JP2003119616A - Minus ion generating modacrylic fiber and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a minus ion generating modacrylic fiber comprising a tourmaline composition with improved minus ion releasing function and having an amount of minus ion generated of practical level. SOLUTION: This minus ion generating modacrylic fiber comprises the composition obtained by mixing tourmaline having <=3 μm average particle diameter with an electrical insulating substance having <=1 μm average particle diameter. The average particle diameter of the tourmaline is preferably >=0.1 μm and <=1 μm. The total content of the tourmaline and the electrical insulating substance is preferably 2-15 wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modacrylic fiber for generating negative ions and a method for producing the same.

[0002]

2. Description of the Related Art Negative ions are usually 0.5 to 1 nm
It is associated with water in small clusters on the ground and exists on the ground, especially in waterfalls and forests. Also, it can be artificially made with a corona discharge device or the like. However, negative ions are extremely reduced in places where many people gather, and for example, in a room full of cigarettes, the number of negative ions is extremely small, which is about one-thousandth of Takiguchi and about one-hundredth of the forest. on the other hand,
The effects of negative ions on the human body are the cerebral cortex,
It is said that most of them are good for the body, such as decreasing the amount of serotonin in blood, increasing the amount of oxygen and SOD enzyme in blood, and increasing the stress-suppressing hormone (cabbage).

Conventionally, tourmaline, which is also called tourmaline, has been known as a substance that releases negative ions.
Its negative ion emission function was weak and not practical.

Further, there has been proposed an electret fiber in which tourmaline kneaded into an acrylic fiber releases active electrons to give an activating effect to living cells (Japanese Patent Laid-Open No. 10-
183422). However, even if only tourmaline was kneaded into the acrylic fiber, the amount of negative ions generated was naturally small, and the utility as negative ion generating fibers was low.

On the other hand, since tourmaline alone has a small amount of negative ion emission, a negative ion generation temperature control body has been proposed which is used in combination with an exciter such as thorium stone to improve the generation efficiency of negative ions (Japanese Patent Laid-Open No. 2001-2001). -21
165). However, since a radioactive substance is used as the stimulant, and even if the product has a weak radiation dose, a large amount of the radioactive substance is handled at the time of manufacture, which poses a safety problem.

[0006]

SUMMARY OF THE INVENTION In view of the above problems, the present inventors have earnestly studied to improve the negative ion generation efficiency of modacrylic fiber, and as a result, have found that tourmaline in the form of fine particles and an electrically insulating substance in the form of fine particles are used. By uniformly kneading the mixed composition into the modacrylic polymer, it was found that the amount of negative ions generated was extremely large, and further, a synergistic effect with the negative charging ability of the modacrylic fiber was found, and the present invention was obtained. completed.

That is, the object of the present invention is to produce a negative ion containing a tourmaline composition having an improved negative ion releasing function without using an exciter such as a radioactive substance and having a practical level of negative ion generation amount. It is intended to provide a modacrylic fiber and a method for producing the same.

[0008]

SUMMARY OF THE INVENTION The gist of the present invention is that tourmaline having an average particle size of 3 μm or less and an average particle size of 1
A negative ion generating modacrylic fiber containing a composition obtained by mixing an electrically insulating substance having a size of not more than μm.

The average particle size of the tourmaline is preferably 0.1 μm or more and 1 μm or less. Further, the total content of the tourmaline and the electrically insulating substance is preferably 2 to 15% by weight.

Further, there are three methods of producing the negative ion generating modacrylic fiber of the present invention. The first method, for a solvent solution of acrylonitrile-halogen-containing monomer copolymer and acrylonitrile-halogen-containing monomer copolymer, tourmaline in a solvent of the same composition as the solvent solution of the acrylonitrile-halogen-containing monomer copolymer. It is characterized in that a mixed solution obtained by wet-grinding and dispersing and then adding and mixing fine particles of an electrically insulating substance is adjusted to a predetermined concentration and mixed, and the obtained solution is used as a stock solution for spinning. There is.

