WO2020218167A1 - 吸水性樹脂粒子 - Google Patents
吸水性樹脂粒子 Download PDFInfo
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- WO2020218167A1 WO2020218167A1 PCT/JP2020/016760 JP2020016760W WO2020218167A1 WO 2020218167 A1 WO2020218167 A1 WO 2020218167A1 JP 2020016760 W JP2020016760 W JP 2020016760W WO 2020218167 A1 WO2020218167 A1 WO 2020218167A1
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- water
- absorbent resin
- resin particles
- absorber
- gel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- 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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
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- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
- A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
- A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
- A61F2013/530583—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the form
- A61F2013/530635—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the form in thin film
- A61F2013/530642—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the form in thin film being cross-linked or polymerised in situ
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2805—Sorbents inside a permeable or porous casing, e.g. inside a container, bag or membrane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/68—Superabsorbents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- 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
- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Definitions
- the present invention relates to water-absorbent resin particles.
- the present inventors have a difference in gel brightness when swelled to about 50 times depending on the water-absorbent resin particles, and when the gel brightness is within a predetermined range, the absorber swelling capacity is excellent. I found it.
- the present invention also provides an absorbent article that is a diaper.
- the absorber using the water-absorbent resin particles obtained by the above-mentioned production method can have a high absorption amount.
- the lightness L * in the present specification is in the L * a * b * color system and is indicated in the range of 0 to 100. A more specific method for measuring the gel brightness L * will be shown in Examples described later.
- the gel lightness L * is preferably 58 or less, more preferably 55 or less, further preferably 50 or less, and further preferably 45 or less, from the viewpoint of further improving the absorption amount of the absorber. Even more preferable.
- the gel brightness L * may be, for example, 10 or more, 20 or more, 30 or more, or 35 or more.
- the water-absorbent resin particles according to the present embodiment may have a lightness L * of 91 or more or 95 or more in a dry state before water absorption.
- the lightness L * in the dry state refers to the lightness L * of the water-absorbent resin particles having a water content of 10% by mass or less.
- Examples of the shape of the water-absorbent resin particles according to the present embodiment include substantially spherical, crushed, and granular shapes. Further, the water-absorbent resin particles according to the present embodiment may be in a form in which fine particles (primary particles) are aggregated (secondary particles) in addition to a form in which each is composed of a single particle.
- the medium particle size of the water-absorbent resin particles (water-absorbent resin particles before water absorption) according to the present embodiment may be 250 to 850 ⁇ m, 300 to 700 ⁇ m, 300 to 600 ⁇ m, 330 to 500 ⁇ m, or 350 to 400 ⁇ m.
- the water-absorbent resin particles according to the present embodiment may have a desired particle size distribution at the time of being obtained by the production method described later, but the particle size distribution can be obtained by performing an operation such as particle size adjustment using classification with a sieve. May be adjusted.
- the water-absorbent resin particles according to the present embodiment are, for example, crosslinked polymers (derived from ethylenically unsaturated monomers) obtained by polymerizing a monomer containing an ethylenically unsaturated monomer as polymer particles.
- a crosslinked polymer having a structural unit to be used) can be included. That is, the water-absorbent resin particles according to the present embodiment can contain a polymer having a structural unit derived from the ethylenically unsaturated monomer, and the structural unit derived from the ethylenically unsaturated monomer can be contained. It can contain polymer particles containing the crosslinked polymer having.
- a water-soluble ethylenically unsaturated monomer can be used as the ethylenically unsaturated monomer.
- the polymerization method include a reverse phase suspension polymerization method, an aqueous solution polymerization method, a bulk polymerization method, and a precipitation polymerization method.
- the reverse phase suspension polymerization method or the aqueous solution polymerization method is preferable from the viewpoint of ensuring good water absorption characteristics (water retention amount, etc.) of the obtained water-absorbent resin particles and easy control of the polymerization reaction.
- a reverse phase suspension polymerization method will be described as an example as a method for polymerizing an ethylenically unsaturated monomer.
- the ethylenically unsaturated monomer is preferably water-soluble, for example, (meth) acrylic acid and a salt thereof, 2- (meth) acrylamide-2-methylpropanesulfonic acid and a salt thereof, (meth) acrylamide, N. , N-dimethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide, polyethylene glycol mono (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylamino Examples thereof include propyl (meth) acrylate and diethylaminopropyl (meth) acrylamide.
