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
  • C08J3/12—Powdering or granulating
• • 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
  • C08J3/12—Powdering or granulating
  • C08J3/124—Treatment for improving the free-flowing characteristics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
  • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
  • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
• • 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
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
• • 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
  • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
  • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

• the present invention relates to a powder product.
• Polymers having a polyvinyl alcohol (PVA) skeleton (hereinafter, in this specification, these will be collectively referred to as "polyvinyl alcohol-based polymers”, “vinyl alcohol-based polymers”, or simply “PVA") are known as synthetic resins with hydrophilic properties, and various applications that take advantage of these properties continue to be developed.
• PVA polyvinyl alcohol
• PVA may be in powder form and may be expected to be dispersed in water. Adjusting the degree of saponification of PVA has been a common practice in order to improve the solubility of PVA, and this is also described in the applicant's introduction of the Denka Poval product.
• the present invention provides the following:
• a powder product comprising: Polymer particles obtained by saponifying a polymer of a vinyl ester monomer or a copolymer of a vinyl ester monomer and another monomer, the polymer particles having a particle size distribution in which the content of particles having a particle size of 180 ⁇ m or less is 50 mass % or more and the content of particles having a particle size of 500 ⁇ m or more is 10 mass % or less; and a water-soluble additive in an amount of 0.1% by mass or more and 10% by mass or less based on the mass of the polymer particles,
• the water-soluble additive has a viscosity at 20°C in the range of 30 to 200 mPa s, and a surface tension at 20°C of a 0.05% by mass aqueous solution of the water-soluble additive measured by a hanging drop method in the range of 50 to 72 mN/m;
• the powder product is characterized in that the powder product has an angle of repose of 60° or less, as measured by a funnel injection method in
• Aspect 2 The powder product of embodiment 1, wherein the difference angle, as measured by the funnel injection method, is 10° or more.
• Aspect 4. The powder product of any one of claims 1 to 3, wherein the polymer particles consist of a polymer of a vinyl ester monomer.
• Aspect 5 The powder product according to any one of claims 1 to 3, wherein the polymer particles are made of a copolymer of a vinyl ester monomer and another monomer.
• Aspect 6 The powder product according to any one of aspects 1 to 3 and 5, wherein the other monomer is a multifunctional monomer.
• Aspect 7 The powder product according to claim 6, wherein the polyfunctional monomer is a compound having two or more polymerizable unsaturated bonds in the molecule.
• the present invention not only provides the effect of the powder product exhibiting high solubility in water even under weak mixing conditions, but also provides the effect of the powder product having the suitability required for the powder product.
• polymers are defined as follows: "A polymer molecule is a molecule of large relative molecular mass having a structure composed of multiple repetitions of units derived, substantially or conceptually, from molecules of small relative molecular mass.”
• the powder product according to an embodiment of the present invention is characterized by containing polymer particles obtained by saponifying a polymer of a vinyl ester monomer or a copolymer of a vinyl ester monomer and another monomer, and a water-soluble additive in a predetermined mass ratio.
• the main purpose of this powder product is to dissolve in water, but it can also be used for dissolving in aqueous solvents other than pure water (tap water, aqueous solutions of hydrophilic solutes, etc.).
• the polymer particles are PVA polymer particles, and by having a specific particle size distribution, the prerequisite for rapid dissolution in an aqueous solvent can be met.
• the particle size distribution of the polymer particles can be measured by sieving using sieves with 180 ⁇ m and 500 ⁇ m openings in accordance with the description of JIS Z8815:1994.