Next, the second method is acrylonitrile-
Halogen-containing monomer copolymer and acrylonitrile-
To a solution of halogen-containing monomer copolymer in a solvent, dry mix the tourmaline and classify it, and then add the particles of the electrically insulating substance to the particles of the tourmaline. It is characterized in that the solution obtained by mixing is used as a stock solution for spinning.

The third method is acrylonitrile-
Halogen-containing monomer copolymer and acrylonitrile-
The tourmaline was wet pulverized in water with respect to the solvent solution of the halogen-containing monomer copolymer, and then dried, crushed and / or re-pulverized to obtain fine particles of tourmaline, and fine particles of an electrically insulating substance were added and mixed. The mixture thus obtained is adjusted to a predetermined concentration and mixed, and the obtained solution is used as a spinning dope.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The modacrylic fiber in the present invention is obtained by spinning a copolymer of acrylonitrile, a halogen-containing monomer (monomer), and another monomer. And
The ratio is not particularly limited, but acrylonitrile / halogen-containing monomer / other monomer = 80 to 30
% / 20 to 70% / 0 to 10% by weight is preferred. And, as the halogen-containing monomer, vinyl chloride,
Examples thereof include vinylidene chloride and vinyl bromide, and these may be used alone or in combination of two or more kinds.
Examples of the other monomer include methyl acrylate, vinyl acetate, sodium allyl sulfonate, sodium methallyl sulfonate, sodium styrene sulfonate, and sodium acrylamido 2-methylpropane sulfonate, which may be used alone or You may use it in combination of 2 or more type.

By the way, a fiber containing 20% by weight or more of a halogen-containing monomer such as vinyl chloride or vinylidene chloride like the modacrylic fiber in the present invention has a strong halogen such as chlorine which tends to be a monovalent anion. Since the element exists in the molecule, when viewed in the charging train, it is easy to charge on the negative side, and a large amount of negative ions are generated due to friction and peeling.

The tourmaline used in the present invention may be one known in the prior art. That is, it is represented by the following general formula. NaX ₃ Al ₆ (BO ₃ ) ₃ Si ₆ O ₁₈ (OH) ₄ However, in the formula, X represents the same or different Mg, Fe, Li. Particularly preferable specific examples are as follows. _{(B) NaFe 3 Al 6 (BO 3} ) 3 Si 6 O 18 (OH) 4 ( _{ii) Na (Li, Al) 3} Al 6 (BO 3) 3 Si 6 O
₁₈ (OH) ₄ (C) NaMg ₃ Al ₆ (BO ₃ ) ₃ Si ₆ O ₁₈ (OH) _{4 In} addition, (a) above is a shawl, (B) is an elbaite,
(C) is sometimes called a drabite.

The average particle size of this tourmaline needs to be 3 μm or less, more preferably 0.1 to 1 μm, depending on the amount of anion release and the spinnability.
Is. If the average particle size of tourmaline exceeds 3 μm,
Not only the amount of negative ions released decreases, but also when the modacrylic fiber is spun, the filter cloth is clogged, and the mouth hole is blocked.
This may cause yarn breakage and reduce operability. On the other hand, the smaller the average particle size of tourmaline, the larger the amount of released negative ions, but if it is smaller than 0.1 μm, the particles of tourmaline are likely to undergo secondary aggregation, and the amount of released negative ions also decreases. There is a tendency.

There are no particular restrictions on the method for adjusting the average particle size of tourmaline to an appropriate size, that is, 0.1 to 1 μm, but wet pulverization or dry pulverization using a general pulverizer is performed. Milling is preferred. Examples of the pulverizer include rolling mills such as rolling ball mills, rod mills and tube mills; stirring mills such as bead mills, sand mills and tower mills; vibration mills; jet mills; planetary mills;
A roller mill or the like can be used, but it is particularly preferable to use balls as a grinding medium because uniform fine particles can be easily obtained. That is, among the crushers, a rolling mill, a stirring mill, a vibration mill, and a planetary mill are applicable. Further, it is more preferable that a large mill container can be industrially used, and a rolling mill or a stirring mill is most suitable.

