阅读说明：本技术 纤维用无机粒子及其制造方法 (Inorganic particles for fibers and method for producing same ) 是由 青山武嗣 大野康晴 于 2020-04-17 设计创作，主要内容包括：本发明的纤维用无机粒子的第1种实施方式是,通过电感带法测定的粒径超过1.562μm的粗大粒子的含量为1500个数ppm以下的纤维用无机粒子；此外,本发明的纤维用无机粒子的第2种实施方式是,通过流式粒子图像分析法测定的粒径超过1.562μm的粗大粒子的含量低于300个数ppm的纤维用无机粒子。(The fiber inorganic particles of the present invention in embodiment 1 are fiber inorganic particles having a content of coarse particles having a particle diameter of more than 1.562 μm of 1500 ppm by number or less as measured by an inductance-belt method; in addition, the inorganic particles for fiber of the present invention of embodiment 2 is an inorganic particle for fiber having a content of coarse particles having a particle diameter of more than 1.562 μm, as measured by a flow particle image analysis method, of less than 300 ppm by number.)

1. An inorganic particle for fiber, wherein,

the content of coarse particles having a particle diameter of more than 1.562 μm as measured by the inductance banding method is 1500 ppm by number or less.

2. An inorganic particle for fiber, wherein,

the content of coarse particles having a particle diameter of more than 1.562 μm as measured by flow particle image analysis is less than 300 ppm by number.

3. The inorganic particle for fiber according to claim 1 or claim 2, wherein the inorganic particle for fiber is a zirconium phosphate particle, a titanium phosphate particle, a hydrotalcite particle, or a zirconium hydroxide particle.

4. The inorganic particle for fiber according to any one of claims 1 to 3, wherein the inorganic particle for fiber is a zirconium phosphate particle.

5. The inorganic particle for fiber according to claim 1, wherein a content of coarse particles having a particle diameter of more than 1.562 μm as measured by a flow particle image analysis method is less than 300 ppm by number.

6. The inorganic particle for fiber according to any one of claims 1 to 5, wherein the median particle diameter is 0.2 to 1.0 μm.

7. The inorganic particle for fiber according to any one of claims 1 to 6, wherein a content of coarse particles having a particle diameter of more than 2.148 μm as measured by an inductance-belt method is 5 ppm by number or less.

8. The inorganic particle for fiber according to any one of claims 1 to 7, wherein a coarse particle having a particle diameter of more than 2.148 μm as measured by an electroinduction belt method is not contained.

9. The inorganic particle for fiber according to any one of claims 1 to 8, wherein the inorganic particle for fiber is a deodorant for fiber.

10. A method for producing inorganic particles for fibers according to any one of claims 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 fiber according to claim 10, wherein the dry classification is performed by a cyclone classifier.

Technical Field

The present invention relates to inorganic particles for fibers and a method for producing the same, and the inorganic particles are suitably used as a deodorant for fibers.

Background

Inorganic particles such as zirconium phosphate particles are used as deodorizers, and for example, "deodorizing products" such as deodorizing sheets, deodorizing curtains, deodorizing filters, and clothes and bedding having a deodorizing function against sweat odor, aged odor, and the like have been put into circulation in pursuing a more comfortable living environment.

As a conventional deodorant for fibers, a deodorant described in patent document 1 is known.

Patent document 1 describes, as particle diameters, a deodorant for fibers containing α -zirconium phosphate and/or α -titanium phosphate having a median particle diameter of 0.2 to 0.7 μm, a maximum particle diameter of 5.0 μm or less, and a D10 diameter of 0.1 μm or more.

Patent document 1 Japanese patent laid-open No. 2018-178313.

Disclosure of Invention

Technical problem to be solved by the invention

Conventionally, a method of coating zirconium phosphate by post-processing after spinning is known, but there is a problem that the zirconium phosphate is removed by washing or the like and thus the deodorant function cannot be maintained. Further, there are problems such as deterioration of productivity due to the post-processing.

On the other hand, incorporation of inorganic particles such as zirconium phosphate particles into fibers during spinning has advantages such as the following: if a textile is produced using a yarn having various functions such as a deodorizing function by the inorganic particles, the textile can be produced without lowering the productivity of a fiber product having a deodorizing function.

Further, regarding the persistence of the deodorizing function and the like, it is considered that the persistence can be maintained for a longer period of time in the case where inorganic particles are incorporated during spinning as compared with a method of coating zirconium phosphate or the like by post-processing because the inorganic particles are incorporated into the fiber.

In addition, as the spinning speed increases for the purpose of improving productivity in the spinning step, the level of the requirement for removing coarse particles increases. Therefore, the present inventors found the following problems: in the case of conventional inorganic particles for fibers, which cannot suppress the generation of coarse particles in the particle production step, a polymer filter for removing coarse particles causing yarn breakage in the spinning step in which the inorganic particles are incorporated is not sufficient, and the frequency of yarn breakage during spinning increases, resulting in a decrease in productivity in the spinning step.

