JP3634789B2 - Negative ion generation modacrylic fiber - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a modacrylic fiber for generating negative ions.
[0002]
[Prior art]
Negative ions are usually associated with small clusters of water of 0.5 to 1 nm on the ground, and are particularly abundant in waterfalls and forests. It can also be made artificially with a corona discharge device or the like. However, negative ions are extremely reduced in places where many people gather. For example, in a room full of cigarettes, the number of negative ions is extremely low, about one-thousandth of a waterfall and one-hundredth of a forest. On the other hand, negative ions have an effect on the human body, such as reducing the amount of serotonin in the cerebral cortex and blood, increasing the amount of oxygen and SOD enzymes in the blood, and increasing the stress-inhibiting hormone (hippo). It is said that most things are good for the body.
[0003]
Conventionally, tourmaline, also called tourmaline, is known as a substance that emits negative ions, but its negative ion release function is weak and impractical.
[0004]
And the electret fiber which the tourmaline knead | mixed in the acrylic fiber discharge | releases an active electron and gives an activation effect to a living cell is proposed (Unexamined-Japanese-Patent No. 10-183422). However, even if only tourmaline was kneaded into acrylic fiber, naturally, the amount of negative ions generated was small, and its practicality as a negative ion generating fiber was low.
[0005]
On the other hand, since tourmaline alone has a small amount of negative ion emission, a negative ion generation temperature regulator with improved negative ion generation efficiency in combination with an excitation agent such as thorium stone has been proposed (Japanese Patent Laid-Open No. 2001-21165). Publication). However, a radioactive substance is used as an exciter, and even if the product has a weak radiation dose, a large amount of radioactive substance is handled at the time of manufacture, so there is a problem in terms of safety.
[0006]
[Problems to be solved by the invention]
In view of the above problems, the present inventors have intensively studied to increase the negative ion generation efficiency of modacrylic fiber. As a result, a composition obtained by mixing fine tourmaline and fine electrical insulating material is modacrylic. The present inventors have found that the amount of negative ions generated becomes extremely large by kneading into the polymer uniformly, and further found the synergistic effect with the negative charging ability of modacrylic fiber, thereby completing the present invention.
[0007]
That is, an object of the present invention is to provide a negative ion-generating modacrylic fiber containing a tourmaline composition having an improved negative ion release function without using an excitation agent such as a radioactive substance and having a practical level of negative ion generation amount, and It is in providing the manufacturing method.
[0008]
[Means for Solving the Problems]
The gist of the present invention is that acrylonitrile / halogen-containing monomer / other monomer containing tourmaline having an average particle size of 0.1 μm or more and 1 μm or less and an electrically insulating material having an average particle size of 1 μm or less. = Negative ion generating modacrylic fiber produced from a copolymer comprising 80 to 30% by weight / 20 to 70% by weight / 0 to 10% by weight .
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The modacrylic fiber in the present invention is obtained by spinning a copolymer of acrylonitrile, a halogen-containing monomer (monomer), and another monomer. The ratio is not particularly limited, but acrylonitrile / halogen-containing monomer / other monomer = 80 to 30% by weight / 20 to 70% by weight / 0 to 10% by weight is preferable. Examples of the halogen-containing monomer include vinyl chloride, vinylidene chloride, and vinyl bromide, but these may be used alone or in combination of two or more. Examples of the other monomer include methyl acrylate, vinyl acetate, sodium allyl sulfonate, sodium methallyl sulfonate, sodium styrene sulfonate, sodium acrylamide 2-methylpropane sulfonate, and the like. Two or more kinds may be used in combination.
[0010]
By the way, like the modacrylic fiber in the present invention, a fiber containing 20% by weight or more of a halogen-containing monomer such as vinyl chloride or vinylidene chloride has a molecule of halogen such as chlorine having a strong tendency to become a monovalent anion as a molecule. Therefore, when viewed from a charged column, it tends to be negatively charged, and a large amount of negative ions are generated due to friction and peeling.
