CN105026033A - Water absorbent - Google Patents

Water absorbent Download PDF

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Publication number
CN105026033A
CN105026033A CN201480013142.XA CN201480013142A CN105026033A CN 105026033 A CN105026033 A CN 105026033A CN 201480013142 A CN201480013142 A CN 201480013142A CN 105026033 A CN105026033 A CN 105026033A
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natural origin
nano fiber
macromolecule
high molecular
biomass nano
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CN201480013142.XA
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CN105026033B (en
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山口正史
宇山浩
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Unicharm Corp
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Unicharm Corp
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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
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    • 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
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  • Absorbent Articles And Supports Therefor (AREA)
  • Polyamides (AREA)

Abstract

The invention provides an absorbent that has excellent water-retention capacity and gel strength and is environmentally friendly. A water absorbent comprising cross-linked naturally derived polymers and biomass nanofibers, characterized in that the cross-linked naturally derived polymers and biomass nanofibers form particles, and the biomass nanofibers are present inside the particles. The water absorbent can be manufactured by dissolving the naturally derived polymers, dispersing the biomass nanofibers in the resulting solution, adding a cross-linking agent to the liquid dispersion and cross-linking the naturally derived polymers, wet-granulating the resulting hydrogel, and dewatering and then drying the hydrogel.

Description

Water absorbing agent
Technical field
The present invention relates to a kind of water absorbing agent.In more detail, a kind of absorbent of the biological degradability obtained by natural origin macromolecule is related to.
Background technology
The absorber of the absorbent commodity such as disposable diaper or physiological articles uses super absorbent polymer (hereinafter also referred to " SAP ") and Time of Fluff Slurry usually.
As SAP, use the synthesized polymer system SAP such as polyacrylate system in a large number at present, but in recent years, the natural origin system SAP such as polyglutamate system get most of the attention from the viewpoint of biological degradability.
Such as, the object of International Publication No. 2007/034785 publication (hereinafter referred to as " patent document 1 ") is, there is provided and be cross-linked the gel with high swelling degree of gamma-polyglutamic acid-with a small amount of polyamine and obtain the method for this gel with high yield, disclose and use water-soluble carbodiimide and N-hydroxy-succinamide as condensing agent and condensation auxiliary agent to the method for the gamma-polyglutamic acid-gel manufacturing polyamine and be cross-linked.
In addition, in order to thinning, the miniaturization of absorbent commodity, attempt the ratio improving SAP relative to Time of Fluff Slurry.But there are the following problems: the ratio of SAP is higher, when absorbing water, more cause the what is called " gel blocking phenomenon " based on SAP characteristic, absorbent product cannot play function with the efficiency as calculated.In order to solve this problem, Japan Patent No. 3016367 description (hereinafter referred to as " patent document 2 ") discloses the method covered with the microfibril with hydrability obtained by cellulose or cellulose derivative on the whole surface of SAP.Method disclosed in patent document 2, if disperse SAP in the decentralized medium of microfibril, the SAP of high concentration then can be made stably to disperse, in the process of removing decentralized medium, self-adhesion and become gypsum shape securely, forms network structure, wrap into SAP particle and mechanical type coated while, microfibril is combined by ionic hydrogen bond action each other, reliably keeps SAP particle (with reference to paragraph [0017]).
Prior art document
Patent document
Patent document 1: International Publication No. 2007/034785 publication
Patent document 2: Japan Patent No. 3016367 description
Summary of the invention
The problem that invention will solve
Method disclosed in patent document 1, can provide the gel (with reference to paragraph [0033]) that a kind of Polyamine residues content is few, crosslink density is low, swellbility is high.Therefore, compression resistant intensity during water conservation is low, as absorbent commodity purposes, and the performance required by the liquid that cannot meet body pressure oozes out etc.
Think method disclosed in patent document 2 to be bonded to each other SAP during water conservation and the gel blockage that causes is effective, but in order to substantially avoid gel blockage, need the compression resistant intensity (gel strength) improving SAP itself.In order to improve gel strength, consider that the addition by increasing crosslinking agent improves the method for crosslink density, but when usually improving crosslink density, water absorbing properties reduces.In addition, from the viewpoint of security and ambient influnence, do not wish the addition increasing crosslinking agent.
Solve the means of problem
The present invention is conceived to such existing issue point and completes.
The present invention is the water absorbing agent containing the natural origin macromolecule be cross-linked and biomass nano fiber, it is characterized in that, the natural origin macromolecule be cross-linked and biomass nano processbearing astrocyte particle, biomass nano fiber is present in the inside of particle.
In addition, method of the present invention is the method for the water absorbing agent manufactured containing the natural origin macromolecule be cross-linked and biomass nano fiber, and it comprises following operation:
Dissolve natural origin macromolecule and prepare the operation of the high molecular solution of natural origin;
In the high molecular solution of natural origin, disperse biomass nano fiber, preparation is dispersed with the operation of the high molecular solution of natural origin of biomass nano fiber; With
Crosslinking agent is added, the crosslinked high molecular operation of natural origin in the high molecular solution of the natural origin being dispersed with biomass nano fiber.
The present invention includes following scheme.
[1] water absorbing agent, it contains the natural origin macromolecule and biomass nano fiber that have been cross-linked, it is characterized in that, the natural origin macromolecule be cross-linked and biomass nano processbearing astrocyte particle, biomass nano fiber is present in the inside of particle.
