Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

• the present invention relates to a masterbatch, a resin composition, a molded product, and a method for producing the same.
• JTETC Fiber Evaluation Technology Council
• SEK mark anti-virus processing mark
• SIAA Antibacterial Product Technology Council
• Such an antiviral material needs to be fixed to the cloth by using an adhesive (binder) such as a fixing resin, but the antiviral material is maintained even after the cloth is washed (improves the washing resistance). ) Therefore, a large amount of fixing resin is required.
• the fixing resin covers the antiviral material, so that the antiviral activity of the material is inhibited. As a result, there was a problem that sufficient effects could not be produced.
• the problem to be solved by the present invention is the metal compound composite containing the antiviral material, that is, titanium oxide containing crystalline rutyl-type titanium oxide and a divalent copper compound (hereinafter, simply "metal compound"). It is an object of the present invention to provide a molded product containing (also referred to as “complex") and having excellent antiviral activity, and a method for producing the same with good processability. Another object to be solved by the present invention is to provide a masterbatch, a resin composition, and a method for producing the same, which can provide such a molded article and a method for producing the same.
• the present inventors produced a masterbatch after removing coarse particles in advance by crushing and classifying the metal compound composite, and further, using a resin for dilution in the masterbatch. They have found that a molded product having excellent antiviral activity and a method for producing the same can be provided by diluting the resin composition and further to a molded product, and have completed the present invention.
• a method for producing a resin composition which comprises a step (2) of melt-kneading the thermoplastic resin (c) in a batch.
• the metal compound composite (b) contains titanium oxide containing crystalline rutile-type titanium oxide and having a specific surface area of 3 m 2 / g or more, and a divalent copper compound, and has a maximum particle size of 45 ⁇ m.
• the present invention relates to a method for producing a resin composition, which comprises a range of less than.
• the present invention also relates to a method for producing the resin composition, wherein the content of the crystalline rutile-type titanium oxide in the titanium oxide is 50 mol% or more and the content of anatase-type titanium oxide is less than 50 mol%. ..
• the present invention in the X-ray diffraction pattern in which the crystalline rutile-type titanium oxide plots the diffraction line intensity with respect to the diffraction angle 2 ⁇ by Cu—K ⁇ rays, the half-value full width of the strongest diffraction peak corresponding to the rutile-type titanium oxide.
• the present invention relates to a method for producing the resin composition, wherein the temperature is 0.65 degrees or less.
• the metal compound composite (b) is melt-kneaded in the range of 10 to 300 parts by mass with respect to 100 parts by mass of the thermoplastic resin (a). Regarding the manufacturing method.
• the present invention also relates to a method for producing the resin composition in which 100 parts by mass of the masterbatch is melt-kneaded in the range of 50 to 5000 parts by mass of the thermoplastic resin (c) in the step (2).
• the present invention also relates to a method for producing the resin composition, wherein the thermoplastic resin (a) is at least one selected from the group consisting of polyester, polyamide, polyolefin, thermoplastic elastomer and silicone resin.
• the thermoplastic resin (a) is at least one selected from the group consisting of polyester, polyamide, polyolefin, thermoplastic elastomer and silicone resin.
• the present invention is a master batch containing the metal compound composite (b) in the range of 10 to 300 parts by mass with respect to 100 parts by mass of the thermoplastic resin (a).
• the metal compound composite (b) in the master batch contains titanium oxide containing crystalline rutile-type titanium oxide and having a specific surface area of 3 m 2 / g or more, and a divalent copper compound, and has a maximum. It relates to a master batch, characterized in that the particle size is in the range of less than 45 ⁇ m.
• the present invention also relates to the masterbatch in which the content of the crystalline rutile-type titanium oxide in the titanium oxide is 50 mol% or more and the content of anatase-type titanium oxide is less than 50 mol%.
• the half-value full width of the strongest diffraction peak corresponding to the rutile-type titanium oxide is titanium oxide having a temperature of 0.65 degrees or less.
• thermoplastic resin (a) is at least one selected from the group consisting of polyester, polyamide, polyolefin, thermoplastic elastomer and silicone resin.
• the present invention also relates to a resin composition obtained by melt-kneading a thermoplastic resin (c) into the masterbatch.
• the present invention also relates to a method for producing a resin composition, which comprises a step of melt-kneading the thermoplastic resin (c) in the master batch.
• the present invention also relates to a molded product obtained by molding the resin composition.
• the present invention also relates to a method for producing a molded product in which the resin composition is melt-molded.
• a method for producing a molded product which further comprises a step (2) of melt-kneading the thermoplastic resin (c) and a step (3) of melt-molding the resin composition obtained in the step (2) in a batch.
• the metal compound composite (b) contains titanium oxide containing crystalline rutile-type titanium oxide and having a specific surface area of 3 m 2 / g or more, and a divalent copper compound, and has a maximum particle size of 45 ⁇ m.
• the present invention relates to a method for producing a molded product, which comprises a range of less than.
• the present invention also relates to a method for producing the molded product, wherein the content of the crystalline rutile-type titanium oxide in the titanium oxide is 50 mol% or more and the content of anatase-type titanium oxide is less than 50 mol%.
• the present invention in the X-ray diffraction pattern in which the crystalline rutile-type titanium oxide plots the diffraction line intensity with respect to the diffraction angle 2 ⁇ by Cu—K ⁇ rays, the half-value full width of the strongest diffraction peak corresponding to the rutile-type titanium oxide
• the present invention relates to a method for producing the molded product, wherein the temperature is 0.65 degrees or less.
• the metal compound composite (b) is melt-kneaded in the range of 10 to 300 parts by mass with respect to 100 parts by mass of the thermoplastic resin (a) to produce the molded product. Regarding the method.
• the present invention also relates to a method for producing the molded product, in which 100 parts by mass of the masterbatch is melt-kneaded in the range of 50 to 5000 parts by mass of the thermoplastic resin (c) in the step (2).
• the present invention also relates to a method for producing the molded product, wherein the thermoplastic resin (a) is at least one selected from the group consisting of polyester, polyamide, polyolefin, thermoplastic elastomer and silicone resin.
• the present invention also relates to a method for producing the molded product, wherein the thermoplastic resin (c) is at least one selected from the group consisting of polyester, polyamide, polyolefin, thermoplastic elastomer and silicone resin.
• the present invention also relates to a method for producing a molded product, wherein the melt molding in the step (3) is a spinning step or a film or sheet forming step.
• the antiviral active material that is, a molded product containing a metal compound composite containing titanium oxide containing crystalline rutile-type titanium oxide and a divalent copper compound and having excellent antiviral activity. It is possible to provide a method for producing it with good processability. Further, according to the present invention, it is possible to provide a master batch, a resin composition, and a method for producing the same, which can provide such a molded product and a method for producing the same.
