CN105026033B - Water absorbing agent - Google Patents
Water absorbing agent Download PDFInfo
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- CN105026033B CN105026033B CN201480013142.XA CN201480013142A CN105026033B CN 105026033 B CN105026033 B CN 105026033B CN 201480013142 A CN201480013142 A CN 201480013142A CN 105026033 B CN105026033 B CN 105026033B
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- 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
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- 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
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
- A61F2013/530131—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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
- A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
- A61F2013/530489—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/68—Superabsorbents
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- 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
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The present invention provides a kind of water retention capability and excellent and good to the environment absorbent of gel strength.The absorbent is the water absorbing agent containing crosslinking natural origin macromolecule and biomass nano fiber, it is characterised in that the natural origin macromolecule and biomass nano fiber being crosslinked form particle, and biomass nano fiber is present in inside particles.The water absorbing agent can be manufactured by following process：Natural origin macromolecule is dissolved, biomass nano fiber is scattered in the solution, crosslinking agent is added in the dispersion liquid makes natural origin high molecular crosslink, the hydrogel case of wet attrition that will be obtained, then hydrogel is dehydrated, and is then dried.
Description
Technical field
The present invention relates to a kind of water absorbing agent.In more detail, it is related to a kind of biodegradation obtained by natural origin macromolecule
The absorbent of property.
Background technology
The absorber of the absorbent commodity such as disposable diaper or physiological articles usually using super absorbent polymer (below
Referred to as " SAP ") and Time of Fluff Slurry.
As SAP, the synthetic polymer system such as polyacrylate system SAP is largely used at present, but in recent years, polyglutamic
The natural origin such as phosphate-gallate series system SAP gets most of the attention from the viewpoint of biological degradability.
The purpose of (hereinafter referred to as " patent document 1 ") is for example, No. 2007/034785 publication of International Publication No., there is provided
The gel with high swelling degree that is formed with a small amount of polyamine crosslinking gamma-polyglutamic acid and to obtain the gel in high yield
Method, disclose using water-soluble carbodiimide and n-hydroxysuccinimide as condensing agent and condensation auxiliary agent to manufacture polyamine
The method of the gamma-polyglutamic acid gel of crosslinking.
In addition, for the thinning of absorbent commodity, miniaturization, attempt to improve SAP ratio relative to Time of Fluff Slurry.But
There are the following problems：SAP ratio is higher, when absorbing water, more causes so-called " gel blocking phenomenon " based on SAP characteristics,
Absorbent product can not play function with the efficiency as calculating.In order to solve the problem, Japanese Patent No. 3016367 is said
Bright book (hereinafter referred to as " patent document 2 ") is disclosed SAP whole surface with being obtained by cellulose or cellulose derivative
The method of microfibril covering with hydrability.According to method disclosed in patent document 2, if in the decentralized medium of microfibril
In disperse SAP, then the SAP of high concentration can be made stably to disperse, during decentralized medium is removed, securely self-adhesion and turn into
Gypsum shape, network structure is formed, while wrapping into SAP particles and mechanically coating, microfibril passes through ion each other
Property hydrogen bond action and combine, reliably keep SAP particles (with reference to paragraph [0017]).
Prior art literature
Patent document
Patent document 1：No. 2007/034785 publication of International Publication No.
Patent document 2：No. 3016367 specifications of Japanese Patent No.
The content of the invention
The invention problem to be solved
According to method disclosed in patent document 1, it is possible to provide a kind of Polyamine residues content is few, crosslink density is low, swellbility is high
Gel (with reference to paragraph [0033]).Therefore, compression resistant low intensity during water conservation, as absorbent commodity purposes, can not meet
Body pressure liquid ooze out wait required by performance.
When thinking the method disclosed in patent document 2 to water conservation SAP be bonded to each other caused by gel blockage it is effective, but be
Gel blockage is substantially avoided, it is necessary to improve the compression resistant intensity (gel strength) of SAP in itself.In order to improve gel strength,
Water absorbing properties drop when considering to improve the method for crosslink density by increasing the addition of crosslinking agent, but generally improving crosslink density
It is low.In addition, from the viewpoint of security and environment influence, it is undesirable to increase the addition of crosslinking agent.
The means to solve the problem
The present invention is conceived to such existing issue point and completed.
The present invention is the water absorbing agent containing crosslinking natural origin macromolecule and biomass nano fiber, and its feature exists
In the natural origin macromolecule and biomass nano fiber being crosslinked form particle, and biomass nano fiber is present in particle
It is internal.
In addition, the method for the present invention is suction of the manufacture containing crosslinking natural origin macromolecule and biomass nano fiber
The method of aqua, it includes following process：
The process for dissolving natural origin macromolecule and preparing the high molecular solution of natural origin；
Disperse biomass nano fiber in the high molecular solution of natural origin, preparation is dispersed with biomass nano fiber
The process of the high molecular solution of natural origin；With
Crosslinking agent is added in the high molecular solution of natural origin for being dispersed with biomass nano fiber, is crosslinked natural origin
High molecular process.
The present invention includes following scheme.
[1] a kind of water absorbing agent, it exists containing crosslinking natural origin macromolecule and biomass nano fiber, its feature
In the natural origin macromolecule and biomass nano fiber being crosslinked form particle, and biomass nano fiber is present in particle
It is internal.
[2] water absorbing agent according to [1], it is characterised in that natural origin macromolecule has condensation property functional group.
[3] water absorbing agent according to [1] or [2], it is characterised in that natural origin macromolecule is polyglutamic acid.
