JP2005179839A - Acrylic synthetic fiber and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic synthetic fiber in which health of the skin can be retained by antimicrobial effect or moisture-retaining effect and to provide a method for producing the synthetic fiber. <P>SOLUTION: The acrylic synthetic fiber comprises an acrylonitrile-based polymer containing polyvinylpyrrolidone and at least one kind of compound selected from a group consisting of carnosol, rosmanol, isorosmanol, epirosmanol, carnosic acid and ursolic acid. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  INDUSTRIAL APPLICABILITY The present invention is suitable for a fiber structure having a form in direct contact with the skin, and is an acrylic synthetic fiber that can maintain skin health due to the excellent moisturizing effect, antibacterial effect, etc. possessed by substances contained in cosmetics And a manufacturing method.

  In recent years, interest in health, hygiene, and the environment has increased greatly, and the need for textile products having hygienic functions such as deodorization and antibacterial has been extremely high, and many products having these functions have been proposed. However, despite the purpose of health and the environment, chemical synthetic drugs are often used as processing agents that exhibit these hygiene functions. For example, quaternary ammonium salts are mainly used as organic antibacterial agents. In general, an antibacterial agent that adheres to the fiber surface is used.

  In addition, a processing agent for fibers and a processing method have been proposed, which are made of a cucumber, carrot, tomato, peach, plant collection material such as avocado, a natural oil-soluble material, and a surfactant (for example, see Patent Document 1).

However, all of these have been proposed as the hydrophilicity of such natural product components enhancing the moisturizing effect of the fiber itself, and in order to impart this function to such a fiber, the adhesion amount is about 5%. However, there were many things that required the texture of the fiber.
JP-A-8-232166

  An object of the present invention is to provide an acrylic synthetic fiber that can maintain the health of the skin by an excellent moisturizing effect without impairing the unique texture of the fiber, and a method for producing the same, in view of the background of the prior art. is there.

  In order to solve the above problems, the present invention employs the following means.

  That is, the acrylic synthetic fiber of the present invention comprises an acrylonitrile-based polymer containing polyvinylpyrrolidone, carnosol, rosmanol, isorosmanol, epirosmanol, carnosic acid. And at least one selected from the group consisting of ursolic acid (ursolic acid).

  The acrylic synthetic fiber referred to in the present invention is a synthetic fiber having an acrylonitrile-based polymer as a constituent component, and is a fiber containing acrylonitrile units in an amount of 85% or more by weight, and fibers containing 35% or more and less than 85% acrylonitrile. It includes any acrylic synthetic fiber.

  The polyvinyl pyrrolidone contained in the acrylic synthetic fiber of the present invention is for imparting a desired high moisture content characteristic to the fiber, and is contained in an amount of 5 to 30% by weight based on the acrylonitrile polymer in order to enhance the moisture retention. It is preferably 5 to 20% by weight. When the content of polyvinyl pyrrolidone is too small, less than 5% by weight, it becomes difficult to obtain sufficient moisture characteristics. On the other hand, if the amount exceeds 30% by weight, a sticky feeling will be developed and the feel will be poor, and the yarn-making property will be poor, making it difficult to produce stably.

  The acrylic synthetic fiber according to the present invention further has a carnosol, rosmanol, isorosmanol, epirosmanol, carnosic acid, and ursol on the surface of the fiber in its swollen state. It is preferable to contain at least one selected from the group consisting of acids (ursolic acid) in an amount of 0.1% by weight to 4% by weight, more preferably 0.5% by weight to 2% by weight, based on the acrylonitrile polymer. . If the content is less than 0.1% by weight, it is difficult to obtain a sufficient skin health condition, and if it exceeds 4% by weight, the effect is sufficient, but the texture and the feeling of wearing are deteriorated, which is not preferable.

  In addition, the method for producing an acrylic synthetic fiber according to the present invention includes blending a polymer containing polyvinylpyrrolidone with an acrylonitrile polymer, wet spinning, and then adding the swelled fiber to carnosol, rosmanol, and isorosmanol. It is characterized in that it is impregnated with at least one selected from the group consisting of (isorosmanol), epirosmanol, carnosic acid, and ursolic acid.

  The fibers obtained in this way are not affected by the texture of the fibers, and have high moisture content characteristics due to polyvinyl pyrrolidone, and are mixed with natural substances and adhered to the fiber surface. By doing so, the moisturizing effect and antibacterial effect are added, and the effect of preventing rough skin is improved, so that the health of the skin can be further maintained.

