WO2015012273A1 - 吸水剤 - Google Patents

吸水剤 Download PDF

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WO2015012273A1
WO2015012273A1 PCT/JP2014/069354 JP2014069354W WO2015012273A1 WO 2015012273 A1 WO2015012273 A1 WO 2015012273A1 JP 2014069354 W JP2014069354 W JP 2014069354W WO 2015012273 A1 WO2015012273 A1 WO 2015012273A1
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naturally
water
biomass
derived polymer
nanofibers
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PCT/JP2014/069354
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English (en)
French (fr)
Japanese (ja)
Inventor
山口　正史
宇山　浩
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ユニ・チャーム株式会社
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Priority to CN201480013142.XA priority Critical patent/CN105026033B/zh
Priority to KR1020167002199A priority patent/KR102284629B1/ko
Publication of WO2015012273A1 publication Critical patent/WO2015012273A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • 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
    • 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
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • 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
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • 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
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
    • 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
    • C08J3/02—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
    • 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
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/04—Polyamides derived from alpha-amino carboxylic acids
    • 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
    • A61F2013/530131—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 being made in fibre but being not pulp
    • A61F2013/530226—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 being made in fibre but being not pulp with polymeric fibres
    • A61F2013/530313—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 being made in fibre but being not pulp with polymeric fibres being biodegradable
    • A61F2013/530321—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 being made in fibre but being not pulp with polymeric fibres being biodegradable in biopolymer, e.g. PHA
    • 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
    • A61F2013/530489—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 being randomly mixed in with other material
    • A61F2013/530496—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 being randomly mixed in with other material being fixed to fibres
    • 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
    • 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
    • C08J2300/16—Biodegradable polymers
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/04—Polyamides derived from alpha-amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

Definitions

  • the present invention relates to a water absorbing agent. More specifically, the present invention relates to a biodegradable absorbent obtained from a naturally derived polymer.
  • SAP superabsorbent polymers
  • fluff pulp fluff pulp
  • SAPs synthetic polymer SAPs
  • polyacrylates are widely used as SAPs.
  • naturally derived SAPs such as polyglutamates have attracted attention from the viewpoint of biodegradability.
  • Patent Document 1 provides a gel having a high degree of swelling, in which ⁇ -polyglutamic acid is crosslinked with a small amount of polyamine, and Disclosed is a method for producing a polyamine-crosslinked ⁇ -polyglutamic acid gel using a water-soluble carbodiimide and N-hydroxysuccinimide as a condensing agent and a condensing aid for the purpose of providing a method for obtaining a high yield. Yes. There are also attempts to increase the SAP ratio relative to fluff pulp in order to make absorbent articles thinner and more compact.
  • Patent Document 2 describes a method in which the entire surface of SAP is coated with hydrated microfibrils obtained from cellulose or a cellulose derivative. Disclosure. According to the method disclosed in Patent Document 2, when SAP is dispersed in a microfibril dispersion medium, high-concentration SAP can be stably dispersed. In the process of removing the dispersion medium, strong self-bonding is achieved.
  • a gel having a low polyamine residue content, a low crosslinking density, and a high degree of swelling is provided (see paragraph [0033]). Therefore, the compressive strength at the time of water retention is low, and it does not satisfy the required performance such as liquid oozing under body pressure as an absorbent article.
  • the method disclosed in Patent Document 2 seems to be effective for gel blocking due to welding of SAPs during water retention, but in order to essentially avoid gel blocking, the compressive strength of SAP (gel Strength) itself needs to be increased.
  • a method of increasing the crosslinking density by increasing the addition amount of the crosslinking agent is conceivable. Usually, when the crosslinking density is increased, the water absorption performance is lowered. Also, it is not desirable to increase the amount of crosslinking agent added from the viewpoint of safety and environmental impact.
  • the present invention has been made paying attention to such conventional problems.
  • the present invention is a water-absorbing agent comprising a crosslinked naturally-derived polymer and biomass nanofibers, wherein the crosslinked naturally-derived polymer and biomass nanofibers form particles, and the biomass nanofibers are present inside the particles. It is characterized by that.