[4] water absorbing agent according to any one of [1]~[3], it is characterised in that the average diameter of biomass nano fiber
For 4~1000nm.
[5] a kind of method for manufacturing the water absorbing agent containing crosslinking natural origin macromolecule and biomass nano fiber,
It includes following process：
The process for dissolving natural origin macromolecule and preparing the high molecular solution of natural origin；
Disperse biomass nano fiber in the high molecular solution of natural origin, preparation is dispersed with biomass nano fiber
The process of the high molecular solution of natural origin；With
Crosslinking agent is added in the high molecular solution of natural origin for being dispersed with biomass nano fiber, is crosslinked natural origin
High molecular process.
[6] according to the method described in [5], it is also included containing being obtained in the high molecular process of natural origin is crosslinked
The process that the high molecular hydrogel of natural origin being crosslinked carries out case of wet attrition.
[7] according to the method described in [6], it is organic molten that it is additionally included in addition water Combination in the hydrogel of case of wet attrition
Agent and by hydrogel be dehydrated process.
[8] method according to [7], it also includes the process for drying the hydrogel being dehydrated.
[9] method according to any one of [5]~[8], it is characterised in that the amount of biomass nano fiber is relative to day
The mass parts of total amount 100 (solid constituent benchmark) of right source macromolecule and biomass nano fiber are 1~30 mass parts (solid
Composition benchmark).
[10] a kind of absorbent commodity, it contains the water absorbing agent described in any one of [1]~[4].
Invention effect
According to the present invention, by formed the natural origin for being compounded with biomass nano fiber super absorbent polymer until
Inside particles, it can obtain the water absorbing agent that water retention property is high and gel strength when absorbing water is big.
In addition, the main material of biomass nano fiber is natural origin, the addition of chemical cross-linking agent can also suppress low
Level, therefore, compared with general polyacrylate system SAP, CO can be reduced2Discharge rate, and discarded in washing is discarded and native
In the case of, also can be promptly biodegradable, environmental suitability is high.And then compared with general polyacrylate system SAP, it is raw
Thing adaptability is also high.
Brief description of the drawings
Fig. 1 is the electron micrograph (100 times of multiplying power) of the outward appearance of the particle of water absorbing agent of the present invention.
Fig. 2 is temporarily will to be made to be swelled thing freeze-drying obtained by the particle swelling of water absorbing agent of the present invention with ion exchange water,
Shoot electron micrograph obtained by its outer surface (500 times of multiplying power).
Fig. 3 is temporarily will to be made to be swelled thing freeze-drying obtained by the particle swelling of water absorbing agent of the present invention with ion exchange water,
Shoot electron micrograph obtained by its outer surface (3000 times of multiplying power).
Fig. 4 is temporarily will to be made to be swelled thing freeze-drying obtained by the particle swelling of water absorbing agent of the present invention with ion exchange water,
Shoot electron micrograph obtained by its section (500 times of multiplying power).
Fig. 5 is temporarily will to be made to be swelled thing freeze-drying obtained by the particle swelling of water absorbing agent of the present invention with ion exchange water,
Shoot electron micrograph obtained by its section (3000 times of multiplying power).
Fig. 6 is the electron micrograph of the biomass nano fiber as the raw material of water absorbing agent of the present invention.
Embodiment
The present invention is the water absorbing agent containing crosslinking natural origin macromolecule and biomass nano fiber, and its feature exists
In the natural origin macromolecule and biomass nano fiber being crosslinked form particle, and biomass nano fiber is present in particle
It is internal.
As long as the macromolecule of the natural origin macromolecule natural origin used in the present invention, is just not particularly limited.My god
Right source macromolecule refers to by using macromolecule obtained from microbial fermentation, by macromolecule of Nature inorganic bone etc., typically
Also referred to as biopolymer.
Natural origin macromolecule preferably has condensation property functional group, preferably hydrophily.Condensation property functional group and crosslinking agent
React and help to be crosslinked natural origin macromolecule.As the example of condensation property functional group, can enumerate：Carboxyl, amino etc., its
In, carboxyl can also assign hydrophily, therefore it is preferred that.
As the high molecular concrete example of natural origin, can enumerate：To polyglutamic acid (hereinafter also referred to " PGA "), poly- asparagus fern
The polysaccharides such as the polyaminoacid such as propylhomoserin, polylysine, poly arginine, alginic acid, hyaluronic acid, chitosan, carboxymethyl cellulose
The material of chemical modification is implemented with Deng natural polymer, but is not limited to this.Polyaminoacid can also 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 10,000~13,000,000, more preferably
For 50,000~10,000,000, more preferably 300,000~5,000,000.If molecular weight is too small, as uncrosslinked point of Unit Weight
Subchain increases, dissolved element is more and the gel of low intensity.If molecular weight is excessive, viscosity when dissolving becomes big, biomass nano
Fiber and crosslinking agent are not can be uniformly dispersed.
The natural origin macromolecule being crosslinked instigates natural origin macromolecule to be reacted with crosslinking agent and carried out crosslinking
Cross-linking agent.On crosslinking, it is described below.
In the present invention, biomass nano fiber refers to the biomass fiber that average diameter is 4~1000nm.Biomass is received
The average diameter of rice fiber is preferably 5~500nm, more preferably 10~100nm.If average diameter is too small, biomass nano
The mechanical strength step-down of fiber itself, can not it is expected enhancing effect.If average diameter is excessive, biomass nano fiber is each other not
Easily interweave.The length of biomass nano fiber is not particularly limited, usually more than the 100 of diameter times.Average diameter and length
It can be determined by electron beam microscopes.