[2] water absorbing agent Gen Ju [1], is characterized in that, natural origin macromolecule has condensation functional group.
[3] according to [1] or the water absorbing agent described in [2], it is characterized in that, natural origin macromolecule is polyglutamic acid.
[4] water absorbing agent according to any one of [1] ~ [3], it is characterized in that, the average diameter of biomass nano fiber is 4 ~ 1000nm.
[5] manufacture a method for the water absorbing agent containing the natural origin macromolecule be cross-linked and biomass nano fiber, it comprises following operation:
Dissolve natural origin macromolecule and prepare the operation of the high molecular solution of natural origin;
In the high molecular solution of natural origin, disperse biomass nano fiber, preparation is dispersed with the operation of the high molecular solution of natural origin of biomass nano fiber; With
Crosslinking agent is added, the crosslinked high molecular operation of natural origin in the high molecular solution of the natural origin being dispersed with biomass nano fiber.
[6] method Gen Ju [5], it also comprises the operation by carrying out case of wet attrition containing the high molecular hydrogel of the natural origin be cross-linked obtained in the high molecular operation of crosslinked natural origin.
[7] method Gen Ju [6], its be also included in the hydrogel of case of wet attrition add water Combination organic solvent and by hydrogel dewater operation.
[8] method Gen Ju [7], it also comprises the operation of the hydrogel drying of having dewatered.
[9] method according to any one of [5] ~ [8], it is characterized in that, the amount of biomass nano fiber is 1 ~ 30 mass parts (solid constituent benchmark) relative to total amount 100 mass parts (solid constituent benchmark) of natural origin macromolecule and biomass nano fiber.
[10] absorbent commodity, it contains [1] ~ any one of [4] described in water absorbing agent.
Invention effect
According to the present invention, being compounded with the super absorbent polymer of the natural origin of biomass nano fiber until inside particles by being formed, the large water absorbing agent of gel strength during the high and water suction of water retention property can be obtained.
In addition, the main material of biomass nano fiber is natural origin, and the addition of chemical cross-linking agent also can suppress in low-level, therefore, compared with general polyacrylate system SAP, can reduce CO 2discharge rate, and when washing discarded in discarded and soil, also can promptly biodegradation, and environmental suitability is high.And then compared with general polyacrylate system SAP, biocompatibility is also high.
Accompanying drawing explanation
Fig. 1 is the electron micrograph (multiplying power 100 times) of the outward appearance of the particle of water absorbing agent of the present invention.
Fig. 2 is the swelling thing freeze drying making the particle of water absorbing agent of the present invention swelling temporary transient ion exchange water and obtain, and takes its outer surface and the electron micrograph (multiplying power 500 times) obtained.
Fig. 3 is the swelling thing freeze drying making the particle of water absorbing agent of the present invention swelling temporary transient ion exchange water and obtain, and takes its outer surface and the electron micrograph (multiplying power 3000 times) obtained.
Fig. 4 is the swelling thing freeze drying making the particle of water absorbing agent of the present invention swelling temporary transient ion exchange water and obtain, and takes its section and the electron micrograph (multiplying power 500 times) obtained.
Fig. 5 is the swelling thing freeze drying making the particle of water absorbing agent of the present invention swelling temporary transient ion exchange water and obtain, and takes its section and the electron micrograph (multiplying power 3000 times) obtained.
Fig. 6 is the electron micrograph of the biomass nano fiber of raw material as water absorbing agent of the present invention.
Detailed description of the invention
The present invention is the water absorbing agent containing the natural origin macromolecule be cross-linked and biomass nano fiber, it is characterized in that, the natural origin macromolecule be cross-linked and biomass nano processbearing astrocyte particle, biomass nano fiber is present in the inside of particle.
As long as the macromolecule of the natural origin macromolecule natural origin used in the present invention, is just not particularly limited.Natural origin macromolecule refers to the macromolecule, the macromolecule etc. by Nature inorganic bone that obtain by utilizing fermentable, generally also referred to as biopolymer.
Natural origin macromolecule preferably has condensation functional group, is preferably hydrophily.Condensation functional group and crosslinking agent react and contribute to crosslinked natural origin macromolecule.As the example of condensation functional group, can enumerate: carboxyl, amino etc., wherein, carboxyl can also give hydrophily, therefore preferably.
As the high molecular concrete example of natural origin, can enumerate: the material natural polymers such as polysaccharide, carboxymethyl cellulose such as polyaminoacid, alginic acid, hyaluronic acid, shitosan such as polyglutamic acid (hereinafter also referred to " PGA "), poly-aspartate, polylysine, poly arginine being implemented to chemical modification, but be not limited thereto.Polyaminoacid also can be copolymer.In addition, natural origin macromolecule can be mixed with two or more.
The high molecular molecular weight of natural origin is not particularly limited, and matter average molecular weight is preferably 10,000 ~ 1,300 ten thousand, is more preferably 50,000 ~ 1,000 ten thousand, and more preferably 300,000 ~ 5,000,000.If molecular weight is too small, then the uncrosslinked strand becoming Unit Weight increases, dissolved element is many and the gel that intensity is low.If molecular weight is excessive, then viscosity when dissolving becomes large, and biomass nano fiber and crosslinking agent do not can be uniformly dispersed.
