KR800000842B1 - Manufacturing method of acrylic fiber having the same feel as wool - Google Patents

Abstract

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Description

Manufacturing method of acrylic fiber having the same feel as wool

1 is an explanatory diagram of a fabric friction test apparatus used for the measurement of a smooth touch (slippery touch),

FIG. 2 is a rectangular coordinate diagram showing the relationship between the frictional resistance recorded by the test apparatus of FIG. 1 and the amount of displacement of the sample cloth.

The present invention relates to a method for producing a novel acrylic fiber having a hand such as hair wool, and in particular, an emulsifier selected from the group of POE (n ') alkylphenyl phosphates for the silicone resin represented by a specific structural formula. The present invention relates to a method for producing a novel acrylic fiber, wherein water is added with stirring to form a weakly acidic emulsion (emulsion), and then the formed emulsion zone is attached to the gel-like swollen acrylic fiber.

It is well known that knitted fabrics made from wool fibers such as wool, cashmere and angora rabbit curls have an excellent touch due to the unique smooth feel. However, such knitted wool fibers are not without any practical defects. For example, when a treatment involving a tumbling action, such as washing, is applied, since the fiber surface tissue is composed of flakes, a unique movement of directionality is generated between the fibers forming the knitted fabric, thereby producing the knitted fabric. Shrinkage defects occur.

Conventionally, in order to remove such defects, a method has been proposed to destroy flaky tissue on the surface of the fiber and to impart shrinkage by acting a chemical solution on the wool fiber or the knitted fabric made of the fiber. It is true that the shrinkage property of the knitted fabric is improved, but this method causes a definite defect in which the final product feel, in particular, the smooth feel, is remarkably lowered and the value of the product is greatly reduced.

On the other hand, in order to solve the defect in the conventional technology and to improve the dimensional stability during washing, a method of forming a knitted fabric by mixing synthetic fibers having no flaky tissue on the surface such as acrylic fibers with woolen fibers, In terms of dimensional stability against entanglement during washing, some improvement was achieved according to this method. However, the level of smooth touch, which is directly involved in maintaining the feel of wool, was originally low, and the result of sensory evaluation of the smooth touch was completely different from the knitted fabric made of wool.

條) 또는 편직포에 매끄러운 촉감을 부여하기 위한 목적으로 다가 알콜형의 비이온 계면 활성제 또는 양이온 계면활성제나 음이온 계면활성제 등을 합성섬유의 표면에 부착시키는 방법이 또한 제안되었으며, 이 방법에 따라 합성섬유에 약간의 매끄러운 촉감이 부여된 것은 사실이다. 그러나 계면활성제에 의하여 부여된 매끄러운 촉감에는 세탁 내구성이 전혀 없어 이들 섬유제품의 상품가치를 급속히 저히시키는 등의 요인이 되므로 이의 해결책을 발견하는 것이 당 업계에서 강하게 요망되고 있다.Also, apart from the attempt to use the above-mentioned woolen fibers as a material for forming a knitted fabric, synthetic fibers or yarns made of these fibers (

Iii) or a method of attaching a polyhydric alcohol type nonionic surfactant or cationic surfactant or anionic surfactant to the surface of a synthetic fiber for the purpose of imparting a smooth touch to a knitted fabric, has also been proposed. It is true that the fibers are given some smooth touch. However, there is a strong desire in the art to find a solution because the smooth touch imparted by the surfactant does not have laundry durability at all, which causes the product value of these textile products to be rapidly lowered.

In recent years, the use of higher esters of acrylic acid or methacrylic acid or vinyl esters of higher fatty acids as a fiber treatment agent has been described in the patent literature, but the smooth touch imparted by these fiber treatment agents is found in wool fiber products. It is completely heterogeneous to a smooth feel, and it is generally difficult to expect the effect of improving the feel of the final product through the use of such a fiber treatment agent.