• the master batch of the present invention is a master batch containing the metal compound composite (b) in the range of 10 to 300 parts by mass with respect to 100 parts by mass of the thermoplastic resin (a), and the metal compound in the master batch.
• the composite (b) contains titanium oxide having a specific surface area of 3 m 2 / g or more containing crystalline rutile type titanium oxide and a divalent copper compound, and has a maximum particle size of less than 45 ⁇ m. It is characterized by being.
• the masterbatch of the present invention has a step (1) of producing a masterbatch by melting and kneading the thermoplastic resin (a) and the metal compound composite (b) as essential raw materials in advance.
• thermoplastic resin (a) used in the present invention will be described.
• the thermoplastic resin (a) used in the present invention is not particularly limited as long as the effects of the present invention are not impaired. Examples thereof include rubber-reinforced styrene resin, polyether ketone resin, polyether resin, polyimide resin, polyarylene sulfide resin, and polyarylene ether resin, among which polyester resin, polycarbonate resin, polyamide resin, polyolefin resin, and thermoplastic elastomer. , Silicone resin is preferred.
• polyester resin it is more preferable to use aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.
• polyamide resin examples include nylon 6 (also referred to as “poly (caprolactam)”), nylon 11 (also referred to as “poly (11-aminoundecanoic acid)”), nylon 12 (“poly (lauryl lactam)” or “poly (12)”.
• nylon 6.6 also called “poly (hexamethylene adipamide)
• nylon 6.9 poly (hexamethylene azelamide) or poly (hexamethylene nonandiamide)
• nylon 6.10 also referred to as “poly (hexamethylene sebacamide)” or “poly (hexanemethylene decandamide)
• nylon 6.12 also referred to as “poly (hexamethylene dodecanodiamide)
• Nylon 4 also called “poly ( ⁇ -butyrolactam)
• nylon 7 also called “poly (7-aminohebutanoic acid)” or “poly (7-aminocaprylic acid)
• nylon 8 Poly (8-aminocaprylic acid) ”or“ poly (8-aminooctanoic acid)
• nylon 10,6 poly (decamethylene / adipamide)
• PARNS partially aromatic nylon
• the metal compound complex (b) used in the present invention will be described.
• the metal compound composite (b) used in the present invention contains titanium oxide containing crystalline rutile-type titanium oxide and having a specific surface area in the range of 3 m 2 / g or more, and a divalent copper compound, and has the maximum particles.
• the diameter is in the range of less than 45 ⁇ m.
• the titanium oxide used in the metal compound complex (b) contains crystalline rutile-type titanium oxide.
• the crystalline rutile-type titanium oxide is an X-ray diffraction pattern in which the diffraction line intensity with respect to the diffraction angle 2 ⁇ by Cu—K ⁇ rays is plotted, and the half-value full width of the strongest diffraction peak corresponding to the rutile-type titanium oxide is 0. It means titanium oxide of .65 degrees or less. If the full width at half maximum is larger than 0.65 degrees, the crystallinity deteriorates and the antiviral property in a dark place is not sufficiently expressed. From this point of view, the full width at half maximum is preferably 0.6 degrees or less, more preferably 0.5 degrees or less, still more preferably 0.4 degrees or less, and even more preferably 0.35 degrees. ..
• the content of crystalline rutile-type titanium oxide in titanium oxide (hereinafter, may be referred to as "rutileization rate”) is preferably 50 mol% or more. When the content is 50 mol% or more, the antiviral activity tends to be sufficient. From this point of view, the rutileization rate is preferably 90 mol% or more, more preferably 94 mol% or more. This rutileization rate is a value measured by XRD as described later.
• anatase conversion rate is preferably low, and the anatase conversion rate is preferably less than 50 mol%. It is preferably less than 10 mol%, more preferably less than 7 mol%, and particularly preferably 0 mol% (ie, it does not contain anatase-type titanium oxide). This anataseization rate is also a value measured by XRD as well as the rutileization rate.
• the specific surface area of titanium oxide containing crystalline rutile-type titanium oxide is in the range of 3 m 2 / g or more. When it is 3 m 2 / g or more, the specific surface area is large, so that the frequency of contact with viruses, bacteria and organic compounds is high, and the antiviral and antibacterial properties are excellent, and this tendency is further increased, which is preferable.
• the range is 5 m 2 / g or more, more preferably 8 m 2 / g or more.
• the upper limit of the specific surface area is not specified, it is preferably in the range of 200 m 2 / g or less, more preferably 100 m 2 / g or less, and more preferably 70 m 2 / g or less from the viewpoint of excellent handleability. ..
• the specific surface area is a value related to the primary particles measured by the BET method by nitrogen adsorption.
• Titanium oxide includes those produced by the vapor phase method and those produced by the liquid phase method, and either of them can be used, but titanium oxide produced by the vapor phase method is more preferable.
• the vapor phase method is a method having a step of obtaining titanium oxide by a vapor phase reaction with oxygen using titanium tetrachloride as a raw material. Titanium oxide obtained by the vapor phase method has a uniform particle size, and at the same time, has high crystallinity because it undergoes a high-temperature process during production. As a result, the obtained photocatalyst has good antiviral properties, organic compound decomposability and antibacterial properties in bright and dark places.
• the liquid phase method is a method for obtaining titanium oxide by hydrolyzing or neutralizing titanyl sulfate obtained from a liquid in which a raw material ore such as ilmenite ore is dissolved. More specifically, there are two types of liquid phase methods, a sulfuric acid method and a chlorine method, and in the present invention, titanium oxide produced by any of the production methods can be preferably used.
• the sulfuric acid method uses ilmenite ore or titanium slag as a raw material, dissolves it in concentrated sulfate to separate iron as iron sulfate, and hydrolyzes the separated solution to obtain a hydroxide precipitate. The precipitate is calcined to take out rutile-type titanium oxide.
• synthetic rutile or natural rutile is used as a raw material, which is reacted with chlorine gas at a high temperature of 950 ° C. or higher to synthesize titanium tetrachloride, and if necessary, a rectification treatment is performed. This is a process of extracting rutile-type titanium oxide by oxidizing it with oxygen.
• the titanium oxide produced by the liquid phase method contains zirconium, niobium, etc. derived from impurities in ilmenite ore and titanium slag as its products.
• the vapor phase method has a step of purifying titanium tetrachloride to remove impurities, titanium oxide hardly contains these impurities.
• the metal compound complex (b) used in the present invention contains a divalent copper compound.
