WO2020218206A1 - 繊維用無機粒子及びその製造方法 - Google Patents
繊維用無機粒子及びその製造方法 Download PDFInfo
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- WO2020218206A1 WO2020218206A1 PCT/JP2020/016918 JP2020016918W WO2020218206A1 WO 2020218206 A1 WO2020218206 A1 WO 2020218206A1 JP 2020016918 W JP2020016918 W JP 2020016918W WO 2020218206 A1 WO2020218206 A1 WO 2020218206A1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
Definitions
- the present invention relates to inorganic particles for fibers and a method for producing the same, and can be suitably used as a deodorant for fibers.
- Inorganic particles such as zirconium phosphate particles are used as deodorants.
- deodorant sheets deodorant sheets, deodorant curtains, deodorant filters, sweat odors, and aging odors are required.
- Deodorant products such as clothing and bedding, which have a deodorant function for such substances, have come into the market.
- Patent Document 1 describes zirconium ⁇ -phosphate and / or ⁇ -phosphorus as particle diameters having a median diameter of 0.2 to 0.7 ⁇ m, a maximum particle diameter of 5.0 ⁇ m or less, and a D10 diameter of 0.1 ⁇ m or more. Deodorants for fibers containing titanium phosphate are described.
- Patent Document 1 Japanese Unexamined Patent Publication No. 2018-178313
- the inorganic particles since the inorganic particles have penetrated into the fiber, it is more durable to knead the inorganic particles during spinning than to apply zirconium phosphate or the like by post-processing. Can be maintained for a long period of time.
- the required level for eliminating coarse particles has increased. Therefore, in the case of conventional inorganic particles for fibers in which the formation of coarse particles cannot be suppressed in the particle manufacturing process, the polymer filter used to eliminate the coarse particles that cause yarn breakage in the spinning process in which the inorganic particles are kneaded is insufficient. Therefore, the present inventors have found a problem that the frequency of yarn breakage during spinning increases and the productivity in the spinning process decreases.
- An object to be solved by the present invention is to provide inorganic particles for fibers having a low yarn breakage rate at the time of spinning, that is, a small number of yarn breakages per unit time, and a method for producing the same.
- Means for solving the above problems include the following aspects.
- ⁇ 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 size of more than 1.562 ⁇ m measured by a flow-type particle image analysis method is less than 300 ppm.
- ⁇ 6> The inorganic particle for fiber according to any one of ⁇ 1> to ⁇ 5>, which has a median diameter of 0.2 ⁇ m to 1.0 ⁇ m.
- ⁇ 7> The inorganic material for fibers according to any one of ⁇ 1> to ⁇ 6>, wherein the content of coarse particles having a particle size of more than 2.148 ⁇ m measured by the electrical detection band method is 5 or less ppm. particle.
- ⁇ 8> The inorganic particle for fiber according to any one of ⁇ 1> to ⁇ 7>, which does not contain coarse particles having a particle size of more than 2.148 ⁇ m measured by an electric detection band method.
- ⁇ 9> The inorganic particles for fibers according to any one of ⁇ 1> to ⁇ 8>, which is a deodorant for fibers.
- ⁇ 10> The method for producing inorganic particles for fibers according to any one of ⁇ 1> to ⁇ 9>, which comprises a step of removing coarse particles in the inorganic particles by dry classification.
- ⁇ 11> The method for producing inorganic particles for fibers according to ⁇ 10>, wherein the dry classification is performed by a swirling airflow classifier.
- FIG. It is a figure which showed 9 coarse particles in order from the larger one detected by the image analysis in Example 1.
- FIG. It is a figure which showed 9 coarse particles in order from the larger one detected by the image analysis in Comparative Example 1.
- the content of coarse particles having a particle size of more than 1.562 ⁇ m measured by the electric detection band method is 1,500 ppm or less, preferably 300. The number is ppm or less.
- a second embodiment of the inorganic particles for fibers of the present invention is coarse particles having a particle size of more than 1.562 ⁇ m, which is measured by a flow-type particle image analysis method (also referred to as “dynamic image analysis method of particles”). The content of is less than 300 ppm.
- the term "inorganic particles for fibers of the present invention” is simply used, it means both the first embodiment and the second embodiment unless otherwise specified.
- the inorganic particles for fibers of the present invention can be suitably used as a deodorant for fibers.
- inorganic particles that are ideally free of coarse particles can be produced by optimizing the conditions of the reaction process, the drying process and the crushing process in the downstream process from the reaction process Therefore, there is a possibility that new coarse particles may be generated, and as a final product, inorganic particles from which the coarse particles have been removed may not be produced.
- the number of coarse particles is indirectly reduced. For example, it was found that the coarse particles that cause yarn breakage during spinning of polyester fibers are coarse particles contained in the order of ppm. .. Further, even if the median diameter D50 is reduced for the purpose of reducing the number of coarse particles, for example, at the stage of addition to the polyester resin or kneading, the particles having a small particle size are easily reaggregated to become coarse particles, and the yarn It has been found that a polymer filter for removing coarse particles and a cause of cutting increases the differential pressure and deteriorates productivity.
- a laser diffraction type particle size distribution meter has a wide measurement range in which a particle size distribution can be measured, but is a measuring instrument that cannot detect coarse particles on the order of ppm in a particle size in the range of 1.5 ⁇ m to 5 ⁇ m. Is.
- the laser diffraction type particle size distribution meter is a precise technique in which the measurement results differ depending on the measuring instrument manufacturer even for the same sample, and the measurement results fluctuate significantly depending on the setting of measurement conditions such as the refractive index. I had a problem in developing.
- inorganic particles for fibers having a low yarn breakage rate during spinning As a result of diligent studies by the present inventors, it has been found that by adopting the above structure, it is possible to provide inorganic particles for fibers having a low yarn breakage rate during spinning.
- the mechanism of action of the excellent effect of this is not clear, but it is estimated as follows. Since it is excellent in detectability as a method for confirming coarse particles having a particle size of more than 1.562 ⁇ m by the electrical detection band method or the flow type particle image analysis method, the content of the coarse particles measured by these methods is determined. It is estimated that inorganic particles for fibers having a low yarn breakage rate during spinning can be obtained by setting the number of the former to 1,500 ppm or less and the latter to less than 300 ppm.
- the inorganic particles for fibers of the present invention are not particularly limited as long as they are inorganic particles used for fibers, but are zirconium phosphate particles, titanium phosphate particles, hydrotalcite particles, zirconium hydroxide particles, alumina particles, and phosphoric acid.
- Aluminum particles, copper silicate particles, zinc silicate particles, manganese silicate particles, cobalt silicate particles, or nickel silicate particles are preferable, and zirconium phosphate particles, titanium phosphate particles, hydrotalcite particles, etc.