  • the method of the present invention is a method for producing a water-absorbing agent comprising a cross-linked naturally-derived polymer and biomass nanofiber, Dissolving a naturally-derived polymer and preparing a solution of the naturally-derived polymer; A process of preparing biomass-derived nanofibers in which biomass nanofibers are dispersed by adding biomass nanofibers to a naturally-occurring polymer solution, and adding a cross-linking agent to the naturally-derived polymer solution in which biomass nanofibers are dispersed. And a step of crosslinking the naturally-derived polymer.
  • a water-absorbing agent comprising a cross-linked naturally-derived polymer and biomass nanofibers, wherein the cross-linked naturally-derived polymer and biomass nanofibers form particles, and the biomass nanofibers are present inside the particles.
  • Water-absorbing agent characterized by [2] The water-absorbing agent according to [1], wherein the naturally-derived polymer has a condensable functional group.
  • a water-absorbing agent having high water retention performance and high gel strength at the time of water absorption can be obtained by using a naturally-derived highly water-absorbing polymer in which biomass nanofibers are combined even inside the particles.
  • the main raw material for biomass nanofibers is naturally derived, and the amount of chemical cross-linking agent added can be kept at a low level. Therefore, CO 2 emissions must be reduced compared to general polyacrylate-based SAPs.
  • the biocompatibility is high as compared with a general polyacrylate SAP.
  • FIG. 1 is an electron micrograph (magnification 100 times) of the appearance of particles of the water-absorbing agent of the present invention.
  • FIG. 2 is an electron micrograph (magnification 500 times) obtained by freeze-drying the water-absorbing agent particles of the present invention once swelled with ion-exchanged water and photographing the outer surface thereof.
  • FIG. 3 is an electron micrograph (magnification 3000 times) of the outer surface of the water-absorbing agent particles of the present invention once swelled with ion-exchanged water and freeze-dried.
  • FIG. 4 is an electron micrograph (magnification 500 times) obtained by freeze-drying the water-absorbing agent particles of the present invention once swelled with ion-exchanged water and photographing a cross section thereof.
  • FIG. 5 is an electron micrograph (magnification 3000 times) of a cross-section of the water-absorbing agent particles of the present invention once swelled with ion-exchanged water and freeze-dried.
  • FIG. 6 is an electron micrograph of biomass nanofibers that are raw materials for the water-absorbing agent of the present invention.
  • the present invention is a water-absorbing agent comprising a crosslinked naturally-derived polymer and biomass nanofibers, wherein the crosslinked naturally-derived polymer and biomass nanofibers form particles, and the biomass nanofibers are present inside the particles. It is characterized by that.
  • the naturally-derived polymer used in the present invention is not particularly limited as long as it is a naturally-derived polymer.
  • Naturally-derived polymers refer to polymers obtained by fermentation with microorganisms, polymers extracted from natural products, and the like, and are generally called biopolymers.
  • the naturally derived polymer preferably has a condensable functional group, and is preferably hydrophilic.
  • the condensable functional group contributes to reacting with the crosslinking agent to crosslink the naturally derived polymer.
  • Examples of the condensable functional group include a carboxyl group and an amino group, and among them, the carboxyl group is preferable because it also imparts hydrophilicity.
  • Naturally-occurring polymers include polyglutamic acid (hereinafter also referred to as “PGA”), polyaspartic acid, polylysine, polyarginine and other polyamino acids, alginic acid, hyaluronic acid, chitosan and other polysaccharides, carboxymethylcellulose and other natural amino acids.
  • PGA polyglutamic acid
  • polyaspartic acid polylysine
  • polyarginine and other polyamino acids alginic acid
  • chitosan alginic acid
  • carboxymethylcellulose and other natural amino acids examples include, but are not limited to, polymers obtained by chemically modifying polymers.
  • the polyamino acid may be a copolymer.
  • Naturally derived polymers may be used as a mixture of two or more.
  • the molecular weight of the naturally derived polymer is not particularly limited, but the mass average molecular weight is preferably 10,000 to 13 million, more preferably 50,000 to 10 million, and still more preferably 300,000 to 5,000,000. If the molecular weight is too small, the number of uncrosslinked molecular chains per weight increases, resulting in a gel with a large amount of elution and low strength. If the molecular weight is too large, the viscosity at the time of dissolution increases, and the biomass nanofibers and the crosslinking agent are not uniformly dispersed.
