WO2020218160A1 - Water-absorbing resin particles, absorbent, and absorbent article - Google Patents

Water-absorbing resin particles, absorbent, and absorbent article Download PDF

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Publication number
WO2020218160A1
WO2020218160A1 PCT/JP2020/016747 JP2020016747W WO2020218160A1 WO 2020218160 A1 WO2020218160 A1 WO 2020218160A1 JP 2020016747 W JP2020016747 W JP 2020016747W WO 2020218160 A1 WO2020218160 A1 WO 2020218160A1
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Prior art keywords
water
resin particles
absorbent resin
jig
absorbent
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PCT/JP2020/016747
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French (fr)
Japanese (ja)
Inventor
河原 徹
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住友精化株式会社
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Priority to JP2021516057A priority Critical patent/JPWO2020218160A1/ja
Publication of WO2020218160A1 publication Critical patent/WO2020218160A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS 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
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53Absorbent 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04Acids, Metal salts or ammonium salts thereof
    • C08F20/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/12Powdering or granulating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • the present invention relates to water-absorbent resin particles, absorbers and absorbent articles.
  • Patent Document 1 discloses water-absorbent resin particles having a particle size that are suitably used for absorbent articles such as diapers.
  • Patent Document 2 describes a method of using a hydrogel-absorbing polymer having specific saline flow inducibility, pressure-lowering performance, etc. as an effective absorbent member for accommodating a body fluid such as urine. It is disclosed.
  • Absorbent articles can cause liquid pools during use. Since the liquid pool can cause discomfort when worn, an absorbent article having an improved liquid pool absorption time is desired.
  • One aspect of the present invention relates to water-absorbent resin particles having a gel layer internal strength of 0.8 to 2.0 N measured by the following procedure.
  • One end is connected to the center of a disk portion having a thickness of 5 mm having a flat surface having a diameter of 2 cm on the front and back, and the first surface which is one flat surface of the disk portion, and the cross section has a diameter of 5 mm.
  • a jig having a circular rod-shaped portion and a cylindrical container having a bottom inner diameter of 5.7 cm containing 176 g of physiological saline are prepared, and the central axis of the cylindrical container in the height direction is the disk portion.
  • the jig and the cylindrical container are arranged so as to be located at the center of the.
  • Another aspect of the present invention provides an absorber containing the above-mentioned water-absorbent resin particles.
  • Another aspect of the invention provides an absorbent article comprising the absorber described above.
  • water-absorbent resin particles capable of obtaining an absorbent article having an improved liquid pool absorption time and a method for producing the same. Further, according to another aspect of the present invention, it is possible to provide an absorber and an absorbent article using the water-absorbent resin particles. According to another aspect of the present invention, it is possible to provide application of resin particles, absorbers and absorbent articles to absorbents. According to another aspect of the present invention, it is possible to provide the application of the water-absorbent resin particles, the absorber and the absorbent article to the adjustment of the liquid pool absorption time in the absorbent article.
  • Water-soluble means that it exhibits a solubility in water of 5% by mass or more at 25 ° C.
  • the materials exemplified in the present specification may be used alone or in combination of two or more.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
  • the internal strength of the gel layer measured by the following procedure of the water-absorbent resin particles according to one embodiment is 0.8 to 2.0 N.
  • the internal strength of the gel layer is 0.8N or more, 0.9N or more, 1.0N or more, 1.1N or more, 1.2N or more, or 1.3N or more from the viewpoint of further improving the liquid pool absorption time. It may be 2.0N or less, 1.9N or less, 1.8N or less, 1.7N or less, 1.6N or less, or 1.5N or less.
  • the internal strength of the gel layer may be, for example, 1.0 to 1.8 N or 1.2 to 1.6 N. When the internal strength of the gel layer is increased, gel blocking in the absorber is less likely to occur, and the liquid pool absorption time tends to be shorter.
  • the internal strength of the gel layer the internal strength of the gel layer at room temperature (25 ⁇ 2 ° C.) can be used.
  • the water-absorbent resin particles exhibiting a gel layer internal strength of 0.8 to 2.0 N are, for example, adjusting the cross-linking density inside and / or the surface layer of the water-absorbent resin particles (for example, forming a uniform cross-linked structure). ) Etc. can be obtained.
  • the gel layer internal strength measured by the above-mentioned procedures (1) to (3) can be specifically measured by the method described in Examples described later.
  • the water-absorbent resin particles according to the present embodiment may be any water-absorbent resin particles as long as they can retain water, and the liquid to be absorbed may contain water.
  • the water-absorbent resin particles according to the present embodiment have excellent absorbency of body fluids such as urine, sweat, and blood (for example, menstrual blood).
  • the water-absorbent resin particles according to the present embodiment can be used as a constituent component of the absorber according to the present embodiment.
  • the water retention amount of the physiological saline of the water-absorbent resin particles according to the present embodiment is 10 g / g or more, 15 g / g or more, 20 g / g or more, 25 g / g or more, 30 g / g or more, 32 g / g or more, or. It may be 34 g / g or more.
  • the water-retaining amount of the physiological saline of the water-absorbent resin particles according to the present embodiment is 80 g / g or less, 70 g / g or less, 60 g / g or less, 55 g / g or less, 52 g / g or less, 50 g / g or less, 48 g / g. It may be g or less, 45 g / g or less, 42 g / g or less, or 40 g / g or less.
  • the water-retaining amount of the physiological saline of the water-absorbent resin particles according to the present embodiment may be, for example, 10 to 80 g / g, 20 to 60 g / g, or 30 to 40 g / g.
  • the water retention amount the water retention amount at room temperature (25 ⁇ 2 ° C.) can be used.
  • the amount of water retained can be measured by the method described in Examples described later.
  • the amount of water absorption of the physiological saline under a load of 4.14 kPa of the water-absorbent resin particles according to the present embodiment may be in the following range.
  • the amount of water absorption is 2 mL / g or more, 5 mL / g or more, 10 mL / g or more, 12 mL / g or more, 15 mL / g or more, 18 mL / g or more, 20 mL / g or more, 22 mL / g or more, or 25 mL / g. That may be the above.
  • the water absorption amount may be 40 mL / g or less, 35 mL / g or less, 30 mL / g or less, 28 mL / g or less, 26 mL / g or less, or 24 mL / g or less.
  • the water absorption amount may be, for example, 2 to 40 mL / g, 5 to 40 mL / g, 10 to 35 mL / g, 12 to 35 mL / g, or 15 to 30 mL / g.
  • the water absorption amount at room temperature 25 ⁇ 2 ° C.
  • the amount of water absorption can be measured by the method described in Examples described later.
  • Examples of the shape of the water-absorbent resin particles according to the present embodiment include substantially spherical, crushed, and granular shapes. Further, the water-absorbent resin particles according to the present embodiment may be in a form in which fine particles (primary particles) are aggregated (secondary particles) in addition to a form in which each is composed of a single particle.
  • the medium particle size of the water-absorbent resin particles (water-absorbent resin particles before water absorption) according to the present embodiment is preferably in the following range.
  • the medium particle size may be, for example, 100 ⁇ m or more, 140 ⁇ m or more, 200 ⁇ m or more, 250 ⁇ m or more, 300 ⁇ m or more, 330 ⁇ m or more, or 350 ⁇ m or more.
  • the medium particle size may be, for example, 600 ⁇ m or less, 550 ⁇ m or less, 500 ⁇ m or less, 450 ⁇ m or less, 400 ⁇ m or less, or 380 ⁇ m or less.
  • the medium particle size may be, for example, 250-600 ⁇ m.
  • the water-absorbent resin particles according to the present embodiment may have a desired particle size distribution at the time of being obtained by the production method described later, but the particle size distribution can be obtained by performing an operation such as particle size adjustment using classification with a sieve. May be adjusted.
  • the water-absorbent resin particles according to the present embodiment are, for example, crosslinked polymers (derived from ethylenically unsaturated monomers) obtained by polymerizing a monomer containing an ethylenically unsaturated monomer as polymer particles.
  • a crosslinked polymer having a structural unit to be used) can be included. That is, the water-absorbent resin particles according to the present embodiment can contain a polymer having a structural unit derived from the ethylenically unsaturated monomer, and the structural unit derived from the ethylenically unsaturated monomer can be contained. It can contain polymer particles containing the crosslinked polymer having.
  • a water-soluble ethylenically unsaturated monomer can be used as the ethylenically unsaturated monomer.
  • the polymerization method include a reverse phase suspension polymerization method, an aqueous solution polymerization method, a bulk polymerization method, and a precipitation polymerization method.
  • the reverse phase suspension polymerization method or the aqueous solution polymerization method is preferable from the viewpoint of ensuring good water absorption characteristics (water retention amount, etc.) of the obtained water-absorbent resin particles and easy control of the polymerization reaction.
  • a reverse phase suspension polymerization method will be described as an example as a method for polymerizing an ethylenically unsaturated monomer.
  • the ethylenically unsaturated monomer is preferably water-soluble, for example, (meth) acrylic acid and a salt thereof, 2- (meth) acrylamide-2-methylpropanesulfonic acid and a salt thereof, (meth) acrylamide, N. , N-dimethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide, polyethylene glycol mono (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylamino Examples thereof include propyl (meth) acrylate and diethylaminopropyl (meth) acrylamide.
  • the amino group may be quaternized.
  • the ethylenically unsaturated monomer may be used alone or in combination of two or more.
  • Functional groups such as the carboxyl group and amino group of the above-mentioned monomers can function as functional groups capable of cross-linking in the surface cross-linking step described later.
  • the ethylenically unsaturated monomer is selected from the group consisting of (meth) acrylic acid and its salts, acrylamide, methacrylamide, and N, N-dimethylacrylamide. It is preferable to contain at least one compound selected, and more preferably to contain at least one compound selected from the group consisting of (meth) acrylic acid and salts thereof, and acrylamide. From the viewpoint of further enhancing the water absorption characteristics (water retention amount and the like), the ethylenically unsaturated monomer further preferably contains at least one compound selected from the group consisting of (meth) acrylic acid and salts thereof. That is, the water-absorbent resin particles may contain a polymer having at least one structural unit selected from the group consisting of structural units derived from (meth) acrylic acid and structural units derived from salts of (meth) acrylic acid. preferable.
  • a monomer other than the above-mentioned ethylenically unsaturated monomer may be used.
  • Such a monomer can be used, for example, by being mixed with an aqueous solution containing the above-mentioned ethylenically unsaturated monomer.
  • the amount of the ethylenically unsaturated monomer used should be the total amount of the monomer (the total amount of the monomer for obtaining the water-absorbent resin particles. For example, the total amount of the monomer giving the structural unit of the crosslinked polymer. The same shall apply hereinafter). On the other hand, it is preferably 70 to 100 mol%.
  • the ratio of (meth) acrylic acid and a salt thereof is more preferably 70 to 100 mol% with respect to the total amount of the monomers.
  • “Ratio of (meth) acrylic acid and its salt” means the ratio of the total amount of (meth) acrylic acid and its salt.
  • the water-absorbent resin particles containing a crosslinked polymer having a structural unit derived from the ethylenically unsaturated monomer and the above-mentioned ethylenically unsaturated monomer.
  • it contains at least one compound selected from the group consisting of (meth) acrylic acid and a salt thereof, and the ratio of the (meth) acrylic acid and a salt thereof is the total amount of the monomer for obtaining the water-absorbent resin particles.
  • 70 to 100 mol% of the total amount of the monomers giving the structural unit of the crosslinked polymer can be provided.
  • the ethylenically unsaturated monomer is usually preferably used as an aqueous solution.
  • concentration of the ethylenically unsaturated monomer in the aqueous solution containing the ethylenically unsaturated monomer (hereinafter, simply referred to as “monomer aqueous solution”) is preferably 20% by mass or more and preferably 25 to 70% by mass. More preferably, 30 to 55% by mass is further preferable.
  • Examples of the water used in the aqueous solution include tap water, distilled water, ion-exchanged water and the like.
  • the monomer aqueous solution may be used by neutralizing the acid group with an alkaline neutralizer.
  • the degree of neutralization of the ethylenically unsaturated monomer by the alkaline neutralizing agent increases the osmotic pressure of the obtained water-absorbent resin particles and further enhances the water absorption characteristics (water retention amount, etc.). It is preferably 10 to 100 mol%, more preferably 50 to 90 mol%, and even more preferably 60 to 80 mol% of the acidic group in the weight.
  • alkaline neutralizing agent examples include alkali metal salts such as sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide and potassium carbonate; ammonia and the like.
  • the alkaline neutralizer may be used alone or in combination of two or more.
  • the alkaline neutralizer may be used in the form of an aqueous solution to simplify the neutralization operation. Neutralization of the acid group of the ethylenically unsaturated monomer can be performed, for example, by adding an aqueous solution of sodium hydroxide, potassium hydroxide or the like to the above-mentioned monomer aqueous solution and mixing them.
  • the monomer aqueous solution is dispersed in a hydrocarbon dispersion medium in the presence of a surfactant, and the ethylenically unsaturated monomer is polymerized using a radical polymerization initiator or the like.
  • a radical polymerization initiator a water-soluble radical polymerization initiator can be used.
  • Nonionic surfactants include sorbitan fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitol fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and polyoxyethylene.
  • Alkyl ether polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, alkylallyl formaldehyde condensed polyoxyethylene ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropyl alkyl ether, Examples thereof include polyethylene glycol fatty acid ester.
  • Anionic surfactants include fatty acid salts, alkylbenzene sulfonates, alkylmethyl taurates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene alkyl ether sulfonates, and polyoxyethylene alkyl ether phosphates. , Phosphate ester of polyoxyethylene alkyl allyl ether and the like.
  • the surfactant may be used alone or in combination of two or more.
  • the surfactant is a sorbitan fatty acid ester. It preferably contains at least one compound selected from the group consisting of polyglycerin fatty acid esters and sucrose fatty acid esters. From the viewpoint that an appropriate particle size distribution of the water-absorbent resin particles can be easily obtained, and from the viewpoint that the water-absorbing characteristics (water retention amount, etc.) of the water-absorbent resin particles and the performance of the absorbent article using the same can be easily improved, the surfactant is used. , Sucrose fatty acid ester is preferably contained, and sucrose stearic acid ester is more preferable.
  • the amount of the surfactant used is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the aqueous monomer solution from the viewpoint of obtaining a sufficient effect on the amount used and economically. .08 to 5 parts by mass is more preferable, and 0.1 to 3 parts by mass is further preferable.
  • a polymer-based dispersant may be used in combination with the above-mentioned surfactant.
  • the polymer dispersant include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene / propylene copolymer, maleic anhydride-modified EPDM (ethylene / propylene / diene / terpolymer), and maleic anhydride.
  • the polymer-based dispersant may be used alone or in combination of two or more.
  • maleic anhydride-modified polyethylene maleic anhydride-modified polypropylene
  • maleic anhydride-modified ethylene / propylene copolymer maleic anhydride / ethylene copolymer weight.
  • maleic anhydride / propylene copolymer, maleic anhydride / ethylene / propylene copolymer, polyethylene, polypropylene, ethylene / propylene copolymer, oxidized polyethylene, oxidized polypropylene, and oxidized ethylene / propylene copolymer At least one selected from the group consisting of coalescing is preferable.
  • the amount of the polymer-based dispersant used is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the monomer aqueous solution from the viewpoint of obtaining a sufficient effect on the amount used and from the viewpoint of economic efficiency. , 0.08 to 5 parts by mass is more preferable, and 0.1 to 3 parts by mass is further preferable.
  • the hydrocarbon dispersion medium may contain at least one compound selected from the group consisting of chain aliphatic hydrocarbons having 6 to 8 carbon atoms and alicyclic hydrocarbons having 6 to 8 carbon atoms.
  • a chain aliphatic hydrocarbon such as n-hexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, n-octane; cyclohexane , Methylcyclohexane, cyclopentane, methylcyclopentane, trans-1,2-dimethylcyclopentane, cis-1,3-dimethylcyclopentane, trans-1,3-dimethylcyclopentane and other alicyclic hydrocarbons; benzene, Examples include aromatic hydrocarbons such as toluene and xylene.
  • the hydrocarbon dispersion medium may be used alone
  • the hydrocarbon dispersion medium may contain at least one selected from the group consisting of n-heptane and cyclohexane from the viewpoint of being industrially easily available and having stable quality. From the same viewpoint, as the mixture of the above-mentioned hydrocarbon dispersion medium, for example, commercially available ExxonHeptane (manufactured by ExxonMobil: containing 75 to 85% of n-heptane and isomeric hydrocarbons) is used. You may.
  • the amount of the hydrocarbon dispersion medium used is preferably 30 to 1000 parts by mass and 40 to 500 parts by mass with respect to 100 parts by mass of the monomer aqueous solution from the viewpoint of appropriately removing the heat of polymerization and easily controlling the polymerization temperature. Is more preferable, and 50 to 400 parts by mass is further preferable.
  • the amount of the hydrocarbon dispersion medium used is 30 parts by mass or more, the polymerization temperature tends to be easily controlled.
  • the amount of the hydrocarbon dispersion medium used is 1000 parts by mass or less, the productivity of polymerization tends to be improved, which is economical.
  • the radical polymerization initiator is preferably water-soluble, and is, for example, a persulfate such as potassium persulfate, ammonium persulfate, sodium persulfate; methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, di-t-butyl peroxide, t.
  • a persulfate such as potassium persulfate, ammonium persulfate, sodium persulfate
  • methyl ethyl ketone peroxide methyl isobutyl ketone peroxide
  • di-t-butyl peroxide di-t-butyl peroxide
  • -Peroxides such as butyl cumylperoxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, hydrogen peroxide; 2,2'-azobis (2-amidinopropane) ) 2 hydrochloride, 2,2'-azobis [2- (N-phenylamidino) propane] 2 hydrochloride, 2,2'-azobis [2- (N-allylamidino) propane] 2 hydrochloride, 2,2 '-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ Dihydrochloride, 2,2'-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide ⁇ , 2,2'-azobis [2-methyl-N-
  • the radical polymerization initiator may be used alone or in combination of two or more.
  • examples of the radical polymerization initiator include potassium persulfate, ammonium persulfate, sodium persulfate, 2,2'-azobis (2-amidinopropane) dihydrochloride, and 2,2'-azobis [2- (2-imidazolin-2-).
  • Is preferable and at least one selected from the group consisting of potassium persulfate, ammonium persulfate, and sodium persulfate is more preferable.
  • the amount of the radical polymerization initiator used may be 0.05 to 10 mmol per 1 mol of the ethylenically unsaturated monomer.
  • the amount of the radical polymerization initiator used is 0.05 mmol or more, the polymerization reaction does not require a long time and is efficient.
  • the amount of the radical polymerization initiator used is 10 mmol or less, it is easy to suppress the occurrence of a rapid polymerization reaction.
  • the above-mentioned radical polymerization initiator can also be used as a redox polymerization initiator in combination with a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, and L-ascorbic acid.
  • a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, and L-ascorbic acid.
  • the monomer aqueous solution used for the polymerization may contain a chain transfer agent.
  • chain transfer agent include hypophosphates, thiols, thiolic acids, secondary alcohols, amines and the like.
  • the monomer aqueous solution used for polymerization may contain a thickener.
  • the thickener include hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, polyethylene glycol, polyacrylamide, polyethyleneimine, dextrin, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide and the like. If the stirring speed at the time of polymerization is the same, the higher the viscosity of the aqueous monomer solution, the larger the medium particle size of the obtained particles tends to be.
  • Cross-linking by self-cross-linking may occur during polymerization, but cross-linking may be performed by using an internal cross-linking agent.
  • an internal cross-linking agent When an internal cross-linking agent is used, it is easy to control the water absorption characteristics (water retention amount, etc.) of the water-absorbent resin particles.
  • the internal cross-linking agent is usually added to the reaction solution during the polymerization reaction.
  • the internal cross-linking agent examples include di or tri (meth) acrylic acid esters of polyols such as ethylene glycol, propylene glycol, trimethylpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin; Unsaturated polyesters obtained by reacting polyols with unsaturated acids (maleic acid, fumaric acid, etc.); bis (meth) acrylamides such as N, N'-methylenebis (meth) acrylamide; polyepoxides and (meth) Di or tri (meth) acrylic acid esters obtained by reacting with acrylic acid; di (meth) obtained by reacting polyisocyanate (tolylene diisocyanate, hexamethylene diisocyanate, etc.) with hydroxyethyl (meth) acrylate.
  • polyols such as ethylene glycol, propylene glycol, trimethylpropane, glycerin, polyoxyethylene glycol, polyoxypropy
  • Acrylic acid carbamil esters compounds having two or more polymerizable unsaturated groups such as allylated starch, allylated cellulose, diallyl phthalate, N, N', N "-triallyl isocyanurate, divinylbenzene; Poly such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, (poly) glycerin triglycidyl ether, (poly) propylene glycol polyglycidyl ether, polyglycerol polyglycidyl ether, etc.
  • Poly such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, (poly) glycerin triglycidyl ether, (poly) propylene
  • Glycidyl compound such as epichlorohydrin, epibromhydrin, ⁇ -methylepichlorohydrin; 2 reactive functional groups such as isocyanate compound (2,4-tolylene diisocyanate, hexamethylene diisocyanate, etc.) Examples thereof include compounds having more than one.
  • the internal cross-linking agent may be used alone or in combination of two or more. As the internal cross-linking agent, a polyglycidyl compound is preferable, and a diglycidyl ether compound is used.
  • the amount of the internal cross-linking agent used is 1 mol of ethylenically unsaturated monomer from the viewpoint that the water-soluble property is suppressed by appropriately cross-linking the obtained polymer and a sufficient amount of water absorption can be easily obtained. 30 mmol or less is preferable, 0.01 to 10 mmol is more preferable, 0.012 to 5 mmol is further preferable, 0.015 to 1 mmol is particularly preferable, 0.02 to 0.1 mmol is extremely preferable, and 0. 025 to 0.06 mmol is highly preferred.
  • An ethylenically unsaturated monomer, a radical polymerization initiator, a surfactant, a polymer-based dispersant, a hydrocarbon dispersion medium, etc. (if necessary, an internal cross-linking agent) are mixed and heated under stirring to obtain oil.
  • Reversed phase suspension polymerization can be performed in a medium water system.
  • a monomer aqueous solution containing an ethylenically unsaturated monomer is used as a hydrocarbon dispersion medium in the presence of a surfactant (more polymer-based dispersant if necessary). Disperse.
  • a surfactant more polymer-based dispersant if necessary. Disperse.
  • the timing of adding the surfactant, the polymer-based dispersant, etc. may be either before or after the addition of the monomer aqueous solution.
  • the surfactant is prepared after the monomer aqueous solution is dispersed in the hydrocarbon dispersion medium in which the polymer-based dispersant is dispersed. It is preferable to carry out the polymerization after further dispersing the above.
  • Reverse phase suspension polymerization can be carried out in one stage or in multiple stages of two or more stages. Reversed phase suspension polymerization is preferably carried out in 2 to 3 steps from the viewpoint of increasing productivity.
  • the reaction mixture obtained in the first step polymerization reaction after the first step reverse phase suspension polymerization is subjected to an ethylenically unsaturated single amount.
  • the body may be added and mixed, and the reverse phase suspension polymerization of the second and subsequent steps may be carried out in the same manner as in the first step.
  • the above-mentioned radical polymerization initiator and / or internal cross-linking agent is used in the reverse phase of each stage of the second and subsequent stages.
  • reverse phase suspension polymerization is carried out by adding within the range of the molar ratio of each component to the above-mentioned ethylenically unsaturated monomer.
  • An internal cross-linking agent may be used in the reverse phase suspension polymerization in each of the second and subsequent stages, if necessary.
  • an internal cross-linking agent it is added within the range of the molar ratio of each component to the above-mentioned ethylenically unsaturated monomer based on the amount of the ethylenically unsaturated monomer provided in each stage, and the suspension is reversed. It is preferable to carry out turbid polymerization.
  • the temperature of the polymerization reaction varies depending on the radical polymerization initiator used, but by advancing the polymerization rapidly and shortening the polymerization time, the efficiency is improved and the heat of polymerization is easily removed to carry out the reaction smoothly. From the viewpoint, 20 to 150 ° C. is preferable, and 40 to 120 ° C. is more preferable.
  • the reaction time is usually 0.5-4 hours.
  • the completion of the polymerization reaction can be confirmed, for example, by stopping the temperature rise in the reaction system. As a result, the polymer of the ethylenically unsaturated monomer is usually obtained in the state of a hydrogel.
  • cross-linking may be performed by adding a cross-linking agent to the obtained hydrogel polymer and heating it.
  • a cross-linking agent By performing cross-linking after the polymerization, the degree of cross-linking of the hydrogel polymer can be increased and the water absorption characteristics (water retention amount, etc.) can be further improved.
  • post-polymerization cross-linking agent examples include polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin; (poly) ethylene glycol diglycidyl ether.
  • polyglycidyl compounds such as (poly) ethylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, (poly) glycerin triglycidyl ether, (poly) propylene glycol polyglycidyl ether, and polyglycerol polyglycidyl ether are preferable. ..
