46μ.
m, the average fiber length was 92.2 mm, and the longest part was 241 mm. Using this sliver, the same yarn as in Example 1 was spun and the same shrinkage test was performed. Table 3 shows the results.

Comparative Example 5 An untreated sliver of the same lot as in Example 6 was subjected to a stretching treatment in the same manner. However, in the fixing after the stretching, the epoxy compound was not used as in Comparative Example 1. This drawn sliver (average fineness 17.41 μm, average fiber length 91.8 mm)
Then, the same yarn as in Example 6 was spun, and the same shrinkage test was performed. Table 3 shows the results.

From Table 3, it can be seen that the present invention is stable in the elongation of slender wool fibers having different wetting liquids.

[0058]

According to the present invention, an elongated state is maintained,
It can be processed under normal production conditions for animal hair fiber products, and fiber products having the original physical properties of animal hair and firmness / stiffness can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a stretching apparatus and a processing bath used in the present invention.

[Explanation of symbols]

 (1)-(24) Bottom roller (31)-(42) Top roller (50) Immersion tank (60) Wetting liquid (70) Animal hair fiber sliver (81)-(84) Chemical treatment baths A-D

[Table 1]

[Table 2]

[Table 3]

Claims (4)

[Claims] 1. An elongated animal hair fiber wherein the animal hair is stretched and then stretched and fixed by a crosslinking agent. 2. A method for producing an elongated animal hair fiber, comprising stretching the animal hair and fixing it using a crosslinking agent. 3. The method according to claim 1, wherein the cross-linking agent is an aldehyde, an acetal, an epoxy compound, an active vinyl compound, an aziridyl compound, a polycarboxylic acid compound, an acid chloride of a polycarboxylic acid compound, an isocyanate compound, or a quaternary ammonium compound. For producing slender animal hair fibers. 4. The method for producing an elongated animal hair fiber according to claim 1, wherein the crosslinking agent is a water-soluble epoxy compound.