  • the cross-linked naturally-derived polymer refers to a polymer obtained by reacting a naturally-derived polymer with a crosslinking agent. The crosslinking will be described later.
  • the biomass nanofiber refers to a biomass fiber having an average diameter of 4 to 1000 nm.
  • the average diameter of the biomass nanofiber is preferably 5 to 500 nm, more preferably 10 to 100 nm. If the average diameter is too small, the mechanical strength of the biomass nanofiber itself is lowered, and a reinforcing effect cannot be expected. If the average diameter is too large, the biomass nanofibers are difficult to interlace.
  • the length of biomass nanofiber is not specifically limited, Usually, it is 100 times or more of a diameter. The average diameter and length can be measured with an electron beam microscope.
  • biomass nanofibers can be produced by high-pressure jetting a biomass dispersion fluid and causing it to collide with a collision hard body to wet-grind the biomass.
  • the pressure of the high pressure injection is preferably 100 to 245 MPa, and the injection speed is preferably 440 to 700 m / s.
  • the dispersed fluid of biomass that has been collided with the collision hard body by high-pressure injection is collected and again injected with high pressure from the nozzle toward the collision hard body, and this operation is performed a required number of times, for example, about 1 to 50 times, preferably Repeat about 1 to 40 times, more preferably about 1 to 30 times, still more preferably about 1 to 20 times, particularly preferably about 1 to 10 times.
  • the fibers are untangled, the fiber diameter is reduced, and the nano size is reduced.
  • shapes such as ball shape and flat plate shape, are mentioned.
  • the diameter of the nozzle for high-pressure injection of the dispersion fluid is preferably 0.1 to 0.8 mm.
  • a method of kneading with a twin-screw kneader to defibrate a strong secondary wall a method such as a high-pressure homogenizer or microfluidizer that pushes pulp slurry into a narrow gap and advances defibration by releasing the pressure, between rotating grinding wheels
  • Cellulose nanofibers can be produced by a grinder method that grinds pulp with cellulose, a method in which the interaction between cellulose nanofibers is greatly reduced by TEMPO oxidation that selectively introduces carboxyl groups on the cellulose surface, and the pulp slurry is simply stirred with a blender. Fiber can also be produced.
  • biomass that is a main raw material for biomass nanofibers
  • examples of biomass that is a main raw material for biomass nanofibers include cellulose, chitin, and chitosan.
  • examples of cellulose include softwood bleached kraft pulp (NBKP), hardwood pulp, cotton pulp such as cotton linter, non-wood pulp such as straw pulp, bagasse pulp, and bacterial cellulose, but from the viewpoint of average molecular weight and cost. NBKP is preferred.
  • Biomass nanofiber is commercially available from Sugino Machine Co., Ltd. under the trade name “BiNFi-s”. Such commercial products can also be used in the present invention.
  • the crosslinked naturally-derived polymer and biomass nanofibers constituting the water-absorbing agent of the present invention form particles.
  • the shape of the particles is not particularly limited, but is preferably spherical.
  • the size of the particle (projected area equivalent circle diameter) is preferably 150 to 850 ⁇ m, more preferably 200 to 600 ⁇ m, and still more preferably 300 to 400 ⁇ m. If the particles are too small, the particle gap at the time of swelling becomes small, and when incorporated in an absorber, blocking is caused. If the particles are too large, the specific surface area becomes small and the water absorption speed becomes slow.
  • the size of the particles (projected area equivalent circle diameter) can be measured with an electron microscope.
  • FIG. 1 shows an electron micrograph (magnification 100 times) of the appearance of the water-absorbing agent particles of the present invention. Also, electron micrographs obtained by freeze-drying particles once swollen with ion-exchanged water and photographing the outer surface are shown in FIG. 2 (magnification 500 times) and FIG. 3 (magnification 3000 times).
  • FIG. 6 is an electron micrograph of biomass nanofibers that are raw materials for the water-absorbing agent of the present invention.
  • biomass nanofibers are added to increase the gel strength.
  • a method of increasing the amount of the crosslinking agent added is conceivable.
  • the gel strength increases even during water absorption due to an increase in the crosslinking density.
  • the cross-linking points are strong because they are cross-linked by chemical bonds, and the density is increased to inhibit swelling deformation.