- the amino group may be quaternized.
- the ethylenically unsaturated monomer may be used alone or in combination of two or more.
- Functional groups such as the carboxyl group and amino group of the above-mentioned monomers can function as functional groups capable of cross-linking in the surface cross-linking step described later.
- the ethylenically unsaturated monomer is a group consisting of (meth) acrylic acid and its salts, acrylamide, methacrylamide, and N, N-dimethylacrylamide. It is preferable to contain at least one compound selected from the above, and it is more preferable to contain at least one compound selected from the group consisting of (meth) acrylic acid and salts thereof, and acrylamide. From the viewpoint of further enhancing the water absorption characteristics (water retention amount and the like), the ethylenically unsaturated monomer further preferably contains at least one compound selected from the group consisting of (meth) acrylic acid and salts thereof. That is, the water-absorbent resin particles preferably have a structural unit derived from at least one selected from the group consisting of (meth) acrylic acid and salts thereof.
- a monomer other than the above-mentioned ethylenically unsaturated monomer may be used.
- Such a monomer can be used, for example, by being mixed with an aqueous solution containing the above-mentioned ethylenically unsaturated monomer.
- the amount of the ethylenically unsaturated monomer used is the total amount of the monomers (the total amount of the monomers for obtaining the water-absorbent resin particles. For example, the total amount of the monomers giving the structural unit of the crosslinked polymer. The same shall apply hereinafter).
- the ratio of (meth) acrylic acid and its salt may be 70 to 100 mol% with respect to the total amount of the monomer, 80 to 100 mol%, 90 to 100 mol%, 95 to 100 mol%, or It may be 100 mol%.
- Ratio of (meth) acrylic acid and its salt means the ratio of the total amount of (meth) acrylic acid and its salt.
- the water-absorbent resin particles containing a crosslinked polymer having a structural unit derived from the ethylenically unsaturated monomer, wherein the ethylenically unsaturated monomer is used.
- At least one compound selected from the group consisting of (meth) acrylic acid and salts thereof, and the ratio of (meth) acrylic acid and its salts is based on the total amount of monomers for obtaining water-absorbent resin particles.
- Water-absorbent resin particles in an amount of 70 to 100 mol% can be provided.
- the ethylenically unsaturated monomer is usually preferably used as an aqueous solution.
- concentration of the ethylenically unsaturated monomer in the aqueous solution containing the ethylenically unsaturated monomer (hereinafter, simply referred to as “monomer aqueous solution”) is preferably 20% by mass or more and preferably 25 to 70% by mass. More preferably, 30 to 55% by mass is further preferable.
- Examples of the water used in the aqueous solution include tap water, distilled water, ion-exchanged water and the like.
- the monomer aqueous solution may be used by neutralizing the acid group with an alkaline neutralizer.
- the degree of neutralization of the ethylenically unsaturated monomer by the alkaline neutralizing agent increases the osmotic pressure of the obtained water-absorbent resin particles and further enhances the water absorption characteristics (water retention amount, etc.). It is preferably 10 to 100 mol%, more preferably 50 to 90 mol%, and even more preferably 60 to 80 mol% of the acidic group in the weight.
- alkaline neutralizing agent examples include alkali metal salts such as sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide and potassium carbonate; ammonia and the like.
- the alkaline neutralizer may be used alone or in combination of two or more.
- the alkaline neutralizer may be used in the form of an aqueous solution to simplify the neutralization operation. Neutralization of the acid group of the ethylenically unsaturated monomer can be performed, for example, by adding an aqueous solution of sodium hydroxide, potassium hydroxide or the like to the above-mentioned monomer aqueous solution and mixing them.
- the monomer aqueous solution is dispersed in a hydrocarbon dispersion medium in the presence of a surfactant, and the ethylenically unsaturated monomer is polymerized using a radical polymerization initiator or the like. Can be done.
- Nonionic surfactants include sorbitan fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitol fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and polyoxyethylene.
- Alkyl ether polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, alkylallyl formaldehyde condensed polyoxyethylene ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropyl alkyl ether, Examples thereof include polyethylene glycol fatty acid ester.
