TW202104072A - Inorganic particle for fiber and method of manufacturing thereof - Google Patents

Abstract

A first embodiment of an inorganic particle for fiber is an inorganic particle for fiber, wherein the content of a coarse particle of more than 1.562 μm particle size measured by an electrical sensing zone method in the inorganic particle for fiber is 1,500 numberppm or less, and a second embodiment of an inorganic particle for fiber is an inorganic particle for fiber, wherein the content of a coarse particle of more than 1.562 μm particle size measured by a flow type particle image analysis method in the inorganic particle for fiber is 300 numberppm or less.

Description

Inorganic particles for fibers and manufacturing method thereof

The present invention relates to an inorganic particle for fibers and a method for producing the same, which can be suitably used as a deodorant for fibers.

Inorganic particles such as zirconium phosphate particles can be used as deodorants, such as deodorizing sheets, deodorizing curtains, deodorizing filters, or deodorizing for perspiration, elderly body odors, etc., when a more comfortable living environment is required. "Deodorant products" such as functional clothes and bedding have become circulated.

As a conventional deodorant for fibers, the deodorant for fibers described in Patent Document 1 is known. Patent Document 1 describes a deodorant for fibers containing α zirconium phosphate and/or α titanium phosphate, and the particle size of the α zirconium phosphate and/or α titanium phosphate has a median particle size of 0.2 to 0.7 μm, and The maximum particle size is 5.0 μm or less, and the D10 particle size is 0.1 μm or more.

Patent Document 1: Japanese Patent Application Publication No. 2018-178313

[The problem to be solved by the invention]

In the past, a method has been known to coat zirconium phosphate by subsequent processing after weaving, but there is a problem that the deodorizing function is removed due to washing or the like, and the continuity of the deodorizing function cannot be maintained. In addition, there are problems such as deterioration of productivity due to the aforementioned subsequent processing. On the other hand, by kneading inorganic particles such as zirconium phosphate particles during fiber spinning, there is, for example, the following advantage: as long as a yarn having various functions such as deodorizing function by the aforementioned inorganic particles is used to produce a fabric, It can be manufactured without deteriorating the productivity of fiber products having deodorizing functions and the like. In addition, regarding the sustainability of the deodorizing function, etc., it is considered that the inorganic particles are incorporated into the fiber, and therefore, the kneading of the inorganic particles during spinning is more likely to maintain the sustainability for a long time than the method of coating zirconium phosphate or the like by subsequent processing.

Furthermore, with the increase in spinning speed for the purpose of improving the productivity of the spinning step, the level of requirements for the elimination of coarse particles is increasing. Therefore, the present inventors found the following problem: In the conventional inorganic particles for fibers, the generation of coarse particles cannot be suppressed in the particle production step. In the case of the inorganic particles for fibers, the coarse particles become in the spinning step of kneading the inorganic particles. The reason for the occurrence of yarn breakage in the process is that the polymer filter for removing the coarse particles is insufficient, and the frequency of yarn breakage during spinning becomes high, and the productivity in the spinning step decreases.

The problem to be solved by the present invention is to provide inorganic particles for fibers and a manufacturing method thereof. The inorganic particles for fibers have a low thread breakage rate during spinning, that is, the number of thread breakage per unit time is small. [Technical means to solve the problem]

The means for solving the aforementioned problems include the following aspects. <1> An inorganic particle for fibers, in which the content of coarse particles with a particle diameter exceeding 1.562 μm as measured by the inductance measurement area method is 1500 several ppm or less. <2> An inorganic particle for fibers, in which the content of coarse particles with a particle size exceeding 1.562 μm as measured by a flow-type particle image analysis method is less than 300 number ppm. <3> The inorganic particles for fibers according to <1> or <2>, wherein the inorganic particles for fibers are zirconium phosphate particles, titanium phosphate particles, hydrotalcite particles, or zirconium hydroxide particles. <4> The inorganic particles for fibers according to any one of <1> to <3>, wherein the inorganic particles for fibers are zirconium phosphate particles. <5> The inorganic particles for fibers according to <1>, wherein the content of coarse particles having a particle diameter of more than 1.562 μm as measured by a flow-type particle image analysis method is less than 300 number ppm. <6> The inorganic particles for fibers according to any one of <1> to <5>, wherein the median particle diameter is 0.2 to 1.0 μm. <7> The inorganic particles for fibers as described in any one of <1> to <6>, wherein the content of coarse particles with a particle size exceeding 2.148 μm as measured by the inductance zone method is 5 several ppm or less . <8> The inorganic particles for fibers as described in any one of <1> to <7>, which do not contain coarse particles with a particle size exceeding 2.148 μm as measured by the inductive sensing area method. <9> The inorganic particles for fibers according to any one of <1> to <8>, wherein the inorganic particles for fibers are a deodorant for fibers. <10> A method of manufacturing inorganic particles for fibers, which is a method for manufacturing the inorganic particles for fibers described in any one of <1> to <9>, which includes the following step: removing the inorganic particles by dry classification Of coarse particles. <11> The method for producing inorganic particles for fibers as described in <10>, wherein the dry classification is performed by a gyratory air current classifier. [Effect of Invention]

According to the present invention, it is possible to provide inorganic particles for fibers which have a low yarn breakage rate during spinning and a method for producing the same.