  • the gel strength is increased by the mechanical strength of the entangled biomass nanofibers. Since it is not as strong as chemical bonds, it has a relatively high degree of freedom for swelling deformation. In addition, it becomes easy to entangle as biomass nanofiber becomes long. Biomass that has not been made into fine fibers is less likely to be entangled. Even if biomass nanofibers are added, if PGA is not chemically crosslinked at all, PGA will be dissolved.
  • the ratio of the cross-linked naturally-derived polymer and biomass nanofiber is preferably 0.1 to 40 mass for biomass nanofiber with respect to 100 mass parts (solid content basis) of the total amount of cross-linked naturally-derived polymer and biomass nanofiber. Parts (solid content basis), more preferably 3 to 30 parts by mass (solid content basis), and further preferably 5 to 20 parts by mass (solid content basis). If the amount of biomass nanofiber is too small, sufficient mechanical strength cannot be obtained. When there is too much quantity of biomass nanofiber, it will become a weak gel because crosslinking efficiency falls.
  • the method for producing a water-absorbing agent of the present invention includes a step of dissolving a naturally-derived polymer and preparing a solution of the naturally-derived polymer (dissolution step), dispersing the biomass nanofiber in the solution of the naturally-derived polymer, A step of preparing a solution of a naturally-derived polymer with dispersed therein (dispersion step), and a step of adding a crosslinking agent to the solution of the naturally-derived polymer in which biomass nanofibers are dispersed to crosslink the naturally-derived polymer (crosslinking step). including.
  • the production method of the present invention further includes a step of wet-grinding a hydrogel containing a cross-linked naturally-derived polymer obtained in the step of cross-linking a naturally-derived polymer (grinding step), a water-miscible organic solvent in the wet-ground hydrogel And may include one or more steps of dehydrating the hydrogel (dehydration step) and drying the dehydrated hydrogel (drying step).
  • the step of preparing the naturally derived polymer solution can be performed by dissolving the aforementioned naturally derived polymer in a solvent such as water.
  • a solvent such as water.
  • water is preferable.
  • an aqueous solution of a naturally derived polymer is obtained.
  • the concentration of the naturally-derived polymer in the solution is preferably 1 to 30% by mass (based on solid content), more preferably 3 to 20% by mass (based on solid content), and further preferably 5 to 10% by mass. (Based on solid content). If the concentration of the naturally derived polymer is too thin, the recovered amount of the composite product is low and the productivity is deteriorated.
  • the method of dissolving is not particularly limited, and it can be dissolved by adding a naturally derived polymer to a solvent and stirring.
  • the naturally-derived polymer crosslinked is obtained by a crosslinking reaction in an aqueous solution, the naturally-derived polymer is preferably in the form of a water-soluble salt.
  • the naturally-derived polymer having a carboxyl group is preferably in the form of a metal salt such as sodium salt or potassium salt, or an ammonium salt or an amine salt, and the naturally-derived polymer having an amino group is hydrochloride, It is preferably in the form of an inorganic acid salt such as sulfate or an organic acid salt such as acetate.
  • the biomass nanofibers are dispersed in the natural polymer solution to prepare a natural polymer solution in which the biomass nanofibers are dispersed (dispersing step).
  • the method for dispersing the biomass nanofibers in the natural polymer solution is not particularly limited.
  • the biomass nanofibers are added to the natural polymer solution and stirred and mixed, and the biomass nanofiber dispersion is prepared in advance.
  • the biomass nanofiber dispersion is added to the naturally occurring polymer solution and mixed, and the biomass that is the raw material of the biomass nanofiber is added to the naturally occurring polymer solution, and the biomass in the naturally occurring polymer solution is added.
  • biomass nanofiber dispersion there is a method of wet-grinding to form nanofibers, but it is preferable to prepare a biomass nanofiber dispersion in advance and add the biomass nanofiber dispersion to the naturally occurring polymer solution and mix.
  • a method for preparing a dispersion of biomass nanofibers the above-described method for producing biomass nanofibers can be employed.
  • a biomass dispersion in which biomass is dispersed in water is injected at a high pressure of 100 to 245 MPa.
  • a biomass nanofiber dispersion can be prepared by colliding with the impacting hard body and wet pulverizing the biomass.
