WO2017061166A1 - Agent absorbant l'eau biodégradable et son procédé de production - Google Patents

Agent absorbant l'eau biodégradable et son procédé de production Download PDF

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Publication number
WO2017061166A1
WO2017061166A1 PCT/JP2016/072850 JP2016072850W WO2017061166A1 WO 2017061166 A1 WO2017061166 A1 WO 2017061166A1 JP 2016072850 W JP2016072850 W JP 2016072850W WO 2017061166 A1 WO2017061166 A1 WO 2017061166A1
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Prior art keywords
water
trehalose
naturally
derived polymer
absorbing agent
Prior art date
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PCT/JP2016/072850
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English (en)
Japanese (ja)
Inventor
山口　正史
宇山　浩
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ユニ・チャーム株式会社
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Publication date
Priority claimed from JP2016123717A external-priority patent/JP6407204B2/ja
Application filed by ユニ・チャーム株式会社 filed Critical ユニ・チャーム株式会社
Publication of WO2017061166A1 publication Critical patent/WO2017061166A1/fr

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Classifications

    • 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
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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

Definitions

  • the present invention relates to an absorbent article containing a biodegradable water-absorbing agent as a constituent element of an absorber, a biodegradable water-absorbing agent, and a method for producing the same.
  • SAP superabsorbent polymers
  • pulp are used for absorbent bodies of absorbent articles such as disposable diapers and sanitary products.
  • synthetic polymer SAPs such as polyacrylates are widely used as SAPs.
  • naturally derived SAPs such as polyglutamates have attracted attention from the viewpoint of biodegradability.
  • International Publication No. 2007/034785 discloses a water-soluble carbodiimide when polyglutamic acid is crosslinked with polyamine in order to obtain a polyglutamic acid gel having excellent swelling degree and moisture retention and biodegradability in high yield.
  • N-hydroxysuccinimide as a condensing agent and a condensing aid is disclosed.
  • Japanese Patent Application Laid-Open No. 2008-169313 discloses a production method in which a water-miscible organic solvent is added in a wet pulverization step in order to easily obtain a natural product-derived dry gel powder.
  • the method disclosed in WO 2007/034785 uses lyophilization to obtain a dry gel powder.
  • freeze-drying equipment is commercially undesirable because of its high cost and low productivity.
  • hydrogel particles are dehydrated with a water-miscible solvent and then dried by blowing to obtain a dry gel powder.
  • the crosslinked water-absorbing network in the dried gel powder shrinks due to dehydration and drying, and is in a state of being in close contact, so that the initial response of water absorption and re-swelling becomes low.
  • the present inventor has found that by incorporating trehalose into the biodegradable water-absorbing agent, the water-absorbing speed and instantaneous water-absorbing factor of the water-absorbing agent can be improved, and the present invention has been completed.
  • the present invention is an absorbent article comprising a granular water-absorbing agent composed of a cross-linked naturally-derived polymer and trehalose as a constituent of the absorber, and the water absorption rate measured by the vortex method of the water-absorbing agent is 25 seconds or less. It is an absorbent article.
  • the present invention is also a particulate water-absorbing agent comprising a cross-linked naturally derived polymer and trehalose, the water-absorbing agent having a water absorption rate of 25 seconds or less measured by vortex method.
  • the instantaneous water absorption ratio of the water absorbing agent is 2.5 or more.
  • the trehalose content in the water-absorbing agent is 0.5 to 30.0% by mass.
  • the naturally derived polymer has a condensable functional group.
  • the naturally derived polymer is polyglutamic acid or carboxymethylcellulose.
  • the present invention is also a method for producing a water-absorbing agent containing a cross-linked naturally-derived polymer and trehalose, a step of preparing a raw material aqueous solution by dissolving the natural-derived polymer and trehalose in water, and a cross-linking agent in the raw material aqueous solution. Or a step of crosslinking the naturally-derived polymer by irradiation with radiation.
  • the method of the present invention preferably further comprises a step of wet-grinding the hydrogel containing the crosslinked naturally-derived polymer obtained in the step of crosslinking the naturally-derived polymer.
  • the method of the present invention preferably further comprises the step of adding a water miscible organic solvent to the wet ground hydrogel to dehydrate the hydrogel.