The manufacture method of biomass nano fiber is not particularly limited, and can manufacture by any method.For example, it can pass through
The dispersing fluid of high-pressure injection biomass and it is collided with collision duromer and by biomass case of wet attrition, so as to manufacture
Biomass nano fiber.The pressure of high-pressure injection is preferably 100~245MPa, and jet velocity is preferably 440~700m/s.Recovery
The dispersing fluid for the biomass collided by high-pressure injection with collision with duromer, again from nozzle to collision with duromer high pressure
Injection, by the operation repeat need number, such as 1~50 time or so, preferably 1~40 time or so, more preferably 1~30 time
Left and right, further preferred 1~20 time or so, particularly preferred 1~10 time or so.Biomass by being collided with collision with duromer,
The winding of fiber is untied, and fibre diameter reduces, and is micronized into nano-scale.It is explained, as collision duromer, can enumerates
The shapes such as spherical, tabular.The diameter of the nozzle of high-pressure injection dispersing fluid is preferably 0.1~0.8mm.
In addition, it can manufacture by the following method cellulose nano-fibrous：With biaxial kneader carry out mediate processing and incite somebody to action
The fine method of firm secondary wall solution, pulp is squeezed into narrow gap and to carry out the fine high pressure of solution by pressure release equal
Method as matter device or microfluidizer, grind between the grinding stone of rotation the polishing of paper pulp, by being selected in cellulose surface
Property introduce carboxyl TEMPO oxidation make the interaction of cellulose nano-fibrous be greatly reduced and merely with mixer stir paper
Method for starching slurry etc..
As the biomass of the main material as biomass nano fiber, can enumerate：Cellulose, chitin, chitosan etc..
As cellulose, can enumerate：Cotton pulp, straw pulp, the bagasses such as coniferous tree bleached kraft pulp (NBKP), hardwood pulp, cotton linter
Non-timber class paper pulp, the bacteria celluloses such as slurry etc., from the viewpoint of mean molecule quantity or cost, preferably NBKP.
In addition, biomass nano fiber trade name city as Co., Ltd. Sugino Machine with " BiNFi-s "
Sell.Such commercially available product can also use in the present invention.
The natural origin macromolecule and biomass nano fiber for forming the crosslinking of water absorbing agent of the present invention form particle.Particle
Shape be not particularly limited, it is but preferably spherical.The size of particle is preferably 150 (equivalent to projected area diameter of a circle)~
850 μm, more preferably 200~600 μm, more preferably 300~400 μm.If particle is too small, particle gap when being swelled
Diminish, cause obstruction when mixing absorber.If particle is excessive, specific surface area diminishes, and absorption speed is slack-off.The size of particle
(equivalent to projected area diameter of a circle) can be determined by electron beam microscopes.
In the water absorbing agent of the present invention, biomass nano fiber is present in the inside of particle.Yet it is not desirable to whole life
Material nanofiber is present in the inside of particle, and a part of outside that can be exposed to particle of biomass nano fiber is (from table
Face out).The electron micrograph (100 times of multiplying power) of the outward appearance of the particle of water absorbing agent of the present invention is shown in Fig. 1.In addition, by grain
Son temporarily with ion exchange it is water-swellable obtained from swelling thing be freeze-dried and shoot its outer surface, the electron microscope that will be obtained
Photo is shown in Fig. 2 (500 times of multiplying power) and Fig. 3 (3000 times of multiplying power).It is in addition, particle is temporarily water-swellable with ion exchange and obtain
Swelling thing be freeze-dried and shoot its section, by obtained electron micrograph be shown in Fig. 4 (500 times of multiplying power) and Fig. 5 (times
3000 times of rate).Fig. 6 is that the raw material of water absorbing agent of the present invention is the electron micrograph of biomass nano fiber.
The present invention adds biomass nano fiber and improves gel strength.In order to improve gel strength, considered that increase was handed over
Join the method for the addition of agent, but in this case, improved by crosslink density, gel strength can also increase when water suction
Greatly.Due to being crosslinked by chemical bond, therefore crosslinking points are firm, by improving its density, turn into the main original for suppressing swelling set
Cause.On the other hand, as the present invention, in the case where addition biomass nano fiber improves gel strength, by mutual
The mechanical strength of the biomass nano fiber of intertexture increases gel strength.Due to not being that chemical bond firmly connects like that, because
This, it is higher relative to the free degree of swelling set.It is explained, biomass nano fiber is longer, easier intertexture.Not fine fibre
The biomass of dimensionization is not easy to interweave.If even if addition biomass nano fiber, PGA is also the state not being chemically crosslinked completely, then
PGA dissolves.
The natural origin macromolecule and the ratio of biomass nano fiber being crosslinked are high relative to the natural origin being crosslinked
The mass parts of total amount 100 (solid constituent benchmark) of molecule and biomass nano fiber, biomass nano fiber is preferably 0.1~
40 mass parts (solid constituent benchmark), more preferably 3~30 mass parts (solid constituent benchmark), more preferably 5~20 matter
Measure part (solid constituent benchmark).If the amount of biomass nano fiber is very few, sufficient mechanical strength can not be obtained.If biomass
The amount of nanofiber is excessive, then cross-linking efficiency reduces, and turns into weak gel.
Then, the manufacture method of water absorbing agent of the present invention is illustrated.
