JP3403982B2 - Acrylic synthetic fiber and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to natural Angora rabbit hair, cashmere, mink having excellent water permeability, dyeability, texture after dyeing and water permeability, and excellent operability during spinning and spinning. The present invention relates to synthetic fibers having animal hair-like texture, continuous dyeing-dyed fibers, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, acrylic synthetic fibers have been recognized as fibers having a texture, luster, and excellent dyeing properties that are the closest to animal hair, and are widely used in the fields of imitation fur and high pile, such as boars assuming natural fur. It is used.

Usually, an oil agent used for acrylic synthetic fibers has a relatively strong squeegee in consideration of spinnability, but a silicone oil agent or a cationic oil agent is used in order to make the texture of natural animal hair closer. There are more examples than ever before. However, while a cationic oil agent can impart flexibility, it is particularly inferior in the slimy texture of animal hair after dyeing.

JP-A-60-21978, JP-A-6-2
0-209048 discloses an example in which a silicone oil is adhered to the surface of the shrinkable fiber of the pile, but the stability of the silicone emulsion is reduced, static electricity is generated during the raw cotton production process and spinning, and it is applied to various rollers. It is difficult to obtain the operability of this production level because the number of windings increases.

Further, the fibers to which the cationic softener and the silicone oil are adhered have strong water repellency, and when processing a high pile product, there is a problem in the permeability of the backing agent due to a decrease in permeability during dyeing and poor permeability. there were. Further, the silicone oil agent has a problem that static electricity is easily generated in the product processing step and the product. Especially when dyeing raw cotton using cationic softener and / or silicone oil, it has the drawback that oils other than silicone oil are washed off and the texture deteriorates and static electricity increases, resulting in poor water permeability. Was there.

[0006]

In view of the above-mentioned drawbacks of the prior art, the present invention provides water permeability, dyeability, texture, adhesiveness,
It is an object of the present invention to provide a synthetic fiber having excellent spinnability, in particular, water permeability, texture after dyeing, and water permeability, and a method for producing the same.

[0007]

The invention according to claims 1 and 2 of the present application is such that at least 0.1% by weight of a cationic softening agent and at least 0.1% by weight of polyoxyethylene alkyl urethane relative to an acrylic synthetic fiber. % Of the synthetic fiber, and in producing the synthetic fiber, a synthetic fiber characterized by being formed by adhering a cationic softening agent and polyoxyethylene alkyl urethane to the gel tow fiber It is a manufacturing method.

The invention according to claims 3 to 6 of the present application is composed of an acrylic copolymer containing 0.5 to 5% by weight of a sulfonic acid group-containing monomer, and is a basic dye in a gel swollen state in wet spinning. Acrylic synthetic fiber characterized by containing at least 0.1% by weight of a cationic softening agent and at least 0.1% by weight of polyoxyethylene alkyl urethane, and an acrylic synthetic fiber At that time, an acrylic copolymer containing 0.5 to 5% by weight of a sulfonic acid group-containing monomer is wet-spun, and the fiber in the gel state after stretching and washing with water contains at least a basic dye and a cationic softener. .1% by weight,
Polyoxyethylene alkyl urethane at least 0.
A method for producing an acrylic synthetic fiber, characterized in that 1% by weight is added.

First, the contents of claims 1 and 2 of the present invention will be described. The present invention relates to a fiber which can be dyed by so-called "cotton dyeing" to obtain a final product, and a method for producing the fiber.

The acrylic synthetic fiber of the present invention means 40% by weight or more of acrylonitrile and 60 other vinyl monomers.
It is composed of not more than wt%. Specific examples of vinyl monomers include acrylic acid, methacrylic acid, or their alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, sodium allyl sulfonate, sodium methallyl sulfonate, sodium vinyl sulfonate, styrene sulfonic acid. Examples thereof include soda and sodium 2-acrylamido-2-methylpropane sulfonate.

The acrylonitrile copolymer used in the inventions according to claims 1 and 2 of the present application particularly preferably has a sulfonic acid group-containing monomer. Examples of the sulfonic acid group-containing monomer include those obtained by appropriately combining sodium allyl sulfonate, sodium methallyl sulfonate, sodium vinyl sulfonate, sodium styrene sulfonate, sodium 2-acrylamido-2-methylpropane sulfonate, and the like.