[0011]
The tourmaline used in the present invention may be a conventionally known one. 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 preferred specific examples are as follows.
(A) NaFe ₃ Al ₆ (BO ₃ ) ₃ Si ₆ O ₁₈ (OH) ₄
(B) 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
Note that (b) may be called a shawl, (b) may be called elbaite, and (c) may be called drabbit.
[0012]
And the average particle diameter of this tourmaline needs to be 3 micrometers or less by the amount of negative ion discharge | release, and spinning operation nature, More preferably, it is 0.1-1 micrometer. When the average particle size of tourmaline exceeds 3 μm, not only the amount of negative ions released, but also the filter cloth is clogged during spinning of modacrylic fiber, the mouthpiece hole is blocked, and the operability is lowered. Cause it. On the other hand, the smaller the average particle size of tourmaline, the larger the amount of negative ion release, but the smaller the amount of less than 0.1 μm, the easier the tourmaline fine particles to form secondary agglomerates and the lower the amount of negative ion release. There is a tendency.
[0013]
And in order to make the average particle diameter of tourmaline into an appropriate size, that is, 0.1 to 1 μm, the method is not particularly limited, but by wet pulverization or dry pulverization using a general pulverizer. 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; roller mills, etc. A medium using a ball is preferable because uniform fine particles can be easily obtained. That is, among the pulverizers, a rolling mill, a stirring mill, a vibration mill, and a planetary mill are applicable. Further, those capable of industrially producing a large mill container are more preferable, and a rolling mill and a stirring mill are optimal.
[0014]
On the other hand, in the case of dry pulverization, a tourmaline pulverizer, a pulverization medium as required, and a pulverization aid as required may be added to the pulverizer and pulverized. In the case of wet pulverization, a solvent is further required. . Among the solvents, water is mentioned from the viewpoint of ease of handling, but other solvents used for modacrylic fibers are also mentioned. In particular, when wet pulverization is performed using a solvent used for modacrylic fiber, the particle size distribution of tourmaline crushed organisms is relatively narrow, and the pulverized solution can be used as it is as a raw material for spinning modacrylic fiber. It is preferable because there is no need for a process.
[0015]
In addition, the electrical insulating material used in the present invention is an inorganic material that does not conduct or hardly conduct electricity, and may be solid at room temperature. Examples include, but are not limited to, talc, mica, tricalcium phosphate, and calcium pyrophosphate. And the average particle diameter of an electrically insulating substance needs to be 1 micrometer or less by the miscibility with tourmaline. When the average particle diameter exceeds 1 μm, it is not preferable because it leads to mixed spots with tourmaline.
[0016]
And, when an electrically insulating substance is used in combination with tourmaline, the amount of negative ions released is significantly improved. There are two possible reasons for this, but the details are not clear. The first point is considered that the electric insulating material disturbs the electric field generated by tourmaline, so that the charge balance in the electric field is disrupted and negative ions are released. Second, since an electrically insulating substance exists between the tourmaline particles, secondary aggregation between the tourmaline particles can be prevented, and tourmaline can be allowed to exist in the modacrylic fiber as it is, thus reducing the amount of negative ions released. It can be prevented. In addition, there is a secondary effect that no decrease in spinning operability is observed.
[0017]
In the present invention, the mixing ratio of tourmaline fine particles and fine particles of an electrically insulating substance is preferably 5 to 49 parts by weight, more preferably 10 to 20 parts by weight, with respect to the former 100 parts by weight. The total content of tourmaline and the electrically insulating material is preferably 2 to 15% by weight with respect to the modacrylic fiber in the present invention. This is because the higher the content, the larger the negative ion release amount, but the higher the content, the lower the operational stability during spinning, and the lower the strength and elongation of the obtained yarn.
[0018]
Next, since there are three methods for producing negative ion generating modacrylic fibers of the present invention, they will be described in order.