• the particle ratio is required to be 10% by mass or less of particles with a particle size of 500 ⁇ m or more (500 ⁇ m sieve) and 50% by mass or more of particles with a particle size of 180 ⁇ m or less (180 ⁇ m sieve). If the particle size distribution does not meet this condition, it may have an adverse effect on the solubility.
• the particle size distribution of the polymer particles may be such that the fraction sieving 500 ⁇ m is 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.1% by mass or less.
• the particle size distribution of the polymer particles may be such that the fraction sieving 180 ⁇ m is 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 85% by mass or more.
• the degree of saponification of the PVA constituting the polymer particles may be 70-100 mol%, more preferably 75-95 mol%, even more preferably 80-95 mol%, and even more preferably 80-90 mol%. If the degree of saponification is within this range, the effect of easily improving solubility in aqueous solvents is obtained.
• the degree of saponification can be measured by the method described in JIS K6726:1994.
• the viscosity of a 4% by mass aqueous solution of PVA constituting the polymer particles at 20° C. may be in the range of 1 to 1000 mPa ⁇ s, more preferably in the range of 1 to 500 mPa ⁇ s, and even more preferably in the range of 1 to 300 mPa ⁇ s, when measured at a shear rate of 10 s ⁇ 1 in accordance with the description of the rotational viscometer method in JIS K6726:1994 and JIS K7117-1999.
• the viscosity is in this range, the effect of improving the solubility in aqueous solvents can be obtained.
• the vinyl ester monomers used as raw materials for the PVA that forms the polymer particles may be, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, etc., or mixtures of these may be used. From the viewpoint of ease of polymerization, vinyl acetate is preferred.
• the PVA may be a saponified homopolymer of a vinyl ester monomer, or a saponified copolymer of a vinyl ester monomer and another monomer.
• examples of monofunctional monomers copolymerizable with vinyl ester monomers include the following compounds: ⁇ -olefin monomers such as ethylene and propylene; (meth)acrylic acid alkyl ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; unsaturated amide monomers such as (meth)acrylamide and N-methylol acrylamide; unsaturated carboxylic acid monomers such as (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, and fumaric acid; alkyl (methyl, ethyl, propyl, etc.) ester monomers of unsaturated carboxylic acids; anhydrides of unsaturated carboxylic acids such as maleic anhydride; sodium, potassium, ammonium, and other salts of uns
• polyfunctional monomers examples include polyfunctional monomers and monofunctional monomers.
• polyfunctional monomers compounds having two or more polymerizable unsaturated bonds in the molecule can be preferably used.
• the number of polymerizable unsaturated sites in the polyfunctional monomer is preferably 2 to 5.
• polyfunctional monomers include the following: Divinyl ethers and divinyl sulfonic acid compounds, such as ethanediol divinyl ether, propanediol divinyl ether, butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, and polypropylene glycol divinyl ether; and diene compounds, such as pentadiene, hexadiene, heptadiene, octadiene, nonadiene, and decadiene.
• Divinyl ethers and divinyl sulfonic acid compounds such as ethanediol divinyl ether, propanediol divinyl ether, butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol diviny
• Diallyl ether compounds such as glycerin diallyl ether, diethylene glycol diallyl ether, ethylene glycol diallyl ether, triethylene glycol diallyl ether, polyethylene glycol diallyl ether, trimethylolpropane diallyl ether, and pentaerythritol diallyl ether.
• Triallyl ether compounds such as glycerin triallyl ether, trimethylolpropane triallyl ether, and pentaerythritol triallyl ether.
• Tetraallyl ether compounds such as pentaerythritol tetraallyl ether.
• Multifunctional monomers containing an allyl ester group such as diallyl phthalate, diallyl maleate, diallyl itaconate, diallyl terephthalate, and diallyl adipate.
• Diallylamine compounds such as diallylamine and diallylmethylamine, and multifunctional monomers containing an allylamino group such as triallylamine.
• Multifunctional monomers containing an allylammonium group such as diallylammonium salts such as diallyldimethylammonium chloride.
• Polyfunctional monomers having (meth)acrylic acid such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, isocyanuric acid tri(meth)acrylate, etc.