The description of the constituent elements described below may be based on the representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In addition, in the specification of this case, the so-called "~" is used in the meaning including the numerical value described before and after it as the lower limit and the upper limit. In the numerical ranges described step by step in this specification, the upper limit value or lower limit value described in one numerical range can be replaced with the upper limit value or lower limit value described in another step. Moreover, in the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range can also be replaced with the value shown in an Example. In the present invention, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Furthermore, in the present invention, a combination of 2 or more preferred aspects is a more preferred aspect. Hereinafter, the content of the present invention is explained in detail.

(Inorganic particles for fiber) In the first embodiment of the inorganic particles for fibers of the present invention, the content of coarse particles with a particle size exceeding 1.562 μm as measured by the inductance measurement area method is 1500 count ppm or less, preferably 300 count ppm or less . In addition, the second embodiment of the inorganic particles for fibers of the present invention is based on the content of coarse particles with a particle size exceeding 1.562 μm measured by the flow-type particle image analysis method (also referred to as the "particle dynamic image analysis method") Less than 300 number ppm. In this specification, when only the "inorganic particles for fibers of the present invention" are described, unless otherwise specified, it means both the aforementioned first aspect and the aforementioned second aspect. In addition, the inorganic particles for fibers of the present invention can be suitably used as a deodorant for fibers.

In the conventional method for producing inorganic particles, for example, even if it is possible to ideally produce inorganic particles without coarse particles by optimizing the conditions of the reaction step, from the reaction step to the downstream step of the drying step and the pulverization step , It is still possible to produce new coarse particles, and sometimes it is impossible to produce inorganic particles after removing the coarse particles as the final product.

Although there is a method of final removal of coarse particles by sieving, there is a limit to the removal of coarse particles by sieve holes.

Although it is possible to indirectly reduce the number of coarse particles by making the particle size distribution sharp, it is known that, for example, the coarse particles that cause yarn breakage during the spinning of polyester fibers are those contained in the ppm order. In addition, it is known that even if the median particle size D50 is reduced for the purpose of reducing coarse particles, for example, in the stage of adding or kneading to a polyester resin, particles with a small particle size are likely to reagglomerate again to become coarse particles and become threads. The cause of the breakage may be due to the increase in differential pressure due to the polymer filter used to remove coarse particles, resulting in poor productivity.

Generally speaking, a laser diffraction particle size distribution meter is a measuring device. Although it can measure the particle size distribution in a wide measurement range, it cannot detect the ppm level in a number of units for the particle size in the range of 1.5 μm to 5 μm. Of coarse particles. In addition, the laser diffraction particle size distribution meter has the following disadvantages in the implementation of sophisticated technology development: even if it is the same sample, the measurement result of each measuring device manufacturer’s product will be different, and the measurement result It changes significantly with the setting of measurement conditions such as refractive index.

In the past, the removal of coarse particles by classification has been revealed in a general way, but it has not specifically revealed how to remove the coarse particles by classification to what level or correctly confirm that the coarse particles have actually been removed. Therefore, the current situation is that there is no technology, such as fiber spinning, that can eliminate the undesirable situation of thread breakage.

As a result of intensive research, the present inventors have found that by adopting the aforementioned constitution, it is possible to provide inorganic particles for fibers that have a low yarn breakage rate during spinning. The mechanism of action of the excellent effect obtained by this is not clear, but it is presumed to be as follows. According to the inductive sensing area method or the flow particle image analysis method, as a method for identifying coarse particles with a particle size of more than 1.562 μm, it is excellent in detection. Therefore, it is assumed that the content of the aforementioned coarse particles measured by these methods is set as The former is 1500 several ppm or less, or the latter is less than 300 several ppm, and it is possible to obtain inorganic particles for fibers having a low yarn breakage rate during spinning.

Hereinafter, the inorganic particles for fibers of the present invention will be explained in detail.

The inorganic particles for fibers of the present invention are not particularly limited as long as they are inorganic particles used for fibers, but zirconium phosphate particles, titanium phosphate particles, hydrotalcite particles, zirconium hydroxide particles, alumina particles, and aluminum silicate particles are preferred. , Copper silicate particles, zinc silicate particles, manganese silicate particles, cobalt silicate particles, or nickel silicate particles, more preferably zirconium phosphate particles, titanium phosphate particles, hydrotalcite particles, or zirconium hydroxide particles, except From the viewpoint of odor, zirconium phosphate particles are particularly preferred. In addition, the inorganic particles for fibers of the present invention may contain impurities other than those mentioned above, and may also include known additives used in applications of fibers. Among them, the inorganic particles for fibers of the present invention are preferably particles containing 90% by mass or more of the aforementioned inorganic components, more preferably particles containing 95% by mass or more of the aforementioned inorganic components, and particularly preferably containing 99% by mass or more of the aforementioned inorganic components. Particles of inorganic ingredients.

