KR800000819B1 - Finishing method for acryl fiber products - Google Patents

Abstract

An acrylic synthetic fiber of which the interfiber entanglement coefficient is as much as to 40 and the interfiber entangling force after hot water-treatment is not more than 50 mg, has a silicon resin of the formula wherein R is R'NH2, R'NH2, R'NR'' 2, R' is CH2 n, n is 1 to 3, R'' is CmH2m+1; m is 1 to 3, X and Y are positive integers and the mol. weight of the silicone resin is not more than 100,000, and said silcone resin is deposited on the fiber surface in an amount of 0.1 to 3.0% based on the dry weight of the fiber.

Description

Acrylic fiber products with the feel of hair

1 is an explanatory diagram of a textile friction test apparatus used for the measurement of smooth texture,

2 is a rectangular coordinate diagram illustrating the relationship between the frictional resistance recorded by the test apparatus and the sample cloth displacement.

The present invention relates to a novel acrylic fiber product having a hair-like feel, and more specifically, to a wool fiber, such as wool, cashmere and the like, and a ratio of attaching a silicone resin represented by a specific structural formula to the surface. The present invention relates to a shrinkable acrylic fiber and an acrylic fiber product having a hair-like texture made by heat treatment after forming a high shrinkable acrylic fiber having a potential shrinkage ratio of 3% or more than the non-shrinkable acrylic fiber by blended yarns.

It is well known that knitted fabrics of wool fibers such as wool, cassia, angora rabbit hair and the like have an excellent hand with a unique smooth feel. However, even a knitted fabric made of such woolen fibers is not recognized at all in practical use, for example, by treatment involving entanglement such as washing due to scaly texture of the fiber surface, It was recognized that defects in which the knitted fabric contracted were caused by the characteristic movement with the orientation between the fibers constituting the knitted fabric. In fact, in the past, in order to solve such defects, a method has been attempted to impart shrinkage by acting a chemical solution on the woolen fabric or a knitted fabric made from two fibers to destroy the flaky tissue on the fiber surface. Although it is true that the shrinkage of the knitted fabric made of woolen fibers is improved by such chemical solution treatment, this method leads to a remarkable decrease in the feel of the final product, especially a smooth feel, which leads to an unreasonable deterioration of the product value. It became.

On the other hand, for the purpose of eliminating the defects of the prior art and improving the dimensional stability during washing, a method of forming a knitted fabric by blending synthetic fibers having no scaly texture with woolen fibers on the surface of acrylic fibers or the like is used. . However, these blended knitted fabrics have a slight improvement in the dimensional stability of the intertwining action, but the level of smooth persimmons directly involved in maintaining the feel of hair is low. It seems to be completely different from the knitted fabric. A polyhydric alcohol-type nonionic surfactant for the purpose of imparting a smooth feeling to synthetic fibers or yarns or knit fabrics obtained from the fibers, apart from the attempt to use the above-mentioned woolen fibers as a material for forming a knitted fabric. Methods of attaching specific cationic or anionic surfactants to synthetic fibers are known. When the surface treatment with such a surfactant gives a slight smooth feeling to the synthetic fiber, washing durability is not recognized at all by the surfactant and the solution is found as a factor that rapidly lowers the product value of the textile product. It is strongly desired in the art.

It is also known to use higher esters of acrylic acid or methacrylic acid or vinyl esters of higher fatty acids as the fiber treatment agent. However, the smooth feel imparted by such a fiber treatment agent is completely different from the smooth feel seen in woolen fiber products, and it is generally difficult to expect a touch improvement effect of the final product by such a fiber treatment agent.

In addition, it is known to improve the feel of the textile products by processing acrylic fibers with silicone resins, but there is no clear reference to the silicone resins used as the fiber treatment agent, and the feel of acrylic fibers products improved by the silicone resin processing is also smooth. It is related to simple flexibility or improvement of antipilling property other than feel. In addition, since the mixed agent of silicone resin and epoxy resin is used as the treatment agent for acrylic fiber products, the texture of the final product becomes rough and hard due to the adhesive curing between fibers, and the epoxy resin inhibits the smooth texture given by the silicone resin. The commodity value of the final product is greatly reduced.