  • the cross-linking agent may be used alone or in combination of two or more.
  • the amount of the cross-linking agent after polymerization is set per 1 mol of ethylenically unsaturated monomer from the viewpoint that suitable water absorption characteristics (water retention amount, etc.) can be easily obtained by appropriately cross-linking the obtained hydrogel-like polymer. , 30 mmol or less, more preferably 10 mmol or less, further preferably 0.01 to 5 mmol, particularly preferably 0.012 to 1 mmol, extremely preferably 0.015 to 0.1 mmol, 0.02 to 0.02 to 0.05 mmol is highly preferred.
  • the timing of adding the cross-linking agent after polymerization may be after the polymerization of the ethylenically unsaturated monomer used for polymerization, and in the case of multi-stage polymerization, it is preferable to add it after multi-stage polymerization.
  • the post-polymerization cross-linking agent contains water in consideration of heat generation during and after polymerization, retention due to process delay, opening of the system when the cross-linking agent is added, and fluctuation of water content due to addition of water accompanying the addition of the cross-linking agent. From the viewpoint of rate (described later), it is preferable to add in the region of [moisture content immediately after polymerization ⁇ 3% by mass].
  • the polymer particles for example, the polymer particles containing a polymer having a structural unit derived from an ethylenically unsaturated monomer
  • a drying method for example, (a) a hydrogel-like polymer is dispersed in a hydrocarbon dispersion medium, and co-boiling distillation is performed by heating from the outside, and the hydrocarbon dispersion medium is refluxed to remove water.
  • Examples thereof include (b) a method of taking out the hydrogel polymer by decantation and drying under reduced pressure, and (c) a method of filtering the hydrogel polymer with a filter and drying under reduced pressure. Above all, it is preferable to use the method (a) because of the simplicity in the manufacturing process.
  • the particle size of the water-absorbent resin particles can be adjusted by adjusting the rotation speed of the stirrer during the polymerization reaction, or by adding a flocculant into the system after the polymerization reaction or in the early stage of drying. By adding a flocculant, the particle size of the obtained water-absorbent resin particles can be increased.
  • an inorganic flocculant can be used as the flocculant.
  • the inorganic flocculant for example, powdered inorganic flocculant
  • the aggregating agent is preferably at least one selected from the group consisting of silica, aluminum oxide, talc and kaolin.
  • the flocculant is previously dispersed in a hydrocarbon dispersion medium or water of the same type as that used in the polymerization, and then the hydrogel polymer is mixed under stirring.
  • a method of mixing in a hydrocarbon dispersion medium containing the mixture is preferable.
  • the amount of the flocculant added is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.5 part by mass, based on 100 parts by mass of the ethylenically unsaturated monomer used for the polymerization. 01 to 0.2 parts by mass is more preferable.
  • the amount of the flocculant added is within the above range, water-absorbent resin particles having the desired particle size distribution can be easily obtained.
  • surface cross-linking of the surface portion (surface and vicinity of the surface) of the hydrogel polymer is performed using a surface cross-linking agent in the drying step (moisture removing step) or subsequent steps. Is preferable.
  • the surface cross-linking is preferably performed at a timing when the hydrogel polymer has a specific water content.
  • the time of surface cross-linking is preferably when the water content of the hydrogel polymer is 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass.
  • the water content (mass%) of the hydrogel polymer is calculated by the following formula.
  • Moisture content [Ww / (Ww + Ws)] x 100
  • Ww Necessary when mixing a flocculant, a surface cross-linking agent, etc. to the amount obtained by subtracting the amount of water discharged to the outside of the system by the drying step from the amount of water contained in the monomer aqueous solution before polymerization in the entire polymerization step The amount of water in the hydrogel polymer to which the amount of water used is added.
  • Ws A solid content calculated from the amount of materials such as an ethylenically unsaturated monomer, a cross-linking agent, and an initiator that constitute a hydrogel polymer.
  • Examples of the surface cross-linking agent include compounds having two or more reactive functional groups.
  • Surface cross-linking agents include polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin; (poly) ethylene glycol diglycidyl ether.
  • the surface cross-linking agent may be used alone or in combination of two or more.
  • a polyglycidyl compound is preferable, and (poly) ethylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, (poly) glycerin triglycidyl ether, (poly) propylene glycol polyglycidyl ether, and polyglycerol are used. At least one selected from the group consisting of polyglycidyl ether is more preferable.
  • the amount of the surface cross-linking agent used is preferably 0.01 to 20 mmol with respect to 1 mol of the ethylenically unsaturated monomer used for polymerization from the viewpoint that suitable water absorption characteristics (water retention amount, etc.) can be easily obtained.
  • 0.05 to 10 mmol is more preferable, 0.1 to 5 mmol is further preferable, 0.15 to 1 mmol is particularly preferable, and 0.2 to 0.5 mmol is extremely preferable.
  • polymer particles which are surface-cross-linked dried products can be obtained by distilling off water and a hydrocarbon dispersion medium by a known method, drying under heating and reduced pressure, and the like.
  • the polymerization reaction can be carried out using various stirrers having stirring blades.
  • a flat plate blade a lattice blade, a paddle blade, a propeller blade, an anchor blade, a turbine blade, a Faudler blade, a ribbon blade, a full zone blade, a max blend blade and the like can be used.
  • the flat plate blade has a shaft (stirring shaft) and a flat plate portion (stirring portion) arranged around the shaft.
  • the flat plate portion may have a slit or the like.
  • the water-absorbent resin particles according to the present embodiment include, for example, a gel stabilizer and a metal chelating agent (ethylenediaminetetraacetic acid and its salt, diethylenetriamine-5 acetic acid and its salt, for example, diethylenetriamine-5 sodium acetate and the like).
  • a gel stabilizer and a metal chelating agent ethylenediaminetetraacetic acid and its salt, diethylenetriamine-5 acetic acid and its salt, for example, diethylenetriamine-5 sodium acetate and the like.
  • Additional components such as fluidity improver (lubricant) can be further included. Additional components may be located inside the polymer particles, on the surface of the polymer particles, or both.
  • the water-absorbent resin particles may contain a plurality of inorganic particles arranged on the surface of the polymer particles.
  • the inorganic particles can be arranged on the surface of the polymer particles.
  • the inorganic particles may be silica particles such as amorphous silica.
  • the content of the inorganic particles may be in the following range based on the total mass of the polymer particles.
  • the content of the inorganic particles may be 0.05% by mass or more, 0.1% by mass or more, 0.15% by mass or more, or 0.2% by mass or more.
  • the content of the inorganic particles may be 5.0% by mass or less, 3.0% by mass or less, 1.0% by mass or less, or 0.5% by mass or less.
  • the inorganic particles here usually have a minute size as compared with the size of the polymer particles.
  • the average particle size of the inorganic particles may be 0.1 to 50 ⁇ m, 0.5 to 30 ⁇ m, or 1 to 20 ⁇ m.
  • the average particle size can be measured by the pore electric resistance method or the laser diffraction / scattering method depending on the characteristics of the particles.
  • the absorber according to this embodiment contains the water-absorbent resin particles according to this embodiment.
  • the absorber according to the present embodiment may contain a fibrous substance, for example, a mixture containing water-absorbent resin particles and the fibrous substance.
  • the structure of the absorber may be, for example, a structure in which the water-absorbent resin particles and the fibrous material are uniformly mixed, and the water-absorbent resin particles are sandwiched between the fibrous material formed in a sheet or layer. It may be a configuration or another configuration.
  • the fibrous material examples include finely pulverized wood pulp; cotton; cotton linter; rayon; cellulosic fibers such as cellulose acetate; synthetic fibers such as polyamide, polyester and polyolefin; and a mixture of these fibers.
  • the average fiber length of the fibrous material is usually 0.1 to 10 mm, and may be 0.5 to 5 mm.
  • the fibrous material may be used alone or in combination of two or more.
  • hydrophilic fibers can be used.
  • the fibers may be adhered to each other by adding an adhesive binder to the fibrous material.
  • the adhesive binder include heat-sealing synthetic fibers, hot melt adhesives, and adhesive emulsions.
  • the adhesive binder may be used alone or in combination of two or more.
  • the heat-bondable synthetic fiber examples include a total fusion type binder such as polyethylene, polypropylene, and an ethylene-propylene copolymer; a non-total fusion type binder having a side-by-side or core-sheath structure of polypropylene and polyethylene.
  • a total fusion type binder such as polyethylene, polypropylene, and an ethylene-propylene copolymer
  • non-total fusion type binder having a side-by-side or core-sheath structure of polypropylene and polyethylene.
  • hot melt adhesive examples include ethylene-vinyl acetate copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer.
  • a mixture of a base polymer such as amorphous polypropylene and a tackifier, a plasticizer, an antioxidant and the like.
  • Examples of the adhesive emulsion include polymers of at least one monomer selected from the group consisting of methyl methacrylate, styrene, acrylonitrile, 2-ethylhexyl acrylate, butyl acrylate, butadiene, ethylene, and vinyl acetate.
  • the absorber according to the present embodiment may contain an inorganic powder (for example, amorphous silica), a deodorant, an antibacterial agent, a pigment, a dye, a fragrance, an adhesive and the like.
  • an inorganic powder for example, amorphous silica
  • the absorber may contain an inorganic powder in addition to the inorganic particles in the water-absorbent resin particles.
  • the shape of the absorber according to the present embodiment may be, for example, a sheet shape.
  • the thickness of the absorber (for example, the thickness of the sheet-shaped absorber) may be 0.1 to 20 mm or 0.3 to 15 mm.
  • the content of the water-absorbent resin particles in the absorber is 2 to 100% by mass, 10 to 80% by mass, or 20 to 20 to 100% by mass with respect to the total of the water-absorbent resin particles and the fibrous material from the viewpoint of easily obtaining sufficient absorption characteristics. It may be 60% by mass.
  • the content of the water-absorbent resin particles in the absorber is preferably 100 to 1000 g, more preferably 150 to 800 g, and even more preferably 200 to 700 g per 1 m 2 of the absorber from the viewpoint of easily obtaining sufficient absorption characteristics.
  • the content of the fibrous substance in the absorber is preferably 50 to 800 g, more preferably 100 to 600 g, and even more preferably 150 to 500 g per 1 m 2 of the absorber from the viewpoint of easily obtaining sufficient absorption characteristics.
  • the absorbent article according to the present embodiment includes an absorber according to the present embodiment.
  • Other constituent members of the absorbent article according to the present embodiment include a core wrap that retains the shape of the absorber and prevents the constituent members of the absorber from falling off or flowing; on the outermost side on the side where the liquid to be absorbed enters.
  • Liquid permeable sheet to be arranged Examples thereof include a liquid permeable sheet arranged on the outermost side opposite to the side where the liquid to be absorbed enters.
  • Absorbent articles include diapers (for example, paper diapers), toilet training pants, incontinence pads, sanitary materials (sanitary napkins, tampons, etc.), sweat pads, pet sheets, simple toilet materials, animal excrement treatment materials, and the like. ..
  • FIG. 1 is a cross-sectional view showing an example of an absorbent article.
  • the absorbent article 100 shown in FIG. 1 includes an absorbent body 10, core wraps 20a and 20b, a liquid permeable sheet 30, and a liquid permeable sheet 40.
  • the liquid permeable sheet 40, the core wrap 20b, the absorbent body 10, the core wrap 20a, and the liquid permeable sheet 30 are laminated in this order.
  • the absorber 10 has a water-absorbent resin particle 10a according to the present embodiment and a fiber layer 10b containing a fibrous material.
  • the water-absorbent resin particles 10a are dispersed in the fiber layer 10b.
  • the core wrap 20a is arranged on one side of the absorber 10 (upper side of the absorber 10 in FIG. 1) in contact with the absorber 10.
  • the core wrap 20b is arranged on the other side of the absorber 10 (lower side of the absorber 10 in FIG. 1) in contact with the absorber 10.
  • the absorber 10 is arranged between the core wrap 20a and the core wrap 20b.
  • Examples of the core wraps 20a and 20b include tissues, non-woven fabrics, woven fabrics, synthetic resin films having liquid permeation holes, net-like sheets having a mesh, and the like.
  • the core wrap 20a and the core wrap 20b have, for example, a main surface having the same size as the absorber 10.
  • the liquid permeable sheet 30 is arranged on the outermost side on the side where the liquid to be absorbed enters.
  • the liquid permeable sheet 30 is arranged on the core wrap 20a in contact with the core wrap 20a.
  • Examples of the liquid permeable sheet 30 include non-woven fabrics made of synthetic resins such as polyethylene, polypropylene, polyester and polyamide, and porous sheets.
  • the liquid permeable sheet 40 is arranged on the outermost side of the absorbent article 100 on the opposite side of the liquid permeable sheet 30.
  • the liquid permeable sheet 40 is arranged under the core wrap 20b in contact with the core wrap 20b.
  • liquid impermeable sheet 40 examples include a sheet made of a synthetic resin such as polyethylene, polypropylene, and polyvinyl chloride, and a sheet made of a composite material of these synthetic resins and a non-woven fabric.
  • the liquid permeable sheet 30 and the liquid permeable sheet 40 have, for example, a main surface wider than the main surface of the absorber 10, and the outer edges of the liquid permeable sheet 30 and the liquid permeable sheet 40 are It extends around the absorber 10 and the core wraps 20a, 20b.
  • the magnitude relationship between the absorbent body 10, the core wraps 20a and 20b, the liquid permeable sheet 30, and the liquid permeable sheet 40 is not particularly limited, and is appropriately adjusted according to the use of the absorbent article and the like. Further, the method of retaining the shape of the absorber 10 by using the core wraps 20a and 20b is not particularly limited, and as shown in FIG. 1, the absorber may be wrapped by a plurality of core wraps, and the absorber is wrapped by one core wrap. It may be.
  • the absorber may be adhered to the top sheet.
  • a hot melt adhesive is applied to the top sheet at predetermined intervals in a striped shape, a spiral shape, etc. in the width direction and adhered; starch, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, etc. Examples thereof include a method of adhering using a water-soluble binder such as a water-soluble polymer.
  • a method of adhering by heat-sealing of the heat-sealing synthetic fibers may be adopted.
  • the liquid absorbing method according to the present embodiment includes a step of bringing the liquid to be absorbed into contact with the water-absorbent resin particles, the absorber or the absorbent article according to the present embodiment.
  • the present embodiment it is a method of adjusting the liquid pool absorption time in the absorbent article, and is a method of adjusting the liquid pool absorption time using the water-absorbent resin particles, the absorber or the absorbent article according to the present embodiment (for example).
  • a method for improving the absorption time of a pool can be provided.
  • the method for adjusting the liquid pool absorption time according to the present embodiment includes an adjustment step for adjusting the internal strength of the gel layer measured by the above-mentioned procedures (1) to (3) for the water-absorbent resin particles according to the present embodiment. .. In the adjusting step, the internal strength of the gel layer can be adjusted to each of the above ranges (for example, 0.8 to 2.0 N).
  • the water-absorbent resin particles according to the present embodiment include a selection step of selecting the water-absorbent resin particles based on the internal strength of the gel layer measured by the above-mentioned procedures (1) to (3).
  • a method for producing water-absorbent resin particles can be provided.
  • the internal strength of the gel layer can be adjusted to each of the above ranges (for example, 0.8 to 2.0 N).
  • the present embodiment it is possible to provide a method for producing an absorber using the water-absorbent resin particles obtained by the above-mentioned method for producing water-absorbent resin particles.
  • the method for producing an absorber according to the present embodiment includes a particle manufacturing step for obtaining water-absorbent resin particles by the above-mentioned method for producing water-absorbent resin particles.
  • the method for producing an absorber according to the present embodiment may include a step of mixing the water-absorbent resin particles and the fibrous material after the particle manufacturing step. According to the present embodiment, it is possible to provide a method for producing an absorbent article using the absorber obtained by the above-mentioned method for producing an absorber.
  • the method for producing an absorbent article according to the present embodiment includes an absorber manufacturing step for obtaining an absorber by the above-mentioned method for manufacturing an absorber.
  • the method for producing an absorbent article according to the present embodiment may include a step of obtaining an absorbent article by using the absorber and other constituent members of the absorbent article after the absorbent body manufacturing step. For example, an absorbent article is obtained by laminating the absorber and other constituent members of the absorbent article with each other.
  • Example 1 A round-bottomed cylindrical separable flask having an inner diameter of 11 cm and an internal volume of 2 L equipped with a reflux condenser, a dropping funnel, a nitrogen gas introduction pipe, and a stirrer was prepared.
  • the stirrer was equipped with a stirrer blade 200 whose outline is shown in FIG.
  • the stirring blade 200 includes a shaft 200a and a flat plate portion 200b.
  • the flat plate portion 200b is welded to the shaft 200a and has a curved tip.
  • the flat plate portion 200b is formed with four slits S extending along the axial direction of the shaft 200a.
  • the four slits S are arranged in the width direction of the flat plate portion 200b, the width of the two inner slits S is 1 cm, and the width of the two outer slits S is 0.5 cm.
  • the length of the flat plate portion 200b is about 10 cm, and the width of the flat plate portion 200b is about 6 cm.
  • a dispersant maleic anhydride-modified ethylene / propylene copolymer, manufactured by Mitsui Chemicals, Inc., high wax 1105A
  • the dispersant was dissolved in n-heptane by heating the mixture in the separable flask to 80 ° C. while stirring with a stirrer. The formed solution was cooled to 50 ° C.
  • sucrose stearic acid ester of HLB3 as a surfactant in 6.62 g of n-heptane (Mitsubishi Chemical Foods Co., Ltd., Ryo).
  • a surfactant solution prepared by heating and dissolving 0.736 g of Tosugar ester S-370) was further added, and the inside of the system was sufficiently replaced with nitrogen while stirring at a stirring speed of 350 rpm.
  • the first-stage polymerized slurry solution was obtained by immersing in a water bath at ° C. to raise the temperature and performing polymerization for 60 minutes.
  • the entire amount of the aqueous solution in the second stage is added to the polymerized slurry solution in the first stage.
  • the flask was again immersed in a water bath at 70 ° C. to raise the temperature, and the polymerization reaction was carried out for 60 minutes to obtain a hydrogel polymer.
  • 0.589 g of a 45% by mass diethylenetriamine-5 sodium acetate aqueous solution was added to the hydrogel polymer after the second stage polymerization under stirring. Then, the flask was immersed in an oil bath set at 125 ° C., and 238.6 g of water was extracted from the system while refluxing n-heptane by azeotropic distillation of n-heptane and water. Then, 4.42 g (0.507 mmol) of a 2% by mass ethylene glycol diglycidyl ether aqueous solution was added to the flask as a surface cross-linking agent, and the flask was kept at 83 ° C. for 2 hours.
  • n-heptane was evaporated at 125 ° C. and dried to obtain polymer particles (dried product).
  • the polymer particles are passed through a sieve having an opening of 850 ⁇ m, and 0.5% by mass of amorphous silica (Oriental Silicas Corporation, Toxile NP-S) with respect to the mass of the polymer particles is mixed with the polymer particles.
  • 226.4 g of water-absorbent resin particles containing amorphous silica were obtained.
  • the medium particle size of the water-absorbent resin particles was 378 ⁇ m.
  • Example 2 231.2 g of water-absorbent resin particles were obtained in the same manner as in Example 1 except that the amount of water extracted by azeotropic distillation of n-heptane and water was changed to 257.2 g.
  • the medium particle size of the water-absorbent resin particles was 359 ⁇ m.
  • Example 3 The rotation speed of the stirrer when obtaining the polymer slurry liquid of the first stage was changed to 425 rpm, the amount of water extracted by co-boiling distillation of n-heptane and water was changed to 271.0 g, and the polymer. 229.0 g of water-absorbent resin particles were obtained in the same manner as in Example 1 except that 0.2% by mass of amorphous silica was mixed with the polymer particles with respect to the mass of the particles. The medium particle size of the water-absorbent resin particles was 360 ⁇ m.
  • Example 4 After changing the rotation speed of the stirrer to obtain the first-stage polymerized slurry liquid to 425 rpm and obtaining the hydrogel polymer, the inside of the separable flask system was cooled to 31 ° C., and then the second stage. The total amount of the aqueous solution of the eye was added to the polymerized slurry solution of the first stage, the amount of water extracted by co-boiling distillation of n-heptane and water was changed to 275.8 g, and the mass of the polymer particles. 232.0 g of water-absorbent resin particles were obtained in the same manner as in Example 1 except that 0.2% by mass of amorphous silica was mixed with the polymer particles. The medium particle size of the water-absorbent resin particles was 148 ⁇ m.
  • Comparative Example 1 As the stirring blade, a stirring blade having two stages of four inclined paddle blades with a blade diameter of 5 cm was used.
  • 2,2'-azobis (2'-azobis (2) as a water-soluble radical polymerization initiator -Amidinopropane) dihydrochloride 0.092 g (0.339 mmol)
  • potassium persulfate 0.018 g (0.068 mmol)
  • ethylene glycol diglycidyl ether 0.0046 g (0.026 mmol) as an internal cross-linking agent.
  • the rotation speed of the stirrer for obtaining the first-stage polymerized slurry liquid was changed to 550 rpm, and 2,2'-azobis (2-amidinopropane) dihydrochloride as a water-soluble radical polymerization initiator.
  • the number of revolutions was changed to 1000 rpm, the amount of water extracted by co-boiling distillation of n-heptane and water was 216.7 g, and 0.2 mass% amorphous with respect to the mass of the polymer particles. 229.0 g of water-absorbent resin particles were obtained in the same manner as in Example 1 except that silica was mixed with the polymer particles. The medium particle size of the water-absorbent resin particles was 348 ⁇ m.
  • Comparative Example 3 As the stirring blade, a stirring blade having two stages of four inclined paddle blades having a blade diameter of 5 cm was used. In the preparation of the aqueous liquid in the first stage, the water-soluble radical polymerization initiator was used as the water-soluble radical polymerization initiator.
  • the water retention amount (room temperature, 25 ° C. ⁇ 2 ° C.) of the physiological saline of the water-absorbent resin particles was measured by the following procedure. First, a cotton bag (Membroad No. 60, width 100 mm x length 200 mm) weighing 2.0 g of water-absorbent resin particles was placed in a 500 mL beaker. Pour 500 g of 0.9 mass% sodium chloride aqueous solution (physiological saline) into a cotton bag containing water-absorbent resin particles at a time so that maco cannot be formed, tie the upper part of the cotton bag with a rubber ring, and let it stand for 30 minutes.
  • the measuring device Y is composed of a burette unit 61, a conduit 62, a measuring table 63, and a measuring unit 64 placed on the measuring table 63.
  • the burette portion 61 has a burette 61a extending in the vertical direction, a rubber stopper 61b arranged at the upper end of the burette 61a, a cock 61c arranged at the lower end of the burette 61a, and one end extending into the burette 61a in the vicinity of the cock 61c. It has an air introduction pipe 61d and a cock 61e arranged on the other end side of the air introduction pipe 61d.
  • the conduit 62 is attached between the burette portion 61 and the measuring table 63.
  • the inner diameter of the conduit 62 is 6 mm.
  • a hole having a diameter of 2 mm is formed in the central portion of the measuring table 63, and the conduit 62 is connected to the hole.
  • the measuring unit 64 has a cylinder 64a (made of acrylic resin (plexiglass)), a nylon mesh 64b adhered to the bottom of the cylinder 64a, and a weight 64c.
  • the inner diameter of the cylinder 64a is 20 mm.
  • the opening of the nylon mesh 64b is 75 ⁇ m (200 mesh).
  • the water-absorbent resin particles 65 to be measured are uniformly sprinkled on the nylon mesh 64b.
  • the diameter of the weight 64c is 19 mm, and the mass of the weight 64c is 119.6 g.
  • the weight 64c is placed on the water-absorbent resin particles 65, and a load of 4.14 kPa can be applied to the water-absorbent resin particles 65.
  • the weight 64c was placed and the measurement was started. Since the same volume of air as the physiological saline absorbed by the water-absorbent resin particles 65 is quickly and smoothly supplied to the inside of the burette 61a from the air introduction pipe, the water level of the physiological saline inside the burette 61a is reduced. However, the amount of physiological saline absorbed by the water-absorbent resin particles 65 is obtained.
  • the scale of the burette 61a is engraved from the top to the bottom in increments of 0 mL to 0.5 mL, and the scale Va of the burette 61a before the start of water absorption and the burette 61a 60 minutes after the start of water absorption are used as the water level of the physiological saline.
  • JIS standard sieves have a mesh size of 850 ⁇ m, a mesh size of 500 ⁇ m, a mesh size of 425 ⁇ m, a mesh size of 300 ⁇ m, a mesh size of 250 ⁇ m, a mesh size of 180 ⁇ m, a mesh size of 150 ⁇ m, and a sieve. Combined in the order of the saucer.