  Hereinafter, the present invention will be described in more detail.

  The acrylic synthetic fiber of the present invention includes an acrylonitrile-based polymer containing polyvinylpyrrolidone (hereinafter sometimes abbreviated as “PVP”), carnosol, rosmanol, isorosmanol, epirose. It contains one or more selected from the group consisting of manol (epirosmanol), carnosic acid (urnoic acid) and ursolic acid (ursolic acid).

  PVP is preferably contained in an amount of 5 to 30% by weight, more preferably 7 to 25% by weight, more preferably 9 to 20% by weight based on the acrylonitrile-based polymer in order to impart desired high moisture content characteristics to the fiber. % Is more preferable. When the content of PVP is too small, less than 5% by weight, it becomes difficult to obtain sufficient moisture characteristics. On the other hand, if the amount exceeds 30% by weight, a sticky feeling will be developed and the feel will be poor, and the yarn production will be poor and it will be difficult to produce stably.

  PVP may be obtained by graft polymerization of acrylonitrile with PVP in a solvent such as dimethyl sulfoxide and blend it with an acrylonitrile-based polymer solution that is a spinning dope, or a solution of PVP dissolved in a solvent such as dimethyl sulfoxide. It is contained in the acrylonitrile polymer by blending with the acrylonitrile polymer solution that is the spinning dope. As the blending method here, a conventional method such as a mixing mixer can be adopted, and it is preferable that the blending is performed uniformly.

  The blend amount of PVP is preferably 5 to 30% by weight, more preferably 7 to 25% by weight, and even more preferably 9 to 20% by weight based on the acrylonitrile-based polymer.

  Further, the PVP used in the present invention preferably has a K value of 20 or more and 70 or less. PVP with too low K value is weakly entangled with the molecular chain of the acrylonitrile polymer no matter how much it is polymerized with acrylonitrile, and many of them are likely to elute in the wet spinning solution and the subsequent drawing bath and washing bath. In order to obtain a high moisture content characteristic, a large amount of PVP must be kneaded, resulting in a reduction in production efficiency. On the other hand, if the K value is too high, the viscosity of the polymer tends to increase, it is difficult to obtain a stable polymer, and the yarn-making property becomes poor.

  The K value is a parameter corresponding to the average molecular weight. When the K value is low, the average molecular weight is low, and when the K value is high, the average molecular weight is large. The average molecular weight is about 40,000 at K = 30, and about 700,000 at K = 90. .

  The acrylonitrile-based polymer used in the present invention preferably contains 2 to 8 mol% of at least 92 mol% of acrylonitrile and an ethylenic vinyl monomer copolymerizable with acrylonitrile and a sulfonic acid-containing monomer. When the content of acrylonitrile is less than 92 mol%, normal physical properties cannot be obtained, which is not preferable. Examples of the ethylenic vinyl monomer copolymerizable with acrylonitrile include acrylic acid, methacrylic acid, or alkyl esters thereof, vinyl halides such as vinyl chloride, vinyl esters such as vinyl acetate, maleic acid, fumaric acid, and itacone. Acid, styrene, vinylidene halide, vinyl ether and the like. Examples of the sulfonic acid-containing monomer include sodium allyl sulfonate, sodium methallyl sulfonate, sodium vinyl sulfonate, sodium styrene sulfonate, 2-acrylamido-2-methylpropane. Examples thereof include sodium sulfonate. The sulfonic acid-containing monomer is preferably copolymerized in an amount of 0.2 to 2.0 mol%.

  The solvent of the acrylonitrile-based polymer solution may be any solvent that dissolves the acrylonitrile-based polymer. Organic solvents such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), dimethylformamide, dimethylacetamide, and acetone, and aqueous rhodium salt solutions. Zinc chloride aqueous solution, nitric acid aqueous solution and the like can be used. The proportion of the acrylonitrile polymer in the acrylonitrile polymer solution is preferably 19 to 25% by weight.

  The acrylonitrile-based synthetic fiber of the present invention is composed of carnosol, rosmanol, isorosmanol, epirosmanol, carnosic acid, and ursolic acid. It is preferable that at least one selected from the group is added in an amount of 0.1 wt% to 4 wt%, more preferably 0.5 wt% to 2 wt%, based on the acrylonitrile-based synthetic fiber. If the amount of adhesion is less than 0.1% by weight, it is difficult to obtain a sufficient skin health state, and if it exceeds 4% by weight, the effect is sufficient, but the texture and wearing feeling are deteriorated, which is not preferable. . In order to improve adhesion durability, a silicon binder or the like may be mixed and applied.