The manufacture method of water absorbing agent of the present invention includes following process：Natural origin macromolecule is dissolved, prepares natural origin height
The process (dissolution process) of the solution of molecule, biomass nano fiber is disperseed in the high molecular solution of natural origin, prepare and divide
Dissipate the process (dispersion step) for the high molecular solution of natural origin for having biomass nano fiber；And it is being dispersed with biomass
Crosslinking agent, the high molecular process of crosslinking natural origin (crosslinking work are added in the high molecular solution of natural origin of nanofiber
Sequence).
The manufacture method of the present invention can also include more than one process in following process：It will contain natural next in crosslinking
The process (pulverizing process) of the natural origin high molecular hydrogel case of wet attrition of the crosslinking obtained in the high molecular process in source；
Water Combination organic solvent is added in hydrogel in case of wet attrition, the process (dehydration procedure) that hydrogel is dehydrated；Will be de-
The process (drying process) that the hydrogel of water is dried.
The process (dissolution process) for preparing the high molecular solution of natural origin can be by making above-mentioned natural origin macromolecule
It is dissolved in water equal solvent to carry out.As solvent, preferably water.During using water as solvent, natural origin macromolecule can obtain
The aqueous solution.The high molecular concentration of natural origin in solution is preferably 1~30 mass % (solid constituent benchmark), more preferably
3~20 mass % (solid constituent benchmark), more preferably 5~10 mass % (solid constituent benchmark).If natural origin is high
The concentration of molecule 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, glues
Degree increases, the dispersiveness variation of biomass nano fiber and crosslinking agent.The method of dissolving is not particularly limited, can be by solvent
Middle addition natural origin macromolecule is simultaneously stirred to make its dissolving.
It is explained, the natural origin macromolecule being crosslinked is obtained by carrying out cross-linking reaction in aqueous, therefore,
Natural origin macromolecule is preferably water miscible salt form.For example, the natural origin macromolecule with carboxyl is preferably sodium salt, potassium
The form of the metal salts such as salt or ammonium salt, amine salt etc., the natural origin macromolecule with amino is preferably hydrochloride, sulfate etc.
The form of the acylate such as inorganic acid salt or acetate.
Then, biomass nano fiber is disperseed in the high molecular solution of natural origin, preparation is dispersed with biomass nano
The high molecular solution of natural origin (dispersion step) of fiber.
The method for disperseing biomass nano fiber in the high molecular solution of natural origin is not particularly limited, such as can lift
Go out：Biomass nano fiber is added to the method being stirred in the high molecular solution of natural origin；Previously prepared biomass
The dispersion liquid of nanofiber, the dispersion liquid of the biomass nano fiber is added in the high molecular solution of natural origin and mixed
The method of conjunction；Biomass as the raw material of biomass nano fiber is added in the high molecular solution of natural origin, in day
In the right high molecular solution in source by biomass case of wet attrition the method for nanofiber, but preferably previously prepared biomass is received
The dispersion liquid of rice fiber, the dispersion liquid of the biomass nano fiber is added in the high molecular solution of natural origin and mixed
Method.As the method for the dispersion liquid for preparing biomass nano fiber, the manufacture of above-mentioned biomass nano fiber can be used
Method, for example, high-pressure injection makes biomass be scattered in the biomass dispersion liquid of water under 100~245MPa, it is allowed to use with collision
Duromer is collided biomass case of wet attrition, thus can prepare the dispersion liquid of biomass nano fiber.
Crosslinking agent is added in the high molecular solution of natural origin for being dispersed with biomass nano fiber, is crosslinked natural origin
Macromolecule (cross-linking process step).As crosslinking agent, just it is not particularly limited as long as natural origin macromolecule can be crosslinked.
For example, in the case where natural origin macromolecule has carboxyl, can use 1,2- ethylenediamines, 1,3- propane diamine,
The Alkylenediamines such as 1,4- butanediamine, 1,5- pentanediamines, 1,6- hexamethylene diamines, diethylenetriamines, trien, four sub- second
The amine of base five, penten, polyethyleneimine etc. have the compound (hereinafter also referred to " polyamine ") of more than 2 amino, gathered
Polymer containing amino such as lysine, chitosan etc. is used as crosslinking agent.
In the case where natural origin macromolecule has amino, as the crosslinking for being crosslinked natural origin high molecular crosslink
Agent, it can use fumaric acid, maleic acid, itaconic acid, citraconic acid, trimellitic acid etc. that there is the compound of 2 more than carboxyls, poly- third
Carboxylic polymer such as olefin(e) acid, polymethylacrylic acid, poly-gamma-glutamic acid, alginic acid, hyaluronic acid etc. is used as crosslinking agent.
The usage amount of crosslinking agent when making natural origin high molecular crosslink is excellent relative to 100 moles of natural origin macromolecule
Elect 0.01~100 mole, more preferably 0.1~20 mole, more preferably 0.3~10 mole as.If the amount mistake of crosslinking agent
Lack, then the easy step-down of crosslink density, it is possible to be difficult to obtain gel state.If the amount of crosslinking agent is excessive, crosslink density is easy
Uprise, the swellbility of obtained absorbent is possible to step-down.
Together with crosslinking agent and with condensing agent or auxiliary agent can also be condensed.And if with condensing agent or condensation auxiliary agent, can be higher
Effect ground forms amido link.