In addition, it has been known to improve the feel of textile products by attaching silicone resins to acrylic fibers. However, in the former, no clear knowledge is known about silicone resins used as a fiber treatment agent, and acrylic fibers improved by such silicone resin processing are known. The product's touch is also a simple improvement in anti-pilling, which is completely different from the smooth feeling. In addition, since the latter uses a mixed treatment agent of silicone resin and epoxy resin as a treatment agent for acrylic fiber products, the touch of the final product becomes rough and hard due to adhesive curing between fibers, and the epoxy resin inhibits the smooth feeling imparted by the silicone resin. The commodity value of the final product is greatly reduced.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in order to discover the industrial knowledge which can give acrylic fiber or its product the smooth touch similar to a woolen fiber product, and softness and a shrinkage | contraction, As a result, the silicone resin and POE (n) represented by a specific structural formula The mixture is stirred with an emulsifier selected from the group of alkylphenyl phosphates, and water is added to form a weakly acidic emulsion, and the immersion is immersed in an acrylic fiber on a swollen gel obtained by wet spinning, and then immediately dried. The present invention has been discovered by discovering that acrylic fibers having a permanent smooth touch can be produced by imparting a spinning oil.

The main object of the present invention is to provide a novel method for producing acrylic fibers having a tactile feel.

Another object of the present invention is to provide an industrial knowledge capable of imparting a silky feel, such as wool, to an acrylic fiber or a product thereof, and imparting durability to a washing treatment with a smooth touch.

It is another object of the present invention to provide new technical knowledge regarding the structural properties of silicone resins suitable for imparting a tactile feel to acrylic fibers, or the emulsion zone of these silicone resins.

Other objects of the present invention will become apparent from the following description.

The object of the present invention is to mix the water of the silicone resin represented by the following general formula (1) with an emulsifier selected from the group of POE (n ') ralalkylphenyl phosphate (where n' is the degree of polymerization of polyoxyethylene) Was added to form a weakly acidic emulsion zone, and the formed emulsion zone was attached to the swelling gel-like acrylic fiber obtained by wet spinning, and immediately dried to fix the silicone resin on the fiber surface, and then impregnated with a spinning emulsion to the acrylic fiber thus obtained. It was effectively achieved by providing a novel acrylic fiber manufacturing method.

From the stomach

R is R'NH ₂ , R'NHR "or R'NR" ₂ ,

이며Where R 'is

And

n is 1 to 3,

R "is C _m H _{2m + 1} , where m is 1 to 3,

X and Y are positive integers which make the molecular weight of a silicone resin 100,000 or less.

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

In the present invention, the acrylic fiber on the swelling gel is composed of acrylonitrile alone or a copolymer of 70% by weight or more of acrylonitrile and other vinyl monomers. As a generic term for 100% of fibers, POE (n ') alkylphenyl phosphates which form together with a silicone resin of the general formula (1) to form a weakly acidic emulsion, polyoxyethylene has a polymerization degree n' of 5 to 15 and an alkyl group. POE (8) octylphenyl phosphate having 8 to 12 carbon atoms, POE (9) octylphenyl phosphate, POE (8) nonylphenyl phosphate, POE (9) nonylphenyl phosphate and POE (10) dodecylphenyl phosphate Can be.

Since it acts as a base in the silicone resin emulsification of general formula (1), it is necessary to select an acidic emulsifier in order to keep the finally obtained emulsion zone weakly acidic. The above-mentioned POE (n ') alkylphenyl phosphates having a polymerization degree n' of 5 to 15 and polyalkylene having 8 to 12 carbon atoms of polyoxyethylene are mixed and stirred with a silicone resin of the general formula (1) and water is added thereto; or When preparing the emulsion zone by the so-called dissolution method, it provides a pH value of 5.5 to 6.8 necessary for improving the stability of the emulsion zone, and in the range satisfying such pH value, the formula (1) It is preferable to mix | blend 50 weight part or more of said POE (n ') alkylphenyl phosphates with respect to 100 weight part of silicone resins.

Furthermore, the temperature at the time of emulsification is preferably maintained in the range of 35 ^° to 60 ° C, and the emulsion temperature is preferably controlled in the range of 40 ^° to 58 ° C.

The present invention is characterized by attaching an emulsion zone obtained by blending a specific silicone resin and an emulsifier to an acrylic fiber on an undried swelling gel after wet spinning as described above, and the reactivity contained in the silicone resin. The NH ₂ groups form a strong ionic bond together with the dyeing sites present in the gel-like swelling acrylic fiber, thereby significantly reducing the durability of silky touch like acrylic hair without impairing the dyeability of the whole fiber. It can be improved.