  • Water-absorbent resin particles were placed in the best combined sieve and classified according to JIS Z8815 (1994) using a low-tap shaker (manufactured by Iida Seisakusho Co., Ltd.). After classification, the mass of the water-absorbent resin particles remaining on each sieve was calculated as a mass percentage with respect to the total amount, and the particle size distribution was obtained. The relationship between the mesh size of the sieve and the integrated value of the mass percentage of the water-absorbent resin particles remaining on the sieve was plotted on a logarithmic probability paper by integrating the particle size distribution on the sieve in order from the one having the largest particle size. By connecting the plots on the probability paper with a straight line, the particle size corresponding to the cumulative mass percentage of 50% by mass was defined as the medium particle size.
  • the gel strength (room temperature, temperature 25 ⁇ 2 ° C.) of this measurement sample was measured using a card meter (manufactured by Ai Techno Engineering Co., Ltd .: Card Meter Mini ME-600).
  • the conditions of the card meter are as follows. ⁇ Pressure sensitive shaft: 16 mm ⁇ ⁇ Spring: for 400g ⁇ Load: 400g ⁇ Rise speed: 1 inch / 21 sec ⁇ Test mode: Viscous
  • stirrer tip (length 40 mm, diameter 8 mm, no ring) was put into a container containing physiological saline.
  • stirrer controller "Product name: Multi-stirrer dedicated controller MC-303 Manufacturer: Sinix Co., Ltd.” was used.
  • FIGS. 4 (A) and 4 (B) show a schematic view of the measuring device used for measuring the maximum gel resistance. 4 (A) and 4 (B) show measuring devices before and after swelling gel formation, respectively.
  • the jig 71 is attached to the load cell 70 of the EZtest.
  • the jig 71 includes a disk portion 71b and a rod-shaped portion 71a.
  • the disk portion 71b has a disk shape, has flat surfaces having a diameter of 2 cm on the front and back surfaces, and has a thickness of 5 mm.
  • the rod-shaped portion 71a has a circular cross section with a diameter of 5 mm, and the rod-shaped portion 71a has a length of 5.5 cm.
  • One end of the rod-shaped portion 71a is connected to the center of the first surface which is one flat surface of the disk portion 71b, and the other end of the rod-shaped portion 71a is connected to the load cell 70.
  • the jig 71 is arranged so that the central axis in the height direction of the container is located at the center of the disk portion 71b of the jig 71.
  • the jig 71 was lowered so that the second surface (lower surface), which is a flat surface opposite to the first surface of the disk portion 71b of the jig 71, was brought into contact with the liquid surface.
  • the contact between the lower surface of the disk portion 71b of the jig 71 and the liquid surface was visually confirmed.
  • the jig 71 was lowered by 32 mm from the contacted position, and that position was set as the measurement start position. By lowering by 32 mm, the distance d1 between the liquid level and the lower surface of the disc portion 71b of the jig 71 and the distance d2 between the lower surface of the disc portion 71b of the jig 71 and the stirrer tip 73 are reduced.
  • the internal strength of the gel layer was measured by operating the jig attached to the EZtest by the software Trapezium X (manufacturing company: Shimadzu Corporation) for Shimadzu autograph. The measurement was performed in an environment with a temperature of 25 ⁇ 2 ° C. and a humidity of 50 ⁇ 10%.
  • the jig embedded in the swelling gel was pushed vertically downward (direction a shown in FIG. 4B) at a speed of 10 cm / min.
  • the load applied to the jig when the jig was pushed in was measured as a test force.
  • the test force was measured at room temperature (temperature 25 ⁇ 2 ° C.).
  • the internal strength of the gel layer was the test force observed when the jig reached a position of 6 mm after being pushed in.
  • the jig was stopped when it reached the position where it was pushed in by 10 mm from the measurement start point.
  • the test force is a value automatically detected by Trapezium X.
  • FIG. 5 is a graph showing an example of the measurement test result of the internal strength of the gel layer.
  • the horizontal axis in FIG. 5 is the vertical movement distance (displacement, unit: mm) of the jig, and the vertical axis is the test force (unit: N).
  • the test force increased as the jig moved in the vertical direction from the measurement start position.
  • the test force when the displacement was 6 mm was obtained as the internal strength of the gel layer.
  • an acrylic resin measuring container composed of a rectangular inclined plate having an inclined surface S 0 inclined by 45 degrees with respect to a horizontal plane and a side plate 80 is used.
  • the length of the inclined plate in the longitudinal direction is 20 cm
  • the length of the inclined plate in the lateral direction is 11 cm
  • the short side is located on the horizontal plane.
  • the rectangular absorbent article 102 is placed on the inclined surfaces S 0, the rectangular absorbent article 102 is placed.
  • the absorbent article 102 is arranged with its lower short side located in the horizontal plane and its long side oriented in a direction inclined with respect to the horizontal plane.
  • the inclined surface S 0 was smooth, and no liquid was retained or absorbed on the plate.
  • the liquid pool absorption rate test of the absorbent article was carried out in the order of i), ii) and iii) below.
  • i) 4.2 g of water-absorbent resin particles and 3.9 g of crushed pulp were uniformly mixed by air papermaking to prepare a sheet-shaped absorber having a size of 10 cm ⁇ 15 cm.
  • the absorber was placed on tissue paper (same size as the absorber and a basis weight of 16 g / m 2 ), and tissue paper (same size as the absorber and a basis weight of 16 g / m 2 ) was placed on the absorber.
  • a load of 588 kPa was applied to the absorber sandwiched by the tissue paper for 30 seconds.
  • a polyethylene-polypropylene air-through porous liquid permeable sheet having a basis weight of 22 g / m 2 and having the same size as the absorber was placed on the sheet. Further, a polyethylene liquid permeable sheet having a size of 10 cm ⁇ 15 cm was attached to the surface opposite to the liquid permeable sheet to obtain an absorbent article for testing.
  • the absorbent article for the test is made of acrylic resin so that the surface to which the liquid permeable sheet is attached is on the upper side and the longitudinal direction of the absorbent article is along the vertical direction (longitudinal direction of the inclined plate). It was attached to a 45-degree inclined surface in the measuring container.
  • Swelling gel 80 ... Side plate, 81 ... Liquid feed pump, 100, 102 ... Absorbent article, 200 ... Stirring blade, 200a ... Shaft, 200b ... Flat plate Part, S ... slit, S 0 ... inclined surface, Y ... measuring device.

Abstract

Water-absorbing resin particles having a gel-layer internal strength, as determined by the following procedure, of 0.8-2.0 N. (1) Prepared is a jig comprising a disk part having front and back flat surfaces with a diameter of 2 cm and having a thickness of 5 mm and a rod part, an end of which has been connected to the center of a first surface of the disk part, which is one of the flat surfaces, the rod part having a circular cross-section with a diameter of 5 mm. Also prepared is a cylindrical vessel containing 176 g of physiological saline and having an inner bottom-surface diameter of 5.7 cm. The jig and the cylindrical vessel are disposed so that the height-direction axis of the cylindrical vessel passes through the center of the disk part. (2) The jig is immersed in the physiological saline so that the second surface of the disk part, which is the flat surface on the reverse side from the first surface, lies below 32 mm from the surface of the physiological saline, and 4.0 g of the water-absorbing resin particles are put into the cylindrical vessel in that state, thereby forming a swollen gel in which the jig has been partly embedded. (3) The jig is pushed down vertically at a speed of 10 cm/min, and a load imposed on the jig at the time when the jig has been pushed down by 6 mm is obtained as the gel-layer internal strength.

Description

吸水性樹脂粒子、吸収体及び吸収性物品Water-absorbent resin particles, absorbers and absorbent articles
 本発明は、吸水性樹脂粒子、吸収体及び吸収性物品に関する。 The present invention relates to water-absorbent resin particles, absorbers and absorbent articles.
 従来、水を主成分とする液体(例えば尿)を吸収するための吸収性物品には、吸水性樹脂粒子を含有する吸収体が用いられている。例えば、下記特許文献1には、おむつ等の吸収性物品に好適に用いられる粒子径を有する吸水性樹脂粒子が開示されている。また、特許文献2には、尿のような体液を収容するのに効果的な吸収性部材として、特定の食塩水流れ誘導性、圧力下性能等を有するヒドロゲル吸収性重合体を使用する方法が開示されている。 Conventionally, an absorber containing water-absorbent resin particles has been used as an absorbent article for absorbing a liquid (for example, urine) containing water as a main component. For example, Patent Document 1 below discloses water-absorbent resin particles having a particle size that are suitably used for absorbent articles such as diapers. Further, Patent Document 2 describes a method of using a hydrogel-absorbing polymer having specific saline flow inducibility, pressure-lowering performance, etc. as an effective absorbent member for accommodating a body fluid such as urine. It is disclosed.
特開平06-345819号公報Japanese Unexamined Patent Publication No. 06-345819 特表平09-510889号公報Special Table No. 09-510889
 吸収性物品は、使用時において液だまりが生じ得る。液だまりは、着用時の不快感等の原因となりうることから、液だまり吸収時間が改善された吸収性物品が望まれている。 Absorbent articles can cause liquid pools during use. Since the liquid pool can cause discomfort when worn, an absorbent article having an improved liquid pool absorption time is desired.
 本発明の一側面は、液だまり吸収時間が改善された吸収性物品を得ることが可能な吸水性樹脂粒子を提供することを目的とする。また、本発明の他の一側面は、当該吸水性樹脂粒子を用いた吸収体及び吸収性物品を提供することを目的とする。 One aspect of the present invention is to provide water-absorbent resin particles capable of obtaining an absorbent article having an improved liquid pool absorption time. Another aspect of the present invention is to provide an absorber and an absorbent article using the water-absorbent resin particles.
 本発明の一側面は、下記の手順により測定されるゲル層内部強度が0.8~2.0Nである、吸水性樹脂粒子に関する。
(1)直径2cmの平坦面を表裏に有する厚さ5mmの円板部、及び、該円板部の一方の平坦面である第1の面の中央に一端が接続され、横断面が直径5mmの円形である棒状部を備える治具と、生理食塩水176gを入れた底面内径5.7cmの円筒形容器と、を用意し、前記円筒形容器の高さ方向の中心軸が前記円板部の中央に位置するように前記治具及び前記円筒形容器を配置する。
(2)前記円板部の前記第1の面とは反対側の平坦面である第2の面が前記生理食塩水の水面から鉛直下方32mmとなる位置に前記治具を浸した状態で、前記円筒形容器内に吸水性樹脂粒子4.0gを入れて、前記治具が埋設された膨潤ゲルを形成させる。
(3)前記治具を鉛直下方に速度10cm/分で6mm押し込んだときに、前記治具に負荷される荷重をゲル層内部強度として得る。
One aspect of the present invention relates to water-absorbent resin particles having a gel layer internal strength of 0.8 to 2.0 N measured by the following procedure.
(1) One end is connected to the center of a disk portion having a thickness of 5 mm having a flat surface having a diameter of 2 cm on the front and back, and the first surface which is one flat surface of the disk portion, and the cross section has a diameter of 5 mm. A jig having a circular rod-shaped portion and a cylindrical container having a bottom inner diameter of 5.7 cm containing 176 g of physiological saline are prepared, and the central axis of the cylindrical container in the height direction is the disk portion. The jig and the cylindrical container are arranged so as to be located at the center of the.
(2) With the jig immersed in a position where the second surface of the disk portion, which is a flat surface opposite to the first surface, is 32 mm vertically downward from the water surface of the physiological saline solution. 4.0 g of water-absorbent resin particles are placed in the cylindrical container to form a swollen gel in which the jig is embedded.
(3) When the jig is pushed vertically downward by 6 mm at a speed of 10 cm / min, the load applied to the jig is obtained as the internal strength of the gel layer.
 上述の吸水性樹脂粒子によれば、液だまり吸収時間が改善された吸収性物品を得ることができる。 According to the above-mentioned water-absorbent resin particles, it is possible to obtain an absorbent article having an improved liquid pool absorption time.
 本発明の他の一側面は、上述の吸水性樹脂粒子を含有する、吸収体を提供する。本発明の他の一側面は、上述の吸収体を備える、吸収性物品を提供する。 Another aspect of the present invention provides an absorber containing the above-mentioned water-absorbent resin particles. Another aspect of the invention provides an absorbent article comprising the absorber described above.
 本発明の一側面によれば、液だまり吸収時間が改善された吸収性物品を得ることが可能な吸水性樹脂粒子及びその製造方法を提供することができる。また、本発明の他の一側面によれば、当該吸水性樹脂粒子を用いた吸収体及び吸収性物品を提供することができる。本発明の他の一側面によれば、吸液への樹脂粒子、吸収体及び吸収性物品の応用を提供することができる。本発明の他の一側面によれば、吸収性物品における液だまり吸収時間の調整への吸水性樹脂粒子、吸収体及び吸収性物品の応用を提供することができる。 According to one aspect of the present invention, it is possible to provide water-absorbent resin particles capable of obtaining an absorbent article having an improved liquid pool absorption time and a method for producing the same. Further, according to another aspect of the present invention, it is possible to provide an absorber and an absorbent article using the water-absorbent resin particles. According to another aspect of the present invention, it is possible to provide application of resin particles, absorbers and absorbent articles to absorbents. According to another aspect of the present invention, it is possible to provide the application of the water-absorbent resin particles, the absorber and the absorbent article to the adjustment of the liquid pool absorption time in the absorbent article.
吸収性物品の一実施形態を示す断面図である。It is sectional drawing which shows one Embodiment of an absorbent article. 実施例で使用した撹拌翼の概形を示す平面図である。It is a top view which shows the outline shape of the stirring blade used in an Example. 吸水性樹脂粒子の荷重下の吸水量の測定装置を示す概略図である。It is the schematic which shows the measuring apparatus of the water absorption amount under the load of the water-absorbing resin particle. ゲル層内部強度の測定方法の一例を示す模式図である。It is a schematic diagram which shows an example of the measuring method of the internal strength of a gel layer. ゲル層内部強度の測定結果の一例を示すグラフである。It is a graph which shows an example of the measurement result of the internal strength of a gel layer. 液だまり吸収時間の測定方法の一例を示す模式図である。It is a schematic diagram which shows an example of the measuring method of the liquid pool absorption time.
 以下、本発明のいくつかの実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
 本明細書において、「アクリル」及び「メタクリル」を合わせて「(メタ)アクリル」と表記する。「アクリレート」及び「メタクリレート」も同様に「(メタ)アクリレート」と表記する。「(ポリ)」とは、「ポリ」の接頭語がある場合及びない場合の双方を意味するものとする。本明細書に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値と任意に組み合わせることができる。本明細書に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。「A又はB」とは、A及びBのどちらか一方を含んでいればよく、両方とも含んでいてもよい。「水溶性」とは、25℃において水に5質量%以上の溶解性を示すことをいう。本明細書に例示する材料は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。 In this specification, "acrylic" and "methacryl" are collectively referred to as "(meth) acrylic". Similarly, "acrylate" and "methacrylate" are also referred to as "(meth) acrylate". "(Poly)" shall mean both with and without the "poly" prefix. In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value of the numerical range of one step can be arbitrarily combined with the upper limit value or the lower limit value of the numerical range of another step. In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. “A or B” may include either A or B, or both. "Water-soluble" means that it exhibits a solubility in water of 5% by mass or more at 25 ° C. The materials exemplified in the present specification may be used alone or in combination of two or more. The content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
 一実施形態に係る吸水性樹脂粒子の下記の手順により測定されるゲル層内部強度は、0.8~2.0Nである。
(1)直径2cmの平坦面を表裏に有する厚さ5mmの円板部、及び、円板部の一方の平坦面である第1の面の中央に一端が接続され、横断面が直径5mmの円形である棒状部を備える治具と、生理食塩水176gを入れた底面内径5.7cmの円筒形容器と、を用意し、円筒形容器の高さ方向の中心軸が円板部の中央に位置するように治具及び円筒形容器を配置する。
(2)円板部の第1の面とは反対側の平坦面である第2の面が生理食塩水の水面から鉛直下方32mmとなる位置に前記治具を浸した状態で、円筒形容器内に吸水性樹脂粒子4.0gを入れて、治具が埋設された膨潤ゲルを形成させる。
(3)治具を鉛直下方に速度10cm/分で6mm押し込んだときに、治具に負荷される荷重をゲル層内部強度として得る。
The internal strength of the gel layer measured by the following procedure of the water-absorbent resin particles according to one embodiment is 0.8 to 2.0 N.
(1) A disk portion having a thickness of 5 mm having a flat surface having a diameter of 2 cm on the front and back, and one end connected to the center of the first surface which is one flat surface of the disk portion, and having a cross section having a diameter of 5 mm. Prepare a jig having a circular rod-shaped portion and a cylindrical container having a bottom inner diameter of 5.7 cm containing 176 g of physiological saline, and the central axis of the cylindrical container in the height direction is at the center of the disk portion. Arrange the jig and the cylindrical container so that they are located.
(2) A cylindrical container in a state where the jig is immersed in a position where the second surface, which is a flat surface opposite to the first surface of the disk portion, is 32 mm vertically below the water surface of the physiological saline solution. 4.0 g of water-absorbent resin particles are put therein to form a swollen gel in which a jig is embedded.
(3) When the jig is pushed vertically downward by 6 mm at a speed of 10 cm / min, the load applied to the jig is obtained as the internal strength of the gel layer.
 ゲル層内部強度が上述した範囲内にある吸水性樹脂粒子によれば、液だまり吸収時間が改善された吸収性物品を得ることができる。 According to the water-absorbent resin particles in which the internal strength of the gel layer is within the above-mentioned range, it is possible to obtain an absorbent article having an improved liquid pool absorption time.
 ゲル層内部強度は、液だまり吸収時間がより一層改善される観点から、0.8N以上、0.9N以上、1.0N以上、1.1N以上、1.2N以上、又は、1.3N以上であってよく、2.0N以下、1.9N以下、1.8N以下、1.7N以下、1.6N以下、又は、1.5N以下であってよい。ゲル層内部強度は、例えば、1.0~1.8N、又は、1.2~1.6Nであってよい。ゲル層内部強度が大きくなると、吸収体におけるゲルブロッキングが起きにくくなり、液だまり吸収時間がより短くなる傾向がある。ゲル層内部強度としては、室温(25±2℃)におけるゲル層内部強度を用いることができる。 The internal strength of the gel layer is 0.8N or more, 0.9N or more, 1.0N or more, 1.1N or more, 1.2N or more, or 1.3N or more from the viewpoint of further improving the liquid pool absorption time. It may be 2.0N or less, 1.9N or less, 1.8N or less, 1.7N or less, 1.6N or less, or 1.5N or less. The internal strength of the gel layer may be, for example, 1.0 to 1.8 N or 1.2 to 1.6 N. When the internal strength of the gel layer is increased, gel blocking in the absorber is less likely to occur, and the liquid pool absorption time tends to be shorter. As the internal strength of the gel layer, the internal strength of the gel layer at room temperature (25 ± 2 ° C.) can be used.
 0.8~2.0Nのゲル層内部強度を示す吸水性樹脂粒子は、例えば、吸水性樹脂粒子の内部及び/又は表層における架橋密度を調整すること(例えば、均一な架橋構造を形成させること)等により、得ることができる。 The water-absorbent resin particles exhibiting a gel layer internal strength of 0.8 to 2.0 N are, for example, adjusting the cross-linking density inside and / or the surface layer of the water-absorbent resin particles (for example, forming a uniform cross-linked structure). ) Etc. can be obtained.
 上述した(1)~(3)の手順により測定されるゲル層内部強度は、具体的には後述する実施例に記載の方法によって測定することができる。 The gel layer internal strength measured by the above-mentioned procedures (1) to (3) can be specifically measured by the method described in Examples described later.
 本実施形態に係る吸水性樹脂粒子は、水を保水可能であればよく、吸液対象の液は水を含むことができる。本実施形態に係る吸水性樹脂粒子は、尿、汗、血液(例えば経血)等の体液の吸収性に優れている。本実施形態に係る吸水性樹脂粒子は、本実施形態に係る吸収体の構成成分として用いることができる。 The water-absorbent resin particles according to the present embodiment may be any water-absorbent resin particles as long as they can retain water, and the liquid to be absorbed may contain water. The water-absorbent resin particles according to the present embodiment have excellent absorbency of body fluids such as urine, sweat, and blood (for example, menstrual blood). The water-absorbent resin particles according to the present embodiment can be used as a constituent component of the absorber according to the present embodiment.
 本実施形態に係る吸水性樹脂粒子の生理食塩水の保水量は、10g/g以上、15g/g以上、20g/g以上、25g/g以上、30g/g以上、32g/g以上、又は、34g/g以上であってよい。本実施形態に係る吸水性樹脂粒子の生理食塩水の保水量は、80g/g以下、70g/g以下、60g/g以下、55g/g以下、52g/g以下、50g/g以下、48g/g以下、45g/g以下、42g/g以下、又は、40g/g以下であってよい。本実施形態に係る吸水性樹脂粒子の生理食塩水の保水量は、例えば、10~80g/g、20~60g/g、又は、30~40g/gであってよい。保水量としては、室温(25±2℃)における保水量を用いることができる。保水量は、後述する実施例に記載の方法によって測定できる。 The water retention amount of the physiological saline of the water-absorbent resin particles according to the present embodiment is 10 g / g or more, 15 g / g or more, 20 g / g or more, 25 g / g or more, 30 g / g or more, 32 g / g or more, or. It may be 34 g / g or more. The water-retaining amount of the physiological saline of the water-absorbent resin particles according to the present embodiment is 80 g / g or less, 70 g / g or less, 60 g / g or less, 55 g / g or less, 52 g / g or less, 50 g / g or less, 48 g / g. It may be g or less, 45 g / g or less, 42 g / g or less, or 40 g / g or less. The water-retaining amount of the physiological saline of the water-absorbent resin particles according to the present embodiment may be, for example, 10 to 80 g / g, 20 to 60 g / g, or 30 to 40 g / g. As the water retention amount, the water retention amount at room temperature (25 ± 2 ° C.) can be used. The amount of water retained can be measured by the method described in Examples described later.
 本実施形態に係る吸水性樹脂粒子の荷重4.14kPa下における生理食塩水の吸水量は、下記の範囲であってよい。前記吸水量は、2mL/g以上、5mL/g以上、10mL/g以上、12mL/g以上、15mL/g以上、18mL/g以上、20mL/g以上、22mL/g以上、又は、25mL/g以上であってよい。前記吸水量は、40mL/g以下、35mL/g以下、30mL/g以下、28mL/g以下、26mL/g以下、又は、24mL/g以下であってよい。前記吸水量は、例えば、2~40mL/g、5~40mL/g、10~35mL/g、12~35mL/g、又は、15~30mL/gであってよい。吸水量としては、室温(25±2℃)における吸水量を用いることができる。吸水量は、後述する実施例に記載の方法によって測定できる。 The amount of water absorption of the physiological saline under a load of 4.14 kPa of the water-absorbent resin particles according to the present embodiment may be in the following range. The amount of water absorption is 2 mL / g or more, 5 mL / g or more, 10 mL / g or more, 12 mL / g or more, 15 mL / g or more, 18 mL / g or more, 20 mL / g or more, 22 mL / g or more, or 25 mL / g. That may be the above. The water absorption amount may be 40 mL / g or less, 35 mL / g or less, 30 mL / g or less, 28 mL / g or less, 26 mL / g or less, or 24 mL / g or less. The water absorption amount may be, for example, 2 to 40 mL / g, 5 to 40 mL / g, 10 to 35 mL / g, 12 to 35 mL / g, or 15 to 30 mL / g. As the water absorption amount, the water absorption amount at room temperature (25 ± 2 ° C.) can be used. The amount of water absorption can be measured by the method described in Examples described later.
 本実施形態に係る吸水性樹脂粒子の形状としては、略球状、破砕状、顆粒状等が挙げられる。また、本実施形態に係る吸水性樹脂粒子は、各々が単一の粒子からなる形態のほかに、微細な粒子(一次粒子)が凝集した形態(二次粒子)であってもよい。本実施形態に係る吸水性樹脂粒子(吸水前の吸水性樹脂粒子)の中位粒子径は、下記の範囲が好ましい。中位粒子径は、例えば100μm以上、140μm以上、200μm以上、250μm以上、300μm以上、330μm以上、又は、350μm以上であってよい。中位粒子径は、例えば、600μm以下、550μm以下、500μm以下、450μm以下、400μm以下、又は、380μm以下であってよい。中位粒子径は、例えば、250~600μmであってよい。本実施形態に係る吸水性樹脂粒子は、後述する製造方法により得られた時点で所望の粒度分布を有していてよいが、篩による分級を用いた粒度調整等の操作を行うことにより粒度分布を調整してもよい。 Examples of the shape of the water-absorbent resin particles according to the present embodiment include substantially spherical, crushed, and granular shapes. Further, the water-absorbent resin particles according to the present embodiment may be in a form in which fine particles (primary particles) are aggregated (secondary particles) in addition to a form in which each is composed of a single particle. The medium particle size of the water-absorbent resin particles (water-absorbent resin particles before water absorption) according to the present embodiment is preferably in the following range. The medium particle size may be, for example, 100 μm or more, 140 μm or more, 200 μm or more, 250 μm or more, 300 μm or more, 330 μm or more, or 350 μm or more. The medium particle size may be, for example, 600 μm or less, 550 μm or less, 500 μm or less, 450 μm or less, 400 μm or less, or 380 μm or less. The medium particle size may be, for example, 250-600 μm. The water-absorbent resin particles according to the present embodiment may have a desired particle size distribution at the time of being obtained by the production method described later, but the particle size distribution can be obtained by performing an operation such as particle size adjustment using classification with a sieve. May be adjusted.