As condensing agent, water-soluble carbodiimide can be enumerated.Water-soluble carbodiimide refers to that intramolecular has carbodiimide
Base (- N=C=N-), there is water miscible compound.As the concrete example of water-soluble carbodiimide, can enumerate：1- ethyls-
3- (3- dimethylamino-propyls) carbodiimide (hereinafter also referred to " EDC ") or its salt, 1- cyclohexyl -3- (2- morpholinyl ethyls) carbon
Diimine-methyl-to toluene sulfuric acid or its salt, dicyclohexylcarbodiimide etc., preferably 1- ethyls -3- (3- dimethylamino-propyls)
Carbodiimide hydrochloride, 1- cyclohexyl -3- (2- morpholinyl ethyls) carbodiimide-methyl-to toluene sulfate.
The usage amount of condensing agent is 0~50 mole relative to 1 mole of used crosslinking agent, preferably 1~40 mole, more
Preferably 2~30 moles.
As condensation auxiliary agent, can enumerate：N- hydroxy imides.N- hydroxy imides refer to that intramolecular has N- hydroxyls acyl sub-
The compound of amido (- (C=O)-(N-OH)-(C=O) -).That is, the compound is expressed by the following formula.
R1- (C=O)-(N-OH)-(C=O)-R2
Here, R can be passed through1And R2It is bonded to form ring structure.It is preferred that R1And R2It is bonded and by R1And R2In 2 carbon and N-
Hydroxy imide base forms pentacyclic compound.In addition, N- hydroxy imides are preferably water solubility.As workable N-
The concrete example of hydroxy imide, it can enumerate：N-hydroxysuccinimide, N- hydroxy maleimides, N- hydroxyl hexahydro neighbours benzene two
Carboximide, N, N '-dihydroxy butylcyclohexane tetramethyl acid imide, HP, N- hydroxyl tetrabromo-phthalic diformazans
Acid imide, N- hydroxyls tetrachloro-phthalimide, N- hydroxy chloride bridges acid imide, N- hydroxyl humics acid imide, N- hydroxyls
Inclined benzene trimellitic imide, the equal diimides of N, N '-dihydroxy, N, N '-carboximide of dihydroxy naphthlene four.It is sub- in N- hydroxyls acyl
In amine, most preferably n-hydroxysuccinimide (hereinafter also referred to " NHS ").
It is 0~50 mole that the usage amount of auxiliary agent, which is condensed, relative to 1 mole of used crosslinking agent, preferably 1~40 mole,
More preferably 2~30 moles.It is explained, being condensed usage amount of the usage amount of auxiliary agent preferably with used condensing agent is
Equimolar.
It is preferably 1~40 mass % to make the high molecular concentration of natural origin during natural origin high molecular crosslink, more preferably
For 2~20 mass %, more preferably 3~15 mass %.If the high molecular excessive concentration of natural origin, obtained water-setting
The viscosity of glue increases, it is possible to is difficult to stir.If the high molecular concentration of natural origin is too low, the yield of combination product is low, raw
Yield is deteriorated.
The condition of cross-linking process step is not particularly limited.It can be room temperature, can also be heated.It is but too low in temperature
In the case of, cross-linking reaction needs the time extremely grown, it is therefore preferable that being heated.The temperature of cross-linking process step is preferably 10~100
DEG C, more preferably 15~70 DEG C, more preferably 20 DEG C~50 DEG C.In the case of too high, natural origin macromolecule is easy
Decompose.It is therefore preferable that carried out near room temperature.PH during cross-linking reaction is not particularly limited, but preferably 5~12, more preferably
For 6~11, more preferably 7~10.
The reaction time of cross-linking process step is preferably 5 minutes~6 hours, more preferably 10 minutes~3 hours, further preferably
For 20 minutes~2 hours.In cross-linking reaction, can also be stood in advance with stirring reaction solution as needed.It is it is preferred that advance
Stand.Cross-linking reaction obtains gel after the sufficient time in reaction solution.By the way that reaction solution (is preferably steamed with water
Stay water) cleaning, the condensing agent and condensation auxiliary agent in reaction solution are removed, is obtained high molecular by cross-linking agents natural origin
Gel.
Then, it is the natural origin containing the crosslinking obtained in the high molecular process of natural origin is crosslinked is high molecular
Hydrogel carries out case of wet attrition (pulverizing process).In the process, hydrogel is ground into desired size (i.e. with saturation state
Case of wet attrition).The crushing is carried out after crushing preferably coarse crushing in advance.Coarse crushing is carried out by operating as follows：Will be anti-by being crosslinked
The hydrogel that should be obtained is such as the stirring with spatula.In the crushing, by hydrogel using such as mixer for well-distribution, homogenizer,
The device that ball mill, pipe-line mixer etc. are suitable to case of wet attrition crushes.In this manual, the hydrogel after crushing is referred to as water
Gel particles.The average grain diameter of hydrogel particle can be according to the purposes of the desiccant gel powder finally given or the dress for crushing
Put suitable selection, but preferably 10 μm~10mm, more preferably 100 μm~3mm.
In the case of viscosity height, crushing difficulty in hydrogel, water Combination organic solvent described later can also be added.
That is, can also be crushed after water Combination organic solvent is added.By adding water Combination organic solvent, hydrogel be dehydrated and
Volume reduces (contraction), and the viscosity of the dispersion liquid in case of wet attrition, mobility is recovered.Situation about being viscosified in crushing process
Under, it can also continue to crush in midway addition water Combination organic solvent.As described above, case of wet attrition process can also with it is rear
The dehydration procedure stated while carry out.