  As the fiber of the present invention, a fiber produced by a wet spinning method is used. That is, according to the wet spinning method, a swollen fiber is produced by a method of densifying the fiber, and the swollen fiber is a porous fiber. During this stage, rosemary oil is used. Are adsorbed and adhered in the pores of the fiber, and then densified to be fixed in the fiber.

  The acrylonitrile-based synthetic fiber of the present invention is, for example, wet-spun of the acrylonitrile-based polymer solution, and then stretched at a ratio of 3 to 7 times in order to provide appropriate yarn strength and elongation, One or more kinds selected from the group consisting of carnosol, rosmanol, isorosmanol, epirosmanol, carnosic acid, ursolic acid Is obtained by the following method.

  The swollen fibers after wet spinning are composed of carnosol, rosmanol, isorosmanol, epirosmanol, carnosic acid, ursolic acid. At least one kind selected from the group is brought into contact, that is, in any process until the swollen fiber is finally densified, it adheres in the pores of the swollen fiber, so that the washing durability of the antibacterial effect In addition, a product with excellent sustainability can be provided.

  In other words, internal voids and surface irregularities generated by, for example, desolvation remain in the swollen fiber spun by the wet spinning method, that is, the fiber at the stage where densification is not completed after spinning. One or more selected from the group consisting of carnosol, rosmanol, isorosmanol, epirosmanol, carnosic acid, ursolic acid used in the present invention. Has a characteristic that it penetrates into the voids inside the fibers and the surface irregularities, and is easily fixed and held on the fibers by densification of the fibers. The final densification step means a final step that substantially increases the polymer density by, for example, a stretching step, and is not limited by the name of the step.

  The acrylonitrile-based polymer solution as described above is wet-spun and extruded into a bath having a coagulant bath concentration of 50 to 70% by weight and a coagulant concentration of water or alcohol such as 30 to 50% by weight. .3 to 2.0, then drawn at a draw ratio of 3.5 to 7.0, washed with water, then carnosol, rosmanol, isorosmanol, epirosmanol (Epirosmanol), carnosic acid (carnosic acid), one or more kinds of oils selected from the group consisting of ursolic acid (ursolic acid) were applied to dry and densify, and after oil was applied, crimped by crimper It can be obtained by heat treatment at 100 to 170 ° C later. Can.

  In the present invention, carnosol, rosmanol, isorosmanol, epirosmanol, carnosic acid, ursolic acid are representative of the family Lamiaceae. It is an oil extracted from the western herb Rosemary (Rosmarinus officinalis), and this oil has excellent safety from the viewpoint of human safety, particularly skin functionality.

  That is, the rosemary is extracted with a lower alcohol having a water content of 10 to 60% by volume, and water is added to the resulting extract to precipitate a water-insoluble component, which is obtained by filtration. Is. In this case, when the water content of the extraction solvent (lower alcohol) exceeds 60% by volume, unnecessary extraction of water-soluble components increases, which is not preferable. The part of rosemary used for such extraction treatment is preferably the above-ground part, particularly the leaf stalk part of rosemary. This extract may be used as it is, or may be used after drying such as sun drying.

  Such an extraction operation may be performed at room temperature, but the extraction can be performed more efficiently by preferably employing a means for heating under reflux cooling. If this extraction operation is repeated further for the residue after extraction, the yield can be increased.

  After the extraction treatment, when the obtained extract is concentrated under reduced pressure, water-insoluble components begin to precipitate as the alcohol content decreases. After removing the alcohol, water is added to this and suspended with stirring, and then the precipitated component is collected by filtration or the like to obtain a water-insoluble component. Preferably, an impure component such as a coloring component is removed by subjecting the obtained extract or an obtained precipitate component redissolved in alcohol to activated carbon treatment.

  As an example of a specific production method, 500 ml of 90 volume% ethanol (water content 10 volume%) was added to 100 g of dried rosemary leaves and heated at an external temperature of 110 ° C. for 9 hours under reflux cooling. After soaking for 16 hours while allowing to cool naturally, the mixture is filtered to separate the filtrate (A) and the insoluble residue, and the insoluble residue is rinsed with 300 ml of 90% by volume ethanol to obtain a rinse liquid (B). These filtrate (A) and rinse solution (B) were combined to obtain 700 ml of an extract (primary extract). Next, 300 ml of the 90% by volume ethanol (water content 10% by volume) is further added to the filtered insoluble residue, followed by heating and extraction for 9 hours under reflux cooling, and the residue is filtered to obtain a filtrate (C). The filtrate (C) and the primary extract were combined to obtain 950 ml of extract (D).

