WO2023276925A1 - Composition de résine absorbant l'eau, absorbeur et article absorbant obtenus à l'aide de celle-ci, et procédé de production d'une composition de résine absorbant l'eau - Google Patents

Composition de résine absorbant l'eau, absorbeur et article absorbant obtenus à l'aide de celle-ci, et procédé de production d'une composition de résine absorbant l'eau Download PDF

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Publication number
WO2023276925A1
WO2023276925A1 PCT/JP2022/025497 JP2022025497W WO2023276925A1 WO 2023276925 A1 WO2023276925 A1 WO 2023276925A1 JP 2022025497 W JP2022025497 W JP 2022025497W WO 2023276925 A1 WO2023276925 A1 WO 2023276925A1
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Prior art keywords
water
resin composition
group
general formula
absorbent resin
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PCT/JP2022/025497
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English (en)
Japanese (ja)
Inventor
裕城 星山
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Ｓｄｐグローバル株式会社
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Priority to JP2023531920A priority Critical patent/JPWO2023276925A1/ja
Priority to CN202280037895.9A priority patent/CN117413028A/zh
Publication of WO2023276925A1 publication Critical patent/WO2023276925A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions 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
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a water absorbent resin composition, absorbent bodies and absorbent articles using the same, and a method for producing a water absorbent resin composition.
  • water-absorbing resin compositions mainly composed of hydrophilic fibers such as pulp and acrylic acid (salt) are widely used as absorbents.
  • the water-absorbing resin composition used for these applications is required to have a high water retention capacity, high gel stability, and low soluble content and non-stickiness. increases, and the feeling of stickiness after use tends to increase.
  • An object of the present invention is to provide a water-absorbing resin composition capable of suppressing change in soluble content while suppressing change in color after long-term storage in a hot and humid environment, and an absorbent body using the same. and to provide an absorbent article and a method for producing a water absorbent resin composition.
  • the present invention a water-soluble vinyl monomer (a1) and/or a vinyl monomer (a2) that becomes a water-soluble vinyl monomer (a1) by hydrolysis, and a crosslinked polymer (A) containing a crosslinking agent (b) as essential structural units;
  • a compound (B) and/or a salt thereof which is one or more selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2); and one or more typical elements selected from the group consisting of iodine, tellurium, antimony and bismuth.
  • X is a single bond or a methylene group
  • R 1 is a COH or nitrogen atom
  • R 2 is a carbon atom or POH
  • R 3 is a methyl group, a carboxy group, or the following general It is an organic group represented by formula (1-1).
  • R 2 is a carbon atom or POH.
  • R 4 is a carbon atom or POH
  • R 5 is R 4 OOH or an organic group represented by the following general formula (2-1).
  • a water-absorbing resin composition capable of suppressing change in soluble content while suppressing change in color after long-term storage in a hot and humid environment, and an absorbent using the same and an absorbent article, and a method for producing a water absorbent resin composition can be provided.
  • the water-absorbing resin composition of the present embodiment (hereinafter, the water-absorbing resin composition of the present embodiment is referred to as water-absorbing resin composition ⁇ ) is a water-soluble vinyl monomer (a1) and/or a vinyl monomer (a2) that becomes a water-soluble vinyl monomer (a1) by hydrolysis, and a crosslinked polymer (A) containing a crosslinking agent (b) as essential structural units; A compound (B) and/or a salt thereof, which is one or more selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2); and one or more typical elements selected from the group consisting of iodine, tellurium, antimony and bismuth.
  • X is a single bond or a methylene group
  • R 1 is a COH or nitrogen atom
  • R 2 is a carbon atom or POH
  • R 3 is a methyl group, a carboxy group, or the following general It is an organic group represented by formula (1-1).
  • R 2 is a carbon atom or POH.
  • R 4 is a carbon atom or POH
  • R 5 is R 4 OOH or an organic group represented by the following general formula (2-1).
  • the water-absorbing resin composition ⁇ it is possible to suppress changes in soluble matter while suppressing changes in color after long-term storage in a hot and humid environment. Although the reason why the water-absorbing resin composition ⁇ exhibits such an effect is not clear, radicals are generated by the metal when the metal ions contained as impurities in the water-absorbing resin composition and the compound (B) are combined. It is considered that the suppression suppresses the decomposition of the polymer chains, and suppresses the change in color and the change in the soluble content.
  • the water-soluble vinyl monomer (a1) is not particularly limited, and known monomers, for example, at least one water-soluble substituent and an ethylenically unsaturated group disclosed in paragraphs 0007 to 0023 of Japanese Patent No.
  • vinyl monomers e.g., anionic vinyl monomers, nonionic vinyl monomers and cationic vinyl monomers
  • anionic vinyl monomers disclosed in paragraphs 0009 to 0024 of JP-A-2003-165883 nonionic vinyl At least selected from the group consisting of monomers and cationic vinyl monomers and carboxy groups, sulfo groups, phosphono groups, hydroxyl groups, carbamoyl groups, amino groups and ammonio groups disclosed in paragraphs 0041 to 0051 of JP-A-2005-75982
  • Vinyl monomers having one can be used.
  • a vinyl monomer (a2) that becomes the water-soluble vinyl monomer (a1) by hydrolysis [hereinafter also referred to as a hydrolyzable vinyl monomer (a2). ] can be used with or instead of the water-soluble vinyl monomer (a1).
  • the hydrolyzable vinyl monomer (a2) is not particularly limited, and includes at least one hydrolyzable substituent that becomes a water-soluble substituent upon hydrolysis as disclosed in Japanese Patent No. 3648553, paragraphs 0024 to 0025. at least one hydrolyzable substituent [1,3-oxo-2-oxapropylene (-CO-O-CO- ) groups, acyl groups, cyano groups, etc.] can be used.
  • the water-soluble vinyl monomer means a vinyl monomer that dissolves at least 100 g in 100 g of water at 25°C.
  • the hydrolyzability of the hydrolyzable vinyl monomer (a2) means the property of being hydrolyzed by the action of water and, if necessary, a catalyst (acid, base, etc.) to become water-soluble.
  • the hydrolysis of the hydrolyzable vinyl monomer (a2) may be performed during polymerization, after polymerization, or at both of these times, but from the viewpoint of the absorption performance of the resulting water-absorbent resin composition ⁇ , it is preferably performed after polymerization. .
  • the water-soluble vinyl monomer (a1) is preferable from the viewpoint of absorption performance, etc., and anionic vinyl monomers, carboxy (salt) groups, sulfo (salt) groups, amino groups, carbamoyl groups, and ammonio are more preferable. or a mono-, di- or tri-alkylammonio group, more preferably a vinyl monomer having a carboxy (salt) group or a carbamoyl group, particularly preferably (meth)acrylic acid (salt) and ( Meth)acrylamide, especially preferred (meth)acrylic acid (salt), most preferred acrylic acid (salt).
  • salts include alkali metal (lithium, sodium, potassium, etc.) salts, alkaline earth metal (magnesium, calcium, etc.) salts, ammonium (NH 4 ) salts, and the like. Among these salts, alkali metal salts and ammonium salts are preferable, alkali metal salts are more preferable, and sodium salts are particularly preferable, from the viewpoint of absorption performance and the like.
  • each one type may be used alone as a structural unit, and if necessary, two or more types may be used as a structural unit. It is good as The same applies to the case where the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2) are used as structural units.
  • the molar ratio [(a1)/(a2)] of these is 75/25 to 99/1. is preferred, more preferably 85/15 to 95/5, particularly preferably 90/10 to 93/7, most preferably 91/9 to 92/8. Within this range, the absorption performance is further improved.
  • crosslinked polymer (A) in addition to the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2), other vinyl monomers (a3) copolymerizable therewith are structural units.
  • the vinyl monomer (a3) is not particularly limited, and is known (for example, hydrophobic vinyl monomers disclosed in paragraphs 0028 to 0029 of Japanese Patent No. 3648553; 2005-75982, paragraph 0058) can be used, and specifically, vinyl monomers (i) to (iii) below can be used.
  • (i) Aromatic ethylenic monomer having 8 to 30 carbon atoms Styrene such as styrene, ⁇ -methylstyrene, vinyltoluene and hydroxystyrene, vinylnaphthalene, and halogen-substituted styrene such as dichlorostyrene.
  • Aliphatic ethylenic monomers having 2 to 20 carbon atoms Alkenes (ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.); and alkadienes (butadiene, isoprene, etc.).
  • the content (mol%) of the vinyl monomer (a3) units is based on the total number of moles of the water-soluble vinyl monomer (a1) units and the hydrolyzable vinyl monomer (a2) units from the viewpoint of absorption performance and the like. , preferably 0 to 5, more preferably 0 to 3, particularly preferably 0 to 2, particularly preferably 0 to 1.5, and from the viewpoint of absorption performance etc., the content of the vinyl monomer (a3) unit is 0 mol % is most preferred.