In the practice of the present invention, the weight of the silicone resin to be attached to the acrylic fiber on the swelling gel in order to give the treated fiber a smooth touch such as wool fiber and to facilitate the attachment of the spinning emulsion in a subsequent step is to dry the fiber of the acrylic fiber. It is preferable to be in the range of 0.1 to 3% by weight, particularly preferably in the range of 0.5 to 2.0%.

That is, when the adhesion amount of the silicone resin is less than 0.1% with respect to the dry weight of the fiber, the smooth feel of the treated fiber is not sufficiently improved, and the final product is not provided with the same feel as the wool fiber.

In addition, when the adhesion amount of the silicone resin specified by the general formula (1) exceeds 3% by weight of the fiber dry weight, the adhesive state occurs between the single fibers, and the coils are wound on the rollers of the carding machine in the spinning process. It is not preferable because obstacles such as phenomenon are derived.

The acrylic fiber after the adhesion treatment of the emulsion zone containing the specific silicone resin specified by the general formula (1) is then dried under a temperature condition of 60 to 140 ° C, more preferably 80 to 120 ° C. Orientation is fixed on a fiber, and it becomes a state which can be supplied to processes, such as a relaxation heat processing and a mechanical crimp. At this time, if the acrylic resin on the swelling gel-like swelling gel is not dried, and is supplied by a process such as relaxation heat treatment and mechanical crimping by a saturated underwater machine, the silicone resin is eliminated and a smooth feel on the wool fiber is not provided.

The silicone resin of the general formula (1) and the attached acrylic fiber are given a spinning emulsion after the drying treatment. In other words, acrylic fiber attached with silicone resin decreases the spinning property due to the decrease in frictional resistance. Therefore, in order to satisfy the feel and the spinning property of the woolen fiber shape, it is necessary to separate the acrylic fiber from the emulsion zone of the silicone resin. In (iv), it is necessary to impart a spinning emulsion to acrylic fibers, that is, acrylic fibers that have undergone the adhesion and drying of silicone resins. Therefore, in performing the method of the present invention, the above-described processes such as relaxation heat treatment or mechanical crimping may be carried out insofar as the processes such as immediately drying the fibers to be treated with silicone resin and then imparting spinning emulsion thereto. It can be carried out in the form of any bonding process of.

As described above, the inventors have found that the acrylic fiber feel can be remarkably improved by the treatment of a weakly acidic emulsion in which a specific silicone resin is dispersed, and a silky fiber-like feel can be given to the treated fiber. Furthermore, it has been clarified that the stress reduction rate tan α during the frictional motion of the knitted fabric made from the treated fiber as a means of grasping the effect of the present invention quantitatively shows a good response to the smooth touch.

In other words, the inventors found that the smooth feel of the acrylic fibers produced by the method of the present invention was such that the frictional properties between the knitted fabrics made of these acrylic fibers, in particular, the frictional reduction rate at the time of motion friction measured by the fabric friction measuring apparatus illustrated in FIG. It was confirmed that it can be determined quantitatively by α, and there are slight differences depending on the structure or structure of the knitted fabric provided in the measurement, but when the value of tan α is within the range of 5-25 g / mm It was clarified that the sample acrylic fibers were imparted with a smooth feel that was very similar to the knitted fabric made of fibers.

According to the experimental results of the present inventors, the friction characteristics of the knitted fabric made of acrylic fiber prepared according to the conventional method without smooth touch shows a clear stickslip wave form, and the tactile characteristics thereof are the stress reduction rate at the time of motion friction. It was not possible to represent tan α.

Hereinafter, a description will be given of a method for measuring the stress reduction rate tan α during motion friction prior to the description of the following examples.