The natural origin macromolecule be cross-linked is the cross-linking agent of instigating natural origin macromolecule and crosslinking agent to react and be cross-linked.About crosslinked, describe below.
In the present invention, biomass nano fiber refers to that average diameter is the biomass fiber of 4 ~ 1000nm.The average diameter of biomass nano fiber is preferably 5 ~ 500nm, is more preferably 10 ~ 100nm.If average diameter is too small, then the mechanical strength step-down of biomass nano fiber self, cannot expect to strengthen effect.If average diameter is excessive, then biomass nano fiber not easily interweaves each other.The length of biomass nano fiber is not particularly limited, and is generally more than 100 times of diameter.Average diameter and length measure by electron beam microscopes.
The manufacture method of biomass nano fiber is not particularly limited, and manufactures by any method.Such as, make by the dispersing fluid of high-pressure injection living beings itself and collision duromer collide and by living beings case of wet attrition, thus biomass nano fiber can be manufactured.The pressure of high-pressure injection is preferably 100 ~ 245MPa, and jet velocity is preferably 440 ~ 700m/s.Reclaim the dispersing fluid of the living beings of being collided with duromer with collision by high-pressure injection, again use duromer high-pressure injection from nozzle to collision, the number of times this operation being repeated to need, such as about 1 ~ 50 time, preferably about 1 ~ 40 time, more preferably about 1 ~ 30 time, further preferably about 1 ~ 20 time, particularly preferably about 1 ~ 10 time.Living beings are by colliding with collision duromer, and the winding of fiber is untied, and fibre diameter reduces, and is micronized into nano-scale.Be explained, as collision duromer, the shapes such as spherical, tabular can be enumerated.The diameter of the nozzle of high-pressure injection dispersing fluid is preferably 0.1 ~ 0.8mm.
In addition, manufacture cellulose nano-fibrous by following method: carry out mediating process by biaxial kneader and by the method for firmly secondary wall solution fibre, pulp clamp-oned narrow gap and carries out separating fine high pressure homogenisers or the such method of microfluidizer by earth pressure release, between the grinding stone rotated, grind the polishing of paper pulp, the interaction of cellulose nano-fibrous is significantly reduced by the TEMPO oxidation at cellulose surface selective introducing carboxyl and only utilizes the method etc. of mixer agitating pulp slurry.
As the living beings of main material becoming biomass nano fiber, can enumerate: cellulose, chitin, shitosan etc.As cellulose, can enumerate: the non-wood type paper pulp of cotton pulp, straw pulp, the bagasse pulps etc. such as coniferous tree bleached kraft pulp (NBKP), hardwood pulp, cotton linter, bacteria cellulose etc., from the viewpoint of mean molecule quantity or cost, preferred NBKP.
In addition, biomass nano fiber is commercially available with the trade name that " BiNFi-s " is such by Co., Ltd. Sugino Machine.Such commercially available product also can use in the present invention.
Form the natural origin macromolecule be cross-linked and the biomass nano processbearing astrocyte particle of water absorbing agent of the present invention.The shape of particle is not particularly limited, but preferably spherical.The size (being equivalent to projected area diameter of a circle) of particle is preferably 150 ~ 850 μm, is more preferably 200 ~ 600 μm, more preferably 300 ~ 400 μm.If particle is too small, then particle gap smaller time swelling, causes obstruction when mixing absorber.If particle is excessive, then specific area diminishes, and absorption speed is slack-off.The size (being equivalent to projected area diameter of a circle) of particle measures by electron beam microscopes.
In water absorbing agent of the present invention, biomass nano fiber is present in the inside of particle.But do not need whole biomass nano fibers to be present in the inside of particle, a part for biomass nano fiber can be exposed to the outside of particle (from outwardly).The electron micrograph (multiplying power 100 times) of the outward appearance of the particle of water absorbing agent of the present invention is shown in Fig. 1.In addition, particle is temporarily swelling with ion exchange water and the swelling thing freeze drying obtained also takes its outer surface, the electron micrograph obtained is shown in Fig. 2 (multiplying power 500 times) and Fig. 3 (multiplying power 3000 times).In addition, particle is temporarily swelling with ion exchange water and the swelling thing freeze drying obtained also takes its section, the electron micrograph obtained is shown in Fig. 4 (multiplying power 500 times) and Fig. 5 (multiplying power 3000 times).Fig. 6 is the raw material of water absorbing agent of the present invention and the electron micrograph of biomass nano fiber.
The present invention adds biomass nano fiber and improves gel strength.In order to improve gel strength, considering the method for the addition increasing crosslinking agent, but in this case, being improved by crosslink density, even if gel strength also can increase when absorbing water.Owing to being cross-linked by chemical bond, therefore crosslinking points is firm, by improving its density, becomes the main cause suppressing swelling set.On the other hand, as the present invention, when improving gel strength when adding biomass nano fiber, by the mechanical strength of the biomass nano fiber interweaved mutually, gel strength is increased.Owing to not being that chemical bond like that firmly connects, therefore, higher relative to the free degree of swelling set.Be explained, biomass nano fiber is longer, more easily interweaves.The living beings of non-microfibre not easily interweave.Even if if add biomass nano fiber, PGA is also the state of completely non-chemical crosslinking, then PGA dissolves.