The present invention aims to provide inorganic particles for fibers which have a low yarn breakage rate during spinning, that is, which have a small number of yarn breakage per unit time, and a method for producing the same.

Technical scheme for solving technical problem

Means for solving the problems include the following aspects.

< 1 > an inorganic particle for fiber, wherein the content of coarse particles having a particle diameter of more than 1.562 μm as measured by an electric induction belt method is 1500 ppm by number or less.

< 2 > an inorganic particle for fiber, wherein the content of coarse particles having a particle diameter of more than 1.562 μm as measured by flow particle image analysis is less than 300 ppm by number.

< 3 > the inorganic particle for fiber according to < 1 > or < 2 >, wherein the inorganic particle for fiber is a zirconium phosphate particle, a titanium phosphate particle, a hydrotalcite particle or a zirconium hydroxide particle.

< 4 > the inorganic particle for fiber according to any one of < 1 > -3 >, wherein the inorganic particle for fiber is a zirconium phosphate particle.

< 5 > the inorganic particles for fiber < 1 > wherein the content of coarse particles having a particle diameter of more than 1.562 μm as measured by flow particle image analysis is less than 300 ppm by number.

< 6 > the inorganic particle for fiber according to any one of < 1 > to < 5 >, wherein the median particle diameter is 0.2 μm to 1.0 μm.

< 7 > the inorganic particle for fiber according to any one of < 1 > to < 6 >, wherein a content of coarse particles having a particle diameter of more than 2.148 μm measured by an inductance-banding method is 5 ppm by number or less.

< 8 > the inorganic particle for fiber according to any one of < 1 > to < 7 >, wherein a coarse particle having a particle diameter of more than 2.148 μm as measured by an inductance banding method is not contained.

< 9 > the inorganic particle for fiber according to any one of < 1 > to < 8 >, wherein the inorganic particle for fiber is a deodorant for fiber.

< 10 > A method for producing inorganic particles for fibers < 1 > -9 >, which comprises a step of removing coarse particles in the inorganic particles by dry classification.

< 11 > the method for producing inorganic particles for fiber < 10 >, wherein the dry classification is performed by a cyclone classifier.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention provides inorganic particles for fibers having a low yarn breakage rate during spinning, and a method for producing the same.

Drawings

Fig. 1 is a diagram showing 9 coarse particles arranged in order from the maximum, which are detected by image analysis in example 1.

Fig. 2 is a diagram showing 9 coarse particles arranged in order from the maximum, which are detected by image analysis in comparative example 1.

Detailed Description

The following description of the constituent elements is based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. Note that in the present specification, "to" is used in a sense including numerical values described before and after the "to" as a lower limit value and an upper limit value.

In the numerical ranges recited in the present specification, the upper limit or the lower limit recited in one numerical range may be replaced with the upper limit or the lower limit recited in another numerical range. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples.

In the present invention, "mass%" is synonymous with "weight%", and "parts by mass" and "parts by weight" are synonymous.

In the present invention, a combination of 2 or more preferred embodiments is a more preferred embodiment.

The present invention will be described in detail below.

(inorganic particles for fiber)

In embodiment 1 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 as measured by the inductance-banding method is 1500 ppm by number or less, preferably 300 ppm by number or less.

In addition, in embodiment 2 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 as measured by a flow particle image analysis method (also referred to as "particle dynamic image analysis method") is less than 300 ppm by number.

In the present specification, the term "inorganic particles for fibers of the present invention" refers to both the 1 st embodiment and the 2 nd embodiment unless otherwise specified.

Further, the inorganic particles for fibers of the present invention are suitably used as a deodorant for fibers.

In the conventional method for producing inorganic particles, for example, even if conditions of the reaction step are optimized, inorganic particles free from coarse particles can be desirably produced, new coarse particles may be generated in the drying step and the pulverizing step which are steps downstream of the reaction step, and inorganic particles from which coarse particles have been removed may not be produced as a final product.

A method of finally removing coarse particles by sieving has also been proposed, but there is a limit to the removal of coarse particles by sieve pores.

It is known that coarse particles contained in ppm order are coarse particles that indirectly reduce coarse particles, for example, coarse particles that cause yarn breakage during spinning of polyester fibers, by concentrating the particle size distribution.

Further, even if the median particle diameter D50 is reduced to reduce coarse particles, it is known that, for example, at the stage of addition or mixing into a polyester resin, particles having small particle diameters are likely to reagglomerate to form coarse particles, resulting in yarn breakage, and that a polymer filter for removing coarse particles increases the differential pressure to deteriorate productivity.