The method of measuring the particle size of inorganic particles according to the inductive sensing area method in the present invention is implemented according to the following method. According to the inductance measuring area method, the measurement is performed with a measuring device (Coulter counter), that is, Multisizer 3 (trade name) manufactured by Beckman Coulter Co., Ltd. The aperture size is set to 30 μm, about 50,000 pieces are measured, and their distribution is measured on a number basis to measure the content of coarse particles with a particle size exceeding 1.562 μm.

In addition, the method of measuring the particle diameter of inorganic particles carried out by the flow-type particle image analysis method in the present invention is carried out according to the following method. The flow-type particle image analysis device FPIA-3000S (trade name) manufactured by Sysmex Co., Ltd. (currently the Malvern Panalytical Division of Spectris Co., Ltd.) was used. In the pure water after passing through a filter to remove foreign substances, inorganic particles were added so that the dispersion concentration became 0.05% by mass, and dispersed by an ultrasonic dispersion device for 3 minutes. The obtained dispersion liquid was dropped into the aforementioned flow-type particle image analyzer, and approximately 30,000 inorganic particles were measured and analyzed to determine the content of coarse particles having a particle diameter of more than 1.562 μm. In addition, the upper limit of the particle size measurement is preferably 100 μm.

In the first embodiment of the inorganic particles for fibers of the present invention, the content of coarse particles having a particle diameter of more than 1.562 μm measured by the inductance zone method is 1500 several ppm or less from the viewpoint of yarn breakage inhibition. Preferably it is 300 ppm or less, more preferably 200 ppm or less, still more preferably 100 ppm or less, particularly preferably 50 ppm or less, most preferably 25 ppm or less.

In the second embodiment of the inorganic particles for fibers of the present invention, the content of coarse particles with a particle size of more than 1.562 μm measured by the flow-type particle image analysis method is less than 300 several ppm from the viewpoint of yarn breakage inhibition. , Preferably 100 several ppm or less, more preferably 10 several ppm or less, still more preferably 1 several ppm or less, particularly preferably not including the particle size measured by the flow-type particle image analysis method exceeding 1.562μm Of coarse particles.

The inorganic particles for fibers of the present invention preferably have a content of coarse particles with a particle size of more than 2.148 μm measured by the inductance measurement zone method of 5 several ppm or less, more preferably 1 A few ppm or less, it is particularly preferred that it does not contain coarse particles with a particle size exceeding 2.148μm as measured by the inductance measurement area method. In addition, in the inorganic particles for fibers of the present invention, it is preferable that the content of coarse particles with a particle diameter exceeding 2.148 μm as measured by the flow-type particle image analysis method is 5 several ppm or less from the standpoint of yarn breakage inhibition. , More preferably 1 several ppm or less, and particularly preferably free of coarse particles with a particle size exceeding 2.148 μm as measured by the flow-type particle image analysis method.

Furthermore, the inorganic particles for fibers of the present invention preferably do not contain coarse particles with a particle diameter of more than 3 μm as measured by the inductance measurement zone method from the viewpoint of yarn breakage inhibition. In addition, the inorganic particles for fibers of the present invention preferably do not contain coarse particles having a particle diameter of more than 3 μm as measured by the flow-type particle image analysis method from the viewpoint of yarn breakage inhibition.

The inorganic particles for fibers of the present invention preferably have a median particle diameter D50 of 0.1 μm ∼ 0.1 μm as measured by the laser diffraction method, from the viewpoint of further exhibiting the functional effects such as thread break inhibition and deodorization effect. 1.2 μm, more preferably 0.2 μm to 1.0 μm, particularly preferably 0.5 μm to 0.9 μm.

In addition, the inorganic particles for fibers of the present invention preferably have a cumulative particle size of 99.9% by the inductance measurement area method from the viewpoint of further exerting the functional effects such as thread breakage suppression and deodorizing effect. D99.9 is 1.562 μm or less, more preferably 0.5 μm to 1.55 μm, particularly preferably 1.0 μm to 1.50 μm.

(Method for manufacturing inorganic particles for fibers) The method for producing the inorganic particles for fibers of the present invention is not particularly limited as long as the inorganic particles for fibers of the present invention can be produced. From the viewpoint of the aforementioned removal of coarse particles, a method including the following steps is preferred: Dry classification is used to remove coarse particles in inorganic particles (also called "dry classification step").

The classification method for removing the coarse particles of inorganic particles may be either dry classification or wet classification. When the sold form of the final product is powder, in wet classification, a drying step is required after classification. Even if coarse particles are removed before drying, coarse particles may be regenerated due to coagulation and aggregation during the drying step. Therefore, dry classification is preferred, which does not require a drying step after classification, the possibility of solidification and agglomeration is low, and the manufacturing steps can be simplified.