  After adding 0.75% by weight of activated carbon to this extract (D) and stirring for 1 hour, the activated carbon was removed by filtration, the extract was concentrated under reduced pressure to distill off the ethanol component, and 210 ml of water was added. In addition, after the water-insoluble component that had been precipitated by stirring was suspended, the precipitated component was collected by filtration and dried at 45 ° C. under reduced pressure to obtain 13.4 g of a solid content. The solid content from this rosemary is the oil used in the present invention. As such a drawing, Mamorec RUH-21 (R) manufactured by Teikoku Chemical Industry Co., Ltd. can be used as a commercial product.

There is no restriction | limiting in particular in the means to contact a fiber and oil, For example, the means used for oil agent provision, such as immersion and a spray, is used preferably. The oil content is preferably 0.1% by weight to 4% by weight, more preferably 0.5% by weight to 2% by weight of the fiber weight. When the amount is less than 0.1% by weight, sufficient skin health cannot be obtained, and when the amount exceeds 4% by weight, the effect is sufficient, but the texture and the feeling of wearing are deteriorated.
<K value>
Polyvinyl pyrrolidone is used as an aqueous solution with a concentration of 1%, the relative viscosity is measured, and determined by the Fikentscher equation.

logZ = C [75 k ² /(1+1.5 kC) + k]
However, Z: Relative viscosity of aqueous solution of concentration C, k: K value × 10 −3, C: concentration of aqueous solution (W / V%).

  In addition, in the commercially available polyvinyl pyrrolidone, since it is normal that the K value is specified and it is usually marketed, the value may be generally followed.

Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the following method was used for quality evaluation in an Example.
[Skin condition]
The skin condition was ranked by observation with a microscope.

  5: The horny part is transparent and fine.

  4: The horny part is almost transparent and the skin is not rough.

  3: Slightly keratinous part, but almost no rough skin.

  2: The horny white part is conspicuous and the skin is slightly rough.

1: Most keratin is white and textured.
[Antimicrobial performance evaluation method]
The method for measuring the number of bacteria was adopted, and Staphylococcus aureus ATTC 6538p was used as a test bacterium. A bouillon suspension of test bacteria was poured onto a sample cloth sterilized by a conventional method, and cultured at 37 ° C. for 18 hours in a sealed container. The number of viable bacteria was measured, and the difference in the number of bacteria increased or decreased represented by the following formula was determined.

(Bacterial count increase / decrease value difference) = log (B1 / C1)
However, log (B1 / A1)> 2
In the formula, A1: Number of bacteria collected and recovered immediately after inoculation on unprocessed cloth
B1: Number of bacteria recovered after dispersion of untreated cloth after culturing at 37 ° C for 18 hours
C1: Number of bacteria collected and dispersed after incubation of processed product at 37 ° C. for 18 hours [Method of evaluating moisture content]
Three test cottons of about 1 g of raw cotton used for the test are prepared. The test cotton is put in a weighing bottle having a known weight, and a hot air dryer set at 60 ° C. is covered and preliminarily dried for 30 minutes. After the preliminary drying, the humidity is adjusted for 24 hours in a thermo-hygrostat set to 20 ° C. × 65% RH. After covering the weighing bottle, take it out of the thermo-hygrostat and immediately weigh it and subtract the weight of the weighing bottle to calculate the weight of the test cotton (calculate to 2 digits after the decimal point. This is W1).
Remove the lid of the weighing bottle with a hot air dryer at 105 ° C. for 2 hours, dry, dry, immediately cover the weighing bottle, place in a desiccator and allow to cool at room temperature for 30 minutes.

  Thereafter, the weighing bottle is taken out from the desiccator and weighed, and the weight of the weighing bottle is subtracted to obtain the absolute weight dry weight of the test cotton. (Calculate up to two decimal places. Let this be W2.)