• Multifunctional monomers having (meth)acrylamide such as N,N'-methylenebis(meth)acrylamide and N,N'-ethylenebis(meth)acrylamide.
• Multifunctional aromatic monomers such as divinylbenzene and trivinylbenzene.
• Multifunctional monomers containing glycidyl groups such as allyl glycidyl ether and glycidyl (meth)acrylate.
• polyfunctional monomers are preferred, compounds having two or more polymerizable unsaturated bonds in the molecule are more preferred, and compounds having three or more polymerizable unsaturated bonds in the molecule are even more preferred.
• the water-soluble additive contained in the powder product (hereinafter, also simply referred to as "additive") is liquid at room temperature (e.g., 20°C) as defined by JIS Z8703:1983, and the viscosity at 20°C is required to be in the range of 30 to 200 mPa ⁇ s when measured at a shear rate of 10 s -1 using a cone-plate type rotational viscometer (rheometer) conforming to JIS Z8803:2011. If the viscosity is outside this range, the mixture with the polymer particles will be insufficient, resulting in poor solubility.
• the viscosity of the additive under the above conditions may be in the range of 30 to 150 mPa ⁇ s, more preferably in the range of 30 to 100 mPa ⁇ s.
• the additive must also have a surface tension of 50 to 72 mN/m when measured by the pendant drop method at 20°C for a 0.05% by mass aqueous solution.
• the pendant drop method refers to the ds/de method. If the surface tension is outside the above range, the solubility of the powder product will be inferior.
• the mass of the additive in the powder product is in the range of 0.1% by mass to 10% by mass, based on the mass of the polymer particles. If the mass of the additive is less than 0.1% by mass, the solubility will be poor under weak stirring conditions. If the mass of the additive is more than 10% by mass, the powder product will be sticky, which will cause problems when using or transporting the product, and will adversely affect the performance of the powder product.
• Additives are not particularly limited as long as they are water-soluble and have a viscosity and surface tension that satisfy the above-mentioned conditions, and examples include polyethers, polyhydric alcohols, polyoxyalkylenes, alcohol alkoxylate compounds, phenol alkoxylate compounds, silicone compounds, and mineral oils. Among these, those that can be used as nonionic surfactants and/or polyethers are preferred. Among polyethers, polyethylene glycol (polyethylene oxide) and polypropylene glycol are preferred. The number average molecular weight of the additive is preferably in the range of 100 to 20,000, more preferably in the range of 200 to 2,000, and even more preferably in the range of 200 to 1,500.
• the powder product containing the polymer particles and additives has a property suitable for dissolving in pure water or other aqueous solvents.
• the powder product is characterized in that the angle of repose measured by the funnel injection method according to the description of JIS R9301-2-2:1999 is 60° or less (in this specification, the measurement is performed with a protractor). If the angle of repose is outside this range, the powder will have too high agglomeration, which will cause problems during use and transportation, and will adversely affect the performance of the powder product.
• the angle of repose may be 20° or more and 60° or less, and more preferably 30° or more and 60° or less.
• the difference angle of the powder product may be 10° or more, and more preferably 10° or more and 40° or less.
• the difference angle corresponds to the value obtained by subtracting the collapse angle from the repose angle, which is measured by dropping a weight onto a sample whose repose angle has been measured by the funnel injection method. If the difference angle is within the above range, the effect of improving solubility in aqueous solvents can be obtained.
• the compressibility of the powder product may be 45% or less, more preferably 10% to 45%, and even more preferably 10% to 40%.
• the initial bulk density and tapped bulk density refer to values measured in accordance with the description of JIS R1628: 1997.
• Example 1 The polymer particles were synthesized according to the following procedure.