• this divalent copper compound By combining this divalent copper compound with titanium oxide containing the above-mentioned crystalline rutile-type titanium oxide, not only excellent antiviral properties but also antibacterial properties are sufficiently exhibited. Further, since this divalent copper compound has less discoloration due to oxidation or the like than the monovalent copper compound, discoloration is suppressed when this divalent copper compound is used.
• the divalent copper compound is not particularly limited, and examples thereof include one or two divalent copper inorganic compounds and divalent copper organic compounds.
• Divalent copper inorganic compounds include copper sulfate, copper nitrate, copper iodide, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amidosulfate and copper ammonium chloride, copper pyrophosphate, and copper carbonate. It is selected from the group consisting of an inorganic acid salt of divalent copper, a halide of divalent copper composed of copper chloride, copper fluoride and copper bromide, and a group consisting of copper oxide, copper sulfide, azulite, malakite and copper azide. Species or two or more species are mentioned.
• divalent copper organic compound examples include a divalent copper carboxylate.
• divalent copper carboxylate examples include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper capricate, and mistinic acid.
• divalent copper organic compounds selected from the group consisting of oxine copper, acetylacetone copper, ethylacetacetate copper, trifluoromethanesulfonate copper, phthalocyanine copper, copper ethoxydo, copper isopropoxide, copper methoxyde, and copper dimethyldithiocarbamate.
• oxine copper acetylacetone copper
• ethylacetacetate copper trifluoromethanesulfonate copper
• phthalocyanine copper copper ethoxydo
• copper isopropoxide copper methoxyde
• copper dimethyldithiocarbamate copper dimethyldithiocarbamate.
• divalent copper compounds preferably one or more of copper oxide, a halide of divalent copper, an inorganic acid salt of divalent copper and a carboxylate of divalent copper, for example, divalent copper.
• divalent copper preferably one or more of copper oxide, a halide of divalent copper, an inorganic acid salt of divalent copper and a carboxylate of divalent copper, for example, divalent copper.
• halides, divalent copper inorganic acid salts and divalent copper carboxylates preferably one or more of copper oxide, a halide of divalent copper, an inorganic acid salt of divalent copper and a carboxylate of divalent copper, for example, divalent copper.
• halides, divalent copper inorganic acid salts and divalent copper carboxylates preferably one or more of copper oxide, a halide of divalent copper, an inorganic acid salt of divalent copper and a carboxylate of divalent copper.
• examples of the divalent copper compound include a divalent copper compound represented by the following general formula (1).
• X is an anion, preferably a halogen such as Cl, Br, I, a conjugate base of a carboxylic acid such as CH 3 COO, or an inorganic acid such as NO 3 , (SO 4 ) 1/2. Conjugate base, or OH.
• divalent copper compounds a divalent copper inorganic compound is more preferable, and copper oxide is further preferable, from the viewpoint of less impurities and economic viewpoint. Further, a divalent copper compound represented by the above general formula (1) is also preferable.
• the divalent copper compound may be anhydrous or hydrated.
• the copper equivalent content of the divalent copper compound is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide.
• it is 0.01 part by mass or more, not only antiviral property but also antibacterial property becomes good.
• the amount is 20 parts by mass or less, the surface of titanium oxide is prevented from being coated and the antiviral property is satisfactorily exhibited, and the antiviral property can be improved with a small amount, which is economical.
• the copper equivalent content of the divalent copper compound is more preferably 0.1 part by mass or more, still more preferably 0.3 part by mass or more, and preferably 20 parts by mass with respect to 100 parts by mass of titanium oxide.
• the range is more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.
• the copper equivalent content of the divalent copper compound with respect to 100 parts by mass of this titanium oxide can be calculated from the charged amount of the raw material of the divalent copper compound and the raw material of titanium oxide.
• the metal compound composite (b) used in the present invention contains titanium oxide containing crystalline rutile-type titanium oxide and a divalent copper compound as essential components, but does not impair the object of the present invention. It may contain other arbitrary components.
• the content of the essential component in the metal compound complex (b) is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 95% by mass or more. It is 99% by mass or more, and particularly preferably 100% by mass.
• the metal compound composite (b) used in the present invention is excellent in dispersibility in the master batch, the resin composition and the molded product, the maximum particle size is less than 45 ⁇ m as a raw material for producing the master batch.
• the range is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less.
• the captured particle size is preferably 45 ⁇ m. preferably 20 [mu] m, more preferably a rate of 700 cm 3/1 hr at 20 ° C. or higher temperature higher than the thermoplastic resin (a) melting point of the component by a single-screw extruder of filtration test (diameter 25mm with 10 ⁇ m filter It can be passed through at a ratio of 5 MPa / 1 kg or less in (melt extrusion with), which is not only excellent in productivity, but also the resin composition and molded product obtained via such a masterbatch are also the metal compound.
• the composite (b) being contained with good dispersibility, not only is it less likely that thread breakage or breakage will occur during processing into threads with low fineness or processing into thin films, but also workability will be improved.
• the dispersibility of the metal compound complex (b) By improving the dispersibility of the metal compound complex (b), more antiviral active surfaces can be exposed on the surface of the molded product, and antiviral activity and antibacterial activity can be improved.
• the method for producing the metal compound complex (b) used in the present invention is not particularly limited, and examples thereof include the following two methods ⁇ 1> and ⁇ 2>.
• the metal compound composite (b) used in the present invention is pulverized by pulverizing the obtained mixture after a mixing step of mixing titanium oxide containing crystalline rutyl-type titanium oxide and a divalent copper compound raw material. It can be produced through a process and a production process having a classification process for classifying the pulverized product. Further, a heat treatment step of heat-treating the mixture obtained by this mixing step may be further carried out, and then a pulverization step and a classification step may be carried out.
• the mixture can also be obtained by suspending titanium oxide in an aqueous solution of a copper compound and adsorbing it.
• the metal compound complex (b) can be produced by the method described in Japanese Patent No. 5343176.
• the crushing step and the classification step are performed by using a crusher or the like to crush the particles so that the average particle size is in the range of 1 [ ⁇ m] or more and 50 [ ⁇ m] or less, and then sieve. It can be obtained by classifying using.
• a generally used standard sieve may be used, and as the size of the opening, 45 [ ⁇ m] or 25 [ ⁇ m] may be selected and used according to the maximum particle size. ..
• the metal compound composite (b) used in the present invention is a mixing step of mixing titanium oxide containing crystalline rutyl-type titanium oxide, a divalent copper compound or a precursor thereof, water, and an alkaline substance. It can also be produced through a production process having a separation step of separating the liquid into a solid content and a liquid phase component. Further, if necessary, the solid content obtained through the separation step is washed with water, crushed, and classified, and after that, titanium oxide containing crystalline rutyl-type titanium oxide and a divalent copper compound raw material are used. Can also be manufactured through a manufacturing step including a step of heat-treating the solid content from the viewpoint that the solids can be firmly bonded to each other.
