JP4338574B2 - Colored moisture absorbing / releasing exothermic fiber and method for producing the same - Google Patents

Description

  The present invention relates to a moisture absorbing / releasing exothermic fiber colored in an arbitrary hue and a method for producing a uniformly colored blended yarn.

  2. Description of the Related Art Conventionally, apparel using moisture-absorbing / releasing heat-generating fibers has been developed using the property of generating heat when absorbing water vapor generated from the human skin.

  However, at the present stage, it is not possible to “dye” the moisture-absorbing / releasing exothermic fibers sufficiently, so when producing the mixed yarn of the moisture-releasing / releasing exothermic fibers and other fibers, only the other fiber side is dyed. . However, the obtained blended yarn is a patch that is a mixture of a dyed portion and an undyed portion. In addition, it is difficult to dye in a dark color.

  Also, a method of dyeing a blended arbitrary fiber by a known technique after blending, knitting, knitting, or any other fiber with an undyed acrylate-based moisture absorbing / releasing exothermic fiber (for example, “Sunburner”, etc.) There is. According to this method, the dyeing effect by the color replenishment effect with other fibers can be obtained.

  However, coloring due to the color replenishment effect by dyeing the existing blended yarn also becomes darker, and acrylate-based moisture absorption and desorption heat fibers that are not dyed are mixed in the spots, impairing the uniform dyeing effect, It has become. That is, the moisture absorbing / releasing exothermic fiber cannot be dyed even if it is carried out by an existing (known) dye / dyeing method.

  Here, the existing (known) dyes and dyeing methods are direct dyes and dyeing methods thereof, acid dyes and dyeing methods thereof, acid metal-containing dyes and dyeing methods thereof, reactive dyes and dyeing methods thereof, cationic dyes and dyeing thereof. It refers to a method, a disperse dye and a dyeing method thereof, a selenium dye and a dyeing method thereof, a vat dye and a dyeing method thereof, and a naphthol dye and a dyeing method thereof.

  Attempts have also been made to use pigments as coloring methods other than these dye / dyeing methods. However, generally, a method of adhering a pigment with a predetermined resin is used. Therefore, a dark color cannot be obtained. The colored fiber becomes hard because the resin is attached. Furthermore, since the adhesive pigment and the resin form a coating on the fiber surface to cover, the hygroscopic effect is impaired, and the expected hygroscopic / heat generating characteristics cannot be obtained. Due to the above problems, a method of bonding a pigment with a predetermined resin has not been put to practical use.

  In addition to the method of adhering the pigment with a predetermined resin, a method of obtaining a moisture absorbing / releasing fiber colored in black after hydrolysis by introducing a crosslinked structure into an acrylic fiber obtained by adding carbon black to an acrylonitrile polymer. (For example, refer to Patent Document 1).

However, since the pigment used in this method is limited to carbon black, there is a problem that the color that can be colored is limited to black. In addition, it is difficult to uniformly mix carbon black with an acrylonitrile-based polymer, and there is a concern that the colored fibers obtained may be non-uniformly colored.
JP 2003-89971 A (Claims)

  While the present inventor has made various studies in order to solve the above problems, the blended monomer is mixed and kneaded with the monomer in the raw material production process of the moisture-absorbing / releasing exothermic fiber to obtain a blend monomer. After polymerization, it was found that moisture-absorbing / releasing exothermic fibers colored in an arbitrary hue can be obtained by introducing a crosslinked structure into the acrylic fiber obtained by spinning and then hydrolyzing it.

  In addition, by producing a blended yarn of colored moisture-absorbing / releasing exothermic fibers and other fibers, and dyeing the other fibers with the same color dye as the colored pigment, it is possible to obtain a uniformly colored darkness that was not possible with the prior art. It becomes possible to produce yarns and fabrics of colored moisture absorbing and releasing heat generation fibers. As a result, the present inventor has learned that the color of clothing is increased and the use of the moisture-absorbing and releasing heat-generating fibers is expanded, and the present invention has been completed.

  Accordingly, an object of the present invention is to provide a moisture absorption / release heat generating fiber colored in an arbitrary hue and a method for producing a uniformly colored blended yarn, which solves the above problems.

  The present invention for achieving the above object is described below.