 本実施形態に係る吸水性樹脂粒子は、例えば、重合体粒子として、エチレン性不飽和単量体を含有する単量体を重合させて得られる架橋重合体(エチレン性不飽和単量体に由来する構造単位を有する架橋重合体)を含むことができる。すなわち、本実施形態に係る吸水性樹脂粒子は、エチレン性不飽和単量体に由来する構造単位を有する重合体を含むことが可能であり、エチレン性不飽和単量体に由来する構造単位を有する架橋重合体を含む重合体粒子を含むことができる。エチレン性不飽和単量体としては、水溶性エチレン性不飽和単量体を用いることができる。重合方法としては、逆相懸濁重合法、水溶液重合法、バルク重合法、沈殿重合法等が挙げられる。これらの中では、得られる吸水性樹脂粒子の良好な吸水特性(保水量等)の確保、及び、重合反応の制御が容易である観点から、逆相懸濁重合法又は水溶液重合法が好ましい。以下においては、エチレン性不飽和単量体を重合させる方法として、逆相懸濁重合法を例にとって説明する。 The water-absorbent resin particles according to the present embodiment are, for example, crosslinked polymers (derived from ethylenically unsaturated monomers) obtained by polymerizing a monomer containing an ethylenically unsaturated monomer as polymer particles. A crosslinked polymer having a structural unit to be used) can be included. That is, the water-absorbent resin particles according to the present embodiment can contain a polymer having a structural unit derived from the ethylenically unsaturated monomer, and the structural unit derived from the ethylenically unsaturated monomer can be contained. It can contain polymer particles containing the crosslinked polymer having. As the ethylenically unsaturated monomer, a water-soluble ethylenically unsaturated monomer can be used. Examples of the polymerization method include a reverse phase suspension polymerization method, an aqueous solution polymerization method, a bulk polymerization method, and a precipitation polymerization method. Among these, the reverse phase suspension polymerization method or the aqueous solution polymerization method is preferable from the viewpoint of ensuring good water absorption characteristics (water retention amount, etc.) of the obtained water-absorbent resin particles and easy control of the polymerization reaction. In the following, a reverse phase suspension polymerization method will be described as an example as a method for polymerizing an ethylenically unsaturated monomer.
 エチレン性不飽和単量体は水溶性であることが好ましく、例えば、(メタ)アクリル酸及びその塩、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸及びその塩、(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、2-ヒドロキシエチル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、ポリエチレングリコールモノ(メタ)アクリレート、N,N-ジエチルアミノエチル(メタ)アクリレート、N,N-ジエチルアミノプロピル(メタ)アクリレート、ジエチルアミノプロピル(メタ)アクリルアミド等が挙げられる。エチレン性不飽和単量体がアミノ基を有する場合、当該アミノ基は4級化されていてもよい。エチレン性不飽和単量体は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。上述の単量体のカルボキシル基、アミノ基等の官能基は、後述する表面架橋工程において架橋が可能な官能基として機能し得る。 The ethylenically unsaturated monomer is preferably water-soluble, for example, (meth) acrylic acid and a salt thereof, 2- (meth) acrylamide-2-methylpropanesulfonic acid and a salt thereof, (meth) acrylamide, N. , N-dimethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide, polyethylene glycol mono (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylamino Examples thereof include propyl (meth) acrylate and diethylaminopropyl (meth) acrylamide. When the ethylenically unsaturated monomer has an amino group, the amino group may be quaternized. The ethylenically unsaturated monomer may be used alone or in combination of two or more. Functional groups such as the carboxyl group and amino group of the above-mentioned monomers can function as functional groups capable of cross-linking in the surface cross-linking step described later.
 これらの中でも、工業的に入手が容易である観点から、エチレン性不飽和単量体は、(メタ)アクリル酸及びその塩、アクリルアミド、メタクリルアミド、並びに、N,N-ジメチルアクリルアミドからなる群より選ばれる少なくとも一種の化合物を含むことが好ましく、(メタ)アクリル酸及びその塩、並びに、アクリルアミドからなる群より選ばれる少なくとも一種の化合物を含むことがより好ましい。吸水特性(保水量等)を更に高める観点から、エチレン性不飽和単量体は、(メタ)アクリル酸及びその塩からなる群より選ばれる少なくとも一種の化合物を含むことが更に好ましい。すなわち、吸水性樹脂粒子は、(メタ)アクリル酸に由来する構造単位及び(メタ)アクリル酸の塩に由来する構造単位からなる群より選ばれる少なくとも一種の構造単位を有する重合体を含むことが好ましい。 Among these, from the viewpoint of industrial availability, the ethylenically unsaturated monomer is selected from the group consisting of (meth) acrylic acid and its salts, acrylamide, methacrylamide, and N, N-dimethylacrylamide. It is preferable to contain at least one compound selected, and more preferably to contain at least one compound selected from the group consisting of (meth) acrylic acid and salts thereof, and acrylamide. From the viewpoint of further enhancing the water absorption characteristics (water retention amount and the like), the ethylenically unsaturated monomer further preferably contains at least one compound selected from the group consisting of (meth) acrylic acid and salts thereof. That is, the water-absorbent resin particles may contain a polymer having at least one structural unit selected from the group consisting of structural units derived from (meth) acrylic acid and structural units derived from salts of (meth) acrylic acid. preferable.
 吸水性樹脂粒子を得るための単量体としては、上述のエチレン性不飽和単量体以外の単量体が使用されてもよい。このような単量体は、例えば、上述のエチレン性不飽和単量体を含む水溶液に混合して用いることができる。エチレン性不飽和単量体の使用量は、単量体全量(吸水性樹脂粒子を得るための単量体全量。例えば、架橋重合体の構造単位を与える単量体の全量。以下同様)に対して70~100モル%であることが好ましい。中でも、(メタ)アクリル酸及びその塩の割合が単量体全量に対して70~100モル%であることがより好ましい。「(メタ)アクリル酸及びその塩の割合」は、(メタ)アクリル酸及びその塩の合計量の割合を意味する。 As the monomer for obtaining the water-absorbent resin particles, a monomer other than the above-mentioned ethylenically unsaturated monomer may be used. Such a monomer can be used, for example, by being mixed with an aqueous solution containing the above-mentioned ethylenically unsaturated monomer. The amount of the ethylenically unsaturated monomer used should be the total amount of the monomer (the total amount of the monomer for obtaining the water-absorbent resin particles. For example, the total amount of the monomer giving the structural unit of the crosslinked polymer. The same shall apply hereinafter). On the other hand, it is preferably 70 to 100 mol%. Above all, the ratio of (meth) acrylic acid and a salt thereof is more preferably 70 to 100 mol% with respect to the total amount of the monomers. "Ratio of (meth) acrylic acid and its salt" means the ratio of the total amount of (meth) acrylic acid and its salt.
 本実施形態によれば、吸水性樹脂粒子の一例として、エチレン性不飽和単量体に由来する構造単位を有する架橋重合体を含む吸水性樹脂粒子であって、前記エチレン性不飽和単量体が、(メタ)アクリル酸及びその塩からなる群より選ばれる少なくとも1種の化合物を含み、前記(メタ)アクリル酸及びその塩の割合が、前記吸水性樹脂粒子を得るための単量体全量(例えば、前記架橋重合体の構造単位を与える単量体の全量)に対して70~100モル%である、吸水性樹脂粒子を提供することができる。 According to the present embodiment, as an example of the water-absorbent resin particles, the water-absorbent resin particles containing a crosslinked polymer having a structural unit derived from the ethylenically unsaturated monomer and the above-mentioned ethylenically unsaturated monomer. However, it contains at least one compound selected from the group consisting of (meth) acrylic acid and a salt thereof, and the ratio of the (meth) acrylic acid and a salt thereof is the total amount of the monomer for obtaining the water-absorbent resin particles. (For example, 70 to 100 mol% of the total amount of the monomers giving the structural unit of the crosslinked polymer) can be provided.
 エチレン性不飽和単量体は、通常、水溶液として用いることが好適である。エチレン性不飽和単量体を含む水溶液(以下、単に「単量体水溶液」という)におけるエチレン性不飽和単量体の濃度は、20質量%以上飽和濃度以下が好ましく、25~70質量%がより好ましく、30~55質量%が更に好ましい。水溶液において使用される水としては、水道水、蒸留水、イオン交換水等が挙げられる。 The ethylenically unsaturated monomer is usually preferably used as an aqueous solution. The concentration of the ethylenically unsaturated monomer in the aqueous solution containing the ethylenically unsaturated monomer (hereinafter, simply referred to as “monomer aqueous solution”) is preferably 20% by mass or more and preferably 25 to 70% by mass. More preferably, 30 to 55% by mass is further preferable. Examples of the water used in the aqueous solution include tap water, distilled water, ion-exchanged water and the like.
 単量体水溶液は、エチレン性不飽和単量体が酸基を有する場合、その酸基をアルカリ性中和剤によって中和して用いてもよい。エチレン性不飽和単量体における、アルカリ性中和剤による中和度は、得られる吸水性樹脂粒子の浸透圧を高くし、吸水特性(保水量等)を更に高める観点から、エチレン性不飽和単量体中の酸性基の10~100モル%であることが好ましく、50~90モル%であることがより好ましく、60~80モル%であることが更に好ましい。アルカリ性中和剤としては、水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、水酸化カリウム、炭酸カリウム等のアルカリ金属塩;アンモニアなどが挙げられる。アルカリ性中和剤は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。アルカリ性中和剤は、中和操作を簡便にするために水溶液の状態で用いられてもよい。エチレン性不飽和単量体の酸基の中和は、例えば、水酸化ナトリウム、水酸化カリウム等の水溶液を上述の単量体水溶液に滴下して混合することにより行うことができる。 When the ethylenically unsaturated monomer has an acid group, the monomer aqueous solution may be used by neutralizing the acid group with an alkaline neutralizer. The degree of neutralization of the ethylenically unsaturated monomer by the alkaline neutralizing agent increases the osmotic pressure of the obtained water-absorbent resin particles and further enhances the water absorption characteristics (water retention amount, etc.). It is preferably 10 to 100 mol%, more preferably 50 to 90 mol%, and even more preferably 60 to 80 mol% of the acidic group in the weight. Examples of the alkaline neutralizing agent include alkali metal salts such as sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide and potassium carbonate; ammonia and the like. The alkaline neutralizer may be used alone or in combination of two or more. The alkaline neutralizer may be used in the form of an aqueous solution to simplify the neutralization operation. Neutralization of the acid group of the ethylenically unsaturated monomer can be performed, for example, by adding an aqueous solution of sodium hydroxide, potassium hydroxide or the like to the above-mentioned monomer aqueous solution and mixing them.
 逆相懸濁重合法においては、界面活性剤の存在下、炭化水素分散媒中で単量体水溶液を分散し、ラジカル重合開始剤等を用いてエチレン性不飽和単量体の重合を行うことができる。ラジカル重合開始剤としては、水溶性ラジカル重合開始剤を用いることができる。 In the reverse phase suspension polymerization method, the monomer aqueous solution is dispersed in a hydrocarbon dispersion medium in the presence of a surfactant, and the ethylenically unsaturated monomer is polymerized using a radical polymerization initiator or the like. Can be done. As the radical polymerization initiator, a water-soluble radical polymerization initiator can be used.
 界面活性剤としては、ノニオン系界面活性剤、アニオン系界面活性剤等が挙げられる。ノニオン系界面活性剤としては、ソルビタン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ショ糖脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ソルビトール脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油、アルキルアリルホルムアルデヒド縮合ポリオキシエチレンエーテル、ポリオキシエチレンポリオキシプロピレンブロックコポリマー、ポリオキシエチレンポリオキシプロピルアルキルエーテル、ポリエチレングリコール脂肪酸エステル等が挙げられる。アニオン系界面活性剤としては、脂肪酸塩、アルキルベンゼンスルホン酸塩、アルキルメチルタウリン酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩、ポリオキシエチレンアルキルエーテルスルホン酸塩、ポリオキシエチレンアルキルエーテルのリン酸エステル、ポリオキシエチレンアルキルアリルエーテルのリン酸エステル等が挙げられる。界面活性剤は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。 Examples of the surfactant include nonionic surfactants and anionic surfactants. Nonionic surfactants include sorbitan fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitol fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and polyoxyethylene. Alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, alkylallyl formaldehyde condensed polyoxyethylene ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropyl alkyl ether, Examples thereof include polyethylene glycol fatty acid ester. Anionic surfactants include fatty acid salts, alkylbenzene sulfonates, alkylmethyl taurates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene alkyl ether sulfonates, and polyoxyethylene alkyl ether phosphates. , Phosphate ester of polyoxyethylene alkyl allyl ether and the like. The surfactant may be used alone or in combination of two or more.
 W/O型逆相懸濁の状態が良好であり、好適な粒子径を有する吸水性樹脂粒子が得られやすく、工業的に入手が容易である観点から、界面活性剤は、ソルビタン脂肪酸エステル、ポリグリセリン脂肪酸エステル及びショ糖脂肪酸エステルからなる群より選ばれる少なくとも一種の化合物を含むことが好ましい。吸水性樹脂粒子の適切な粒度分布が得られやすい観点、並びに、吸水性樹脂粒子の吸水特性(保水量等)及びそれを用いた吸収性物品の性能が向上しやすい観点から、界面活性剤は、ショ糖脂肪酸エステルを含むことが好ましく、ショ糖ステアリン酸エステルがより好ましい。 From the viewpoint that the W / O type reverse phase suspension is in a good state, water-absorbent resin particles having a suitable particle size can be easily obtained, and industrially available, the surfactant is a sorbitan fatty acid ester. It preferably contains at least one compound selected from the group consisting of polyglycerin fatty acid esters and sucrose fatty acid esters. From the viewpoint that an appropriate particle size distribution of the water-absorbent resin particles can be easily obtained, and from the viewpoint that the water-absorbing characteristics (water retention amount, etc.) of the water-absorbent resin particles and the performance of the absorbent article using the same can be easily improved, the surfactant is used. , Sucrose fatty acid ester is preferably contained, and sucrose stearic acid ester is more preferable.
 界面活性剤の使用量は、使用量に対する効果が充分に得られる観点、及び、経済的である観点から、単量体水溶液100質量部に対して、0.05~10質量部が好ましく、0.08~5質量部がより好ましく、0.1~3質量部が更に好ましい。 The amount of the surfactant used is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the aqueous monomer solution from the viewpoint of obtaining a sufficient effect on the amount used and economically. .08 to 5 parts by mass is more preferable, and 0.1 to 3 parts by mass is further preferable.
 逆相懸濁重合では、上述の界面活性剤と共に高分子系分散剤を併せて用いてもよい。高分子系分散剤としては、無水マレイン酸変性ポリエチレン、無水マレイン酸変性ポリプロピレン、無水マレイン酸変性エチレン・プロピレン共重合体、無水マレイン酸変性EPDM(エチレン・プロピレン・ジエン・ターポリマー)、無水マレイン酸変性ポリブタジエン、無水マレイン酸・エチレン共重合体、無水マレイン酸・プロピレン共重合体、無水マレイン酸・エチレン・プロピレン共重合体、無水マレイン酸・ブタジエン共重合体、ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体、酸化型ポリエチレン、酸化型ポリプロピレン、酸化型エチレン・プロピレン共重合体、エチレン・アクリル酸共重合体、エチルセルロース、エチルヒドロキシエチルセルロース等が挙げられる。高分子系分散剤は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。高分子系分散剤としては、単量体の分散安定性に優れる観点から、無水マレイン酸変性ポリエチレン、無水マレイン酸変性ポリプロピレン、無水マレイン酸変性エチレン・プロピレン共重合体、無水マレイン酸・エチレン共重合体、無水マレイン酸・プロピレン共重合体、無水マレイン酸・エチレン・プロピレン共重合体、ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体、酸化型ポリエチレン、酸化型ポリプロピレン、及び、酸化型エチレン・プロピレン共重合体からなる群より選ばれる少なくとも一種が好ましい。 In reverse phase suspension polymerization, a polymer-based dispersant may be used in combination with the above-mentioned surfactant. Examples of the polymer dispersant include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene / propylene copolymer, maleic anhydride-modified EPDM (ethylene / propylene / diene / terpolymer), and maleic anhydride. Modified polybutadiene, maleic anhydride / ethylene copolymer, maleic anhydride / propylene copolymer, maleic anhydride / ethylene / propylene copolymer, maleic anhydride / butadiene copolymer, polyethylene, polypropylene, ethylene / propylene copolymer Examples thereof include coalescence, oxidized polyethylene, oxidized polypropylene, oxidized ethylene / propylene copolymer, ethylene / acrylic acid copolymer, ethyl cellulose, ethyl hydroxyethyl cellulose and the like. The polymer-based dispersant may be used alone or in combination of two or more. As the polymer-based dispersant, from the viewpoint of excellent dispersion stability of the monomer, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene / propylene copolymer, and maleic anhydride / ethylene copolymer weight. Combined, maleic anhydride / propylene copolymer, maleic anhydride / ethylene / propylene copolymer, polyethylene, polypropylene, ethylene / propylene copolymer, oxidized polyethylene, oxidized polypropylene, and oxidized ethylene / propylene copolymer At least one selected from the group consisting of coalescing is preferable.
 高分子系分散剤の使用量は、使用量に対する効果が充分に得られる観点、及び、経済的である観点から、単量体水溶液100質量部に対して、0.05~10質量部が好ましく、0.08~5質量部がより好ましく、0.1~3質量部が更に好ましい。 The amount of the polymer-based dispersant used is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the monomer aqueous solution from the viewpoint of obtaining a sufficient effect on the amount used and from the viewpoint of economic efficiency. , 0.08 to 5 parts by mass is more preferable, and 0.1 to 3 parts by mass is further preferable.
 炭化水素分散媒は、炭素数6~8の鎖状脂肪族炭化水素、及び、炭素数6~8の脂環式炭化水素からなる群より選ばれる少なくとも一種の化合物を含んでいてもよい。炭化水素分散媒としては、n-ヘキサン、n-ヘプタン、2-メチルヘキサン、3-メチルヘキサン、2,3-ジメチルペンタン、3-エチルペンタン、n-オクタン等の鎖状脂肪族炭化水素;シクロヘキサン、メチルシクロヘキサン、シクロペンタン、メチルシクロペンタン、trans-1,2-ジメチルシクロペンタン、cis-1,3-ジメチルシクロペンタン、trans-1,3-ジメチルシクロペンタン等の脂環式炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素などが挙げられる。炭化水素分散媒は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。 The hydrocarbon dispersion medium may contain at least one compound selected from the group consisting of chain aliphatic hydrocarbons having 6 to 8 carbon atoms and alicyclic hydrocarbons having 6 to 8 carbon atoms. As the hydrocarbon dispersion medium, a chain aliphatic hydrocarbon such as n-hexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, n-octane; cyclohexane , Methylcyclohexane, cyclopentane, methylcyclopentane, trans-1,2-dimethylcyclopentane, cis-1,3-dimethylcyclopentane, trans-1,3-dimethylcyclopentane and other alicyclic hydrocarbons; benzene, Examples include aromatic hydrocarbons such as toluene and xylene. The hydrocarbon dispersion medium may be used alone or in combination of two or more.
 炭化水素分散媒は、工業的に入手が容易であり、かつ、品質が安定している観点から、n-ヘプタン及びシクロヘキサンからなる群より選ばれる少なくとも一種を含んでいてもよい。また、同様の観点から、上述の炭化水素分散媒の混合物としては、例えば、市販されているエクソールヘプタン(エクソンモービル社製:n-ヘプタン及び異性体の炭化水素75~85%含有)を用いてもよい。 The hydrocarbon dispersion medium may contain at least one selected from the group consisting of n-heptane and cyclohexane from the viewpoint of being industrially easily available and having stable quality. From the same viewpoint, as the mixture of the above-mentioned hydrocarbon dispersion medium, for example, commercially available ExxonHeptane (manufactured by ExxonMobil: containing 75 to 85% of n-heptane and isomeric hydrocarbons) is used. You may.
 炭化水素分散媒の使用量は、重合熱を適度に除去し、重合温度を制御しやすい観点から、単量体水溶液100質量部に対して、30~1000質量部が好ましく、40~500質量部がより好ましく、50~400質量部が更に好ましい。炭化水素分散媒の使用量が30質量部以上であることにより、重合温度の制御が容易である傾向がある。炭化水素分散媒の使用量が1000質量部以下であることにより、重合の生産性が向上する傾向があり、経済的である。 The amount of the hydrocarbon dispersion medium used is preferably 30 to 1000 parts by mass and 40 to 500 parts by mass with respect to 100 parts by mass of the monomer aqueous solution from the viewpoint of appropriately removing the heat of polymerization and easily controlling the polymerization temperature. Is more preferable, and 50 to 400 parts by mass is further preferable. When the amount of the hydrocarbon dispersion medium used is 30 parts by mass or more, the polymerization temperature tends to be easily controlled. When the amount of the hydrocarbon dispersion medium used is 1000 parts by mass or less, the productivity of polymerization tends to be improved, which is economical.
 ラジカル重合開始剤は水溶性であることが好ましく、例えば、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム等の過硫酸塩;メチルエチルケトンパーオキシド、メチルイソブチルケトンパーオキシド、ジ-t-ブチルパーオキシド、t-ブチルクミルパーオキシド、t-ブチルパーオキシアセテート、t-ブチルパーオキシイソブチレート、t-ブチルパーオキシピバレート、過酸化水素等の過酸化物;2,2’-アゾビス(2-アミジノプロパン)2塩酸塩、2,2’-アゾビス[2-(N-フェニルアミジノ)プロパン]2塩酸塩、2,2’-アゾビス[2-(N-アリルアミジノ)プロパン]2塩酸塩、2,2'-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]2塩酸塩、2,2’-アゾビス{2-[1-(2-ヒドロキシエチル)-2-イミダゾリン-2-イル]プロパン}2塩酸塩、2,2’-アゾビス{2-メチル-N-[1,1-ビス(ヒドロキシメチル)-2-ヒドロキシエチル]プロピオンアミド}、2,2’-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-プロピオンアミド]、4,4’-アゾビス(4-シアノ吉草酸)等のアゾ化合物などが挙げられる。ラジカル重合開始剤は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。ラジカル重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム、2,2’-アゾビス(2-アミジノプロパン)2塩酸塩、2,2'-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]2塩酸塩、及び、2,2’-アゾビス{2-[1-(2-ヒドロキシエチル)-2-イミダゾリン-2-イル]プロパン}2塩酸塩からなる群より選ばれる少なくとも一種が好ましく、過硫酸カリウム、過硫酸アンモニウム、及び、過硫酸ナトリウムからなる群より選ばれる少なくとも一種がより好ましい。 The radical polymerization initiator is preferably water-soluble, and is, for example, a persulfate such as potassium persulfate, ammonium persulfate, sodium persulfate; methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, di-t-butyl peroxide, t. -Peroxides such as butyl cumylperoxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, hydrogen peroxide; 2,2'-azobis (2-amidinopropane) ) 2 hydrochloride, 2,2'-azobis [2- (N-phenylamidino) propane] 2 hydrochloride, 2,2'-azobis [2- (N-allylamidino) propane] 2 hydrochloride, 2,2 '-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} Dihydrochloride, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-Hydroxyethyl) -propionamide], azo compounds such as 4,4'-azobis (4-cyanovaleric acid) and the like can be mentioned. The radical polymerization initiator may be used alone or in combination of two or more. Examples of the radical polymerization initiator include potassium persulfate, ammonium persulfate, sodium persulfate, 2,2'-azobis (2-amidinopropane) dihydrochloride, and 2,2'-azobis [2- (2-imidazolin-2-). Il) Propane] dihydrochloride and at least one selected from the group consisting of 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propan} 2 hydrochloride. Is preferable, and at least one selected from the group consisting of potassium persulfate, ammonium persulfate, and sodium persulfate is more preferable.
 ラジカル重合開始剤の使用量は、エチレン性不飽和単量体1モルに対して0.05~10ミリモルであってよい。ラジカル重合開始剤の使用量が0.05ミリモル以上であると、重合反応に長時間を要さず、効率的である。ラジカル重合開始剤の使用量が10ミリモル以下であると、急激な重合反応が起こることを抑制しやすい。 The amount of the radical polymerization initiator used may be 0.05 to 10 mmol per 1 mol of the ethylenically unsaturated monomer. When the amount of the radical polymerization initiator used is 0.05 mmol or more, the polymerization reaction does not require a long time and is efficient. When the amount of the radical polymerization initiator used is 10 mmol or less, it is easy to suppress the occurrence of a rapid polymerization reaction.
 上述のラジカル重合開始剤は、亜硫酸ナトリウム、亜硫酸水素ナトリウム、硫酸第一鉄、L-アスコルビン酸等の還元剤と併用して、レドックス重合開始剤として用いることもできる。 The above-mentioned radical polymerization initiator can also be used as a redox polymerization initiator in combination with a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, and L-ascorbic acid.