- the zirconium hydroxide particles are more preferable, and the zirconium phosphate particles are particularly preferable from the viewpoint of deodorizing property.
- the inorganic particles for fibers of the present invention may contain impurities other than those described above, and may contain known additives used for applications in fibers.
- the inorganic particles for fibers of the present invention are preferably particles containing 90% by mass or more of the inorganic component, more preferably 95% by mass or more, and preferably 99% by mass or more. Especially preferable.
- the method for measuring the particle size of inorganic particles by the electrical detection band method in the present invention shall be carried out by the following method. Measurement is performed with a multisizer 3 manufactured by Beckman Coulter Co., Ltd., which is a measuring device (Coulter counter) by the electric detection band method.
- the aperture size is set to 30 ⁇ m, about 50,000 particles are measured, the distribution in the aperture size is measured based on the number of particles, and the content of coarse particles having a particle size exceeding 1.562 ⁇ m is measured.
- the method for measuring the particle size of the inorganic particles by the flow type particle image analysis method in the present invention shall be carried out by the following method.
- a flow-type particle image analyzer FPIA-3000S manufactured by Simex Co., Ltd. (currently Spectris Co., Ltd. Malvern PANalytical Division) is used.
- Inorganic particles are added to pure water from which foreign substances have been removed through a filter so that the dispersion concentration is 0.05% by mass, and the particles are dispersed in an ultrasonic disperser for 3 minutes.
- the obtained dispersion liquid shall be dropped onto the flow-type particle image analyzer, and approximately 30,000 inorganic particles shall be measured and analyzed to measure the content of coarse particles having a particle size of more than 1.562 ⁇ m. ..
- the upper limit of the particle size measurement is preferably 100 ⁇ m.
- the content of coarse particles having a particle size exceeding 1.562 ⁇ m measured by the electric detection band method is 1,500 from the viewpoint of suppressing thread breakage. It is ppm or less, preferably 300 number ppm or less, more preferably 200 number ppm or less, further preferably 100 number ppm or less, particularly preferably 50 number ppm or less, and 25 number number. Most preferably, it is ppm or less.
- the content of coarse particles having a particle size exceeding 1.562 ⁇ m measured by a flow-type particle image analysis method is 300 ppm from the viewpoint of suppressing thread breakage.
- the particle size is less than, preferably 100 ppm or less, more preferably 10 ppm or less, still more preferably 1 ppm or less, and the particle size measured by the flow-type particle image analysis method. It is particularly preferable that it does not contain coarse particles larger than 562 ⁇ m.
- the inorganic particles for fibers of the present invention preferably have a content of coarse particles having a particle size of more than 2.148 ⁇ m, which is measured by the electric detection band method, of 5 parts per million or less from the viewpoint of suppressing thread breakage. It is more preferable that the number of particles is 1 ppm or less, and it is particularly preferable that the particles do not contain coarse particles having a particle size of more than 2.148 ⁇ m as measured by the electric detection band method. Further, the inorganic particles for fibers of the present invention have a content of coarse particles having a particle size of more than 2.148 ⁇ m measured by a flow-type particle image analysis method of 5 or less ppm from the viewpoint of suppressing thread breakage. It is more preferable that the number of particles is 1 ppm or less, and it is particularly preferable that coarse particles having a particle size of more than 2.148 ⁇ m as measured by the flow particle image analysis method are not contained.
- the inorganic particles for fibers of the present invention preferably do not contain coarse particles having a particle size of more than 3 ⁇ m as measured by the electrical detection band method from the viewpoint of suppressing thread breakage. Further, the inorganic particles for fibers of the present invention preferably do not contain coarse particles having a particle size of more than 3 ⁇ m as measured by the flow-type particle image analysis method from the viewpoint of suppressing thread breakage.
- the inorganic particles for fibers of the present invention have a median diameter D50 measured by a laser diffraction method at 0.1 ⁇ m to 1.2 ⁇ m from the viewpoint of further exerting functional effects such as thread breakage suppression and deodorizing effect. It is preferably 0.2 ⁇ m to 1.0 ⁇ m, more preferably 0.5 ⁇ m to 0.9 ⁇ m, and particularly preferably 0.5 ⁇ m to 0.9 ⁇ m.
- the cumulative 99.9 number% particle size D99.9 measured by the electric detection band method further exerts functional effects such as thread breakage suppression and deodorizing effect. From the viewpoint of the above, it is preferably 1.562 ⁇ m or less, more preferably 0.5 ⁇ m to 1.55 ⁇ m, and particularly preferably 1.0 ⁇ m to 1.50 ⁇ m.
- 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, but from the viewpoint of the removability of the coarse particles, the inorganic particles can be produced by dry classification.
- a method including a step of removing coarse particles also referred to as a "dry classification step" is preferable.
- the classification method for removing coarse particles of inorganic particles may be either dry classification or wet classification.
- wet classification when the final product is sold in the form of powder, a drying step is required after the classification, and even if the coarse particles are removed before the drying, the coarse particles are reconsolidated and aggregated in the drying step. It may occur. Therefore, a dry classification is preferable because a drying step is not required after the classification, the possibility of solidification and aggregation is low, and the manufacturing process can be simplified.
- the dry classifier examples include a mechanical type and a swirling airflow type, but the classifier is not limited as long as it can classify coarse particles.
- the classification rotor mechanically rotates at high speed, and mechanical accuracy is required to prevent vibration, so there is a limit to the classification point.
- the particle size to be excluded as coarse particles is in the region of particles of 1.5 ⁇ m to 5 ⁇ m, there is a limit in the mechanical classifier, and there is a possibility that the coarse particles cannot be excluded with high accuracy.
- metal contamination mixture due to wear due to sliding of the metal portion may occur.
- an airflow classifier (swirl airflow classifier) using a swirling flow structurally without a mechanical rotating portion.
- the swirling airflow type classifier described in International Publication No. 2011/132301 is preferably mentioned.
- the pressure and amount of the high-pressure gas to be blown onto the inorganic particles during the dry classification are not particularly limited, but a pressure of 0.1 MPa to 1.0 MPa is preferable.
- the air volume during dry classification is not particularly limited, but 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, a pulverization step of pulverizing the inorganic particles or agglomerated particles of the inorganic particles, a sieving step of sieving the inorganic particles, and the like.
- the timing of performing the dry classification step is not particularly limited, and may be, for example, either before or after the pulverization step and the sieving step, or both before and after.
- dry classification can be carried out in order to further eliminate coarse particles.