  • the cross-linking agent (b) is not particularly limited and is known (for example, a cross-linking agent having two or more ethylenically unsaturated groups disclosed in paragraphs 0031 to 0034 of Japanese Patent No.
  • a water-soluble substituent and a A cross-linking agent having at least one functional group capable of reacting with at least one ethylenically unsaturated group and a cross-linking agent having at least two functional groups capable of reacting with a water-soluble substituent
  • JP-A-2003-165883 A cross-linking agent having two or more ethylenically unsaturated groups, a cross-linking agent having an ethylenically unsaturated group and a reactive functional group, and a cross-linking having two or more reactive substituents disclosed in paragraphs 0028 to 0031 of the publication crosslinkable vinyl monomers disclosed in paragraph 0059 of JP-A-2005-75982 and crosslinkable vinyl monomers disclosed in paragraphs 0015-0016 of JP-A-2005-95759). can.
  • the cross-linking agent (b) is preferably a cross-linking agent having two or more ethylenically unsaturated groups, and suppresses change in soluble matter while suppressing color change after long-term storage in a hot and humid environment.
  • One or more selected from the group consisting of compounds and compounds represented by the following general formula (3) are preferable, and pentaerythritol triallyl ether is more preferable.
  • the said crosslinking agent (b) may be used individually by 1 type, or may use 2 or more types together.
  • R 6 and R 7 are each independently a hydrogen atom or a methyl group.
  • X 1 is an n-valent organic group having an aliphatic group having 1 or more carbon atoms and optionally containing a nitrogen atom, an oxygen atom, or a sulfur atom, and the aliphatic group may be linear or branched. may have.
  • n is an integer from 2 to 6; ]
  • R6 and R7 are each independently a hydrogen atom or a methyl group.
  • R 6 and R 7 are preferably hydrogen atoms from the viewpoint of good polymerization reactivity.
  • X 1 is an n-valent organic group having an aliphatic group having 1 or more carbon atoms and optionally containing a nitrogen atom, an oxygen atom or a sulfur atom.
  • the aliphatic group may be linear or branched.
  • the aliphatic group is from —O— and —NX 2 — (wherein X 2 is a hydrogen atom, an alkyl group, or a (meth)acryloyl group). It is preferable that they are linked via a selected divalent linking group.
  • the linking group is preferably one or more selected from —O— and —NX 2 — (where X 2 is a (meth)acryloyl group) from the viewpoint of absorption performance and the like.
  • the number of linking groups is preferably 1 to 4, more preferably 1 to 3, from the viewpoint of absorption performance and the like.
  • n is an integer of 2 to 6, and preferably an integer of 2 to 4 from the viewpoint of absorption performance and the like.
  • X 1 is preferably an organic group represented by the following general formula (b1) or the following general formula (b2) from the viewpoint of absorption performance and the like.
  • R 8 is an alkylene group having 1 to 6 carbon atoms
  • R 9 is a hydrogen atom or a methyl group
  • x is an integer of 2 to 4
  • r is an integer of 1 to 6
  • R 10 is a single bond or an alkylene group having 1 to 6 carbon atoms.
  • R 11 is an alkylene group having 1 to 3 carbon atoms
  • y is an integer of 2 to 4
  • s is an integer of 1 to 6
  • R 12 is a single bond or an alkylene group having 1 to 3 carbon atoms. be.
  • R 8 is an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an ethylene group, from the viewpoint of availability of raw materials.
  • R 9 is a hydrogen atom or a methyl group, preferably a hydrogen atom, from the viewpoint of good polymerization reactivity.
  • x is an integer of 2 to 4, preferably 2 or 3, more preferably 2, from the viewpoint of availability of raw materials.
  • r is an integer of 1 to 6, preferably 1 or 2, from the viewpoint of availability of raw materials.
  • R 10 is a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond, from the viewpoint of availability of raw materials.
  • R 11 is an alkylene group having 1 to 3 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms, and more preferably a propylene group, from the viewpoint of availability of raw materials.
  • y is an integer of 2 to 4, preferably 3, from the viewpoint of raw material availability.
  • s is an integer of 1 to 6, preferably 2 to 5, more preferably 3 or 4, from the viewpoint of availability of raw materials.
  • R 12 is a single bond or an alkylene group having 1 to 3 carbon atoms, preferably a methylene group, from the viewpoint of availability of raw materials.
  • cross-linking agent (b) when X 1 is an organic group represented by the general formula (b1), a specific example of the cross-linking agent (b) is represented by the following general formula (b1-1) Cross-linking agents (b1-1), cross-linking agents (b1-2) represented by the following general formula (b1-2), and the like.
  • a specific example of the cross-linking agent (b) when X 1 is an organic group represented by the general formula (b2) is represented by the following general formula (b2-1).
  • X 1 is preferably an organic group represented by the following general formula (b3) from the viewpoint of absorption performance and the like.
  • R 13 is a single bond or an alkylene group having 1 to 3 carbon atoms, preferably an alkylene group having 1 to 2 carbon atoms, more preferably a methylene group, from the viewpoint of availability of raw materials. preferable.
  • z is an integer of 2 to 4, preferably 2 or 3, more preferably 2, from the viewpoint of raw material availability.
  • t is an integer of 1 to 6, preferably an integer of 1 to 4, more preferably 1, from the viewpoint of availability of raw materials.
  • R 14 is a single bond or an alkylene group having 1 to 3 carbon atoms, preferably an alkylene group having 1 or 2 carbon atoms, more preferably a methylene group, from the viewpoint of availability of raw materials. preferable.
  • X 1 is an organic group represented by the general formula (b3)
  • a specific example of the cross-linking agent (b) is represented by the following general formula (b3-1).
  • examples thereof include a cross-linking agent (b3-1) and a cross-linking agent (b3-2) represented by the following general formula (b3-2).
  • Examples of commercially available products of the compound represented by the general formula (3) include methylenebisacrylamide and FOM-03006, FOM-03007, FOM-03008, and FOM-03009 manufactured by Fujifilm Corporation.
  • the proportion of the substance amount of the cross-linking agent (b) in the cross-linked polymer (A) is the sum of the water-soluble vinyl monomer (a1) units and the hydrolyzable vinyl monomer (a2) units.
  • vinyl monomer (a3) is preferably 0.001 to 5 mol parts, more preferably 0.005 to 1 mol part, per 100 mol parts in total of (a1) to (a3).
  • the compound (B) is one or more selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2).
  • X is a single bond or a methylene group from the viewpoint of suppressing change in soluble matter while suppressing change in color after long-term storage in a hot and humid environment, A single bond is preferred.
  • R 1 is COH or a nitrogen atom from the viewpoint of suppressing change in soluble matter while suppressing change in color after long-term storage in a hot and humid environment, COH is preferred.
  • R 2 is a carbon atom or POH from the viewpoint of suppressing change in soluble content while suppressing change in color after long-term storage in a hot and humid environment, POH is preferred.
  • R 3 is a methyl group, a carboxy group, or It is an organic group represented by the general formula (1-1), preferably a methyl group or a carboxy group, more preferably a methyl group.
  • R 4 is a carbon atom or POH from the viewpoint of suppressing change in soluble content while suppressing change in color after long-term storage in a hot and humid environment, Carbon atoms are preferred.
  • R 5 is R 4 OOH from the viewpoint of suppressing change in soluble content while suppressing change in color after long-term storage in a hot and humid environment.
  • it is an organic group represented by the general formula (2-1), preferably an organic group represented by the general formula (2-1).
  • the salt of the compound (B) is preferably a monovalent salt selected from alkali metal salts, ammonium salts and amine salts of the compound (B), more preferably an alkali metal salt, and sodium salt, lithium salt and potassium salt. Selected alkali metal salts are more preferred.
  • the compound (B) include citric acid, 1-hydroxyethane-1,1-diphosphonic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotrimethylphosphonic acid, and ethylenediaminetetramethylenephosphonic acid. be done.
  • citric acid, 1-hydroxyethane-1 from the viewpoint of suppressing changes in soluble matter and cost effectiveness while suppressing changes in color after long-term storage in a hot and humid environment.
  • 1-diphosphonic acid and diethylenetriaminepentaacetic acid are preferred, and 1-hydroxyethane-1,1-diphosphonic acid is more preferred.
  • the content of the compound (B) and its salt is, from the viewpoint of suppressing changes in soluble matter while suppressing changes in color after long-term storage in a hot and humid environment,
  • the total amount of the salts is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, relative to 100 parts by weight of the crosslinked polymer (A), and 2.0 parts by weight from the viewpoint of cost effectiveness. parts by weight or less is preferable, and 1.0 parts by weight or less is more preferable.
  • the water absorbent resin composition ⁇ contains at least one typical element selected from the group consisting of iodine, tellurium, antimony and bismuth from the viewpoint of suppressing coloration.