The natural origin macromolecule be cross-linked and the ratio of biomass nano fiber are relative to total amount 100 mass parts (solid constituent benchmark) of the natural origin macromolecule be cross-linked and biomass nano fiber, biomass nano fiber is preferably 0.1 ~ 40 mass parts (solid constituent benchmark), be more preferably 3 ~ 30 mass parts (solid constituent benchmark), more preferably 5 ~ 20 mass parts (solid constituent benchmark).If the amount of biomass nano fiber is very few, then cannot obtain sufficient mechanical strength.If the amount of biomass nano fiber is too much, then cross-linking efficiency reduces, and becomes weak gel.
Then, the manufacture method of water absorbing agent of the present invention is described.
The manufacture method of water absorbing agent of the present invention comprises following operation: dissolve natural origin macromolecule, prepare the operation (dissolution process) of the high molecular solution of natural origin, in the high molecular solution of natural origin, disperse biomass nano fiber, preparation is dispersed with the operation (dispersion step) of the high molecular solution of natural origin of biomass nano fiber; And, in the high molecular solution of the natural origin being dispersed with biomass nano fiber, add crosslinking agent, the crosslinked high molecular operation of natural origin (cross-linking process step).
Manufacture method of the present invention can also comprise more than one operation in following operation: by the operation (pulverizing process) containing the high molecular hydrogel case of wet attrition of the natural origin be cross-linked obtained in the high molecular operation of crosslinked natural origin; Water Combination organic solvent is added, by the operation (dehydration procedure) that hydrogel dewaters in hydrogel in case of wet attrition; By the operation (drying process) of hydrogel drying of having dewatered.
The operation (dissolution process) preparing the high molecular solution of natural origin is carried out in water equal solvent by making above-mentioned natural origin macromolecule dissolution.As solvent, preferred water.When using water as solvent, the high molecular aqueous solution of natural origin can be obtained.The high molecular concentration of natural origin in solution is preferably 1 ~ 30 quality % (solid constituent benchmark), be more preferably 3 ~ 20 quality % (solid constituent benchmark), more preferably 5 ~ 10 quality % (solid constituent benchmark).If the high molecular concentration of natural origin is too low, then the yield of combination product is low, and productivity ratio is deteriorated.If the high molecular excessive concentration of natural origin, then viscosity increases, and the dispersiveness of biomass nano fiber and crosslinking agent is deteriorated.The method of dissolving is not particularly limited, and makes it dissolve by adding natural origin macromolecule in a solvent and stirring.
Be explained, the natural origin macromolecule be cross-linked is by carrying out cross-linking reaction in aqueous and obtaining, and therefore, natural origin macromolecule is preferably water miscible salt form.Such as, the natural origin macromolecule with carboxyl is preferably the form of the slaine such as sodium salt, sylvite or ammonium salt, amine salt etc., has the form that amino natural origin macromolecule is preferably the acylates such as the inorganic acid salt such as hydrochloride, sulfate or acetate.
Then, in the high molecular solution of natural origin, disperse biomass nano fiber, preparation is dispersed with the high molecular solution of natural origin (dispersion step) of biomass nano fiber.
In the high molecular solution of natural origin, disperse the method for biomass nano fiber to be not particularly limited, such as, can enumerate: biomass nano fiber is joined the method be uniformly mixed in the high molecular solution of natural origin; The dispersion liquid of previously prepared biomass nano fiber, joins the method carrying out in the high molecular solution of natural origin mixing by the dispersion liquid of this biomass nano fiber; The living beings of the raw material as biomass nano fiber are joined in the high molecular solution of natural origin, in the high molecular solution of natural origin by living beings case of wet attrition the method for nanofiber, but the dispersion liquid of preferred previously prepared biomass nano fiber, joins the method carrying out in the high molecular solution of natural origin mixing by the dispersion liquid of this biomass nano fiber.As the method for dispersion liquid preparing biomass nano fiber, the manufacture method of above-mentioned biomass nano fiber can be adopted, such as, under 100 ~ 245MPa, high-pressure injection makes living beings be scattered in the living beings dispersion liquid of water, make it collide with collision duromer and by living beings case of wet attrition, the dispersion liquid of biomass nano fiber can be prepared thus.
Crosslinking agent is added, crosslinked natural origin macromolecule (cross-linking process step) in the high molecular solution of the natural origin being dispersed with biomass nano fiber.As crosslinking agent, be just not particularly limited as long as natural origin macromolecule can be cross-linked.
Such as, when natural origin macromolecule has carboxyl, can 1 be used, 2-ethylenediamine, 1,3-propane diamine, 1, Alkylenediamine, diethylenetriamines, trien, tetren, penten, the polymines etc. such as 4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylene diamine have more than 2 amino compounds (hereinafter also referred to " polyamine "), polylysine, shitosan etc. containing amino polymer etc. as crosslinking agent.
When natural origin macromolecule has amino, as the crosslinking agent for crosslinked natural origin high molecular crosslink, fumaric acid, maleic acid, itaconic acid, citraconic acid, trimellitic acid etc. can be used to have carboxylic polymer such as compound, polyacrylic acid, polymethylacrylic acid, poly-gamma-glutamic acid, alginic acid, hyaluronic acid of more than 2 carboxyls etc. as crosslinking agent.
The use amount of crosslinking agent when making natural origin high molecular crosslink, relative to natural origin macromolecule 100 moles, is preferably 0.01 ~ 100 mole, is more preferably 0.1 ~ 20 mole, more preferably 0.3 ~ 10 mole.If the amount of crosslinking agent is very few, then the easy step-down of crosslink density, is likely difficult to obtain gel state.If the amount of crosslinking agent is too much, then crosslink density easily uprises, the swellbility likely step-down of the absorbent obtained.