- the pulverization step and the sieving step can be carried out. Considering that new coarse particles may be generated in the pulverization step and the sieving step, the dry classification step is preferably performed after the pulverization step and the sieving step.
- the classification point in the dry classification step may be appropriately set as desired.
- the single yarn of the fiber is about 10 ⁇ m, when inorganic particles are added or kneaded into the resin forming the fiber, spinning is performed. From the viewpoint of suppressing thread breakage at the time, it is preferable to eliminate coarse particles having a particle size of more than 3 ⁇ m, more preferably to eliminate coarse particles having a particle size of more than 2.148 ⁇ m, and coarse particles having a particle size of more than 1.562 ⁇ m. Is particularly preferable.
- the method for producing inorganic particles for fibers of the present invention may include a step of producing the inorganic particles.
- the inorganic particles used in the method for producing inorganic particles for fibers of the present invention may be prepared inorganic particles such as commercially available products or produced inorganic particles.
- the method for producing the inorganic particles is not particularly limited, and a known method can be used.
- the method for producing zirconium phosphate particles will be described below as an example.
- the zirconium phosphate in the present invention is produced by a known method using zirconium oxychloride, oxalic acid, and phosphoric acid as starting materials. For example, it can be produced by the method described in JP-A-60-10308 or JP-A-2018-178313. However, the method for producing zirconium phosphate is not limited to this.
- the obtained zirconium phosphate may be dried after solid-liquid separation or without solid-liquid separation.
- solid-liquid separation there is a filter press, a pressure filter, or the like, and the hydrous cake (mud) after solid-liquid separation is dried.
- Suitable examples of the method for drying the water-containing cake include a paddle dryer, a conical dryer, a vibration dryer, and an inverted conical stirring dryer.
- Examples of the method of drying without solid-liquid separation include a spray dryer, a fluidized bed dryer containing balls, and a jet turbo dryer.
- the dried product of zirconium phosphate particles may or may not be crushed, pulverized, or sieved. In order to adjust the particle size to be uniform, it is preferable to crush or crush and further pass through a sieve.
- the water content of the inorganic particles for fibers of the present invention is that when the inorganic particles are kneaded with a raw material resin for synthetic fibers such as polyester resin by an extruder or the like before spinning, the water content remains in the inorganic particles for fibers. Moisture may evaporate during heat kneading with an extruder, and the resin for the raw material may foam. In order to prevent foaming, the water content of the inorganic particles for fibers of the present invention is preferably 1% by mass or less, more preferably 0.6% by mass or less.
- the fiber of the present invention is a fiber containing the inorganic particles for fibers of the present invention, and is preferably a deodorant fiber containing the inorganic particles for fibers of the present invention.
- the method for producing the fiber containing the inorganic particles for fibers of the present invention is not particularly limited, and a known method can be used. For example, a method of kneading the inorganic particles for fibers of the present invention into fibers and spinning the fibers can be mentioned.
- the fiber of the present invention is preferably a resin fiber, more preferably a chemical fiber.
- 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 preferable, and polyester is more preferable.
- preferable specific examples of polyester include, for example, polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polybutylene terephthalate and the like. Of these, polyethylene terephthalate is preferable.
- These resins may be homopolymers or copolymers.
- the polymerization ratio of each copolymer component there is no particular limitation on the polymerization ratio of each copolymer component.
- the method for adding the inorganic particles for fibers of the present invention to the resin is not particularly limited.
- the resin may be added in the polymerization step, or the polymerized resin may be used and kneaded with an extruder. ..
- the inorganic particles for fibers of the present invention of the present invention can be preferably used as a deodorant for kneading fibers.
- Specific examples of the method for producing the deodorant fiber in this case include a method in which the inorganic particles for fibers of the present invention are kneaded into a melted liquid fiber resin or a dissolved fiber resin solution and spun. ..
- the content of the inorganic particles for fibers of the present invention in the fibers of the present invention is not particularly limited. Generally, if the content is increased, the deodorizing property can be exerted strongly and can be maintained for a long period of time. However, even if the content is increased to a certain extent or more, the deodorizing effect does not differ significantly, and from the viewpoint of 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 0.5 parts by weight to 2. More preferably, it is 0 parts by weight.
- the deodorant fiber using the inorganic particles for fibers of the present invention can be used in various fields requiring deodorant properties, for example, underwear, stockings, socks, duvets, duvet covers, cushions, blankets, carpets, etc. It can be used for many textile products such as curtains, sofas, car seats, air filters and nursing clothing.
- % and parts mean “% by weight” and “part by weight”, respectively, unless otherwise specified.
- the thread breakage rate which indicates the frequency of thread breakage in the case, was measured by the following method.
- the particle size of zirconium phosphate was measured by an electrical detection band method, a so-called Coulter counter, a multisizer 3 manufactured by Beckman Coulter Co., Ltd.
- the aperture size was set to 30 ⁇ m, 50,000 pieces were measured, and the distribution among them was measured on the basis of the number.
- a masterbatch was prepared in which the produced zirconium phosphate particles were mixed with 100% of polyester resin (MA2101M manufactured by Unitika Ltd., polyethylene terephthalate resin) at 20%. Then, this masterbatch was mixed with a regular polyester resin pellet containing no zirconium phosphate and adjusted to 2% by weight. This was spun using a multifilament spinning machine at a spinning temperature of 275 ° C. and a spinning speed of 500 m / min for 2 hours, stretched at 120 ° C. so that the elongation was 280% to 320%, and contained zirconium phosphate particles. Polyester fibers were obtained.
- polyester resin MA2101M manufactured by Unitika Ltd., polyethylene terephthalate resin
- Thread breakage is 0 times / 2 hours
- Thread breakage is 1 time / 2 hours or more and less than 3 times / 2 hours
- C Thread breakage is 3 times / 2 hours or more and less than 6 times / 2 hours
- D Thread Number of breaks is 6 times / 2 hours or more and less than 10 times / 2 hours
- E Number of thread breaks is 10 times / 2 hours or more
- F Evaluation not possible
- zirconium phosphate particles As a result of measuring the obtained zirconium phosphate particles with an X-ray diffractometer, it was confirmed that they were ⁇ -zirconium phosphate particles.
- the ⁇ zirconium phosphate particles were dissolved by heating with phosphoric acid and nitric acid, elemental analysis was performed with an ICP (Inductively Coupled Plasma) emission spectrometer, and thermogravimetric differential thermal analysis was performed.
- ICP Inductively Coupled Plasma
- Example 1 Zirconium phosphate particles produced according to the reference example were classified using a classifier (Aerofine Classifier AC-20 type: manufactured by Nisshin Engineering Co., Ltd.).
- the air volume sucked by the suction blower was 2.5 m 3 / min.