  • the method of the present invention preferably further comprises the step of drying the dehydrated hydrogel.
  • the crosslinking agent is a polyamine or a compound having two or more epoxy groups.
  • the water miscible organic solvent is methanol.
  • the amount of trehalose in the aqueous raw material solution is 10 to 100 parts by mass based on 100 parts by mass of the naturally derived polymer.
  • the amount of the crosslinking agent is 0.5 to 25 parts by mass based on 100 parts by mass of the naturally derived polymer.
  • the present invention is also a method for producing a water-absorbing agent containing a cross-linked natural polymer and trehalose, the step of absorbing the trehalose aqueous solution into the cross-linked natural polymer, the cross-linked natural high polymer that has absorbed the trehalose aqueous solution.
  • the method includes a step of wet-grinding and dehydrating molecules in a water-miscible organic solvent, and a step of drying the dehydrated crosslinked naturally-derived polymer.
  • the water-absorbing agent contained in the absorbent article of the present invention is biodegradable, has a high water absorption rate, and has a high instantaneous water absorption ratio.
  • the present invention is an absorbent article comprising a granular water-absorbing agent composed of a cross-linked naturally-derived polymer and trehalose as a constituent of the absorber, and the water absorption rate measured by the vortex method of the water-absorbing agent is 25 seconds or less. It is an absorbent article.
  • the present invention is also a particulate water-absorbing agent comprising a cross-linked naturally derived polymer and trehalose, the water-absorbing agent having a water absorption rate of 25 seconds or less measured by vortex method.
  • Trehalose is one of disaccharides in which two molecules of D-glucose are bound to each other through their reducing groups. There are three isomers, ⁇ , ⁇ -, ⁇ , ⁇ -, ⁇ , ⁇ -, depending on whether the binding mode is ⁇ -bond or ⁇ -bond, and any of these isomers can be used. Among them, ⁇ , ⁇ -trehalose is Are preferred because they exist in nature. The chemical formula is C 12 H 22 O 11 . ⁇ , ⁇ -trehalose includes dihydrate and anhydride.
  • Naturally-derived polymer is not particularly limited as long as it is a naturally-derived polymer.
  • Naturally-derived polymers refer to polymers obtained by fermentation with microorganisms, polymers extracted from natural products, and the like, and are generally called biopolymers.
  • Naturally derived polymers include polyamino acids such as polyglutamic acid, polyaspartic acid, polylysine, polyarginine or salts thereof, polysaccharides such as alginic acid, hyaluronic acid, chitosan, and natural polymers such as carboxymethylcellulose. Although what was given is mentioned, It is not limited to these. Among these, preferred natural polymers are polyglutamic acid or carboxymethylcellulose.
  • the polyamino acid may be a copolymer.
  • Naturally derived polymers may be used as a mixture of two or more.
  • the naturally derived polymer may have a condensable functional group.
  • the condensable functional group contributes to react with the cross-linking agent to cross-link the naturally derived polymer.
  • the condensable functional group include a carboxyl group and an amino group, and among them, the carboxyl group is preferable because it also imparts hydrophilicity.
  • the naturally-derived polymer preferably has a carboxyl group in order to exhibit high water absorption, although the presence or absence of a condensable functional group is not involved in the cross-linking.
  • the naturally-derived polymer is preferably hydrophilic and more preferably in the form of a water-soluble salt.
  • the naturally-derived polymer having a carboxyl group is preferably in the form of a metal salt such as sodium salt or potassium salt, or an ammonium salt or an amine salt, and the naturally-derived polymer having an amino group is hydrochloride, It is preferably in the form of an inorganic acid salt such as sulfate or an organic acid salt such as acetate.
  • the molecular weight of the naturally derived polymer is not particularly limited, but the mass average molecular weight is preferably 10,000 to 13 million, more preferably 50,000 to 10 million, and still more preferably 300,000 to 5,000,000. If the molecular weight is too small, the number of uncrosslinked molecular chains per unit mass increases, resulting in a gel with a large amount of elution and low strength. If the molecular weight is too large, the viscosity at the time of dissolution increases, and trehalose and the crosslinking agent are not uniformly dispersed.
  • the cross-linked naturally-derived polymer means a polymer obtained by reacting a naturally-derived polymer with a crosslinking agent and chemically crosslinking, or a polymer obtained by irradiating a naturally-derived polymer with radiation.