On the other hand, in the case of dry crushing, a tourmaline crushing agent, an optional crushing medium and an optional crushing aid may be charged into a crusher and crushed. In the case of wet crushing, a solvent is further added. Will be needed. Among the solvents, water is mentioned in terms of easy handling, but other solvents used for modacrylic fiber are also mentioned. In particular, when wet crushing is performed using a solvent used for modacrylic fiber, the particle size distribution of tourmaline crushed organisms is relatively narrow, and the solution after crushing can be used as it is as a raw material for modacrylic fiber spinning. It is preferable because there is no need for steps.

The electrically insulating substance used in the present invention is an inorganic substance that does not or hardly conducts electricity, and may be solid at room temperature. Examples thereof include, but are not limited to, talc, mica, tricalcium phosphate, and calcium pyrophosphate. The average particle size of the electrically insulating substance needs to be 1 μm or less due to the miscibility with tourmaline. If the average particle size exceeds 1 μm, it is not preferable because it leads to mixed spots with tourmaline.

When an electrically insulating substance is used in combination with tourmaline, the amount of released negative ions is remarkably improved. There are two possible reasons for this, but the details are not clear.
Firstly, it is considered that the electric insulating material disturbs the electric field generated by tourmaline, so that the charge balance in the electric field is lost and negative ions are emitted. The second point is that since there is an electrically insulating substance between the tourmaline particles, it is possible to prevent secondary aggregation of the tourmaline particles and to allow the tourmaline to remain in the modacrylic fiber as the particles, thus reducing the amount of negative ion emission. It can be prevented. In addition, there is a secondary effect that the spinning operability is not deteriorated.

Further, in the present invention, the ratio of the tourmaline fine particles and the fine particles of the electrically insulating material is 10
With respect to 0 parts by weight, the latter is preferably 5 to 49 parts by weight,
It is preferably 10 to 20 parts by weight. The total content of tourmaline and the electrically insulating substance is preferably 2 to 15% by weight with respect to the modacrylic fiber in the present invention. This is because the larger the content, the larger the amount of released negative ions, but the larger the content, the lower the operational stability during spinning and the lower the strength and elongation of the obtained yarn.

Next, since there are three methods for producing the negative ion generating modacrylic fiber of the present invention, they will be described in order.

In the first method, first, tourmaline is wet-ground using a solvent having the same composition as the solvent solution of the acrylonitrile-halogen-containing monomer copolymer. Then, the particles of the electrically insulating substance are added to the solvent solution in which the tourmaline particles are dispersed, and further mixed and stirred to obtain a mixed solution. Next, the solvent solution of the acrylonitrile-halogen-containing monomer copolymer and the acrylonitrile-halogen-containing monomer copolymer and the mixed solution are mixed and stirred so that the tourmaline and the electrically insulating substance have a predetermined content. Adjust the concentration. Then, the obtained solution is used as an undiluted solution for spinning and fiberized by ordinary wet or dry spinning.

Examples of the solvent solution include dimethylformamide, dimethylacetamide, dimethylsulfoxide,
Organic solvents such as acetone are preferred. As the method of wet pulverization, the pulverizer described above may be used. The spun yarn can be obtained by a conventional method, that is, a spinning, drawing, washing, drying, oiling and crimping process.

Next, in the second method, first, tourmaline is dry pulverized. Then, after classifying the obtained tourmaline fine particles, the fine particles of the electrically insulating substance are added and further mixed and stirred to obtain a mixture. Next, acrylonitrile-
Halogen-containing monomer copolymer and acrylonitrile-
A solvent solution of a halogen-containing monomer copolymer and the above mixture are mixed and stirred to adjust the concentrations of tourmaline and the electrically insulating substance so that they have predetermined contents. Then, the obtained solution is used as an undiluted solution for spinning and fiberized by ordinary wet or dry spinning.

As the dry pulverization method, the pulverizer described above may be used. Moreover, the classification method is not particularly limited, but classification using a general sieving machine or classifier may be used as long as predetermined fine particles of tourmaline can be obtained. As the classifier, there are wet and dry gravity classifiers, wet and dry centrifugal force classifiers, dry inertial force classifiers, etc., but especially when a dry classifier is used, a drying step etc. is required after classification. None preferred. If a wet classifier is used, it is preferable to use the solvent used for modacrylic fiber as the solvent. This is because it is only necessary to add fine particles of the electrically insulating substance to the solution after classification, and a drying step is not necessary.