Dry classifiers include mechanical types, swirling airflow types, etc.; as long as they can classify coarse particles, the classifier is not limited. In a mechanical classifier, since the classifying rotor mechanically rotates at a high speed, mechanical precision is required to prevent vibration, so there is a limit to the classifying point. Specifically, when the coarse particles are in a region where particles with a particle diameter of 1.5 μm to 5 μm are to be excluded, the mechanical classifier has a limit, and it may not be possible to eliminate the coarse particles with high accuracy. In addition, the classification performed by the mechanical rotation of the classification rotor may cause metal contamination (mixing) due to abrasion caused by the sliding of the metal part. From the above point of view, it is preferable to perform dry classification by an air flow classifier (swirling air flow classifier) that does not have a mechanical rotating part in the structure and uses a swirling flow. Preferably, for example, the swirling air flow classifier described in International Publication No. 2011/132301 can be cited.

In dry classification, the pressure and amount of the high-pressure gas sprayed to the inorganic particles are not particularly limited, but the pressure is preferably 0.1 MPa to 1.0 MPa. In addition, the air volume during dry classification is not particularly limited, but it is preferably 1 m ³ /min to 10 m ³ /min.

The method for producing inorganic particles for fibers of the present invention may include, for example, the following steps: a pulverizing step, pulverizing inorganic particles or aggregated particles of inorganic particles; and a sieving step, sieving inorganic particles, and the like. The timing of performing the aforementioned dry classification step is not particularly limited. For example, it may be any timing before or after the pulverization step and the sieving step, or it may be performed both before and after. After adjusting the particle size temporarily in the pulverization step and the sieving step, dry classification can be further performed in order to eliminate coarse particles. In addition, after performing dry classification, a pulverization step and a sieving step can be performed. Considering that coarse particles may be generated in the pulverizing step and the sieving step, the dry classification step is preferably performed after the pulverizing and sieving steps.

The classification point in the aforementioned dry classification step can be appropriately set as desired. For example, since the single-strand fiber is about 10 μm, when inorganic particles are added or kneaded to the resin used to form the fiber, From the standpoint of yarn breakage inhibition during spinning, it is preferable to exclude coarse particles with a particle size exceeding 3μm, more preferably to exclude coarse particles with a particle size exceeding 2.148μm, and particularly preferably to exclude coarse particles with a particle size exceeding 1.562μm particle.

The method for producing inorganic particles for fibers of the present invention may include a step of producing inorganic particles. The inorganic particles used in the method for producing inorganic particles for fibers of the present invention may be inorganic particles prepared by commercially available products or the like, or may be prepared inorganic particles. There is no particular limitation on the method of producing inorganic particles, and a known method can be used. As an example, the method of producing zirconium phosphate particles will be described below.

Zirconium oxychloride, oxalic acid, and phosphoric acid can be used as starting materials, and the zirconium phosphate in the present invention can be produced by a known method. It can be manufactured according to the method described in Japanese Unexamined Patent Publication No. 60-103008 or Japanese Patent Application Publication No. 2018-178313, for example. However, the production method of zirconium phosphate is not limited to these methods.

The obtained zirconium phosphate may be dried after solid-liquid separation, or may be dried without solid-liquid separation. As a specific method of solid-liquid separation, there is a filter press, a pressure filter, etc., and the water-containing filter cake (sludge) is dried after the solid-liquid separation. As a method of drying the water-containing filter cake, a paddle dryer, a conical dryer, a vibration dryer, or an inverted-conical stirring dryer, etc. can be suitably cited. As a method of drying without performing solid-liquid separation, a spray dryer, a ball-containing fluidized bed dryer, a jet turbo dryer, and the like can be cited. Zirconium phosphate becomes clay-like when subjected to solid-liquid separation, has strong adhesion, and is difficult to handle. Therefore, it is preferable to dry without solid-liquid separation to obtain zirconium phosphate particles.

The dried product of zirconium phosphate particles can be crushed, crushed, or sieved, or not crushed, crushed, or sieved. In order to adjust to a uniform particle size, it is preferable to disintegrate or pulverize, and then pass through a sieve.

The moisture in the inorganic particles for fibers of the present invention, before spinning, when the inorganic particles are kneaded with the resin for raw materials for synthetic fibers such as polyester resins by an extruder, if the inorganic particles for fibers remain Moisture will evaporate during heating and kneading with an extruder, and the resin for the raw material may foam. In order to prevent foaming, the moisture content of the inorganic particles for fibers of the present invention is preferably 1% by mass or less, and more preferably 0.6% by mass or less.