[0019]
In the first method, tourmaline is first wet-pulverized using a solvent having the same composition as the solvent solution of the acrylonitrile-halogen-containing monomer copolymer. Then, fine particles of an electrically insulating substance are added to a solvent solution in which tourmaline fine 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 density. The obtained solution is used as a stock solution for spinning, and fiberized by ordinary wet or dry spinning.
[0020]
The solvent solution is preferably an organic solvent such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and acetone. As a wet pulverization method, the above-described pulverizer may be used. The spun yarn is obtained by a conventional method, that is, through spinning, drawing, washing, drying, oiling, and crimping processes.
[0021]
Next, in the second method, tourmaline is first dry-pulverized. Then, after classifying the obtained tourmaline fine particles, fine particles of an electrically insulating substance are added, and further mixed and stirred to obtain a mixture. Next, the solvent solution of the acrylonitrile-halogen-containing monomer copolymer and the acrylonitrile-halogen-containing monomer copolymer and the mixture are mixed and stirred so that the tourmaline and the electrical insulating substance have a predetermined content. Adjust. The obtained solution is used as a stock solution for spinning, and fiberized by ordinary wet or dry spinning.
[0022]
As a dry pulverization method, the pulverizer described above may be used. The classification method is not particularly limited, and classification using a general sieving machine or classifier may be used as long as predetermined tourmaline fine particles can be obtained. Examples of classifiers include wet and dry gravity classifiers, wet and dry centrifugal classifiers, and dry inertia classifiers.In particular, when a dry classifier is used, a drying process is required after classification. Less preferred. If a wet classifier is used, it is preferable to use the solvent used for the modacrylic fiber as the solvent. This is because there is no need for a drying step because fine particles of an electrically insulating substance may be added to the solution after classification.
[0023]
And a 3rd method wet-grinds tourmaline first using water. Then, the aqueous solution in which the tourmaline fine particles are dispersed is dried, and the dried aggregate of the obtained tourmaline fine particles is crushed and / or re-ground, and then the electrically insulating substance fine particles are added, and further mixed and stirred. A mixture is obtained. Next, the solvent solution of the acrylonitrile-halogen-containing monomer copolymer and the acrylonitrile-halogen-containing monomer copolymer and the mixture are mixed and stirred so that the tourmaline and the electrical insulating substance have a predetermined content. Adjust. The obtained solution is used as a stock solution for spinning, and fiberized by ordinary wet or dry spinning.
[0024]
As a wet pulverization method, the pulverizer described above may be used. The drying method is not particularly limited, and may be natural drying or drying using a general dryer as long as water can be separated. Examples of the dryer include a diffusion type, a hot air type, a vacuum type, a freezing type, and the like, but the hot air type is preferable in view of the simplicity of equipment and the manufacturing cost. Furthermore, as a method of crushing and / or re-pulverizing as necessary, a general crusher and / or a general crusher may be used, and in particular, a crusher such as a cage mill or an impact mill and / or a jet. It is preferable to use a mill grinder. The spun yarn is obtained by a conventional method, that is, through spinning, drawing, washing, drying, oiling, and crimping processes.
[0025]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.
[0026]
-Negative ion measurement method (Method A)
The amount of negative ions is measured using an ion counter SC-50 (manufactured by Sigma Tech). That is, a sample (nonwoven fabric) is placed in the box, and air of 60 liters / minute 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 mL is obtained, and compared with the number of negative ions in the absence of the sample, the increased number is confirmed.
[0027]
-Negative ion measurement method (Method B)
The amount of negative ions is measured using an ion tester KST-900 (manufactured by Kobe Radio). That is, a sample (nonwoven fabric) is rubbed lightly with the skin for 30 seconds in an atmosphere of 60% ^{RH at} 20 ° C., measured with the instrument, and the average value of the number of negative ions per mL is obtained.