The above-mentioned sulfonic acid group-containing monomer is preferably used for anionic synthetic fibers as anion seats for cation dyeing. Although the amount of the sulfonic acid group-containing monomer used in the present invention is not particularly limited, it is preferably at least 0.5% by weight from the viewpoint of fiber flexibility, and preferably 5% by weight or less from the viewpoint of production operability. With an excessive number of seats larger than the anion seats required for dyeing, the cationic softening agent is positively attached and left in the fiber. Therefore, not only the raw cotton but also the cationic softening agent is likely to remain after dyeing, so that the texture after dyeing is excellent, and an excellent animal hair texture can be achieved when the product is made.
Further, the hydrophilicity of the fiber itself becomes high, and the wettability at the time of dyeing can be improved.

The cationic softening agent used in the present invention includes polyoxyethylene polyamines, polyoxyethylene polyamine polyamides, polyamines such as polyoxyethylene alkyl polyamine derivatives, aliphatic amine salts and their quaternary ammonium salts, and aromatic salts. Examples thereof include a quaternary ammonium salt, a condensate of mono- or diacryloyl polyethylene polyamide and urea, and a cationic surfactant such as an epichlorhydrin reaction product salt thereof.

The polyoxyethylene may be polyoxypropylene, a block copolymer type polyether of polyoxyethylene and polyoxypropylene, or a random copolymer type polyether, and the molecular weight is preferably 200 to 8000, and particularly preferably the molecular weight. 500 to 3000 is preferable from the viewpoint of water permeability.

The alkyl group preferably has a long chain, because of its flexibility and maintaining the texture after dyeing, more preferably C
An alkyl group of 5 to 80 is preferable, and an alkyl group of C to 12 to 50 is particularly preferable from the texture after dyeing. It is preferable that the acrylic fiber is wet-spun and applied in a gel-swelling state as in the method of the present invention, since the amount of the acrylic fiber remains in the fiber and the durability against washing is increased.

The content of the cationic softening agent in the acrylic synthetic fiber is at least 0.1% by weight,
Good flexibility can be imparted with a content of 0.1% by weight or more, and the content is 0.1
If it is less than 5% by weight, the fiber lacks in flexibility and a good animal hair texture cannot be obtained. The range of 0.1 to 1% by weight is preferable.

The polyoxyethylene alkyl urethane used in the present invention is represented by the following formula.

[0018]

[Chemical 1] In the formula, R1 represents an alkyl group, and R2 and R3 represent polyoxyethylene or H.

The alkyl group having a long chain is flexible and tends to remain after dyeing, and preferably R1 has a carbon number of C = 5 to 5
80, more preferably C = 12 to 50, and particularly preferably 16 to 40 alkyl groups, which tend to remain after dyeing. R
At least one of 2 and R3 is polyoxyethylene, which is effective for raw cotton and water permeability after dyeing. The polyoxyethylene may be polyoxypropylene, a block copolymer type polyether of polyoxyethylene and polyoxypropylene, or a random copolymer type polyether, and has a molecular weight of 2
0 to 8000 is preferable, and the molecular weight is particularly 500 to 30.
00 is preferable because it easily remains after dyeing and has water permeability after dyeing.

As the compound represented by the formula, alkyl (C30) -OCONH-POE (2000), alkyl (C30) -OCONH-POE (3000), alkyl (C40) -OCONH-POE (2000), alkyl (C40) -OCONH-POE (2000) C40) -OCONH-POE (3000), alkyl (C30) -OCON- (POE (2000)) 2, alkyl (C30) -OCON- (POE (3000)) 2,
Alkyl (C40) -OCON- (POE (2000))
2, alkyl (C40) -OCON- (POE (300
0)) 2, alkyl (C12) -OCONH-POE (5
00), alkyl (C12) -OCONH-POE (20
00), alkyl (C12) -OCONH-POE (30
00), alkyl (C18) -OCONH-POE (50
0), alkyl (C18) -OCONH-POE (200
0), alkyl (C18) -OCONH-POE (500
0), and the like.