In the case where using the natural origin macromolecule with carboxyl as raw material, as described above, by natural origin height
The carboxy moiety of molecule forms the water miscible salt forms such as sodium salt and prepares hydrogel.But by the hydrogel system of salt form
In the case of desiccant gel powder, it is possible in an atmosphere moisture absorption and cause powder to stick to each other.Therefore, water can prepared
Inorganic acid or organic acid are added after gel and free acid form is made by salt form in one part.By the water-setting of free acid form
The desiccant gel powder that glue obtains can reduce hygroscopicity compared with the desiccant gel powder of salt form, therefore be not easy to cause 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..It is inorganic
Acid or organic acid are preferably mixed with water Combination organic solvent and are added in hydrogel particle.If because add inorganic acid
Or organic acid, then hydrogel equably neutralized, can obtain the hydrogel particle of uniform free acid form.
Then, add water Combination organic solvent in the hydrogel after case of wet attrition and hydrogel is dehydrated (dehydration work
Sequence).If making hydrogel particle be impregnated in water Combination organic solvent, contained water is discharged to water Combination in hydrogel particle
In organic solvent.Sometimes hydrogel particle is dehydrated and is shrunk to particle size.And then for making natural origin high molecular crosslink
The unwanted material such as unreacted crosslinking agent, condensing agent is also discharged together with water from hydrogel particle.
Water Combination organic solvent is not particularly limited.Such as it can enumerate：Methanol, ethanol, isopropanol, normal propyl alcohol, tertiary fourth
The lower alcohols such as alcohol, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, third
Glycol ethers and the acetone such as glycol list ethylether.Wherein, preferably methanol, ethanol, isopropanol and acetone.These water Combination
Organic solvent can be used alone, and can also be mixed with two or more, or can also gradually add two or more according to dispersity
Solvent.
Dipping of the hydrogel particle into water Combination organic solvent can be repeatedly.Now, by filtering or being decanted
The solvent of the water containing discharge is removed from hydrogel particle, water Combination organic solvent is added to hydrogel particle again
In.By repeatedly impregnating as above, hydrogel particle is further dehydrated and shunk, and it is low-down micro- to turn into moisture content
Grain.In the case where repeatedly impregnating, dipping can use different water Combination organic solvents every time.
The usage amount of water Combination organic solvent is different according to amount of water when its species, hydrogel preparation etc., to every 1
For secondary dipping, relative to hydrogel, preferably 1 times of capacity (equivalent)~20 times capacity, more preferably 2 times of capacity~10 times
Capacity, more preferably 3 times of capacity~7 times capacity.
Make hydrogel particle be impregnated in water Combination organic solvent time it is different according to the species of solvent, amount etc., it is right
It is preferably 1 minute~2 hours, more preferably 2 minutes~1 hour, further excellent if considering workability for the dipping of every 1 time
Elect as 3 minutes~30 minutes.
The hydrogel particle after being impregnated in water Combination organic solvent can also be rushed with appropriate liquid as needed
Wash.
Then, the hydrogel of dehydration is dried into (drying process).The moisture content of the hydrogel particle obtained after dehydration procedure
It is low, it is practically free of moisture.Therefore, water Combination organic solvent is removed by filtering or being decanted, preferably in room temperature~150 DEG C, more
It is preferred that 35 DEG C~125 DEG C, further preferably carried out at 50 DEG C~100 DEG C air-supply dry or standing and drying, it can thus be concluded that arriving
Desiccant gel powder.As described above, hydrogel particle is not exposed under harsh drying condition, therefore, in the drying process
Particle each other will not adhesion.
The particle diameter of obtained desiccant gel powder is contemplated that purposes of desiccant gel powder etc. and determined, does not limit especially
It is fixed.That is, can be obtained according to the reducing mechanism (mixer for well-distribution, homogenizer etc.) and its crush force that are used in above-mentioned pulverizing process
With the desiccant gel powder for it is expected particle diameter.
Generally, it is polymer impregnated to be dissolved when solvent in the case where polymer does not keep eyed structure (gel state).
But be swelled by the way that the desiccant gel powder infusion that the above method obtains is insoluble when the water, regenerate hydrogel.Cause
This, the desiccant gel powder obtained by the above method keeps eyed structure (gel state).
Embodiment
Embodiment 1
By γ-PGA (Na types, 500KDa, Co., Ltd.'s バ イ オ リ ー ダ ー ズ systems) 1.359g (glutamic acid units 9mmol
(unit of glutamic acid 1 for forming γ-PGA is 151g/mol)) it is dissolved in ion exchange water, prepare the aqueous solution.Then, addition is fine
Tie up the plain aqueous dispersions of nanofiber 5% (BiNFi-s NMa, average degree of polymerization 530,0.02 μm of average diameter, 2 μm of average length,
Co., Ltd.'s Sugino Machine systems) 3.02g (with respect to the mass % of γ-PGA 10), prepare the mass %'s of solid component concentration 7
Dispersion liquid, using homogenizer (AHG-160D, axle generator HT1018, ASONE Co. Ltd. system) under conditions of 1000rpm
Mixing.
Then, successively by penten (Wako Pure Chemical Industries, Ltd.'s system) with relative glutamic acid units
2mol%, n-hydroxysuccinimide (hereinafter also referred to " NHS ") (Wako Pure Chemical Industries, Ltd.'s system) are with relative glutamic acid
Unit 6mol%, 1- ethyl -3- (3- dimethylamino-propyls) carbodiimide (hereinafter also referred to " EDC ") hydrochloride (and the pure medicine of light
Industrial Co., Ltd's system) stirred with relative glutamic acid units 6mol% while adding.The water of gonorrhoea was obtained at 3 minutes or so
Gel.