  • the content of the typical element in the solid content of the water absorbent resin composition is preferably 0.0005 to 1.0% by weight, from the viewpoint of suppressing coloring and water absorption performance, and 0.005 to 0.5% by weight is more preferred.
  • the content of the typical element in the solid content of the water absorbent resin composition is measured by the method described in Examples.
  • the typical element is preferably iodine from the viewpoint of suppressing coloration.
  • the iodine contained in the water absorbent resin composition ⁇ may be contained in the form of an iodine compound.
  • non-metal salts of iodine, metal salts, and the like can be used.
  • nonmetallic salts of iodine include various imidazole salt compounds (e.g., 1-methyl-3-methyl-imidazolium iodide (EMIZI), 1-ethyl-3-methylimidazolium bromide (EMIZBr)), various pyridine salt compounds ( For example, 2-chloro-1-methylpyridinium iodide (CMPI)), various quaternary amine salt compounds (for example, tetrabutylammonium iodide (BNI), tetrabutylammonium triiodide (BNI3), tributylsulfonium iodide ( BSI), diphenyliodonium iodide (PII), various phosphonium salt compounds (e.g., methyltributylphosphonium iodide (BMPI),
  • EMIZI 1-methyl
  • the water absorbent resin composition ⁇ preferably has a structure in which the surface of the crosslinked polymer (A) is crosslinked by the surface crosslinking agent (d).
  • the gel strength of the water-absorbing resin composition ⁇ can be improved, and the water-absorbing resin composition ⁇ satisfies the desired water retention amount and the absorption amount under load.
  • the surface cross-linking agent (d) can be inorganic or organic.
  • the surface cross-linking agent (d) known (polyvalent glycidyl compounds, polyvalent amines, polyvalent aziridine compounds and polyvalent isocyanate compounds described in JP-A-59-189103, etc., JP-A-58-180233 And the polyhydric alcohol of JP-A-61-16903, the silane coupling agent described in JP-A-61-211305 and JP-A-61-252212, the JP-A-5-508425 described Organic surface cross-linking agents such as alkylene carbonates and polyvalent oxazoline compounds described in JP-A-11-240959 can be used.
  • polyhydric glycidyl compounds, polyhydric alcohols and polyhydric amines are preferred from the viewpoint of economy and absorption properties, more preferred are polyhydric glycidyl compounds and polyhydric alcohols, and particularly preferred are polyhydric glycidyl compounds and polyhydric alcohols.
  • the surface cross-linking agent (d) may be used alone or in combination of two or more.
  • the water-absorbing resin composition ⁇ may contain some other components such as residual solvent and residual cross-linking components within a range that does not impair its performance.
  • the other components include preservatives, antifungal agents, antibacterial agents, ultraviolet absorbers, antioxidants, colorants, fragrances, deodorants, liquid permeability improvers, inorganic powders and organic fibers. and the like.
  • the amount is usually 5% by weight or less based on the weight of the water absorbent resin composition ⁇ .
  • the water-absorbing resin composition ⁇ is preferably under the following conditions (1) and (2). ).
  • Condition (1) The amount of change in the YI value before and after the deterioration test is 20 or less, preferably 10 or less, more preferably 4 or less
  • Condition (2) The amount of change in the soluble content before and after the deterioration test is 15 or less, preferably 5 or less, more preferably 1.5 or less
  • the YI value of the water absorbent resin composition ⁇ before the deterioration test is preferably 8 or less. If the YI value of the water absorbent resin composition ⁇ before the deterioration test exceeds 8, there is a tendency for complaints due to appearance to occur. Further, in the present specification, the deterioration test, the amount of change in the YI value, and the amount of change in the soluble content are performed by the methods described in Examples.
  • the shape of the water absorbent resin composition ⁇ is not particularly limited, but from the viewpoint of improving the absorption performance, it is preferably in the form of particles.
  • the weight average particle diameter ( ⁇ m) of the particulate water absorbent resin composition ⁇ (hereinafter also referred to as water absorbent resin composition ⁇ particles) is preferably 250 to 600, more preferably 300 to 500, and still more preferably. is 340-460.
  • the weight-average particle size is less than 250 ⁇ m, the liquid permeability deteriorates, and when it exceeds 600 ⁇ m, the absorption speed deteriorates.
  • the weight average particle size was measured using a low-tap test sieve shaker and a standard sieve (JISZ8801-1:2006), Perry's Chemical Engineers Handbook 6th Edition (McGraw-Hill Book Company, 1984, page 21). That is, JIS standard sieves of 1000 ⁇ m, 850 ⁇ m, 710 ⁇ m, 500 ⁇ m, 425 ⁇ m, 355 ⁇ m, 250 ⁇ m, 150 ⁇ m, 125 ⁇ m, 75 ⁇ m and 45 ⁇ m and a saucer are combined in this order from the top. About 50 g of the particles to be measured are placed in the top sieve and shaken for 5 minutes with a Rotap test sieve shaker.
  • the weight of the particles to be measured on each sieve and the tray is weighed, the total is 100% by weight, and the weight fraction of the particles on each sieve is obtained. ) and the weight fraction on the vertical axis], draw a line connecting the points, determine the particle diameter corresponding to a weight fraction of 50% by weight, and take this as the weight average particle diameter.
  • the water-absorbent resin having a particle diameter of less than 150 ⁇ m in the total weight of all the water-absorbent resin composition ⁇ -particles The weight ratio (% by weight) of the composition ⁇ -particles is 3 or less, preferably 1 or less.
  • the weight ratio of the water-absorbing resin composition ⁇ particles having a particle size of less than 150 ⁇ m can be determined using the graph prepared when determining the weight average particle size.
  • the shape of the ⁇ -particles of the water-absorbing resin composition is not particularly limited, and examples thereof include irregular crushed shape, scaly shape, pearl-like shape, rice grain-like shape, and the like. Of these, irregularly crushed forms are preferred from the viewpoints of good entanglement with fibrous materials for use in paper diapers and the like, and no fear of falling off from fibrous materials.
  • the content of the crosslinked polymer (A) in the water absorbent resin composition ⁇ is preferably 50% by weight or more, more preferably 60% by weight or more, from the viewpoint of obtaining a water absorbent resin composition having sufficient water retention capacity. preferable.
  • the content of the crosslinked polymer (A) in the water absorbent resin composition ⁇ is preferably 99.5% by weight or less, more preferably 99% by weight or less.
  • the water retention capacity (g/g) of the water absorbent resin composition ⁇ is preferably 25 or more, more preferably 28 or more, and particularly preferably 32 or more, from the viewpoint of absorption capacity. Moreover, the upper limit is preferably 60 or less, more preferably 55 or less, and particularly preferably 50 or less, from the viewpoint of stickiness.
  • the amount of water retention can be appropriately adjusted by the amount (% by weight) of the cross-linking agent (b) and the surface cross-linking agent (d) used.
  • the water retention capacity (g/g) of the water absorbent resin composition ⁇ can be measured by the method described in Examples.
  • the absorbency under load (g/g) of the water absorbent resin composition ⁇ is preferably 10 or more, more preferably 15 or more, and particularly preferably 20 or more from the viewpoint of the absorbency of the diaper under load. be. It is empirically known that the absorbency under load conflicts with the water retention capacity, and there are cases where a high water retention capacity is required and cases where a high absorption capacity under load is required depending on the configuration of the diaper.
  • the absorption under load (g/g) of the water absorbent resin composition ⁇ can be measured by the method described in Examples.
  • the soluble content (% by weight) of the water absorbent resin composition ⁇ is preferably less than 20%, more preferably less than 15%, relative to the water absorbent resin composition ⁇ , from the viewpoint of liquid permeability and water absorption rate. . If the soluble content exceeds 20%, the soluble content will be eluted at the time of water absorption, resulting in gel blocking and adversely affecting liquid permeability and water absorption capacity, which is undesirable.
  • the soluble content (% by weight) of the water absorbent resin composition ⁇ can be measured by the method described in Examples.
  • the deterioration index of the water-absorbing resin composition ⁇ is preferably 60 or less from the viewpoint of suppressing change in soluble matter while suppressing change in color after long-term storage in a hot and humid environment, and 30 Below is more preferable, 15 or less is still more preferable, and 4.0 or less is particularly preferable. If the deterioration index exceeds 60, it becomes difficult to achieve both color and control of soluble matter, and complaints due to stickiness and appearance tend to occur when sanitary materials such as diapers are used.
  • the deterioration index is a value that indicates how much change in color and change in soluble matter after long-term storage is suppressed, and how sticky sanitary products such as diapers are when used after long-term storage. Indicates whether the increase and color change can be suppressed.