Also can together with crosslinking agent and with condensing agent or condensation auxiliary agent.And if with condensing agent or condensation auxiliary agent, more efficiently amido link can be formed.
As condensing agent, water-soluble carbodiimide can be enumerated.Water-soluble carbodiimide refers in molecule to have carbodiimide (-N=C=N-), has a water miscible compound.As the concrete example of water-soluble carbodiimide, can enumerate: 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide (hereinafter also referred to " EDC ") or its salt, 1-cyclohexyl-3-(2-morpholinyl ethyl) carbodiimide-methyl-to toluene sulfuric acid or its salt, dicyclohexylcarbodiimide etc., preferred 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, 1-cyclohexyl-3-(2-morpholinyl ethyl) carbodiimide-methyl-to toluene sulfate.
The use amount of condensing agent is 0 ~ 50 mole relative to used crosslinking agent 1 mole, is preferably 1 ~ 40 mole, is more preferably 2 ~ 30 moles.
As condensation auxiliary agent, can enumerate: N-hydroxy imide.N-hydroxy imide refers in molecule the compound with N-hydroxy imide base (-(C=O)-(N-OH)-(C=O)-).That is, this compound is expressed by the following formula.
R 1-(C＝O)-(N-OH)-(C＝O)-R 2
At this, by R 1and R 2bonding forms ring structure.Preferred R 1and R 2bonding and by R 1and R 2in 2 carbon and N-hydroxy imide base define pentacyclic compound.In addition, N-hydroxy imide is preferably water-soluble.As the concrete example of spendable N-hydroxy imide, can enumerate: N-hydroxy-succinamide, N-hydroxy maleimide, N-hydroxyl hexahydrophthalic phthalimide, N, N '-dihydroxy cyclohexane four carboximide, HP, N-hydroxyl tetrabromo phthalimide, N-hydroxyl tetrachloro-phthalimide, N-hydroxyl HET acid acid imide, N-hydroxyl humic acid acid imide, the inclined benzene trimellitic imide of N-hydroxyl, N, the equal diimides of N '-dihydroxy, N, N '-dihydroxy naphthlene four carboximide.In N-hydroxy imide, most preferably N-hydroxy-succinamide (hereinafter also referred to " NHS ").
The use amount of condensation auxiliary agent is 0 ~ 50 mole relative to used crosslinking agent 1 mole, is preferably 1 ~ 40 mole, more preferably 2 ~ 30 moles.Be explained, the use amount of condensation auxiliary agent is preferably to wait mole with the use amount of used condensing agent.
Make the high molecular concentration of natural origin during natural origin high molecular crosslink be preferably 1 ~ 40 quality %, be more preferably 2 ~ 20 quality %, more preferably 3 ~ 15 quality %.If the high molecular excessive concentration of natural origin, then the viscosity of the hydrogel obtained increases, and is likely difficult to stir.If the high molecular concentration of natural origin is too low, then the yield of combination product is low, and productivity ratio is deteriorated.
The condition of cross-linking process step is not particularly limited.Can be room temperature, also can heat.But when temperature is too low, cross-linking reaction needs the time extremely grown, and therefore, preferably heats.The temperature of cross-linking process step is preferably 10 ~ 100 DEG C, is more preferably 15 ~ 70 DEG C, more preferably 20 DEG C ~ 50 DEG C.When too high, natural origin macromolecule easily decomposes.Therefore, preferably carry out near room temperature.PH during cross-linking reaction is not particularly limited, but is preferably 5 ~ 12, is more preferably 6 ~ 11, more preferably 7 ~ 10.
The reaction time of cross-linking process step is preferably 5 minutes ~ 6 hours, is more preferably 10 minutes ~ 3 hours, more preferably 20 minutes ~ 2 hours.When cross-linking reaction, as required can stirring reaction solution, also can leave standstill in advance.Preferably leave standstill in advance.Cross-linking reaction, after the sufficient time, obtains gel in reaction solution.By by reaction solution water (preferably steam and stay water) cleaning, remove the condensing agent in reaction solution and condensation auxiliary agent, obtain by the high molecular gel of cross-linking agents natural origin.
Then, case of wet attrition (pulverizing process) is carried out by containing the high molecular hydrogel of the natural origin be cross-linked obtained in the high molecular operation of crosslinked natural origin.In this operation, hydrogel is ground into the size (i.e. case of wet attrition) of expectation with saturation state.This pulverizing is carried out after pulverizing preferably coarse crushing in advance.Coarse crushing is undertaken by following operation: by the hydrogel that obtained by cross-linking reaction such as with stirrings such as spatulas.In this pulverizing, the device being used by hydrogel such as mixer for well-distribution, homogenizer, ball mill, pipe-line mixer etc. to be suitable for case of wet attrition is pulverized.In this manual, the hydrogel after pulverizing is called hydrogel particle.The average grain diameter of hydrogel particle according to the purposes of the desiccant gel powder finally obtained or the suitable selection of the device for pulverizing, but can be preferably 10 μm ~ 10mm, is more preferably 100 μm ~ 3mm.