In general, a laser diffraction particle size distribution meter is a measuring instrument that can measure a wide range of particle size distribution and cannot detect ppm-order coarse particles having a particle size in the range of 1.5 μm to 5 μm in number units. Further, the laser diffraction particle size distribution meter has a problem in that a fine technique is developed, and for example, even if the same sample is used, the measurement result varies depending on the manufacturer of the measuring instrument, and the measurement result significantly varies depending on the setting of the measurement condition such as the refractive index.

Conventionally, the removal of coarse particles by classification has been disclosed as a general method, but there is no specific disclosure of how coarse particles are removed to what level by classification, and the precise confirmation of whether coarse particles can be actually removed.

Therefore, for example, no technique for solving the problem of yarn breakage in spinning fibers is currently available.

The present inventors have conducted extensive studies and have found that by adopting the above-mentioned structure, inorganic particles for fibers having a low yarn breakage rate during spinning can be provided.

The mechanism of action of the compound to produce a good effect is not clear, but is presumed as follows.

Since the detection performance is excellent as a method for confirming coarse particles having a particle diameter of more than 1.562 μm by the inductance belt method or the flow particle image analysis method, it is presumed that inorganic particles for fibers having a low yarn breakage rate at the time of spinning can be obtained by adjusting the content of the coarse particles measured by these methods to 1500 ppm or less in the former case and to 300 ppm or less in the latter case.

The inorganic particles for fibers of the present invention will be described in detail below.

The inorganic particles for fibers of the present invention are not particularly limited as long as they are used for fibers, and zirconium phosphate particles, titanium phosphate particles, hydrotalcite particles, zirconium hydroxide particles, alumina particles, aluminum silicate particles, copper silicate particles, zinc silicate particles, manganese silicate particles, cobalt silicate particles or nickel silicate particles are preferred, zirconium phosphate particles, titanium phosphate particles, hydrotalcite particles or zirconium hydroxide particles are more preferred, and zirconium phosphate particles are particularly preferred from the viewpoint of deodorization properties.

The inorganic particles for fibers of the present invention may contain impurities other than those described above, and may contain known additives used for fiber applications.

Among them, the inorganic particles for fibers of the present invention are preferably particles having a content of the inorganic component of 90 mass% or more, more preferably 95 mass% or more, particularly preferably 99 mass% or more.

The method for measuring the particle size of the inorganic particles by the inductive band method of the present invention is performed by the following method.

The measurement was performed by Multisizer 3 manufactured by beckman coulter as a measuring apparatus (coulter counter) by an electric induction band method.

The aperture size was set to 30 μm, about 50000 pieces were measured, the distribution thereof was measured on a number basis, and the content of coarse particles having a particle diameter exceeding 1.562 μm and the like was measured.

The method for measuring the particle size of the inorganic particles by the flow particle image analysis method of the present invention is performed by the following method.

A flow-type particle image analyzer FPIA-3000S manufactured by Sheximexican K.K. (Marknparak division, now Cibacco) was used.

Inorganic particles were added to pure water from which foreign matter was removed by passing through a filter so that the dispersion concentration reached 0.05 mass%, and the mixture was dispersed for 3 minutes by an ultrasonic dispersion apparatus. The obtained dispersion was dropped into the flow particle image analyzer, and about 30000 inorganic particles were measured and analyzed, and the content of coarse particles having a particle diameter of more than 1.562 μm or the like was measured.

The upper limit of the particle size is preferably 100. mu.m.

In embodiment 1 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 as measured by the inductance banding method is 1500 ppm by number or less, preferably 300 ppm by number or less, more preferably 200 ppm by number or less, further preferably 100 ppm by number or less, particularly preferably 50 ppm by number or less, most preferably 25 ppm by number or less, from the viewpoint of yarn breakage suppression.

In embodiment 2 of the inorganic particles for fibers of the present invention, from the viewpoint of yarn breakage suppression, the content of coarse particles having a particle size of more than 1.562 μm as measured by flow particle image analysis is less than 300 ppm, preferably 100 ppm, more preferably 10 ppm, further more preferably 1 ppm, and particularly preferably contains no coarse particles having a particle size of more than 1.562 μm as measured by flow particle image analysis.

From the viewpoint of yarn breakage suppression, the inorganic particles for fibers of the present invention preferably contain 5 ppm by number or less, more preferably 1 ppm by number or less, of coarse particles having a particle diameter of more than 2.148 μm as measured by the inductance banding method, and particularly preferably do not contain coarse particles having a particle diameter of more than 2.148 μm as measured by the inductance banding method.