 重合反応の際、重合に用いる単量体水溶液は、連鎖移動剤を含んでいてもよい。連鎖移動剤としては、次亜リン酸塩類、チオール類、チオール酸類、第2級アルコール類、アミン類等が挙げられる。 At the time of the polymerization reaction, the monomer aqueous solution used for the polymerization may contain a chain transfer agent. Examples of the chain transfer agent include hypophosphates, thiols, thiolic acids, secondary alcohols, amines and the like.
 吸水性樹脂粒子の粒子径を制御するために、重合に用いる単量体水溶液は、増粘剤を含んでいてもよい。増粘剤としては、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルセルロース、カルボキシメチルセルロース、ポリエチレングリコール、ポリアクリルアミド、ポリエチレンイミン、デキストリン、アルギン酸ナトリウム、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレンオキサイド等が挙げられる。なお、重合時の撹拌速度が同じであれば、単量体水溶液の粘度が高いほど、得られる粒子の中位粒子径は大きくなる傾向にある。 In order to control the particle size of the water-absorbent resin particles, the monomer aqueous solution used for polymerization may contain a thickener. Examples of the thickener include hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, polyethylene glycol, polyacrylamide, polyethyleneimine, dextrin, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide and the like. If the stirring speed at the time of polymerization is the same, the higher the viscosity of the aqueous monomer solution, the larger the medium particle size of the obtained particles tends to be.
 重合の際に自己架橋による架橋が生じ得るが、内部架橋剤を用いることで架橋を施してもよい。内部架橋剤を用いると、吸水性樹脂粒子の吸水特性(保水量等)を制御しやすい。内部架橋剤は、通常、重合反応の際に反応液に添加される。内部架橋剤としては、例えば、エチレングリコール、プロピレングリコール、トリメチロールプロパン、グリセリン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリグリセリン等のポリオール類のジ又はトリ(メタ)アクリル酸エステル類;上述のポリオール類と不飽和酸(マレイン酸、フマール酸等)とを反応させて得られる不飽和ポリエステル類;N,N’-メチレンビス(メタ)アクリルアミド等のビス(メタ)アクリルアミド類;ポリエポキシドと(メタ)アクリル酸とを反応させて得られるジ又はトリ(メタ)アクリル酸エステル類;ポリイソシアネート(トリレンジイソシアネート、ヘキサメチレンジイソシアネート等)と(メタ)アクリル酸ヒドロキシエチルとを反応させて得られるジ(メタ)アクリル酸カルバミルエステル類;アリル化澱粉、アリル化セルロース、ジアリルフタレート、N,N’,N”-トリアリルイソシアヌレート、ジビニルベンゼン等の、重合性不飽和基を2個以上有する化合物;(ポリ)エチレングリコールジグリシジルエーテル、(ポリ)プロピレングリコールジグリシジルエーテル、(ポリ)グリセリンジグリシジルエーテル、(ポリ)グリセリントリグリシジルエーテル、(ポリ)プロピレングリコールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル等のポリグリシジル化合物;エピクロロヒドリン、エピブロムヒドリン、α-メチルエピクロロヒドリン等のハロエポキシ化合物;イソシアネート化合物(2,4-トリレンジイソシアネート、ヘキサメチレンジイソシアネート等)などの、反応性官能基を2個以上有する化合物などが挙げられる。内部架橋剤は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。内部架橋剤としては、ポリグリシジル化合物が好ましく、ジグリシジルエーテル化合物がより好ましく、(ポリ)エチレングリコールジグリシジルエーテル、(ポリ)プロピレングリコールジグリシジルエーテル、及び、(ポリ)グリセリンジグリシジルエーテルからなる群より選ばれる少なくとも一種が更に好ましい。 Cross-linking by self-cross-linking may occur during polymerization, but cross-linking may be performed by using an internal cross-linking agent. When an internal cross-linking agent is used, it is easy to control the water absorption characteristics (water retention amount, etc.) of the water-absorbent resin particles. The internal cross-linking agent is usually added to the reaction solution during the polymerization reaction. Examples of the internal cross-linking agent include di or tri (meth) acrylic acid esters of polyols such as ethylene glycol, propylene glycol, trimethylpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin; Unsaturated polyesters obtained by reacting polyols with unsaturated acids (maleic acid, fumaric acid, etc.); bis (meth) acrylamides such as N, N'-methylenebis (meth) acrylamide; polyepoxides and (meth) Di or tri (meth) acrylic acid esters obtained by reacting with acrylic acid; di (meth) obtained by reacting polyisocyanate (tolylene diisocyanate, hexamethylene diisocyanate, etc.) with hydroxyethyl (meth) acrylate. ) Acrylic acid carbamil esters; compounds having two or more polymerizable unsaturated groups such as allylated starch, allylated cellulose, diallyl phthalate, N, N', N "-triallyl isocyanurate, divinylbenzene; Poly such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, (poly) glycerin triglycidyl ether, (poly) propylene glycol polyglycidyl ether, polyglycerol polyglycidyl ether, etc. Glycidyl compound; haloepoxy compound such as epichlorohydrin, epibromhydrin, α-methylepichlorohydrin; 2 reactive functional groups such as isocyanate compound (2,4-tolylene diisocyanate, hexamethylene diisocyanate, etc.) Examples thereof include compounds having more than one. The internal cross-linking agent may be used alone or in combination of two or more. As the internal cross-linking agent, a polyglycidyl compound is preferable, and a diglycidyl ether compound is used. Is more preferable, and at least one selected from the group consisting of (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, and (poly) glycerin diglycidyl ether is further preferable.
 内部架橋剤の使用量は、得られる重合体が適度に架橋されることにより水溶性の性質が抑制され、充分な吸水量が得られやすい観点から、エチレン性不飽和単量体1モル当たり、30ミリモル以下が好ましく、0.01~10ミリモルがより好ましく、0.012~5ミリモルが更に好ましく、0.015~1ミリモルが特に好ましく、0.02~0.1ミリモルが極めて好ましく、0.025~0.06ミリモルが非常に好ましい。 The amount of the internal cross-linking agent used is 1 mol of ethylenically unsaturated monomer from the viewpoint that the water-soluble property is suppressed by appropriately cross-linking the obtained polymer and a sufficient amount of water absorption can be easily obtained. 30 mmol or less is preferable, 0.01 to 10 mmol is more preferable, 0.012 to 5 mmol is further preferable, 0.015 to 1 mmol is particularly preferable, 0.02 to 0.1 mmol is extremely preferable, and 0. 025 to 0.06 mmol is highly preferred.
 エチレン性不飽和単量体、ラジカル重合開始剤、界面活性剤、高分子系分散剤、炭化水素分散媒等(必要に応じて更に内部架橋剤)を混合した状態において撹拌下で加熱し、油中水系において逆相懸濁重合を行うことができる。 An ethylenically unsaturated monomer, a radical polymerization initiator, a surfactant, a polymer-based dispersant, a hydrocarbon dispersion medium, etc. (if necessary, an internal cross-linking agent) are mixed and heated under stirring to obtain oil. Reversed phase suspension polymerization can be performed in a medium water system.
 逆相懸濁重合を行う際には、界面活性剤(必要に応じて更に高分子系分散剤)の存在下で、エチレン性不飽和単量体を含む単量体水溶液を炭化水素分散媒に分散させる。このとき、重合反応を開始する前であれば、界面活性剤、高分子系分散剤等の添加時期は、単量体水溶液の添加の前後どちらであってもよい。 When performing reverse phase suspension polymerization, a monomer aqueous solution containing an ethylenically unsaturated monomer is used as a hydrocarbon dispersion medium in the presence of a surfactant (more polymer-based dispersant if necessary). Disperse. At this time, before the start of the polymerization reaction, the timing of adding the surfactant, the polymer-based dispersant, etc. may be either before or after the addition of the monomer aqueous solution.
 その中でも、得られる吸水性樹脂に残存する炭化水素分散媒の量を低減しやすい観点から、高分子系分散剤を分散させた炭化水素分散媒に単量体水溶液を分散させた後に界面活性剤を更に分散させてから重合を行うことが好ましい。 Among them, from the viewpoint of easily reducing the amount of the hydrocarbon dispersion medium remaining in the obtained water-absorbent resin, the surfactant is prepared after the monomer aqueous solution is dispersed in the hydrocarbon dispersion medium in which the polymer-based dispersant is dispersed. It is preferable to carry out the polymerization after further dispersing the above.
 逆相懸濁重合は、1段、又は、2段以上の多段で行うことができる。逆相懸濁重合は、生産性を高める観点から、2~3段で行うことが好ましい。 Reverse phase suspension polymerization can be carried out in one stage or in multiple stages of two or more stages. Reversed phase suspension polymerization is preferably carried out in 2 to 3 steps from the viewpoint of increasing productivity.
 2段以上の多段で逆相懸濁重合を行う場合には、1段目の逆相懸濁重合を行った後、1段目の重合反応で得られた反応混合物にエチレン性不飽和単量体を添加して混合し、1段目と同様の方法で2段目以降の逆相懸濁重合を行えばよい。2段目以降の各段における逆相懸濁重合では、エチレン性不飽和単量体の他に、上述のラジカル重合開始剤及び/又は内部架橋剤を、2段目以降の各段における逆相懸濁重合の際に添加するエチレン性不飽和単量体の量を基準として、上述のエチレン性不飽和単量体に対する各成分のモル比の範囲内で添加して逆相懸濁重合を行うことが好ましい。なお、2段目以降の各段における逆相懸濁重合では、必要に応じて内部架橋剤を用いてもよい。内部架橋剤を用いる場合は、各段に供するエチレン性不飽和単量体の量を基準として、上述のエチレン性不飽和単量体に対する各成分のモル比の範囲内で添加して逆相懸濁重合を行うことが好ましい。 When reverse phase suspension polymerization is carried out in two or more stages, the reaction mixture obtained in the first step polymerization reaction after the first step reverse phase suspension polymerization is subjected to an ethylenically unsaturated single amount. The body may be added and mixed, and the reverse phase suspension polymerization of the second and subsequent steps may be carried out in the same manner as in the first step. In the reverse phase suspension polymerization in each stage of the second and subsequent stages, in addition to the ethylenically unsaturated monomer, the above-mentioned radical polymerization initiator and / or internal cross-linking agent is used in the reverse phase of each stage of the second and subsequent stages. Based on the amount of ethylenically unsaturated monomer added during suspension polymerization, reverse phase suspension polymerization is carried out by adding within the range of the molar ratio of each component to the above-mentioned ethylenically unsaturated monomer. Is preferable. An internal cross-linking agent may be used in the reverse phase suspension polymerization in each of the second and subsequent stages, if necessary. When an internal cross-linking agent is used, it is added within the range of the molar ratio of each component to the above-mentioned ethylenically unsaturated monomer based on the amount of the ethylenically unsaturated monomer provided in each stage, and the suspension is reversed. It is preferable to carry out turbid polymerization.
 重合反応の温度は、使用するラジカル重合開始剤によって異なるが、重合を迅速に進行させ、重合時間を短くすることにより、経済性を高めると共に、容易に重合熱を除去して円滑に反応を行う観点から、20~150℃が好ましく、40~120℃がより好ましい。反応時間は、通常、0.5~4時間である。重合反応の終了は、例えば、反応系内の温度上昇の停止により確認することができる。これにより、エチレン性不飽和単量体の重合体は、通常、含水ゲルの状態で得られる。 The temperature of the polymerization reaction varies depending on the radical polymerization initiator used, but by advancing the polymerization rapidly and shortening the polymerization time, the efficiency is improved and the heat of polymerization is easily removed to carry out the reaction smoothly. From the viewpoint, 20 to 150 ° C. is preferable, and 40 to 120 ° C. is more preferable. The reaction time is usually 0.5-4 hours. The completion of the polymerization reaction can be confirmed, for example, by stopping the temperature rise in the reaction system. As a result, the polymer of the ethylenically unsaturated monomer is usually obtained in the state of a hydrogel.
 重合後、得られた含水ゲル状重合体に重合後架橋剤を添加して加熱することで架橋を施してもよい。重合後に架橋を行うことで含水ゲル状重合体の架橋度を高めて吸水特性(保水量等)を更に向上させることができる。 After polymerization, cross-linking may be performed by adding a cross-linking agent to the obtained hydrogel polymer and heating it. By performing cross-linking after the polymerization, the degree of cross-linking of the hydrogel polymer can be increased and the water absorption characteristics (water retention amount, etc.) can be further improved.
 重合後架橋剤としては、エチレングリコール、プロピレングリコール、1,4-ブタンジオール、トリメチロールプロパン、グリセリン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリグリセリン等のポリオール;(ポリ)エチレングリコールジグリシジルエーテル、(ポリ)プロピレングリコールジグリシジルエーテル、(ポリ)グリセリンジグリシジルエーテル等の、2個以上のエポキシ基を有する化合物;エピクロルヒドリン、エピブロムヒドリン、α-メチルエピクロルヒドリン等のハロエポキシ化合物;2,4-トリレンジイソシアネート、ヘキサメチレンジイソシアネート等の、2個以上のイソシアネート基を有する化合物;1,2-エチレンビスオキサゾリン等のオキサゾリン化合物;エチレンカーボネート等のカーボネート化合物;ビス[N,N-ジ(β-ヒドロキシエチル)]アジプアミド等のヒドロキシアルキルアミド化合物などが挙げられる。これらの中でも、(ポリ)エチレングリコールジグリシジルエーテル、(ポリ)グリセリンジグリシジルエーテル、(ポリ)グリセリントリグリシジルエーテル、(ポリ)プロピレングリコールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル等のポリグリシジル化合物が好ましい。架橋剤は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。 Examples of the post-polymerization cross-linking agent include polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin; (poly) ethylene glycol diglycidyl ether. Compounds having two or more epoxy groups, such as (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether; haloepoxy compounds such as epichlorohydrin, epibromhydrin, α-methylepicrolhydrin; 2,4- Compounds having two or more isocyanate groups such as tolylene diisocyanate and hexamethylene diisocyanate; oxazoline compounds such as 1,2-ethylenebisoxazoline; carbonate compounds such as ethylenecarbonate; bis [N, N-di (β-hydroxy) Ethyl)] Hydroxyalkylamide compounds such as adipamide can be mentioned. Among these, polyglycidyl compounds such as (poly) ethylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, (poly) glycerin triglycidyl ether, (poly) propylene glycol polyglycidyl ether, and polyglycerol polyglycidyl ether are preferable. .. The cross-linking agent may be used alone or in combination of two or more.
 重合後架橋剤の量は、得られる含水ゲル状重合体が適度に架橋されることにより、好適な吸水特性(保水量等)が得られやすい観点から、エチレン性不飽和単量体1モル当たり、30ミリモル以下が好ましく、10ミリモル以下がより好ましく、0.01~5ミリモルが更に好ましく、0.012~1ミリモルが特に好ましく、0.015~0.1ミリモルが極めて好ましく、0.02~0.05ミリモルが非常に好ましい。 The amount of the cross-linking agent after polymerization is set per 1 mol of ethylenically unsaturated monomer from the viewpoint that suitable water absorption characteristics (water retention amount, etc.) can be easily obtained by appropriately cross-linking the obtained hydrogel-like polymer. , 30 mmol or less, more preferably 10 mmol or less, further preferably 0.01 to 5 mmol, particularly preferably 0.012 to 1 mmol, extremely preferably 0.015 to 0.1 mmol, 0.02 to 0.02 to 0.05 mmol is highly preferred.
 重合後架橋剤の添加時期としては、重合に用いられるエチレン性不飽和単量体の重合後であればよく、多段重合の場合は、多段重合後に添加されることが好ましい。なお、重合時及び重合後の発熱、工程遅延による滞留、架橋剤添加時の系の開放、及び架橋剤添加に伴う水の添加等による水分の変動を考慮して、重合後架橋剤は、含水率(後述)の観点から、[重合直後の含水率±3質量%]の領域で添加することが好ましい。 The timing of adding the cross-linking agent after polymerization may be after the polymerization of the ethylenically unsaturated monomer used for polymerization, and in the case of multi-stage polymerization, it is preferable to add it after multi-stage polymerization. The post-polymerization cross-linking agent contains water in consideration of heat generation during and after polymerization, retention due to process delay, opening of the system when the cross-linking agent is added, and fluctuation of water content due to addition of water accompanying the addition of the cross-linking agent. From the viewpoint of rate (described later), it is preferable to add in the region of [moisture content immediately after polymerization ± 3% by mass].
 引き続き、得られた含水ゲル状重合体から水分を除去するために乾燥を行うことにより重合体粒子(例えば、エチレン性不飽和単量体に由来する構造単位を有する重合体を含む重合体粒子)が得られる。乾燥方法としては、例えば、(a)含水ゲル状重合体が炭化水素分散媒に分散した状態で、外部から加熱することにより共沸蒸留を行い、炭化水素分散媒を還流させて水分を除去する方法、(b)デカンテーションにより含水ゲル状重合体を取り出し、減圧乾燥する方法、(c)フィルターにより含水ゲル状重合体をろ別し、減圧乾燥する方法等が挙げられる。中でも、製造工程における簡便さから、(a)の方法を用いることが好ましい。 Subsequently, the polymer particles (for example, the polymer particles containing a polymer having a structural unit derived from an ethylenically unsaturated monomer) are dried to remove water from the obtained hydrogel polymer. Is obtained. As a drying method, for example, (a) a hydrogel-like polymer is dispersed in a hydrocarbon dispersion medium, and co-boiling distillation is performed by heating from the outside, and the hydrocarbon dispersion medium is refluxed to remove water. Examples thereof include (b) a method of taking out the hydrogel polymer by decantation and drying under reduced pressure, and (c) a method of filtering the hydrogel polymer with a filter and drying under reduced pressure. Above all, it is preferable to use the method (a) because of the simplicity in the manufacturing process.
 重合反応時の撹拌機の回転数を調整することによって、あるいは、重合反応後又は乾燥の初期において凝集剤を系内に添加することによって吸水性樹脂粒子の粒子径を調整することができる。凝集剤を添加することにより、得られる吸水性樹脂粒子の粒子径を大きくすることができる。凝集剤としては、無機凝集剤を用いることができる。無機凝集剤(例えば粉末状無機凝集剤)としては、シリカ、ゼオライト、ベントナイト、酸化アルミニウム、タルク、二酸化チタン、カオリン、クレイ、ハイドロタルサイト等が挙げられる。凝集効果に優れる観点から、凝集剤としては、シリカ、酸化アルミニウム、タルク及びカオリンからなる群より選ばれる少なくとも一種が好ましい。 The particle size of the water-absorbent resin particles can be adjusted by adjusting the rotation speed of the stirrer during the polymerization reaction, or by adding a flocculant into the system after the polymerization reaction or in the early stage of drying. By adding a flocculant, the particle size of the obtained water-absorbent resin particles can be increased. As the flocculant, an inorganic flocculant can be used. Examples of the inorganic flocculant (for example, powdered inorganic flocculant) include silica, zeolite, bentonite, aluminum oxide, talc, titanium dioxide, kaolin, clay, hydrotalcite and the like. From the viewpoint of excellent aggregating effect, the aggregating agent is preferably at least one selected from the group consisting of silica, aluminum oxide, talc and kaolin.
 逆相懸濁重合において、凝集剤を添加する方法としては、重合で用いられるものと同種の炭化水素分散媒又は水に凝集剤を予め分散させてから、撹拌下で、含水ゲル状重合体を含む炭化水素分散媒中に混合する方法が好ましい。 In the reverse phase suspension polymerization, as a method of adding the flocculant, the flocculant is previously dispersed in a hydrocarbon dispersion medium or water of the same type as that used in the polymerization, and then the hydrogel polymer is mixed under stirring. A method of mixing in a hydrocarbon dispersion medium containing the mixture is preferable.
 凝集剤の添加量は、重合に使用するエチレン性不飽和単量体100質量部に対して、0.001~1質量部が好ましく、0.005~0.5質量部がより好ましく、0.01~0.2質量部が更に好ましい。凝集剤の添加量が上述の範囲内であることによって、目的とする粒度分布を有する吸水性樹脂粒子が得られやすい。 The amount of the flocculant added is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.5 part by mass, based on 100 parts by mass of the ethylenically unsaturated monomer used for the polymerization. 01 to 0.2 parts by mass is more preferable. When the amount of the flocculant added is within the above range, water-absorbent resin particles having the desired particle size distribution can be easily obtained.
 吸水性樹脂粒子の製造においては、乾燥工程(水分除去工程)又はそれ以降の工程において、表面架橋剤を用いて含水ゲル状重合体の表面部分(表面及び表面近傍)の表面架橋が行われることが好ましい。表面架橋を行うことで、吸水性樹脂粒子の吸水特性(保水量等)などを制御しやすい。表面架橋は、含水ゲル状重合体が特定の含水率であるタイミングで行われることが好ましい。表面架橋の時期は、含水ゲル状重合体の含水率が5~50質量%である時点が好ましく、10~40質量%である時点がより好ましく、15~35質量%である時点が更に好ましい。なお、含水ゲル状重合体の含水率(質量%)は、次の式で算出される。
  含水率=[Ww/(Ww+Ws)]×100
 Ww:全重合工程の重合前の単量体水溶液に含まれる水分量から、乾燥工程により系外部に排出された水分量を差し引いた量に、凝集剤、表面架橋剤等を混合する際に必要に応じて用いられる水分量を加えた含水ゲル状重合体の水分量。
 Ws:含水ゲル状重合体を構成するエチレン性不飽和単量体、架橋剤、開始剤等の材料の仕込量から算出される固形分量。
In the production of water-absorbent resin particles, surface cross-linking of the surface portion (surface and vicinity of the surface) of the hydrogel polymer is performed using a surface cross-linking agent in the drying step (moisture removing step) or subsequent steps. Is preferable. By performing surface cross-linking, it is easy to control the water absorption characteristics (water retention amount, etc.) of the water-absorbent resin particles. The surface cross-linking is preferably performed at a timing when the hydrogel polymer has a specific water content. The time of surface cross-linking is preferably when the water content of the hydrogel polymer is 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass. The water content (mass%) of the hydrogel polymer is calculated by the following formula.
Moisture content = [Ww / (Ww + Ws)] x 100
Ww: Necessary when mixing a flocculant, a surface cross-linking agent, etc. to the amount obtained by subtracting the amount of water discharged to the outside of the system by the drying step from the amount of water contained in the monomer aqueous solution before polymerization in the entire polymerization step The amount of water in the hydrogel polymer to which the amount of water used is added.
Ws: A solid content calculated from the amount of materials such as an ethylenically unsaturated monomer, a cross-linking agent, and an initiator that constitute a hydrogel polymer.
 表面架橋剤としては、例えば、反応性官能基を2個以上有する化合物を挙げることができる。表面架橋剤としては、エチレングリコール、プロピレングリコール、1,4-ブタンジオール、トリメチロールプロパン、グリセリン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリグリセリン等のポリオール類;(ポリ)エチレングリコールジグリシジルエーテル、(ポリ)グリセリンジグリシジルエーテル、(ポリ)グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル(ポリ)プロピレングリコールポリグリシジルエーテル、(ポリ)グリセロールポリグリシジルエーテル等のポリグリシジル化合物;エピクロロヒドリン、エピブロムヒドリン、α-メチルエピクロロヒドリン等のハロエポキシ化合物;2,4-トリレンジイソシアネート、ヘキサメチレンジイソシアネート等のイソシアネート化合物;3-メチル-3-オキセタンメタノール、3-エチル-3-オキセタンメタノール、3-ブチル-3-オキセタンメタノール、3-メチル-3-オキセタンエタノール、3-エチル-3-オキセタンエタノール、3-ブチル-3-オキセタンエタノール等のオキセタン化合物;1,2-エチレンビスオキサゾリン等のオキサゾリン化合物;エチレンカーボネート等のカーボネート化合物;ビス[N,N-ジ(β-ヒドロキシエチル)]アジプアミド等のヒドロキシアルキルアミド化合物などが挙げられる。表面架橋剤は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。表面架橋剤としては、ポリグリシジル化合物が好ましく、(ポリ)エチレングリコールジグリシジルエーテル、(ポリ)グリセリンジグリシジルエーテル、(ポリ)グリセリントリグリシジルエーテル、(ポリ)プロピレングリコールポリグリシジルエーテル、及び、ポリグリセロールポリグリシジルエーテルからなる群より選ばれる少なくとも一種がより好ましい。 Examples of the surface cross-linking agent include compounds having two or more reactive functional groups. Surface cross-linking agents include polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin; (poly) ethylene glycol diglycidyl ether. , (Poly) Glycerin diglycidyl ether, (Poly) Glycerin triglycidyl ether, Trimethylol propantriglycidyl ether (Poly) propylene glycol Polyglycidyl ether, (Poly) Oxetane Polyglycidyl ether and other polyglycidyl compounds; Epichlorohydrin, Haloepoxy compounds such as epibromhydrin and α-methylepichlorohydrin; isocyanate compounds such as 2,4-tolylene diisocyanate and hexamethylenediisocyanate; 3-methyl-3-oxetanemethanol, 3-ethyl-3-oxetanemethanol , 3-butyl-3-oxetane methanol, 3-methyl-3-oxetane ethanol, 3-ethyl-3-oxetane ethanol, 3-butyl-3-oxetane ethanol and other oxetane compounds; 1,2-ethylenebisoxazoline and the like. Examples thereof include oxazoline compounds; carbonate compounds such as ethylene carbonate; hydroxyalkylamide compounds such as bis [N, N-di (β-hydroxyethyl)] adipamide. The surface cross-linking agent may be used alone or in combination of two or more. As the surface cross-linking agent, a polyglycidyl compound is preferable, and (poly) ethylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, (poly) glycerin triglycidyl ether, (poly) propylene glycol polyglycidyl ether, and polyglycerol are used. At least one selected from the group consisting of polyglycidyl ether is more preferable.