When the acrylic fiber is wet-spun and applied in a gel-swelling state as in the method of the present invention, a large amount of the acrylic fiber remains in the fiber and it is preferable from the viewpoint of washing durability. The content of polyoxyethylene alkyl urethane with respect to the acrylic synthetic fiber is at least 0.1% by weight, and the content is 0.1% by weight.
If the amount is less than the above, static electricity is increased in the carding process, and the water permeability is reduced depending on the amount of the oil agent adhered, resulting in fibers that are difficult to dye. The range of 0.1 to 1% by weight is preferable.

The component ratio of the cationic softening agent to the polyoxyethylene alkyl urethane is 0.5 to 2 parts by weight of the polyoxyethylene alkyl urethane relative to 1 part by weight of the cationic softening agent.
Part by weight, particularly 0.7 to 1.5 parts by weight, is preferable from the viewpoint of dyeability, texture after dyeing, static electricity suppression and water permeability. When the ratio of the components of the cationic softening agent is too large, static electricity is generated so much that the tows are largely scattered in the pre-drying step, which causes a winding problem.

The spinning may be carried out in the same manner as in the case of ordinary acrylic synthetic fibers, and it is passed through several stages of baths and sequentially drawn and washed to obtain gel swollen fibers. The fiber cross section may be round, flat, or any other type of cross section.

In the method of the present invention, the above-obtained fiber is provided with the cationic softening agent and the polyoxyethylene alkyl urethane-containing emulsion described above, and then dried and densified. At that time, it is preferable to perform the treatment using a roller dryer having a surface temperature of 120 to 160 ° C. and / or a hot air dryer having a dry heat of 120 to 180 ° C. Processing temperature is 12
When the temperature is 0 to 180 ° C., fibers having sufficient densification and excellent transparency can be obtained, and there is almost no coloring or deterioration of physical properties of the fibers due to heat treatment, which is preferable.

If necessary, an oil agent containing an antistatic component as a main component is applied before or after drying, and then post-treatment such as crimping and cutting is performed. Anti-static oil component is higher amine salt,
Examples include cationic surfactants such as quaternary ammonium salts, phosphoric acid ester surfactants, anionic surfactants such as sulfonates, and nonionic surfactants such as polyhydric alcohols, but especially cationic interfaces. Activators are preferred.

Next, the inventions of claims 3 to 6 of the present application will be described. These inventions relate to so-called "dyed fibers" and methods for their production. The acrylic copolymer used in the present invention also has the same composition as that described above. However, the copolymer used in the present invention must contain the sulfonic acid group-containing monomer in an amount of 0.5 to 5% by weight. If it is less than 0.5% by weight, the adhesion of the dye is poor under the conditions of medium-color and dark-color dyeing, and uneven dyeing occurs, or the adhered dye almost falls off. On the other hand, if it is more than 5% by weight, the hydrophilicity is too high, so that the coagulability, hot water resistance and stretchability are deteriorated.
As a result, single yarn breakage occurs in each process, roller winding troubles occur, and production operability is poor.

The acrylic synthetic fiber of the present invention is obtained by spinning the above-mentioned acrylic copolymer by a wet method, stretching and washing it in a gel state after washing with a basic dye and at least 0.1% by weight of a cationic softening agent, At least 0.1% by weight of ethylene alkyl urethane is added. At this time, the cationic softening agent to be attached and the polyoxyethylene alkyl urethane are as described above.

The basic dye used in the present invention refers to a dye generally called a cationic dye, for example, BSF of BASF Corporation.
asacryl series and Mitsubishi Chemical's Diacryl
There are series etc.

To briefly explain the dyeing conditions in the present invention, the pH is preferably 6 or less. Above this, the dye does not develop the desired color. Dyeing temperature is over 30 ℃ 80
Desirably below ℃. This is because it is easy to perform continuous dyeing uniformly in this range. The dyeing density varies greatly depending on the type of fiber and the target color, but it is about 1-40g
/ L range. In addition, "g / l" represents the weight of the dye contained in 1 liter of the dyeing solution. Normally, no auxiliary agent is required, but when the amount of dye adhering is less than 1.0% owf, a slow-dyeing agent may be used in order to prevent uneven dyeing. The primary acrylic synthetic fiber of the present invention can be produced in exactly the same equipment as a normal acrylic synthetic fiber, and it is not necessary to add any equipment other than the dye supplying device to the dyeing tank.