In addition, from the viewpoint of yarn breakage inhibition, the inorganic particles for fibers of the present invention preferably contain 5 ppm by number or less, more preferably 1 ppm by number or less, of coarse particles having a particle diameter of more than 2.148 μm as measured by flow particle image analysis, and particularly preferably do not contain coarse particles having a particle diameter of more than 2.148 μm as measured by flow particle image analysis.

In addition, from the viewpoint of yarn breakage suppression, 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 electroinduction banding method.

In addition, from the viewpoint of yarn breakage suppression, 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 a flow particle image analysis method.

The inorganic particles for fibers of the present invention preferably have a median particle diameter D50 of 0.1 to 1.2 μm, more preferably 0.2 to 1.0 μm, particularly preferably 0.5 to 0.9 μm, as measured by laser diffraction, from the viewpoint of further exhibiting functional effects such as yarn breakage inhibitory properties and deodorizing effects.

Further, from the viewpoint of further exhibiting functional effects such as yarn breakage suppressing property and deodorizing effect, the cumulative 99.9% by number particle diameter D99.9 measured by the inductance tape method of the inorganic particles for fibers of the present invention is preferably 1.562 μm or less, more preferably 0.5 to 1.55 μm, particularly preferably 1.0 to 1.50 μm.

(method for producing inorganic particles for fiber)

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, and from the viewpoint of the removability of the coarse particles, a method including a step of removing the coarse particles in the inorganic particles by dry classification (also referred to as "dry classification step") is preferred.

The method of classifying the inorganic particles to remove coarse particles may be either dry classification or wet classification. In the wet classification, when the final product is sold as a separate product, a drying step is required after the classification, and even if coarse particles are removed before the drying, coarse particles may be produced again by consolidation and aggregation in the drying step. Therefore, dry fractionation is preferred because it does not require a drying step after fractionation, has low possibility of consolidation and aggregation, and can simplify the production process.

The dry classifier is not limited as long as it can classify coarse particles, and examples thereof include a mechanical classifier and a cyclone classifier. In the mechanical classifier, since the mechanical classifying rotor rotates at a high speed and mechanical accuracy is required to prevent vibration, there is a limit to the classifying point. Specifically, when it is desired to exclude particles having a particle diameter in the range of 1.5 μm to 5 μm as coarse particles, there is a limit to the mechanical classifier, and there is a possibility that the coarse particles cannot be excluded with high accuracy.

In addition, in the classification using the mechanical rotation of the classifying rotor, contamination (mixing-in) of metal due to friction generated by sliding of metal parts may occur. From the above-mentioned viewpoint, it is preferable to perform dry classification by an air classifier (cyclone classifier) using a cyclone which does not have a mechanical rotating part in its structure. For example, a cyclone classifier described in International publication No. 2011/132301 is preferable.

The pressure and amount of the high-pressure gas blown onto the inorganic particles in the dry classification are not particularly limited, but the pressure is preferably from 0.1MPa to 1.0 MPa.

The air volume in dry classification is not particularly limited, but is preferably 1m³10 m/min³In terms of a/minute.

The method for producing inorganic particles for fibers of the present invention may include, for example, a pulverization step of pulverizing inorganic particles or aggregated particles of inorganic particles, and a sieving step of sieving inorganic particles.

The timing of performing the dry classification step is not particularly limited, and may be performed before or after the pulverization step and the sieving step, for example. After the particle size is once adjusted by the pulverizing step and the sieving step, dry classification may be further performed to remove coarse particles.

After the dry classification, the pulverization step and the sieving step may be performed.

In consideration of the possibility of generating new coarse particles in the pulverizing step and the classifying step, the dry classifying step is preferably performed after the pulverizing step and the classifying step.

The classification point in the dry classification step may be appropriately set as needed, and for example, when inorganic particles are added or mixed to the resin forming the fibers, it is preferable to exclude coarse particles having a particle diameter of more than 3 μm, more preferable to exclude coarse particles having a particle diameter of more than 2.148 μm, and particularly preferable to exclude coarse particles having a particle diameter of more than 1.562 μm, from the viewpoint of yarn breakage suppression during spinning, because the monofilament diameter of the fibers is about 10 μm.

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 those prepared from commercially available products or the like, or may be those produced.

The method for producing the inorganic particles is not particularly limited, and known methods can be used.

Hereinafter, a method for producing zirconium phosphate particles will be described 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 Japanese patent laid-open No. Sho 60-103008 or Japanese patent laid-open No. 2008-178313. However, the method for producing zirconium phosphate is not limited to this.

The obtained zirconium phosphate may be dried after solid-liquid separation or may be dried without solid-liquid separation. As a specific method of solid-liquid separation, there is a filter press, a pressure filter or the like, and a water-containing cake (sludge) after solid-liquid separation is dried. As a method for drying the hydrous cake, a paddle dryer, a cone dryer, a vibration dryer, an inverted cone type stirring dryer, or the like can be preferably mentioned. Examples of the method for drying without performing solid-liquid separation include a spray dryer, a pellet fluidized bed dryer, and a pneumatic dryer.