(fiber) The fiber of the present invention is a fiber containing the inorganic particles for fibers of the present invention, preferably a deodorizing fiber containing the inorganic particles for fibers of the present invention. As a method of manufacturing the fiber containing the inorganic particle for fibers of this invention, there is no restriction|limiting in particular, A well-known method can be used. For example, a method of kneading and spinning the inorganic particles for fibers of the present invention into fibers, and the like can be mentioned.

The fiber of the present invention is preferably a resin fiber, more preferably a chemical fiber. As the resin for fibers that can be used, any known chemical fiber can be used. Preferred specific examples of the material of the chemical fiber include, for example, polyester, polyurethane, nylon, rayon, acrylic resin, vinylon, polypropylene, and the like. Among them, polyester, nylon or acrylic resin is preferred, and polyester is more preferred. In addition, preferred specific examples of polyester include, for example, polyethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, and polybutylene terephthalate. . Among them, polyethylene terephthalate is preferred. These resins can be homopolymers or copolymers. In the case of a copolymer, the polymerization ratio of each copolymer component is not particularly limited. In addition, the method of adding the inorganic particles for fibers of the present invention to the resin is not particularly limited. For example, it can be added by a polymerization step of the resin, or it can be kneaded with an extruder.

The inorganic particles for fibers of the present invention can be preferably used as a deodorant for kneading fibers. At this time, as a specific manufacturing method of deodorizing fibers, the following method can be cited: kneading the inorganic particles for fibers of the present invention into a molten resin for liquid fibers or a dissolved resin solution for fibers, and Its spinning.

The content of the inorganic particles for fibers of the present invention in the fibers of the present invention is not particularly limited. Generally, as long as the content is increased, strong deodorization can be exerted and sustained for a long period of time. However, even if it is contained to a certain level, there will be no significant difference in the deodorization effect and the strength of the resin. The content of the inorganic particles for fibers of the present invention in the fibers of the present invention is preferably 0.1 parts by weight to 3.0 parts by weight, and more preferably 0.5 parts by weight to 2.0 parts by weight, relative to 100 parts by weight of the resin.

The deodorizing fiber using the inorganic particles for fibers of the present invention can be used in various fields where deodorizing properties are required. For example, it can be used in various fiber products such as underwear, stockings, socks, quilts, quilts, cushions, Blankets, carpets, curtains, sofas, car seats, air filters and nursing clothing, etc. [Example]

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples. Furthermore, in this embodiment, unless otherwise specified, "%" and "parts" mean "% by weight" and "parts by weight", respectively.

The size of coarse particles, the number of coarse particles, the content of coarse particles relative to the effective N number, the measurement of coarse particles by image analysis, and the thread breakage rate are measured according to the following methods. The thread breakage rate is shown below The frequency of yarn breakage in the above case: after adding or kneading zirconium phosphate particles to the polyester resin, spinning is performed.

(1) The size and number of coarse particles The particle size of zirconium phosphate is measured by the inductive zone method, the so-called Coulter counter, which is Multisizer 3 manufactured by Beckman Coulter Co., Ltd. The pore size is set to 30 μm, 50,000 pieces are measured, and the distribution is measured on the basis of the number.

(2) The concentration of coarse particles relative to the effective N number As a result of measurement on a number basis using Multisizer 3 manufactured by Beckman Coulter Co., Ltd., the cumulative particle number of 1.562 μm or more and less than 2.148 μm is defined as coarse particles. The concentration of coarse particles relative to the actual measured effective N number is calculated according to the following formula. Cumulative number of particles above 1.562μm and less than 2.148μm ÷ actual measured effective N number×1000000 = Cumulative concentration of coarse particles above 1.562μm and less than 2.148μm relative to the effective N number in ppm

(3) Measurement of coarse particles by flow particle image analysis (particle dynamic image analysis) The measurement was carried out with the FPIA-3000S manufactured by Sysmex Co., Ltd. (currently the Malvern Panalytical Division of Spectris Co., Ltd.), which is a flow-type particle image analysis device. In the pure water after passing the filter to remove the foreign matter, the powder was added so that the dispersion concentration became 0.05%, and the powder was dispersed for 3 minutes with an ultrasonic dispersion device. The dispersion liquid is dropped into a flow-type particle image analysis device, and approximately 30,000 particles are measured and analyzed. The flow-type particle image analysis device rearranges the detected particles in larger order, and measures the size of the larger particles and the photos of the particles.