In the present invention, a specific method for adding a basic dye, a cationic softening agent, and a polyoxyethylene alkyl urethane to the gel-state fiber is, for example, preparing a solution of these to prepare the gel-state fiber. The method of immersing the in the solution is mentioned. In this case, each may be prepared and applied as a separate solution, but a method of preparing a mixed solution of three kinds and immersing the gel-state fiber in this solution is preferable.

In the present invention, any known additives may be added to the fiber. For example, flame retardants, light stabilizers, ultraviolet absorbers, pigments, antistatic agents and the like can be mentioned as specific additives.

[0032]

INDUSTRIAL APPLICABILITY The production method of the present invention is a method which can industrially easily and inexpensively produce an acrylic synthetic fiber having a soft animal hair-like texture which is excellent in spinning property and durability. Further, when the fiber obtained by the present invention is used for high pile, boar, napped products such as blanket of Meyer and clothing, it has a texture very similar to that of natural rabbit hair and cashmere, especially the texture of raw cotton and water penetration. Even after dyeing, the texture remains the same and the water permeability remains.

[0033]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, “%” means “% by weight”.

The amount of deposited oil was determined by refluxing and extracting with a Soxhlet extractor.

The static electricity on the card was measured with a current collector-type potentiometer manufactured by Kasuga Electric Co., Ltd. under the condition that the doffer rotation speed was 25 rpm and the humidity was controlled at 20 ° C. × 60% RH.

The raw cotton and the texture after dyeing were evaluated by five experts in three grades of ⊚ (very good), ◯ (good) and × (poor). The dyeing conditions at that time were as follows: a cationic dye was used and the bath ratio was 1:50 and the dyeing was performed at 100 ° C. for 60 minutes.

For the water permeability of the raw cotton and the dyed cloth, 1 g of cut cotton was made into a ball shape having a diameter of about 5 cm, and the time from floating in water at about 20 ° C. until sinking was measured (n = 3 average value). ◎
(Very good: less than 1 minute), ○ (Good: 1 minute to 30)
Min) and x (poor: does not sink in 30 minutes).

Examples 1-5, Comparative Examples 1-2 Acrylonitrile (AN) / vinylidene chloride (VDC)
/ 2-acrylamido-2-methylpropanesulfonic acid soda (SAM) = (58-X) / 42 / X was added to the acrylic copolymer shown in Table 1 so that the polymer concentration was 27%. )) Was spun into a coagulating bath of DMF / water = 58/42%, 20 ° C. through a 0.055 mmφ × 80,000 hole spinneret, and stretched 6 times, and then washed with water to obtain a gel swollen fiber. .
As shown in Table 1, a cationic softening agent (A1), a polyoxyethylene alkyl urethane (B1) and an antistatic agent (C1) were applied to the fiber obtained by the above method, and a surface temperature of 150
It was densified with a roller dryer at ℃. After that, crimping and cutting were carried out to obtain 3d × 51 mm acrylic fiber and evaluated. The evaluation results are also shown in Table 1.

[0039]

[Table 1]

Examples 6 to 9 and Comparative Examples 3 to 4 AN / methyl acrylate (MA) /SAM=89.9/
A spinning dope was prepared by dissolving an acrylic copolymer of 7.6 / 2.5 in DMF so that the polymer concentration was 25%. Then, 1.2% by weight of titanium oxide in a DMF dispersion liquid was added to this spinning dope to obtain 0.451 mm × 0.038 m.
After being spun through a 25,000-hole flat die with a DMF / water = 55/45%, 21 ° C. coagulation bath and drawn 5.5 times, it was washed with water to obtain gel swollen fibers. And
A solution of a basic dye, a cationic softener, a polyoxyethylene alkyl urethane and an antistatic agent is prepared, placed in the same tank, and the above-mentioned gel swollen fiber is dipped in it,
It was densified with a roller dryer having a surface temperature of 150 ° C. After that, crimping and cutting were performed to obtain flat fibers of 10 d × 51 mm. The evaluation results are also shown in Table 2.