  [1] A spinning solution obtained by polymerizing a blend monomer composed of acrylic fiber raw material monomers and pigment particles is spun to obtain a pigment-colored acrylic fiber, and then a crosslinked structure is introduced into the pigment-colored acrylic fiber, followed by the crosslinking A method for producing colored moisture-absorbing / releasing exothermic fibers, which comprises hydrolyzing an acrylic fiber having a structure introduced therein.

  [2] A colored blended yarn obtained by blending the colored moisture-absorbing / releasing moisture exothermic fiber produced by the production method according to [1] and other fibers to obtain a blended yarn, and then dyeing the blended yarn Manufacturing method.

  [3] A method for producing a colored blended yarn comprising blending the colored moisture-absorbing / releasing heat-generating fiber produced by the production method according to [1] and a pre-dyed fiber.

  According to the production method of the present invention, since the pigment particles are mixed with the monomer in the raw material production process of the moisture absorption / release heat generation fiber, the moisture absorption / release heat generation fiber having a uniform hue and easy mixing of the pigment and the monomer is obtained. be able to.

  In addition, the moisture-absorbing / releasing heat-generating fiber colored in an arbitrary hue may be blended with easily dyeable fiber after dyeing with easily dyeable fiber or with previously dyed easily dyeable fiber. As a result, it is possible to obtain a blended yarn and fabric of a dark-colored moisture-absorbing / releasing heat-generating fiber that is uniformly colored, which was not possible with the prior art.

  Hereinafter, the present invention will be described in detail.

  The method of producing moisture absorbing / releasing exothermic fibers of the present invention is a method of mixing acrylic fiber raw material monomer and pigment particles as a colorant to obtain a blend monomer, and polymerizing the blend monomer and then spinning it to crosslink the acrylic fiber obtained by spinning. It is characterized by hydrolyzing after introducing the structure.

  As an acrylic fiber raw material monomer, in order to promote the reaction of acrylonitrile and the said bridge | crosslinking and hydrolysis, it is preferable to contain 20 mass% or less of comonomer units which have an acidic group, and it is especially preferable to contain 1-15 mass%. preferable. When the content of the acidic group-containing comonomer unit exceeds 15% by mass, the properties of the acidic group-containing comonomer unit include a decrease in coagulation property during wet spinning, and the associated yarns are bonded together to form a bundle. ing. This produces a so-called adhesive thread. Furthermore, since the heat resistance of a copolymer falls extremely, it is unpreferable.

  Examples of the comonomer having an acidic group include a commonly used vinyl monomer having an acidic group that can be copolymerized with acrylonitrile. Specific examples include monomers having a carboxyl group such as acrylic acid, methacrylic acid, and itaconic acid or salts thereof, and monomers having a sulfonic acid group such as allyl sulfonic acid and methacryl sulfonic acid, or salts thereof.

  In the method for producing moisture absorbing / releasing exothermic fibers of the present invention, pigment particles are mixed with the acrylic fiber raw material monomer. The pigment particles to be mixed are not particularly limited, and are organic pigments (phthalocyanine, azo, condensed polycyclic, etc.), inorganic (natural inorganic, oxide, hydroxide, sulfide, silicate, phosphate, carbonate, etc. Salt, metal powder, carbon powder).

  By appropriately using these pigment particles appropriately, moisture-absorbing / releasing exothermic fibers colored in an arbitrary hue can be obtained. Specifically, when cobalt blue or cerulean blue is used as the pigment particles, moisture-absorbing and releasing heat-generating fibers colored amber can be obtained.

  The pigment particles preferably have an average particle size of 0.5 μm or less, particularly preferably 0.1 to 0.5 μm. The addition amount of the pigment particles is preferably 0.5 to 5.0% by mass, particularly preferably 1.0 to 5.0% by mass with respect to the total amount of the blend components.

  The blend monomer in which the pigment particles and the monomer are mixed is added to a solvent such as dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide, acetone, nitric acid, zinc chloride aqueous solution, and rhodium soda aqueous solution as necessary. The added amount of the blend component is preferably 10 to 50 parts by mass, particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the solvent.