- the air volume sucked by the suction blower corresponds to the air volume of the normal pressure gas sucked from between the guide vanes.
- the angle of the guide vane was set to 80 ° (tangential direction).
- the condition of the high pressure gas ejected from the upper air nozzle was 0.7 MPa, and the condition of the high pressure gas ejected from the lower air nozzle was 0.6 MPa.
- the powder before classification was continuously supplied at 2 kg / h with a quantitative feeder at 478 g for 13 minutes. 415 g of powder on the fine side after classification could be recovered. The yield with respect to the amount input to the classifier was 86.8%.
- the powder on the fine side after classification was measured with a Coulter counter. The aperture size was set to 30 ⁇ m, 50,000 pieces were measured, and the distribution among them was measured on the basis of the number.
- the median diameter D50 was 0.731 ⁇ m, and D99.9 was 1.442 ⁇ m.
- the number of coarse particles having a particle size of more than 1.562 ⁇ m and less than 2.148 ⁇ m was 15. In addition, coarse particles having a particle size of more than 2.148 ⁇ m were not detected.
- the particle size was measured by the flow type particle image analysis method. Specifically, the particle size was measured using a flow-type particle image analyzer FPIA-3000S manufactured by Simex Co., Ltd. (currently Spectris Co., Ltd. Malvern PANalytical Division). The number of measured particles was 30,000. As a result, no coarse particles having a particle size exceeding 1.562 ⁇ m were observed. The concentration with respect to the number of measured particles was 0 parts per million. The results are shown in Tables 1 and 2. Table 2 summarizes the nine particle sizes from the largest observed particles, and FIG. 1 shows the coarser particles in order from the larger one detected by image analysis. Further, each numerical value shown in FIG. 1 represents the size (unit: ⁇ m) of each coarse particle. When the number of yarn breaks was evaluated, the number of yarn breaks was 0 times / 2 hours, and the spinning was extremely stable. The evaluation result of the number of thread breaks was A.
- Example 2 Zirconium phosphate produced according to the reference example was classified using a classifier (Aerofine Classifier AC-20, manufactured by Nisshin Engineering Co., Ltd.).
- the air volume sucked by the suction blower was set to 2.3 m 3 / min.
- the air volume sucked by the suction blower corresponds to the air volume of the normal pressure gas sucked from between the guide vanes.
- the angle of the guide vane was 90 ° (tangential direction).
- the condition of the high pressure gas ejected from the upper air nozzle was a pressure of 0.6 MPa
- the condition of the high pressure gas ejected from the lower air nozzle was a pressure of 0.6 MPa.
- the powder before classification was continuously supplied at 2 kg / h with a quantitative feeder at 505 g for 15 minutes. 387 g of powder on the fine side after classification could be recovered. The yield with respect to the amount input to the classifier was 76.6%.
- the powder on the fine side after classification was measured with a Coulter counter.
- the aperture size was set to 30 ⁇ m, 50,000 pieces were measured, and the distribution among them was measured on the basis of the number.
- the median diameter D50 was 0.719 ⁇ m, and D99.9 was 1.366 ⁇ m.
- the number of coarse particles having a particle size of more than 1.562 ⁇ m and less than 2.148 ⁇ m was one. In addition, coarse particles having a particle size of more than 2.148 ⁇ m were not detected.
- the detailed results of the coarse particle part are shown in Table 1. When the number of yarn breaks was evaluated, the number of yarn breaks was 0 times / 2 hours, and the spinning was extremely stable. The evaluation result of the number of thread breaks was A.
- Example 3 In Example 2, the powder before classification was classified under the same conditions except that 3,924 g of the powder before classification was continuously supplied at 2 kg / h for 120 minutes with a quantitative feeder. 2911 g of fine powder after classification could be recovered. The yield with respect to the amount charged into the classifier was 74.2%.
- the obtained fine powder on the fine side after classification was measured for coarse particles with a Coulter counter (Multisizer 3 manufactured by Beckman Coulter Co., Ltd.). The aperture size was set to 30 ⁇ m, 50,000 pieces were measured, and the distribution among them was measured on the basis of the number.
- the median diameter D50 was 0.722 ⁇ m, and D99.9 was 1.406 ⁇ m.
- the number of coarse particles having a particle size of more than 1.562 ⁇ m and less than 2.148 ⁇ m was 9. In addition, coarse particles having a particle size of more than 2.148 ⁇ m were not detected.
- the detailed results of the coarse particle part are shown in Table 1. When the number of yarn breaks was evaluated, the number of yarn breaks was 0 times / 2 hours, and the spinning was extremely stable. The evaluation result of the number of thread breaks was A.
- the coarse particles of zirconium phosphate produced according to the reference example were measured with a Coulter counter (Multisizer 3 manufactured by Beckman Coulter Co., Ltd.) as it was without dry classification.
- the aperture size was set to 30 ⁇ m, 50,000 pieces were measured, and the distribution among them was measured on the basis of the number.
- the median diameter D50 was 0.760 ⁇ m, and D99.9 was 1.606 ⁇ m.
- the number of coarse particles having a particle size of more than 1.562 ⁇ m and less than 2.148 ⁇ m was 77. In addition, coarse particles having a particle size of more than 2.148 ⁇ m were not detected.
- the particle size was measured by analyzing the image using a flow-type particle image analyzer FPIA-3000S manufactured by Simex Co., Ltd. (currently Spectris Co., Ltd. Malvern Panasonic Division).
- the number of measured particles was 30,000.
- 9 coarse particles having a particle size of more than 1.562 ⁇ m were observed.
- FIG. 2 shows the nine coarse particles detected by image analysis in descending order.
- each numerical value shown in FIG. 2 represents the size (unit: ⁇ m) of each coarse particle.
- the number of thread breaks was 1 time / 2 hours or more and less than 3 times / 2 hours, and several thread breaks occurred.
- the evaluation result of the number of thread breaks was B.
- Example 2 The powder on the coarse side after the dry classification carried out in Example 1 was recovered, and the coarse particles were measured with a Coulter counter (Multisizer 3 manufactured by Beckman Coulter Co., Ltd.). The aperture size was set to 30 ⁇ m, 50,000 pieces were measured, and the distribution among them was measured on the basis of the number.
- the median diameter D50 was 0.770 ⁇ m, and D99.9 was 1.661 ⁇ m.
- the number of coarse particles having a particle size of more than 1.562 ⁇ m and less than 2.148 ⁇ m was 127. In addition, coarse particles having a particle size of more than 2.148 ⁇ m were not detected.