When the zirconium phosphate is subjected to solid-liquid separation, it is in a clay form, has strong adhesiveness, and is not easy to handle, and therefore, it is preferable to obtain zirconium phosphate particles by drying without performing solid-liquid separation.

The dried zirconium phosphate particles may or may not be subjected to crushing, pulverizing or sieving. In order to adjust the particle size to a uniform size, it is preferable to crush or pulverize the particles and then sieve the particles.

In the case where the inorganic particles for fiber of the present invention are kneaded with a resin for raw material for synthetic fiber such as polyester resin by an extruder or the like before spinning, if water remains in the inorganic particles for fiber, the water evaporates during heating and kneading by the extruder, and the resin for raw material may foam. The water content of the inorganic particles for fibers of the present invention is preferably 1 mass% or less, more preferably 0.6 mass% or less, for preventing foaming.

(fiber)

The fiber of the present invention is a fiber containing the inorganic particle for fiber of the present invention, and is preferably a deodorizing fiber containing the inorganic particle for fiber of the present invention.

The method for producing the fiber containing the inorganic particles for fiber of the present invention is not particularly limited, and a known method can be used.

For example, a method of spinning a fiber by mixing the inorganic particles for fiber of the present invention into the fiber may be mentioned.

The fibers of the present invention are preferably resin fibers, more preferably chemical fibers.

As the fiber resin that can be used, any of known chemical fibers can be used.

Preferable specific examples of the material of the chemical fiber include polyester, polyurethane, nylon, rayon, acrylic, vinylon, polypropylene, and the like. Among them, polyester, nylon or acrylic is preferable, and polyester is more preferable.

Further, as preferable specific examples of the polyester, polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, and the like can be mentioned. Among them, polyethylene terephthalate is preferred.

These resins may be homopolymers or copolymers. In the case of the copolymer, the polymerization ratio of each copolymerization component is not particularly limited.

The method for adding the inorganic particles for fibers to the resin of the present invention is not particularly limited, and the inorganic particles for fibers may be added in the polymerization step of the resin, or may be mixed in an extruder using the polymerized resin.

The inorganic particles for fibers of the present invention are suitably used as a deodorant for fiber incorporation.

As a specific method for producing the deodorizing fibers in this case, a method of mixing the inorganic particles for fibers of the present invention into a liquid resin for fibers obtained by melting or a resin solution for fibers obtained by dissolving, and spinning the mixture may be mentioned.

The content of the inorganic particles for fibers of the present invention in the fibers of the present invention is not particularly limited.

In general, if the content is increased, the deodorizing ability can be exerted strongly and continued for a long period of time, but if the content is more than a certain level, the deodorizing effect does not vary greatly, and the content of the inorganic particles for fibers of the present invention in the fibers of the present invention is preferably 0.1 to 3.0 parts by weight, more preferably 0.5 to 2.0 parts by weight, based on 100 parts by weight of the resin, from the viewpoint of the strength of the resin.

The deodorizing fibers using the inorganic particles for fibers of the present invention can be used in various fields requiring deodorizing properties, and can be used for most of fiber products such as underwear, silk stockings, socks, bedclothes, quilt covers, seat cushions, blankets, carpets, curtains, sofas, car seats, air filters, and nursing clothes.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In this example, "%" and "part" mean "% by weight" and "part by weight", respectively, unless otherwise specified.

The size of the coarse particles, the number of coarse particles, the content of coarse particles relative to the effective N number, the measurement of the coarse particles by image analysis, and the yarn breakage rate indicating the yarn breakage frequency in the case of spinning after adding or mixing zirconium phosphate particles to or with a polyester resin were measured by the following methods.

(1) Size of coarse particles and number of coarse particles

The particle size of the zirconium phosphate was measured by an inductance-band method, that is, by using Multisizer 3 manufactured by beckmann coulter, which is a so-called coulter counter.

The aperture size was set to 30 μm, about 50000 pieces were measured, and the distribution thereof was measured on a number basis.

(2) Concentration of coarse particles relative to effective N number

The number of particles was measured by Multisizer 3 manufactured by Beckmann Corp.K., and the cumulative number of particles of 1.562 μm or more and less than 2.148 μm was defined as coarse particles.

The concentration of coarse particles with respect to the number of effective N actually measured was calculated by the following equation.