(4) Number of thread breaks 100% of polyester resin (manufactured by UNITIKA Co., Ltd., trade name: MA2101M, polyethylene terephthalate resin) was blended with 20% of the manufactured zirconium phosphate particles to produce a masterbatch. Then, this masterbatch is mixed with general polyester resin pellets not containing zirconium phosphate, and adjusted to 2% by weight. Use a multi-filament spinning machine to spin it for 2 hours at a spinning temperature of 275°C and a spinning speed of 500m/min, and stretch it at 120°C so that the elongation becomes 280% to 320%. Polyester fiber containing zirconium phosphate particles. In this case, the water-soluble oil used for spinning of ordinary polyester fibers (deleted by 10 times of DELION 6033 manufactured by Takemoto Oil & Fat Co., Ltd.) is used as the oil. Perform continuous spinning for 2 hours, and evaluate spinnability according to the following judgment method. A: The number of thread breaks is 0 times/2 hours B: The number of thread breaks is 1 time/2 hours or more but less than 3 times/2 hours C: The number of thread breaks is 3 times/2 hours or more but less than 6 times/2 hours D: The number of thread breaks is 6 times/2 hours or more but less than 10 times/2 hours E: The number of thread breaks is 10 times/2 hours or more F: Cannot be evaluated

The method of producing zirconium phosphate particles is shown as a reference example.

(Reference example: production of zirconium phosphate particles) 3611 kg of deionized water and 363 kg of 35% hydrochloric acid were charged into a 6m ³ reactor, and 603 kg of a 20% aqueous solution of 0.18% hafnium-containing zirconium oxychloride octahydrate was added. Dissolve 250 kg of oxalic acid dihydrate. While stirring the solution evenly, add 275 kg of 75% phosphoric acid. The temperature was raised to 98°C over 2 hours, stirred and refluxed for 12 hours. After cooling, the obtained precipitate was sufficiently washed with water, and then dried at 105°C, thereby obtaining zirconium phosphate particles. The zirconium phosphate particles were crushed with a crusher. Then, the sieving process is carried out. The obtained zirconium phosphate particles were measured with an X-ray diffraction device, and as a result, they were confirmed to be α zirconium phosphate particles. The alpha zirconium phosphate particles are heated and dissolved in hydrofluoric acid and nitric acid, and then elemental analysis is performed with an inductively coupled plasma (ICP) luminescence analyzer, and thermogravimetric thermal difference analysis is further performed. The result is that the composition formula is Zr _0.99 Hf _0.01 H _2.03 (PO ₄ ) _2.01 ･0.05H ₂ O.

(Example 1) A classifier (trade name: Aerofine Classifier AC-20 type, manufactured by Nissin Engineering Co., Ltd.) was used to classify the zirconium phosphate particles produced in accordance with the reference example. The air volume sucked by the exhaust fan was set to 2.5 m ³ /min. Here, the air volume sucked by the exhaust fan is equivalent to the air volume of the atmospheric gas sucked from between the guide vanes. In addition, the angle of the guide vane is set to 80° (tangential direction). The condition of the high-pressure gas ejected from the upper air nozzle was set to a pressure of 0.7 MPa, and the condition of the high-pressure gas ejected from the lower air nozzle was set to a pressure of 0.6 MPa. The powder before classification was continuously supplied with 478 g in 13 minutes at a rate of 2 kg/h using a quantitative feeder. After classification, 415 g of finer powder was recovered. Relative to the quantity put into the classifier, the yield was 86.8%. Furthermore, the obtained powder on the finer side after classification was measured with a Coulter counter. The pore size is set to 30 μm, 50,000 pieces are measured, and the distribution is measured on the basis of the number. The median diameter D50 is 0.731 μm, and D99.9 is 1.442 μm. The number of coarse particles with a particle size exceeding 1.562 μm and 2.148 μm or less was 15. In addition, no coarse particles with a particle size exceeding 2.148 μm were detected. Compared to the actual measured effective N number, which is 51008, the concentration (content) is 15÷51008×1000000=294 number ppm. The detailed results of the coarse particles are shown in Table 1.

In addition, the particle size was measured according to the flow-type particle image analysis method. Specifically, the flow particle image analyzer FPIA-3000S manufactured by Sysmex Co., Ltd. (currently the Malvern Panalytical Division of Spectris Co., Ltd.) was used to measure the particle size. The number of measured particles is set to 30,000. As a result, no coarse particles with a particle diameter exceeding 1.562 μm were observed. Relative to the number of measured particles, the concentration is 0 number ppm. The results are shown in Table 1 and Table 2. Table 2 summarizes the diameters of 9 particles from the observed larger particles. The first figure starts with the larger particles detected by image analysis. The coarse particles are shown in order. In addition, each numerical value described in Fig. 1 represents the size of each coarse particle (unit: μm). Furthermore, evaluation of the number of yarn breaks was performed, and as a result, the number of yarn breaks was 0 times/2 hours, and it was possible to spin extremely stably. The evaluation result of the number of thread breaks is A.