, pulverizing high in the viscosity of hydrogel is difficult, also can add water Combination organic solvent described later.That is, also can pulverize after adding water Combination organic solvent.By adding water Combination organic solvent, hydrogel is dehydrated and volume reduces (contraction), the viscosity of the dispersion liquid in case of wet attrition, and mobility is recovered.In crushing process when thickening, also can add water Combination organic solvent in midway and continue to pulverize.As mentioned above, case of wet attrition operation also can be carried out with dehydration procedure described later simultaneously.
When use there is carboxyl natural origin macromolecule as raw material, as mentioned above, high molecular for natural origin carboxy moiety formed the water miscible salt forms such as sodium salt and prepare hydrogel.But, when the hydrogel of salt form is made desiccant gel powder, likely moisture absorption and cause powder to stick to each other in an atmosphere.Therefore, inorganic acid or organic acid can be added and its part is made free acid form by salt form after preparing hydrogel.The desiccant gel powder obtained by the hydrogel of free acid form, compared with the desiccant gel powder of salt form, can reduce hygroscopicity, therefore not easily causes powder adhesion each other.As inorganic acid and organic acid, such as, can enumerate: sulfuric acid, hydrochloric acid, nitric acid, p-methyl benzenesulfonic acid etc.Inorganic acid or organic acid preferably mix with water Combination organic solvent and join in hydrogel particle.If this is because add inorganic acid or organic acid, then hydrogel is neutralized equably, the hydrogel particle of uniform free acid form can be obtained.
Then, add water Combination organic solvent in the hydrogel after case of wet attrition and hydrogel is dewatered (dehydration procedure).If make hydrogel particle impregnated in water Combination organic solvent, then contained in hydrogel particle water is discharged in water Combination organic solvent.Sometimes hydrogel particle dewaters and is shrunk to particle size.And then, also discharge from hydrogel particle together with water for making the unwanted material such as unreacted crosslinking agent, condensing agent of natural origin high molecular crosslink.
Water Combination organic solvent is not particularly limited.Such as can enumerate: glycol ethers and the acetone such as the lower alcohols such as methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, the tert-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl.Wherein, particular methanol, ethanol, isopropyl alcohol and acetone.These water Combination organic solvents can be used alone, and also can be mixed with two or more, or also can successively add solvent of more than two kinds according to dispersity.
Hydrogel particle can be repeatedly to the dipping in water Combination organic solvent.Now, from hydrogel particle, remove the solvent containing the water of discharging by filtration or decant, again water Combination organic solvent is joined in hydrogel particle.By repeatedly flooding as above, hydrogel particle dewaters further and shrinks, and becomes the low-down particulate of moisture content.When repeatedly flooding, each dipping can use different water Combination organic solvents.
Amount of the water when use amount of water Combination organic solvent is prepared according to its kind, hydrogel etc. and different, for the dipping of every 1 time, relative to hydrogel, be preferably 1 times of capacity (equivalent) ~ 20 times capacity, be more preferably 2 times of capacity ~ 10 times capacity, more preferably 3 times of capacity ~ 7 times capacity.
Hydrogel particle is made to impregnated in time of water Combination organic solvent different according to the kind, amount etc. of solvent, for the dipping of every 1 time, if consider workability, be preferably 1 minute ~ 2 hours, be more preferably 2 minutes ~ 1 hour, more preferably 3 minutes ~ 30 minutes.
Also can as required by the suitable liquid wash of hydrogel particle after dipping in water Combination organic solvent.
Then, by the hydrogel drying (drying process) of dehydration.The moisture content of the hydrogel particle obtained after dehydration procedure is low, hardly moisture content.Therefore, by filter or decant except the Combination organic solvent that anhydrates, preferably in room temperature ~ 150 DEG C, more preferably 35 DEG C ~ 125 DEG C, preferably further at 50 DEG C ~ 100 DEG C, carry out air-supply drying or standing and drying, desiccant gel powder can be obtained thus.As mentioned above, under hydrogel particle is not exposed to harsh drying condition, therefore, in dry run, particle each other can not adhesion.
The particle diameter of the desiccant gel powder obtained can be considered purposes of desiccant gel powder etc. and determine, is not particularly limited.That is, can obtain according to the reducing mechanism used in above-mentioned pulverizing process (mixer for well-distribution, homogenizer etc.) and crush force thereof that there is the desiccant gel powder expecting particle diameter.
Usually, when polymer does not keep eyed structure (gel state), polymer impregnatedly to dissolve when solvent.But the desiccant gel powder infusion obtained by said method is not dissolved and swelling when water, regeneration hydrogel.Therefore, the desiccant gel powder obtained by said method keeps eyed structure (gel state).
Embodiment
Embodiment 1
By γ-PGA (Na type, 500KDa, Co., Ltd. バ イ オ リ ー ダ ー ズ system) 1.359g (glutamic acid units 9mmol (glutamic acid 1 unit forming γ-PGA is 151g/mol)) is dissolved in ion exchange water, prepares the aqueous solution.Then, add cellulose nano-fibrous 5% aqueous dispersions (BiNFi-s NMa, average degree of polymerization 530, average diameter 0.02 μm, average length 2 μm, Co., Ltd. Sugino Machine system) 3.02g (relative γ-PGA 10 quality %), prepare the dispersion liquid of solid component concentration 7 quality %, homogenizer (AHG-160D, axle generator HT1018, ASONE Co., Ltd. system) is used to mix under the condition of 1000rpm.