- Example 1 the cumulative number of coarse particles having a particle size of 1.562 ⁇ m or more and less than 2.148 ⁇ m was 15 and 1, respectively, based on the measurement results of the powder on the fine side after classification. The number of coarse particles is smaller than that of 77 before classification, and the coarse particles can be removed.
- Example 3 even when the classification treatment amount of Example 2 is increased, the number of integrated coarse particles having a particle size of 1.562 ⁇ m or more and less than 2.148 ⁇ m is as small as 9, and the coarse particles can be eliminated. Is shown.
- Comparative Example 1 is a case where zirconium phosphate particles that have not been classified are measured with a Coulter counter, and the number of integrated coarse particles having a particle size of 1.562 ⁇ m or more and less than 2.148 ⁇ m is as large as 77. Is shown. It can be seen that a large amount of coarse particles are contained without the classification treatment.
- Comparative Example 2 the coarse particle side after the classification treatment of Example 1 was recovered. Since it is on the coarse particle side, the cumulative number of coarse particles having a particle size of 1.562 ⁇ m or more and less than 2.148 ⁇ m is 127 as compared with the fine side after the classification treatment, which is the case of Example 1. It is more than the 15 on the fine side after classification.
- the number of coarse particles is larger than 77, which is the number of coarse particles when the classification treatment of Comparative Example 1 is not performed. This is the result of removing the coarse particles by the classification in Example 1, and shows that the coarse particles that could be removed by the classification could be separated and recovered as the coarse particles after the classification of Comparative Example 2.
- the number of effective counts of coarse particles is set to about 50,000, so that the number of coarse particles can be quantitatively compared.
- Quantitative comparison of coarse particles is possible in terms of ppm as the cumulative concentration of coarse particles with a particle size of 1.562 ⁇ m or more and less than 2.148 ⁇ m with respect to the effective N number.
- Example 2 the maximum particle size of the coarse particles detected in the measurement of the coarse particles by the flow type particle image analyzer was 1.494 ⁇ m, and the particle size was 1.562 ⁇ m or less. It is shown that there is, and it can be seen that coarse particles having a particle size of more than 1.562 ⁇ m can be removed by the dry classification.
- Comparative Example 1 the maximum particle size of the coarse particles detected in the measurement of the coarse particles by the flow type particle image analyzer is 9.443 ⁇ m, which is a coarse particle having a particle size exceeding 1.562 ⁇ m. It can be seen that, since the dry classification was not carried out, the coarse particles having a particle size of more than 1.562 ⁇ m could not be removed and were contained.
- the inorganic particles for fibers of Examples 1 to 3 which are the inorganic particles for fibers of the present invention, have a lower number of yarn breaks during spinning than the inorganic particles of Comparative Examples 1 and 2. It was.