In the third method, first, tourmaline is wet-milled with water. Then, the aqueous solution in which the tourmaline particles are dispersed is dried, and the obtained dried aggregate of tourmaline particles is crushed and / or re-ground, and then the particles of the electrically insulating substance are added, and further mixed and stirred. A mixture is obtained. Next, the acrylonitrile-halogen-containing monomer copolymer and the solvent solution of the acrylonitrile-halogen-containing monomer copolymer are mixed and stirred with the mixture, and tourmaline and the electrically insulating substance are concentrated to a predetermined content. Adjust. Then, the obtained solution is used as an undiluted solution for spinning and fiberized by ordinary wet or dry spinning.

As the method of wet pulverization, the pulverizer described above may be used. The drying method is not particularly limited, and may be natural drying or drying using a general drier as long as water can be separated. Examples of dryers include diffusion type, hot air type, vacuum type, and freeze type.
The hot air method is preferable in consideration of the facility simplicity and manufacturing cost. Further, as a method of crushing and / or re-grinding as required, a general crusher and / or a general crusher may be used, but in particular, a crusher such as a cage mill or an impact mill and / or a jet mill. It is preferred to use a mill grinder. The spun yarn can be obtained by a conventional method, that is, a spinning, drawing, washing, drying, oiling and crimping process.

[0029]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Negative ion measurement method (method A) The amount of negative ions is measured using an ion counter SC-50 (manufactured by Sigma Tech Co.). That is, the sample (nonwoven fabric) is placed in the box and 60 liters / minute of air is sucked from the opposite side of the box. The amount of negative ions is measured at the midpoint between the sample and the suction outlet for 5 minutes, the average value of the number of negative ions per 1 cc is calculated, and compared with the number of negative ions when the sample is absent to confirm the increased number.

Negative ion measurement method (method B) The amount of negative ions is measured using an ion tester KST-900 (Kobe Denpa Co., Ltd.). That is, the sample (nonwoven fabric) is gently rubbed with the skin for 30 seconds in an atmosphere of 60% ^{RH and} 20 ° C., measured with the device, and the average value of the number of negative ions per 1 cc is determined.

Method for evaluating spinning operability Filtration area 7 cm ² , filter cloth Gozamin, 5000 H *
Discharge rate 320cc / min using 0.06mmφ
Spinning was carried out for 1 hour at a winding speed of 10.5 m / min, and evaluation was made based on a pressure increase (filterability) on a filter cloth and a single yarn breakage condition (yarn breakage). a) Filterability A ... 0 or more and less than 0.1 O ... 0.1 or more and less than 0.5 B A ... 0.5 or more and less than 1.0 X ... 1.0 or more and less than 2.0 XX ... 2.0 or more ( Each value is a pressure rise value: kg / cm ² ) b) Thread break ◎ ... 0 or more and less than 3 ○ ... 3 or more and less than 6 △
… 6 or more and less than 12 ×… 12 or more and less than 20 XX… 20
Above (each number is the number of single yarn breaks)

Examples 1 to 6 and Comparative Example 1 (first production method: wet grinding using a solvent solution) A rolling ball mill having a volume of 300 m ³ has 100 kg of shawl tourmaline # 325 and 120 kg of 20 mmφ balls.
Then, 180 kg of a 10 mmφ ball and 150 kg of dimethylformamide were added and pulverized for 240 hours. The average particle size of the shawl tourmaline in the obtained stock solution was 0.8 μm. Further, 15 kg of tricalcium phosphate having an average particle diameter of 0.5 μm was added and mixed for another 5 hours. 50 kg of modacrylic dope (concentration of modacrylic polymer 20% dimethylformamide of acrylonitrile / vinylidene chloride / 2 sodium acrylamido 2-methylpropanesulfonic acid = 55/42/3 (wt%) composition) was added to the solution obtained by removing the balls by filtration. And dimethylformamide solvent were added, and the concentration was adjusted so that the total content of shawl tourmaline and tricalcium phosphate was 20%.