  • a crosslinking agent is added to the solution of the naturally derived polymer in which the biomass nanofibers are dispersed to crosslink the naturally derived polymer (crosslinking step).
  • the crosslinking agent is not particularly limited as long as it can crosslink naturally derived polymers.
  • alkylene such as 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-heptanediamine, 1,6-hexanediamine, etc.
  • polyamine Compounds having two or more amino groups such as diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine (hereinafter also referred to as “polyamine”), amino group-containing polymers such as polylysine and chitosan, etc. It can be used as a crosslinking agent.
  • the crosslinking agent used for crosslinking the naturally-derived polymer includes two carboxyl groups such as fumaric acid, maleic acid, itaconic acid, citraconic acid, and trimellitic acid.
  • the compounds having the above, carboxyl group-containing polymers such as polyacrylic acid, polymethacrylic acid, poly- ⁇ -glutamic acid, alginic acid, and hyaluronic acid can be used as the crosslinking agent.
  • the amount of the crosslinking agent used for crosslinking the naturally-derived polymer is preferably 0.01 to 100 mol, more preferably 0.1 to 20 mol, and still more preferably 100 mol of the naturally-derived polymer. Is 0.3 to 10 mol. If the amount of the crosslinking agent is too small, the crosslinking density tends to be low, and the gel state may be difficult to obtain. When there is too much quantity of a crosslinking agent, there exists a possibility that a crosslinking density may become high easily and the swelling degree of the absorber obtained may become low.
  • a condensing agent and a condensing aid may be used in combination with the crosslinking agent.
  • a condensing agent and a condensing aid are used in combination, an amide bond can be formed more efficiently.
  • a water-soluble carbodiimide is mentioned as a condensing agent.
  • the water-soluble carbodiimide is a compound having a carbodiimide group (—N ⁇ C ⁇ N—) in the molecule and having water solubility.
  • water-soluble carbodiimide examples include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (hereinafter also referred to as “EDC”) or a salt thereof, 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide- Meto-p-toluenesulfuric acid or a salt thereof, dicyclohexylcarbodiimide, and the like are preferable.
  • EDC 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide- Meto-p-toluene sulfate.
  • the amount of the condensing agent to be used is 0 to 50 mol, preferably 1 to 40 mol, more preferably 2 to 30 mol, per 1 mol of the crosslinking agent used.
  • N-hydroxyimide is a compound having an N-hydroxyimide group (— (C ⁇ O) — (N—OH) — (C ⁇ O) —) in the molecule. That is, this compound is represented by the following general formula. R 1 — (C ⁇ O) — (N—OH) — (C ⁇ O) —R 2
  • a ring structure may be formed by combining R 1 and R 2 .
  • a compound in which R 1 and R 2 are combined to form a 5-membered ring with the two carbons in R 1 and R 2 and an N-hydroxyimide group is preferred.
  • N-hydroxyimide is preferably water-soluble.
  • N-hydroxyimide that can be used include N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N, N'-dihydroxycyclohexanetetracarboxylic imide, N -Hydroxyphthalic acid imide, N-hydroxytetrabromophthalic acid imide, N-hydroxytetrachlorophthalic acid imide, N-hydroxyhetic acid imide, N-hydroxyhymic acid imide, N-hydroxytrimellitic acid imide, N, N Examples include '-dihydroxypyromellitic imide and N, N'-dihydroxynaphthalene tetracarboxylic imide.
  • N-hydroxysuccinimide (hereinafter also referred to as “NHS”) is most preferable.
  • the amount of the condensation aid used is 0 to 50 mol, preferably 1 to 40 mol, more preferably 2 to 30 mol, per 1 mol of the crosslinking agent used.
  • the usage-amount of a condensation adjuvant shall be equimolar with the usage-amount of the condensing agent used.
  • the concentration of the naturally-derived polymer when the naturally-derived polymer is crosslinked is preferably 1 to 40% by mass, more preferably 2 to 20% by mass, and further preferably 3 to 15% by mass. If the concentration of the naturally-derived polymer is too high, the resulting hydrogel has a high viscosity and may be difficult to stir. If the concentration of the naturally derived polymer is too low, the recovered amount of the composite product is low and the productivity is deteriorated.