- Anionic surfactants include fatty acid salts, alkylbenzene sulfonates, alkylmethyl taurates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene alkyl ether sulfonates, and polyoxyethylene alkyl ether phosphates. , Phosphate ester of polyoxyethylene alkyl allyl ether and the like.
- the surfactant may be used alone or in combination of two or more.
- the surfactant is a sorbitan fatty acid ester. It preferably contains at least one compound selected from the group consisting of polyglycerin fatty acid esters and sucrose fatty acid esters.
- the amount of the surfactant used is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the aqueous monomer solution from the viewpoint of obtaining a sufficient effect on the amount used and economically. .08 to 5 parts by mass is more preferable, and 0.1 to 3 parts by mass is further preferable.
- a polymer-based dispersant may be used in combination with the above-mentioned surfactant.
- the polymer dispersant include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene / propylene copolymer, maleic anhydride-modified EPDM (ethylene / propylene / diene / terpolymer), and maleic anhydride.
- the polymer-based dispersant may be used alone or in combination of two or more.
- maleic anhydride-modified polyethylene maleic anhydride-modified polypropylene
- maleic anhydride-modified ethylene / propylene copolymer maleic anhydride / ethylene copolymer weight.
- maleic anhydride / propylene copolymer, maleic anhydride / ethylene / propylene copolymer, polyethylene, polypropylene, ethylene / propylene copolymer, oxidized polyethylene, oxidized polypropylene, and oxidized ethylene / propylene copolymer At least one selected from the group consisting of is preferable.
- the monomer aqueous solution used for the polymerization may contain a chain transfer agent.
- chain transfer agent include hypophosphates, thiols, thiolic acids, secondary alcohols, amines and the like.
- Reverse phase suspension polymerization can be carried out in one stage or in multiple stages of two or more stages. Reversed phase suspension polymerization is preferably carried out in 2 to 3 steps from the viewpoint of increasing productivity.
- the reaction mixture obtained in the first step polymerization reaction after the first step reverse phase suspension polymerization is subjected to an ethylenically unsaturated single amount.
- the body may be added and mixed, and the reverse phase suspension polymerization of the second and subsequent steps may be carried out in the same manner as in the first step.
- the above-mentioned radical polymerization initiator and / or internal cross-linking agent is used in the reverse phase of each stage of the second and subsequent stages.
- reverse phase suspension polymerization is carried out by adding within the range of the molar ratio of each component to the above-mentioned ethylenically unsaturated monomer.
- An internal cross-linking agent may be used in the reverse phase suspension polymerization in each of the second and subsequent stages, if necessary.
- an internal cross-linking agent it is added within the range of the molar ratio of each component to the above-mentioned ethylenically unsaturated monomer based on the amount of the ethylenically unsaturated monomer provided in each stage, and the suspension is reversed. It is preferable to carry out turbid polymerization.
- liquid permeable top sheet 30 examples include non-woven fabrics and porous sheets.
- non-woven fabric examples include thermal bond non-woven fabric, air-through non-woven fabric, resin-bond non-woven fabric, spun-bond non-woven fabric, melt-blow non-woven fabric, spunbond / melt-blow / spunbond non-woven fabric, air-laid non-woven fabric, spunlace non-woven fabric, point-bond non-woven fabric and the like.
- thermal bond non-woven fabrics, air-through non-woven fabrics, spunbond non-woven fabrics, and spunbond / melt blow / spunbond non-woven fabrics are preferably used.
- Examples of the bonding method include a method of applying a hot melt adhesive to the liquid permeable top sheet 30 at predetermined intervals in the width direction in a vertical stripe shape, a spiral shape, or the like, and bonding starch or carboxymethyl cellulose. , Polyvinyl alcohol, polyvinylpyrrolidone and other methods of bonding using a water-soluble binder selected from water-soluble polymers.
- a method of adhering by heat-sealing may be adopted.
- Example 1 A round-bottomed cylindrical separable flask having an inner diameter of 11 cm and an internal volume of 2 L equipped with a reflux condenser, a dropping funnel, a nitrogen gas introduction pipe, and a stirrer was prepared.
- the stirrer was equipped with a stirrer blade (flat blade) 200 whose outline is shown in FIG.