  • the crosslinking method will be described later.
  • the water-absorbing agent of the present invention has a water absorption rate (hereinafter also simply referred to as “water absorption rate”) measured by a vortex method of 25 seconds or less.
  • the water absorption rate is preferably as the value is small, preferably 20 seconds or less, and more preferably 15 seconds or less.
  • the lower limit of the water absorption speed is not particularly limited, but is usually about 5 seconds.
  • the water absorption rate is measured as follows. (1) Take 25 g of physiological saline (0.9 mass% sodium chloride aqueous solution) in a 50 mL beaker. (2) Place a 50 mL beaker on a magnetic stirrer (RS-1DN manufactured by ASONE) and stir at 550 rpm. (3) Precisely weigh 1.00 g of the sample (classified with a sieve in advance and use one having a particle size in the range of 500 to 850 ⁇ m) and put it into the beaker of (2). The stopwatch is started at the same time as the sample is added. When the liquid surface in the beaker becomes flat, the stopwatch is stopped, the time (seconds) is read, and this is taken as the value of the water absorption speed.
  • physiological saline 0.9 mass% sodium chloride aqueous solution
  • the instantaneous water absorption ratio of the water absorbing agent is preferably 2.5 or more.
  • the instantaneous water absorption ratio is preferably as high as possible, more preferably 3.5 or more, and further preferably 5.0 or more.
  • the upper limit of the instantaneous water absorption magnification is not particularly limited, but is usually about 10.
  • the trehalose content in the water-absorbing agent is preferably 0.5 to 30.0% by mass, more preferably 1.0 to 20.0% by mass, and further preferably 5.0 to 15.0% by mass. %. If the trehalose content is too small, a sufficient function improvement effect cannot be obtained. If the amount is too large, the ratio of the water-absorbing skeleton decreases, so that the water-absorbing performance decreases.
  • the mass of trehalose shall be expressed in terms of C 12 H 22 O 11 converted mass, that is, a mass not including bound water.
  • the mass of a water absorbing agent shall be represented by the mass in a dry state. The mass in the dry state of the water-absorbing agent means the mass after being dried at 70 ° C. for 90 minutes.
  • the water absorbent of the present invention is granular.
  • the shape and particle size of the water-absorbing agent particles are not limited as long as the effects of the present invention are exhibited.
  • the average particle size of the water-absorbing agent is preferably 10 ⁇ m to 10 mm, more preferably 100 ⁇ m to 3 mm, and still more preferably. Is 300 ⁇ m to 1 mm.
  • D ⁇ (D1 ⁇ R1) + (D2 ⁇ R2) +... (Dn ⁇ Rn) ⁇ / 100
  • Dn Average particle diameter in each pair of sieves
  • Rn Test sample residual ratio (%) of sieves with smaller openings in each pair
  • the method for producing a water-absorbing agent containing a cross-linked naturally-derived polymer and trehalose according to the present invention prepares a raw material aqueous solution by dissolving the natural-derived polymer and trehalose in water (hereinafter also referred to as “raw aqueous solution preparing step”). And a step of adding a crosslinking agent to the raw material aqueous solution or irradiating radiation to crosslink the naturally-derived polymer (hereinafter also referred to as “crosslinking step”).
  • the production method of the present invention further includes a step of wet-grinding a hydrogel containing a cross-linked naturally-derived polymer obtained in the step of cross-linking a naturally-derived polymer (hereinafter also referred to as “grinding step”), and a wet-pulverized hydrogel. And a step of dehydrating the hydrogel (hereinafter also referred to as “dehydration step”) and a step of drying the dehydrated hydrogel (hereinafter also referred to as “drying step”). But you can.
  • the raw material aqueous solution preparation step can be performed by dissolving the naturally derived polymer and trehalose in water.
  • the method of dissolution is not limited, but can be carried out by adding the naturally-derived polymer and trehalose to water and stirring.
  • the order of dissolution is not limited, and a natural aqueous polymer and trehalose may be added to water at the same time and stirred to prepare a raw material aqueous solution.
  • the raw material aqueous solution may be prepared by adding the natural polymer to the mixture and stirring.