Therefore, the present inventors have completely solved the deficiencies of the prior art, and have provided the industrial knowledge of blending acrylic fibers with woolen fibers or giving a smooth texture and shrinkage properties very similar to woolen fiber products to knitted fabrics obtained from the blended yarns. In order to find out, research is carried out to attach the silicone resin represented by a specific structural formula to the acrylic fiber blended with the woolen fiber, and to control the short fiber denier and the potential shrinkage rate of the acrylic fiber for the manipulation of entanglement such as washing. The present invention has also been found by discovering that acrylic fiber products having a permanent smooth texture can be produced with remarkably improved dimensional stability.

The main object of the present invention is to provide a novel acrylic fiber product having a woolly touch.

Another major object of the present invention is to provide an industrial knowledge for imparting a silky feel to the woolen fabric and dimensional stability against washing.

It is still another object of the present invention to provide structural properties of silicone resins which are blended with wool fibers to form yarns or knit fabrics, and short fiber deniers and latent shrinkage ratios of these acrylic fibers, which are very suitable for the improvement of smooth texture. It is to provide a novel acrylic fiber product maintained in the range of.

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

The object of the present invention is that the silicone resin represented by Structural Formula (I) having a wool fiber and a short fiber denier of 50-100% relative to the average short fiber denier of this wool fiber is 0.1-3.0% by weight of the fiber dry weight. It is effective to provide an acrylic fiber product in which a non-shrinkable acrylic fiber attached and a highly shrinkable acrylic fiber having a potential shrinkage ratio of at least 3% compared to the non-shrinkable acrylic fiber are mixed to form yarns or knitted fabrics and then heat treated. Can be achieved.

In the above formula, R is R′NH _2, R′NHR ″ or R′NR ″ ₂ , R ′ is-(-CH _2- ) n-, n is 1-3, and R ″ is C _m H _{2m + 1} , m is 1-3, and X and Y are integers which make the molecular weight of silicone resin 100,000 or less.

In the present invention, the wool fiber is a general term such as wool, mohair, alpaca, cheviot, cassia or angora rabbit hair, and the acrylic fiber is an acrylonitrile alone or air of 70% by weight or more of acrylonitrile and other vinyl monomers. Generic term for fibers to be coalesced.

In the process of surface-attaching the silicone resin represented by Structural Formula (I) in the practice of the present invention, the strict limit as seen in the adhesion amount of the silicone resin is not recognized, and it contains water of 100% or less after hot stretching. The silicone resin can be surface-attached in a gel swelled state or in a state in which the fibers are subjected to relaxation heat treatment, mechanical crimping or drying. However, in order to enhance the adhesion ability of the silicone resin to the fiber to be treated and impart a permanent smooth feel, the silicone resin may be exemplified by POE alkylphenyl phosphate or the like while the fiber to be treated is in a gel-swelled state containing predetermined moisture. It is preferable to immerse in the emulsion zone dispersed in the emulsifier and to surface-attach the silicone resin represented by the structural formula (I) by 0.1-3.0%, preferably 0.5-2.0%, based on the fiber dry weight.

In the practice of the present invention, when the adhesion amount of the silicone resin is 0.1% or less with respect to the dry weight of the fiber, the smooth feel of the non-shrinkable acrylic fiber is not sufficiently improved, and the final product cannot be given the feel of the hair fiber. In addition, when the surface adhesion amount of the silicone resin represented by Structural Formula (I) exceeds 3% by weight of the fiber dry weight, it may cause adhesion between the single fibers and thus the tacker in which is a taker of a carding machine in the spinning process. It is not preferable because obstacles such as being wound on a roller) occur.

The short fiber denier of the non-shrinkable acrylic fiber with the silicone resin represented by the formula (I) is in the range of 50-100%, preferably in the range of 50-80% with respect to the short fiber denier of the wool fiber blended with the acrylic fiber. It is necessary to keep it. By selecting such a short fiber fineness range in the non-shrinkable acrylic fiber, the bending hardness of the non-shrinkable acrylic fiber is substantially the same as the bending hardness of the wool fiber, and the acrylic fiber having the silicone resin of the formula (I) Synergistically with the formation of the surface portion of the blended yarn, the feel of the finished textile product, in particular the smooth feel, is significantly improved.