- the stirring blade 200 includes a shaft 200a and a flat plate portion 200b.
- the flat plate portion 200b is welded to the shaft 200a and has a curved tip.
- the flat plate portion 200b is formed with four slits S extending along the axial direction of the shaft 200a.
- the obtained monomer aqueous solution was added to the separable flask containing the solution containing sorbitan monolaurate, and the inside of the system was sufficiently replaced with nitrogen.
- the polymerization reaction was allowed to proceed by holding the reaction solution in the separable flask in a warm water bath at 70 ° C. for 60 minutes while stirring at a rotation speed of 700 rpm.
- the physiological saline solution used in this example is a 0.9 mass% NaCl aqueous solution.
- the burette portion 1 has an air introduction pipe 25 and a cock 24 connected to the burette.
- the burette portion 1 is fixed by a clamp 3.
- the flat plate-shaped measuring table 13 has a through hole 13a having a diameter of 2 mm formed in the central portion thereof, and is supported by a frame 11 having a variable height.
- the through hole 13a of the measuring table 13 and the cock 22 of the burette portion 1 are connected by a conduit 5.
- the inner diameter of the conduit 5 is 6 mm.
- the nylon mesh sheet 15 on which the water-absorbent resin particles 10a were placed was quickly moved so that the center thereof was at the position of the through hole 13a so that the water-absorbent resin particles 10a did not dissipate, and the measurement was started. ..
- the time when the air bubbles were first introduced from the air introduction pipe 25 into the burette pipe 21 was defined as the start of water absorption (0 seconds).
- the amount of pure water absorbed by the water-absorbent resin particles (room temperature, 25 ° C. ⁇ 2 ° C.) was measured by the following procedure. 1000 g of ion-exchanged water was weighed into a 2 L beaker, and 0.5 g of water-absorbent resin particles were added while stirring with a spatula so as not to generate maco. After continuing stirring for 20 seconds, the water-absorbent resin particles were sufficiently swollen by leaving them to stand for 30 minutes in a stationary state.