• CuX 2 (2) (In formula (2), X represents a halogen atom, CH 3 COO, NO 3 or (SO 4 ) 1/2 .)
• the X in the formula (2) is more preferably a halogen atom, and even more preferably a chlorine atom.
• the amount of the divalent copper compound or its precursor used in the mixing step is preferably 0.01 part by mass or more, more preferably 0.1 part by mass with respect to 100 parts by mass of the titanium oxide. It is in the range of parts or more, more preferably 0.3 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.
• the water is a solvent in the mixing step, and water alone is preferable, but other solvents may be contained if necessary.
• the other solvent for example, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; dimethylformamide and tetrahydrofuran can be used. These solvents may be used alone or in combination of two or more.
• the amount of water used in the mixing step is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and further preferably 100 parts by mass or more with respect to 100 parts by mass of the titanium oxide.
• the range is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less.
• alkaline substance for example, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, a basic surfactant and the like can be used.
• sodium hydroxide is preferably used.
• the alkaline substance is preferably added as a solution from the viewpoint of easy control of the reaction, and the concentration of the alkaline solution to be added is preferably 0.1 mol / L or more, more preferably 0.3 mol / L or more on the right side, and further.
• the range is preferably 0.5 mol / L or more, and preferably 5 mol / L or less, more preferably 4 mol / L or less, still more preferably 3 mol / L or less.
• the titanium oxide, the divalent copper compound or its precursor, water, and an alkaline substance may be mixed.
• the titanium oxide is first mixed with water and if necessary. Then, the divalent copper compound or a precursor thereof is mixed and stirred, and then an alkaline substance is added and stirred.
• the divalent copper compound or the divalent copper compound derived from the precursor thereof is supported on the titanium oxide.
• the total stirring time in the mixing step is not particularly limited, but for example, 5 minutes or more is preferable, 10 minutes or more is more preferable, 120 minutes or less is preferable, and 60 minutes or less is more preferable.
• the temperature during the mixing step is not particularly limited, and examples thereof include a range of room temperature or higher to 70 ° C. or lower.
• the titanium oxide, the divalent copper compound or its precursor, and water are mixed and stirred, and then the alkaline substance is mixed, because the support of the divalent copper compound on the titanium oxide is good.
• the pH of the mixture after stirring is not particularly limited as long as it is basic, but is preferably 8 or more, more preferably 9.0 or more, and preferably 11 or less, more preferably 10.5 or less. Is the range of.
• the mixed liquid can be separated as a solid content.
• the method for performing the separation include filtration, sedimentation separation, centrifugation, evaporation and drying, and the like, but filtration is preferable.
• the separated solid content may then be washed with water, if necessary, and further crushed, classified, or the like in the same manner as in ⁇ 1>.
• the divalent copper compound supported on the titanium oxide or a divalent copper compound derived from a precursor thereof can be more firmly bonded to the solid. It is preferable to heat the minutes.
• the heat treatment temperature is preferably 150 ° C. or higher, more preferably 250 ° C. or higher, and preferably 600 ° C. or lower, more preferably 450 ° C. or lower.
• the heat treatment time is not particularly limited, but is preferably in the range of 1 hour or more, more preferably 2 hours or more, and preferably 10 hours or less, more preferably 5 hours or less.
• the metal compound complex (b) can be obtained by the above production method of ⁇ 1> or ⁇ 2>.
• the amount of the divalent copper compound supported on the titanium oxide is in the range of 0.01 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the titanium oxide, which includes antiviral properties. It is preferable from the viewpoint of photocatalytic activity.
• the amount of the divalent copper compound carried can be adjusted by adjusting the amount of the divalent copper compound or its raw material used in the mixing step. The method for measuring the amount of the divalent copper compound supported will be described in Examples described later.
• the composition ratios of the thermoplastic resin (a) and the metal compound complex salt (b) contained in the master batch used in the present invention are excellent in dispersibility and antiviral property in the molded product obtained via the master batch.
• the metal compound composite (b) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 25 parts by mass or more, based on 100 parts by mass of the thermoplastic resin (a). In consideration of suppression of blocking and cost merit during transportation, the range is preferably 300 parts by mass or less, more preferably 150 parts by mass or less, and further preferably 100 parts by mass or less.
• the masterbatch of the present invention may contain various known additives as long as the effects of the present invention are not impaired.
• various additives include halogen-based flame retardants, nitrogen-based flame retardants, phosphate ester-based flame retardants, inorganic flame retardants such as metal hydroxides and oxides, and organic phosphate metal salts such as silicone flame retardants (b).
• Antioxidants such as hindered phenol compounds, hydroquinone compounds, phosphite compounds and their substitutes, resorcinol compounds, salicylate compounds, benzotriazole compounds, benzophenone compounds, Weather resistant agents such as hindered amine compounds, mold release agents or lubricants such as aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisurea compounds and polyethylene wax, pigments such as phthalocyanine and carbon black, niglosin, aniline black and the like.
• Dyes crystal nucleating agents such as talc, silica, kaolin, clay, plasticizing agents such as octyl p-oxybenzoate, N-butylbenzene sulfonamide, etc., alkyl sulfate type anionic antistatic agents, quaternary ammonium Antistatic agents such as salt-type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, antistatic agents such as betaine amphoteric antistatic agents, graphite, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate.
• Antimon oxide Aluminum oxide, Zinc oxide, Iron oxide, Zinc sulfide, Zinc, Lead, Nickel, Aluminum, Iron, Stainless steel, Bentnite, Montmorillonite, Synthetic mica, etc.
• reinforcing materials such as glass fibers, glass flakes, carbon fibers, boron nitride, potassium titanate, and aluminum borate.
• the blending amount thereof is not particularly limited as long as the effects of the present invention are not impaired, but the total mass of the thermoplastic resin (a) and the metal compound composite (b) is 100 mass.
• the type and amount of these additives preferably in the range of 0.1 part by mass or more and 300 parts by mass or less, the desired function can be freely adjusted.
• the masterbatch of the present invention can be produced by melting and kneading the thermoplastic resin (a) and the metal compound composite (b) in advance as essential raw materials.
• the antiviral masterbatch of the present invention can be produced by a method having a step of blending a thermoplastic resin (a) and a metal compound composite (b) and melt-kneading them. More specifically, each of the above-mentioned components is blended so that the thermoplastic resin (a) and the metal compound composite (b) have a predetermined blending amount, and if necessary, a V-type blender, a ribbon blender, and a henshell are blended.