- the method for producing inorganic particles for fibers of the present invention a small amount of coarse particles contained in the ppm order that cannot be detected by a laser diffraction type particle size distribution meter can be easily removed. Further, the inorganic particles for fibers of the present invention can reduce the frequency of yarn breakage during spinning in applications such as kneading into fibers such as polyester fibers, can improve productivity in the spinning process, and are industrial. Above useful.
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Abstract
Description
特許文献1は、粒子径として、メジアン径が0.2~0.7μm、且つ最大粒子径が5.0μm以下で、D10径が0.1μm以上である、αリン酸ジルコニウム及び/又はαリン酸チタンを含む繊維用消臭剤が記載されている。
一方、リン酸ジルコニウム粒子等の無機粒子を繊維の紡糸時に練り込むことにより、例えば、前記無機粒子により消臭機能等の各種機能を有する糸を使用して、織物を製造すれば、消臭機能等を有する繊維製品の生産性を低下させることなく製造できる利点がある。
また、消臭機能等の持続性については、無機粒子が繊維の中に入り込んでいることから、後加工によるリン酸ジルコニウム等を塗布する方法より、紡糸時に無機粒子を練り込んだほうが、持続性が長期間、維持できると考える。
<1> 電気的検知帯法により測定される粒径1.562μmを超える粗大粒子の含有量が、1,500個数ppm以下である繊維用無機粒子。
<2> フロー式粒子像分析法により測定される粒径1.562μmを超える粗大粒子の含有量が、300個数ppm未満である繊維用無機粒子。
<3> 前記繊維用無機粒子が、リン酸ジルコニウム粒子、リン酸チタン粒子、ハイドロタルサイト粒子、又は、水酸化ジルコニウム粒子である<1>又は<2>に記載の繊維用無機粒子。
<4> 前記繊維用無機粒子が、リン酸ジルコニウム粒子である<1>~<3>のいずれか1つに記載の繊維用無機粒子。
<5> フロー式粒子像分析法により測定される粒径1.562μmを超える粗大粒子の含有量が、300個数ppm未満である<1>に記載の繊維用無機粒子。
<6> メジアン径が0.2μm~1.0μmである<1>~<5>のいずれか1つに記載の繊維用無機粒子。
<7> 電気的検知帯法により測定される粒径2.148μmを超える粗大粒子の含有量が、5個数ppm以下である<1>~<6>のいずれか1つに記載の繊維用無機粒子。
<8> 電気的検知帯法により測定される粒径2.148μmを超える粗大粒子を含まない<1>~<7>のいずれか1つに記載の繊維用無機粒子。
<9> 繊維用消臭剤である<1>~<8>のいずれか1つに記載の繊維用無機粒子。
<10> 乾式分級により、無機粒子における粗大粒子を除去する工程を含む<1>~<9>のいずれか1つに記載の繊維用無機粒子の製造方法。
<11> 前記乾式分級が、旋回式気流分級機により行われる<10>に記載の繊維用無機粒子の製造方法。
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本発明において、「質量%」と「重量%」とは同義であり、「質量部」と「重量部」とは同義である。
また、本発明において、2以上の好ましい態様の組み合わせは、より好ましい態様である。
以下において、本発明の内容について詳細に説明する。
本発明の繊維用無機粒子の第1の実施態様は、電気的検知帯法により測定される粒径1.562μmを超える粗大粒子の含有量が、1,500個数ppm以下であり、好ましくは300個数ppm以下である。
また、本発明の繊維用無機粒子の第2の実施態様は、フロー式粒子像分析法(「粒子の動的画像解析法」ともいう。)により測定される粒径1.562μmを超える粗大粒子の含有量が、300個数ppm未満である。
本明細書において、単に「本発明の繊維用無機粒子」と記載する場合、特に断りのない限り、前記第1の実施態様、及び、前記第2の実施態様の両方を指すものとする。
また、本発明の繊維用無機粒子は、繊維用消臭剤として好適に用いることができる。
また、粗大粒子を少なくする目的で、メジアン径D50を小さくしても、例えば、ポリエステル樹脂への添加、又は、練り込みの段階で、小さい粒径の粒子が再凝集し易く粗大粒子となり、糸切れの原因となることや粗大粒子を除去するためのポリマーフィルタで差圧が上昇して生産性が悪くなることがわかってきた。
そのため、例えば、繊維の紡糸時の糸切れの不具合を解消する技術がないのが現状である。
これによる優れた効果の作用機構は明確ではないが、以下のように推定している。
電気的検知帯法、又は、フロー式粒子像分析法により、粒径1.562μmを超える粗大粒子の確認方法として検出性に優れるため、これらの方法により測定された前記粗大粒子の含有量を、前者では1,500個数ppm以下、また、後者では300個数ppm未満とすることにより、紡糸時の糸切れ率が低い繊維用無機粒子が得られると推定される。
また、本発明の繊維用無機粒子は、前述した以外の不純物を含んでいてもよく、繊維に使用する用途に用いる公知の添加剤を含んでいてもよい。
中でも、本発明の繊維用無機粒子は、前記無機成分を90質量%以上含む粒子であることが好ましく、95質量%以上含む粒子であることがより好ましく、99質量%以上含む粒子であることが特に好ましい。
電気的検知帯法による測定装置(コールターカウンター)であるベックマン・コールター株式会社製マルチサイザー3で測定する。
アパチャーサイズは、30μmの設定で、およそ50,000個測定し、その中の分布を個数基準で測定し、粒径1.562μmを超える粗大粒子等の含有量を測定するものとする。
シメックス株式会社(現スペクトリス株式会社マルバーン・パナリティカル事業部)製フロー式粒子像分析装置FPIA-3000Sを使用する。
フィルターを通して異物を除去した純水に、分散濃度が0.05質量%になるように無機粒子を添加し、超音波分散装置で3分間分散させる。得られた分散液を前記フロー式粒子像分析装置に滴下し、およそ30,000個の無機粒子を測定及び解析し、粒径1.562μmを超える粗大粒子等の含有量を測定するものとする。
また、粒子径の測定上限は、100μmであることが好ましい。
また、本発明の繊維用無機粒子は、フロー式粒子像分析法により測定される粒径2.148μmを超える粗大粒子の含有量が、糸切れ抑制性の観点から、5個数ppm以下であることが好ましく、1個数ppm以下であることがより好ましく、フロー式粒子像分析法により測定される粒径2.148μmを超える粗大粒子を含まないことが特に好ましい。
また、本発明の繊維用無機粒子は、糸切れ抑制性の観点から、フロー式粒子像分析法により測定される粒径3μmを超える粗大粒子を含まないことが好ましい。
本発明の繊維用無機粒子の製造方法としては、本発明の繊維用無機粒子を製造可能であれは、特に制限はないが、前記粗大粒子の除去性の観点から、乾式分級により、無機粒子における粗大粒子を除去する工程(「乾式分級工程」ともいう。)を含む方法であることが好ましい。
また、分級ローターの機械的回転による分級では、金属部分の摺動による摩耗に起因する金属のコンタミネーション(混入)が生じる場合がある。上記の観点より、構造的に機械的回転部分のない旋回流を用いた気流分級機(旋回気流式分級機)により乾式分級を行うことが好ましい。例えば、国際公開第2011/132301号に記載の旋回気流式分級機が好ましく挙げられる。
また、乾式分級時の風量は、特に制限はないが、1m3/分~10m3/分であることが好ましい。
前記乾式分級工程を行うタイミングは、特に制限はなく、例えば、粉砕工程、及び、篩分工程の前後のいずれであってもよいし、前後の両方で行ってもよい。粉砕工程、及び、篩分工程にて、一旦、粒度調整をした後、更に、粗大粒子を排除するため、乾式分級を実施することができる。