- a laminated body was obtained by applying a load of 141 kPa to the absorber sandwiched by the core wraps for 30 seconds.
- a SMMS non-woven fabric (basis weight 13 g / m 2 ) having a size of 32.5 cm ⁇ 45.0 cm was folded to a size of 45 cm ⁇ 16.25 cm, and then the above-mentioned laminate was wrapped with the non-woven fabric.
- the open three sides of the non-woven fabric wrapping the laminate were crimped with a heat sealer (Fuji Impulse Sealer, model number: FI-450-5, manufactured by Fuji Impulse) to seal the laminate.
- a heat sealer Fuji Impulse Sealer, model number: FI-450-5, manufactured by Fuji Impulse
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Abstract
Description
(A)内径30mmの色差計用無色透明丸型セル内に、吸水性樹脂粒子0.1gを均一に散布する。
(B)イオン交換水5.0gを上記丸型セルに添加し、上記吸水性樹脂粒子に吸水させる。
(C)イオン交換水添加5分後に、得られたゲルの明度L*を黒色背景で測定する。
(A)内径30mmの色差計用無色透明丸型セル内に、吸水性樹脂粒子0.1gを均一に散布する。
(B)イオン交換水5.0gを上記丸型セルに添加し、上記吸水性樹脂粒子に吸水させる。
(C)イオン交換水添加5分後に、得られたゲルの明度L*を黒色背景で測定する。
(A)内径30mmの色差計用無色透明丸型セル内に、吸水性樹脂粒子0.1gを均一に散布する。
(B)イオン交換水5.0gを上記丸型セルに添加し、上記吸水性樹脂粒子に吸水させる。
(C)イオン交換水添加5分後に、得られたゲルの明度L*を黒色背景で測定する。
(A)内径30mmの色差計用無色透明丸型セル内に、吸水性樹脂粒子0.1gを均一に散布する。
(B)イオン交換水5.0gを上記丸型セルに添加し、上記吸水性樹脂粒子に吸水させる。
(C)イオン交換水添加5分後に、得られたゲルの明度L*を黒色背景で測定する。
含水率=[Ww/(Ww+Ws)]×100
Ww:全重合工程の重合前の単量体水溶液に含まれる水分量から、乾燥工程により系外部に排出された水分量を差し引いた量に、凝集剤、表面架橋剤等を混合する際に必要に応じて用いられる水分量を加えた含水ゲル状重合体の水分量。
Ws:含水ゲル状重合体を構成するエチレン性不飽和単量体、架橋剤、開始剤等の材料の仕込量から算出される固形分量。
[実施例1]
還流冷却器、滴下ロート、窒素ガス導入管、及び撹拌機を備えた内径11cm、内容積2Lの丸底円筒型セパラブルフラスコを準備した。撹拌機には、図2に概形を示す撹拌翼(平板翼)200を取り付けた。撹拌翼200は、軸200a及び平板部200bを備えている。平板部200bは、軸200aに溶接されているとともに、湾曲した先端を有している。平板部200bには、軸200aの軸方向に沿って延びる4つのスリットSが形成されている。4つのスリットSは平板部200bの幅方向に配列されており、内側の二つのスリットSの幅は1cmであり、外側二つのスリットSの幅は0.5cmである。平板部200bの長さは約10cmであり、平板部200bの幅は約6cmである。準備したセパラブルフラスコ内で、n-ヘプタン293g、及び分散剤として無水マレイン酸変性エチレン・プロピレン共重合体(三井化学株式会社製、ハイワックス1105A)0.736gを混合した。セパラブルフラスコ内の混合物を撹拌機で撹拌しつつ、80℃まで昇温することにより、分散剤をn-ヘプタンに溶解させた。形成された溶液を50℃まで冷却した。
共沸蒸留により系外へ抜き出す水の量を271.0gに変更したこと、及び、重合体粒子と混合する非晶質シリカの量を重合体粒子質量に対して0.2質量%に変更したこと以外は実施例1と同様にして、229.0gの吸水性樹脂粒子を得た。吸水性樹脂粒子の中位粒子径は360μm、純水吸水量は684g/gであった。