  In addition, blend monomer solutions include sodium persulfate, hydrogen peroxide, ammonium persulfate, benzoyl peroxide, homopolymerization initiators such as azo-bis-isobutyronitrile, or hydrogen peroxide-iron oxide salt, persulfate. Redox polymerization initiators such as salt-reducing sulfoxy compounds, potassium persulfate-ferrous iron salt, potassium persulfate-silver nitrate, potassium persulfate-triethanolamine, sodium chlorate-sodium sulfite, potassium permanganate-oxalic acid Is added and the polymerization reaction is processed. As a polymerization reaction method, aqueous solution redox polymerization, solution redox polymerization, solution polymerization, aqueous solution polymerization, bulk polymerization, and the like can be appropriately used. The polymerization reaction temperature is preferably 20 to 70 ° C. The polymerization reaction time is preferably 1 to 5 hours.

  By this polymerization reaction, a polymer solution having a polymer concentration of 5 to 30% by mass and an average molecular weight of 5 to 500,000 is obtained.

  The obtained polymer solution is filtered with a cotton cloth filter cloth or the like to remove impurities in the polymer solution.

  A gel fiber is obtained by spinning the polymer solution in a spinning bath at 5 to 30 ° C. made of a solution of an organic solvent such as DMF and water using a spinning nozzle.

  The resulting gel fiber is passed through a cold stretching bath at 5 to 30 ° C., followed by a hot stretching bath at 80 to 95 ° C. in a stretch of 3 to 15 times, and subjected to a solvent removal (wet heat stretching) treatment.

  The wet-heat-stretched fiber is free of fiber moisture (dry heat drying) with a suction drum dryer or the like set to an internal temperature of 90 to 150 ° C., and the internal structure of the fiber is densified to give an arbitrary fineness of 0.5 to 15 dtex. An original acrylic fiber colored in hue is obtained.

  The obtained original acrylic fiber is hydrolyzed using an inorganic base such as sodium hydroxide or sodium carbonate at the same time as or after the crosslinking treatment of the nitrile group in the acrylic fiber using a hydrazine compound. The

  The case where the hydrolysis treatment is performed using an inorganic base after the crosslinking treatment using the hydrazine compound is as follows.

  In the crosslinking treatment, the acrylic fiber containing 15% by mass or less of the comonomer unit having an acidic group is reacted with a hydrazine compound so that the increase in the nitrogen content of the acrylic fiber is 1.0 to 8.0% by mass. Thus, a crosslinked structure is introduced.

  The reaction conditions are not particularly limited. For example, an acrylic fiber containing 15% by mass or less of an acidic group-containing comonomer unit is used in an aqueous solution having a hydrazine concentration of 5 to 20% by mass at a temperature of 90 to 120 ° C. and 1 to 5%. It is preferable to perform a cross-linking treatment for a time.

  As the hydrazine compound, hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate, hydrazine carbonate and the like can be used, and there is no particular limitation.

  Here, the hydrazine concentration refers to the concentration of the hydrazine component in the hydrazine compound.

  Next, the nitrile group in the acrylic fiber introduced with the crosslinked structure is hydrolyzed using an inorganic base.

  In the hydrolysis reaction, it is desirable to control the amount of carboxyl groups in the acrylic fiber to 2 to 5 meq / g.

  The hydrolysis reaction using an inorganic base is preferably performed in an aqueous solution or a mixed solution with a solvent miscible with water. The inorganic base concentration is preferably 2.0 to 10.0% by mass. The reaction temperature is preferably 90 to 120. The reaction time is preferably 1 to 3 hours. After the hydrolysis treatment, neutralization and water washing are performed with a 1% by weight aqueous solution of formic acid to obtain moisture-absorbing and releasing exothermic fibers having a moisture absorption rate of 20 to 40% and a lightness L value (coloring degree) of 10 to 50.

  In order to increase the strength of the moisture-absorbing / releasing exothermic fiber of the present invention produced by the above production method, it is preferable that the fiber is spun together with other high-strength fibers to form a blended yarn. In order to prevent uneven coloring due to the difference in coloring between the other fiber portion in the blended yarn and the moisture absorbing / releasing exothermic fiber colored in dark color, the moisture absorbing / releasing exothermic fiber of the present invention is: After blending with other easily dyeable fibers, the obtained blended yarn is dyed or blended with other fibers dyed in advance.

  Examples of other easily dyeable fibers to be blended include natural fibers such as cotton, hemp, wool, and silk, regenerated fibers such as rayon, semi-synthetic fibers such as acetate, and synthetic fibers such as nylon and tetron.