[0028]
・ Spinning operability evaluation method Filtration area 7cm ² , filter cloth gozamin, 5000H * 0.06mmφ mouthpiece, spinning amount 320mL / min, winding speed 10.5m / min, spinning for 1 hour, filter cloth Evaluation was based on pressure increase (filterability) and single yarn breakage (thread breakage).
a) Filterability ◎… 0 or more and less than 0.1 ○… 0.1 or more and less than 0.5 Δ… 0.5 or more and less than 1.0 ×… 1.0 or more and less than 2.0 ××… 2.0 or more ( Each value is the pressure increase: kg / cm ² )
b) Thread breakage ◎ ... 0 or more and less than 3 ○ ... 3 or more and less than 6 △ ... 6 or more but less than 12 ×… 12 or more but less than 20 XX… 20 or more (Each number is the number of single yarn breakage: 1)
[0029]
Examples 1 to 6 and Comparative Example 1 (first production method: wet pulverization using a solvent solution)
100 kg of shawl tourmaline # 325, 120 kg of 20 mmφ balls, 180 kg of 10 mmφ balls and 150 kg of dimethylformamide were added to a rolling ball mill having a capacity of 300 m 3 and pulverized for 240 hours. The average particle diameter of the shawl tourmaline in the obtained stock solution was 0.8 μm. Further, 15 kg of calcium triphosphate having an average particle size of 0.5 μm was added and further mixed for 5 hours. 50 kg of modacrylic dope (acrylonitrile / vinylidene chloride / 2 acrylamide 2-methylpropane sodium sulfonate = 55/42/3 (wt%) composition of 20% dimethylformamide solution of modacrylic polymer) was added to the solution after removing the balls by filtration. And dimethylformamide solvent were added, and the concentration was adjusted so that the total amount of shoal tourmaline and tricalcium phosphate was 20%.
[0030]
This additive solution was added to the modacrylic dope (polymer concentration: 25% dimethylformamide solution) having the above composition at the ratio shown in Table 1, and the dimethylformamide 60% aqueous solution was spun and coagulated with a 0.06 mmφ die. Thereafter, a fiber of about 3.3 dtex was obtained through drawing, washing with water, drying, oiling, crimping, and heat setting at 110 ° C. The fiber was applied to a card spinning machine / needle punch machine to prepare a 50 g / m ² nonwoven fabric, and negative ions were measured.
[0031]
In Comparative Example 1, an acrylic polymer having a composition of acrylonitrile / methyl acrylate / sodium methallyl sulfonate = 91/8/1 (wt%) was used instead of the modacrylic polymer used in Examples 1-6. The other conditions were exactly the same as in Example 3 to obtain an acrylic fiber.
[0032]
[Table 1]
[0033]
As is apparent from the results shown in Table 1, in Method A, the increase in negative ions increases as the total content of tourmaline and tricalcium phosphate increases, but the spinning operability tends to decrease. . In Method B, even if the total content of tourmaline and tricalcium phosphate is small, it can be seen that there is a very high level of negative ions due to friction between the example fibers and the skin. However, it can be seen that the negative ion generation amount by the B method is remarkably low in the case of acrylic fiber instead of modacrylic fiber as in Comparative Example 1.
[0034]
Examples 7 to 10 and Comparative Example 2 (first production method: wet pulverization using a solvent solution)
Shoal tourmaline # 325 was pulverized by a rolling ball mill in the same manner as in Examples 1 to 6 to obtain fine particles of 0.8 μm. After adding tricalcium phosphate of each average particle size shown in Table 2 to this, it was added to the modacrylic dope so that the total content of tourmaline and tricalcium phosphate was 5% by weight as in Example 3. Then, spinning was performed in exactly the same manner as in Examples 1-6.
[0035]
[Table 2]
[0036]
As is apparent from Table 2, when the average particle size of tribasic calcium 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, when the thickness exceeds 1 μm, the amount of negative ions generated is reduced, which causes a problem in spinning operability. This is because mixed spots of tourmaline and tricalcium phosphate occur, and a tendency to clog the filter cloth during spinning is recognized.