  • the conditions for the crosslinking step are not particularly limited. It may be room temperature or may be heated. However, if the temperature is too low, the crosslinking reaction takes a very long time, so it is preferable to perform heating.
  • the temperature in the crosslinking step is preferably 10 to 100 ° C., more preferably 15 to 70 ° C., and further preferably 20 ° C. to 50 ° C. When it is too high, the naturally-derived polymer is easily decomposed. Therefore, it is preferable to carry out at around room temperature.
  • the pH during the crosslinking reaction is not particularly limited, but is preferably 5 to 12, more preferably 6 to 11, and still more preferably 7 to 10.
  • the reaction time in the crosslinking step is preferably 5 minutes to 6 hours, more preferably 10 minutes to 3 hours, and further preferably 20 minutes to 2 hours.
  • the reaction solution may be stirred or allowed to stand as necessary. Preferably, it is left still. After sufficient time for the crosslinking reaction, a gel is obtained in the reaction solution. By washing this reaction solution with water (preferably distilled water), the condensing agent and the condensation aid in the reaction solution are removed, and a gel in which the naturally derived polymer is crosslinked with a crosslinking agent is obtained.
  • the hydrogel containing the crosslinked naturally-derived polymer obtained in the step of crosslinking the naturally-derived polymer is wet-pulverized (pulverization step).
  • the hydrogel is pulverized to a desired size in a water-containing state (ie, wet pulverization).
  • the pulverization is preferably carried out after coarse pulverization in advance.
  • Coarse pulverization is performed by stirring the hydrogel obtained by the crosslinking reaction with, for example, a spatula.
  • the hydrogel is pulverized using an apparatus suitable for wet pulverization such as a homomixer, a homogenizer, a bead mill, and a pipe mixer.
  • the ground hydrogel is referred to as hydrogel particles.
  • the average particle size of the hydrogel particles can be appropriately set depending on the use of the finally obtained dry gel powder or depending on the apparatus used for pulverization, but is preferably 10 ⁇ m to 10 mm, more preferably 100 ⁇ m to 3 mm.
  • a water-miscible organic solvent described later may be added. That is, you may grind
  • a water-miscible organic solvent By adding a water-miscible organic solvent, the hydrogel is dehydrated and volume-reduced (shrinks), the viscosity of the dispersion during wet grinding is lowered, and fluidity is restored. Even when the viscosity is increased during the pulverization, the water-miscible organic solvent can be added on the way to continue the pulverization. Thus, the wet pulverization step and the dehydration step described later may be performed simultaneously.
  • the hydrogel is prepared by converting the carboxyl group portion of the naturally-derived polymer into a water-soluble salt form such as a sodium salt.
  • a water-soluble salt form such as a sodium salt.
  • salt-form hydrogels are made into dry gel powders, they may absorb moisture in the atmosphere and the powders may coalesce. Therefore, after preparing the hydrogel, an inorganic acid or an organic acid may be added to partially change the salt form to the free acid form.
  • the dry gel powder obtained from the hydroacid in the free acid form has reduced hygroscopicity compared to the dry gel powder in the salt form, so that the powders are less likely to coalesce.
  • the inorganic acid and organic acid examples include sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid and the like.
  • the inorganic acid or organic acid is preferably mixed with a water-miscible organic solvent and added to the hydrogel particles. This is because when an inorganic acid or an organic acid is added, the hydrogel is uniformly neutralized to obtain hydrogel particles in a uniform free acid form.
  • a water-miscible organic solvent is added to the wet-pulverized hydrogel to dehydrate the hydrogel (dehydration step).
  • the hydrogel particles When the hydrogel particles are immersed in the water-miscible organic solvent, the water contained in the hydrogel particles is discharged into the water-miscible organic solvent.
  • the hydrogel particles may be dehydrated and shrink to a fine particle size. Furthermore, unnecessary substances such as unreacted crosslinking agents and condensing agents used for crosslinking the naturally derived polymer are also discharged together with water from the hydrogel particles.
  • the water miscible organic solvent is not particularly limited.
  • lower alcohols such as methanol, ethanol, isopropanol, n-propanol, tertiary butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.
  • Glycol ethers, and acetone are preferable.
  • These water-miscible organic solvents may be used singly or in combination of two or more, or two or more solvents may be added sequentially according to the dispersion state.