  • the method for producing the water absorbent resin composition ⁇ of the first embodiment includes: A method for producing the water absorbent resin composition ⁇ having a polymerization step of obtaining a hydrous gel containing the crosslinked polymer (A), In the polymerization step, the polymerization of the monomer composition is performed in the presence of an organic main group element compound represented by the following general formula (4), It is characterized by having an addition step B of adding the compound (B) and/or a salt thereof after the polymerization step.
  • X3 is iodine, tellurium, antimony or bismuth
  • R15 is -COOX4 , -CONR18R19 , an aromatic group, or a cyano group
  • X4 is a hydrogen atom, an aliphatic group, an alkali metal, an alkaline earth metal, an organic ammonium, or an ammonium
  • R 16 , R 17 , R 18 , and R 19 are each independently a hydrogen atom, an aromatic group, or an aliphatic group.
  • a monomer composition containing the water-soluble vinyl monomer (a1) and/or the hydrolyzable vinyl monomer (a2) and the crosslinking agent (b) is polymerized to form the crosslinked polymer (A) It is a step of obtaining a hydrous gel containing
  • the monomer composition is polymerized with the organic main group element compound represented by the general formula (4) to improve the gel strength, the absorption amount under load, and the gel permeation rate at the time of water absorption.
  • X3 is iodine, tellurium, antimony, or bismuth, and iodine is preferable from the viewpoint of improving gel strength, absorption under load, and gel permeation rate when water is absorbed.
  • R 15 is —COOX 4 , —CONR 18 R 19 , an aromatic group, or a cyano group
  • X 4 is a hydrogen atom, an aliphatic group, an alkali metal, an alkaline earth metal, or an organic ammonium. , or ammonium
  • R 16 , R 17 , R 18 , and R 19 are each independently a hydrogen atom, an aromatic group, or an aliphatic group.
  • the aliphatic group for R 16 , R 17 , R 18 , R 19 and X 4 is an optionally substituted linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aliphatic hydrocarbon group having 3 to 12 carbon atoms. and preferably a linear or branched alkyl group having 1 to 12 carbon atoms.
  • the number of substituents is not particularly limited as long as it can be substituted, and is one or more.
  • Linear or branched aliphatic hydrocarbon groups having 1 to 12 carbon atoms include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-octyl and n-dodecyl groups, etc.) and branched Alkyl groups (such as isopropyl, isobutyl, sec-butyl, tert-butyl, and 2-ethylhexyl groups) can be mentioned.
  • Examples of alicyclic hydrocarbon groups having 3 to 12 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, bicyclohexyl group, cyclooctyl group, cyclohexylmethyl group, cyclohexylethyl group and methylcyclohexyl group. be done.
  • the group that may be substituted for the aliphatic group includes a halogen atom, a hydroxyl group, an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms, and an optionally substituted aromatic group.
  • Alkali metals, alkaline earth metals , and organic ammonium in X3 include alkali metals: sodium, potassium, etc., alkaline earth metals: calcium, magnesium, etc., and organic ammonium: trimethylammonium, tetramethylammonium, triethylammonium, ethyltrimethylammonium. , tetraethylammonium, and the like.
  • the aromatic group for R 15 , R 16 , R 17 , R 18 and R 19 includes an aromatic hydrocarbon ring group, an aromatic heterocyclic group, etc. Specific examples include a phenyl group, a biphenylyl group, a terphenylyl group, naphthyl group, binaphthyryl group, azulenyl group, anthracenyl group, phenanthrenyl group, furyl group, thienyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, isoxazolyl group, thiazolyl group, thiadiazolyl group, pyridyl group, benzofuranyl group, indolyl group, benzothiazolyl group , a carbazolyl group, and the like.
  • This aromatic group may be substituted, and the number of substituents in this case is not particularly limited as long as it can be substituted, and is one or more.
  • groups that may be substituted for the aromatic group include halogen atoms, hydroxyl groups, optionally substituted linear or branched alkyl groups having 1 to 12 carbon atoms, and optionally substituted aromatic groups.
  • linear or branched C 1-12 alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
  • linear or branched C 1-12 alkoxy groups include methoxy, ethoxy, propoxy, butoxy, isopropoxy, isobutoxy, tert-butoxy, and sec-butoxy. group, isopentyloxy group, neopentyloxy group, tert-pentyloxy group, 1,2-dimethylpropoxy group and the like.
  • halogen atoms include atoms such as fluorine, chlorine, bromine and iodine atoms.
  • a non-aromatic heterocyclic group is a monocyclic, bicyclic or tricyclic 5- to 14-membered non-aromatic group containing one or more heteroatoms selected from the group consisting of nitrogen, sulfur and oxygen atoms.
  • Specific examples of such groups include pyrrolidinyl, pyrrolyl, piperidinyl, piperazinyl, imidazolyl, pyrazolidyl, imidazolidyl, morpholyl, tetrahydrofuryl, tetrahydropyranyl, pyrrolinyl, and dihydrofuryl. group, dihydropyranyl group, imidazolinyl group, oxazolinyl group, and the like.
  • two or more groups among R 16 , R 17 , R 18 , R 19 and X 4 are bonded to each other to form a saturated or unsaturated 5- or 6-membered ring; may For example, (i) Ring to which R 16 and R 17 are bonded: cyclopentane ring, pyrrolidine ring, oxazolidine ring, thiazolidine ring, tetrahydrofuran ring, cyclohexane ring, dioxane ring, tetrahydrothiophene ring, etc.
  • R 18 and R 19 are bonded Ring: pyrrolidine ring, pyrrole ring, triazole ring, piperidine ring, piperazine ring, piperazinone ring, morpholine ring, etc.
  • Ring in which X4 and R16 or R17 are bonded: ⁇ - butyrolactone ring, ⁇ -valerolactone ring, etc. Ring in which R 16 and R 18 are bonded: 2-pyrrolidone ring, succinimide ring, 2-piperidone ring, glutarimide ring and the like can be mentioned.
  • the organic main group element compound represented by the general formula (4) preferably has a solubility in water of 0.5% by weight or more at 20°C from the viewpoint of handling property during radical polymerization and molecular weight control.
  • the polymerization is preferably performed in the presence of water from the same viewpoint.
  • the organic main group element compound having a solubility in water of 0.5% by weight or more at 20° C. includes a hydrophilic functional group (specifically, carboxyl group and salts thereof, hydroxyl group, amide group, etc.), and may further have a group that does not inhibit hydrophilicity.
  • a hydrophilic functional group specifically, carboxyl group and salts thereof, hydroxyl group, amide group, etc.
  • at least one of R 15 to R 17 has a hydrophilic functional group or has a hydrophilic functional group as a substituent, and at least one of R 15 to R 17 has a hydrophilic functional group.
  • it may alternatively have a group that does not have a hydrophilic functional group but does not interfere with the hydrophilicity.
  • Such compounds include 2-iodoacetic acid, 2-iodopropionic acid, 2-iodopropionitrile, 2-iodopropionic amide, 2-iodo-2-methylpropionic acid, 2-iodo-2-methylpropionate.
  • the amount of the organic main group element compound used is the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2) from the viewpoint of improving the gel strength at the time of water absorption, the absorption amount under load, and the gel flow rate.
  • the weight of (a1) to (a3) is preferably 0.0005 to 0.1% by weight, more preferably 0.005 to 0.05% by weight. %.
  • Examples of the method for polymerizing the monomer composition include known solution polymerization and known reversed-phase suspension polymerization.
  • the solution polymerization method preferred is the solution polymerization method, and particularly preferred is the aqueous solution polymerization method because it does not require the use of an organic solvent or the like and is advantageous in terms of production cost.
  • the aqueous solution adiabatic polymerization method is most preferable because it provides a water-absorbing resin composition ⁇ containing a large amount of water and a small amount of water-soluble components, and does not require temperature control during polymerization.
  • the monomer composition is polymerized by aqueous solution polymerization
  • a mixed solvent containing water and an organic solvent can be used, and the organic solvent includes methanol, ethanol, acetone, methyl ethyl ketone, N,N-dimethylformamide, Dimethylsulfoxide and mixtures of two or more thereof may be mentioned.
  • the amount (% by weight) of the organic solvent used is preferably 40 or less, more preferably 30 or less based on the weight of water.
  • radical polymerization catalysts can be used, for example, azo compounds [azobisisobutyronitrile, azobiscyanovaleric acid and 2,2′-azobis(2-amidinopropane) hydrochloride etc.], inorganic peroxides (hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate, etc.), organic peroxides [benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, persuccinic acid oxide and di(2-ethoxyethyl) peroxydicarbonate, etc.] and redox catalysts (alkali metal sulfites or bisulfites, ammonium sulfite, ammonium bisulfite and reducing agents such as ascorbic acid and alkali metal persulfates, A combination with an oxidizing agent such as ammonium persulfate, hydrogen peroxid
  • the amount (% by weight) of the radical polymerization catalyst used is the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2). Preferably 0.0005 to 5, more preferably 0.001 to 2, based on total weight.