On the other hand, a highly shrinkable acrylic fiber having a potential shrinkage rate of at least 3% or more compared to the non-shrinkable acrylic fiber is a fiber in which an acrylic fiber tow spun by a conventional method is re-stretched with a turbostapler or the like under wet or dry heat. As long as it is a general term, and is within the range which satisfies the said suitable range of the potential shrinkage rate, the monocomponent fiber obtained from a single acrylonitrile-type polymer or two types of acrylonitrile-type polymers which differ in heat shrinkage or gel swellability are used. Any composite fiber eccentrically bonded along the fiber axis direction is also good. In addition, the upper limit of the potential shrinkage of highly shrinkable acrylic fibers is not limited, as shown in the lower limit, but the potential shrinkage rate is 15% in order to improve the uniformity of knitting and to give a texture similar to woolen fibers. It is preferable to keep it below.

When making a blended yarn made of such wool fibers and acrylic fibers, the blend ratio of wool fibers is preferably maintained in the range of 10-70%, preferably 20-50%, based on the total weight of the blended yarns. In addition, the highly shrinkable acrylic fibers are preferably blended at least 20% by weight, preferably at least 30% by weight in order to facilitate the expression of latent shrinkage. It is also recommended that the upper limit of the blend ratio of the highly shrinkable acrylic fiber be in the range of 70% or less and preferably 50% or less in order to maintain the volume of the final product at a predetermined level.

The blended yarn obtained in this way exhibits shrinking potential latent by heat treatment, placing the highly shrinkable acrylic fiber in the center of yarn, and the acrylic fiber having the loosely crimped woolen hair around it and the silicone resin of formula (I). The placement of the fibers significantly improves the smooth feel of the final product. The present inventors have confirmed that the smooth texture of the knitted fabric can be quantitatively determined by the friction characteristics between the knitted fabrics, in particular, the stress reduction rate tan α during the motion friction measured by the fabric friction measuring apparatus illustrated in FIG. It was found that, although slightly different depending on the structure or structure of the knitted fabric used for the measurement, the sample acrylic fiber product is given a smooth texture similar to that of the woolen fabric when the tan α is in the range of 5-25 g / min. . According to the experimental results of the present inventors, the friction characteristics of nonwoven fabrics with a smooth feel exhibit a clear stick-slip waveform, and their tactile characteristics cannot be expressed as the stress reduction rate tan α during motion friction. . In order to reduce tan α and give a silky feel to acrylic fiber products, it is suggested that non-shrinkable acrylic fibers located on the outside of yarns have friction characteristics close to those of wool fibers, and in this sense, structural formulas for non-shrinkable acrylic fibers The adhesion amount of the silicone resin of (I), the short fiber denier of the said fiber, etc. have an extremely important critical meaning.

In the present invention, the stress reduction rate (tan α), hot water shrinkage rate, average fineness, silicon deposition amount, and wash shrinkage rate during kinetic friction quantitatively indicating a smooth feel are measured by the following method.

(1) Stress Reduction Rate in Motion Friction tan α

Using the fabric friction test apparatus shown in FIG. In detail using FIG. 2 together, the sample cloth 1 is placed on the sample stage 2 in a humidified atmosphere at 20 ° C. and a relative humidity of 65%, and one end thereof is fixed to the sample support 3. At the other end, a 36 g load 4 is applied to hold the tension state, and a slider 6 having an effective contact area of 3 cm 2 (2 cm x 1.5 cm) having a compressive load 5 of 450 g is placed thereon. The specimen piece 7 is fixed to the lower surface thereof, the sample stage 2 is moved at a constant speed of 12 mm / min, and the friction force generated between the specimens is transferred to the resistance wire stress gauge 8 connected to the slider 6. It is detected and recorded in the recorder 9. At the time of measurement, when the motion frictional force indicates the normal state, the needle of the recorder is moved to zero, and then the detection sensitivity is magnified 5 to 10 times as indicated by the points F and G to measure and measure the subtle change of the motion frictional force. The stress reduction rate α at motion friction refers to the slope of the stress reduction portion at which the slippage occurs between the sample fabrics in the magnification measurement, and can be expressed as the stress reduction rate per 1 mm of displacement of the sample fabric. Therefore, the smaller the value of tan α, the greater the smooth texture.