  • the immersion of the hydrogel particles in the water-miscible organic solvent may be repeated several times.
  • the solvent containing water discharged from the hydrogel particles is removed by filtration or decantation, and a new water-miscible organic solvent is added to the hydrogel particles.
  • the hydrogel particles are dehydrated and contracted to become fine particles having a very low water content.
  • a different water-miscible organic solvent may be used for each soaking.
  • the amount of the water-miscible organic solvent used varies depending on the type and the amount of water at the time of hydrogel preparation, but preferably 1 volume (equal amount) to 20 times the hydrogel per immersion.
  • the capacity is more preferably 2 to 10 times the capacity, and further preferably 3 to 7 times the capacity.
  • the time for immersing the hydrogel particles in the water-miscible organic solvent varies depending on the type and amount of the solvent, but is preferably 1 minute to 2 hours in consideration of workability per one time of immersion. Preferably it is 2 minutes to 1 hour, more preferably 3 minutes to 30 minutes. If necessary, the hydrogel particles immersed in a water-miscible organic solvent may be rinsed with an appropriate liquid.
  • the dehydrated hydrogel is dried (drying step).
  • the hydrogel particles obtained after the dehydration step have a low water content and hardly contain moisture. Therefore, the water-miscible organic solvent is removed by filtration or decantation, and air drying or standing drying is preferably performed at room temperature to 150 ° C., more preferably 35 ° C. to 125 ° C., and even more preferably 50 ° C. to 100 ° C. Thus, a dry gel powder is obtained. Thus, since the hydrogel particles are not exposed to severe drying conditions, the particles do not coalesce during drying.
  • the particle size of the obtained dried gel powder can be determined in consideration of the use of the dried gel powder and is not particularly limited. That is, a dry gel powder having a desired particle size can be obtained according to the pulverization apparatus (homomixer, homogenizer, etc.) used in the above pulverization step and the pulverization force thereof.
  • pulverization apparatus homomixer, homogenizer, etc.
  • the dry gel powder obtained by the above method swells without dissolving when immersed in water, and regenerates the hydrogel. Therefore, the dry gel powder obtained by the above method retains a network structure (gel state).
  • Example 1 1.359 g of ⁇ -PGA (Na type, 500 KDa, manufactured by Bio Leaders Co., Ltd.) (9 mmol of glutamic acid unit (1 unit of glutamic acid constituting ⁇ -PGA is 151 g / mol)) is dissolved in ion-exchanged water to obtain an aqueous solution.
  • ⁇ -PGA ⁇ -PGA
  • ion-exchanged water ion-exchanged water
  • 3.02 g of cellulose nanofiber 5% aqueous dispersion (BiNFi-s NMa, average polymerization degree 530, average diameter 0.02 ⁇ m, average length 2 ⁇ m, manufactured by Sugino Machine Co., Ltd.) (vs.
  • EDC 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide
  • Comparative Example 1 A water-absorbing agent was prepared in the same manner as in Example 1 except that 1.51 g of ⁇ -PGA (glutamate unit 10 mmol) was used and cellulose nanofibers were not added, and the gel strength and water retention capacity were measured. The measurement results are shown in Table 1.
  • Example 2 The cellulose nanofiber 5% aqueous dispersion was changed from BiNFi-s NMa to BiNFi-s AMa (average polymerization degree 200, average diameter 0.02 ⁇ m, average length 2 ⁇ m, manufactured by Sugino Machine Co., Ltd.). In the same procedure as described above, a water-absorbing agent was prepared, and the gel strength and water retention capacity were measured. The measurement results are shown in Table 1.
  • Example 3 The cellulose nanofiber 5% aqueous dispersion was changed from BiNFi-s NMa to BiNFi-s FMa (average polymerization degree 600, average diameter 0.02 ⁇ m, average length 2 ⁇ m, manufactured by Sugino Machine Co., Ltd.). In the same procedure as described above, a water-absorbing agent was prepared, and the gel strength and water retention capacity were measured. The measurement results are shown in Table 1.
  • Example 4 A water-absorbing agent was prepared in the same manner as in Example 1 except that ⁇ -PGA was changed to one having a molecular weight of 50 KDa (manufactured by Bioleaders Co., Ltd.), and the gel strength and water retention capacity were measured. The measurement results are shown in Table 1.