  • a polymerization control agent such as a chain transfer agent may be used in combination as necessary.
  • a polymerization control agent such as a chain transfer agent
  • Specific examples thereof include sodium hypophosphite, sodium phosphite, alkyl mercaptan, alkyl halide, thiocarbonyl compound etc.
  • These polymerization control agents may be used alone, or two or more of them may be used in combination.
  • the amount (% by weight) of the polymerization control agent used is the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2). Preferably 0.0005 to 5, more preferably 0.001 to 2, based on total weight.
  • polymerization may be carried out in the presence of a conventionally known dispersant or surfactant, if necessary.
  • the polymerization can be carried out using conventionally known hydrocarbon solvents such as xylene, normal hexane and normal heptane.
  • the polymerization initiation temperature can be appropriately adjusted depending on the type of catalyst used, but is preferably 0 to 100°C, more preferably 2 to 80°C.
  • the solvent organic solvent, water, etc.
  • the content (% by weight) of the organic solvent after distillation is preferably 0 to 10, more preferably 0 to 5, particularly preferably 0 to 5, based on the weight of the crosslinked polymer (A). is 0-3, most preferably 0-1. Within this range, the absorption performance of the water absorbent resin composition ⁇ is further improved.
  • the water content (% by weight) after distillation is preferably 0 to 20, more preferably 1 to 10, particularly preferably 2 to 9, based on the weight of the crosslinked polymer (A). Most preferably 3-8. Within this range, the absorption performance is further improved.
  • a water-containing gel-like substance (hereinafter also referred to as a water-containing gel) in which the crosslinked polymer (A) contains water can be obtained by the polymerization method described above.
  • the water-containing gel may be neutralized with a base.
  • the degree of neutralization of acid groups is preferably 50 to 80 mol %. If the degree of neutralization is less than 50 mol %, the resulting hydrous gel polymer will have high adhesiveness, and workability during production and use may deteriorate. Furthermore, the water-retaining capacity of the obtained water-absorbent resin composition ⁇ may decrease. On the other hand, if the degree of neutralization exceeds 80%, the resulting resin will have a high pH and may be unsafe for human skin.
  • the neutralization may be carried out at any stage after the polymerization of the crosslinked polymer (A) in the production of the water-absorbing resin composition ⁇ . Illustrated as an example.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkali metal carbonates such as sodium carbonate, sodium hydrogencarbonate and potassium carbonate
  • the content and moisture of the organic solvent were measured by a heat drying moisture meter [MS-70 manufactured by A&D Co., Ltd., setting temperature: 120 ° C., setting time: 45 minutes, atmospheric temperature and humidity before heating: 25 ⁇ 2°C, 50 ⁇ 10% RH].
  • the compound (B) suppresses changes in soluble matter while suppressing changes in color after long-term storage in a hot and humid environment. It is added after the polymerization step from the point of view and from the point of view of widening the substrate selectivity during polymerization.
  • the method of adding the compound (B) is not particularly limited.
  • a method of cutting, a method of kneading the water absorbent resin composition obtained in the drying step (described later) and the compound (B), and a surface cross-linking step (described later) with the crosslinked polymer (A) and the surface cross-linking agent (d) A method of mixing with the compound (B) can be exemplified.
  • Methods for kneading the hydrous gel and the compound (B) include a cylindrical mixer, a screw mixer, a screw extruder, a turbulizer, a Nauta mixer, a twin-arm kneader, a fluid mixer, The hydrogel and the compound (B ) and uniformly mixed.
  • the method for producing the water-absorbent resin composition ⁇ of the present embodiment may have a shredding step of shredding the water-containing gel, if necessary.
  • the size (maximum diameter) of the gel after shredding is preferably 50 ⁇ m to 10 cm, more preferably 100 ⁇ m to 2 cm, particularly preferably 1 mm to 1 cm. Within this range, the drying property in the drying process is further improved.
  • the weight average particle size (D50) of the gel after shredding is preferably 10 ⁇ m to 5000 ⁇ m, more preferably 100 ⁇ m to 4000 ⁇ m, and particularly preferably 200 ⁇ m to 3000 ⁇ m. Within this range, the drying property in the drying step is further improved.
  • the gel weight average particle size can be measured by the method described in WO2011/126079.
  • Shredding can be performed by a known method, and can be performed using a shredding device (eg, Vex mill, rubber chopper, farmer mill, mincing machine, impact pulverizer, and roll pulverizer).
  • a shredding device eg, Vex mill, rubber chopper, farmer mill, mincing machine, impact pulverizer, and roll pulverizer.
  • the compound (B) may be added while shredding the hydrous gel in the shredding step.
  • the method for producing the water-absorbing resin composition ⁇ of the present embodiment comprises drying the water-containing gel, distilling off the solvent (including water) in the water-containing gel, and obtaining the water-absorbing resin containing the crosslinked polymer (A). It may have a drying step to obtain the composition.
  • the water absorbent resin composition obtained by drying in the drying step is the water absorbent resin composition ⁇ .
  • microwave drying As a drying method in the drying step, microwave drying, a thin film drying method using a drum dryer, etc., a (heating) vacuum drying method, a freeze drying method, an infrared drying method, decantation, filtration, and the like can be applied.
  • the drying temperature in the drying step is 100-300°C, preferably 150-250°C. If the drying temperature is high, the drying time will be shortened, resulting in improved productivity. The color tone of the water absorbent resin composition may deteriorate. If the drying temperature is lower than 100°C, the water-absorbing resin composition cannot be sufficiently dried, resulting in a decrease in productivity.
  • the drying time is preferably within 60 minutes, more preferably within 40 minutes, from the viewpoint of suppressing changes in soluble matter while suppressing changes in color after long-term storage in a hot and humid environment. preferable. Also, the drying time is generally preferably 10 minutes or more. Short drying times can lead to undried material and clogging later in the milling process.
  • the water absorbent resin composition obtained in the drying step is pulverized to obtain a particulate water absorbent resin composition containing the crosslinked polymer (A). It may have a pulverization step to obtain.
  • the method for pulverizing the water-absorbent resin composition containing the crosslinked polymer (A) is not particularly limited, and a pulverizing device (e.g., hammer pulverizer, impact pulverizer, roll pulverizer, machine and jet stream type pulverizer), etc. can be used.
  • a pulverizing device e.g., hammer pulverizer, impact pulverizer, roll pulverizer, machine and jet stream type pulverizer, etc.
  • the pulverized crosslinked polymer (A) can be adjusted in particle size by sieving or the like, if necessary.
  • the compound (B) may be added while pulverizing the water absorbent resin composition containing the crosslinked polymer (A) in the pulverization step.
  • the pulverization When the addition of the compound (B) is performed while pulverizing the water-absorbent resin composition containing the crosslinked polymer (A) in the pulverization step, or when the addition is performed before the pulverization step, the pulverization
  • the water absorbent resin particles obtained in the step are the water absorbent resin composition ⁇ particles.
  • the method for producing the water-absorbing resin composition ⁇ of the present embodiment includes the crosslinked polymer ( It has a surface cross-linking step of surface cross-linking the water absorbent resin composition containing A).
  • the amount (% by weight) of the surface cross-linking agent (d) used is not particularly limited because it can be varied depending on the type of the surface cross-linking agent, cross-linking conditions, target performance, etc., but is not particularly limited from the viewpoint of absorption characteristics and the like. Therefore, it is preferably 0.001 to 3, more preferably 0.005 to 2, and particularly preferably 0.01 to 1.5, based on the weight of the crosslinked polymer (A).
  • the surface cross-linking of the cross-linked polymer (A) can be performed by mixing the water-absorbing resin composition containing the cross-linked polymer (A) and the surface cross-linking agent (d) and heating the mixture.
  • the method for mixing the water absorbent resin composition containing the crosslinked polymer (A) and the surface cross-linking agent (d) includes a cylindrical mixer, a screw mixer, a screw extruder, a turbulizer, and a Nauta mixer. mixer, double-arm kneader, fluidized mixer, V-shaped mixer, mincing mixer, ribbon mixer, fluidized mixer, airflow mixer, rotating disc mixer, conical blender, roll mixer, etc.
  • a method of uniformly mixing the water-absorbent resin composition containing the crosslinked polymer (A) and the surface cross-linking agent (d) using an apparatus can be mentioned.
  • the surface cross-linking agent (d) may be diluted with water and/or any solvent before use.
  • the compound (B) may be added while mixing the water absorbent resin composition containing the crosslinked polymer (A) and the surface crosslinking agent (d) in the surface crosslinking step.
  • the addition of the compound (B) is performed while mixing the water-absorbent resin composition containing the crosslinked polymer (A) and the surface cross-linking agent (d) in the surface cross-linking step, or from the surface cross-linking step If performed before, the water absorbent resin composition obtained in the surface cross-linking step is the water absorbent resin composition ⁇ .