(2) laundry 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 then use a household washing machine with 1g / l Monogen Uni (detergent). ) To maintain a bath ratio of 50: 1, wash for 5 minutes, and wash for 7 minutes. Next, take out the sample cloth without dehydration, dry it on the surface and dry it naturally, measure the diameter in the longitudinal and transverse directions of the circle drawn on the sample cloth, and determine the average value of the shrinkage rate in the longitudinal and transverse directions as the laundry shrinkage rate. .

(3) Silicone resin adhesion rate

Absorption intensity of 800cm ^-1 by infrared spectroscopy device 521 of Perkin Elmer Co. made by preparing the organic solvent phase which changed the concentration of the same kind of silicone resin and the silicone resin previously attached to the sample cloth Draw a calibration curve to indicate.

Next, the acrylic fiber used for the test was cut into 0.1 to 0.3 mm in length, weighed 3 mg, mixed with 200 mg of potassium bromide weighed separately, mixed and ground by a conventional method, and then formed into tablets (Sample A). In the same manner as described above, tablets of acrylic fibers without silicone resin were prepared (Sample B).

Subsequently, the infrared spectrometer type 521 of Perkin Elma Co., Ltd. was used at 800 cm < -1 > due to the structure of Si-CH ₃ and Si-CH _{3) 2} , which was obtained first by placing sample A on the sample side and sample B on the compensation side. The adhesion amount of silicone resin is calculated | required from the calibration curve which shows absorption strength.

(4) heat shrinkage rate

Both ends of the bundle of fibers having a potential shrinkage capacity of about 10 acrylic fibers are bonded to each other, and the gap is fixed to a constant length (L ₀ ) and treated in hot water at 100 ° C. for 15 minutes. After cooling to 60 ° C. or lower, the fiber bundle described above was taken out, dried in an air dryer at 80 ° C. for 30 minutes, and left at room temperature moistened at 65% relative humidity at 20 ° C. for at least 1 hour. L ₁ ) is measured and only the acrylic short fibers are cut. Next, measure the length L ₂ of the second shortest sample fiber and cut the fiber in the same manner. The same operation is repeated to measure the length of the exhibition material constituting the fiber bundle. This fiber bundle is made of 5 pieces, and the total length (L ₁ , L ₂ ,..., L ₅₀ ) after the hydrothermal treatment of a total of 50 sample acrylic fibers is calculated, and the hydrothermal shrinkage of the sample fiber is calculated by the following formula. do.

Hydrothermal shrinkage (%) = 100 (L ₁ + L ₂ + ‥‥‥ + L ₅₀ ) / (50 × L ₀ )

(5) Average fineness (short fiber denier)

The quantitative fineness of JISL-1074 is based on the A method.

Next, although an Example of this invention is described, this invention is not restrict | limited at all by the said Example.

In addition, all parts and percentages are shown by weight unless there is particular notice.

Example 1

The spinning stock solution obtained by dissolving a copolymer of 90% acrylonitrile in which 9.8% methyl acrylate and 0.2% sodium metalylsulfate was dissolved in an aqueous sodium thiocyanate solution was wet-spun in cold water, and then washed with water in the usual manner. Swelling gel fiber tow having a water content of 80% was prepared. This fiber tow was formulated in the formula (I) with 2% silicone resin with R ₂ CH ₂ NH ₂ , 1% POE (9) nonylphenylphosphate, and catalyst Sumitex accelerator SX-70 A0.2 manufactured by Sumitomo Chemical Co., Ltd. After soaking for 3 seconds in the emulsion-dispersed emulsion solution for 3 seconds, press the sample fiber tow so that the adhesion amount of the emulsion zone becomes 80% of the fiber dry weight, and then treat it for 15 minutes in an atmosphere having a dry bulb temperature of 125 ° C and a wet bulb temperature of 60 ° C. The silicon resin was bonded to the acrylic fiber to be treated while destroying the space in the fiber structure.