A cumulative particle number of 1.562 μm or more and less than 2.148 μm ÷ an actually measured effective N number × 1000000 ═ a cumulative coarse particle concentration ppm of 1.562 μm or more and less than 2.148 μm relative to the effective N number

(3) Measurement of coarse particles by flow particle image analysis (also referred to as "particle dynamic image analysis method")

The measurement was performed using FPIA-3000S, manufactured by Sheximexican K.K. (Marknparak division, now, Seebitk corporation) as a flow-type particle image analyzer.

The powder was added to pure water from which foreign matter was removed by passing through a filter under a condition that the dispersion concentration reached 0.05%, and the mixture was dispersed for 3 minutes by an ultrasonic dispersion apparatus. The dispersion was dropped to a flow-type particle image analyzer, and about 30000 particles were measured and analyzed.

The flow particle image analyzer aligns the detected particles from the maximum, and measures the particle size of the large particles and a photograph of the particles.

(4) Number of yarn breaks

A master batch containing 20% of the produced zirconium phosphate particles was prepared based on 100% of a polyester resin (MA 2101M, available from Unigilk corporation, polyethylene terephthalate resin). Subsequently, the master batch was mixed with general polyester resin pellets not containing zirconium phosphate, and adjusted to 2% by weight. The polyester fiber is spun by a multifilament spinning machine at the spinning temperature of 275 ℃ and the spinning speed of 500 m/min for 2 hours, and is stretched at the temperature of 120 ℃ until the elongation reaches 280-320 percent, so that the polyester fiber containing the zirconium phosphate particles is obtained.

In this case, a water-soluble oil (obtained by diluting 10 times with water Delion 6033, manufactured by nippon oil and fat co., ltd.) for spinning of a general polyester fiber was used as the oil.

The continuous spinning was carried out for 2 hours, and the spinning performance was evaluated according to the following evaluation method.

A, the number of broken yarns is 0 times/2 hours

B, the number of yarn breakage is more than 1 time/2 hours and less than 3 times/2 hours

C, the number of broken yarns is more than 3 times/2 hours and less than 6 times/2 hours

D, the number of broken yarns is more than 6 times/2 hours and less than 10 times/2 hours

E, the number of broken yarns is more than 10 times/2 hours

F failure to evaluate

As a reference example, a method for producing zirconium phosphate particles is shown.

(reference example: production of zirconium phosphate particles)

To 6m³3611kg of deionized water and 363kg of 35% hydrochloric acid were charged into the reactor, and 603kg of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium was added thereto, followed by dissolving 250kg of oxalic acid dihydrate. While the solution was sufficiently stirred, 275kg of 75% phosphoric acid was added. It was warmed to 98 ℃ over 2 hours and stirred under reflux for 12 hours. After cooling, the obtained precipitate was sufficiently washed with water and dried at 105 ℃. Crushing the mixture by a crusher. Then, a sieving treatment is performed. The obtained zirconium phosphate particles were measured with an X-ray diffraction apparatus, and as a result, they were confirmed to be α -zirconium phosphate particles.

The α -zirconium phosphate particles were dissolved by heating with hydrofluoric acid and nitric acid, elemental analysis was performed with an Inductively Coupled Plasma (Inductively Coupled Plasma) luminescence analyzer, and thermogravimetric/differential thermal analysis was performed, and as a result, the composition formula was as follows.

Zr_0.99Hf_0.01H_2.03(PO₄)_2.01·0.05H₂O

Example 1

The zirconium phosphate particles prepared in accordance with the reference example were classified by a Classifier (Aerofine Classifier AC-20: manufactured by Nisshin engineering Co., Ltd. (NISSHIN ENGINEERING INC)). The air quantity sucked by the exhaust fan is set to be 2.5m³In terms of a/minute. Here, the air volume sucked by the suction fan corresponds to the air volume of the atmospheric gas sucked from between the guide vanes. The angle of the guide vane is set to 80 ° (tangential direction).

The pressure of the high-pressure gas discharged from the upper gas nozzle was set to 0.7MPa, and the pressure of the high-pressure gas discharged from the lower gas nozzle was set to 0.6 MPa.

The powder before classification was continuously supplied by a constant-volume feeder at 2kg/h for 13 minutes by 478 g.

415g of the classified powder on the finer side was recovered. The yield of the classifier based on the amount charged was 86.8%. Wherein the obtained powder on the finer side after classification is measured by means of a coulter counter.

The aperture size was set to 30 μm, about 50000 pieces were measured, and the distribution thereof was measured on a number basis.

The median particle diameter D50 was 0.731. mu.m, and D99.9 was 1.442. mu.m.

The number of coarse particles having a particle diameter of more than 1.562 μm and not more than 2.148 μm was 15.

In addition, coarse particles having a particle size of more than 2.148 μm were not detected.

The concentration (content) of 51008 effective N numbers relative to the actual measured effective N number is

15 ÷ 51008 × 1000000 ═ 294 ppm by number.