  • the temperature at which the crosslinked polymer (A) and the surface cross-linking agent (d) are mixed is not particularly limited, but is preferably 10 to 150°C, more preferably 20 to 100°C, and particularly preferably 25 to 80°C. .
  • the heating temperature is preferably 100 to 180°C, more preferably 110 to 175°C, particularly preferably 120 to 170°C, from the viewpoint of breakage resistance of the water absorbent resin composition. Heating at 180° C. or less enables indirect heating using steam, which is advantageous in terms of facilities. Heating temperatures below 100° C. may result in poor absorption performance.
  • the heating time can be appropriately set depending on the heating temperature, but from the viewpoint of absorption performance, it is preferably 5 to 60 minutes, more preferably 10 to 40 minutes. It is also possible to further surface-crosslink the water-absorbing resin composition obtained by surface-crosslinking using a surface-crosslinking agent that is the same as or different from the surface-crosslinking agent used first.
  • the particle size is adjusted by sieving if necessary.
  • the average particle size of the obtained particles is preferably 100-600 ⁇ m, more preferably 200-500 ⁇ m.
  • the content of fine particles is preferably as small as possible, the content of particles of 100 ⁇ m or less is preferably 3% by weight or less, and the content of particles of 150 ⁇ m or less is more preferably 3% by weight or less.
  • the method for producing the water absorbent resin composition ⁇ of the second embodiment includes: A method for producing the water absorbent resin composition ⁇ having a polymerization step of obtaining a hydrous gel containing the crosslinked polymer (A), an adding step A of adding a salt of one or more main group elements selected from the group consisting of iodine, tellurium, antimony and bismuth; It is characterized by having an addition step B of adding the compound (B) and/or a salt thereof after the polymerization step.
  • the polymerization step in the method for producing the water absorbent resin composition ⁇ of the present embodiment is similar to the polymerization step in the method for producing the water absorbent resin composition ⁇ of the first embodiment.
  • the polymerization of the monomer composition may be carried out in the presence of the main group element compound, or may be carried out in the absence of the organic main group element compound.
  • the polymerization step in the method for producing the water absorbent resin composition ⁇ of the present embodiment includes the water absorbent resin composition of the first embodiment. It is the same as the polymerization step in the method for producing ⁇ .
  • the polymerization step in the method for producing the water-absorbing resin composition ⁇ of the present embodiment includes polymerizing the monomer composition as described above.
  • the polymerization step is the same as in the method for producing the water absorbent resin composition ⁇ of the first embodiment, except that the polymerization step is performed in the absence of the organic main group element compound.
  • the addition step is performed from the viewpoint of suppressing changes in the soluble content while suppressing changes in color after long-term storage in a hot and humid environment.
  • the typical element is preferably iodine from the viewpoint of suppressing coloration.
  • the salt of the main group element may be a metal salt or a non-metal salt.
  • iodine salt examples include the above-mentioned iodine compounds, and among these, metal salts of iodine are preferable from the viewpoint of suppressing coloration and cost effectiveness, more preferably alkali metal salts of iodine and / or alkaline earth Metal salts, most preferably sodium iodide or potassium iodide.
  • the said iodine compound may be used individually and may use 2 or more types together.
  • the method of adding these salts of the main group elements is not particularly limited, and includes a method of kneading the hydrous gel and the main group element, a method of adding the main group element and shredding the hydrous gel in the chopping step, and a method of adding the main group element to shreds in the drying step.
  • Examples include a method of kneading the obtained water-absorbent resin composition and the representative element, and a method of mixing the crosslinked polymer (A), the surface cross-linking agent (d) and the representative element in the surface cross-linking step.
  • the addition step B, the shredding step, the drying step, the pulverization step, and the surface cross-linking step in the method for producing the water-absorbing resin composition ⁇ of the second embodiment can include the addition step A. These are the same as the adding step B, the shredding step, the drying step, the pulverizing step, and the surface cross-linking step in the method for producing the water absorbent resin composition ⁇ of the embodiment.
  • An absorbent body can be obtained using the water absorbent resin composition ⁇ .
  • the water absorbent resin composition ⁇ may be used alone, or may be used together with other materials to form an absorbent.
  • Such other materials include fibrous materials and the like.
  • the structure and manufacturing method of the absorbent when used with fibrous materials are the same as those of known ones (Japanese Patent Laid-Open Nos. 2003-225565, 2006-131767 and 2005-097569). be.
  • Cellulose fibers, organic synthetic fibers, and mixtures of cellulosic fibers and organic synthetic fibers are preferable as the fibrous material.
  • cellulosic fibers include natural fibers such as fluff pulp, and cellulosic chemical fibers such as viscose rayon, acetate and cupra.
  • the raw material softwood, hardwood, etc.
  • manufacturing method chemical pulp, semi-chemical pulp, mechanical pulp, CTMP, etc.
  • bleaching method and the like of this cellulose-based natural fiber are not particularly limited.
  • organic synthetic fibers examples include polypropylene fibers, polyethylene fibers, polyamide fibers, polyacrylonitrile fibers, polyester fibers, polyvinyl alcohol fibers, polyurethane fibers, and heat-fusible composite fibers (the above fibers having different melting points). (sheath-and-core type, eccentric type, side-by-side type, etc.), fibers obtained by blending at least two of the above fibers, and fibers obtained by modifying the surface layer of the above fibers.
  • cellulosic natural fibers polypropylene fibers, polyethylene fibers, polyester fibers, heat-fusible conjugate fibers and mixed fibers thereof are preferred, and more preferred are fluff pulp, heat-fusible conjugate fibers and mixed fibers thereof in that they are excellent in shape retention after water absorption by the water absorbing agent.
  • the length and thickness of the above-mentioned fibrous material are not particularly limited, and if the length is in the range of 1 to 200 mm and the thickness is in the range of 0.1 to 100 denier, it can be suitably used.
  • the shape is not particularly limited as long as it is fibrous, and examples include a thin cylindrical shape, a split yarn shape, a staple shape, a filament shape, a web shape, and the like.
  • the weight ratio of the water absorbent resin composition ⁇ particles to the fibers is preferably 40/60 to 95/5, more preferably 50/50 to 90/10.
  • An absorbent article can be obtained using the water absorbent resin composition ⁇ . Specifically, the absorber described above is used.
  • Absorbent products include not only sanitary goods such as paper diapers and sanitary napkins, but also anti-condensation agents, water retention agents for agriculture and gardening, waste blood solidification agents, disposable body warmers, etc. It can be applied for various uses such as retention agent use and gelling agent use.
  • the manufacturing method of the absorbent article and the like are the same as those known (described in JP-A-2003-225565, JP-A-2006-131767, JP-A-2005-097569, etc.).
  • ⁇ Deterioration test of water absorbent resin composition 2.0 g of the water-absorbing resin composition was placed in a glass container having an inner diameter of 26.6 mm and a depth of 14.6 mm, and the surface was evenly leveled. This was stored in a thermo-hygrostat at 80 ⁇ 2° C. and 80 ⁇ 5% RH for 7 days. After that, the glass container was taken out from the constant temperature and humidity chamber and left in an environment of 25 ⁇ 2° C. and 50 ⁇ 10% RH for 1 hour to obtain a water absorbent resin composition after the deterioration test.
  • ⁇ Method for measuring water content of water absorbent resin composition Heat drying moisture meter [MS-70 manufactured by A&D Co., Ltd., set temperature: 120 ° C., set time: 45 minutes, atmospheric temperature and humidity before heating: 25 ⁇ 2 ° C., 50 ⁇ 10% RH] A 2.0 g sample was heated, and the ratio of the reduced weight to the weight of the sample before drying was taken as the moisture content (%).
  • ⁇ Method for measuring the soluble content of the water absorbent resin composition 200.0 g of 0.9% by weight saline solution was weighed into a 300 ml glass beaker (inner diameter 73 mm, height 110 mm), and a stirrer tip (length 50 mm, diameter 8 mm) was used to rotate the stirrer at 500 rpm to stir the saline solution. , 1.20 g of the water-absorbent resin composition was added to the salt solution, sealed with plastic wrap, and stirred for 3 hours to prepare a soluble extract from which the soluble components of the water-absorbent resin composition were extracted. Then, this soluble extract was filtered using filter paper manufactured by ADVANTEC Toyo Co., Ltd.
  • a blank solution of 50 g of 0.9% by weight saline solution was titrated with an N/50 KOH aqueous solution until the pH of the saline solution reached 10. Then, the titration amount ([W KOH,b ] ml) of the N/50 KOH aqueous solution required to bring the pH of the 0.9 wt% saline solution to 10 was obtained. Then titration with N/10 HCl aqueous solution was performed until the pH of the saline solution was 2.7. Then, the titration amount ([W HCl,b ] ml) of N/10 HCl aqueous solution required for the pH of the 0.9 wt % saline solution to reach 2.7 was obtained.