  • the natural polymer aqueous solution and the trehalose aqueous solution may be prepared separately, and the natural polymer aqueous solution and the trehalose aqueous solution may be mixed together to prepare
  • An aqueous solution may be prepared, but from the viewpoint of more uniformly dispersing trehalose, a trehalose aqueous solution is prepared in advance and the naturally derived polymer is dissolved therein. It was preferred to prepare a raw material aqueous solution.
  • the raw material aqueous solution contains a naturally-derived polymer, trehalose and water.
  • the concentration of the naturally derived polymer in the raw material aqueous solution is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and further preferably 5 to 15% by mass. If the concentration of the naturally derived polymer is too thin, the recovered amount of the water-absorbing agent is low and the productivity is deteriorated. If the concentration of the naturally-derived polymer is too high, the viscosity increases and the dispersibility of trehalose and the crosslinking agent deteriorates.
  • the mass of the naturally derived polymer is represented by the mass in the dry state. The mass of the naturally derived polymer in the dry state refers to the mass after being dried at 70 ° C.
  • the concentration of trehalose in the raw material aqueous solution (based on C 12 H 22 O 11 ) is not particularly limited, but is, for example, 1 to 10% by mass.
  • the amount of trehalose in the raw material aqueous solution is not particularly limited, and is, for example, 10 to 100 parts by mass based on 100 parts by mass of the naturally-derived polymer.
  • the aqueous raw material solution may contain substances other than naturally-derived polymers, trehalose and water (for example, a dispersant, an emulsifier, an organic solvent, etc.) as long as the effects of the present invention are not impaired.
  • Crosslinking may be performed by reacting a naturally occurring polymer with a crosslinking agent (chemical crosslinking) or by irradiating the naturally occurring polymer with radiation (radiation crosslinking). From the viewpoint of mass productivity, chemical crosslinking is preferred.
  • chemical crosslinking is preferred.
  • the crosslinking agent is not particularly limited as long as it can crosslink naturally derived polymers.
  • a compound having two or more epoxy groups such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether can be used as the crosslinking agent.
  • alkylene such as 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-heptanediamine, 1,6-hexanediamine, etc.
  • polyamine Compounds having two or more amino groups such as diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine (hereinafter also referred to as “polyamine”), amino group-containing polymers such as polylysine and chitosan, etc. It can be used as a crosslinking agent.
  • the naturally-derived polymer has an amino group
  • compounds having two or more carboxyl groups such as fumaric acid, maleic acid, itaconic acid, citraconic acid, trimellitic acid, polyacrylic acid, polymethacrylic acid, polyglutamic acid, alginic acid
  • a carboxyl group-containing polymer such as hyaluronic acid can be used as a crosslinking agent.
  • the amount of the crosslinking agent used for crosslinking the naturally derived polymer is preferably 0.5 to 25 parts by mass, more preferably 1.0 to 20 parts by mass with respect to 100 parts by mass of the naturally derived polymer. More preferably, it is 1.5 to 15 parts by mass. If the amount of the crosslinking agent is too small, the crosslinking density tends to be low, and the gel state may be difficult to obtain. If the amount of the crosslinking agent is too large, the crosslinking density tends to be high, and the swelling degree of the resulting water-absorbing agent may be lowered.
  • a condensing agent and a condensing aid may be used in combination with the crosslinking agent.
  • a condensing agent and a condensing aid are used in combination, an amide bond can be formed more efficiently.
  • a water-soluble carbodiimide is mentioned as a condensing agent.
  • the water-soluble carbodiimide is a compound having a carbodiimide group (—N ⁇ C ⁇ N—) in the molecule and having water solubility.
  • water-soluble carbodiimide examples include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide or a salt thereof, 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide-meth-p-toluenesulfuric acid or a salt thereof And dicyclohexylcarbodiimide, preferably 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide-meth-p-toluene sulfate.
  • the amount of the condensing agent to be used is 0 to 50 mol, preferably 1 to 40 mol, more preferably 2 to 30 mol, per 1 mol of the crosslinking agent used.
  • N-hydroxyimide is a compound having an N-hydroxyimide group (—C ( ⁇ O) —N (—OH) —C ( ⁇ O) —) in the molecule. That is, this compound is represented by the following general formula.
  • a ring structure may be formed by combining R 1 and R 2 .