Then, penten (Wako Pure Chemical Industries, Ltd.'s system) to be stirred with relative glutamic acid units 6mol% with relative glutamic acid units 6mol%, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide (hereinafter also referred to " EDC ") hydrochloride (Wako Pure Chemical Industries, Ltd.'s system) with relative glutamic acid units 2mol%, N-hydroxy-succinamide (hereinafter also referred to " NHS ") (Wako Pure Chemical Industries, Ltd.'s system) add successively.The hydrogel of gonorrhoea is obtained at about 3 minutes.
Add end after 30 minutes, by the gonorrhoea hydrogel spatula coarse crushing obtained.Then, in the hydrogel after coarse crushing, add 20g methyl alcohol (Wako Pure Chemical Industries, Ltd.'s system), use homogenizer (AHG-160D, axle generator HT1018, ASONE Co., Ltd. system) case of wet attrition under the condition of 750rpm.After case of wet attrition, when being left standstill by dispersion liquid, translucent hydrogel particle sedimentation, therefore, by decant except desolventizing, rejoins 20g methyl alcohol and stirs.Repeat sequence of operations, carry out dewatering until hydrogel particle shrinks and becomes white particles.
The particle dewatered to be blown under the condition of 70 DEG C, 90 minutes drying, obtain desiccant gel powder.
Using the desiccant gel powder that obtains as water absorbing agent, measure gel strength and water retention capability by aftermentioned method.Measurement result is shown in table 1.
Comparative example 1
Use γ-PGA 1.51g (glutamic acid units 10mmol), do not add cellulose nano-fibrous, in addition, prepare water absorbing agent by step similarly to Example 1, measure gel strength and water retention capability.Measurement result is shown in table 1.
Comparative example 2
Be used as cellulose powder (" KC Flock " (registration mark) W-50GK of fine cellulose raw material, average degree of polymerization 530, average diameter 25 μm, average length 45 μm, Nippon Paper Chemicals Co., Ltd.'s system) replace cellulose nano-fibrous, in addition, prepare water absorbing agent by step similarly to Example 1, measure gel strength and water retention capability.Measurement result is shown in table 1.
Embodiment 2
Cellulose nano-fibrous 5% aqueous dispersions is changed to BiNFi-s AMa (average degree of polymerization 200 by BiNFi-s NMa, average diameter 0.02 μm, average length 2 μm, Co., Ltd. SuginoMachine system), in addition, prepare water absorbing agent by step similarly to Example 1, measure gel strength and water retention capability.Measurement result is shown in table 1.
Embodiment 3
Cellulose nano-fibrous 5% aqueous dispersions is changed to BiNFi-s FMa (average degree of polymerization 600 by BiNFi-s NMa, average diameter 0.02 μm, average length 2 μm, Co., Ltd. SuginoMachine system), in addition, prepare water absorbing agent by step similarly to Example 1, measure gel strength and water retention capability.Measurement result is shown in table 1.
Embodiment 4
γ-PGA is changed to the material (Co., Ltd. バ イ オ リ ー ダ ー ズ system) that molecular weight is 50KDa, in addition, prepare water absorbing agent by step similarly to Example 1, measure gel strength and water retention capability.Measurement result is shown in table 1.
Embodiment 5
γ-PGA is changed to the material (Co., Ltd. バ イ オ リ ー ダ ー ズ system) that molecular weight is 2000KDa, in addition, prepare water absorbing agent by step similarly to Example 1, measure gel strength and water retention capability.Measurement result is shown in table 1.
Embodiment 6
γ-PGA is changed to material (Co., Ltd. バ イ オ リ ー ダ ー ズ system) that molecular weight is 2000KDa and fine cellulose fiber 5% aqueous dispersions is changed to BiNFi-sFMa by BiNFi-s NMa, in addition, prepare water absorbing agent by step similarly to Example 1, measure gel strength and water retention capability.Measurement result is shown in table 2.
Embodiment 7
Cellulose nano-fibrous addition is changed to relative γ-PGA20 quality %, in addition, prepare water absorbing agent by step similarly to Example 6, measure gel strength and water retention capability.Measurement result is shown in table 2.
Embodiment 8
Cellulose nano-fibrous addition is changed to relative γ-PGA30 quality %, in addition, prepare water absorbing agent by step similarly to Example 6, measure gel strength and water retention capability.Measurement result is shown in table 2.
Comparative example 3
Do not add cellulose nano-fibrous, in addition, prepare water absorbing agent by step similarly to Example 6, measure gel strength and water retention capability.Measurement result is shown in table 2.
Comparative example 4
The addition of the penten as crosslinking agent is changed to relative PGA6mol%, in addition, prepares water absorbing agent by the step same with comparative example 3, measure gel strength and water retention capability.Measurement result is shown in table 2.
Comparative example 5
The addition of the penten as crosslinking agent is changed to relative PGA9mol%, in addition, prepares water absorbing agent by the step same with comparative example 3, measure gel strength and water retention capability.Measurement result is shown in table 2.
Comparative example 6
Gel strength and water retention capability are measured to commercially available acrylic acid series SAP (Sumitomo refine Zhu Shihui Inc., Aquakeep SA60S).Measurement result is shown in table 2.
[water retention capability mensuration]
(1) prepare bag (10 × 20cm) with 250 order nylon wires (Co., Ltd. NBC Meshtec system, N-NO.250HD) and load working sample 0.3g.