The stress reduction rate tan α at the time of motion friction is obtained by expanding the measurement of the motion friction between the sample cloths using the fabric friction test apparatus shown in FIG. In more detail with reference to FIG. 2, a sample fabric 1 is placed on the sample stage 2 at 20 ° C. and 65% relative humidity, and one end thereof is placed on the sample press 3. The other end is held in tension under the action of 30 g of load (4), and the slider 6 having an effective contact area of 3 cm 2 (2 cm x 1.5 cm) with a compressive load of 450 g is applied. (1), the sample piece 7 is fixed to the lower surface of the slider 6, and then the sample stand 2 is generated between the sample cloths while moving at a constant speed of 12 mm / min. The frictional force is detected by a resistance strain meter 8 (resistance strain meter) connected to the slider 6 and recorded in the recorder 9. At the time of measurement, when the exercise frictional force is in a steady state, the display needle of the recorder is set to zero point, and then the detection sensitivity is increased by 5 to 10 times as shown in points F and G to reduce the minute change in the exercise frictional force. Measure enlarged. Stress reduction rate at the time of motion friction tan α means the slope of the stress reduction portion in which the slide between the sample cloths in the enlarged measurement diagram can be expressed as the stress reduction rate per mm of displacement of the sample cloth. Therefore, less tan α means that the touch is smooth.

The acrylic fiber produced by the method of the present invention has excellent spinning and unique silky feel, such as wool fiber, especially wool, and does not drop silicone resin by post-processing such as refining and dyeing, and is extremely durable for washing. .

In this regard, the method of the present invention will provide notable knowledge as a means of improving the feel of acrylic fibers or products thereof.

Hereinafter, examples of the present invention will be described.

Parts and percentages in this example are all based on weight unless otherwise indicated.

Example 1

The copolymer obtained by copolymerizing 90% acrylonitrile with 9.8% methyl acrylate and 0.2% sodium metaallylsulfonate was dissolved in an aqueous solution of sodium thiocyanate, and the resulting spinning solution was wet spun in cold water. Water washing and stretching were carried out in accordance with the following conventional method to prepare a swelling gel-like acrylic fiber tow having a water content of 80%. This fiber tow was obtained by using Sumitex SX-70A (manufactured by Sumitomo Chemical Co., Ltd.) with 2% of a silicone resin having R ₂ CH ₂ NH ₂ in formula (1) and 1% and 0.2% of POE (9) nonylphenyl phosphate. It was immersed in an emulsion zone of pH value 6.8 obtained by blending and emulsifying for 3 seconds, and then compressed to make the adhesion zone of the emulsion zone 80% of the dry weight of the fiber. Drying was performed for a minute to structure the fiber structure, while at the same time allowing the silicone resin to be orientation-bonded to the treated acrylic fiber.

Subsequently, the fiber toe was treated in a pressurized steam at 130 ° C. for 8 minutes to relax the fiber structure, then supplied to a stuffer box to be crimped, and Nissan Unilube 50MB-169 (manufactured by Nippon Oils and Fats Co.) as a spinning oil. Was dried in an amount of 0.33% by weight based on the dry weight of the fiber, and then cut into different fiber lengths in the range of 60 to 140 mm to prepare acrylic fibers having a short fiber fineness of 2.5 denier (acrylic fiber 1). The silicon adhesion of this fiber was 0.95%.

Next, an acrylonitrile copolymer having the same composition as the acrylic fiber was wet-spun according to a conventional method to prepare an acrylic fiber tow of 3 fiber denier with short fibers, and then the fiber tow was supplied to a turbo stapler at a temperature of 1.16 times at a hot plate temperature of 150 ° C. Secondary stretching was performed, followed by mechanical crimping, followed by cutting to prepare a highly shrinkable acrylic fiber staple with a potential of 12.8% of hot water shrinkage (acrylic fiber 2).

Subsequently, 60% of the non-shrinkable acrylic fiber (acrylic fiber 1) and 40% of the highly shrinkable acrylic fiber (acrylic fiber 2) were mixed according to a conventional method to prepare a 52nd-number double yarn (metric count).

The obtained mixed yarn was immersed in a salt solution of a cationic dye and stained according to a conventional method to give a shrinkage ability which was latent at the same time as dyeing to impart bulkiness. The flat knitting machine was fed to knit a flat knitting machine, stretched 4% in the longitudinal direction, and Hoffmanset was performed (letter 1).