  • a compound in which R 1 and R 2 are bonded to form a 5-membered ring with two carbons in R 1 and R 2 and an N-hydroxyimide group is preferable.
  • N-hydroxyimide is preferably water-soluble.
  • N-hydroxyimide that can be used include N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N, N'-dihydroxycyclohexanetetracarboxylic imide, N -Hydroxyphthalic acid imide, N-hydroxytetrabromophthalic acid imide, N-hydroxytetrachlorophthalic acid imide, N-hydroxyhetic acid imide, N-hydroxyhymic acid imide, N-hydroxytrimellitic acid imide, N, N Examples include '-dihydroxypyromellitic imide and N, N'-dihydroxynaphthalene tetracarboxylic imide.
  • N-hydroxysuccinimide is most preferable.
  • the amount of the condensation aid used is 0 to 50 mol, preferably 1 to 40 mol, more preferably 2 to 30 mol, per 1 mol of the crosslinking agent used.
  • the usage-amount of a condensation adjuvant shall be equimolar with the usage-amount of the condensing agent used.
  • the conditions for the crosslinking step are not particularly limited. It may be room temperature or may be heated. However, if the temperature is too low, the crosslinking reaction takes a very long time, so it is preferable to perform heating.
  • the temperature in the crosslinking step is preferably 10 to 100 ° C., more preferably 15 to 70 ° C., and further preferably 20 ° C. to 50 ° C. When it is too high, the naturally-derived polymer is easily decomposed. Therefore, it is preferable to carry out at around room temperature.
  • the pH during the crosslinking reaction is not particularly limited, but is preferably 5 to 12, more preferably 6 to 11, and still more preferably 7 to 10.
  • the reaction time in the crosslinking step is preferably 5 minutes to 6 hours, more preferably 10 minutes to 3 hours, and further preferably 20 minutes to 2 hours.
  • the reaction solution may be stirred or allowed to stand as necessary. Preferably, it is left still.
  • a gel is obtained in the reaction solution.
  • water preferably ion-exchanged water or distilled water
  • the unreacted crosslinking agent, condensing agent and condensation aid in the reaction solution are removed, and the naturally derived polymer is crosslinked with the crosslinking agent. Gel is obtained.
  • the hydrogel containing the cross-linked naturally-derived polymer obtained in the cross-linking step is wet-pulverized (grinding step).
  • the hydrogel is pulverized to a desired size in a water-containing state (ie, wet pulverization).
  • the pulverization is preferably carried out after coarse pulverization in advance.
  • Coarse pulverization is performed by stirring the hydrogel obtained by the crosslinking reaction with, for example, a spatula.
  • the hydrogel is pulverized using an apparatus suitable for wet pulverization such as a homomixer, a homogenizer, a bead mill, and a pipe mixer.
  • the ground hydrogel is referred to as hydrogel particles.
  • the average particle size of the hydrogel particles can be appropriately set depending on the use of the finally obtained dry gel powder or depending on the apparatus used for pulverization, but is preferably 10 ⁇ m to 10 mm, more preferably 100 ⁇ m to 3 mm.
  • a water-miscible organic solvent described later may be added. That is, you may grind
  • a water-miscible organic solvent By adding a water-miscible organic solvent, the hydrogel is dehydrated and volume-reduced (shrinks), the viscosity of the dispersion during wet grinding is lowered, and fluidity is restored. Even when the viscosity is increased during the pulverization, the water-miscible organic solvent can be added on the way to continue the pulverization. Thus, the wet pulverization step and the dehydration step described later may be performed simultaneously.
  • the hydrogel is prepared by converting the carboxyl group portion of the naturally-derived polymer into a water-soluble salt form such as a sodium salt.
  • a water-soluble salt form such as a sodium salt.
  • salt-form hydrogels are made into dry gel powders, they may absorb moisture in the atmosphere and the powders may coalesce. Therefore, after preparing the hydrogel, an inorganic acid or an organic acid may be added to partially change the salt form to the free acid form.
  • the dry gel powder obtained from the hydroacid in the free acid form has reduced hygroscopicity compared to the dry gel powder in the salt form, so that the powders are less likely to coalesce.
  • the inorganic acid and organic acid examples include sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid and the like.