第1段目の重合スラリー液の調製において窒素置換時の撹拌機回転数を350rpmに変更したこと、共沸蒸留により系外へ抜き出す水の量を257.2gに変更したこと、及び、重合体粒子と混合する非晶質シリカの量を重合体粒子質量に対して0.2質量%に変更したこと以外は実施例1と同様にして、231.2gの吸水性樹脂粒子を得た。吸水性樹脂粒子の中位粒子径は359μm、純水吸水量は452g/gであった。
第1段目の水性液の調製において内部架橋剤としてのエチレングリコールジグリシジルエーテルの添加量を0.0156g(0.090ミリモル)に変更したこと、第1段目重合スラリー液の調製において窒素置換時の撹拌機回転数を350rpmに変更したこと、第2段目の水性液の調製において内部架橋剤としてのエチレングリコールジグリシジルエーテルの添加量を0.0129g(0.074ミリモル)に変更したこと、共沸蒸留により系外へ抜き出す水の量を254.5gに変更したこと、及び、重合体粒子と混合する非晶質シリカの量を重合体粒子質量に対して0.2質量%に変更したこと以外は実施例1と同様にして、231.1gの吸水性樹脂粒子を得た。吸水性樹脂粒子の中位粒子径は370μm、純水吸水量は334g/gであった。
撹拌翼を翼径5cmの4枚傾斜パドル翼を2段で有するものに変更したこと、第1段目の水性液調製において、使用するラジカル重合開始剤を2,2’-アゾビス(2-アミジノプロパン)2塩酸塩0.092g(0.339ミリモル)及び過硫酸カリウム0.018g(0.068ミリモル)に変更したこと、内部架橋剤としてのエチレングリコールジグリシジルエーテル添加量を0.0046g(0.026ミリモル)に変更したこと、第1段目の重合スラリー液の調製において窒素置換時の撹拌機回転数を550rpmに変更したこと、第2段目の水性液調製において、使用するラジカル重合開始剤を2,2’-アゾビス(2-アミジノプロパン)2塩酸塩0.129g(0.475ミリモル)及び過硫酸カリウム0.026g(0.095ミリモル)に変更したこと、第2段目の水性液の調製後に、セパラブルフラスコ系内を25℃に冷却する際の撹拌機回転数を1000rpmに変更したこと、共沸蒸留により系外へ抜き出す水の量を216.7gに変更したこと、並びに、重合体粒子と混合する非晶質シリカの量を重合体粒子質量に対して0.2質量%に変更したこと以外は実施例1と同様にして、229.0gの吸水性樹脂粒子を得た。吸水性樹脂粒子の中位粒子径は348μmであった。
第2段目の水性液の調製後、セパラブルフラスコ系内の冷却温度を28℃に変更したこと、共沸蒸留により系外へ抜き出す水の量を204.7gに変更したこと以外は比較例1と同様にして、231.5gの吸水性樹脂粒子を得た。吸水性樹脂粒子の中位粒子径は337μmであった。
還流冷却器、滴下ロート、窒素ガス導入管、及び撹拌機を備えた、内径110mm、2L容の、4箇所の側壁バッフル付き丸底円筒型セパラブルフラスコ(バッフル幅:7mm)を準備した。撹拌機に、フッ素樹脂で表面処理された翼径50mmの4枚傾斜パドル翼を2段有する撹拌翼を装着した。準備したセパラブルフラスコ内でn-ヘプタン660mL、及びソルビタンモノラウレート(商品名:ノニオンLP-20R、HLB値8.6、日油株式会社製)0.984gを混合した。セパラブルフラスコ内の混合物を撹拌機で撹拌しつつ、50℃まで昇温することにより、ソルビタンモノラウレートをn-ヘプタンに溶解させた。形成された溶液を40℃まで冷却した。
吸水性樹脂の粒子の無加圧DWは、図4に示す測定装置を用いて測定した。測定は1種類の吸水性樹脂粒子に関して5回実施し、最低値と最高値とを除いた3点の測定値の平均値を求めた。
当該測定装置は、ビュレット部1、導管5、測定台13、ナイロンメッシュシート15、架台11、及びクランプ3を有する。ビュレット部1は、目盛が記載されたビュレット管21と、ビュレット管21の上部の開口を密栓するゴム栓23と、ビュレット管21の下部の先端に連結されたコック22と、ビュレット管21の下部に連結された空気導入管25及びコック24とを有する。ビュレット部1はクランプ3で固定されている。平板状の測定台13は、その中央部に形成された直径2mmの貫通孔13aを有しており、高さが可変の架台11によって支持されている。測定台13の貫通孔13aとビュレット部1のコック22とが導管5によって連結されている。導管5の内径は6mmである。
無加圧DW値(mL/g)=Wa/1.00