The moisture content is calculated from the weight of the test cotton before and after the absolute drying determined as described above by the following formula. Measurement is carried out by performing this test as n times 3 times, and the average value of the 3 times is shown. (Calculate to one decimal place)
Moisture content = [(W1-W2) / W2] × 100 (%)
Examples 1-4
As the PVP, a commercially available PVP having a K value of 30 (BASF “LUVITEC” K30 POWDER: hereinafter abbreviated as “K30”) was used as the PVP. This PVP is dissolved in dimethyl sulfoxide (DMSO), and acrylonitrile (AN) / methyl acrylate (MEA) / sodium methacryl sulfonate (SMAS) = 95.5 / 4.2 / 0.3 (molar ratio). Was mixed with a dimethyl sulfoxide (DMSO) solution of an acrylonitrile-based copolymer comprising 20% by weight of PVP with respect to the acrylonitrile-based polymer, and wet-spun into a 57% DMSO aqueous solution. Thereafter, the resultant was stretched 6 times, washed with water, and a commercially available mamorec RUH-21 (R) (manufactured by Teikoku Kagaku) was blended into a 5% by weight aqueous solution on the swollen fiber, and 0.4% owf, 0.8% owf, After antibacterial treatment so as to be 1% owf and 3% owf, it was dried and densified at 130 ° C. to obtain an antibacterial acrylic fiber according to the present invention. The resulting fibers were prepared with a water jet punch to produce a 70 g / m ² non-woven fabric and the antibacterial performance was measured. It is shown in 1.

Comparative Example 1
As PVP, commercially available PVP (K30) having a K value of 30 synthesized by a usual method was used. This PVP is dissolved in dimethyl sulfoxide (DMSO), and acrylonitrile (AN) / methyl acrylate (MEA) / sodium methacryl sulfonate (SMAS) = 95.5 / 4.2 / 0.3 (molar ratio). Was mixed with a dimethyl sulfoxide (DMSO) solution of an acrylonitrile-based copolymer comprising 10% by weight of PVP with respect to the acrylonitrile-based polymer, and wet-spun into a 57% DMSO aqueous solution. Thereafter, the film was stretched 6 times, washed with water, applied with an oil agent, dried and densified with hot air drying at 160 ° C., applied with an oil agent, and then crimped and dried to obtain a fiber. The resulting fibers were prepared with a water jet punch to produce a 70 g / m ² non-woven fabric, and antibacterial performance was measured. A new non-woven fabric was stuck to the heel of the right arm every day for 1 week, and the skin condition was observed with a microscope. It is shown in 1.

Comparative Example 2
A dimethyl sulfoxide (DMSO) solution of an acrylonitrile copolymer consisting of acrylonitrile (AN) / methyl acrylate (MA) / sodium methacryl sulfonate (SMAS) = 93.5 / 6.0 / 0.5 (weight ratio), Wet spinning was performed in a 30% 60% DMSO aqueous solution. After stretching and washing the obtained unstretched solidified fiber, a commercially available mamorec RUH-21 (R) (manufactured by Teikoku Kagaku) as a rosemary oil was prepared in a 5 wt% aqueous solution and treated with 0.2% owf, The fiber was obtained by drying and densifying at 130 ° C., crimping and drying. The resulting fibers were made with a water jet punch to produce a 70 g / m ² non-woven fabric and measured for antibacterial performance, and a new non-woven fabric was applied to the arm of the right arm every day for 1 week to observe the skin condition with a microscope. The results are shown in Table 1.
All the examples had high antibacterial properties, and the skin condition was fine and healthy.

  As is apparent from Table 1, the fibers of Examples 1 to 4 have antibacterial performance and can maintain skin health.

  The acrylic synthetic fiber of the present invention is suitable for maintaining the health of skin due to its antibacterial effect and moisturizing effect, and is used in various clothing and the like.

Claims (6)

A group consisting of acrylonitrile-based polymers containing polyvinylpyrrolidone and carnosol, rosmanol, isorosmanol, epirosmanol, carnosic acid, and ursolic acid An acrylic synthetic fiber comprising at least one selected from the group consisting of: The acrylic synthetic fiber according to claim 1, wherein the polyvinyl pyrrolidone is contained in an amount of 5 to 30% by weight based on the acrylonitrile polymer. Acrylonitrile-based at least one selected from the group consisting of carnosol, rosmanol, isorosmanol, epirosmanol, carnosic acid, and ursolic acid The acrylic synthetic fiber according to claim 1, wherein the acrylic synthetic fiber is contained in an amount of 0.1 to 4% by weight based on the polymer. A fabric comprising the acrylic synthetic fiber according to any one of claims 1 to 3. The clothing which uses the fabric of Claim 4. A polymer containing polyvinylpyrrolidone is blended with an acrylonitrile-based polymer, and after wet spinning, the swollen fiber is added to carnosol, rosmanol, isorosmanol, epirosmanol, carnosic acid (carnosic acid). acid) and at least one selected from the group consisting of ursolic acid is impregnated.