• the resin set temperature is set using a known mixer such as a single-screw extrusion type kneader, an open roll mixer, a pressurized kneader, a Banbury mixer, and a twin-screw extrusion type kneader. Melt and knead above the melting point. Of these, the twin-screw extrusion type kneader is preferable in terms of kneading property and productivity.
• the master batch of the present invention can be obtained by processing into pellets or the like according to a conventional method.
• the metal compound complex (b) may be an aqueous dispersion containing the metal compound complex (b). That is, the antiviral master batch of the present invention further mixes the metal compound complex (b), the dispersant, and water in advance to obtain an aqueous dispersion containing the metal compound complex (b). It is produced by a method having a step (I) of preparing, and a step (II) of blending the metal compound composite (b) with a thermoplastic resin (a) as the aqueous dispersion and melt-mixing the mixture. You can also.
• an anionic, nonionic, cationic, amphoteric or other surfactant can be used as the dispersant.
• a comb-shaped structure polymer compound obtained by adding polyester to polyethyleneimine, an alkylamine derivative of an ⁇ -olefin maleic acid polymer, and the like can be mentioned.
• Specific examples thereof include the Sol Spurs series (LUBRIZOL), the Azisper series (Ajinomoto), and the Homogenol series (Kao).
• BYK series (Big Chemie), EFKA series (EFKA) and the like can also be used as appropriate.
• the aqueous dispersion used in the present invention makes it possible to disperse the metal compound complex (b) in water in the presence of such a dispersant.
• the blending amount of the dispersant is not particularly limited, but from the viewpoint of excellent dispersibility, it is preferably 1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the metal compound composite (b). It may be in the range of 10 parts by mass or more, preferably 100% by mass or less, and more preferably 50% by mass or less.
• the blending amount of the water is not particularly limited, but from the viewpoint of excellent dispersibility, the total amount of the metal compound complex (b), the dispersant and water (that is, the aqueous dispersion) is relative to the total amount.
• the metal compound composite (b) may be appropriately adjusted to be in the range of preferably 1% by mass or more, more preferably 10% by mass or more, preferably 80% by mass or less, more preferably 50% by mass or less. ..
• the aqueous dispersion prepared in the step (I) is blended so that the thermoplastic resin (a) and the metal compound composite (b) have a predetermined blending amount, and the resin set temperature is adjusted.
• the thermoplastic resin (a) is melted and kneaded more than melted.
• a kneader such as an extruder (single-screw extruder, twin-screw extruder), kneader, or Banbury mixer can be used.
• the kneading extruder is capable of continuous kneading. Is preferable.
• the master batch of the present invention can be obtained by processing into pellets or the like according to a conventional method.
• the resin composition of the present invention is obtained by adding a thermoplastic resin (c) as a diluting resin to the above masterbatch and melt-kneading it.
• a thermoplastic resin (c) as a diluting resin
• melt-kneading it By obtaining the resin composition via the masterbatch in this way, the metal compound complex (b), which is an antiviral component, can be stably and uniformly dispersed, and can be added at a higher concentration. It can impart an excellent antiviral effect to the body.
• thermoplastic resin (c) used in the present invention examples include the same as the thermoplastic resin (a).
• the same type of resin is used as the thermoplastic resin (a) and the thermoplastic resin (c) depending on the purpose.
• different types of resins may be used, it is preferable to use the same type of resin from the viewpoint of compatibility.
• the above-mentioned masterbatch of the present invention and the thermoplastic resin (c) for dilution are heated with respect to 100 parts by mass of the masterbatch.
• the plastic resin (c) is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, further preferably 500 parts by mass or more, preferably 5000 parts by mass or less, more preferably 3000 parts by mass or less, still more preferably 2000 parts by mass or more. It may be adjusted so as to be within the range of parts by mass or less, and melt-kneaded.
• the method of melt-kneading is not particularly limited, and for example, a method similar to the method for producing the masterbatch can be adopted.
• the resin composition obtained by melt-kneading is then directly or once processed into pellets or the like according to a conventional method, kneaded in a molding machine, and subjected to extrusion molding, injection molding, calendar molding, hollow molding, vacuum molding.
• a resin molded body is manufactured by various known molding methods such as molding and pressure molding.
• the resin composition of the present invention is known as long as the effects of the present invention are not impaired.
• Various additives can also be blended. Examples of the various additives include those similar to the various additives that can be blended in the sex masterbatch.
• the molded product of the present invention is extremely excellent in antiviral and antibacterial properties, and can be used in applications requiring these activities. Therefore, the molded product of the present invention is suitably used for applications such as films, sheets, fibers, and tubes, and a plurality of films or sheets are laminated to form a multilayer film or a multilayer sheet, or a fabric in which fibers are woven. Further, it can be applied to various molded products such as injection molding, compression molding, extrusion molding, drawing molding, blow molding, and transfer molding.
• a three-dimensional object is formed by using a Fused Deposition Modeling (FDM) method, a stereolithography method (STL), a Selective Laser Sintering method (SLS), an inkjet method, an inkjet powder lamination method, or the like. It is also possible to model.
• FDM Fused Deposition Modeling
• STL stereolithography method
• SLS Selective Laser Sintering method
• a modeling material based on the resin composition of the present invention is melted at a high temperature equal to or higher than the melting temperature of the resin, and the molten modeling material is extruded from a nozzle of a head portion to form a model, and a plurality of layers are stacked to form a three-dimensional object. Can be modeled.
• the form of the cloth may be any form such as a woven fabric, a knitted fabric, and a non-woven fabric. Further, if necessary, the fabric may be colored with a disperse dye, an acid dye, a direct dye, a reactive dye, a pigment or the like.
• the fabric of the present invention can be used for various textile products, for example, clothing products for general use, inner wear, sports, medical use, bedding materials such as duvet covers and sheets, curtains, carpets, chairs, etc. Interior products such as cushion covers and wallpaper, industrial materials such as tent sheets, flags and curtains, seat materials for transportation vehicles such as automobiles, aircraft and railroad vehicles, sanitary materials, textile materials for air treatment, and water. It can be used as a fiber material for processing.
• molded products not only are they processed and used for food packaging containers, bathtubs, fittings, housing applications such as registers, personal computers, smartphones, etc., but also for stents and coil embolization. It can also be applied to medical applications such as children, catheter tubes, syringes (needle, body), shunt tubes, drain tubes, and implant medical devices.
• the fiber diameter (number average fiber diameter) obtained by melt-spinning the resin composition of the present invention varies depending on the application and can be any diameter, but the smaller the fiber diameter, the more antiviral activity. It is preferably in the range of 100 ⁇ m or less, more preferably 40 ⁇ m or less, further preferably 20 ⁇ m or less, particularly preferably 10 ⁇ m or less, and the lower limit is not limited, but is preferably 0.01 ⁇ m or more, more preferably. Is in the range of 0.1 ⁇ m or more, more preferably 1 ⁇ m or more.