The detailed results of the coarse particles are shown in table 1.

In addition, the particle size was measured by flow particle image analysis. Specifically, particle size measurement was performed using a flow particle image analyzer FPIA-3000S manufactured by shimexican corporation (marvapanca, now abridha). The number of particles measured was 30000. As a result, no coarse particles having a particle diameter of more than 1.562 μm were observed.

The concentration of the compound was 0 ppm by number relative to the number of the particles measured.

The results are shown in tables 1 and 2, and 9 particle diameters from the maximum observed particle size are summarized in table 2, and coarse particles sequentially arranged from the maximum detected by image analysis are shown in fig. 1. In addition, each numerical value shown in FIG. 1 represents the size (unit: μm) of each coarse particle.

Further, the number of yarn breakage was evaluated, and as a result, the number of yarn breakage was 0/2 hours, and very stable spinning was possible.

The evaluation result of the number of yarn breakage was A.

Example 2

The zirconium phosphate prepared in accordance with the reference example was classified by a Classifier (Aerofine Classifier AC-20, manufactured by Nisshin engineering Co., Ltd. (NISSHIN ENGINEERING INC)). The air quantity sucked by the exhaust fan is set to be 2.3m³In terms of a/minute. The air quantity sucked in by the suction fan corresponds to the suction from between the guide vanesThe air volume of the entering normal pressure gas. The angle of the guide vane is set to 90 ° (tangential direction).

The pressure of the high-pressure gas discharged from the upper gas nozzle was set to 0.6MPa, and the pressure of the high-pressure gas discharged from the lower gas nozzle was set to 0.6 MPa.

The powder before classification was continuously supplied at 2kg/h by a quantitative feeder for 15 minutes to 505 g.

387g of the classified powder on the finer side is recovered. The yield of the classifier based on the amount charged was 76.6%.

Wherein the obtained powder on the finer side after classification is measured by means of a coulter counter.

The aperture size was set to 30 μm, about 50000 pieces were measured, and the distribution thereof was measured on a number basis.

Median particle diameter D50 was 0.719 μm and D99.9 was 1.366. mu.m.

The number of coarse particles having a particle diameter of more than 1.562 μm and not more than 2.148 μm was 1.

In addition, coarse particles having a particle size of more than 2.148 μm were not detected.

The concentration (content) of 50969 effective N numbers relative to the actual measured effective N number is

1 ÷ 50969 × 1000000 ═ 20 ppm by number.

The detailed results of the coarse particles are shown in table 1.

Among them, the number of yarn breakage was evaluated, and as a result, the number of yarn breakage was 0/2 hours, and a very stable spinning was possible.

The evaluation result of the number of yarn breakage was A.

Example 3

In example 2, classification was performed under the same conditions except that 3924g of the powder before classification was continuously supplied for 120 minutes at 2kg/h by a quantitative supply device. 2911g of the classified fine powder was collected. The yield of the classifier based on the amount charged was 74.2%.

The obtained powder on the finer side after classification was measured for coarse particles by a coulter counter (Multisizer 3 manufactured by beckman coulter corporation).

The aperture size was set to 30 μm, about 50000 pieces were measured, and the distribution thereof was measured on a number basis.

The median particle diameter D50 was 0.722 μm, D99.9 was 1.406. mu.m.

The number of coarse particles having a particle diameter of more than 1.562 μm and not more than 2.148 μm was 9.

In addition, coarse particles having a particle size of more than 2.148 μm were not detected.

The concentration (content) of 51121 effective N numbers relative to the actually measured effective N number is

9 ÷ 51121 × 1000000 ÷ 176 ppm by number.

The detailed results of the coarse particles are shown in table 1.

Among them, the number of yarn breakage was evaluated, and as a result, the number of yarn breakage was 0/2 hours, and a very stable spinning was possible.

The evaluation result of the number of yarn breakage was A.

Comparative example 1

The zirconium phosphate prepared in the reference example was subjected to measurement of coarse particles without dry classification by a coulter counter (Multisizer 3 manufactured by beckmann coulter co., ltd.).

The aperture size was set to 30 μm, about 50000 pieces were measured, and the distribution thereof was measured on a number basis.

The median particle diameter D50 was 0.760. mu.m, and D99.9 was 1.606. mu.m.

The number of coarse particles having a particle diameter of more than 1.562 μm and not more than 2.148 μm was 77.

In addition, coarse particles having a particle size of more than 2.148 μm were not detected.

The concentration (content) of 51097 effective N numbers relative to the actual measurement is

77 ÷ 51097 × 1000000 ═ 1507 ppm by number.

Further, particle size measurement was performed by image analysis using a flow particle image analyzer FPIA-3000S manufactured by shimexican corporation (marvaphon division, now abrikaga corporation). The number of particles measured was 30000. As a result, 9 coarse particles having a particle size of more than 1.562 μm were observed.