(Example 2) A classifier (trade name: Aerofine Classifier AC-20 type, manufactured by Nissin Engineering Co., Ltd.) was used to classify the zirconium phosphate particles produced in accordance with the reference example. The air volume sucked by the exhaust fan was set to 2.3 m ³ /min. Here, the air volume sucked by the exhaust fan is equivalent to the air volume of the atmospheric gas sucked from between the guide vanes. In addition, the angle of the guide vane is set to 90° (tangential direction). The condition of the high-pressure gas ejected from the upper air nozzle was set to a pressure of 0.6 MPa, and the condition of the high-pressure gas ejected from the lower air nozzle was set to a pressure of 0.6 MPa. The powder before classification was continuously supplied with 505 g in 15 minutes at a rate of 2 kg/h using a quantitative feeder. After classification, 387 g of finer powder was recovered. Relative to the quantity put into the classifier, the yield was 76.6%. Furthermore, the obtained powder on the finer side after classification was measured with a Coulter counter. The pore size is set to 30 μm, 50,000 pieces are measured, and the distribution is measured on the basis of the number. The median diameter D50 is 0.719 μm, and D99.9 is 1.366 μm. The number of coarse particles having a particle size exceeding 1.562 μm and 2.148 μm or less was one. In addition, no coarse particles with a particle size exceeding 2.148 μm were detected. Compared to the actual measured effective N number, which is 50969, the concentration (content) is 1÷50969×1000000=20 number ppm. The detailed results of the coarse particles are shown in Table 1. Furthermore, evaluation of the number of yarn breaks was performed, and as a result, the number of yarn breaks was 0 times/2 hours, and it was possible to spin extremely stably. The evaluation result of the number of thread breaks is A.

(Example 3) Regarding Example 2, the powder before classification was continuously supplied with 3,924 g at 2 kg/h within 120 minutes using a quantitative feeder, except that the classification was performed under the same conditions. After classification, 2911g of finer powder was recovered. Relative to the amount put into the classifier, the yield was 74.2%. Furthermore, a Coulter counter (Multisizer 3 manufactured by Beckman Coulter Co., Ltd.) was used to measure the coarse particles of the obtained powder on the finer side after classification. The pore size is set to 30 μm, 50,000 pieces are measured, and the distribution is measured on the basis of the number. The median diameter D50 is 0.722 μm, and D99.9 is 1.406 μm. The number of coarse particles having a particle size exceeding 1.562 μm and 2.148 μm or less was nine. In addition, no coarse particles with a particle size exceeding 2.148 μm were detected. Compared to the actual measured effective N number, which is 51121, the concentration (content) is 9÷51121×1000000=176 number ppm. The detailed results of the coarse particles are shown in Table 1. Furthermore, evaluation of the number of yarn breaks was performed, and as a result, the number of yarn breaks was 0 times/2 hours, and it was possible to spin extremely stably. The evaluation result of the number of thread breaks is A.

(Comparative example 1) Without performing dry classification, the zirconium phosphate particles manufactured in accordance with the reference example were directly measured with a Coulter counter (Multisizer 3 manufactured by Beckman Coulter Co., Ltd.). The pore size is set to 30 μm, 50,000 pieces are measured, and the distribution is measured on the basis of the number. The median particle size D50 is 0.760 μm, and D99.9 is 1.606 μm. The number of coarse particles with a particle size exceeding 1.562 μm and 2.148 μm or less was 77. In addition, no coarse particles with a particle size exceeding 2.148 μm were detected. Compared to the actual measured effective N number, which is 51097, the concentration (content) is 77÷51097×1000000=1507 number ppm.

In addition, the flow-type particle image analyzer FPIA-3000S manufactured by Sysmex Co., Ltd. (currently the Malvern Panalytical Division of Spectris Co., Ltd.) was used, and the particle size was measured by image analysis. The number of measured particles is set to 30,000. As a result, 9 coarse particles with a particle size exceeding 1.562 μm were observed. Relative to the number of measured particles, the concentration is 9÷30000×1000000=300 number ppm. The results are shown in Table 1 and Table 2. In Figure 2, the 9 coarse particles detected by image analysis are shown in sequence starting from the larger particles. In addition, each numerical value described in FIG. 2 represents the size (unit: μm) of each coarse particle. Furthermore, the evaluation of the number of thread breaks showed that the number of thread breaks was 1 time/2 hours or more but less than 3 times/2 hours, and thread breakage occurred several times. The evaluation result of the number of thread breaks is B.

(Comparative example 2) The powder on the coarse side after drying and classifying in Example 1 was collected, and the coarse particles were measured with a Coulter counter (Multisizer 3 manufactured by Beckman Coulter Co., Ltd.). The pore size is set to 30 μm, 50,000 pieces are measured, and the distribution is measured on the basis of the number. The median diameter D50 is 0.770 μm, and D99.9 is 1.661 μm. The number of coarse particles having a particle size exceeding 1.562 μm and 2.148 μm or less was 127. In addition, no coarse particles with a particle size exceeding 2.148 μm were detected. Compared to the actual measured effective N number, which is 50953, the concentration (content) is 127÷50953×1000000=2492 number ppm. Furthermore, the evaluation of the number of thread breaks showed that thread breaks frequently occurred. The evaluation result of the number of thread breaks is F.