• ultrafine fibers such as fibers in the range of 8 ⁇ m or less (referred to as microfibers in the present invention) are particularly preferable because they tend to have a large surface area and high antiviral activity.
• the fiber length is also not limited, and may be a so-called filament (long fiber) having a long fiber length or a so-called staple (short fiber) having a short fiber length.
• the thickness of the sheet or film obtained by molding the resin composition of the present invention into a sheet or film may vary depending on the intended use and may be any thickness, but is preferably 1 ⁇ m or more.
• the range is preferably 3 ⁇ m or more, preferably 200 ⁇ m or less, and more preferably 150 ⁇ m or less.
• sheet or film in the present invention is not intended to strictly distinguish between a sheet and a film, but is used to clarify that both are included, and as long as it has the characteristics of the present invention, it is a sheet.
• the film can be interpreted as broadly as possible, and the term sheet shall include what is referred to as a plate or plate as long as it has the characteristics of the present invention. Even so, when it is necessary to distinguish between a sheet and a film, the sheet is usually used when the thickness exceeds about 0.5 mm in the above range, and the film is usually used when the thickness is about 500 ⁇ m. Can be used for up to.
• the metal compound composite (b) used in the present invention is a particle of a metal compound, and basically changes in the range of the maximum particle size even in melt kneading with the thermoplastic resin (a) and the thermoplastic resin (c).
• the maximum particle size in the resin composition and molded product produced through the master batch is the same as above, but when the maximum particle size exceeds the above range, the maximum particle size is in the above range. It is preferable to adjust the melt-kneading conditions such as shearing force and filter installation so as to be.
• the maximum particle size of the metal compound complex (b) in the resin composition and molded article of the present invention can be in the range of less than 45 ⁇ m. More preferably, after pressing the resin composition or molded product into a film with a preparation, a particle image is obtained by observation with an optical microscope (magnification: 200 times), and at least 1000 particles (primary particles) randomly selected are obtained. When the particle size (equivalent to a circle) is measured for each of the particles (which may or may contain secondary particles), the number of particles of the metal compound composite (b) having a maximum particle size of 20 ⁇ m or more is 5 or less. The range is, and particularly preferably one or less.
• a molded body obtained by melt-molding the resin composition of the present invention is a metal having a maximum particle size of less than 45 [ ⁇ m].
• the compound composite (b) is once master-batched with the thermoplastic resin (a), and then a diluted resin is further blended to produce a resin composition and a molded product thereof, thereby being an antiviral active ingredient.
• the metal compound complex (b) can be stably and uniformly dispersed at a high concentration, and as a result, not only excellent antiviral activity and antibacterial activity can be exhibited, but also their effects can be prolonged.
• Example 1 -Production of metal compound composite 6 g (100 parts by mass) of titanium oxide raw material (manufactured by Showa Denko Ceramics Co., Ltd., BET specific surface area, rutileization rate, anataseization rate, brookite formation rate, half-value full width and primary particles) in 100 mL of distilled water diameter were suspended in Table 1), was added 0.0805g (CuCl 2 ⁇ 2H 2 O ( Kanto Chemical Co., Ltd. 0.5 parts by weight of copper equivalent)) and stirred for 10 minutes.
• titanium oxide raw material manufactured by Showa Denko Ceramics Co., Ltd., BET specific surface area, rutileization rate, anataseization rate, brookite formation rate, half-value full width and primary particles
• a 1 mol / L sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) aqueous solution was added so that the pH became 10, and the mixture was stirred and mixed for 30 minutes to obtain a slurry.
• This slurry is filtered, the obtained powder is washed with pure water, dried at 80 ° C., crushed with a horizontal jet crusher (“Single Track Jet Mill” manufactured by Seishin Enterprise Co., Ltd.) with heated air, and then continuously.
• Coarse particles of 45 ⁇ m or more were removed by a swirling air flow type sieving device (“Spin Air Sheave” manufactured by Seishin Enterprise Co., Ltd.) to obtain a metal compound composite (1) which is a copper and titanium-containing composition.
• the BET specific surface area of the obtained metal compound complex (1) was 10 m 2 / g.
• BET specific surface area The BET specific surface area of the titanium oxide raw material and the metal compound composite was measured using a fully automatic BET specific surface area measuring device "Macsorb, HM model-1208" manufactured by Mountech Co., Ltd.
• anatase-type titanium oxide anatase conversion rate
• brookite-type titanium oxide brookite conversion rate
• the filament (1) was false-twisted with a false twisting machine, and a 20-gauge knitted fabric (1) was prepared using a tubular knitting machine.
• Example 2 Manufacture of masterbatch Polyethylene terephthalate was changed to polyamide-6 ("UBE NYLON 1013B" manufactured by Ube Industries, Ltd.), and the set temperature at the time of extrusion was changed from 280 ° C to 260 ° C. A batch (2) was obtained.
• a masterbatch (2) 10 parts by mass was mixed with 100 parts by mass of polyamide-6 ("UBE NYLON 1018" manufactured by Ube Industries, Ltd.), vacuum dried at 110 ° C. for 12 hours, and then using a spinning machine. The spinning was carried out at a spinning temperature of 260 ° C., and the filament (2) of 144d / 48F was obtained by three-fold stretching.
• a knitted fabric (2) was prepared in the same manner as in Example 1 except that the filament was changed from (1) to (2).
• Example 3 Manufacture of masterbatch
• the masterbatch (masterbatch) was performed in the same manner as in Example 1 except that polyethylene terephthalate was changed to polypropylene ("Y-2000GV" manufactured by Prime Polymer Co., Ltd.) and the set temperature at the time of extrusion was changed from 280 ° C to 230 ° C. 3) was obtained.
• a knitted fabric (3) was prepared in the same manner as in Example 1 except that the filament was changed from (1) to (3).
• Example 4 Manufacture of masterbatch
• polyethylene terephthalate was changed to high-density polyethylene ("Suntech HD J320" manufactured by Asahi Kasei Corporation) and the set temperature during extrusion was changed from 280 ° C to 160 ° C. (4) was obtained.
• a knitted fabric (4) was prepared in the same manner as in Example 1 except that the filament was changed from (1) to (4).
• Example 5 Manufacture of masterbatch Example 1 except that polyethylene terephthalate was changed to poly-4-methyl-1-pentene ("TPX DX818" manufactured by Mitsui Chemicals, Inc.) and the set temperature at the time of extrusion was changed from 280 ° C to 260 ° C. The same procedure was carried out to obtain a master batch (5).