 表面架橋剤の使用量は、好適な吸水特性(保水量等)が得られやすい観点から、重合に使用するエチレン性不飽和単量体1モルに対して、0.01~20ミリモルが好ましく、0.05~10ミリモルがより好ましく、0.1~5ミリモルが更に好ましく、0.15~1ミリモルが特に好ましく、0.2~0.5ミリモルが極めて好ましい。 The amount of the surface cross-linking agent used is preferably 0.01 to 20 mmol with respect to 1 mol of the ethylenically unsaturated monomer used for polymerization from the viewpoint that suitable water absorption characteristics (water retention amount, etc.) can be easily obtained. 0.05 to 10 mmol is more preferable, 0.1 to 5 mmol is further preferable, 0.15 to 1 mmol is particularly preferable, and 0.2 to 0.5 mmol is extremely preferable.
 表面架橋後において、公知の方法で水及び炭化水素分散媒を留去すること、加熱減圧下で乾燥すること等により、表面架橋された乾燥品である重合体粒子を得ることができる。 After surface cross-linking, polymer particles which are surface-cross-linked dried products can be obtained by distilling off water and a hydrocarbon dispersion medium by a known method, drying under heating and reduced pressure, and the like.
 重合反応は、撹拌翼を有する各種撹拌機を用いて行うことができる。撹拌翼としては、平板翼、格子翼、パドル翼、プロペラ翼、アンカー翼、タービン翼、ファウドラー翼、リボン翼、フルゾーン翼、マックスブレンド翼等を用いることができる。平板翼は、軸(撹拌軸)と、軸の周囲に配置された平板部(撹拌部)とを有している。平板部は、スリット等を有していてもよい。撹拌翼として平板翼を用いた場合には、重合体粒子における架橋反応を均一に行いやすく、保水量等の吸水特性を維持しながらゲル層内部強度を好適な範囲に調整しやすい。 The polymerization reaction can be carried out using various stirrers having stirring blades. As the stirring blade, a flat plate blade, a lattice blade, a paddle blade, a propeller blade, an anchor blade, a turbine blade, a Faudler blade, a ribbon blade, a full zone blade, a max blend blade and the like can be used. The flat plate blade has a shaft (stirring shaft) and a flat plate portion (stirring portion) arranged around the shaft. The flat plate portion may have a slit or the like. When a flat plate blade is used as the stirring blade, it is easy to uniformly carry out the cross-linking reaction in the polymer particles, and it is easy to adjust the internal strength of the gel layer to a suitable range while maintaining the water absorption characteristics such as the amount of water retained.
 本実施形態に係る吸水性樹脂粒子は、重合体粒子に加えて、例えば、ゲル安定剤、金属キレート剤(エチレンジアミン4酢酸及びその塩、ジエチレントリアミン5酢酸及びその塩、例えばジエチレントリアミン5酢酸5ナトリウム等)、流動性向上剤(滑剤)等の追加成分を更に含むことができる。追加成分は、重合体粒子の内部、重合体粒子の表面上、又は、これらの両方に配置され得る。 In addition to the polymer particles, the water-absorbent resin particles according to the present embodiment include, for example, a gel stabilizer and a metal chelating agent (ethylenediaminetetraacetic acid and its salt, diethylenetriamine-5 acetic acid and its salt, for example, diethylenetriamine-5 sodium acetate and the like). , Additional components such as fluidity improver (lubricant) can be further included. Additional components may be located inside the polymer particles, on the surface of the polymer particles, or both.
 吸水性樹脂粒子は、重合体粒子の表面上に配置された複数の無機粒子を含んでいてもよい。例えば、重合体粒子と無機粒子とを混合することにより、重合体粒子の表面上に無機粒子を配置することができる。この無機粒子は、非晶質シリカ等のシリカ粒子であってもよい。 The water-absorbent resin particles may contain a plurality of inorganic particles arranged on the surface of the polymer particles. For example, by mixing the polymer particles and the inorganic particles, the inorganic particles can be arranged on the surface of the polymer particles. The inorganic particles may be silica particles such as amorphous silica.
 吸水性樹脂粒子が、重合体粒子の表面上に配置された無機粒子を含む場合、無機粒子の含有量は、重合体粒子の全質量を基準として下記の範囲であってよい。無機粒子の含有量は、0.05質量%以上、0.1質量%以上、0.15質量%以上、又は、0.2質量%以上であってよい。無機粒子の含有量は、5.0質量%以下、3.0質量%以下、1.0質量%以下、又は、0.5質量%以下であってよい。 When the water-absorbent resin particles contain inorganic particles arranged on the surface of the polymer particles, the content of the inorganic particles may be in the following range based on the total mass of the polymer particles. The content of the inorganic particles may be 0.05% by mass or more, 0.1% by mass or more, 0.15% by mass or more, or 0.2% by mass or more. The content of the inorganic particles may be 5.0% by mass or less, 3.0% by mass or less, 1.0% by mass or less, or 0.5% by mass or less.
 ここでの無機粒子は、通常、重合体粒子の大きさと比較して微小な大きさを有する。例えば、無機粒子の平均粒子径は、0.1~50μm、0.5~30μm、又は、1~20μmであってよい。平均粒子径は、粒子の特性に応じて、細孔電気抵抗法又はレーザー回折・散乱法によって測定できる。 The inorganic particles here usually have a minute size as compared with the size of the polymer particles. For example, the average particle size of the inorganic particles may be 0.1 to 50 μm, 0.5 to 30 μm, or 1 to 20 μm. The average particle size can be measured by the pore electric resistance method or the laser diffraction / scattering method depending on the characteristics of the particles.
 本実施形態に係る吸収体は、本実施形態に係る吸水性樹脂粒子を含有する。本実施形態に係る吸収体は、繊維状物を含有していてもよく、例えば、吸水性樹脂粒子及び繊維状物を含む混合物である。吸収体の構成としては、例えば、吸水性樹脂粒子及び繊維状物が均一混合された構成であってよく、シート状又は層状に形成された繊維状物の間に吸水性樹脂粒子が挟まれた構成であってもよく、その他の構成であってもよい。 The absorber according to this embodiment contains the water-absorbent resin particles according to this embodiment. The absorber according to the present embodiment may contain a fibrous substance, for example, a mixture containing water-absorbent resin particles and the fibrous substance. The structure of the absorber may be, for example, a structure in which the water-absorbent resin particles and the fibrous material are uniformly mixed, and the water-absorbent resin particles are sandwiched between the fibrous material formed in a sheet or layer. It may be a configuration or another configuration.
 繊維状物としては、微粉砕された木材パルプ;コットン;コットンリンター;レーヨン;セルロースアセテート等のセルロース系繊維;ポリアミド、ポリエステル、ポリオレフィン等の合成繊維;これらの繊維の混合物などが挙げられる。繊維状物の平均繊維長は、通常0.1~10mmであり、0.5~5mmであってもよい。繊維状物は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。繊維状物としては、親水性繊維を用いることができる。 Examples of the fibrous material include finely pulverized wood pulp; cotton; cotton linter; rayon; cellulosic fibers such as cellulose acetate; synthetic fibers such as polyamide, polyester and polyolefin; and a mixture of these fibers. The average fiber length of the fibrous material is usually 0.1 to 10 mm, and may be 0.5 to 5 mm. The fibrous material may be used alone or in combination of two or more. As the fibrous material, hydrophilic fibers can be used.
 吸収体の使用前及び使用中における形態保持性を高めるために、繊維状物に接着性バインダーを添加することによって繊維同士を接着させてもよい。接着性バインダーとしては、熱融着性合成繊維、ホットメルト接着剤、接着性エマルジョン等が挙げられる。接着性バインダーは、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。 In order to enhance the shape retention before and during use of the absorber, the fibers may be adhered to each other by adding an adhesive binder to the fibrous material. Examples of the adhesive binder include heat-sealing synthetic fibers, hot melt adhesives, and adhesive emulsions. The adhesive binder may be used alone or in combination of two or more.
 熱融着性合成繊維としては、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体等の全融型バインダー;ポリプロピレンとポリエチレンとのサイドバイサイド又は芯鞘構造からなる非全融型バインダーなどが挙げられる。上述の非全融型バインダーにおいては、ポリエチレン部分のみ熱融着することができる。 Examples of the heat-bondable synthetic fiber include a total fusion type binder such as polyethylene, polypropylene, and an ethylene-propylene copolymer; a non-total fusion type binder having a side-by-side or core-sheath structure of polypropylene and polyethylene. In the above-mentioned non-total fusion type binder, only the polyethylene portion can be heat-sealed.
 ホットメルト接着剤としては、例えば、エチレン-酢酸ビニルコポリマー、スチレン-イソプレン-スチレンブロックコポリマー、スチレン-ブタジエン-スチレンブロックコポリマー、スチレン-エチレン-ブチレン-スチレンブロックコポリマー、スチレン-エチレン-プロピレン-スチレンブロックコポリマー、アモルファスポリプロピレン等のベースポリマーと、粘着付与剤、可塑剤、酸化防止剤等との混合物が挙げられる。 Examples of the hot melt adhesive include ethylene-vinyl acetate copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer. , A mixture of a base polymer such as amorphous polypropylene and a tackifier, a plasticizer, an antioxidant and the like.
 接着性エマルジョンとしては、例えば、メチルメタクリレート、スチレン、アクリロニトリル、2-エチルヘキシルアクリレート、ブチルアクリレート、ブタジエン、エチレン、及び、酢酸ビニルからなる群より選ばれる少なくとも一種の単量体の重合物が挙げられる。 Examples of the adhesive emulsion include polymers of at least one monomer selected from the group consisting of methyl methacrylate, styrene, acrylonitrile, 2-ethylhexyl acrylate, butyl acrylate, butadiene, ethylene, and vinyl acetate.
 本実施形態に係る吸収体は、無機粉末(例えば非晶質シリカ)、消臭剤、抗菌剤、顔料、染料、香料、粘着剤等を含有してもよい。吸水性樹脂粒子が無機粒子を含む場合、吸収体は、吸水性樹脂粒子中の無機粒子とは別に無機粉末を含有してよい。 The absorber according to the present embodiment may contain an inorganic powder (for example, amorphous silica), a deodorant, an antibacterial agent, a pigment, a dye, a fragrance, an adhesive and the like. When the water-absorbent resin particles contain inorganic particles, the absorber may contain an inorganic powder in addition to the inorganic particles in the water-absorbent resin particles.
 本実施形態に係る吸収体の形状は、例えばシート状であってよい。吸収体の厚さ(例えば、シート状の吸収体の厚さ)は、0.1~20mm又は0.3~15mmであってよい。 The shape of the absorber according to the present embodiment may be, for example, a sheet shape. The thickness of the absorber (for example, the thickness of the sheet-shaped absorber) may be 0.1 to 20 mm or 0.3 to 15 mm.
 吸収体における吸水性樹脂粒子の含有量は、充分な吸収特性を得やすい観点から、吸水性樹脂粒子及び繊維状物の合計に対して、2~100質量%、10~80質量%又は20~60質量%であってよい。 The content of the water-absorbent resin particles in the absorber is 2 to 100% by mass, 10 to 80% by mass, or 20 to 20 to 100% by mass with respect to the total of the water-absorbent resin particles and the fibrous material from the viewpoint of easily obtaining sufficient absorption characteristics. It may be 60% by mass.
 吸収体における吸水性樹脂粒子の含有量は、充分な吸収特性を得やすい観点から、吸収体1m当たり、100~1000gが好ましく、150~800gがより好ましく、200~700gが更に好ましい。吸収体における繊維状物の含有量は、充分な吸収特性を得やすい観点から、吸収体1mあたり、50~800gが好ましく、100~600gがより好ましく、150~500gが更に好ましい。 The content of the water-absorbent resin particles in the absorber is preferably 100 to 1000 g, more preferably 150 to 800 g, and even more preferably 200 to 700 g per 1 m 2 of the absorber from the viewpoint of easily obtaining sufficient absorption characteristics. The content of the fibrous substance in the absorber is preferably 50 to 800 g, more preferably 100 to 600 g, and even more preferably 150 to 500 g per 1 m 2 of the absorber from the viewpoint of easily obtaining sufficient absorption characteristics.
 本実施形態に係る吸収性物品は、本実施形態に係る吸収体を備える。本実施形態に係る吸収性物品の他の構成部材としては、吸収体を保形すると共に吸収体の構成部材の脱落や流動を防止するコアラップ;吸液対象の液が浸入する側の最外部に配置される液体透過性シート;吸液対象の液が浸入する側とは反対側の最外部に配置される液体不透過性シート等が挙げられる。吸収性物品としては、おむつ(例えば紙おむつ)、トイレトレーニングパンツ、失禁パッド、衛生材料(生理用ナプキン、タンポン等)、汗取りパッド、ペットシート、簡易トイレ用部材、動物排泄物処理材などが挙げられる。 The absorbent article according to the present embodiment includes an absorber according to the present embodiment. Other constituent members of the absorbent article according to the present embodiment include a core wrap that retains the shape of the absorber and prevents the constituent members of the absorber from falling off or flowing; on the outermost side on the side where the liquid to be absorbed enters. Liquid permeable sheet to be arranged; Examples thereof include a liquid permeable sheet arranged on the outermost side opposite to the side where the liquid to be absorbed enters. Absorbent articles include diapers (for example, paper diapers), toilet training pants, incontinence pads, sanitary materials (sanitary napkins, tampons, etc.), sweat pads, pet sheets, simple toilet materials, animal excrement treatment materials, and the like. ..
 図1は、吸収性物品の一例を示す断面図である。図1に示す吸収性物品100は、吸収体10と、コアラップ20a,20bと、液体透過性シート30と、液体不透過性シート40と、を備える。吸収性物品100において、液体不透過性シート40、コアラップ20b、吸収体10、コアラップ20a、及び、液体透過性シート30がこの順に積層している。図1において、部材間に間隙があるように図示されている部分があるが、当該間隙が存在することなく部材間が密着していてよい。 FIG. 1 is a cross-sectional view showing an example of an absorbent article. The absorbent article 100 shown in FIG. 1 includes an absorbent body 10, core wraps 20a and 20b, a liquid permeable sheet 30, and a liquid permeable sheet 40. In the absorbent article 100, the liquid permeable sheet 40, the core wrap 20b, the absorbent body 10, the core wrap 20a, and the liquid permeable sheet 30 are laminated in this order. In FIG. 1, there is a portion shown so that there is a gap between the members, but the members may be in close contact with each other without the gap.
 吸収体10は、本実施形態に係る吸水性樹脂粒子10aと、繊維状物を含む繊維層10bと、を有する。吸水性樹脂粒子10aは、繊維層10b内に分散している。 The absorber 10 has a water-absorbent resin particle 10a according to the present embodiment and a fiber layer 10b containing a fibrous material. The water-absorbent resin particles 10a are dispersed in the fiber layer 10b.
 コアラップ20aは、吸収体10に接した状態で吸収体10の一方面側(図1中、吸収体10の上側)に配置されている。コアラップ20bは、吸収体10に接した状態で吸収体10の他方面側(図1中、吸収体10の下側)に配置されている。吸収体10は、コアラップ20aとコアラップ20bとの間に配置されている。コアラップ20a,20bとしては、ティッシュ、不織布、織布、液体透過孔を有する合成樹脂フィルム、網目を有するネット状シート等が挙げられる。コアラップ20a及びコアラップ20bは、例えば、吸収体10と同等の大きさの主面を有している。 The core wrap 20a is arranged on one side of the absorber 10 (upper side of the absorber 10 in FIG. 1) in contact with the absorber 10. The core wrap 20b is arranged on the other side of the absorber 10 (lower side of the absorber 10 in FIG. 1) in contact with the absorber 10. The absorber 10 is arranged between the core wrap 20a and the core wrap 20b. Examples of the core wraps 20a and 20b include tissues, non-woven fabrics, woven fabrics, synthetic resin films having liquid permeation holes, net-like sheets having a mesh, and the like. The core wrap 20a and the core wrap 20b have, for example, a main surface having the same size as the absorber 10.
 液体透過性シート30は、吸収対象の液が浸入する側の最外部に配置されている。液体透過性シート30は、コアラップ20aに接した状態でコアラップ20a上に配置されている。液体透過性シート30としては、ポリエチレン、ポリプロピレン、ポリエステル、ポリアミド等の合成樹脂からなる不織布、多孔質シートなどが挙げられる。液体不透過性シート40は、吸収性物品100において液体透過性シート30とは反対側の最外部に配置されている。液体不透過性シート40は、コアラップ20bに接した状態でコアラップ20bの下側に配置されている。液体不透過性シート40としては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等の合成樹脂からなるシート、これらの合成樹脂と不織布との複合材料からなるシートなどが挙げられる。液体透過性シート30及び液体不透過性シート40は、例えば、吸収体10の主面よりも広い主面を有しており、液体透過性シート30及び液体不透過性シート40の外縁部は、吸収体10及びコアラップ20a,20bの周囲に延在している。 The liquid permeable sheet 30 is arranged on the outermost side on the side where the liquid to be absorbed enters. The liquid permeable sheet 30 is arranged on the core wrap 20a in contact with the core wrap 20a. Examples of the liquid permeable sheet 30 include non-woven fabrics made of synthetic resins such as polyethylene, polypropylene, polyester and polyamide, and porous sheets. The liquid permeable sheet 40 is arranged on the outermost side of the absorbent article 100 on the opposite side of the liquid permeable sheet 30. The liquid permeable sheet 40 is arranged under the core wrap 20b in contact with the core wrap 20b. Examples of the liquid impermeable sheet 40 include a sheet made of a synthetic resin such as polyethylene, polypropylene, and polyvinyl chloride, and a sheet made of a composite material of these synthetic resins and a non-woven fabric. The liquid permeable sheet 30 and the liquid permeable sheet 40 have, for example, a main surface wider than the main surface of the absorber 10, and the outer edges of the liquid permeable sheet 30 and the liquid permeable sheet 40 are It extends around the absorber 10 and the core wraps 20a, 20b.
 吸収体10、コアラップ20a,20b、液体透過性シート30、及び、液体不透過性シート40の大小関係は、特に限定されず、吸収性物品の用途等に応じて適宜調整される。また、コアラップ20a,20bを用いて吸収体10を保形する方法は、特に限定されず、図1に示すように複数のコアラップにより吸収体を包んでよく、1枚のコアラップにより吸収体を包んでもよい。 The magnitude relationship between the absorbent body 10, the core wraps 20a and 20b, the liquid permeable sheet 30, and the liquid permeable sheet 40 is not particularly limited, and is appropriately adjusted according to the use of the absorbent article and the like. Further, the method of retaining the shape of the absorber 10 by using the core wraps 20a and 20b is not particularly limited, and as shown in FIG. 1, the absorber may be wrapped by a plurality of core wraps, and the absorber is wrapped by one core wrap. It may be.
 吸収体は、トップシートに接着されていてもよい。吸収体がコアラップにより挟持又は被覆されている場合、少なくともコアラップとトップシートとが接着されていることが好ましく、コアラップとトップシートとが接着されていると共にコアラップと吸収体とが接着されていることがより好ましい。吸収体の接着方法としては、ホットメルト接着剤をトップシートに対して所定間隔で幅方向にストライプ状、スパイラル状等に塗布して接着する方法;デンプン、カルボキシメチルセルロース、ポリビニルアルコール、ポリビニルピロリドン、その他の水溶性高分子等の水溶性バインダーを用いて接着する方法などが挙げられる。また、吸収体が熱融着性合成繊維を含む場合、熱融着性合成繊維の熱融着によって接着する方法を採用してもよい。 The absorber may be adhered to the top sheet. When the absorber is sandwiched or covered by the core wrap, it is preferable that at least the core wrap and the top sheet are adhered, and the core wrap and the top sheet are adhered and the core wrap and the absorber are adhered to each other. Is more preferable. As a method of adhering the absorber, a hot melt adhesive is applied to the top sheet at predetermined intervals in a striped shape, a spiral shape, etc. in the width direction and adhered; starch, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, etc. Examples thereof include a method of adhering using a water-soluble binder such as a water-soluble polymer. Further, when the absorber contains heat-sealing synthetic fibers, a method of adhering by heat-sealing of the heat-sealing synthetic fibers may be adopted.
 本実施形態によれば、本実施形態に係る吸水性樹脂粒子、吸収体又は吸収性物品を用いた吸液方法を提供することができる。本実施形態に係る吸液方法は、本実施形態に係る吸水性樹脂粒子、吸収体又は吸収性物品に吸液対象の液を接触させる工程を備える。 According to the present embodiment, it is possible to provide a liquid absorbing method using the water-absorbent resin particles, the absorbent body or the absorbent article according to the present embodiment. The liquid absorbing method according to the present embodiment includes a step of bringing the liquid to be absorbed into contact with the water-absorbent resin particles, the absorber or the absorbent article according to the present embodiment.
 本実施形態によれば、吸収性物品における液だまり吸収時間の調整方法であって、本実施形態に係る吸水性樹脂粒子、吸収体又は吸収性物品を用いた液だまり吸収時間の調整方法(例えば、液だまり吸収時間の改善方法)を提供することができる。本実施形態に係る液だまり吸収時間の調整方法は、本実施形態に係る吸水性樹脂粒子に関して上述した(1)~(3)の手順により測定されるゲル層内部強度を調整する調整工程を備える。調整工程では、ゲル層内部強度を上述の各範囲(例えば0.8~2.0N)に調整することができる。 According to the present embodiment, it is a method of adjusting the liquid pool absorption time in the absorbent article, and is a method of adjusting the liquid pool absorption time using the water-absorbent resin particles, the absorber or the absorbent article according to the present embodiment (for example). , A method for improving the absorption time of a pool) can be provided. The method for adjusting the liquid pool absorption time according to the present embodiment includes an adjustment step for adjusting the internal strength of the gel layer measured by the above-mentioned procedures (1) to (3) for the water-absorbent resin particles according to the present embodiment. .. In the adjusting step, the internal strength of the gel layer can be adjusted to each of the above ranges (for example, 0.8 to 2.0 N).
 本実施形態によれば、本実施形態に係る吸水性樹脂粒子に関して上述した(1)~(3)の手順により測定されるゲル層内部強度に基づき吸水性樹脂粒子を選定する選定工程を備える、吸水性樹脂粒子の製造方法を提供することができる。選定工程では、ゲル層内部強度を上述の各範囲(例えば0.8~2.0N)に調整することができる。 According to the present embodiment, the water-absorbent resin particles according to the present embodiment include a selection step of selecting the water-absorbent resin particles based on the internal strength of the gel layer measured by the above-mentioned procedures (1) to (3). A method for producing water-absorbent resin particles can be provided. In the selection step, the internal strength of the gel layer can be adjusted to each of the above ranges (for example, 0.8 to 2.0 N).
 本実施形態によれば、上述の吸水性樹脂粒子の製造方法により得られた吸水性樹脂粒子を用いた、吸収体の製造方法を提供することができる。本実施形態に係る吸収体の製造方法は、上述の吸水性樹脂粒子の製造方法により吸水性樹脂粒子を得る粒子製造工程を備える。本実施形態に係る吸収体の製造方法は、粒子製造工程の後に、吸水性樹脂粒子と繊維状物とを混合する工程を備えてよい。本実施形態によれば、上述の吸収体の製造方法により得られた吸収体を用いた、吸収性物品の製造方法を提供することができる。本実施形態に係る吸収性物品の製造方法は、上述の吸収体の製造方法により吸収体を得る吸収体製造工程を備える。本実施形態に係る吸収性物品の製造方法は、吸収体製造工程の後に、吸収体と吸収性物品の他の構成部材とを用いて吸収性物品を得る工程を備えてよく、当該工程では、例えば、吸収体と吸収性物品の他の構成部材とを互いに積層することにより吸収性物品を得る。 According to the present embodiment, it is possible to provide a method for producing an absorber using the water-absorbent resin particles obtained by the above-mentioned method for producing water-absorbent resin particles. The method for producing an absorber according to the present embodiment includes a particle manufacturing step for obtaining water-absorbent resin particles by the above-mentioned method for producing water-absorbent resin particles. The method for producing an absorber according to the present embodiment may include a step of mixing the water-absorbent resin particles and the fibrous material after the particle manufacturing step. According to the present embodiment, it is possible to provide a method for producing an absorbent article using the absorber obtained by the above-mentioned method for producing an absorber. The method for producing an absorbent article according to the present embodiment includes an absorber manufacturing step for obtaining an absorber by the above-mentioned method for manufacturing an absorber. The method for producing an absorbent article according to the present embodiment may include a step of obtaining an absorbent article by using the absorber and other constituent members of the absorbent article after the absorbent body manufacturing step. For example, an absorbent article is obtained by laminating the absorber and other constituent members of the absorbent article with each other.