Add after terminating 30 minutes, the gonorrhoea hydrogel spatula coarse crushing that will be obtained.Then, the water-setting after coarse crushing
In glue add 20g methanol (Wako Pure Chemical Industries, Ltd.'s system), using homogenizer (AHG-160D, axle generator HT1018,
ASONE Co. Ltd. systems) case of wet attrition under conditions of 750rpm.After case of wet attrition, when dispersion liquid is stood, translucent water
Gel particles settle, and therefore, remove solvent by being decanted, rejoin 20g methanol and be stirred.Sequence of operations is repeated, is entered
Row dehydration turns into white particles until hydrogel particle shrinks.
The particle being dehydrated is blown drying under conditions of 70 DEG C, 90 minutes, obtains desiccant gel powder.
Using obtained desiccant gel powder as water absorbing agent, gel strength and water retention capability are determined by aftermentioned method.Survey
Determine result and be shown in table 1.
Comparative example 1
Using γ-PGA 1.51g (glutamic acid units 10mmol), do not add cellulose nano-fibrous, in addition, pass through
Similarly to Example 1 the step of, prepares water absorbing agent, determines gel strength and water retention capability.Measurement result is shown in table 1.
Comparative example 2
(" KC Flock " (registration mark) W-50GK, averagely gathered using the cellulose powder as fine cellulose raw material
Right 530,25 μm of average diameter, 45 μm of average length, Nippon Paper Chemicals Co., Ltd.'s system) instead of cellulose nano-fibrous,
In addition, by similarly to Example 1 the step of prepare water absorbing agent, determine gel strength and water retention capability.Measurement result is shown
In table 1.
Embodiment 2
Cellulose nano-fibrous 5% aqueous dispersions are changed to BiNFi-s AMa (averages degree of polymerization by BiNFi-s NMa
200,0.02 μm of average diameter, 2 μm of average length, Co., Ltd.'s Sugino Machine systems), in addition, by with implementation
The same step of example 1 prepares water absorbing agent, determines gel strength and water retention capability.Measurement result is shown in table 1.
Embodiment 3
Cellulose nano-fibrous 5% aqueous dispersions are changed to BiNFi-s FMa (averages degree of polymerization by BiNFi-s NMa
600,0.02 μm of average diameter, 2 μm of average length, Co., Ltd.'s Sugino Machine systems), in addition, by with implementation
The same step of example 1 prepares water absorbing agent, determines gel strength and water retention capability.Measurement result is shown in table 1.
Embodiment 4
By γ-PGA be changed to molecular weight be 50KDa material (Co., Ltd.'s バ イ オ リ ー ダ ー ズ systems), except this with
Outside, by similarly to Example 1 the step of prepare water absorbing agent, determine gel strength and water retention capability.Measurement result is shown in table 1.
Embodiment 5
By γ-PGA be changed to molecular weight be 2000KDa material (Co., Ltd.'s バ イ オ リ ー ダ ー ズ systems), except this with
Outside, by similarly to Example 1 the step of prepare water absorbing agent, determine gel strength and water retention capability.Measurement result is shown in table 1.
Embodiment 6
By γ-PGA be changed to molecular weight be 2000KDa material (Co., Ltd.'s バ イ オ リ ー ダ ー ズ systems) and will be micro-
The aqueous dispersions of fine cellulose fiber 5% are changed to BiNFi-sFMa by BiNFi-s NMa, in addition, by same with embodiment 1
The step of sample, prepares water absorbing agent, determines 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, by with implementation
The same step of example 6 prepares water absorbing agent, determines 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, by with implementation
The same step of example 6 prepares water absorbing agent, determines gel strength and water retention capability.Measurement result is shown in table 2.
Comparative example 3
Be not added with it is cellulose nano-fibrous, in addition, by similarly to Example 6 the step of prepare water absorbing agent, determine
Gel strength and water retention capability.Measurement result is shown in table 2.
Comparative example 4
Addition as the penten of crosslinking agent is changed to relative PGA6mol%, in addition, by with
The same step of comparative example 3 prepares water absorbing agent, determines gel strength and water retention capability.Measurement result is shown in table 2.
Comparative example 5
Addition as the penten of crosslinking agent is changed to relative PGA9mol%, in addition, by with
The same step of comparative example 3 prepares water absorbing agent, determines gel strength and water retention capability.Measurement result is shown in table 2.
Comparative example 6
To commercially available acrylic acid series SAP (Sumitomo refine plant formula can a company system, Aquakeep SA60S) measure gel strength
And water retention capability.Measurement result is shown in table 2.
[water retention capability measure]
(1) bag (10 × 20cm) is prepared simultaneously with 250 mesh nylon wires (Co., Ltd.'s NBC Meshtec systems, N-NO.250HD)
Load determination sample 0.3g.
(2) measure includes the quality A including nylon wire.
(3) load physiological saline 1L in beaker, impregnate the ready nylon wire equipped with sample and place 1 hour.
(4) bag is lifted, the short side that bag is clamped with clothes washing clamp is hung, control water 15 minutes.
(5) and then, it is dehydrated (150G, 90 seconds) with centrifugal separator.
(6) the quality B after measure dehydration.
(7) water retention capability (g/g) is calculated by following formula.