また、乾式分級を実施した後に、粉砕工程、及び、篩分工程を実施することができる。
粉砕工程、及び、篩分工程で新規に粗大粒子が発生する可能性があることを考えると、乾式分級工程は、粉砕工程、及び、篩分工程の後に行うことが好ましい。
本発明の繊維用無機粒子の製造方法に用いられる無機粒子は、市販品等の準備した無機粒子であっても、作製した無機粒子であってもよい。
無機粒子の作製方法としては、特に制限はなく、公知の方法を用いることができる。
以下に一例として、リン酸ジルコニウム粒子の作製方法を説明する。
リン酸ジルコニウムは、固液分離すると、粘土状となり、付着性が強く、取り扱いが困難であるので、固液分離なしで乾燥し、リン酸ジルコニウム粒子を得ることが好ましい。
本発明の繊維は、本発明の繊維用無機粒子を含む繊維であり、本発明の繊維用無機粒子を含む消臭性繊維であることが好ましい。
本発明の繊維用無機粒子を含む繊維を製造する方法としては、特に制限はなく、公知の方法を用いることができる。
例えば、本発明の繊維用無機粒子を繊維に練り込み紡糸する方法等が挙げられる。
使用できる繊維用樹脂としては、公知の化学繊維はいずれも使用することができる。
化学繊維の材質の好ましい具体例としては、例えばポリエステル、ポリウレタン、ナイロン、レーヨン、アクリル樹脂、ビニロン及びポリプロピレン等が挙げられる。中でも、ポリエステル、ナイロン、又は、アクリル樹脂であることが好ましく、ポリエステルであることがより好ましい。
また、ポリエステルの好ましい具体例としては、例えばポリエチレンテレフタレート、ポリエチレンナフタレート、ポリトリメチレンテレフタレート及びポリブチレンテレフタレート等が挙げられる。中でも、ポリエチレンテレフタレートが好ましい。
これらの樹脂は、単独重合体であっても共重合体であってもよい。共重合体の場合、各共重合成分の重合割合に特に制限はない。
また、樹脂への本発明の繊維用無機粒子の添加方法は、特に制限はなく、例えば、樹脂の重合工程での添加であっても、重合後の樹脂を用い、押出機で練り込んでもよい。
この場合における消臭性繊維の具体的な製造方法としては、溶融した液状繊維用樹脂又は溶解した繊維用樹脂溶液に本発明の繊維用無機粒子を練り込み、これを紡糸する方法等が挙げられる。
一般に含有量を増やせば消臭性を強力に発揮させ、長期間持続させることができるが、ある程度以上に含有させても消臭効果に大きな差が生じないこと、及び、樹脂の強度の観点から、本発明の繊維における本発明の繊維用無機粒子の含有量は、樹脂100重量部に対し、0.1重量部~3.0重量部であることが好ましく、0.5重量部~2.0重量部であることがより好ましい。
リン酸ジルコニウムの粒子径の測定は、電気的検知帯法、いわゆるコールターカウンターであるベックマン・コールター株式会社製マルチサイザー3で測定した。
アパチャーサイズは、30μmの設定で、50,000個測定し、その中の分布を個数基準で測定した。
ベックマン・コールター株式会社製マルチサイザー3での個数基準で測定した結果、1.562μm以上2.148μm未満の積算の粒子数を粗大粒子と定義した。
実際に測定した有効N数に対する粗大粒子の濃度は、次式で算出した。
1.562μm以上2.148μm未満の積算の粒子数÷実際に測定した有効N数×100,0000=有効N数に対する1.562μm以上2.148μm未満の積算の粗大粒子の濃度ppm
フロー式粒子像分析装置であるシメックス株式会社(現スペクトリス株式会社マルバーン・パナリティカル事業部)製FPIA-3000Sで測定した。
フィルターを通して異物を除去した純水に、分散濃度が0.05%になるように粉体を添加し、超音波分散装置で3分間、分散させた。分散液をフロー式粒子像分析装置に滴下し、およそ30,000パーティクルを測定し、解析した。
フロー式粒子像分析装置が、検知したパーティクルを大きい順に並べ替え、大きい粒子の粒子径と粒子の写真を測定した。
製造したリン酸ジルコニウム粒子をポリエステル樹脂(ユニチカ(株)製MA2101M、ポリエチレンテレフタレート樹脂)100%に対して20%配合したマスターバッチを作製した。そして、このマスターバッチを、リン酸ジルコニウムを含まないレギュラーポリエステル樹脂ペレットと混合し、2重量%となるように調整した。これをマルチフィラメント紡糸機を用いて、紡糸温度275℃、紡糸速度500m/分で2時間紡糸し、伸度が280%~320%になるように120℃で延伸して、リン酸ジルコニウム粒子含有ポリエステル繊維を得た。
この際、油剤には通常のポリエステル繊維紡糸用の水溶性油剤(竹本油脂(株)製デリオン6033を水で10倍希釈したもの)を使用した。
2時間連続紡糸を行い、紡糸性を次の判定方法に従い、評価した。
A:糸切れ回数が0回/2時間
B:糸切れ回数が1回/2時間以上3回/2時間未満
C:糸切れ回数が3回/2時間以上6回/2時間未満
D:糸切れ回数が6回/2時間以上10回/2時間未満
E:糸切れ回数が10回/2時間以上
F:評価不可
6m3反応器に脱イオン水3,611kg及び35%塩酸363kgを入れ、ハフニウム0.18%含有オキシ塩化ジルコニウム8水和物20%水溶液603kgを追加後、シュウ酸2水和物250kgを溶解させた。この溶液をよく攪拌しながら、75%リン酸275kgを加えた。これを2時間で98℃に昇温し、12時間撹拌還流した。冷却後、得られた沈殿物をよく水洗浄した後、105℃で乾燥することにより、リン酸ジルコニウム粒子を得た。これを粉砕機で解砕した。その後、篩分処理をした。この得られたリン酸ジルコニウム粒子についてX線回折装置で測定した結果、αリン酸ジルコニウム粒子であることを確認した。
このαリン酸ジルコニウム粒子をフッ酸及び硝酸で加熱して溶解し、ICP(Inductively Coupled Plasma)発光分析装置で元素分析を実施し、更に熱重量示差熱分析を行った結果、組成式は、
Zr0.99Hf0.01H2.03(PO4)2.01・0.05H2O
であった。
参考例に従って製造した、リン酸ジルコニウム粒子を分級機(エアロファインクラシファイアAC-20型:日清エンジニアリング株式会社製)を用い分級した。吸引ブロアで吸引する風量を2.5m3/分とした。ここで、吸引ブロアにより吸入する風量はガイドベーン間から吸入される常圧気体の風量に該当する。また、ガイドベーンの角度を80°(接線方向)とした。
上部エアノズルから噴出する高圧気体の条件を、圧力0.7MPa、下部エアノズルから噴出する高圧気体の条件を、圧力0.6MPaとした。
分級前の粉体は定量フィーダーで2kg/hで13分間で478gを連続的に供給した。
分級後の細かい側の粉体が415g回収できた。分級機へ投入量に対する収率は86.8%であった。なお、得られた分級後の細かい側の粉体をコールターカウンターで測定した。
アパチャーサイズは、30μmの設定で、50,000個測定し、その中の分布を個数基準で測定した。
メジアン径D50は0.731μm、D99.9は、1.442μmであった。
粒径1.562μmを超え2.148μm以下の粗大粒子数は、15個であった。
また、粒径2.148μmを超える粗大粒子は、検出されなかった。
実際に測定した有効N数である51,008個に対する濃度(含有量)は、
15÷51,008×1,000,000=294個数ppm
であった。粗大粒子の部分の詳しい結果は表1に示した。
測定パーティクル数に対する濃度は0個数ppmであった。
結果は表1及び表2に示し、表2には観察された粒子の大きい方から9つの粒径をまとめ、図1には画像解析により検出された大きいほうから順に粗大粒子を示した。また、図1に記載の各数値はそれぞれ、各粗大粒子の大きさ(単位:μm)を表す。
なお、糸切れ回数の評価をしたところ、糸切れ回数が0回/2時間で、極めて安定して紡糸できた。
糸切れ回数の評価結果は、Aだった。