[Table 1]

[Table 2]

In Examples 1 and 2, according to the measurement results of the powder on the finer side after classification, the cumulative number of coarse particles with a particle size of 1.562 μm or more and less than 2.148 μm is 15 and 1, respectively, compared with 77 before classification. In contrast, there are fewer coarse particles, and coarse particles can be removed. Example 3 shows that even when the classification treatment amount of Example 2 is increased, the cumulative number of coarse particles having a particle size of 1.562 μm or more and less than 2.148 μm is 9 and is small, and the coarse particles can be eliminated.

In Comparative Example 1, a Coulter counter was used to measure zirconium phosphate particles that were not classified, and it was shown that the cumulative number of coarse particles having a particle size of 1.562 μm or more and less than 2.148 μm was 77, which was large. It can be seen that when there is no classification treatment, many coarse particles are contained. In Comparative Example 2, the coarse particle side after the classification treatment of Example 1 was recovered. Since it is the coarse particle side, the cumulative number of coarse particles with a particle size of 1.562 μm or more and less than 2.148 μm is 127 compared to the finer side after the classification treatment. 15 on the thinner side. Furthermore, the number of coarse particles in the case where the classification treatment is not performed is more than that of Comparative Example 1, which is 77. This situation shows that Example 1 is the result of removing coarse particles by classification, and the coarse particles removed by classification can be separated and recovered as the classified coarse particles of Comparative Example 2.

In addition, in any measurement, the effective count of coarse particles is uniformly about 50,000, so the number of coarse particles can be quantitatively compared. It can be set as the cumulative concentration of coarse particles having a particle size of 1.562 μm or more and less than 2.148 μm relative to the effective N number, and the number of coarse particles can be quantitatively compared in ppm units.

In addition, according to Table 2, Example 1 shows that in the measurement of coarse particles performed by the flow-type particle image analysis device, the largest coarse particle detected has a particle size of 1.494 μm, which means that the particle size is below 1.562 μm. It can be seen that dry classification can remove coarse particles with a particle size exceeding 1.562 μm. In contrast, Comparative Example 1 shows that in the measurement of coarse particles by a flow-type particle image analyzer, the largest coarse particle detected has a diameter of 9.443 μm, which is a coarse particle with a diameter of more than 1.562 μm. It can be seen that since dry classification is not performed, coarse particles with a particle diameter exceeding 1.562 μm cannot be removed and coarse particles with a particle diameter exceeding 1.562 μm are contained.

As described above, compared with the inorganic particles of Comparative Examples 1 and 2, the inorganic particles for fibers of the present invention, that is, the inorganic particles for fibers of Examples 1 to 3, have fewer yarn breaks during spinning. [Industrial availability]

According to the method for producing inorganic particles for fibers of the present invention, it is possible to easily remove the minute amount of coarse particles contained in the ppm level that cannot be detected by the laser diffraction particle size distribution meter. In addition, the inorganic particles for fibers of the present invention can be kneaded into fibers such as polyester fibers to reduce the frequency of yarn breakage during spinning, and can improve the productivity in the spinning step, which is industrially beneficial. .

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Figure 1 is a diagram showing the nine coarse particles detected by image analysis in Example 1, starting from the larger coarse particles in sequence. Figure 2 is a diagram showing nine coarse particles detected by image analysis in Comparative Example 1, starting from the larger coarse particles in sequence.

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Claims (11)

An inorganic particle for fibers, wherein the content of coarse particles with a particle diameter of more than 1.562 μm measured according to the inductance measurement area method is 1500 several ppm or less. An inorganic particle for fibers, wherein the content of coarse particles with a particle diameter of more than 1.562 μm measured according to a flow-type particle image analysis method is less than 300 number ppm. The inorganic particles for fibers according to claim 1, wherein the inorganic particles for fibers are zirconium phosphate particles, titanium phosphate particles, hydrotalcite particles, or zirconium hydroxide particles. The inorganic particles for fibers according to claim 1, wherein the inorganic particles for fibers are zirconium phosphate particles. The inorganic particles for fibers according to claim 1, wherein the content of coarse particles having a particle diameter of more than 1.562 μm as measured by a flow-type particle image analysis method is less than 300 number ppm. The inorganic particles for fibers according to claim 1, wherein the median particle diameter is 0.2 to 1.0 μm. The inorganic particles for fibers according to claim 1, wherein the content of coarse particles with a particle size exceeding 2.148 μm as measured by the inductance measurement area method is 5 several ppm or less. The inorganic particles for fibers according to claim 1, which do not contain coarse particles with a particle diameter of more than 2.148 μm as measured by the inductance measurement area method. The inorganic particle for fibers according to claim 1, wherein the inorganic particle for fibers is a deodorant for fibers. A method for producing inorganic particles for fibers is a method for producing the inorganic particles for fibers according to any one of claims 1 to 9, which includes the step of removing coarse particles in the inorganic particles by dry classification. The method for producing inorganic particles for fibers according to claim 10, wherein the dry classification is performed by a gyratory air classifier.

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