  When blending, it is preferable to employ the raw cotton blend mix method in the blended cotton process. Thereby, the physical properties of the material of the blended partner are helped, and the blended yarn can be easily manufactured. The blend ratio is arbitrary as long as it is normally performed.

  The present invention will be described more specifically with reference to the following examples and comparative examples. The moisture absorption / release fibers obtained, the moisture absorption rate of the blended yarn, and the coloration degree are determined by the following methods.

Moisture absorption: Hygroscopic fibers or blended yarns were dried at 100 ° C. for 3 hours, and the mass (W1) was measured. Next, the moisture-absorbing / releasing fiber is put in a thermostat having a temperature of 20 ° C. and a relative humidity of 65% until it reaches a constant weight, the mass (W2) is measured, and the moisture absorption rate (mass%) = [(W2− W1) / W1] × 100
Thus, the moisture absorption rate was obtained.

  Coloring degree: Based on JIS-Z-8730, measured with a colorimeter CCMCOLOR-7E manufactured by Kurabo Industries, Ltd.

Example 1
In a DMF solvent, a blend component of 88 parts by mass of acrylonitrile, 9 parts by mass of acrylic acid methyl ester, and 3 parts by mass of a carbon pigment having an average particle diameter of 0.5 μm [trade name Seast FY, manufactured by Tokai Carbon Co., Ltd.] is used as a colorant. The mixture was uniformly mixed with a blender to obtain a blended monomer DMF solution.

  A polymerization oxidation catalyst sodium persulfate 0.5 part by mass and a polymerization reduction catalyst sodium hydrogen bisulfite 0.8 part by mass are added to the blend monomer DMF solution with respect to 100 parts by mass of the blend component, and redox polymerization is carried out for 3 hours. went.

  During the polymerization reaction, the temperature in the polymerization vessel was maintained in the range of 53 to 57 ° C. The polymer concentration of the polymer DMF solution after the polymerization reaction was 30% by mass, and the viscosity was 45 seconds.

The obtained polymer DMF solution was filtered twice with a cotton filter cloth [differential pressure 3.1 kPa (3 kgf / m ² )] to remove impurities in the polymer DMF solution.

  The polymer DMF solution is spun from a spinning nozzle made of gold / platinum (60/40) having 0.09 mmφ × 36,000 holes into a DMF aqueous solution in a spinning bath at a draft rate of 28.5%. Got. The DMF concentration in the spinning bath was 25% by mass, and the bath temperature was 19 ° C.

  The gel-like fiber thus obtained was passed through a cold drawing bath at 25 ° C. and then a hot drawing bath at 93 ° C. with a stretch of 1.3 times to remove the solvent of the gel-like fiber (wet heat drawing).

  Moist heat-stretched fiber is removed by 14-drum and suction drum dryer set at an internal temperature of 110-155 ° C to remove fiber moisture (dry heat drying) and densify the internal structure of the fiber to make the original acrylic with a fineness of 1.7 dtex Fiber was obtained.

  The obtained original acrylic fiber was put in an autoclave, and a crosslinked acrylic fiber was obtained by crosslinking in an aqueous hydrazine solution in which 5% by mass of hydrated hydrazine was dissolved while circulating the aqueous hydrazine solution at 100 ° C. for 3 hours. It was.

  Next, the fiber-crosslinked acrylic fiber was hydrolyzed in a sodium hydroxide aqueous solution in which 3% by mass of sodium hydroxide was dissolved in the same type autoclave at 100 ° C. for 1 hour. After the treatment, neutralization and water washing were performed with a 1% by weight aqueous solution of formic acid to obtain moisture absorbing / releasing exothermic fibers. The obtained moisture absorption / release exothermic fiber had a moisture absorption rate of 30%, and the coloration degree was as high as a lightness L value of 30.

  Using this moisture-absorbing / releasing fiber, a spun yarn (mixed yarn) having a meter count of 2/30 blended with wool (WOOL # 64) was produced by the eyelash method. The blend ratio was moisture-absorbing fiber: wool = 30: 70 (mass basis).