参考例に従って製造した、リン酸ジルコニウムを分級機(エアロファインクラシファイアAC-20型、日清エンジニアリング株式会社製)を用い分級した。吸引ブロアで吸引する風量を2.3m3/分とした。ここで、吸引ブロアにより吸入する風量はガイドベーン間から吸入される常圧気体の風量に該当する。また、ガイドベーンの角度を90°(接線方向)とした。
上部エアノズルから噴出する高圧気体の条件を、圧力0.6MPa、下部エアノズルから噴出する高圧気体の条件を、圧力0.6MPaとした。
分級前の粉体は定量フィーダーで2kg/hで15分間で505gを連続的に供給した。
分級後の細かい側の粉体が387g回収できた。分級機へ投入量に対する収率は76.6%であった。
なお、得られた分級後の細かい側の粉体をコールターカウンターで測定した。
アパチャーサイズは、30μmの設定で、50,000個測定し、その中の分布を個数基準で測定した。
メジアン径D50は0.719μm、D99.9は、1.366μmであった。
粒径1.562μmを超え2.148μm以下の粗大粒子数は、1個であった。
また、粒径2.148μmを超える粗大粒子は、検出されなかった。
実際に測定した有効N数である50,969個に対する濃度(含有量)は、
1÷50,969×1,000,000=20個数ppm
であった。粗大粒子の部分の詳しい結果は表1に示した。
なお、糸切れ回数の評価をしたところ、糸切れ回数が0回/2時間で、極めて安定して紡糸できた。
糸切れ回数の評価結果は、Aだった。
実施例2において、分級前の粉体は定量フィーダーで2kg/hで120分間、連続的に3,924gを供給した以外は、同じ条件で分級を行った。分級後の細かい側の粉体が2911g回収できた。分級機へ投入量に対する収率は74.2%であった。
なお、得られた分級後の細かい側の粉体をコールターカウンター(ベックマン・コールター株式会社製マルチサイザー3)で粗大粒子を測定した。
アパチャーサイズは、30μmの設定で、50,000個測定し、その中の分布を個数基準で測定した。
メジアン径D50は0.722μm、D99.9は、1.406μmであった。
粒径1.562μmを超え2.148μm以下の粗大粒子数は、9個であった。
また、粒径2.148μmを超える粗大粒子は、検出されなかった。
実際に測定した有効N数である51,121個に対する濃度(含有量)は、
9÷51,121×1,000,000=176個数ppm
であった。粗大粒子の部分の詳しい結果は表1に示した。
なお、糸切れ回数の評価をしたところ、糸切れ回数が0回/2時間で、極めて安定して紡糸できた。
糸切れ回数の評価結果は、Aだった。
参考例に従って製造した、リン酸ジルコニウムを乾式分級することなく、そのまま、コールターカウンター(ベックマン・コールター株式会社製マルチサイザー3)で粗大粒子を測定した。
アパチャーサイズは、30μmの設定で、50,000個測定し、その中の分布を個数基準で測定した。
メジアン径D50は0.760μm、D99.9は、1.606μmであった。
粒径1.562μmを超え2.148μm以下の粗大粒子数は、77個であった。
また、粒径2.148μmを超える粗大粒子は、検出されなかった。
実際に測定した有効N数である51,097個に対する濃度(含有量)は、
77÷51,097×1,000,000=1,507個数ppm
であった。
測定パーティクル数に対する濃度は9÷30,000×1,000,000=300個数ppmであった。
結果は表1及び表2に示し、図2には画像解析により検出された9つの粗大粒子を大きいほうから順に示した。また、図2に記載の各数値はそれぞれ、各粗大粒子の大きさ(単位:μm)を表す。
なお、糸切れ回数の評価をしたところ、糸切れ回数が1回/2時間以上3回/2時間未満で、数回の糸切れが発生した。糸切れ回数の評価結果は、Bであった。
実施例1で実施した乾式分級後の粗大側の粉体を回収し、コールターカウンター(ベックマン・コールター株式会社製マルチサイザー3)で粗大粒子を測定した。
アパチャーサイズは、30μmの設定で、50,000個測定し、その中の分布を個数基準で測定した。
メジアン径D50は0.770μm、D99.9は、1.661μmであった。
粒径1.562μmを超え2.148μm以下の粗大粒子数は、127個であった。
また、粒径2.148μmを超える粗大粒子は、検出されなかった。
実際に測定した有効N数である50,953個に対する濃度(含有量)は、
127÷50,953×1,000,000=2,492個数ppm
であった。
なお、糸切れ回数の評価をしたところ、糸切れが、頻発した。糸切れ回数の評価結果は、Fであった。
実施例3は、実施例2の分級処理量を多くした場合においても、粒径1.562μm以上2.148μm未満の積算の粗大粒子の数が9個と少なく、粗大粒子が排除できていることを示している。
比較例2は、実施例1の分級処理後の粗大粒子側を回収したものである。
粗大粒子側であることから、分級処理後の細かい側と比較して、粒径1.562μm以上2.148μm未満の積算の粗大粒子の数が、127個であり、実施例1の場合である分級後の細かい側の15個と比較して多い。さらに、比較例1の分級処理をしていない場合の粗大粒子の数である77個よりも多い。これは、実施例1では、分級により、粗大粒子を除去した結果であり、分級で除去できた粗大粒子は、比較例2の分級後の粗大粒子として分離回収できたことを示している。
粗大粒子の定量的な比較は、有効N数に対する粒径1.562μm以上2.148μm未満の積算の粗大粒子の濃度としてppmの単位で可能である。
それに対し、比較例1では、フロー式粒子像分析装置による粗大粒子の測定において、検知した最大の粗大粒子の粒径は、9.443μmであり、粒径が1.562μmを超える粗大粒子であることを示しており、乾式分級を実施していないため、粒径1.562μmを超える粗大粒子が除去できずに、含有していることが分かる。
また、本発明の繊維用無機粒子は、ポリエステル繊維等の繊維に練り込む用途において、紡糸時の糸切れの頻度を低減することができ、紡糸工程での生産性を向上することができ、産業上有益である。
本明細書に記載された全ての文献、特許出願、及び、技術規格は、個々の文献、特許出願、及び、技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (11)
- 電気的検知帯法により測定される粒径1.562μmを超える粗大粒子の含有量が、1,500個数ppm以下である
繊維用無機粒子。 - フロー式粒子像分析法により測定される粒径1.562μmを超える粗大粒子の含有量が、300個数ppm未満である
繊維用無機粒子。 - 前記繊維用無機粒子が、リン酸ジルコニウム粒子、リン酸チタン粒子、ハイドロタルサイト粒子、又は、水酸化ジルコニウム粒子である請求項1又は請求項2に記載の繊維用無機粒子。
- 前記繊維用無機粒子が、リン酸ジルコニウム粒子である請求項1~請求項3のいずれか1項に記載の繊維用無機粒子。
- フロー式粒子像分析法により測定される粒径1.562μmを超える粗大粒子の含有量が、300個数ppm未満である請求項1に記載の繊維用無機粒子。
- メジアン径が0.2μm~1.0μmである請求項1~請求項5のいずれか1項に記載の繊維用無機粒子。
- 電気的検知帯法により測定される粒径2.148μmを超える粗大粒子の含有量が、5個数ppm以下である請求項1~請求項6のいずれか1項に記載の繊維用無機粒子。
- 電気的検知帯法により測定される粒径2.148μmを超える粗大粒子を含まない請求項1~請求項7のいずれか1項に記載の繊維用無機粒子。
- 繊維用消臭剤である請求項1~請求項8のいずれか1項に記載の繊維用無機粒子。
- 乾式分級により、無機粒子における粗大粒子を除去する工程を含む請求項1~請求項9のいずれか1項に記載の繊維用無機粒子の製造方法。
- 前記乾式分級が、旋回式気流分級機により行われる請求項10に記載の繊維用無機粒子の製造方法。
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