Water retention capability=(B-A)/0.3
[gel strength measure]
(1) by using the hydrogel that same method preparation water conservation state is determined with water retention capability.
(2) sample is loaded in diameter 27mm PP pipes (new PP sample cells NO.5,22mL, M Co., Ltd.'s aruemu systems)
Product 6.0g.
(3) diameter 25mm sieve is placed on sample.
(4) with digital force gauge pressing sieve (intrusion speed 1mm/s).
(5) starting point will be set at the time of the 3rd takes place change after the decimal point in terms of the measured value of digital force gauge, read
The numerical value of maximum load when pressing 10 seconds (10mm) gels is taken, as gel strength.
[table 1]
[table 2]
In the comparison (W-50GK and NMa) of the cellulose fibre with not carrying out cellulose nanometer pulverization, find to carry out
The raising effect of the gel strength of the cellulose fibre of nanometer pulverization, on the other hand, it is fine that discovery does not carry out comminuted fibres element
The gel strength of dimension does not improve.
In the different comparison (AMa of cellulose nano-fibrous average degree of polymerization<NMa<FMa in), the big fiber of the degree of polymerization
The high tendency of raising effect of gel strength be present in plain nanofiber.
In addition, relative to because cellulose nano-fibrous average degree of polymerization is different and result that gel strength is different, for
Water retention capability, the different and different of average degree of polymerization because of composite are not found.
Understand, in order to improve gel strength, big cellulose nano-fibrous of the degree of polymerization can be added.
Mixing 10% it is cellulose nano-fibrous under conditions of, in the average mark of the high molecular polyglutamic acid of natural origin
Son is measured in different comparisons, and the big polyglutamic acid of mean molecule quantity has the tendency that gel strength becomes big.
In the result of water retention capability, there is liquid in the side that the mean molecule quantity of the high molecular polyglutamic acid of natural origin is small
The tendency that the retentivity of body reduces.In addition, on the contrary, the big side of mean molecule quantity has found the raising of gel strength, on the other hand,
For water retention capability, find relative to mean molecule quantity to be that moderate polyglutamic acid has the tendency of reduction.
Understand, in order to improve gel strength, the big polyglutamic acid of mean molecule quantity can be used.
In the case where controlling gel physical property merely with crosslinking agent, if crosslinker concentration when excessively improving synthesis, instead
And the tendency of gel strength reduction be present.Equally, the feelings of gel strength are improved in the cellulose nano-fibrous addition of increase
Under condition, if excessively increasing addition, the tendency reduced there is also gel strength (is qualitatively said to disappear for elongation and becomes crisp
State).
Understand, compared with situation of the increase crosslinker concentration to improve gel strength, improved by adding cellulose solidifying
The decline degree of the water retention capability of the situation of glue intensity is relatively low.
Industry usability
The water absorbing agent of the present invention is preferably used as the absorption for forming the absorbent commodities such as disposable diaper, sanitary napkin
The raw material of body.
Symbol description
The particle of 1 absorbent
The 2 natural origin macromolecules being crosslinked
3 biomass nano fibers
Claims (4)
1. the manufacture method of the water absorbing agent containing crosslinking natural origin macromolecule and biomass nano fiber, methods described bag
Include following process：
The process for dissolving natural origin macromolecule and preparing the high molecular solution of natural origin；
Disperse biomass nano fiber in the high molecular solution of natural origin, preparation is dispersed with the natural of biomass nano fiber
The process of the high molecular solution in source；With
Crosslinking agent is added in the high molecular solution of natural origin for being dispersed with biomass nano fiber, is crosslinked natural origin high score
The process of son,
Wherein,
Natural origin macromolecule is polyaminoacid,
The average diameter of biomass nano fiber is 4~1000nm,
The length of biomass nano fiber is more than 100 times of diameter,
The content of biomass nano fiber relative to natural origin macromolecule and biomass nano fiber the mass parts of total amount 100
For 10~30 mass parts,
Crosslinking agent is polyamine.
2. the method described in claim 1, in addition to the crosslinking obtained in the high molecular process of natural origin is crosslinked will be contained
The high molecular hydrogel of the natural origin process that carries out case of wet attrition.
3. the method described in claim 2, be additionally included in the hydrogel of case of wet attrition add water Combination organic solvent and
The process that hydrogel is dehydrated.
4. the method described in claim 3, in addition to the process that the hydrogel being dehydrated is dried.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-153082 | 2013-07-23 | ||
| JP2013153082A JP6168892B2 (en) | 2013-07-23 | 2013-07-23 | Water absorbent |
| PCT/JP2014/069354 WO2015012273A1 (en) | 2013-07-23 | 2014-07-22 | Water absorbent |
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|---|---|
| CN105026033A CN105026033A (en) | 2015-11-04 |
| CN105026033B true CN105026033B (en) | 2018-01-05 |
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| JP (1) | JP6168892B2 (en) |
| KR (1) | KR102284629B1 (en) |
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| KR101680830B1 (en) | 2013-12-06 | 2016-11-29 | 주식회사 엘지화학 | Super Absorbent Polymer Resin and the Method for Preparing of the Same |
| CN105601952B (en) * | 2016-01-14 | 2018-07-10 | 北京化工大学 | A kind of poly-aspartate composite hydrogel and preparation method thereof |
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| WO2015012273A1 (en) | 2015-01-29 |
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| CN105026033A (en) | 2015-11-04 |
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| JP6168892B2 (en) | 2017-07-26 |
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