This additive solution was used as a modacrylic dope of the above composition (polymer concentration 25% dimethylformamide solution).
To the dimethylformamide 60 at a ratio shown in Table 1.
% Aqueous solution was spun with a 0.06 mmφ die and solidified. After that, about 3.3 dtex after stretching, washing with water, drying, oiling, crimping, and 110 ° C heat setting process.
Fibers were obtained. The fiber was applied to a card spinning machine / needle punch machine to prepare a non-woven fabric of 50 g / m ² , and negative ions were measured.

In Comparative Example 1, instead of the modacrylic polymer used in Examples 1 to 6, acrylonitrile / methyl acrylate / sodium methallyl sulfonate = 91 /
An acrylic polymer having a composition of 8/1 (% by weight) was used, and other conditions were exactly the same as in Example 3,
Acrylic fiber was obtained.

[0036]

[Table 1]

As is clear from the results shown in Table 1, A
In the method, as the total content of tourmaline and tricalcium phosphate increases, the amount of increase of negative ions increases, but the spinnability tends to decrease. Further, it can be seen that in Method B, even if the total content of tourmaline and tricalcium phosphate is small, there is an extremely high level of negative ion amount due to friction between the fibers of the Examples and the skin. However, it can be seen that the amount of negative ions generated by the B method is remarkably low in the case of using acrylic fibers instead of modacrylic fibers as in Comparative Example 1.

Examples 7 to 10 and Comparative Example 2 (first production method: wet pulverization using a solvent solution) Shawl tourmaline # 325 was pulverized to 0 by a rolling ball mill in the same manner as in Examples 1 to 6. Fine particles of 0.8 μm were obtained. After adding tribasic calcium phosphate having each average particle size shown in Table 2 to this, it was added to modacrylic dope so that the total content of tourmaline and tribasic calcium phosphate was 5% by weight as in Example 3. Then, spinning was carried out by the same method as in Examples 1 to 6.

[0039]

[Table 2]

As is clear from Table 2, when the average particle size of the tricalcium phosphate is 1 μm or less, the amount of negative ions generated is high, and there is no problem in spinning operability. On the other hand, 1 μm
If it exceeds, the amount of negative ions generated will be small, and there will be a problem in the spinnability. This is because mixed spots of tourmaline and tricalcium phosphate occur, and the filter cloth tends to be clogged during spinning.

Comparative Examples 3 to 8 (First Production Method: Wet Grinding Using Solvent Solution) In the same manner as in Examples 1 to 6, Shoal Tourmaline # 325 was crushed with a rolling ball mill to obtain 0.8 μm fine particles. Got To this, without adding tricalcium phosphate as an electrically insulating substance, other than that was added to the modacrylic dope in the ratio shown in Table 3 in the same manner as in Examples 1 to 6 to obtain modacrylic fiber.

[0042]

[Table 3]

As is clear from Table 3, it is found that with only shawl tourmaline, even if the content thereof is increased, the number of increase of negative ions is extremely small, and the spinning operability is remarkably reduced, which is not practical. . That is, if there is no electrically insulating substance such as tricalcium phosphate,
This is because secondary agglomeration also immediately occurs in the shawl tourmaline made into fine particles.

Examples 11 to 15 and Comparative Example 9 (second manufacturing method: dry crushing) Shawl tourmaline # 325 was dry crushed with a rolling ball mill and classified with a dry gravity classifier to obtain Table 4. 100 parts of fine particles having the respective average particle diameters shown were obtained. After that, 0.5μ
50 parts of modacrylic dope (concentration of 20% modacrylic polymer of acrylonitrile / vinyl chloride / sodium styrene sulfonate = 42/56/2 (wt%) composition in acetone) mixed with 10 parts of synthetic mica of m. And an acetone solvent were added to obtain a 20% by weight tourmaline acetone solution. This was added to modacrylic dope so that the total content of shawl tourmaline and synthetic mica was 5% by weight, and acetone / water = 55 /
Spinning was performed in a 45 (wt%) solution to obtain tourmaline-containing modacrylic fiber.

[0045]

[Table 4]

As is clear from Table 4, when the average particle size of tourmaline exceeds 3 μm, the spinning operability is remarkably reduced,
The amount of negative ions generated also decreases. On the other hand, the smaller the average particle size, the greater the amount of negative ions generated,
Spinning operability tended to decrease slightly.