(2) the quality A comprising nylon wire is measured.
(3) in beaker, load physiological saline 1L, flood and readyly the nylon wire of sample is housed and places 1 hour.
(4) mention bag, the minor face clamping bag with clothes washing clamp hangs, control water 15 minutes.
(5) and then, with centrifugal separator dehydration (150G, 90 seconds).
(6) the quality B after dehydration is measured.
(7) water retention capability (g/g) is calculated by following formula.
Water retention capability=(B-A)/0.3
[gel strength mensuration]
(1) measure with water retention capability the hydrogel that same method prepares water conservation state by adopting.
(2) in the PP of diameter 27mm manages (new PP sample cell NO.5,22mL, M Co., Ltd. aruemu system), sample 6.0g is loaded.
(3) on sample, place the sieve of diameter 25mm.
(4) with digital force gauge pressing sieve (invading speed 1mm/s).
(5) be set to starting point by the 3rd moment starting to change after the measured value decimal point of digital force gauge, the numerical value of maximum load during reading pressing 10 seconds (10mm) gels, as gel strength.
[table 1]
[table 2]
With cellulose is not carried out nanometer pulverization cellulose fibre compare in (W-50GK and NMa), find the raising effect of having carried out the gel strength of the cellulose fibre of nanometer pulverization, on the other hand, find that the gel strength of not carrying out comminuted fibres cellulose fiber does not improve.
In the comparison (AMa<NMa<FMa) that cellulose nano-fibrous average degree of polymerization is different, there is the high tendency of the raising effect of gel strength in large cellulose nano-fibrous of the degree of polymerization.
In addition, the result different relative to the gel strength because cellulose nano-fibrous average degree of polymerization is different, for water retention capability, does not find because of the difference of the average degree of polymerization of composite different.
Known, in order to improve gel strength, large cellulose nano-fibrous of the degree of polymerization can be added.
Under the cellulose nano-fibrous condition of mixing 10%, the mean molecule quantity of the high molecular polyglutamic acid of natural origin different relatively in, there is the tendency that gel strength becomes large in the polyglutamic acid that mean molecule quantity is large.
In the result of water retention capability, the tendency that the retentivity that the side that the mean molecule quantity of the high molecular polyglutamic acid of natural origin is little exists liquid reduces.In addition, on the contrary, the side that mean molecule quantity is large finds the raising of gel strength, on the other hand, for water retention capability, finds that relative to mean molecule quantity be the tendency that moderate polyglutamic acid has reduction.
Known, in order to improve gel strength, the polyglutamic acid that mean molecule quantity is large can be used.
When only utilizing crosslinking agent to control gel physical property, if crosslinker concentration when too improving synthesis, there is the tendency that gel strength reduces on the contrary.Equally, when increase cellulose nano-fibrous addition and improve gel strength, if too increase addition, also exist gel strength reduce tendency (say qualitatively for percentage elongation disappear and become crisp state).
Known, compared with improving the situation of gel strength with increase crosslinker concentration, the decline degree usually being improved the water retention capability of the situation of gel strength by interpolation fiber is lower.
Industry usability
Water absorbing agent of the present invention can be preferably used as the raw material of the absorber forming the absorbent commodity such as disposable diaper, sanitary napkin.
Symbol description
The particle of 1 absorbent
The 2 natural origin macromolecules be cross-linked
3 biomass nano fibers

Claims (10)

1. water absorbing agent, it contains the natural origin macromolecule and biomass nano fiber that have been cross-linked, it is characterized in that, the natural origin macromolecule be cross-linked and biomass nano processbearing astrocyte particle, biomass nano fiber is present in inside particles.
2. water absorbing agent according to claim 1, is characterized in that, natural origin macromolecule has condensation functional group.
3. the water absorbing agent described in claim 1 or 2, is characterized in that, natural origin macromolecule is polyglutamic acid.
4. the water absorbing agent described in any one of claims 1 to 3, is characterized in that, the average diameter of biomass nano fiber is 4 ~ 1000nm.
5. the manufacture method of the water absorbing agent containing the natural origin macromolecule be cross-linked and biomass nano fiber, it comprises following operation:
Dissolve natural origin macromolecule and prepare the operation of the high molecular solution of natural origin;
In the high molecular solution of natural origin, disperse biomass nano fiber, preparation is dispersed with the operation of the high molecular solution of natural origin of biomass nano fiber; With
Crosslinking agent is added, the crosslinked high molecular operation of natural origin in the high molecular solution of the natural origin being dispersed with biomass nano fiber.
6. method according to claim 5, also comprises the operation by carrying out case of wet attrition containing the high molecular hydrogel of the natural origin be cross-linked obtained in the high molecular operation of crosslinked natural origin.
7. method according to claim 6, be also included in the hydrogel of case of wet attrition add water Combination organic solvent and by hydrogel dewater operation.
8. method according to claim 7, also comprises the operation of the hydrogel drying of having dewatered.
9. the method described in any one of claim 5 ~ 8, it is characterized in that, the amount of biomass nano fiber, relative to total amount 100 mass parts (solid constituent benchmark) of natural origin macromolecule and biomass nano fiber, is 0.1 ~ 40 mass parts (solid constituent benchmark).
10. absorbent commodity, containing the water absorbing agent described in any one of Claims 1 to 4.
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