  • Example 5 A water-absorbing agent was prepared in the same manner as in Example 1 except that ⁇ -PGA was changed to one having a molecular weight of 2000 KDa (manufactured by Bioleaders Co., Ltd.), and gel strength and water retention capacity were measured. The measurement results are shown in Table 1.
  • Example 6 The ⁇ -PGA was changed to one having a molecular weight of 2000 KDa (manufactured by BioLeaders Co., Ltd.), and the fine cellulose fiber 5% aqueous dispersion was changed from BiNFi-s NMa to BiNFi-s FMa.
  • the water absorbing agent was prepared by the procedure described above, and the gel strength and water retention capacity were measured. The measurement results are shown in Table 2.
  • Example 7 A water absorbing agent was prepared in the same manner as in Example 6 except that the amount of cellulose nanofiber added was changed to 20% by mass of ⁇ -PGA, and the gel strength and water retention capacity were measured. The measurement results are shown in Table 2.
  • Example 8 A water-absorbing agent was prepared in the same manner as in Example 6 except that the amount of cellulose nanofiber added was changed to 30% by mass of ⁇ -PGA, and the gel strength and water retention capacity were measured. The measurement results are shown in Table 2.
  • Comparative Example 3 A water-absorbing agent was prepared in the same manner as in Example 6 except that cellulose nanofibers were not added, and gel strength and water retention capacity were measured. The measurement results are shown in Table 2.
  • Comparative Example 4 A water absorbing agent was prepared in the same manner as in Comparative Example 3 except that the amount of addition of pentaethylenehexamine as a cross-linking agent was changed to 6 mol% with respect to PGA, and the gel strength and water retention capacity were measured. The measurement results are shown in Table 2.
  • Comparative Example 5 A water-absorbing agent was prepared in the same manner as in Comparative Example 3 except that the addition amount of pentaethylenehexamine as a cross-linking agent was changed to 9 mol% relative to PGA, and the gel strength and water retention capacity were measured. The measurement results are shown in Table 2.
  • the gel strength tended to increase with the higher average molecular weight.
  • the water retention capacity when the average molecular weight of the polyglutamic acid, which is a naturally derived polymer, is small, the liquid retention tends to be low.
  • the gel strength was improved in the case where the average molecular weight was large, while the water retention capacity tended to be lower than that in the middle where the average molecular weight was medium. It can be seen that for the purpose of increasing the gel strength, it is better to use polyglutamic acid having a large average molecular weight.
  • the gel strength tends to be lowered if the crosslinking agent concentration at the time of synthesis is excessively increased.
  • the gel strength tends to decrease if the addition amount is excessively increased (qualitatively, the elongation is lost and the state becomes brittle). It can be seen that when the gel strength is increased by increasing the concentration of the crosslinking agent, the degree of decrease in the water retention capacity is lower when the gel strength is increased by adding cellulose.
  • the water-absorbing agent of the present invention can be suitably used as a raw material constituting an absorbent body of absorbent articles such as disposable diapers and sanitary napkins.

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WO2023070185A1 (pt) * 2021-10-25 2023-05-04 Cnpem - Centro Nacional De Pesquisa Em Energia E Materiais Espuma porosa para retenção de compostos orgânicos e inorgânicos, processo de produção da mesma e seus usos

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CN105601952B (zh) * 2016-01-14 2018-07-10 北京化工大学 一种聚天冬氨酸复合水凝胶及其制备方法
CN107262048B (zh) * 2017-05-11 2020-07-24 海南椰国食品有限公司 细菌纤维素复合吸湿剂的低温再生除湿材料
KR102259576B1 (ko) 2017-10-31 2021-06-02 주식회사 씨앤엘테크놀로지 천연성분의 고흡수성 고분자 섬유원사 및 그 제조방법
CN111378201B (zh) * 2020-05-13 2022-08-12 海南大学 一种环境友好型高吸水保水材料的制备方法
CN113582770A (zh) * 2021-08-12 2021-11-02 吉林隆源农业服务有限公司 一种玉米种植用缓释长效复合肥及其制备方法
CN115716924A (zh) * 2022-11-15 2023-02-28 西北农林科技大学 一种高分子水凝胶及其制备方法、应用

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