Examples 16 to 18 Here, the first production method (wet grinding using a solvent solution)
Examples of the second manufacturing method (dry grinding) and the third manufacturing method (wet grinding with water) will be shown. Elbaite Tourmaline # 325 product is used in Examples 1 to 10 and Comparative Examples 1 to 8.
When carried out in an organic solvent in the same manner as in (Example 16),
Similar to Examples 11 to 15 and Comparative Example 9, those pulverized by a dry method (Example 17), wet pulverized with water using a rolling ball mill, dried with hot air, and crushed with a cage mill. With what was passed (Example 18), tourmaline was pulverized to have an average particle size of 0.7 μm, and 15 parts by weight of calcium pyrophosphate having an average particle size of 0.7 μm was mixed with tourmaline. Thereafter, as in Example 3, the modacrylic fiber was kneaded so as to be 5% by weight. The spinning experiment was carried out for 8 hours in order to confirm the difference in the grinding method.

[0048]

[Table 5]

As is clear from Table 5, all of the 8 hour spinning were good, but especially Example 16 pulverized in dimethylformamide was extremely good without rise in spinneret pressure.

[0050]

As an effect of the present invention, the amount of negative ion generation of tourmaline is increased to a practical range by an extremely simple means of simply mixing an electrically insulating substance without using an exciting agent such as a radioactive substance. It is industrially very great that anion generating modacrylic fiber can be easily produced industrially. Furthermore, since negative ions are also generated by friction and peeling, extremely high negative ions, which are higher than the tourmaline effect, are generated. Of course, the fiber can be used for construction bedding such as blankets, sheets, carpets and curtains, and clothing such as underwear and sweaters.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Chieko Iwamoto             4-1, Kanebocho, Hofu City, Yamaguchi Prefecture Kanebo Go             Fiber Co., Ltd. F-term (reference) 4C053 MM02 MM04 MM08                 4L035 AA04 BB06 BB11 BB17 CC01                       EE08 EE20 FF04 FF05 JJ01                       JJ05 JJ08 KK01 KK05 MB10                       MB15 MB19

Claims (6)

[Claims] 1. A negative ion generating modacrylic fiber comprising a composition obtained by mixing tourmaline having an average particle size of 3 μm or less and an electrically insulating substance having an average particle size of 1 μm or less. 2. The average particle size of the tourmaline is 0.1 μm.
The negative ion generating modacrylic fiber according to claim 1, wherein the fiber has a size of m or more and 1 μm or less. 3. The negative ion generating modacrylic fiber according to claim 1, wherein the total content of the tourmaline and the electrically insulating substance is 2 to 15% by weight. 4. Acrylonitrile-halogen-containing monomer copolymer and acrylonitrile-halogen-containing monomer copolymer in a solvent solution
The tourmaline is wet pulverized and dispersed in a solvent having the same composition as the solvent solution of the halogen-containing monomer copolymer, and then fine particles of an electrically insulating substance are added and mixed to obtain a mixed solution having a predetermined concentration. A method for producing anion-generating modacrylic fiber, which comprises mixing and using the obtained solution as a spinning dope. 5. Fine particles of tourmaline obtained by dry-grinding tourmaline in a solvent solution of an acrylonitrile-halogen-containing monomer copolymer and an acrylonitrile-halogen-containing monomer copolymer and fine particles of an electrically insulating substance are obtained. A method for producing a negative ion generating modacrylic fiber, characterized in that the mixture obtained by additionally mixing is adjusted to a predetermined concentration and mixed, and the obtained solution is used as a stock solution for spinning. 6. A solution of acrylonitrile-halogen-containing monomer copolymer and a solvent solution of acrylonitrile-halogen-containing monomer copolymer obtained by wet-milling tourmaline in water and then drying, crushing and / or re-milling. The mixture obtained by adding the fine particles of the electrically insulating substance to the fine particles of tourmaline and mixing them is adjusted to a predetermined concentration and mixed,
A method for producing modal fiber of negative ion generation, characterized in that the obtained solution is used as a stock solution for spinning.