Next, the fiber structure was relaxed for 8 minutes in a 130 ° C pressurized submersible and then fed to a stuffer box to impart crimping. Nissan unilube, Japan Oil Holding Co., Ltd. 50MB After adhering 0.33% of -168 and drying, the length was cut differently in the range of 60mm to 140mm to make non-shrinkable acrylic fiber of short fiber denier 2.5 denier (acrylic fiber 1). The silicon adhesion of this fiber was 0.97%.

An acrylonitrile copolymer having the same composition as the non-shrinkable acrylic fibers was wet-spun according to a conventional method, and an acrylic fiber tow having 3 deniers of short fibers was supplied to a turbo stapler and subjected to secondary heat at 1.16 times at a hot plate temperature of 150 ° C. After stretching, mechanical crimping was applied and then cut to make a highly shrinkable fiber staple with a potential of 12.8% of hydrothermal shrinkage (acrylic fiber 2).

)를 만들었다.40% of non-shrinkable acrylic fibers (acrylic fibers 1), 30% of high shrinkable acrylic fibers (acrylic fibers 2), and 30% of wool fibers having an average short fiber denier of 3.6 deniers were mixed and spun by conventional methods.雙

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The resultant mixed yarn was immersed in the mixed dye solution of cationic dye and acid dye to carry out skein dyeing in one bath according to a conventional method, and at the same time, the potential shrinkage was expressed to increase the volume. . Subsequently, two blended yarns were stacked and fed to a 14G knitting machine, knitted into flat knitting, stretched by 4% in the transverse direction, and Hoffmanset was performed (letter 1).

Next, as a comparative example, a non-shrinkable acrylic fiber to which only the cationic softener ZONTES TA460-15 manufactured by Matsudodo Oil & Fat Co., Ltd., which was not subjected to the silicone emulsion zone bath treatment recommended in the present invention was used, was used instead of one of the acrylic fibers. Letters of flat weave were made under the same conditions as in the above example (letter 2).

In addition, a disassembled letter of a flat knitted sweater made of commercially available wool fibers was prepared as another comparative feed (letter 3).

Although the stress reduction rate tan α washing shrinkage rate at the exercise friction of the letter is shown in Table I, from these results, the letter 1 satisfying all the conditions suggested by the present invention has a permanent smooth texture similar to that of wool. I can understand that. In addition, tan alpha of the letter after washing is measured using the sample which measured the washing shrinkage rate.

TABLE 1

Next, sensory evaluation of the smooth texture was performed separately from the above Table 1. It was confirmed that letter 1 had a good smooth texture similar to that of letter 3 and difficult to distinguish with eyes. In addition, the letter 1 also has other sensory evaluation factors, such as bulge, stiffness, and hardness, which have markedly improved product value.

In addition, other sample acrylic fibers which increased the silicone resin concentration in the emulsion zone and decreased the compression rate after the emulsion zone dipping treatment to adjust the silicone adhesion amount to 3.7% were frequently curled up due to the adhesion during the carding process during immersion processing. Couldn't make

Claims (1)

Non-shrinkable acrylic fibers having 50-100% short fiber denier for the average short fiber denier of this wool fiber and 0.1-3.0% surface-attached to the fiber dry weight of a silicone resin defined by Structural Formula (I). And acrylic fiber products having a woolen touch made by blending high shrinkable acrylic fibers with a potential shrinkage of at least 3% or more compared to the non-shrinkable acrylic fibers to form yarns or knitted fabrics and then heat-treating them;

Wherein R is R′NH ₂ , R′NHR ″ or R′NR ″ ₂ , R ¹ is-(-CH _2- ) _N- , n is 1-3, and R ″ is C _m H _{2m + 1} , m is 1-3, and X and Y are integers which make the molecular weight of a silicone resin 100,000 or less.

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