As a comparative example, the non-shrinkable acrylic fiber, which omits the emulsion zone treatment of the silicone resin recommended in the present invention and was attached with only the cationic softener Zontes TA460-15 (manufactured by Matsumoto Oils and Facts Co.), was used instead of the acrylic fiber 1 described above. According to the same conditions as in Example 1, a letter of flat weave was produced (letter 2).

In addition, a disassembly letter of a flat knitted sheeter made of commercially available wool fibers alone was prepared as a sample for comparison with another one (letter 3).

The stress reduction rate tan α during the motion friction of these letters is shown in Table 1, and from these results, it can be understood that the letter 1 satisfying all of the conditions proposed in the present invention has a permanent smooth touch very similar to that of the wool fiber. . After washing, the letter α was measured using a sample whose wash shrinkage was measured.

TABLE 1

In addition, it was sensationally evaluated smooth touch separately from Table 1 above. It was confirmed that the letter 1 had a good smooth touch similar to the letter 3 to be difficult to distinguish from the letter 3. Letter 1 was also recognized for its markedly improved merchandise value, with good other sensory evaluation factors such as bulkiness, lecture and hardness.

However, other sample acrylic fibers that increased the silicone resin concentration in the emulsion zone, decreased the compression ratio after the emulsion zone dipping treatment, and controlled the silicon adhesion amount to 3.7% are frequently wound due to adhesion in the carding process during the spinning process. Generated, and it was impossible to manufacture satisfactory yarns.

In the above embodiment, since the laundry shrinkage ratio was used as the physical property value for evaluating the form safety of the acrylic fabric knitted fabric, a schematic description thereof will be described next together with the method for measuring the silicone resin adhesion rate.

Wash Shrinkage:

Prepare two sample cloths with a length of 50 cm on one side, draw a circle with a diameter of 20 cm at the center of each sample cloth, and use a 1 g / l detergent Monogen Uni in a household washing machine (waist winding). It charged, washed for 5 minutes, maintaining the bath ratio 50: 1, and then rinsed for 7 minutes. Subsequently, the sample cloth was taken out and dried directly on the track without dehydration. The diameters of the longitudinal and transverse directions of the circle drawn on each sample cloth were measured, and the average value of the shrinkage rates in the longitudinal and transverse directions was obtained. Shall be.

Silicone resin adhesion rate:

First, several kinds of organic solvent phases having various concentrations of the same type of silicone resin as the silicone resin to be attached to the sample fiber were prepared and prepared by using an infrared spectrometer of Model 521 (Perkin Elmer Co.). after obtaining the absorption intensity of ㎝ ^-1, was determined by a calibration curve (檢量線) showing the relationship between the absorption intensity in the silicone resin of the amount of Si-CH ₃ and Si- (CH _{3) 2} group 800㎝ ^-1 .

Next, 3 mg of the acrylic fiber provided in the test was cut to a length of 0.1 to 0.3 mm, weighed and mixed with 200 mg of potassium bromide, which was separately weighed, and then mixed and ground in a conventional manner to form a tablet (Sample A). Subsequently, the tablet of the acrylic fiber to which the silicone resin was not attached was molded in the same manner (Sample B).

Next, using the infrared spectrometer of Model 521 (product of Perkin Elmer Co.), the feed A was placed on the sample side and the sample B on the compensating side, and the Si-CH ₃ and Si- (CH ₃ ) ₂ structures The adhesion amount of silicone resin is calculated | required from the analytical curve which shows the absorption strength in 800 cm <^-1> .

Claims (1)

Next, water is added to form a weakly acidic emulsion by mixing and stirring the emulsifier selected from the group consisting of the silicone resin represented by the following general formula (1) and POE (n ') alkylphenyl phosphate (where n' is the degree of polymerization of polyoxyethylene). The formed emulsion zone is attached to the swelling gel-like acrylic fiber obtained by wet spinning, and then immediately dried to fix the silicone resin on the fiber surface, and then a spinning oil is applied to the obtained acrylic fiber. Method for producing an acrylic fiber having a touch such as).

Wherein R is R'NH ₂ , R'NHR "or R'NR" ₂ , where R 'is

And n is 1 to 3, R ″ is C _m H _{2m + 1} , wherein m is 1 to 3, and X and Y are integers having a molecular weight of the silicone resin of 100,000 or less.

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