ゲル明度の測定は色差計(ZE6000、日本電色株式会社製)を用いて行った。測定は温度25±2℃、湿度50±10%の環境下で行なわれた。図3は、ゲル明度測定に用いた器具Xの模式断面図である。まず、筒状器具31の中に、内径30mm、高さ13mmで光学ガラス(パイレックス)製の無色透明である色差計用丸型セル32を入れた。丸型セル32内に、0.1gの吸水性樹脂粒子を均一に散布し、ピペットを用いて速やかにイオン交換水5.0gを添加し、蓋33を閉めた。筒状器具31及び蓋33は黒色である。イオン交換水の添加から5分間静置することにより、吸水性樹脂粒子を膨潤させ、測定用のゲル34を得た。色差計のゼロ校正、及び標準白板による標準校正を行い、ゲル34を含む器具Xを色差計にセットした後、反射測定モードにより明度L*を3回測定し、平均値を得た。結果を表1に示す。実施例及び比較例のいずれにおいても、添加したイオン交換水の全量が吸水性樹脂粒子に吸水され、吸水性樹脂粒子のダマ(未膨潤の小塊)は発生しなかった。丸型セル32に何も入れない状態で同様に測定したところ、明度L*は7.7であった。実施例1及び比較例3で得られた吸水性樹脂粒子の明度測定用ゲルの光学写真を、それぞれ図5(a)、図5(b)に示す。図5(a)、(b)の写真はゲル34の入った丸型セル32を黒色背景で下方から撮影したものである。
丸型セル32内に2.0gの乾燥状態の吸水性樹脂粒子を均一に散布し、イオン交換水を添加しなかったこと以外は上記ゲル明度の評価と同様にして、乾燥状態の吸水性樹脂粒子の明度L*を測定した。実施例及び比較例の吸水性樹脂粒子の明度L*はいずれも91~96の範囲内であった。
吸水性樹脂粒子の上述の中位粒子径は、温度25±2℃、湿度50±10%の環境下において、下記手順により測定した。すなわち、JIS標準篩を上から、目開き600μmの篩、目開き500μmの篩、目開き425μmの篩、目開き300μmの篩、目開き250μmの篩、目開き180μmの篩、目開き150μmの篩、及び受け皿の順に組み合わせた。組み合わせた最上の篩に、吸水性樹脂粒子50gを入れ、ロータップ式振とう器(株式会社飯田製作所製)を用いてJIS Z 8815(1994)に準じて分級した。分級後、各篩上に残った粒子の質量を全量に対する質量百分率として算出し粒度分布を求めた。この粒度分布に関して粒子径の大きい方から順に篩上を積算することにより、篩の目開きと篩上に残った粒子の質量百分率の積算値との関係を対数確率紙にプロットした。確率紙上のプロットを直線で結ぶことにより、積算質量百分率50質量%に相当する粒子径を中位粒子径として得た。
吸水性樹脂粒子の生理食塩水の保水量(室温、25℃±2℃)を下記手順で測定した。まず、吸水性樹脂粒子2.0gを量り取った綿袋(メンブロード60番、横100mm×縦200mm)を内容積500mLのビーカー内に設置した。吸水性樹脂粒子の入った綿袋内に0.9質量%塩化ナトリウム水溶液(生理食塩水)500gを、ママコができないように一度に注ぎ込んだ後、綿袋の上部を輪ゴムで縛り、30分静置させることで吸水性樹脂粒子を膨潤させた。30分経過後の綿袋を、遠心力が167Gとなるように設定した脱水機(株式会社コクサン製、品番:H-122)を用いて1分間脱水した後、脱水後の膨潤ゲルを含んだ綿袋の質量Wb[g]を測定した。吸水性樹脂粒子を添加せずに同様の操作を行い、綿袋の湿潤時の空質量Wc[g]を測定し、下記式から吸水性樹脂粒子の生理食塩水の保水量を算出した。結果を表1に示す。
保水量[g/g]=(Wb-Wc)/2.0
吸水性樹脂粒子の純水吸水量(室温、25℃±2℃)を下記手順で測定した。2L容のビーカーにイオン交換水1000gを量り取り、吸水性樹脂粒子0.5gを、ママコが発生しないようにスパチュラにて撹拌しつつ添加した。20秒間撹拌を続けた後、静置状態で30分間放置し、吸水性樹脂粒子を十分に膨潤させた。その後、目開き75μmのJIS標準篩を用いて、上記ビーカーの内容物をろ過し、該篩を水平に対して約30度の傾斜角となるように傾けた状態で30分間放置することにより、余剰の水分をろ別した。目開き75μm標準篩単独の質量Wd(g)はあらかじめ測定しておいた。吸水ゲルの入った該篩の質量We(g)を測定し、以下の式により、純水吸水量を求めた。
純水吸水量(g/g)=[We-Wd](g)/吸水性樹脂粒子の質量(g)
(評価用物品の作製)
気流型混合装置(有限会社オーテック社製、パッドフォーマー)を用いて、吸水性樹脂粒子10g及び粉砕パルプ10gを空気抄造によって均一混合することにより、40cm×12cmの大きさのシート状の吸収体を作製した。次に、吸収体と同じ大きさを有する坪量16g/m2のコアラップ(ティッシュペーパー)の上に吸収体を配置した後、吸収体の上面に、吸収体と同じ大きさを有する坪量16g/m2のコアラップ(ティッシュペーパー)を配置した。コアラップによって挟まれた吸収体に対して、141kPaの荷重を30秒間加えることにより積層体を得た。32.5cm×45.0cmの大きさのSMMS不織布(坪量13g/m2)を45cm×16.25cmのサイズになるように折り、その後、不織布で上述の積層体を包んだ。積層体を包んだ不織布の開放している三辺をヒートシーラー(富士インパルスシーラー、型番:FI-450-5形、富士インパルス製)で圧着して、積層体を密封した。これにより、評価用物品を得た。