[0041]

[Table 2]

Dyeing spots of Geltow staining were judged by the following three grades from the results of the visual judgment of 5 persons. ◯: Almost no stain spots Δ: Partial stain spots ×: Many stain spots

The loss of the dye in the step after dyeing was judged by observing the stain with the naked eye and by the following three steps. ○: Almost no omission △: Some omission ×: Very omission

Regarding the production operability, the presence or absence of trouble such as roller winding was judged by the following two stages. ◯: There is no trouble such as single fiber breakage and winding. X: There is a problem such as single fiber breakage and winding.

The concentration of the dye was adjusted to 2% gel tow.
A medium color and a 5% dark color were dyed. A solution of a basic dye, a cationic softening agent, a polyoxyethylene alkyl urethane and an antistatic agent was prepared and put in the same tank, and this tank was installed after the water washing step in the acrylic fiber manufacturing step.

Examples 10-14, Comparative Examples 5-6 Acrylonitrile (AN) / vinylidene chloride (VDC)
/ 2-acrylamido-2-methylpropanesulfonic acid sodium (SAM) = (58-X) / 42 / X, using an acrylic copolymer, fibers in gel swelling state after drawing and water washing steps Was immersed in the bath described above. As a basic dye, Basacryl Blue X3GL (BASF
(Made by the company) was used. Then, it was dried and densified, crimped, and cut to obtain 3d × 38 mm undyed cotton. The evaluation results are also shown in Table 3.

[0047]

[Table 3]

In Examples 10 to 14, 2% of medium-colored dyeing spots, 5% of highly dark-colored dyeing spots did not drop out of the dye in the washing tank, and the production operability had problems such as roller winding. It did not occur and everything was good. The water permeability was also good.

However, in Comparative Example 5, the adhesion of the dye was not good, and not only the uneven dyeing occurred, but also the adhered dye almost fell off. However, no problems occurred during spinning, and the workability was good.

On the contrary, in Comparative Example 6, there was almost no loss of the dye, and there was no problem of uneven dyeing (middle color, dark color) of the dyed cotton. However, since the hydrophilicity was too high, the coagulability, hot water resistance, and drawability were deteriorated. As a result, single yarn breakage occurred in each process, roller winding problems occurred, and operability was poor.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiro Sakata 4-1 Kanebocho, Hofu-shi, Yamaguchi Kanebo Synthetic Co., Ltd. (56) Reference JP 2000-336579 (JP, A) JP 8-337930 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) D06M 13/00-15/72

Claims (6)

(57) [Claims] 1. An acrylic synthetic fiber comprising at least 0.1% by weight of a cationic softening agent and at least 0.1% by weight of a polyoxyethylene alkyl urethane based on the acrylic synthetic fiber. 2. When manufacturing an acrylic synthetic fiber,
The acrylic copolymer is wet-spun, drawn and washed with water, and at least 0.
A method for producing an acrylic synthetic fiber, which comprises depositing 1% by weight and at least 0.1% by weight of polyoxyethylene alkyl urethane. 3. A sulfonic acid group-containing monomer is added in an amount of 0.5-5.
It is composed of an acrylic copolymer containing 10% by weight, is dyed with a basic dye in a gel swollen state of wet spinning, and contains at least 0.1% by weight of a cationic softening agent and at least 0.1% by weight of polyoxyethylene alkyl urethane. Acrylic synthetic fiber characterized by being contained. 4. When producing an acrylic synthetic fiber,
An acrylic copolymer containing 0.5 to 5% by weight of a sulfonic acid group-containing monomer is wet-spun, stretched and washed with water, and at least 0.1% by weight of a basic dye and a cationic softening agent are added to fibers in a gel state. %, Polyoxyethylene alkyl urethane at least 0.1% by weight is attached, and a method for producing an acrylic synthetic fiber, comprising: 5. The fiber in gel state is
The manufacturing method according to claim 4, wherein the solution is attached by being dipped in the solution. 6. The fiber in a gel state,
The production method according to claim 5, wherein the solution is attached by immersing it in the mixed solution of.