  • the inorganic acid or organic acid is preferably mixed with a water-miscible organic solvent and added to the hydrogel particles. This is because when an inorganic acid or an organic acid is added, the hydrogel is uniformly neutralized to obtain hydrogel particles in a uniform free acid form.
  • a water-miscible organic solvent is added to the wet-pulverized hydrogel to dehydrate the hydrogel (dehydration step).
  • water contained in the hydrogel particles is discharged into the water-miscible organic solvent.
  • the hydrogel particles may be dehydrated and shrink to a fine particle size. Furthermore, unnecessary substances such as unreacted crosslinking agents, condensing agents, and condensation aids used for crosslinking the naturally-derived polymer are also discharged from the hydrogel particles together with water.
  • the water miscible organic solvent is not particularly limited.
  • lower alcohols such as methanol, ethanol, isopropanol, n-propanol, tertiary butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.
  • Glycol ethers, and acetone are preferable, and methanol is particularly preferable.
  • These water-miscible organic solvents may be used singly or in combination of two or more, or two or more solvents may be added sequentially according to the dispersion state.
  • the immersion of the hydrogel particles in the water-miscible organic solvent may be repeated several times.
  • the solvent containing water discharged from the hydrogel particles is removed by filtration or decantation, and a new water-miscible organic solvent is added to the hydrogel particles.
  • the hydrogel particles are dehydrated and contracted to become fine particles having a very low water content.
  • a different water-miscible organic solvent may be used for each soaking.
  • the amount of the water-miscible organic solvent used varies depending on the type and the amount of water at the time of hydrogel preparation, but preferably 1 volume (equal amount) to 20 times the hydrogel per immersion.
  • the capacity is more preferably 2 to 10 times the capacity, and further preferably 3 to 7 times the capacity.
  • the time for immersing the hydrogel particles in the water-miscible organic solvent varies depending on the type and amount of the solvent, but is preferably 1 minute to 2 hours in consideration of workability per one time of immersion. Preferably it is 2 minutes to 1 hour, more preferably 3 minutes to 30 minutes. If necessary, the hydrogel particles immersed in a water-miscible organic solvent may be rinsed with an appropriate liquid.
  • the dehydrated hydrogel is dried (drying step).
  • the hydrogel particles obtained after the dehydration step have a low water content and hardly contain moisture. Therefore, the water-miscible organic solvent is removed by filtration or decantation, and air drying or standing drying is preferably performed at room temperature to 150 ° C., more preferably 35 ° C. to 125 ° C., and even more preferably 50 ° C. to 100 ° C. Thus, a dry gel powder is obtained. Thus, since the hydrogel particles are not exposed to severe drying conditions, the particles do not coalesce during drying.
  • the particle size of the obtained dried gel powder can be determined in consideration of the use of the dried gel powder and is not particularly limited. That is, a dry gel powder having a desired particle size can be obtained according to the pulverization apparatus (homomixer, homogenizer, etc.) used in the above pulverization step and the pulverization force thereof.
  • pulverization apparatus homomixer, homogenizer, etc.
  • the dry gel powder obtained by the above method swells without dissolving when immersed in water, and regenerates the hydrogel. Therefore, the dry gel powder obtained by the above method retains a network structure (gel state).
  • Another method for producing a water-absorbing agent containing a cross-linked naturally-derived polymer and trehalose includes a step of absorbing a trehalose aqueous solution into the cross-linked natural-derived polymer, and a cross-linked naturally-derived polymer that has absorbed the trehalose aqueous solution. It is a method comprising a step of performing wet pulverization and dehydration in a water-miscible organic solvent, and a step of drying the dehydrated crosslinked naturally-derived polymer.
  • the crosslinked naturally-derived polymer is subjected to the raw material aqueous solution preparation step without adding trehalose to the raw material aqueous solution, and then the crosslinking step, pulverization step, dehydration step, and drying step are performed.
  • the cross-linked naturally-derived polymer may be immersed in a trehalose aqueous solution, or the trehalose aqueous solution may be added to the cross-linked naturally-derived polymer by spraying or dropping.
  • the crosslinked naturally-derived polymer used in this step is preferably dried.
  • the concentration of the aqueous trehalose solution used in this step is not limited, but is preferably 0.03 to 30% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.5 to 5% by mass.