[0037]
Comparative Examples 3 to 8 (first production method: wet pulverization using a solvent solution)
Shoal tourmaline # 325 was pulverized by a rolling ball mill in the same manner as in Examples 1 to 6 to obtain fine particles of 0.8 μm. Without adding tricalcium phosphate as an electrically insulating substance, modacrylic fibers were obtained by adding to the modacrylic dope in the proportions shown in Table 3 in the same manner as in Examples 1-6.
[0038]
[Table 3]
[0039]
As is apparent from Table 3, it can be seen that, only with shawl tourmaline, even if the content is increased, not only the number of negative ions is increased, but also the spinning operability is remarkably lowered and there is no practicality. That is, if there is no electrical insulating material such as tricalcium phosphate, the shoal tourmaline in the form of bent fine particles will immediately undergo secondary aggregation.
[0040]
Reference Examples 1-2, Examples 11-13, Comparative Example 9 (second production method: dry pulverization)
Shoal tourmaline # 325 product was dry pulverized with a rolling ball mill and classified with a dry gravity classifier to obtain 100 parts of fine particles having respective average particle sizes shown in Table 4. Thereafter, 10 parts of 0.5 μm synthetic mica was added and mixed with shawl tourmaline, and modacrylic dope (acrylonitrile / vinyl chloride / sodium styrenesulfonate = 42/56/2 (weight%) concentration of modacrylic polymer 20%. 50 kg of acetone solution) 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 spinning was performed in an acetone / water = 55/45 (wt%) solution to obtain a tourmaline-containing modacrylic fiber. It was.
[0041]
[Table 4]
[0042]
As is apparent from Table 4, when the average particle size of tourmaline exceeds 3 μm, the spinning operability is remarkably lowered and the amount of negative ions generated is also reduced. On the other hand, the negative ion generation amount increased as the average particle size decreased, but the spinning operability tended to decrease slightly.
[0043]
Examples 14 to 16
Here, examples of the first production method (wet pulverization using a solvent solution), the second production method (dry pulverization), and the third production method (wet pulverization with water) are shown.
When the Elba eye tourmaline # 325 product is carried out in an organic solvent in the same manner as in Examples 1 to 10 and Comparative Examples 1 to 8 ( Example 14 ), Reference Examples 1 to 2, Examples 11 to 13 and Comparative Example 9 In the same manner as in Example 1 , the powder was pulverized by the dry method ( Example 15 ), and was wet pulverized with water using a rolling ball mill, dried with hot air, and then crushed and passed through a jet mill ( Example 16 ). Then, 15 parts by weight of calcium pyrophosphate having an average particle size of 0.7 μm is mixed with the one crushed so that the tourmaline has an average particle size of 0.7 μm, and then modacrylic as in Example 3. It knead | mixed so that it might become 5 weight% in a fiber. The spinning experiment was carried out for 8 hours in order to confirm the difference in the grinding method.
[0044]
[Table 5]
[0045]
As is apparent from Table 5, all of the eight-hour spinning was good, but in particular, Example 14 pulverized in dimethylformamide was very good without an increase in the die pressure.
[0046]
【The invention's effect】
As an effect of the present invention, the negative ion generation modacrylic fiber in which the amount of negative ions generated in tourmaline is increased to a practical range by simply mixing an electrically insulating substance without using an excitation agent such as a radioactive substance. It is extremely large in the industry that can be easily manufactured industrially. Furthermore, since negative ions are also generated by friction and peeling, extremely high negative ions exceeding the tourmaline effect are generated. Of course, the fibers are used for bedding products such as blankets, sheets, carpets, curtains, and clothing items such as underwear and sweaters.

Claims (1)

Acrylonitrile / halogen-containing monomer / other monomer = 80-30 wt% / 20- containing tourmaline having an average particle size of 0.1 μm or more and 1 μm or less and an electrically insulating material having an average particle size of 1 μm or less A negative ion generating modacrylic fiber produced from a copolymer comprising 70% by weight / 0 to 10% by weight .