  1 kg of the obtained blended yarn was dyed with an acid dye having a pH of 5.5 using a Hisaka Co., Ltd./Over Meyer high pressure dyeing machine to obtain a dyed yarn. Under the dyeing conditions at this time, the dyeing bath was heated to 100 ° C. at a rate of 1 ° C./min, kept at the top temperature for 60 minutes, and gradually cooled under the conditions of 1 ° C./min.

  Thereafter, it was washed with soft water using water at room temperature (25 ° C.) for 15 minutes. The dyed yarn was washed at 60 ° C. for 20 minutes using a solution (washing bath) prepared to 2 g / L using a decontamination agent Neotex CD-500 manufactured by Nikka Chemical and soft water. The temperature rise and slow cooling of the washing bath are the same as the conditions at the time of dyeing. Then, it washed with water for 15 minutes on 30 degreeC conditions using soft water.

  Dehydration and drying: The yarn after washing with water was dehydrated to a dehydration rate of 40% by mass with a dehydrator and then dried with a vacuum dryer at 80 ° C. for 60 minutes.

  The blended yarn subjected to this dyeing had a moisture absorption rate of 20%, a coloration degree as high as a lightness L value of 30, and was uniformly colored.

Example 2
1 kg of the wool (WOOL # 64) before blending used in Example 1 was dyed with an acid dye having a pH of 5.5 using a Hisaka Co., Ltd./Over Meyer high pressure dyeing machine to obtain a dyed yarn. Under the dyeing conditions at this time, the dyeing bath was heated to 96 ° C. at a rate of 1 ° C./min, kept at the top temperature for 60 minutes, and gradually cooled under the conditions of 1 ° C./min.

  Thereafter, it was washed with soft water using water at room temperature (25 ° C.) for 15 minutes. The dyed yarn was washed at 60 ° C. for 20 minutes using a liquid (cleaning bath) prepared to 2 g / L using a decontamination agent Neotex CD-500 manufactured by Nikka Chemical and soft water. The temperature rise and slow cooling of the washing bath are the same as the conditions at the time of dyeing. Then, it washed with water for 15 minutes using 30 degreeC conditions using soft water.

  Dehydration and drying: The yarn after washing with water was dehydrated to a dehydration rate of 40% by mass with a dehydrator and then dried with a vacuum dryer at 80 ° C. for 60 minutes.

  Using the dyed wool, a spun yarn (mixed yarn) of metric number 2/30 blended with moisture-absorbing and releasing fibers obtained in Example 1 was produced by the eyelash method. The blend ratio was moisture-absorbing fiber: dyed wool = 30: 70 (mass basis).

  The blended yarn of this dyed wool and moisture-absorbing / releasing fibers had a moisture absorption rate of 20% and a coloration degree as high as a lightness L value of 30 and was uniformly colored.

Comparative Example 1
A blended yarn dyed was obtained in the same manner as in Example 1 except that no pigment was added to the DMF solvent in the preparation of the blended monomer DMF solution of Example 1.

  However, the blended yarn subjected to this dyeing had a poorly colored portion of the moisture absorbing / releasing exothermic fiber and was colored unevenly.

Comparative Example 2
In the polymer DMF solution obtained in Comparative Example 1, 3 parts by mass of carbon pigment with an average particle size of 0.5 μm (trade name Seast FY, manufactured by Tokai Carbon Co., Ltd.) (based on 100 parts by mass of the total amount of the polymer and the carbon pigment) Amount) was added. However, the pigment was poorly dispersed in the polymer DMF solution. For this reason, the obtained moisture absorbing / releasing exothermic fiber was unevenly dyed.

Claims (3)

A spinning solution obtained by polymerizing a blend monomer composed of acrylic fiber raw material monomers and pigment particles is spun to obtain a pigment-colored acrylic fiber, and then the crosslinked structure is introduced into the pigment-colored acrylic fiber. A method for producing a colored moisture-absorbing / releasing exothermic fiber, wherein the acrylic fiber is hydrolyzed. A method for producing a colored blended yarn, comprising: blending a colored moisture-absorbing / releasing exothermic fiber produced by the production method according to claim 1 with another fiber to obtain a blended yarn, and then dyeing the blended yarn. . A method for producing a colored blended yarn comprising blending the colored moisture-absorbing / releasing exothermic fiber produced by the production method according to claim 1 and a pre-dyed fiber.