  • the measurement solution is subjected to the same operation as the above titration operation, and the titration amount of the N / 50 KOH aqueous solution ([W KOH, S ] ml) necessary for the pH of the measurement solution to become 10 , and a method for obtaining the titration amount ([W HCl,S ] ml) of the N/10 HCl aqueous solution necessary for the pH of the measurement solution to become 2.7.
  • ⁇ Method for measuring YI value (yellowness) of water absorbent resin composition The initial coloring (coloring immediately after production) of the water-absorbing resin composition and the easiness of coloration progressing during long-term storage or application products are tristimulus values in the XYZ color system with a standard white plate and a standard black plate. Using a digital colorimetric color difference meter (NF-333 type manufactured by Nippon Denshoku Industries Co., Ltd.) with X, Y, and Z corrected ⁇ deterioration test of water-absorbing resin composition> before and after the YI value (yellowness) is measured. It was evaluated by The higher the yellowness, the more advanced the coloring.
  • ⁇ YI 100 ⁇ (1 ⁇ (0.847Z/Y))
  • Y value of tristimulus value
  • Z value of tristimulus value Z in the XYZ color system
  • ⁇ YI change in yellowness
  • ⁇ Method for Measuring Water Retention Amount of Water Absorbent Resin Composition> 1.00 g of a water-absorbing resin composition was placed in a tea bag (20 cm long, 10 cm wide) made of nylon mesh with an opening of 63 ⁇ m (JIS Z8801-1: 2006), and physiological saline (salt concentration 0.9%) 1 ,000 ml without stirring for 1 hour, then taken out and hung for 15 minutes to drain. After that, the whole tea bag was placed in a centrifuge and dehydrated by centrifugation at 150 G for 90 seconds to remove excess physiological saline. The physiological saline used and the temperature of the measurement atmosphere were 25°C ⁇ 2°C. Water retention amount of the water absorbent resin composition (g / g) (h1) - (h2) In addition, (h2) is the weight of the tea bag measured by the same operation as above without the measurement sample.
  • ⁇ Method for measuring absorption under load of water absorbent resin composition In a cylindrical plastic tube (inner diameter: 25 mm, height: 34 mm) with a mesh opening of 63 ⁇ m (JIS Z8801-1: 2006) attached to the bottom, 250 to 500 ⁇ m using a 30 mesh sieve and a 60 mesh sieve. 0.16 g of the water-absorbing resin composition sieved to the range is weighed, and the cylindrical plastic tube is set vertically so that the measurement sample has a substantially uniform thickness on the nylon net. A weight (weight: 200.0 g, outer diameter: 24.5 mm) was put on it.
  • the water-absorbing resin composition and the weight were placed in a petri dish (diameter: 12 cm) containing 60 ml of physiological saline (salt concentration: 0.9%).
  • a cylindrical plastic tube was set up vertically, immersed with the nylon mesh side down, and allowed to stand for 60 minutes. After 60 minutes, pull up the cylindrical plastic tube from the petri dish, tilt it obliquely, collect the water adhering to the bottom in one place and drop it as water droplets to remove excess water, and then add the water-absorbent resin composition and the weight.
  • the weight (M2) of the entire cylindrical plastic tube containing the was weighed, and the absorption under load was obtained from the following formula.
  • the physiological saline used and the temperature of the measurement atmosphere were 25°C ⁇ 2°C.
  • Absorption amount under load (g/g) of water absorbent resin composition ⁇ (M2) - (M1) ⁇ /0.16
  • ⁇ Method for measuring the content of typical elements in the solid content of the water-absorbing resin composition 1.0 g of the water-absorbing resin composition after the water content measurement was acid-decomposed with a microwave acid decomposition device [Nova WAVE manufactured by SCP SCIENCE], and then ICP-MS [7500cs manufactured by Agilent] was used to determine the typical element content by the standard addition method. was measured to measure the content (%) of typical elements in the solid content of the water absorbent resin composition.
  • ⁇ Preparation of absorbent article (model absorbent body)> 80 parts by weight of fluff pulp and 120 parts by weight of the evaluation sample ⁇ water-absorbing resin composition ⁇ were mixed with an airflow mixer ⁇ Pad Former manufactured by Autec Co., Ltd. ⁇ to obtain a mixture, and then the basis weight of the mixture was It was uniformly laminated on an acrylic plate (thickness: 4 mm) so as to have a weight of about 500 g/m 2 and was pressed at a pressure of 5 kg/cm 2 for 30 seconds to obtain an absorbent.
  • This absorber was cut into rectangles of 14 cm x 36 cm, and water-absorbing paper (basis weight: 15.5 g/m 2 , manufactured by Advantech, filter paper No.
  • a model absorbent body was prepared by placing a polyethylene sheet (polyethylene film UB-1 manufactured by Tamapoly Co., Ltd.) on the back side and a non-woven fabric (basis weight: 20 g/m 2 , Eltas Guard manufactured by Asahi Kasei Co., Ltd.) on the front side.
  • a polyethylene sheet polyethylene film UB-1 manufactured by Tamapoly Co., Ltd.
  • a non-woven fabric basic weight: 20 g/m 2 , Eltas Guard manufactured by Asahi Kasei Co., Ltd.
  • model absorbent body was stored for 7 days in a thermo-hygrostat at a temperature of 80 ⁇ 2° C. and a relative humidity of 80 ⁇ 5% RH. Thereafter, the model absorbent body was taken out from the thermo-hygrostat and left in an environment of 25 ⁇ 2° C. and 50 ⁇ 10% RH for 1 hour to obtain a model absorbent body after the deterioration test.
  • ⁇ Surface dryness value by SDME method A paper diaper in which the detector of an SDME (Surface Dryness Measurement Equipment) tester (manufactured by WK system) is sufficiently moistened ⁇ artificial urine (potassium chloride 0.03% by weight, magnesium sulfate 0.08% by weight, sodium chloride 0.8% by weight % and deionized water 99.09% by weight) and left for 60 minutes. ⁇ , set the 0% dryness value, and then set the detector of the SDME tester to a dry paper diaper ⁇ Paper diaper was prepared by heating and drying at 80° C. for 2 hours. ⁇ and set 100% dryness to calibrate the SDME tester.
  • SDME Surface Dryness Measurement Equipment
  • a metal ring (inner diameter 70 mm, length 50 mm) is set in the center of the model absorber to be measured, 90 ml of artificial urine is injected, and from the start of injection to the end of absorbing the artificial urine ⁇ gloss due to artificial urine can be confirmed.
  • remove the metal ring immediately, place the SDME detector on the center of the model absorber, and start measuring the surface dryness value.
  • the model absorbent body after the deterioration test was also measured in the same manner to obtain the surface dryness value (2).
  • Example 1 (Polymerization process) 310 parts of acrylic acid (manufactured by Mitsubishi Chemical Corporation), 0.853 parts of pentaerythritol triallyl ether (manufactured by Daiso Corporation) as a cross-linking agent (b), and 681 parts of deionized water were stirred and mixed to prepare an aqueous monomer solution. , this mixed solution was put into a polymerization vessel capable of adiabatic polymerization. By introducing nitrogen gas into the solution, the dissolved oxygen content in the solution was adjusted to 0.2 ppm or less, and the solution temperature was adjusted to 5°C.
  • the neutralized water-containing gel was dried for 45 minutes in a ventilation dryer ⁇ 150° C., wind speed 2 m/sec ⁇ to obtain a dry product.
  • the dried product was pulverized with a juicer mixer (Osterizer Blender manufactured by Oster), sieved, and adjusted to a particle size range of 710 to 150 ⁇ m in opening to obtain a crosslinked polymer (A-1).
  • Example 2 A particulate water-absorbent resin composition (P-2) of the present invention was obtained in the same manner as in Example 1, except that 6.20 parts of the 10% aqueous citric acid solution in Example 1 was changed to 15.5 parts.
  • Example 3 0.853 parts of pentaerythritol triallyl ether (manufactured by Daiso Co., Ltd.) in Example 1 was changed to 1.008 parts, and 6.20 parts of a 10% aqueous citric acid solution was added to 10% 1-hydroxyethane-1,1-diphosphonic acid.
  • Aqueous solution prepared by diluting 60% 1-hydroxyethane-1,1-diphosphonic acid aqueous solution (manufactured by TCI) with ion-exchanged water) in the same manner as in Example 1 except that the amount was changed to 6.20 parts.
  • a particulate water absorbent resin composition (P-3) was obtained.
  • Example 4 The particulate water-absorbing resin composition of the present invention was prepared in the same manner as in Example 3, except that the 10% aqueous solution of 1-hydroxyethane-1,1-diphosphonic acid in Example 3 was changed from 6.20 parts to 15.5 parts. (P-4) was obtained.