 以下、実施例を挙げて本発明についてさらに具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
1.吸水性樹脂粒子の作製
実施例1
 還流冷却器、滴下ロート、窒素ガス導入管、及び、撹拌機を備えた内径11cm、内容積2Lの丸底円筒型セパラブルフラスコを準備した。撹拌機には、図2に概形を示す撹拌翼200を取り付けた。撹拌翼200は、軸200a及び平板部200bを備えている。平板部200bは、軸200aに溶接されると共に、湾曲した先端を有している。平板部200bには、軸200aの軸方向に沿って延びる4つのスリットSが形成されている。4つのスリットSは平板部200bの幅方向に配列されており、内側の二つのスリットSの幅は1cmであり、外側二つのスリットSの幅は0.5cmである。平板部200bの長さは約10cmであり、平板部200bの幅は約6cmである。準備したセパラブルフラスコ内でn-ヘプタン293g、及び分散剤(無水マレイン酸変性エチレン・プロピレン共重合体、三井化学株式会社製、ハイワックス1105A)0.736gを混合した。セパラブルフラスコ内の混合物を、撹拌機で撹拌しつつ、80℃まで昇温することにより、分散剤をn-ヘプタンに溶解させた。形成された溶液を50℃まで冷却した。
1. 1. Preparation of water-absorbent resin particles Example 1
A round-bottomed cylindrical separable flask having an inner diameter of 11 cm and an internal volume of 2 L equipped with a reflux condenser, a dropping funnel, a nitrogen gas introduction pipe, and a stirrer was prepared. The stirrer was equipped with a stirrer blade 200 whose outline is shown in FIG. The stirring blade 200 includes a shaft 200a and a flat plate portion 200b. The flat plate portion 200b is welded to the shaft 200a and has a curved tip. The flat plate portion 200b is formed with four slits S extending along the axial direction of the shaft 200a. The four slits S are arranged in the width direction of the flat plate portion 200b, the width of the two inner slits S is 1 cm, and the width of the two outer slits S is 0.5 cm. The length of the flat plate portion 200b is about 10 cm, and the width of the flat plate portion 200b is about 6 cm. In the prepared separable flask, 293 g of n-heptane and 0.736 g of a dispersant (maleic anhydride-modified ethylene / propylene copolymer, manufactured by Mitsui Chemicals, Inc., high wax 1105A) were mixed. The dispersant was dissolved in n-heptane by heating the mixture in the separable flask to 80 ° C. while stirring with a stirrer. The formed solution was cooled to 50 ° C.
 一方、内容積300mLのビーカーに、水溶性エチレン性不飽和単量体として80.5質量%のアクリル酸水溶液92.0g(1.03モル)をとり、外部より冷却しつつ、20.9質量%の水酸化ナトリウム水溶液147.7gを滴下して75モル%の中和を行った後、増粘剤としてヒドロキシルエチルセルロース0.092g(住友精化株式会社、HECAW-15F)、水溶性ラジカル重合開始剤として過硫酸ナトリウム0.0648g(0.272ミリモル)、内部架橋剤としてエチレングリコールジグリシジルエーテル0.010g(0.057ミリモル)を加えて溶解し、第1段目の水性液を調製した。 On the other hand, 92.0 g (1.03 mol) of an 80.5 mass% aqueous acrylic acid solution as a water-soluble ethylenically unsaturated monomer was placed in a beaker having an internal volume of 300 mL, and cooled from the outside by 20.9 mass. After adding 147.7 g of a% sodium hydroxide aqueous solution to neutralize 75 mol%, 0.092 g of hydroxylethyl cellulose (Sumitomo Seika Co., Ltd., HECAW-15F) as a thickener, water-soluble radical polymerization was started. 0.0648 g (0.272 mmol) of sodium hydroxide was added as an agent, and 0.010 g (0.057 mmol) of ethylene glycol diglycidyl ether was added as an internal cross-linking agent and dissolved to prepare an aqueous solution of the first stage.
 そして、上記にて調製した水性液をセパラブルフラスコに添加して、10分間撹拌した後、n-ヘプタン6.62gに界面活性剤としてHLB3のショ糖ステアリン酸エステル(三菱化学フーズ株式会社、リョートーシュガーエステルS-370)0.736gを加熱溶解した界面活性剤溶液を、さらに添加して、撹拌機の回転数を350rpmとして撹拌しながら系内を窒素で充分に置換した後、フラスコを70℃の水浴に浸漬して昇温し、重合を60分間行うことにより、第1段目の重合スラリー液を得た。 Then, the aqueous solution prepared above was added to the separable flask, and after stirring for 10 minutes, sucrose stearic acid ester of HLB3 as a surfactant in 6.62 g of n-heptane (Mitsubishi Chemical Foods Co., Ltd., Ryo). A surfactant solution prepared by heating and dissolving 0.736 g of Tosugar ester S-370) was further added, and the inside of the system was sufficiently replaced with nitrogen while stirring at a stirring speed of 350 rpm. The first-stage polymerized slurry solution was obtained by immersing in a water bath at ° C. to raise the temperature and performing polymerization for 60 minutes.
 一方、別の内容積500mLのビーカーに水溶性エチレン性不飽和単量体として80.5質量%のアクリル酸水溶液128.8g(1.44モル)をとり、外部より冷却しつつ、27質量%の水酸化ナトリウム水溶液159.0gを滴下して75モル%の中和を行った後、水溶性ラジカル重合開始剤として過硫酸ナトリウム0.0907g(0.381ミリモル)、内部架橋剤としてエチレングリコールジグリシジルエーテル0.0116g(0.067ミリモル)を加えて溶解し、第2段目の水性液を調製した。 On the other hand, 128.8 g (1.44 mol) of an 80.5 mass% acrylic acid aqueous solution as a water-soluble ethylenically unsaturated monomer was placed in another beaker having an internal volume of 500 mL, and 27 mass% while cooling from the outside. After 159.0 g of the aqueous sodium hydroxide solution was added dropwise to neutralize 75 mol%, 0.0907 g (0.381 mmol) of sodium persulfate was used as the water-soluble radical polymerization initiator, and ethylene glycol di was used as the internal cross-linking agent. 0.0116 g (0.067 mmol) of glycidyl ether was added and dissolved to prepare a second-stage aqueous solution.
 撹拌機の回転数を650rpmとして撹拌しながら、上記のセパラブルフラスコ系内を25℃に冷却した後、上記第2段目の水性液の全量を、第1段目の重合スラリー液に添加して、系内を窒素で30分間置換した後、再度、フラスコを70℃の水浴に浸漬して昇温し、重合反応を60分間行って、含水ゲル状重合体を得た。 After cooling the inside of the separable flask system to 25 ° C. while stirring at a stirring speed of 650 rpm, the entire amount of the aqueous solution in the second stage is added to the polymerized slurry solution in the first stage. After replacing the inside of the system with nitrogen for 30 minutes, the flask was again immersed in a water bath at 70 ° C. to raise the temperature, and the polymerization reaction was carried out for 60 minutes to obtain a hydrogel polymer.
 第2段目の重合後の含水ゲル状重合体に、45質量%のジエチレントリアミン5酢酸5ナトリウム水溶液0.589gを撹拌下で添加した。その後、125℃に設定した油浴にフラスコを浸漬し、n-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら、238.6gの水を系外へ抜き出した。その後、フラスコに表面架橋剤として2質量%のエチレングリコールジグリシジルエーテル水溶液4.42g(0.507ミリモル)を添加し、83℃で2時間保持した。 0.589 g of a 45% by mass diethylenetriamine-5 sodium acetate aqueous solution was added to the hydrogel polymer after the second stage polymerization under stirring. Then, the flask was immersed in an oil bath set at 125 ° C., and 238.6 g of water was extracted from the system while refluxing n-heptane by azeotropic distillation of n-heptane and water. Then, 4.42 g (0.507 mmol) of a 2% by mass ethylene glycol diglycidyl ether aqueous solution was added to the flask as a surface cross-linking agent, and the flask was kept at 83 ° C. for 2 hours.
 その後、n-ヘプタンを125℃にて蒸発させて乾燥させることによって、重合体粒子(乾燥品)を得た。この重合体粒子を目開き850μmの篩に通過させ、重合体粒子の質量に対して0.5質量%の非晶質シリカ(オリエンタルシリカズコーポレーション、トクシールNP-S)を重合体粒子と混合し、非晶質シリカを含む吸水性樹脂粒子を226.4g得た。該吸水性樹脂粒子の中位粒子径は378μmであった。 Then, n-heptane was evaporated at 125 ° C. and dried to obtain polymer particles (dried product). The polymer particles are passed through a sieve having an opening of 850 μm, and 0.5% by mass of amorphous silica (Oriental Silicas Corporation, Toxile NP-S) with respect to the mass of the polymer particles is mixed with the polymer particles. , 226.4 g of water-absorbent resin particles containing amorphous silica were obtained. The medium particle size of the water-absorbent resin particles was 378 μm.
実施例2
 n-ヘプタンと水との共沸蒸留により抜き出す水の量を257.2gに変更したこと以外は、実施例1と同様にして、吸水性樹脂粒子を231.2g得た。該吸水性樹脂粒子の中位粒子径は359μmであった。
Example 2
231.2 g of water-absorbent resin particles were obtained in the same manner as in Example 1 except that the amount of water extracted by azeotropic distillation of n-heptane and water was changed to 257.2 g. The medium particle size of the water-absorbent resin particles was 359 μm.
実施例3
 第1段目の重合スラリー液を得る際の撹拌機の回転数を425rpmに変更したこと、n-ヘプタンと水との共沸蒸留により抜き出す水の量を271.0gに変更したこと、重合体粒子の質量に対して0.2質量%の非晶質シリカを重合体粒子と混合したこと以外は、実施例1と同様にして、吸水性樹脂粒子を229.0g得た。該吸水性樹脂粒子の中位粒子径は360μmであった。
Example 3
The rotation speed of the stirrer when obtaining the polymer slurry liquid of the first stage was changed to 425 rpm, the amount of water extracted by co-boiling distillation of n-heptane and water was changed to 271.0 g, and the polymer. 229.0 g of water-absorbent resin particles were obtained in the same manner as in Example 1 except that 0.2% by mass of amorphous silica was mixed with the polymer particles with respect to the mass of the particles. The medium particle size of the water-absorbent resin particles was 360 μm.
実施例4
 第1段目の重合スラリー液を得る際の撹拌機の回転数を425rpmに変更したこと、含水ゲル状重合体を得る際に、セパラブルフラスコ系内を31℃に冷却した後、第2段目の水性液の全量を、第1段目の重合スラリー液に添加したこと、n-ヘプタンと水との共沸蒸留により抜き出す水の量を275.8gに変更したこと、重合体粒子の質量に対して0.2質量%の非晶質シリカを重合体粒子と混合したこと以外は、実施例1と同様にして、吸水性樹脂粒子を232.0g得た。該吸水性樹脂粒子の中位粒子径は148μmであった。
Example 4
After changing the rotation speed of the stirrer to obtain the first-stage polymerized slurry liquid to 425 rpm and obtaining the hydrogel polymer, the inside of the separable flask system was cooled to 31 ° C., and then the second stage. The total amount of the aqueous solution of the eye was added to the polymerized slurry solution of the first stage, the amount of water extracted by co-boiling distillation of n-heptane and water was changed to 275.8 g, and the mass of the polymer particles. 232.0 g of water-absorbent resin particles were obtained in the same manner as in Example 1 except that 0.2% by mass of amorphous silica was mixed with the polymer particles. The medium particle size of the water-absorbent resin particles was 148 μm.
比較例1
 撹拌翼として、翼径5cmの4枚傾斜パドル翼を2段有する撹拌翼を用いたこと、第1段目の水性液の調製において、水溶性ラジカル重合開始剤として2,2’-アゾビス(2-アミジノプロパン)2塩酸塩0.092g(0.339ミリモル)、および過硫酸カリウム0.018g(0.068ミリモル)、内部架橋剤としてエチレングリコールジグリシジルエーテル0.0046g(0.026ミリモル)を加えたこと、第1段目の重合スラリー液を得る際の撹拌機の回転数を550rpmに変更したこと、水溶性ラジカル重合開始剤として2,2’-アゾビス(2-アミジノプロパン)2塩酸塩0.129g(0.475ミリモル)、および過硫酸カリウム0.026g(0.095ミリモル)を加えたこと、含水ゲル状重合体を得る際の撹拌機の回転数を1000rpmに変更したこと、n-ヘプタンと水との共沸蒸留により抜き出す水の量を207.9gとしたこと、重合体粒子の質量に対して0.2質量%の非晶質シリカを重合体粒子と混合したこと以外は、実施例1と同様にして、吸水性樹脂粒子を232.5g得た。吸水性樹脂粒子の中位粒子径は360μmであった。
Comparative Example 1
As the stirring blade, a stirring blade having two stages of four inclined paddle blades with a blade diameter of 5 cm was used. In the preparation of the aqueous liquid in the first stage, 2,2'-azobis (2'-azobis (2) as a water-soluble radical polymerization initiator -Amidinopropane) dihydrochloride 0.092 g (0.339 mmol), potassium persulfate 0.018 g (0.068 mmol), and ethylene glycol diglycidyl ether 0.0046 g (0.026 mmol) as an internal cross-linking agent. In addition, the rotation speed of the stirrer for obtaining the first-stage polymerized slurry liquid was changed to 550 rpm, and 2,2'-azobis (2-amidinopropane) dihydrochloride as a water-soluble radical polymerization initiator. Addition of 0.129 g (0.475 mmol) and 0.026 g (0.095 mmol) of potassium persulfate, changing the rotation speed of the stirrer for obtaining a hydrogel polymer to 1000 rpm, n -Except that the amount of water extracted by co-boiling distillation of heptane and water was 207.9 g, and 0.2% by mass of amorphous silica with respect to the mass of the polymer particles was mixed with the polymer particles. , 232.5 g of water-absorbent resin particles were obtained in the same manner as in Example 1. The medium particle size of the water-absorbent resin particles was 360 μm.
比較例2
 撹拌翼として、翼径5cmの4枚傾斜パドル翼を2段有する撹拌翼を用いたこと、第1段目の水性液の調製において、水溶性ラジカル重合開始剤として2,2’-アゾビス(2-アミジノプロパン)2塩酸塩0.092g(0.339ミリモル)、および過硫酸カリウム0.018g(0.068ミリモル)、内部架橋剤としてエチレングリコールジグリシジルエーテル0.0046g(0.026ミリモル)を加えたこと、第1段目の重合スラリー液を得る際の撹拌機の回転数を550rpmに変更したこと、第2段目の水性液の調製において、水溶性ラジカル重合開始剤として2,2’-アゾビス(2-アミジノプロパン)2塩酸塩0.129g(0.475ミリモル)、および過硫酸カリウム0.026g(0.095ミリモル)を加えたこと、含水ゲル状重合体を得る際の撹拌機の回転数を1000rpmに変更したこと、n-ヘプタンと水との共沸蒸留により抜き出す水の量を216.7gとしたこと、重合体粒子の質量に対して0.2質量%の非晶質シリカを重合体粒子と混合したこと以外は、実施例1と同様にして、吸水性樹脂粒子を229.0g得た。吸水性樹脂粒子の中位粒子径は348μmであった。
Comparative Example 2
As the stirring blade, a stirring blade having two stages of four inclined paddle blades with a blade diameter of 5 cm was used. In the preparation of the aqueous liquid in the first stage, 2,2'-azobis (2'-azobis (2) as a water-soluble radical polymerization initiator -Amidinopropane) dihydrochloride 0.092 g (0.339 mmol), potassium persulfate 0.018 g (0.068 mmol), and ethylene glycol diglycidyl ether 0.0046 g (0.026 mmol) as an internal cross-linking agent. In addition, the rotation speed of the stirrer when obtaining the polymerized slurry liquid in the first stage was changed to 550 rpm, and in the preparation of the aqueous liquid in the second stage, 2,2'as a water-soluble radical polymerization initiator. -Addition of 0.129 g (0.475 mmol) of azobis (2-amidinopropane) dihydrochloride and 0.026 g (0.095 mmol) of potassium persulfate, and a stirrer for obtaining a hydrogel polymer. The number of revolutions was changed to 1000 rpm, the amount of water extracted by co-boiling distillation of n-heptane and water was 216.7 g, and 0.2 mass% amorphous with respect to the mass of the polymer particles. 229.0 g of water-absorbent resin particles were obtained in the same manner as in Example 1 except that silica was mixed with the polymer particles. The medium particle size of the water-absorbent resin particles was 348 μm.
比較例3
 撹拌翼として、翼径5cmの4枚傾斜パドル翼を2段有する撹拌翼を用いたこと、第1段目の水性液の調製において、水溶性ラジカル重合開始剤として水溶性ラジカル重合開始剤として2,2’-アゾビス(2-アミジノプロパン)2塩酸塩0.092g(0.339ミリモル)、および過硫酸カリウム0.018g(0.068ミリモル)、内部架橋剤としてエチレングリコールジグリシジルエーテル0.0046g(0.026ミリモル)を加えたこと、第1段目の重合スラリー液を得る際の撹拌機の回転数を550rpmに変更したこと、第2段目の水性液の調製において、水溶性ラジカル重合開始剤として2,2’-アゾビス(2-アミジノプロパン)2塩酸塩0.129g(0.475ミリモル)、および過硫酸カリウム0.026g(0.095ミリモル)を加えたこと、含水ゲル状重合体を得る際の撹拌機の回転数を1000rpmに変更したこと、n-ヘプタンと水との共沸蒸留により抜き出す水の量を232.0gとしたこと、重合体粒子の質量に対して0.2質量%の非晶質シリカを重合体粒子と混合したこと以外は、実施例1と同様にして、吸水性樹脂粒子を228.5g得た。吸水性樹脂粒子の中位粒子径は354μmであった。
Comparative Example 3
As the stirring blade, a stirring blade having two stages of four inclined paddle blades having a blade diameter of 5 cm was used. In the preparation of the aqueous liquid in the first stage, the water-soluble radical polymerization initiator was used as the water-soluble radical polymerization initiator. , 2'-azobis (2-amidinopropane) dihydrochloride 0.092 g (0.339 mmol), and potassium persulfate 0.018 g (0.068 mmol), ethylene glycol diglycidyl ether 0.0046 g as internal cross-linking agent (0.026 mmol) was added, the rotation speed of the stirrer when obtaining the polymerized slurry liquid in the first stage was changed to 550 rpm, and water-soluble radical polymerization was carried out in the preparation of the aqueous liquid in the second stage. Addition of 0.129 g (0.475 mmol) of 2,2'-azobis (2-amidinopropane) dihydrochloride and 0.026 g (0.095 mmol) of potassium persulfate as an initiator, and a hydrogel-like weight. The rotation speed of the stirrer for obtaining coalescence was changed to 1000 rpm, the amount of water extracted by co-boiling distillation of n-heptane and water was set to 232.0 g, and 0. 228.5 g of water-absorbent resin particles were obtained in the same manner as in Example 1 except that 2% by mass of amorphous silica was mixed with the polymer particles. The medium particle size of the water-absorbent resin particles was 354 μm.
2.評価
<生理食塩水保水量>
 吸水性樹脂粒子の生理食塩水の保水量(室温、25℃±2℃)を下記手順で測定した。まず、吸水性樹脂粒子2.0gを量り取った綿袋(メンブロード60番、横100mm×縦200mm)を500mL容のビーカー内に設置した。吸水性樹脂粒子の入った綿袋中に0.9質量%塩化ナトリウム水溶液(生理食塩水)500gをママコができないように一度に注ぎ込み、綿袋の上部を輪ゴムで縛り、30分静置させることで吸水性樹脂粒子を膨潤させた。30分経過後の綿袋を、遠心力が167Gとなるよう設定した脱水機(株式会社コクサン製、品番:H-122)を用いて1分間脱水し、脱水後の膨潤ゲルを含んだ綿袋の質量Wa(g)を測定した。吸水性樹脂粒子を添加せずに同様の操作を行い、綿袋の湿潤時の空質量Wb(g)を測定し、以下の式から生理食塩水保水量を算出した。
 生理食塩水保水量(g/g)=[Wa-Wb]/2.0
2. Evaluation <Saline water retention>
The water retention amount (room temperature, 25 ° C. ± 2 ° C.) of the physiological saline of the water-absorbent resin particles was measured by the following procedure. First, a cotton bag (Membroad No. 60, width 100 mm x length 200 mm) weighing 2.0 g of water-absorbent resin particles was placed in a 500 mL beaker. Pour 500 g of 0.9 mass% sodium chloride aqueous solution (physiological saline) into a cotton bag containing water-absorbent resin particles at a time so that mamaco cannot be formed, tie the upper part of the cotton bag with a rubber ring, and let it stand for 30 minutes. The water-absorbent resin particles were swollen with. After 30 minutes, the cotton bag is dehydrated for 1 minute using a dehydrator (manufactured by Kokusan Co., Ltd., product number: H-122) set to have a centrifugal force of 167 G, and the cotton bag containing the swelling gel after dehydration. The mass Wa (g) of was measured. The same operation was performed without adding the water-absorbent resin particles, the empty mass Wb (g) of the cotton bag when wet was measured, and the amount of physiological saline water retained was calculated from the following formula.
Saline water retention (g / g) = [Wa-Wb] /2.0
<荷重下の吸水量>
 吸水性樹脂粒子の荷重下(加圧下)の生理食塩水の吸水量(室温、25℃±2℃)を、図3に示す測定装置Yを用いて測定した。測定装置Yは、ビュレット部61、導管62、測定台63、及び、測定台63上に置かれた測定部64から構成される。ビュレット部61は、鉛直方向に伸びるビュレット61aと、ビュレット61aの上端に配置されたゴム栓61bと、ビュレット61aの下端に配置されたコック61cと、コック61cの近傍において一端がビュレット61a内に伸びる空気導入管61dと、空気導入管61dの他端側に配置されたコック61eとを有している。導管62は、ビュレット部61と測定台63との間に取り付けられている。導管62の内径は6mmである。測定台63の中央部には、直径2mmの穴があいており、導管62が連結されている。測定部64は、円筒64a(アクリル樹脂(プレキシグラス)製)と、円筒64aの底部に接着されたナイロンメッシュ64bと、重り64cとを有している。円筒64aの内径は20mmである。ナイロンメッシュ64bの目開きは75μm(200メッシュ)である。そして、測定時にはナイロンメッシュ64b上に測定対象の吸水性樹脂粒子65が均一に撒布される。重り64cの直径は19mmであり、重り64cの質量は119.6gである。重り64cは、吸水性樹脂粒子65上に置かれ、吸水性樹脂粒子65に対して4.14kPaの荷重を加えることができる。
<Amount of water absorption under load>
The water absorption amount (room temperature, 25 ° C. ± 2 ° C.) of the physiological saline under the load (pressurization) of the water-absorbent resin particles was measured using the measuring device Y shown in FIG. The measuring device Y is composed of a burette unit 61, a conduit 62, a measuring table 63, and a measuring unit 64 placed on the measuring table 63. The burette portion 61 has a burette 61a extending in the vertical direction, a rubber stopper 61b arranged at the upper end of the burette 61a, a cock 61c arranged at the lower end of the burette 61a, and one end extending into the burette 61a in the vicinity of the cock 61c. It has an air introduction pipe 61d and a cock 61e arranged on the other end side of the air introduction pipe 61d. The conduit 62 is attached between the burette portion 61 and the measuring table 63. The inner diameter of the conduit 62 is 6 mm. A hole having a diameter of 2 mm is formed in the central portion of the measuring table 63, and the conduit 62 is connected to the hole. The measuring unit 64 has a cylinder 64a (made of acrylic resin (plexiglass)), a nylon mesh 64b adhered to the bottom of the cylinder 64a, and a weight 64c. The inner diameter of the cylinder 64a is 20 mm. The opening of the nylon mesh 64b is 75 μm (200 mesh). Then, at the time of measurement, the water-absorbent resin particles 65 to be measured are uniformly sprinkled on the nylon mesh 64b. The diameter of the weight 64c is 19 mm, and the mass of the weight 64c is 119.6 g. The weight 64c is placed on the water-absorbent resin particles 65, and a load of 4.14 kPa can be applied to the water-absorbent resin particles 65.