  • the trehalose aqueous solution may be warmed or kept at room temperature.
  • the present invention is also an absorbent article containing the water-absorbing agent as a constituent element of the absorber.
  • absorbent articles include disposable diapers and sanitary napkins.
  • Absorbent articles are usually composed of at least a water-permeable top sheet, an absorbent body and a water-impermeable back sheet, and the absorbent body is often composed of pulp and a water-absorbing agent.
  • the absorbent article of the present invention contains the water-absorbing agent as a constituent element of the absorber.
  • the water-absorbing agent of the present invention is excellent in water absorption speed and instantaneous water absorption magnification. According to the method of the present invention, a water-absorbing agent having excellent water absorption speed and instantaneous water absorption ratio can be obtained.
  • the trehalose molecule is taken into the network of the cross-linked structure, and water is removed during the dehydration / drying process.
  • the trehalose molecule does not escape from the network of the cross-linked structure even if it comes off. That is, during the dehydration, trehalose is replaced with water so that the network is maintained wide.
  • the obtained water-absorbing agent is presumed to be excellent in the initial response of water absorption and re-swelling.
  • the water-absorbing agent produced by the method of the present invention was subjected to liquid chromatography and elemental analysis, it was confirmed that trehalose was incorporated into the water-absorbing agent.
  • the present invention is not limited by the above theory.
  • PGA polyglutamic acid
  • the PGA concentration was 7%.
  • DETA diethylenetriamine
  • NHS N-hydroxysuccinimide
  • EDC / HCl 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride
  • the resulting cloudy hydrogel was coarsely pulverized with a spatula.
  • 20 g of methanol manufactured by Wako Pure Chemical Industries, Ltd.
  • methanol manufactured by Wako Pure Chemical Industries, Ltd.
  • a homogenizer AHG-160D, shaft generator HT1018, manufactured by ASONE Corporation
  • a series of operations was repeated, and dehydration was performed until the hydrogel particles contracted to become white particles.
  • the dehydrated particles were blown and dried at 70 ° C. for 90 minutes to obtain a water-absorbing agent of dry gel powder.
  • the water absorbing agent was prepared in the same procedure.
  • the water absorbing agent was prepared in the same procedure.
  • PGA: trehalose 90: 10 (mass ratio)
  • Example 7 An absorbent was prepared in the same procedure as in Example 6 except that trehalose was adjusted to 7.0 g.
  • Comparative Example 1 A water-absorbing agent was prepared in the same procedure as in Example 1 except that trehalose was not added.
  • Example 8 To a sodium hydroxide aqueous solution prepared by dissolving 7.62 g of NaOH in 190.7 g of ion-exchanged water, 35.0 g of carboxymethyl cellulose (Na type, F800FC, manufactured by Nippon Paper Industries Co., Ltd.) (hereinafter also referred to as “CMC-Na”). was added and dissolved by mixing for 3 minutes at 1000 rpm using a homogenizer (AHG-160D, shaft generator HT1018, manufactured by ASONE Co., Ltd.). The CMC-Na concentration was 15% by mass.
  • CMC-Na carboxymethyl cellulose
  • ethylene glycol diglycidyl ether (hereinafter also referred to as “EGDE”) (manufactured by Nagase Chemtech Co., Ltd.) was added and mixed again with a homogenizer (same as above), followed by crosslinking at 70 ° C. for 15 hours.
  • EGDE ethylene glycol diglycidyl ether
  • the obtained hydrogel was coarsely pulverized with a spatula, then twice the amount of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the coarsely pulverized hydrogel, and wet pulverization was performed using a homogenizer (same as above) at 750 rpm. .
  • Comparative Example 2 A water-absorbing agent was prepared in the same procedure as in Example 8 except that trehalose was not added.
  • the trehalose content was determined by the following two methods. [Measurement of trehalose content by liquid chromatography] (1) Standard solution ⁇ calibration curve About 50 mg of trehalose was accurately weighed and dissolved in water to make exactly 100 mL. This solution was diluted to prepare 4 standard solutions of 0.5 to 5 ⁇ g / mL. (2) Sample solution About 0.1 g of a sample was collected, and 100 mL of water was added to perform reflux extraction. The extract was filtered and the resulting filtrate was lyophilized. The total amount of the dried solid was dissolved in water to make exactly 10 mL. This solution was diluted 400 times with water and filtered through a membrane filter (pore diameter 0.45 ⁇ m) to obtain a sample solution.