The concentration of the particles to be measured was 9 ÷ 30000 × 1000000 ═ 300 ppm by number.

The results are shown in tables 1 and 2, and 9 coarse particles detected by image analysis are shown in fig. 2 in order from the maximum. In addition, each numerical value shown in FIG. 2 represents the size (unit: μm) of each coarse particle.

Further, the number of yarn breakage was evaluated, and as a result, the number of yarn breakage was 1/2 hours or more and less than 3/2 hours, and several yarn breakage occurred. The result of the evaluation of the number of yarn breaks was B.

Comparative example 2

The powder on the coarse side after dry classification performed in example 1 was collected, and the coarse particles were measured with a coulter counter (Multisizer 3 manufactured by beckmann coulter corporation).

The aperture size was set to 30 μm, about 50000 pieces were measured, and the distribution thereof was measured on a number basis.

The median particle diameter D50 was 0.770. mu.m, and D99.9 was 1.661. mu.m.

The number of coarse particles having a particle diameter of more than 1.562 μm and not more than 2.148 μm was 127.

In addition, coarse particles having a particle size of more than 2.148 μm were not detected.

50953 concentrations (contents) of effective N relative to the actual measurement are

127 ÷ 50953 × 1000000 ═ 2492 ppm by number.

Further, the number of yarn breakage was evaluated, and as a result, yarn breakage occurred frequently. The result of the evaluation of the number of yarn breaks was F.

[ Table 1]

[ Table 2]

In examples 1 and 2, the cumulative number of coarse particles having particle diameters of 1.562 μm or more and less than 2.148 μm was 15 and 1, respectively, from the measurement results of the powder on the finer side after classification, and the coarse particles were less and removed than the 77 particles before classification.

In example 3, even when the classifying treatment amount of example 2 was increased, the number of the cumulative coarse particles having a particle diameter of 1.562 μm or more and less than 2.148 μm was as small as 9, indicating that the coarse particles were removed.

In comparative example 1, zirconium phosphate particles not subjected to classification were measured by a coulter counter, and it was revealed that the number of coarse particles having a particle diameter of 1.562 μm or more and less than 2.148 μm was accumulated to be as many as 77. It was found that the coarse particles were contained in a large amount in the case of the non-classification treatment.

Comparative example 2 is an example in which the coarse particle side after the classification treatment of example 1 was recovered.

Since the particles are coarse particles, the cumulative number of coarse particles having a particle diameter of 1.562 μm or more and less than 2.148 μm is 127 compared with the finer side after the classification treatment, and is more than 15 in the finer side after the classification in example 1. Further, the number of coarse particles was also larger than 77 coarse particles in the case of comparative example 1 in which no classification treatment was performed. This shows that, in example 1, as a result of removing the coarse particles by classification, the coarse particles removed by classification were separated and collected as coarse particles after classification in comparative example 2.

In each measurement, the effective counts of coarse particles are concentrated on about 50000 particles, and therefore the number of coarse particles can be quantitatively compared.

Quantitative comparison of coarse particles can be performed in ppm units as a cumulative coarse particle concentration with respect to the effective N number of particles having a particle diameter of 1.562 μm or more and less than 2.148 μm.

Further, from table 2, in example 1, in the measurement of coarse particles by the flow particle image analyzer, it was found that the maximum coarse particle size detected was 1.494 μm, the particle size was 1.562 μm or less, and coarse particles having a particle size exceeding 1.562 μm were removed.

In contrast, in comparative example 1, the maximum coarse particle size detected in the measurement of coarse particles by the flow particle image analyzer was 9.443 μm, indicating that the coarse particles had a particle size of more than 1.562 μm, and it was found that the coarse particles having a particle size of more than 1.562 μm were not removed and contained because the dry classification was not performed.

As described above, the inorganic particles for fibers of examples 1 to 3, which are the inorganic particles for fibers of the present invention, had a lower number of yarn breaks during spinning than the inorganic particles of comparative examples 1 and 2.

Possibility of industrial utilization

According to the method for producing inorganic particles for fibers of the present invention, it is possible to easily remove a trace amount of coarse particles contained in the ppm range, which cannot be detected by a laser diffraction particle size distribution analyzer.

In addition, the inorganic particles for fiber of the present invention can reduce the frequency of yarn breakage during spinning in the application of mixing into fibers such as polyester fibers, can improve productivity in the spinning process, and are industrially advantageous.

The disclosure of japanese patent application 2019-083181 filed 24.4.2019 is incorporated by reference in its entirety into this specification.

All documents, patent applications, and specifications described in the present specification are incorporated by reference into the present specification as if each document, patent application, and specification were specifically and individually described.