• a polymerization vessel equipped with a reflux condenser, a dropping funnel, and a stirrer was charged with 100 parts by mass of vinyl acetate, 117 parts by mass of methanol, and 0.016 parts by mass of Perloyl (registered trademark) NPP (manufactured by NOF Corporation) as an initiator, and polymerization was carried out for 5 hours at boiling point while stirring in a nitrogen atmosphere (polymerization rate 88%).
• unreacted vinyl acetate monomer was removed from the polymerization system to obtain a methanol solution of polyvinyl acetate polymer.
• a methanol solution of sodium hydroxide was added to this solution (calculated as 0.007 moles of sodium hydroxide relative to the structural unit derived from vinyl acetate), and a saponification reaction was carried out at 45°C for 90 minutes to obtain a PVA with a saponification degree of 88.1 mol%.
• the obtained PVA was pulverized with an ACM pulverizer, and the PVA particles obtained after classification were sieved using sieves with 180 ⁇ m and 500 ⁇ m openings in accordance with the description of JIS Z8815:1994 to measure the particle size distribution.
• the 500 ⁇ m sieve was 0.1 mass% and the 180 ⁇ m sieve was 99.1 mass%.
• the viscosity of a 4 mass% aqueous solution of the PVA was measured at 20° C.
• Polyethylene glycol (PEG-300) with a number average molecular weight of 300 was prepared as an additive, and its viscosity was measured with a rheometer at a shear rate of 10 s -1 in accordance with the description of JIS Z8803:2011, which was 70 mPa ⁇ s.
• a 0.05% by mass aqueous solution of the additive was also prepared, and its surface tension was measured by the hanging drop method at 20°C using DMs-301 (Kyowa Interface Science Co., Ltd.), which was 68.8 mN/m. The surface tension of the water used as a control was also measured, which was 70.2 mN/m.
• the additive was mixed to a concentration of 3% by mass relative to the mass of the PVA to obtain the powder product of Example 1.
• the physical properties of the following examples were measured in the same manner as in Example 1.
• Example 2 The powder product of Example 2 was obtained in the same manner as in Example 1, except that the following procedure was used as the method for producing polymer particles. 100 parts by mass of vinyl acetate, 15 parts by mass of methanol, and 5.0x10-3 parts by mass of Perloyl NPP (manufactured by NOF Corporation) as an initiator were charged into a polymerization vessel equipped with a reflux condenser, a dropping funnel, and a stirrer, and polymerization was carried out for 5 hours at boiling point while stirring in a nitrogen atmosphere (polymerization rate 55%). Next, unreacted vinyl acetate monomer was removed from the polymerization system to obtain a methanol solution of polyvinyl acetate polymer.
• Perloyl NPP manufactured by NOF Corporation
• a methanol solution of sodium hydroxide was added to this solution (calculated as 0.007 moles of sodium hydroxide relative to the structural unit derived from vinyl acetate), and a saponification reaction was carried out at 45°C for 90 minutes to obtain a PVA with a saponification degree of 87.9 mol%.
• the viscosity of a 4% by mass aqueous solution of the PVA was 56.8 mPa ⁇ s.
• Example 3 The powder product of Example 3 was obtained in the same manner as in Example 1, except that the following procedure was used as the method for producing polymer particles. 100 parts by mass of vinyl acetate, 5 parts by mass of methanol, and 1.0x10-3 parts by mass of Peroyl NPP (manufactured by NOF Corporation) as an initiator were charged into a polymerization vessel equipped with a reflux condenser, a dropping funnel, and a stirrer, and polymerization was carried out for 5 hours at boiling point while stirring in a nitrogen atmosphere (polymerization rate 40%). Next, unreacted vinyl acetate monomer was removed from the polymerization system to obtain a methanol solution of polyvinyl acetate polymer.
• Peroyl NPP manufactured by NOF Corporation
• a methanol solution of sodium hydroxide was added to this solution (calculated as 0.007 moles of sodium hydroxide relative to the structural unit derived from vinyl acetate), and a saponification reaction was carried out at 45°C for 90 minutes to obtain a PVA with a saponification degree of 88.8 mol%.
• the viscosity of a 4% by mass aqueous solution of the PVA was 114.3 mPa ⁇ s.
• Example 4 to 6 Polymer particles were prepared according to the manufacturing method of Example 1 of WO 2019/163490. Specifically, 100 parts by mass of vinyl acetate, 0.16 parts by mass of triallyl isocyanurate (TAIC), 66.7 parts by mass of methanol, and 0.07 parts by mass of Peroyl NPP (manufactured by NOF Corporation) as an initiator were charged into a polymerization vessel equipped with a reflux condenser, a dropping funnel, and a stirrer, and polymerization was carried out at the boiling point for 5 hours while stirring in a nitrogen atmosphere (polymerization rate 50%).