• TPX DX818 poly-4-methyl-1-pentene
• a knitted fabric (5) was prepared in the same manner as in Example 1 except that the filament was changed from (1) to (5).
• Example 6 Manufacture of masterbatch A masterbatch (6) was obtained in the same manner as in Example 1 except that polyethylene terephthalate was changed to polycarbonate (“Iupilon S-3000” manufactured by Mitsubishi Engineering Plastics).
• a knitted fabric (6) was prepared in the same manner as in Example 1 except that the filament was changed from (1) to (6).
• the obtained metal compound composite (c1) was observed with an optical microscope (magnification: 200 times) to obtain a particle image, and at least 1000 randomly selected particles (even if they were primary particles, further contained secondary particles). When the particle size (equivalent to a circle) was measured for each of them, those having a maximum particle size of 82 ⁇ m were included.
• the BET specific surface area of the obtained metal compound complex (c1) was 10 m 2 / g.
• Example 2 (Comparative Example 2) -Manufacture of masterbatch Same as Example 1 except that the metal compound composite (1) was changed to titanium oxide (c2) (photocatalytic titanium oxide "ST-21" manufactured by Ishihara Sangyo Co., Ltd., specific surface area 50 m 2 / g). A master batch (c2) was obtained.
• titanium oxide (c2) photocatalytic titanium oxide "ST-21" manufactured by Ishihara Sangyo Co., Ltd., specific surface area 50 m 2 / g).
• a master batch (c2) was obtained.
• Example 3 (Comparative Example 3) -Manufacture of masterbatch The same procedure as in Example 1 was carried out except that the metal compound composite (1) was changed to titanium oxide (c3) (Titanium oxide "JA-1" manufactured by TAYCA Corporation, specific surface area 9 m 2 / g). A masterbatch (c3) was obtained.
• c3 titanium oxide "JA-1" manufactured by TAYCA Corporation, specific surface area 9 m 2 / g.
• Example 4 (Comparative Example 4) -Manufacture of filament
• the filament (c4) was obtained in the same manner as in Example 1 except that 100 parts by mass of polyethylene terephthalate "SA-1206" was changed to 3 parts by mass of the metal compound complex (1) without using a masterbatch. ..
• thermoplastic resin composition 100 parts by mass of polyethylene terephthalate "SA-1206" and 3 parts by mass of the metal compound composite (1) are mixed in a ⁇ 30 mm biaxial vent type extruder (set temperature 280 ° C., supplementary particle size 40 ⁇ m mesh filter). It was melt-kneaded with. The obtained thermoplastic resin composition was pelletized. Subsequently, the obtained pellets were vacuum dried at 150 ° C. for 12 hours, then melt-spun at a spinning temperature of 290 ° C. using a spinning machine, and 144d / 48F (48 pieces were bundled) by triple stretching. A filament (c4) of 144 dtex) was obtained.
• Differential pressure is 1MPa or less ⁇ Differential pressure is more than 1MPa and 5MPa or less ⁇ Differential pressure is more than 5MPa and 10MPa or less ⁇ Does not pass through the filter
• ⁇ 1 or less particles of 20 ⁇ m or more ⁇ : More than 1 particle of 20 ⁇ m or more and 5 or less ⁇ : More than 5 particles of 20 ⁇ m or more and 20 or less ⁇ : More than 20 particles of 20 ⁇ m or more And one or more particles of 45 ⁇ m or more
• the light of the white fluorescent lamp was cut off from ultraviolet rays by the N113 filter, and the illuminance was set to 1000 lux.
• a 100 ⁇ L Q ⁇ phage solution having a known concentration was dropped on a 5 cm ⁇ 5 cm evaluation knitted fabric or film, and then sandwiched between 5 cm ⁇ 5 cm glass plates.
• the sample irradiated with light for 4 hours was collected with SCDLP solution, appropriately diluted, infected with Escherichia coli, applied to an agar medium, and evaluated by counting the number of plaques after culturing.
• Antiviral property is evaluated by the degree of inactivation of Q ⁇ phage (the logarithmic value when the relative phage concentration (N / N 0 ) is calculated from the initial phage concentration N 0 and the phage concentration N after a predetermined time), and is inactivated.
• the degree of activation of -2 to -5 was evaluated as having antiviral properties. The results are shown in Tables 4 and 5.
• the degree of inactivation is -1: 90%, the degree of inactivation is -2: 99%, and the degree of inactivation is -3: 99.9%, indicating that the antiviral property is high.
• the detection limit is inactivation degree -5.
• Inactivity is from -5.0 or more to less than -4.0
• Inactivity is from -4.0 or more to less than -3.0
• Inactivity is from -3.0 or more to- Less than 2.0
• Inactivity is -2.0 or more
• Example 7 -Film manufacturing 10 parts by mass of masterbatch (1) was mixed with 100 parts by mass of polyethylene terephthalate "SA-1206", and then a film forming temperature of 280 ° C. was used using a 20 mm single-screw extruder connected to a 100 mm wide T-die. A single-layer film (1) having a thickness of 10 ⁇ m was obtained.
• Measurement Example 7 Measurement of agglomerated particles in a film (Measurement of agglomerates) 0.1 g of the obtained films (1) and (c1) were cut out, pressed into a film with a slide, and then observed with an optical microscope (magnification 200 times) to obtain particle images, and at least 1000 randomly selected particles were obtained. The particle size (equivalent to a circle) was measured for each of the particles (which may be primary particles or may further contain secondary particles), and evaluated based on the criteria of Measurement Example 3. The results are shown in Table 5.
• Examples 1 to 7 in which coarse particles were removed in advance by crushing and classifying the metal compound composite a master batch in which the metal compound composite was highly dispersed could be prepared, and processing into threads having a lower fineness could be made. Not only is it less likely to break or break when processing into a thin film, it is also excellent in workability, but it is also possible to expose more antiviral active surfaces to the surface of the molded body due to the fine dispersion of the metal compound composite. It has been clarified that even a small amount exerts an antiviral activity effect.
• Example 8 -Production of metal oxide Titanium oxide raw material (crystalline rutile type, manufactured by sulfuric acid method, BET specific surface area, rutileization rate and primary particle size are shown in Table 6) 600 parts by mass, copper (ii) dihydrate 8 parts by mass and 900 parts by mass of water were mixed in a stainless steel container.
• the mixture was stirred with a stirrer (“Robomics” manufactured by Tokushu Kagaku Kogyo Co., Ltd.), and a 1 mol / L sodium hydroxide aqueous solution was added dropwise until the pH of the mixture reached 10.