 測定装置Yの円筒64aの中に0.100gの吸水性樹脂粒子65を入れた後、重り64cを載せて測定を開始した。吸水性樹脂粒子65が吸水した生理食塩水と同容積の空気が、空気導入管より、速やかにかつスムーズにビュレット61aの内部に供給されるため、ビュレット61aの内部の生理食塩水の水位の減量が、吸水性樹脂粒子65が吸水した生理食塩水量となる。ビュレット61aの目盛は、上から下方向に0mLから0.5mL刻みで刻印されており、生理食塩水の水位として、吸水開始前のビュレット61aの目盛りVaと、吸水開始から60分後のビュレット61aの目盛りVbとを読み取り、下記式より荷重下の吸水量を算出した。結果を表1に示す。
  荷重下の吸水量[mL/g]=(Vb-Va)/0.1
After 0.100 g of the water-absorbent resin particles 65 were placed in the cylinder 64a of the measuring device Y, the weight 64c was placed and the measurement was started. Since the same volume of air as the physiological saline absorbed by the water-absorbent resin particles 65 is quickly and smoothly supplied to the inside of the burette 61a from the air introduction pipe, the water level of the physiological saline inside the burette 61a is reduced. However, the amount of physiological saline absorbed by the water-absorbent resin particles 65 is obtained. The scale of the burette 61a is engraved from the top to the bottom in increments of 0 mL to 0.5 mL, and the scale Va of the burette 61a before the start of water absorption and the burette 61a 60 minutes after the start of water absorption are used as the water level of the physiological saline. The scale Vb of the above was read, and the amount of water absorption under load was calculated from the following formula. The results are shown in Table 1.
Water absorption under load [mL / g] = (Vb-Va) /0.1
<中位粒子径>
 吸水性樹脂粒子50gを中位粒子径測定用に用いた。測定は温度25±2℃、湿度50±10%の環境下で行った。
<Medium particle size>
50 g of water-absorbent resin particles were used for measuring the medium particle size. The measurement was performed in an environment with a temperature of 25 ± 2 ° C. and a humidity of 50 ± 10%.
 JIS標準篩を上から、目開き850μmの篩、目開き500μmの篩、目開き425μmの篩、目開き300μmの篩、目開き250μmの篩、目開き180μmの篩、目開き150μmの篩、及び受け皿の順に組み合わせた。 From the top, JIS standard sieves have a mesh size of 850 μm, a mesh size of 500 μm, a mesh size of 425 μm, a mesh size of 300 μm, a mesh size of 250 μm, a mesh size of 180 μm, a mesh size of 150 μm, and a sieve. Combined in the order of the saucer.
 組み合わせた最上の篩に、吸水性樹脂粒子を入れ、ロータップ式振とう器(株式会社飯田製作所製)を用いてJIS Z 8815(1994)に準じて分級した。分級後、各篩上に残った吸水性樹脂粒子の質量を全量に対する質量百分率として算出し粒度分布を求めた。この粒度分布に関して粒子径の大きい方から順に篩上を積算することにより、篩の目開きと篩上に残った吸水性樹脂粒子の質量百分率の積算値との関係を対数確率紙にプロットした。確率紙上のプロットを直線で結ぶことにより、積算質量百分率50質量%に相当する粒子径を中位粒子径とした。 Water-absorbent resin particles were placed in the best combined sieve and classified according to JIS Z8815 (1994) using a low-tap shaker (manufactured by Iida Seisakusho Co., Ltd.). After classification, the mass of the water-absorbent resin particles remaining on each sieve was calculated as a mass percentage with respect to the total amount, and the particle size distribution was obtained. The relationship between the mesh size of the sieve and the integrated value of the mass percentage of the water-absorbent resin particles remaining on the sieve was plotted on a logarithmic probability paper by integrating the particle size distribution on the sieve in order from the one having the largest particle size. By connecting the plots on the probability paper with a straight line, the particle size corresponding to the cumulative mass percentage of 50% by mass was defined as the medium particle size.
<カードメータによるゲル強度>
 容量100mLのガラスビーカーに、生理食塩水49.0gを量り取り、マグネチックスターラーバー(8mmφ×30mmのリング無し)を投入し、マグネチックスターラー(小池精密機器製作所製:M-20G)の上に配置した。引き続き、マグネチックスターラーバーを600回転/分で回転するように調整した。
<Gel strength by card meter>
Weigh 49.0 g of physiological saline into a glass beaker with a capacity of 100 mL, put a magnetic stirrer bar (without a ring of 8 mmφ x 30 mm), and place it on a magnetic stirrer (manufactured by Koike Precision Instruments Mfg. Co., Ltd .: M-20G). Placed. Subsequently, the magnetic stirrer bar was adjusted to rotate at 600 rpm.
 次に、吸水性樹脂粒子1.0gを撹拌中のビーカー内に投入し、回転渦が消えて液面が水平になるまで撹拌を続け、ゲルを調製した。このゲルを、恒温恒湿槽にて25℃、60%RHの条件下で1時間保管し、測定試料とした。 Next, 1.0 g of water-absorbent resin particles were put into a beaker being stirred, and stirring was continued until the rotating vortex disappeared and the liquid level became horizontal to prepare a gel. This gel was stored in a constant temperature and humidity chamber at 25 ° C. and 60% RH for 1 hour to prepare a measurement sample.
 この測定試料のゲル強度(室温、温度25±2℃)を、カードメータ(株式会社アイテクノエンジニアリング社製:カードメータ・ミニME-600)を用いて測定した。なお、カードメータの条件は以下の通りである。
 ・感圧軸:16mmφ
 ・スプリング:400g用
 ・荷重:400g
 ・上昇速度:1inch/21sec
 ・試験モード:粘調
The gel strength (room temperature, temperature 25 ± 2 ° C.) of this measurement sample was measured using a card meter (manufactured by Ai Techno Engineering Co., Ltd .: Card Meter Mini ME-600). The conditions of the card meter are as follows.
・ Pressure sensitive shaft: 16 mmφ
・ Spring: for 400g ・ Load: 400g
・ Rise speed: 1 inch / 21 sec
・ Test mode: Viscous
<ゲル層内部強度>
(EZtestの準備)
 EZtest(株式会社島津製作所、製品名:EZtest、型番:EZ-SX)の測定台上に小型スターラー(製品名:マルチスターラー MS-101 製造会社:株式会社サイニクス)を配置した。次いで、小型スターラー上に、生理食塩水176gが入った容量200mLの容器(メーカー:ハリオ 製品名:トールビーカー 200mL 品番:TB-200 SCI)を載置した。容器は、内径5.7cm、高さ11.1cmの円筒形状のガラスビーカーである。次に、生理食塩水が入った容器内に、スターラーチップ(長さ40mm、直径8mm、リングなし)を投入した。スターラーのコントローラーは「製品名:マルチスターラー専用コントローラー MC-303 製造会社:株式会社サイニクス」を使用した。
<Internal strength of gel layer>
(Preparation for EZtest)
A small stirrer (product name: multi-stirrer MS-101 manufacturer: Sinix Co., Ltd.) was placed on the measuring table of EZtest (Shimadzu Corporation, product name: EZtest, model number: EZ-SX). Next, a container having a capacity of 200 mL (manufacturer: Hario product name: tall beaker 200 mL product number: TB-200 SCI) containing 176 g of physiological saline was placed on a small stirrer. The container is a cylindrical glass beaker with an inner diameter of 5.7 cm and a height of 11.1 cm. Next, a stirrer tip (length 40 mm, diameter 8 mm, no ring) was put into a container containing physiological saline. As the stirrer controller, "Product name: Multi-stirrer dedicated controller MC-303 Manufacturer: Sinix Co., Ltd." was used.
 図4(A)及び(B)にゲル最大抵抗力の測定に用いた測定装置の概略図を示す。図4(A)及び(B)は、それぞれ膨潤ゲル形成前後の測定装置を示す。図4(A)及び(B)に示すように、EZtestのロードセル70に治具71が装着されている。治具71は、円板部71bと棒状部71aとを備えている。円板部71bは、円板状であり、直径2cmの平坦面を表裏に有し、厚さは5mmである。棒状部71aにおいて、横断面は直径5mmの円形であり、棒状部71aの長さは5.5cmである。棒状部71aの一端は円板部71bの一方の平坦面である第1の面の中央に接続されており、棒状部71aの他端はロードセル70に接続されている。治具71は、容器の高さ方向の中心軸が治具71の円板部71bの中央に位置するように配置されている。 FIGS. 4 (A) and 4 (B) show a schematic view of the measuring device used for measuring the maximum gel resistance. 4 (A) and 4 (B) show measuring devices before and after swelling gel formation, respectively. As shown in FIGS. 4A and 4B, the jig 71 is attached to the load cell 70 of the EZtest. The jig 71 includes a disk portion 71b and a rod-shaped portion 71a. The disk portion 71b has a disk shape, has flat surfaces having a diameter of 2 cm on the front and back surfaces, and has a thickness of 5 mm. The rod-shaped portion 71a has a circular cross section with a diameter of 5 mm, and the rod-shaped portion 71a has a length of 5.5 cm. One end of the rod-shaped portion 71a is connected to the center of the first surface which is one flat surface of the disk portion 71b, and the other end of the rod-shaped portion 71a is connected to the load cell 70. The jig 71 is arranged so that the central axis in the height direction of the container is located at the center of the disk portion 71b of the jig 71.
 治具71を下げ、治具71の円板部71bの第1の面とは反対側の平坦面である第2の面(下方の面)を、液面に接触させた。治具71の円板部71bの下方の面と液面との接触は目視により確認した。その後、接触した位置から治具71を32mm下降させ、その位置を測定開始位置とした。32mm下降させることで、液面と治具71の円板部71bの下方の面までの距離d1、及び、治具71の円板部71bの下方の面とスターラーチップ73までの距離d2は、約32mmとなる。図4(A)に示すように、測定開始位置において、治具71を生理食塩水72に浸した状態で、600rpmの撹拌下で、容器内に吸水性樹脂粒子4.0gを入れた。吸水性樹脂粒子が膨潤し、液表面の渦が収束したことを確認した後、撹拌を止めた。その後10分間静置し、45倍膨潤ゲルを得た。図4(B)に示すように、ロードセル70に接続された治具71は膨潤ゲル74に埋設されている。 The jig 71 was lowered so that the second surface (lower surface), which is a flat surface opposite to the first surface of the disk portion 71b of the jig 71, was brought into contact with the liquid surface. The contact between the lower surface of the disk portion 71b of the jig 71 and the liquid surface was visually confirmed. After that, the jig 71 was lowered by 32 mm from the contacted position, and that position was set as the measurement start position. By lowering by 32 mm, the distance d1 between the liquid level and the lower surface of the disc portion 71b of the jig 71 and the distance d2 between the lower surface of the disc portion 71b of the jig 71 and the stirrer tip 73 are reduced. It will be about 32 mm. As shown in FIG. 4 (A), at the measurement start position, 4.0 g of the water-absorbent resin particles were placed in the container with the jig 71 immersed in the physiological saline 72 under stirring at 600 rpm. After confirming that the water-absorbent resin particles had swollen and the vortices on the liquid surface had converged, stirring was stopped. Then, it was allowed to stand for 10 minutes to obtain a 45-fold swollen gel. As shown in FIG. 4B, the jig 71 connected to the load cell 70 is embedded in the swelling gel 74.
(EZtestによる測定)
 ゲル層内部強度の測定は、島津オートグラフ用ソフトウェア トラペジウムX(製造会社:株式会社島津製作所)によりEZtestに装着した治具を操作することで行った。測定は温度25±2℃、湿度50±10%の環境下で行った。
(Measurement by EZtest)
The internal strength of the gel layer was measured by operating the jig attached to the EZtest by the software Trapezium X (manufacturing company: Shimadzu Corporation) for Shimadzu autograph. The measurement was performed in an environment with a temperature of 25 ± 2 ° C. and a humidity of 50 ± 10%.
 撹拌を止めてから10分後に、膨潤ゲルに埋設された治具を10cm/分の速度で鉛直下方(図4(B)に示すa方向)に押し込んだ。治具を押し込んだときに治具に負荷される荷重を試験力として測定した。試験力の測定は、室温(温度25±2℃)において、実施した。ゲル層内部強度は、治具を押し込んでから6mmの位置に到達したときに観測した試験力とした。治具は測定開始地点から10mm押し込んだ位置に到達した時点で停止させた。試験力は、トラペジウムXにより自動で検出される値である。図5は、ゲル層内部強度の測定試験結果の一例を示すグラフである。図5中の横軸は、治具の鉛直方向の移動距離(変位、単位:mm)であり、縦軸は試験力(単位:N)を示す。図5に示すように、測定開始位置から治具が鉛直方向に移動するにつれて試験力は上昇した。変位が6mmであるときの試験力をゲル層内部強度として得た。 Ten minutes after the stirring was stopped, the jig embedded in the swelling gel was pushed vertically downward (direction a shown in FIG. 4B) at a speed of 10 cm / min. The load applied to the jig when the jig was pushed in was measured as a test force. The test force was measured at room temperature (temperature 25 ± 2 ° C.). The internal strength of the gel layer was the test force observed when the jig reached a position of 6 mm after being pushed in. The jig was stopped when it reached the position where it was pushed in by 10 mm from the measurement start point. The test force is a value automatically detected by Trapezium X. FIG. 5 is a graph showing an example of the measurement test result of the internal strength of the gel layer. The horizontal axis in FIG. 5 is the vertical movement distance (displacement, unit: mm) of the jig, and the vertical axis is the test force (unit: N). As shown in FIG. 5, the test force increased as the jig moved in the vertical direction from the measurement start position. The test force when the displacement was 6 mm was obtained as the internal strength of the gel layer.
<吸収性物品の評価>
(液だまり吸収時間試験)
(1)人工尿の調製
 塩化ナトリウム、塩化カルシウム及び硫酸マグネシウムを下記の濃度でイオン交換水に溶解させた。得られた溶液に少量の青色1号加えて、青色に着色した人工尿を得た。下記の濃度は、人工尿の全質量を基準とする濃度である。
 人工尿組成
  NaCl:0.780質量%
  CaCl:0.022質量%
  MgSO:0.038質量%
  青色一号:0.002質量%
<Evaluation of absorbent articles>
(Liquid pool absorption time test)
(1) Preparation of artificial urine Sodium chloride, calcium chloride and magnesium sulfate were dissolved in ion-exchanged water at the following concentrations. A small amount of Blue No. 1 was added to the obtained solution to obtain artificial urine colored blue. The following concentrations are based on the total mass of artificial urine.
Artificial urine composition NaCl: 0.780% by mass
CaCl 2 : 0.022% by mass
0054 4 : 0.038% by mass
Blue No. 1: 0.002% by mass
(2)吸収性物品の液だまり吸収時間試験
 図6に示す装置を用いて、温度25±2℃、湿度50±10%の環境下において、吸収性物品の液だまり吸収時間試験を行った。概略としては、アクリル樹脂製の測定容器内の傾斜板上に載置した試験用の吸収性物品の鉛直上方から送液ポンプ(INTEGRA社製 DOSEIT P910 投入口径0.5cmφ)で人工尿を投入し、人工尿が流れ下るまでの間に吸収する能力と、吸収し切れずに測定容器内の底部に溜まった人工尿を吸い上げていく能力の二つのバランスを評価する機構である。以下に詳細な仕様を示す。
(2) Liquid pool absorption time test of absorbent article Using the device shown in FIG. 6, a liquid pool absorption time test of the absorbent article was performed in an environment of a temperature of 25 ± 2 ° C. and a humidity of 50 ± 10%. Roughly speaking, artificial urine is injected from vertically above the absorbent article for testing placed on the inclined plate in the measuring container made of acrylic resin with a liquid feed pump (DOSEIT P910 input diameter 0.5 cmφ manufactured by INTEGRA). It is a mechanism to evaluate the balance between the ability to absorb artificial urine before it flows down and the ability to suck up artificial urine that has not been completely absorbed and has accumulated at the bottom of the measuring container. Detailed specifications are shown below.
 液だまり吸収時間試験では、水平面に対して45度傾斜した傾斜面Sを有する長方形状の傾斜板と、側板80とから構成されるアクリル樹脂製の測定容器を用いる。傾斜板の長手方向の長さ(長辺の長さ)が20cmであり、傾斜板の短手方向の長さ(短辺の長さ)が11cmであり、短辺が水平面に位置する。傾斜面S上には、長方形状の吸収性物品102が配置される。吸収性物品102は、下方の短辺が水平面に位置し、長辺が水平面に対して傾斜する方向に沿う向きで配置される。傾斜面Sは滑らかであり、板に液体が滞留したり吸収されたりすることはなかった。 In the liquid pool absorption time test, an acrylic resin measuring container composed of a rectangular inclined plate having an inclined surface S 0 inclined by 45 degrees with respect to a horizontal plane and a side plate 80 is used. The length of the inclined plate in the longitudinal direction (length of the long side) is 20 cm, the length of the inclined plate in the lateral direction (length of the short side) is 11 cm, and the short side is located on the horizontal plane. On the inclined surfaces S 0, the rectangular absorbent article 102 is placed. The absorbent article 102 is arranged with its lower short side located in the horizontal plane and its long side oriented in a direction inclined with respect to the horizontal plane. The inclined surface S 0 was smooth, and no liquid was retained or absorbed on the plate.
 吸収性物品の液だまり吸収速度試験は、以下のi)、ii)及びiii)の順で行った。
 i)吸水性樹脂粒子4.2g及び粉砕パルプ3.9gを空気抄造によって均一混合することにより、10cm×15cmの大きさのシート状の吸収体を作製した。吸収体をティッシュペーパー(吸収体と同じ大きさで坪量16g/m)に載せ、吸収体の上にティッシュペーパー(吸収体と同じ大きさで坪量16g/m)を載せた。ティッシュペーパーによって挟まれた吸収体に対して、588kPaの荷重を30秒間加えた。その上に、吸収体と同じ大きさで、坪量22g/mのポリエチレン-ポリプロピレン製エアスルー型多孔質液体透過性シートを配置した。更に、10cm×15cmの大きさのポリエチレン製液体不透過性シートを液体透過性シートとは反対側の面に貼り付けて、試験用の吸収性物品を得た。
 ii)上記試験用の吸収性物品を、液体透過性シートを貼り付けた面を上側として、吸収性物品の長手方向が縦方向(傾斜板の長手方向)に沿うようにして、アクリル樹脂製の測定容器内の45度の傾斜面に貼り付けた。
 iii)サンプル上部から7.0cmの位置を投入点とし、送液ポンプ81を用いて、液温25±1℃に調整した人工尿40.0mLを流量4mL/秒で鉛直上方1cmの位置から1分おきに注入した。人工尿注入後に、吸収し切れずに測定容器内の底部に溜まった人工尿が完全に吸いきられるまでの時間(秒)を測定し、吸収性物品の液だまり吸収時間(秒)とした。液だまり吸収時間は短い方が好ましく、60秒以内に吸収し終わることができなくなるまでの投入回数を優劣の判断基準とした。
The liquid pool absorption rate test of the absorbent article was carried out in the order of i), ii) and iii) below.
i) 4.2 g of water-absorbent resin particles and 3.9 g of crushed pulp were uniformly mixed by air papermaking to prepare a sheet-shaped absorber having a size of 10 cm × 15 cm. The absorber was placed on tissue paper (same size as the absorber and a basis weight of 16 g / m 2 ), and tissue paper (same size as the absorber and a basis weight of 16 g / m 2 ) was placed on the absorber. A load of 588 kPa was applied to the absorber sandwiched by the tissue paper for 30 seconds. A polyethylene-polypropylene air-through porous liquid permeable sheet having a basis weight of 22 g / m 2 and having the same size as the absorber was placed on the sheet. Further, a polyethylene liquid permeable sheet having a size of 10 cm × 15 cm was attached to the surface opposite to the liquid permeable sheet to obtain an absorbent article for testing.
ii) The absorbent article for the test is made of acrylic resin so that the surface to which the liquid permeable sheet is attached is on the upper side and the longitudinal direction of the absorbent article is along the vertical direction (longitudinal direction of the inclined plate). It was attached to a 45-degree inclined surface in the measuring container.
iii) With a position 7.0 cm from the top of the sample as the input point, 40.0 mL of artificial urine adjusted to a liquid temperature of 25 ± 1 ° C. using a liquid feed pump 81 is 1 from a position 1 cm vertically above at a flow rate of 4 mL / sec. Infused every minute. After the injection of artificial urine, the time (seconds) until the artificial urine accumulated at the bottom of the measuring container without being completely absorbed was completely absorbed was measured and used as the pool absorption time (seconds) of the absorbent article. It is preferable that the liquid pool absorption time is short, and the number of injections until the absorption cannot be completed within 60 seconds was used as a criterion for judging superiority or inferiority.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 表1によれば、ゲル層内部強度を調整することが、液だまり吸収時間が改善された吸収性物品を得ることに有効であることが確認される。 According to Table 1, it is confirmed that adjusting the internal strength of the gel layer is effective in obtaining an absorbent article having an improved liquid pool absorption time.
 10…吸収体、10a,65…吸水性樹脂粒子、10b…繊維層、20a,20b…コアラップ、30…液体透過性シート、40…液体不透過性シート、61…ビュレット部、61a…ビュレット、61b…ゴム栓、61c…コック、61d…空気導入管、61e…コック、62…導管、63…測定台、64…測定部、64a…円筒、64b…ナイロンメッシュ、64c…重り、70…ロードセル、71…治具、72…生理食塩水、73…スターラーチップ、74…膨潤ゲル、80…側板、81…送液ポンプ、100,102…吸収性物品、200…撹拌翼、200a…軸、200b…平板部、S…スリット、S…傾斜面、Y…測定装置。

 
10 ... Absorbent, 10a, 65 ... Water-absorbent resin particles, 10b ... Fiber layer, 20a, 20b ... Core wrap, 30 ... Liquid permeable sheet, 40 ... Liquid permeable sheet, 61 ... Burette part, 61a ... Burette, 61b ... rubber stopper, 61c ... cock, 61d ... air introduction pipe, 61e ... cock, 62 ... conduit, 63 ... measuring table, 64 ... measuring unit, 64a ... cylinder, 64b ... nylon mesh, 64c ... weight, 70 ... load cell, 71 ... Jig, 72 ... Physiological saline, 73 ... Stirrer tip, 74 ... Swelling gel, 80 ... Side plate, 81 ... Liquid feed pump, 100, 102 ... Absorbent article, 200 ... Stirring blade, 200a ... Shaft, 200b ... Flat plate Part, S ... slit, S 0 ... inclined surface, Y ... measuring device.

Claims (5)

  1.  下記の手順により測定されるゲル層内部強度が0.8~2.0Nである、吸水性樹脂粒子。
    (1)直径2cmの平坦面を表裏に有する厚さ5mmの円板部、及び、該円板部の一方の平坦面である第1の面の中央に一端が接続され、横断面が直径5mmの円形である棒状部を備える治具と、生理食塩水176gを入れた底面内径5.7cmの円筒形容器と、を用意し、前記円筒形容器の高さ方向の中心軸が前記円板部の中央に位置するように前記治具及び前記円筒形容器を配置する。
    (2)前記円板部の前記第1の面とは反対側の平坦面である第2の面が前記生理食塩水の水面から鉛直下方32mmとなる位置に前記治具を浸した状態で、前記円筒形容器内に吸水性樹脂粒子4.0gを入れて、前記治具が埋設された膨潤ゲルを形成させる。
    (3)前記治具を鉛直下方に速度10cm/分で6mm押し込んだときに、前記治具に負荷される荷重をゲル層内部強度として得る。
    Water-absorbent resin particles having a gel layer internal strength of 0.8 to 2.0 N measured by the following procedure.
    (1) One end is connected to the center of a disk portion having a thickness of 5 mm having a flat surface having a diameter of 2 cm on the front and back, and the first surface which is one flat surface of the disk portion, and the cross section has a diameter of 5 mm. A jig having a circular rod-shaped portion and a cylindrical container having a bottom inner diameter of 5.7 cm containing 176 g of physiological saline are prepared, and the central axis of the cylindrical container in the height direction is the disk portion. The jig and the cylindrical container are arranged so as to be located at the center of the.
    (2) With the jig immersed in a position where the second surface of the disk portion, which is a flat surface opposite to the first surface, is 32 mm vertically downward from the water surface of the physiological saline solution. 4.0 g of water-absorbent resin particles are placed in the cylindrical container to form a swollen gel in which the jig is embedded.
    (3) When the jig is pushed vertically downward by 6 mm at a speed of 10 cm / min, the load applied to the jig is obtained as the internal strength of the gel layer.
  2.  (メタ)アクリル酸に由来する構造単位及び(メタ)アクリル酸の塩に由来する構造単位からなる群より選ばれる少なくとも一種の構造単位を有する重合体を含む、請求項1に記載の吸水性樹脂粒子。 The water-absorbent resin according to claim 1, which comprises a polymer having at least one structural unit selected from the group consisting of structural units derived from (meth) acrylic acid and structural units derived from salts of (meth) acrylic acid. particle.
  3.  請求項1又は2に記載の吸水性樹脂粒子を含有する、吸収体。 An absorber containing the water-absorbent resin particles according to claim 1 or 2.
  4.  請求項3に記載の吸収体を備える、吸収性物品。 An absorbent article comprising the absorber according to claim 3.
  5.  おむつである、請求項4に記載の吸収性物品。

     
    The absorbent article according to claim 4, which is a diaper.

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