  • Example 5 0.853 parts of pentaerythritol triallyl ether (manufactured by Daiso Co., Ltd.) in Example 1 was changed to 1.178 parts, and 6.20 parts of 10% aqueous citric acid solution was added to 10% diethylenetriaminepentaacetic acid pentasodium salt aqueous solution (Chelest P ( A particulate water-absorbing resin composition (P-5) of the present invention was obtained in the same manner as in Example 1, except that the content was changed to 6.20 parts (prepared by diluting (manufactured by Cherest Co., Ltd.) with ion-exchanged water).
  • Example 6 The particulate water-absorbing resin composition (P-6) of the present invention was prepared in the same manner as in Example 5 except that the 10% diethylenetriaminepentaacetic acid pentasodium salt aqueous solution in Example 5 was changed from 6.20 parts to 15.5 parts. got
  • Example 7 In Example 3, 1.008 parts of pentaerythritol triallyl ether was replaced with 0.434 parts of methylenebisacrylamide (manufactured by TCI), and 0.31 parts of a 20% potassium iodide aqueous solution was changed to 0.22 parts. was carried out in the same manner as in Example 3 to obtain a particulate water absorbent resin composition (P-7) of the present invention.
  • Example 8 In the same manner as in Example 3 except that 1.008 parts of pentaerythritol triallyl ether (manufactured by Daiso Co., Ltd.) in Example 3 was changed to 0.329 parts of FOM-03006 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) A particulate water absorbent resin composition (P-8) was obtained.
  • Example 9 The present invention was prepared in the same manner as in Example 3, except that 0.329 parts of FOM-03006 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in Example 7 was changed to 0.341 parts of FOM-03007 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). A particulate water absorbent resin composition (P-9) of the invention was obtained.
  • Example 10 The present invention was prepared in the same manner as in Example 7 except that 0.329 parts of FOM-03006 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in Example 7 was changed to 0.434 parts of FOM-03008 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). A particulate water absorbent resin composition (P-10) of the invention was obtained.
  • Example 11 The present invention was prepared in the same manner as in Example 7, except that 0.329 parts of FOM-03006 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in Example 7 was changed to 0.353 parts of FOM-03009 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). A particulate water absorbent resin composition (P-11) of the invention was obtained.
  • Example 12 In the polymerization step of Example 4, 4.65 parts of 2% aqueous 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] solution, 1.24 parts of 1% aqueous hydrogen peroxide solution and In addition to 2.33 parts of a 2% ascorbic acid aqueous solution, 0.05 part of 2-iodo-2-methylpropionitrile is added and mixed to initiate polymerization, and a 20% potassium iodide aqueous solution is added in the gel shredding step.
  • a particulate water-absorbent resin composition (P-12) of the present invention was obtained in the same manner as in Example 4, except that it was not added.
  • Example 13 The particulate form of the present invention was prepared in the same manner as in Example 12 except that 15.5 parts of the 10% 1-hydroxyethane-1,1-diphosphonic acid aqueous solution in Example 12 was changed to 15.5 parts of the 10% citric acid aqueous solution. to obtain a water absorbent resin composition (P-13).
  • Example 14 The procedure of Example 12 was repeated except that 15.5 parts of the 10% 1-hydroxyethane-1,1-diphosphonic acid aqueous solution in Example 12 was changed to 15.5 parts of the 10% diethylenetriaminepentaacetic acid pentasodium salt aqueous solution. A particulate water absorbent resin composition (P-14) of the invention was obtained.
  • Example 15 In the gel shredding step of Example 12, the particulate water-absorbing resin composition (P-15) of the present invention was prepared in the same manner as in Example 12 except that 0.22 parts of a 20% potassium iodide aqueous solution was added. Obtained.
  • Example 16 In the gel shredding step of Example 4, 10% 1-hydroxyethane-1,1-diphosphonic acid aqueous solution and 20% potassium iodide aqueous solution were not added, and 0.09 part of ethylene glycol diglycidyl ether was added in the surface cross-linking step.
  • a particulate water-absorbent resin composition (P-16) of the present invention was obtained in the same manner as in Example 4, except that the mixture was changed to a mixture of 0.33 parts of an acid aqueous solution and 1.7 parts of water.
  • the neutralized water-containing gel was dried for 45 minutes in a ventilation dryer ⁇ 150° C., wind speed 2 m/sec ⁇ to obtain a dry product. After pulverizing the dried body with a juicer mixer (Osterizer Blender manufactured by Oster), it is sieved and adjusted to a particle size range of 710 to 150 ⁇ m with an opening of 710 to 150 ⁇ m, and the particulate water absorbent resin composition of the present invention (P- 17) was obtained.
  • a juicer mixer Ole Blender manufactured by Oster
  • Example 17 the present invention was prepared in the same manner as in Example 17, except that 6.20 parts of the 10% 1-hydroxyethane-1,1-diphosphonic acid aqueous solution was changed to 6.20 parts of the 10% diethylenetriaminepentaacetic acid pentasodium salt aqueous solution. A particulate water absorbent resin composition (P-18) of the invention was obtained.
  • ⁇ Comparative Example 2> A particulate water absorbent resin composition was prepared in the same manner as in Comparative Example 1, except that 0.853 parts of pentaerythritol triallyl ether (manufactured by Daiso Co., Ltd.) in Comparative Example 1 was changed to 0.434 parts of methylenebisacrylamide (manufactured by TCI Co., Ltd.). A product (P-20) was obtained.
  • Example 4 A particulate water absorbent resin composition (P-22) was obtained in the same manner as in Example 3 except that 6.20 parts of the 10% 1-hydroxyethane-1,1-diphosphonic acid aqueous solution of Example 1 was not added. rice field.
  • Table 1 shows the results of the evaluation performed for Examples 1 to 18.
  • Table 2 shows the results of the evaluation performed on Comparative Examples 1 to 4.
  • the water absorbent resin composition of the present invention can suppress changes in soluble matter while suppressing changes in color after long-term storage in a hot and humid environment.

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Abstract

La présente invention concerne une composition de résine absorbant l'eau qui contient : un polymère réticulé (A) contenant, en tant que motifs constitutifs essentiels, un monomère vinylique soluble dans l'eau (a1) et/ou un monomère vinylique (a2) qui forme le monomère vinylique soluble dans l'eau (a1) après hydrolyse, et un agent de réticulation (b) ; un composé (B) qui est d'un ou de plusieurs types choisis dans le groupe constitué par un composé représenté par la formule générale (1) et un composé représenté par la formule générale (2), et/ou un sel de celui-ci ; et un ou plusieurs éléments classiques choisis dans le groupe constitué par l'iode, le tellure, l'antimoine et le bismuth. La présente invention est apte à fournir : une composition de résine absorbant l'eau qui peut supprimer les variations en termes de matière soluble tout en supprimant les variations en termes de teinte de couleur après un stockage à long terme dans un environnement à haute température et à humidité élevée ; un absorbeur et un article absorbant obtenus à l'aide de celle-ci ; et un procédé de production de la composition de résine absorbant l'eau.
PCT/JP2022/025497 2021-06-28 2022-06-27 Composition de résine absorbant l'eau, absorbeur et article absorbant obtenus à l'aide de celle-ci, et procédé de production d'une composition de résine absorbant l'eau WO2023276925A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013073614A1 (fr) * 2011-11-15 2013-05-23 株式会社日本触媒 Composition absorbant l'eau et procédé pour sa production, ainsi que son procédé d'entreposage et de stockage
WO2017057706A1 (fr) * 2015-10-02 2017-04-06 Ｓｄｐグローバル株式会社 Particules de résine absorbant l'eau et leur procédé de production
JP2018111806A (ja) * 2017-01-06 2018-07-19 Ｓｄｐグローバル株式会社 吸水性樹脂粒子の製造方法
WO2020059871A1 (fr) * 2018-09-21 2020-03-26 株式会社日本触媒 Procédé de production d'une résine absorbant l'eau, contenant un agent chélatant
JP2020056025A (ja) * 2018-10-01 2020-04-09 三洋化成工業株式会社 吸収性樹脂粒子及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013073614A1 (fr) * 2011-11-15 2013-05-23 株式会社日本触媒 Composition absorbant l'eau et procédé pour sa production, ainsi que son procédé d'entreposage et de stockage
WO2017057706A1 (fr) * 2015-10-02 2017-04-06 Ｓｄｐグローバル株式会社 Particules de résine absorbant l'eau et leur procédé de production
JP2018111806A (ja) * 2017-01-06 2018-07-19 Ｓｄｐグローバル株式会社 吸水性樹脂粒子の製造方法
WO2020059871A1 (fr) * 2018-09-21 2020-03-26 株式会社日本触媒 Procédé de production d'une résine absorbant l'eau, contenant un agent chélatant
JP2020056025A (ja) * 2018-10-01 2020-04-09 三洋化成工業株式会社 吸収性樹脂粒子及びその製造方法

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