• the obtained mixed solution was filtered under reduced pressure using a qualitative filter paper (5C) to separate the solid content from the mixed solution, and further washed with ion-exchanged water. Then, the washed solid was dried at 120 ° C. for 12 hours to remove water. After drying, a powdery composition was obtained with a mill (“Miller” manufactured by Iwatani Corporation). Next, the obtained composition was heat-treated at 450 ° C.
• a precision incubator (“DH650” manufactured by Yamato Scientific Co., Ltd.) to obtain a powder.
• the obtained powder is washed with pure water, dried at 80 ° C., crushed with a horizontal jet crusher ("Single Track Jet Mill” manufactured by Seishin Enterprise Co., Ltd.) with heated air, and then a continuous swirling airflow type sieving device ( A metal compound composite (2) that is a copper and titanium-containing composition in which coarse particles of 45 ⁇ m or more are removed by Seishin Enterprise Co., Ltd.) and the maximum particle size is 10 ⁇ m or less with a micromesh (opening 10 ⁇ m). ) was obtained.
• a bead mill containing zirconia beads (TSG type manufactured by Imex Co., Ltd.) is subjected to 1000 rotations and a dispersion treatment for 4 hours, and the beads are filtered and separated, and then further passed through a filter (opening 1 ⁇ m) to form an aqueous dispersion (1). ) was obtained.
• the maximum particle size of the metal oxide composite in the obtained aqueous dispersion was 1 ⁇ m or less.
• the filament (7) was false-twisted with a false twisting machine, and a 20-gauge knitted fabric (7) was prepared using a tubular knitting machine.
• Example 9 Manufacture of masterbatch Perform the same procedure as in Example 8 except that the polyethylene terephthalate was changed to polyamide-6 ("UBE NYLON 1013B" manufactured by Ube Industries, Ltd.) and the extrusion processing temperature was changed to 260 ° C., and the masterbatch (8) was prepared. Obtained.
• a knitted fabric (8) was prepared in the same manner as in Example 8 except that the filament was changed from (7) to (8).
• Example 10 Manufacture of masterbatch
• polyethylene terephthalate was changed to polypropylene ("Y-2000GV” manufactured by Prime Polymer Co., Ltd.) and the extrusion temperature was changed to 230 ° C. to obtain a masterbatch (9). ..
• a knitted fabric (9) was prepared in the same manner as in Example 8 except that the filament was changed from (7) to (9).
• Example 11 Manufacture of masterbatch Performed in the same manner as in Example 8 except that the polyethylene terephthalate was changed to high-density polyethylene ("Suntech HD J320" manufactured by Asahi Kasei Corporation) and the extrusion processing temperature was changed to 160 ° C. to obtain a masterbatch (10). rice field.
• Polyethylene terephthalate was changed to high-density polyethylene ("Suntech HD J320" manufactured by Asahi Kasei Corporation) and the extrusion processing temperature was changed to 160 ° C. to obtain a masterbatch (10). rice field.
• a knitted fabric (10) was prepared in the same manner as in Example 8 except that the filament was changed from (7) to (10).
• Example 12 Manufacture of masterbatch Perform the same procedure as in Example 8 except that polyethylene terephthalate was changed to poly-4-methyl-1-pentene ("TPX DX818" manufactured by Mitsui Chemicals, Inc.) and the extrusion temperature was changed to 260 ° C. A batch (11) was obtained.
• a knitted fabric (11) was prepared in the same manner as in Example 8 except that the filament was changed from (1) to (11).
• Example 13 Manufacture of masterbatch Performed in the same manner as in Example 8 except that polyethylene terephthalate was made of polycarbonate ("Iupilon S-3000" manufactured by Mitsubishi Engineering Plastics) and vacuum dried at 120 ° C. for 12 hours. Masterbatch (12) Got
• a knitted fabric (12) was prepared in the same manner as in Example 8 except that the filament was changed from (7) to (12).
• Example 14 -Production of an aqueous dispersion
• a liquid obtained by mixing 280 parts by mass of water as a dispersion medium with 100 parts by mass of a metal compound composite (2) and 40 parts by mass of a wet dispersant ("DISPERBYK 194N" manufactured by BIC Chemie) was added to the same volume.
• a bead mill containing zirconia beads (TSG type manufactured by Imex Co., Ltd.) was subjected to a dispersion treatment for 1000 rotations for 4 hours, and the beads were filtered and separated to obtain an aqueous dispersion (2).
• the filament (13) was false-twisted with a false twisting machine, and a 20-gauge knitted fabric (13) was prepared using a tubular knitting machine.
• Example 15 -Production of an aqueous dispersion
• a liquid obtained by mixing 280 parts by mass of water as a dispersion medium with 100 parts by mass of a metal compound composite (2) and 40 parts by mass of a wet dispersant ("DISPERBYK 2010" manufactured by BIC Chemie) is mixed in the same volume.
• a bead mill containing zirconia beads (TSG type manufactured by Imex Co., Ltd.) was subjected to a dispersion treatment for 1000 rotations for 4 hours, and the beads were filtered and separated to obtain an aqueous dispersion (3).
• the filament (14) was false-twisted with a false twisting machine, and a 20-gauge knitted fabric (14) was prepared using a tubular knitting machine.
• Example 16 Manufacture of masterbatch The same procedure as in Example 8 was carried out except that the polyethylene terephthalate was changed to low density polyethylene ("Petrosen 250R" manufactured by Tosoh Corporation) and the extrusion temperature was changed to 140 ° C. to obtain a masterbatch (15). ..
• Example 17 Manufacture of microfibers and non-woven fabrics 42 parts by mass of low-density polyethylene ("Petrosen 250R” manufactured by Toso Co., Ltd.), 16 parts by mass of masterbatch (8) vacuum-dried at 105 ° C for 12 hours, and 6-nylon (Ube Industries, Ltd.) 42 parts by mass of "UBE NYLON 1013B") manufactured by UBE Industries, Ltd. was mixed, and then melt spinning was performed at a spinning temperature of 280 ° C. using a spinning machine to obtain a 220d / 48F filament (15) by three-fold stretching. The obtained filament sample was used to produce an entangled non-woven fabric through each step of cutting, curd, cloth wrapper, and needle punching. Polyethylene was eluted from the obtained entangled nonwoven fabric using toluene to obtain an entangled nonwoven fabric (1) made of microfibers having an average fiber diameter of 1 ⁇ m.
• Low-density polyethylene (“Petrosen 250R” manufactured by Tos
• Example 18 Manufacture of multilayer film
• Measurement Example 16 Measurement of agglomerated particles in a non-woven fabric (measurement of agglomerates) The obtained filament (15) was evaluated in the same manner as in Measurement Example 3. The results are shown in Table 11.

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