温度25±2℃、湿度50±10%の環境下において、測定を行った。バットに、金網(開き目のサイズ:20mm×20mm、線径3mm)及び20Lの生理食塩水を入れて、液温を25.0±0.2℃に調整した。次いで、評価用物品を金網上に広げて配置し、生理食塩水水溶液中に10分間浸漬させた。その後、評価用物品ごと金網を持ち上げ、5分間水切りを行ってから、評価用物品の質量を測定した。吸収体膨潤容量(単位:g)は、試験前後の評価用物品の質量の差であり、以下の式により算出される。吸収体膨潤容量が大きいほど、吸収体の吸収量が大きいことを示す。
吸収体膨潤容量=試験後の評価用物品の質量(g)-試験前の評価用物品の質量(g)
Claims (8)
- 下記工程(A)、(B)及び(C)をこの順で含む方法により測定されるゲル明度L*が8~60である、吸水性樹脂粒子。
(A)内径30mmの色差計用無色透明丸型セル内に、吸水性樹脂粒子0.1gを均一に散布する。
(B)イオン交換水5.0gを前記丸型セルに添加し、前記吸水性樹脂粒子に吸水させる。
(C)イオン交換水添加5分後に、得られたゲルの明度L*を黒色背景で測定する。 - 生理食塩水保水量が30~60g/gである、請求項1に記載の吸水性樹脂粒子。
- 無加圧DW5分値が30ml/g以上である、請求項1又は2に記載の吸水性樹脂粒子。
- 請求項1~3のいずれか一項に記載の吸水性樹脂粒子を含有する、吸収体。
- 請求項4に記載の吸収体を備える、吸収性物品。
- おむつである、請求項5に記載の吸収性物品。
- 下記工程(A)、(B)及び(C)をこの順で含む方法により測定されるゲル明度L*が8~60である吸水性樹脂粒子を選別することを含む、吸水性樹脂粒子の製造方法。
(A)内径30mmの色差計用無色透明丸型セル内に、吸水性樹脂粒子0.1gを均一に散布する。
(B)イオン交換水5.0gを前記丸型セルに添加し、前記吸水性樹脂粒子に吸水させる。
(C)イオン交換水添加5分後に、得られたゲルの明度L*を黒色背景で測定する。 - 下記工程(A)、(B)及び(C)をこの順で含む方法により測定される吸水性樹脂粒子のゲル明度L*を調整することを含む、前記吸水性樹脂粒子を含有する吸収体の吸収量を向上させる方法。
(A)内径30mmの色差計用無色透明丸型セル内に、吸水性樹脂粒子0.1gを均一に散布する。
(B)イオン交換水5.0gを前記丸型セルに添加し、吸水性樹脂粒子に吸水させる。
(C)イオン交換水添加5分後に、得られたゲルの明度L*を黒色背景で測定する。
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| KR1020217036696A KR102947836B1 (ko) | 2019-04-23 | 2020-04-16 | 흡수성 수지 입자 |
| JP2021516063A JP7733572B2 (ja) | 2019-04-23 | 2020-04-16 | 吸水性樹脂粒子 |
| CN202080030277.2A CN113767136A (zh) | 2019-04-23 | 2020-04-16 | 吸水性树脂颗粒 |
| US17/604,949 US12533658B2 (en) | 2019-04-23 | 2020-04-16 | Water-absorbent resin particles |
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| WO2022210115A1 (ja) * | 2021-03-30 | 2022-10-06 | 住友精化株式会社 | 吸収体及び吸収性物品 |
| CN117098521A (zh) * | 2021-03-30 | 2023-11-21 | 住友精化株式会社 | 吸收体及吸收性物品 |
| EP4316441A4 (en) * | 2021-03-30 | 2025-03-05 | Sumitomo Seika Chemicals Co., Ltd. | ABSORBENT AND ABSORBENT ARTICLES |
Also Published As
| Publication number | Publication date |
|---|---|
| US20220219140A1 (en) | 2022-07-14 |
| US12533658B2 (en) | 2026-01-27 |
| KR102947836B1 (ko) | 2026-04-02 |
| EP3960792A4 (en) | 2023-01-04 |
| JPWO2020218167A1 (ja) | 2020-10-29 |
| EP3960792A1 (en) | 2022-03-02 |
| KR20220005483A (ko) | 2022-01-13 |
| JP7733572B2 (ja) | 2025-09-03 |
| CN113767136A (zh) | 2021-12-07 |
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