• TAIC triallyl isocyanurate
• methanol 66.7 parts by mass of methanol
• Peroyl NPP manufactured by NOF Corporation
• PVA particles were obtained by crushing and classifying in the same manner as in Example 1, and the additives and PVA particles were mixed in the ratios shown in the table to obtain the powder products according to Examples 4 to 6.
• Comparative Example 1 A powder product according to Comparative Example 1 was obtained in the same manner as in Example 1, except that no additive was added.
• Comparative Example 2 A powder product according to Comparative Example 2 was obtained in the same manner as in Example 4, except that no additive was added.
• Comparative Example 3 A powder product according to Comparative Example 3 was obtained in the same manner as in Example 1, except that ADEKA NOL UH-420 (manufactured by ADEKA CORPORATION, a special non-ionic polymer surfactant) was used as the additive.
• ADEKA NOL UH-420 manufactured by ADEKA CORPORATION, a special non-ionic polymer surfactant
• Comparative Example 4 A powder product according to Comparative Example 4 was obtained in the same manner as in Example 4, except that glycerin was used as the additive.
• Comparative Examples 7 to 8 Powder products according to Comparative Examples 7 and 8 were obtained in the same manner as in Example 4, except that SN DEFORMER PC (a polyoxyalkylene-type nonionic surfactant manufactured by San Nopco Ltd.) was used as the additive.
• SN DEFORMER PC a polyoxyalkylene-type nonionic surfactant manufactured by San Nopco Ltd.
• Comparative Example 9 A powder product according to Comparative Example 9 was obtained in the same manner as in Example 4, except that Noptum 740A (a mixture of polyoxyalkylene-type nonionic surfactant, silica, water, etc., manufactured by San Nopco) was used as the additive.
• Noptum 740A a mixture of polyoxyalkylene-type nonionic surfactant, silica, water, etc., manufactured by San Nopco
• Comparative Example 10 A powder product according to Comparative Example 10 was obtained in the same manner as in Example 4, except that the amount of additive was excessive.
• a funnel was set on a funnel injection platform provided on a Powder Tester (registered trademark) PT-E (manufactured by Hosokawa Micron Corporation), and 80 grams of each powder product according to the example was poured from the funnel and accumulated in a tray.
• the angle of repose of the pile of powder products accumulated on the tray was measured using a protractor.
• a collapse angle measuring weight provided on the measuring device was dropped three times on the pile whose repose angle was measured according to the specifications of the measuring device, and the angle of the collapsed pile was measured with a protractor to obtain the collapse angle.
• the difference angle was calculated as the value obtained by subtracting the collapse angle from the repose angle. The results are shown in the table.
• the evaluation was carried out using a Powder Tester PT-E (manufactured by Hosokawa Micron Corporation).
• the powder product of each example was filled heapedly into a 100 mL metal container equipped with the device, the surface was scraped off using a blade, and the mass of the metal container was measured.
• the initial bulk density also called loose bulk density
• the measurement mode of the device was switched to tapping mode, and the container was tapped for 180 seconds, after which the surface was scraped off with a blade and the mass of the container was measured.
• the tapped bulk density also called compacted bulk density
• Comparative Examples 1 to 9 dissolved under strong stirring conditions, but the solubility was poor under weak stirring conditions. Comparative Example 10 showed sufficient solubility, but was sticky and unsuitable for use as a product.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=92905349

Family Applications (1)

Country Status (4)

Citations (10)

• 2024
  • 2024-02-28 JP JP2025510040A patent/JPWO2024202880A1/ja active Pending
  • 2024-02-28 CN CN202480017524.3A patent/CN120858130A/zh active Pending
  • 2024-02-28 WO PCT/JP2024/007427 patent/WO2024202880A1/ja not_active Ceased
  • 2024-02-28 EP EP24779019.9A patent/EP4692176A1/en active Pending

Patent Citations (10)

Also Published As

Similar Documents

Legal Events