  • Ion chromatograph Detector Electrochemical detector Column: CarboPac PA1 Mobile phase: 10 mmol / L sodium hydroxide solution Flow rate: 1.0 mL / min Analysis time: 15 minutes Injection volume: 15 ⁇ L
  • the absorbent article of the present invention can be suitably used as a disposable diaper, a sanitary napkin, or the like.
  • the water-absorbing agent of the present invention can be suitably used as a component of an absorbent body of an absorbent article.

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Abstract

La présente invention concerne l'amélioration de la réponse initiale d'absorption de l'eau et de nouveau gonflement, c'est-à-dire une vitesse d'absorption de l'eau et une vitesse d'absorption de l'eau instantanée, dans un agent absorbant l'eau biodégradable qui peut être utilisé comme un constituant d'un matériau absorbant pour un article absorbant tel qu'une couche jetable et une serviette hygiénique. Un article absorbant contient un agent absorbant l'eau particulaire, qui est composé d'un polymère d'origine naturelle réticulé et de tréhalose, sous forme de constituant d'un matériau absorbant, la vitesse d'absorption d'eau de l'agent absorbant l'eau étant de 25 secondes ou moins telle que mesurée par un procédé de tourbillon. L'agent absorbant l'eau peut être produit : en ajoutant un agent de réticulation à une solution de matière première aqueuse préparée par dissolution d'un polymère d'origine naturelle et de tréhalose dans l'eau ou en irradiant la solution de matière première aqueuse avec un rayon radioactif afin d'amener le polymère d'origine naturelle à être réticulé ou en amenant une solution de tréhalose aqueuse à être absorbée dans un polymère d'origine naturelle réticulé ; et en soumettant le produit résultant à un broyage en mode humide puis en déshydratant et en séchant le produit broyé.
PCT/JP2016/072850 2015-10-05 2016-08-03 Agent absorbant l'eau biodégradable et son procédé de production WO2017061166A1 (fr)

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JP2015197712 2015-10-05
JP2016123717A JP6407204B2 (ja) 2015-10-05 2016-06-22 生分解性吸水剤およびその製法
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113582770A (zh) * 2021-08-12 2021-11-02 吉林隆源农业服务有限公司 一种玉米种植用缓释长效复合肥及其制备方法

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Publication number Priority date Publication date Assignee Title
JPH1160729A (ja) * 1997-02-07 1999-03-05 Mitsui Chem Inc 吸水性樹脂及びその製造方法
JP2006511281A (ja) * 2002-12-23 2006-04-06 キンバリー クラーク ワールドワイド インコーポレイテッド 低蒸発性超吸収性物品と活用方法
WO2010122687A1 (fr) * 2009-04-20 2010-10-28 独立行政法人日本原子力研究開発機構 Procédé de fabrication d'un gel de sel de métal alcalin de carboxyméthyl cellulose
JP2010535911A (ja) * 2007-08-10 2010-11-25 サンニーノ、アレッサンドロ 高分子ヒドロゲルおよびその調製方法
JP2011019569A (ja) * 2009-07-13 2011-02-03 Uni Charm Corp 吸収体及び吸収性物品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160729A (ja) * 1997-02-07 1999-03-05 Mitsui Chem Inc 吸水性樹脂及びその製造方法
JP2006511281A (ja) * 2002-12-23 2006-04-06 キンバリー クラーク ワールドワイド インコーポレイテッド 低蒸発性超吸収性物品と活用方法
JP2010535911A (ja) * 2007-08-10 2010-11-25 サンニーノ、アレッサンドロ 高分子ヒドロゲルおよびその調製方法
WO2010122687A1 (fr) * 2009-04-20 2010-10-28 独立行政法人日本原子力研究開発機構 Procédé de fabrication d'un gel de sel de métal alcalin de carboxyméthyl cellulose
JP2011019569A (ja) * 2009-07-13 2011-02-03 Uni Charm Corp 吸収体及び吸収性物品

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113582770A (zh) * 2021-08-12 2021-11-02 吉林隆源农业服务有限公司 一种玉米种植用缓释长效复合肥及其制备方法

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